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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This is a continuation of International Application No. PCT/CN2015/076393, filed on Apr. 13, 2015, which claims the priority benefits of China Application No. 201410635972.8, filed on Nov. 12, 2014. The entirety of each of the above-mentioned patent applications is hereby incorporated by reference herein and made a part of this specification.
BACKGROUND OF THE INVENTION
[0002] Technical Field
[0003] The present invention relates to the field of protective grids, and more particularly, to a protective grid with an adjustable size.
[0004] 2. Description of Related Art
[0005] Existing protective grids are usually composed of frames and grids, and there are two ways of connection: first, the stainless steel materials or iron art products are connected via welding; secondly, the aluminum alloy materials are connected via mortising. The assemblies of frames and grids are transported to an installation site after being fixed in the factory. The deficiencies are as follows: the size of the width and height must be determined by a professional who pays a visit to measure the size of a window, which generates more costs; it is hard to put into standardized production due to a plurality of sizes.
BRIEF SUMMARY OF THE INVENTION
[0006] This invention provides a protective grid with an adjustable size, which solves the problem of the length and width of a protective grid being unadjustable and the grid being difficult to install by way of adding connecting blocks.
[0007] The present invention provides a protective grid with an adjustable size, comprising frames which are composed of horizontal frames and vertical frames, an adjusting device which is used for connecting the horizontal frames and the vertical frames and comprises connecting blocks, and screws via which the connecting blocks are connected between the horizontal frames and the vertical frames. The length of the frames is adjusted in such a manner that the connecting blocks are sequentially connected for the purpose of adjusting the protective grid.
[0008] A further technical solution of the present invention is that the connecting block comprises a first mating protrusion and a first mating recess used for engaging the first mating protrusion, so as to facilitate the connection and alignment between the connecting blocks.
[0009] A further technical solution of the present invention is that the connecting block is provided with a first threaded protrusion and a first threaded recess capable of engaging the first threaded protrusion, so as to facilitate the connection and alignment between the connecting blocks.
[0010] A further technical solution of the present invention is that the connecting block is further provided with through holes, so as to facilitate the passing of the screws and fasten the fixation.
[0011] A further technical solution of the present invention is that the adjusting device further comprises rectangular blocks, wherein two end faces of the rectangular blocks which are vertical to each other are connected with the connecting blocks, with the end faces of the rectangular blocks provided with through holes, so as to facilitate the connection between the two frames which are vertical to each other.
[0012] A further technical solution of the present invention is that the adjusting device further comprises T-portion connecting blocks, and the T-portion connecting blocks further comprise a second mating protrusion and a third mating protrusion used for engaging the first connecting recess; the vertical frame further comprises an axis and is further provided on the side parallel to the axis with a second mating recess used for engaging the second mating protrusion, so as to facilitate the connection of the internal frames of the protective grid, as well as the alignment, and to fasten the connection.
[0013] To solve the above technical problems, a technical solution further provided in the invention is a protective grid with an adjustable size, comprising frames which are composed of horizontal frames and vertical frames, an adjusting device which is used for connecting the horizontal frames and the vertical frames and comprises a first mating block and a sleeving block used for sleeving the mating block on the outer side, and screws via which the first mating block and the sleeving block are connected between the horizontal frames and the vertical frames. The purpose of adjusting the overall length of the frame by way of increasing or decreasing the sleeving block is achieved in the manner of internal orientation and external adjustment.
[0014] A further technical solution of the present invention is that the first mating block comprises drawers and rectangular blocks used for connecting two of the drawers vertical to each other, and the end faces of the rectangular blocks which are connected with the drawers are provided with through holes, so as to facilitate the connection of the internal frames of the protective grid as well as the alignment, and secure the connection.
[0015] To solve the above technical problems, a technical solution further provided in the invention is a protective grid with an adjustable size, comprising frames which are composed of horizontal frames and vertical frames, an adjusting device which is used for connecting the horizontal frames and the vertical frames and comprises a third mating block, and screws via which the third mating block is connected between the horizontal frames and the vertical frames. The adjusting device is integrally designed to facilitate manufacturing, and the length of the frame can be adjusted by way of cutting the length of the third block.
[0016] A further technical solution of the present invention is that the third mating block is provided with an adjusting portion and a connecting portion used for connecting the adjusting portion, wherein the adjusting portion of a hollow structure is provided with sequentially connected recesses and protrusions, and the end faces of the connecting portion which are connected with the adjusting portion are provided with through holes. The recess facilitates the cutting of the third mating block while the end portion within the recess can also be inserted into the frame for fixation, and the outer edge of the protrusion is consistent with the frame in size so as to facilitate the positioning and fixation.
[0017] The beneficial effects of the present invention are as below: it is convenient to adjust and can fit the size of different window frames. The modular setting makes the production convenient and is favorable for large-scale production.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0018] FIG. 1 is an overall view of all embodiments of the present invention;
[0019] FIG. 2 is a perspective view of the connecting block provided according to Embodiment 1 of the present invention;
[0020] FIG. 3 is another perspective view of a connecting block provided according to Embodiment 1 of the present invention;
[0021] FIG. 4 is a perspective view of the T-portion connecting block provided according to Embodiment 1 of the present invention;
[0022] FIG. 5 is a perspective view of the connecting block according to Embodiment 2 of the present invention;
[0023] FIG. 6 is a perspective view of the rectangular block provided according to Embodiment 2 of the present invention;
[0024] FIG. 7 is another perspective view of the rectangular block provided according to the Embodiment 2 of the present invention;
[0025] FIG. 8 is a perspective view of the first mating block provided according to Embodiment 3 of the present invention;
[0026] FIG. 9 is a perspective view of the sleeving block provided according to Embodiment 3 of the present invention; and
[0027] FIG. 10 is a perspective view of the third mating block provided in Embodiment 4 of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0028] Embodiment 1 as shown in FIG. 1 to FIG. 3 : a protective grid with an adjustable size, comprising frames which are composed of horizontal frames 1 and vertical frames 3 , an adjusting device 2 which is used for connecting the horizontal frames 1 and the vertical frames 3 and comprises connecting blocks, and screws via which the connecting blocks are connected between the horizontal frames 1 and the vertical frames 3 . The connecting blocks are sequentially connected to form the adjusting device 2 , and the length of the adjusting device 2 is adjusted by way of adjusting the number of the connecting blocks. The length of the frame is changed by way of adding the adjusting device 2 and changing the number of the connecting blocks. It can facilitate the adjustment of the width of the protective grid so as to meet the needs of most customers.
[0029] The connecting block in the embodiment is the connecting block 21 , which comprises a first mating protrusion 211 and a first mating recess 212 used for engaging the first mating protrusion 211 . In the process of interconnection between the connecting blocks 21 , the first mating protrusion 211 of the previous connecting block 21 can be inserted into the first mating recess 212 of the latter connecting block so as to facilitate the alignment to avoid deviation in the process of fixation via screws. It can ensure the interconnection between the blocks and secure the connection, which facilitates the installation.
[0030] The connecting block 21 is further provided with through holes 210 . The axis of the through hole 210 is parallel to the connecting direction of the connecting block, or parallel to the direction of the long axis of the frame. The screw can be fixed through a through hole into a screw groove on the frame.
[0031] The adjusting device 2 further comprises a rectangular block which is similar to the rectangular blocks in FIG. 6 and FIG. 7 , and two end faces of the rectangular blocks perpendicular to each other are connected with the connecting blocks, that is, the two faces of the rectangular block are provided with the first mating protrusion 211 instead of the threaded protrusion as shown in FIG. 7 . The end faces of the rectangular block are provided with through holes. It facilitates the connection between the rectangular block and the connecting block.
[0032] The adjusting device 2 further comprises T-portion connecting blocks 24 , and the T-portion connecting blocks 24 further comprise a second mating protrusion 241 and a third mating protrusion 242 used for engaging the first connecting recess; the vertical frame 3 further comprises an axis and is further provided on the side parallel to the axis with a second mating recess used for engaging the second mating protrusion 241 , that is, a protruding end is provided on one side of the vertical frame 3 and it engages the vertical frame 3 to fix the T-portion connecting block 24 .
[0033] Embodiment 2 as shown in FIG. 1 , FIG. 5 , FIG. 6 and FIG. 7 : a protective grid with an adjustable size, comprising frames which are composed of horizontal frames 1 and vertical frames 3 , an adjusting device 2 which is used for connecting the horizontal frames I and the vertical frames 3 and comprises connecting blocks, and screws via which the connecting blocks are connected between the horizontal frames 1 and the vertical frames 3 . The connecting blocks are sequentially connected to form the adjusting device 2 , and the length of the adjusting device 2 is adjusted by way of adjusting the number of the connecting blocks. The length of the frame is changed by way of adding the adjusting device 2 and changing the number of the connecting blocks. It can facilitate the adjustment of the width of the protective grid so as to meet the needs of most customers.
[0034] The connecting block 22 in Embodiment 2 is provided with a first threaded protrusion and a first threaded recess 221 capable of engaging the first threaded protrusion, as shown in FIG. 5 , that is, the connection between the blocks is realized via the thread, so that the connection is tighter and not easy to loosen.
[0035] The connecting block is further provided with through holes 210 . The axis of the through hole is parallel to the connecting direction of the connecting block, or parallel to the frame. The screw can be fixed through a through hole into a screw groove on the frame.
[0036] The adjusting device 2 further comprises rectangular blocks, as shown in FIG. 6 and FIG. 7 , wherein two end faces of the rectangular blocks which are vertical to each other are connected with the connecting blocks, with the end faces of the rectangular blocks provided with through holes. And meanwhile the end faces of the rectangular block used for connecting the connecting block in Embodiment 1 are further provided with a first threaded protrusion which facilitates the connection between the rectangular block and the connecting block.
[0037] The adjusting device 2 further comprises T-portion connecting blocks, and the T-portion connecting blocks further comprise a second mating protrusion 241 and a second threaded protrusion used for engaging the first threaded recess 221 ; the vertical frame 3 further comprises an axis and is further provided on the side parallel to the axis with a second mating recess used for engaging the second mating protrusion 241 . The T-portion connecting block in this embodiment is similar to that shown in FIG. 4 , but the threaded protrusion is used instead of the mating protrusion in the figure so as to facilitate the connection of the connecting block 22 with the threaded groove in this embodiment.
[0038] Embodiment 3 as shown in FIG. 1 , FIG. 8 and FIG. 9 : a protective grid with an adjustable size, comprising frames which are composed of horizontal frames 1 and vertical frames 3 , an adjusting device 2 which is used for connecting the horizontal frames 1 and the vertical frames 3 and comprises a first mating block 25 and a sleeving block 26 used for sleeving the mating block on the outer side, and screws via which the first mating block 25 and the sleeving block 26 are connected between the horizontal frames 1 and the vertical frames 3 .
[0039] The first mating block 25 comprises drawers 251 and rectangular blocks 252 used for connecting two of the drawers 251 vertical to each other, wherein the drawer 251 has a U-shaped cross section, and the end faces of the rectangular blocks 252 which are connected with the drawers 251 are provided with through holes.
[0040] The sleeving block 26 is of a hollow structure, with both end faces provided with mating protrusions and mating recesses which facilitate the engagement with the mating protrusions.
[0041] The process of the implementation: the sleeving block 26 is sleeved on the drawer 251 , and the drawer 251 is inserted into the frame and fixed on the frame via the screws which are inserted into the through holes of the rectangular block 252 . The length and width of the protective grid are adjusted by way of adjusting the number of the sleeving blocks 26 .
[0042] Embodiment 4 as shown in FIG. 1 and FIG. 10 : a protective grid with an adjustable size, comprising frames which are composed of horizontal frames 1 and vertical frames 3 , an adjusting device 2 which is used for connecting the horizontal frames 1 and the vertical frames 3 and comprises third blocks 27 , and screws via which the third mating blocks 27 are connected between the horizontal frames 1 and the vertical frames 3 .
[0043] The third mating block 27 is provided with an adjusting portion and a connecting portion used for connecting the adjusting portion, wherein the adjusting portion of a hollow structure is provided with sequentially connected recesses 271 and protrusions 272 , and the end faces of the connecting portion which are connected with the adjusting portion are provided with through holes.
[0044] The adjusting portion refers to the recess 271 and the protrusion 272 sequentially connected on the third mating block 27 . The connecting portion refers to the rectangular block which is used for connecting the two adjusting portions vertical to each other in the figure, wherein the rectangular block is provided with the through holes which facilitates the passing of the screws which can pass through the adjusting portion of a hollow structure to be fixed onto the frames.
[0045] The foregoing are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements based on the spirit and principle of the present invention shall be covered in the protection scope of the present invention.
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The present invention relates to the field of protective grids, and more particularly, to a protective grid with an adjustable size, comprising frames which are composed of horizontal frames and vertical frames, an adjusting device which is used for connecting the horizontal frames and the vertical frames and comprises connecting blocks, and screws via which the connecting blocks are connected between the horizontal frames and the vertical frames. It is convenient to adjust and can fit the size of different window frames; the modular setting makes the production convenient and is favorable for a large-scale production.
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TECHNICAL FIELD
[0001] This invention is related to food freezing processes, and specifically it refers to freezing equipment operating with liquid nitrogen, for food confined in a container destined for distribution to final consumer, in order to preserve the food so frozen.
BACKGROUND OF THE INVENTION
[0002] Storing of food for long time periods has several difficulties that must be solved. Food can be stored at environmental temperature for a very short and limited time and, in general, it is not possible to store food for a long time even at low temperature.
[0003] To allow the storing of food for relatively long periods of time and in particular at environmental temperature or in some cases at low temperatures, it is required to prevent food deterioration caused by microorganisms growing, such as bacteria, fungi, etc. Growing of such organisms in food can depend of the presence of water in the food as well as of the conditions such as storing temperature, environmental temperature, etc. Growing of microorganisms, including bacteria, is accelerated al environmental or higher temperature, in such a way that the velocity of food deterioration is increased at higher temperatures, decaying in a shorter time period.
[0004] For that reason, food is stored at low temperature, wherein organisms have a low possibility to grow-up; multiplication of organisms can be controlled and deterioration of food can be prevent. However, storage of food in such low temperatures can produce new problems on the food, when frozen or refrigerated food is defrosted, as described below.
[0005] Nowadays the best option to maintain fresh or raw food for a certain time without causing deterioration is to freeze or refrigerate it and to maintain preserved in a cooling chamber.
[0006] Food freezing is a way of preservation based on the solidification of water content in it. For this reason it must be taken into account the water content in the product as a factor. The freezing latent heat depends on the water quantity. Other factors are the starting and ending temperature because they determine the amount of heat to be extracted from the product. In the field of food, freezing is defined as the application of intense cold capable to stop bacterial and enzymatic processes that destroy food.
[0007] Freezing of food consists in diminishing the water temperature (sensible heat) and further change of phase from liquid to solid (latent heat); because water is the major component (from 50 to 90%). Water freezing in food is more complex than in pure water, because the presence of structures that conforms the food itself: lipids, proteins, fiber, starch, sugars and water that modify freezing parameters.
[0008] As the first step of freezing, part of the water diminishes its temperature to reach the freezing point (0° C.) and then small ice nuclei (“freezing seeds”) begin to be produced. Ice starts to be formed around such nuclei and depending on freezing velocity, ice crystals could be elongated, end-softened, big, small, or be produced inside/outside of the cell. Depending on freezing velocity, the following phenomena could be present:
Protein denaturalization: Whenever the product has been frozen slowly, or fluctuation of temperature are present during storing, ice crystals produced extract the water linked to proteins when growing, in such a way that proteins are disorganized and they are incapable to recover the water when defrosted, so said water when lost, drags hydro-soluble nutrients. This process changes food texture, producing hardening and diminishing its solubility and nutritional value. Starch retraction: Starch is made from glucose linear chains, called amylose, and complex branched-chain structures called amylopectin. Starch granules when in a cold suspension, tend to blow up, retaining water and when reach certain temperature, they gelatinize and thicken the liquid. When this gel rests, the amylose linear chains aggregate as if crystallize and liberate the water previously retained in its structure, a process called syneresis. That is why it is convenient to select starch in food with a very low rate of amylose. By example, rice has an amylose rate of 16%, corn has 24%, sorghum and tapioca have no amylose. Lipid contraction: A lipid in solid state is called fat, whereas if it is in liquid state is called oil. Change of state from solid to liquid depends on the melting point of the lipid. If a food is frozen, oils solidify and they can contract.
[0012] Food with low percent of humidity, have a lower initial freezing point, because vapor pressure diminishes due to the solutes. It is not possible to freeze the entire content of water, because just the so called free water (around 75%) is frozen during the process.
[0013] Types of freezing:
By air: a cold air current extracts heat from the product until the final temperature is reached. By contact: a cold surface in touch with the product extracts the heat. Cryogenic: Cryogenic fluids, nitrogen or carbon dioxide, are used, replacing the cold air to reach the freezing effect.
Freezing Effects
[0017] Drying up: Approximately 80% of the total weight in an animal or even more in a plant, it is water. Water is the major component in food derived from animals and plants. When a food is frozen, water is transformed into ice and a drying up effect is produced.
[0018] Nucleation: When food is frozen at a normal atmospheric pressure, its temperature falls to 0° C., at this time water starts to convert into ice. It stills at that temperature by a while and when crystallization is complete, temperature descends until equilibrates the environmental temperature. The time when there is not a drop of temperature is the time required to extract latent freezing heat (80 cal/g). During this time the effect of the cold is equilibrated with heat liberated by water because the change of state. Temperature stills constant and produces a horizontal line in a graph, of which longitude depends on the velocity of heat dissipation. During this time there is a equilibrium between crystal forming and melting.
[0019] At beginning of the horizontal section, a light depression is observed, indicating an overcooling in water before crystallization starts (this is more noticeable in small volumes such as cells and microorganisms). This occurs with a great velocity of heat elimination and it assures a fast formation of ice crystals. Since water in food is not pure but it is a solution of salts, sugars and soluble proteins, and further a complex of protein molecules in colloidal suspension, its freezing pint is lower. This lowering is proportional to the concentration of dissolved elements.
[0020] The most common food freezes between 0° C. and −4° C. This zone is known as that of a maximum crystal formation zone. When water frozen, the concentration of dissolved elements in the rest of water is increased gradually, producing a higher descent in the freezing point.
[0021] Crystallization: In order to facilitate crystallization, it is needed the existence of a particle or insoluble salt acting as a crystallization nucleus. The lower the temperature, easier the phenomenon occurs, producing a higher number of crystal aggregates, and therefore, crystal size is lower. On the contrary, with a temperature close to the melting point, nucleation is slow, crystal nuclei are few and therefore, relatively large crystals result. Studying under microscope the shapes of ice crystals it is observed that a quick freezing produces crystals more or less rounded, while a slow freezing produces larger, elongated or needled crystals. This slow freezing has as consequence, breaking fibers and cell walls, and the food loses its properties. In solid or high viscosity food, size of crystals varies from zone to zone of the food. In peripheral zones, crystals are formed quickly and they have short size, whereas heat transfer inside is more difficult and crystals grown slowly, reaching larger sizes. When temperature reduces, reach a point in which the rest of water and concentrated solutes solidify together, in a saturation point, called eutectic point. Such a point is many times lower to that which many industrial freezers get, permitting small quantities of non-frozen water that allowing the survival of microorganisms, while it is not possible their growing and reproduction.
[0022] Changes in volume: Passing from liquid water to ice, includes an increase in volume close to 9%. Because this phenomenon, food rich in water expand more than those with lower content. This can cause fractures or cracks. It is important to consider it when producing the container, if the container is stretch.
[0023] Velocity of freezing: Quality in a frozen product depends on the velocity to which this has been frozen. Said velocity is defined as the minimum distance between the surface ant the critical point divided by the time in which the critical point has moved from 0° C. to −15° C. Thus, a freezing process is characterized as:
Slow: <1 cm/h, i.e. a domestic freezer with motionless air at −18° C. It is carried out basically in cold rooms, built and equipped to operate at low temperatures. The equipment offers an extra capacity for refrigeration, being further equipped with fans for air circulation. These systems have a low freezing velocity and they are used for products such as: margarines and steaks or carcasses which does not need high quality. Difficulties in this kind of freezing are: dehydration (between 5 and 10%) and frosts in product. Further, there are problems with cold balance, because if the chamber is saturated, the system is overloaded and it does not reach the desired freezing temperature. Medium: 1-5 cm/h, in a cold air tunnel at 20 km/h and −40° C. These are equipments designed for high efficiency in air circulation, they reach very high heat transfer velocities and they have dehydration losses from 2 to 6% of product weight. The equipment must be selected according to characteristics of process and product. In this kind of freezing are integrated the Blast Freezer, Fluidized bed and Gyro freezer equipments.
Blast Freezer. In this equipment, cold air is circulated at high velocity within a room with platforms arranged in a predetermined way. Almost all the products can be frozen with this equipment but freezing must be done until it is packed, in order to avoid dehydration or frosts. It is used too for carcass meat freezing which is transported by rails. Fluidized bed: These equipments are used for small size products (they were originally designed for peas processing). In this equipment gusts of wind are projected upwards from the lower part, almost suspending the product, rotating it, to perform a homogeneous and quick freezing. The major problem of this equipment is that gusts of wind can spoil or frost the product because the high velocity and cold intensity. Gyro Freezer. This system is one of the most modern and efficient mechanical systems. In this equipment, turbulence is generated from fans designed to generate a uniform cold. Products rotates in a spiral band and it is cooled in periods from 45 min to 1 h. Due to the flow of air is not direct, it lesser spoils the product by dehydration (from 1% to 2%). As is a spiral system it does not need a high space. The only inconvenient for this kind of equipments use to be the initial costs for acquisition and installation.
Fast.>5 cm/h, with immersion in liquid nitrogen. A quick freezing is carried out with liquid nitrogen at very low temperatures (−196° C.), either by immersion or aspersion, depending on characteristics of the food. With this kind of freezing, a high Individually Quick Frozen (IQF) quality is obtained, where the pieces of food are separated and they not adhere to the band. This kind of freezing permits to maintain better quality of products than in others because of:
It creates ice micro-crystals which not deform the cell, avoiding looses in texture and dehydration, maintaining the quality of product. Product is not deformed because there are not gusts of wind, and it dos not adhere to the band.
Storing effect: It has been demonstrated that temperature of −18° C. is a suitable and safe level to preserve frozen food. Microorganisms can not grow at this temperature, and action by enzymes is very slow, however, the storing itself produces alterations in the food:
Re-crystallization: During storing there is a tendency for the small crystals to join among them producing larger new ones. That is because small crystals are more unstable than larger crystals due to the higher energy per mass unit. This phenomenon is accentuated if the product is stored at temperatures near to 0° C. As lower the temperature is, smaller the effects, being almost negligible below of 60° C. Cold Frosts Any hot air entrance into the freezing chamber produces a temperature gradient between cold inside air and hot air penetrating. When air is heated, its humidity absorption capacity increases. In a freezing chamber, the only source of humidity available is the ice contained in the frozen food. Hot air takes humidity of the poorly protected food, dehydrating it. Then, the humidity is deposed on the cold surfaces of the freezer when air is cooled. The formation of ice from air humidity, without pass through liquid state is called sublimation. Frosts by cold is a major surface desiccation in a frozen food, produced by the dehydration above. They appears in the surface of the product as dark stains when pigments are concentrating and oxidizing in the most superficial layers. Also appear white-greyish zones due to gaps left by ice after sublimation. If the phenomenon lasts enough, superficial layers begin to make spongy and inferior layers begin to dehydrate. If frost is small, the phenomenon is reversible by exposing to humidity and rehydration. This is verified by cooking a lightly frost zone. If on the contrary, frost has been deeper, oxidations have been produced and chemical changes are irreversible. It is therefore important to use a suitable packing capable to reduce 4 to 20 times, the loss of water. Cold frost causes an important loss of product and a loss of its value causes the organoleptic quality diminishes.
[0035] In the past and nowadays, food cryogenic freezing, although provides the best quality, harmlessness and shelf life to it, has been and it is used little because the high costs of gases, equipments and installations.
SCOPE OF THE INVENTION
[0036] In the view of limitations that have the developments proposed until now in the prior art, an object of the invention herein is to provide an ultrafast food freezing equipment by direct contact with dosed liquid nitrogen.
[0037] It is another object to provide an ultrafast food freezing equipment in a way to conserve its original properties and taste, without modification, when defrosted after preservation in a refrigerating chamber during a extended period of time.
[0038] Another object of the invention is to provide an ultrafast cryogenic freezing equipment for food.
[0039] Still other object of the invention is to provide an ultrafast cryogenic food freezing equipment in which food can be introduced to the process as individual portions confined in a container for exhibition and sale.
[0040] Yet another object of the invention is to provide an ultrafast food freezing equipment that permits to establish a steady state production process, due to the food to be frozen can be contained in its final packing previous to sealing.
[0041] It is another object of the invention to provide an ultrafast food freezing equipment with maximum efficiency in the consumption of liquid nitrogen used.
[0042] Another object of the invention is to provide an ultrafast food freezing equipment in which freezing is obtained trough a fast and precise dosing of liquid nitrogen directly to product to be frozen.
[0043] It is still other object of the invention to provide an ultrafast food freezing equipment in which a precise dose of liquid nitrogen for such food is used.
[0044] Other object of this invention yet, it is to provide an ultrafast food freezing equipment with highly competitive costs.
[0045] These and other objects and advantages of the invention are going to be evident in the light of the following description, which is accompanied of a series of Figures for the preferred embodiments of the invention, which must be understand as made for illustrative purposes and not limitative of the teachings of the invention.
BRIEF DESCRIPTION OF THE INVENTION
[0046] In view of the previous developments, specially in the field of food preservation by freezing, it is needed a development of an equipment capable to reduce costs of cryogenic freezing in order to make it affordable to freezing food enterprises, so that to offer maximum quality, harmlessness and shelf life to market; equipment of the invention, hereinafter called UFGF (ultra-fast gravity freezing) has been developed to obtain high efficiency in the consumption of liquid nitrogen based on the quick and precise dosing of liquid nitrogen to the product to be frozen, resulting in highly competitive costs.
[0047] UFGF equipment of the invention represents a great improvement to the technology applied by the methods known nowadays to freeze food, which not provide quality and life shelf for the frozen product as the equipment of the invention.
[0048] An advantage of the equipment of the invention is that it not produces elongated crystals in the product because it uses dosed liquid nitrogen which gets quick and precise contact with the food, freezing the water molecules and forming micro-crystals which, due to their size, do not produce damages to the wall of the cells; this kind of freezing is obtained because the speed in the contact of the liquid nitrogen with the food (at −196° C. or −325 F) and because the dose in the exact quantity of the liquid nitrogen, as required by the objective food.
[0049] The equipment of the invention provides a series of advantages when provides a real ultrafast freezing; it not requires large spaces for install, it is light weighed, its costs are reasonably lower than those for conventional tunnels with equivalent capacity of processing which freezes by gas aspersion, where it is the gas and not the liquid that contacts the surface of the food to be frozen, delaying the freezing and producing crystals with sizes that can produce damages to the food cells.
[0050] UFGF technology is effective and optimizes the quality of the food, preserving their original properties such as vitamins, minerals and proteins, maintaining them without changes during freezing, transporting and storing, under suitable conditions, therefore the properties of the food maintains intact.
[0051] UFGF equipment not requires high investments in acquisition, installing or operation areas, compared to the high costs of the conventional cryogenic freezing equipments, such as gas aspersion tunnel or immersion tub, with costs up to 10 times higher than in the equipment of the invention.
[0052] Cost impact of cryogenic freezing, either by aspersion or immersion is from 15% to 50%, whereas in UFGF equipment it is 5% to 25% depending on the food to be frozen; the productive line in the case of aspersion or immersion is intermittent (batch), whereas in the UFGF it is continuous (steady state), avoiding costs for extra time and excess of personnel.
[0053] When comparing the areas for install and operate the equipments by aspersion and that of the invention, this one just requires 2 to 6 square meters, while the aspersion tunnel requires at least of 40 m 2 .
BRIEF DESCRIPTION OF THE FIGURES
[0054] For a better understanding of the advantages of the system of the invention, following is a series of Figures and drawings intended to show in an illustrative way, the characteristics of a preferred embodiment of the system, without intend to be limitative of it.
[0055] FIG. 1 is a schematic illustration of a frontal view of a preferred embodiment of the invention.
[0056] FIG. 2 a is a schematic illustration of a lateral view showing the right side of the preferred embodiment of the equipment of the invention.
[0057] FIG. 2 b is a schematic illustration of a upper view of the bottom of the liquid nitrogen contention tank in the preferred embodiment of the equipment of the invention of FIGS. 1 and 2 a.
[0058] FIG. 3 is a schematic illustration of the phase separator in the preferred embodiment of the equipment of the invention in FIG. 1 .
[0059] FIG. 4 is a schematic illustration of the front view of the preferred embodiment of the equipment of the invention in FIG. 1 , showing the main components.
[0060] FIG. 5 is a schematic illustration of the front view of the preferred embodiment of the equipment of the invention in FIG. 1 , showing the main control components.
[0061] FIG. 6 is a schematic illustration of the right side view of the preferred embodiment of the equipment of the invention in FIG. 1 , showing the main control components.
[0062] FIG. 7 is a schematic illustration of the preferred embodiment of the equipment of the invention.
[0063] FIG. 8 is a perspective view of a container capable to be used for freezing in the equipment of the invention.
[0064] FIG. 9 is a schematic illustration of the container in FIG. 8 , showing the id of the discharge nozzles considered in the tests of dispensing for the equipment of the invention.
[0065] FIG. 10 is a graph showing the variation in the amount of liquid nitrogen dispensed, as a function of the dispensing time, in a test for dispensing homogeneity of liquid nitrogen trough the nozzle.
[0066] FIG. 11 is a graph showing the distribution of temperatures at two locations in an article processed with the equipment of the invention, as a function of the time, during and after the dispensing of liquid nitrogen.
DETAILED DESCRIPTION OF THE INVENTION
[0067] The description below will be referred to the Figures referred above, that must be understood as illustrative of the preferred embodiment of the invention and not as limitative of the inventive concept. Common elements in Figures show the same numbers in all of them.
[0068] This invention is referred to an equipment for freezing of articles, preferably food, either raw or cooked, in groups of individual portions arranged and confined into a pack for public sale.
[0069] FIGS. 1 and 2 schematically illustrate an embodiment of the equipment of the invention, referred as a whole by number ( 100 ), comprising a phase separator ( 110 ), a dispensing zone for liquid nitrogen ( 120 ), control means for dispensing ( 130 ), a band ( 140 ) for conveying the material to be frozen towards and from the equipment, a tunnel type cold chamber ( 150 ), and an exit for nitrogen gas to the atmosphere ( 160 ).
[0070] In FIG. 2 it is shown in detail, in a schematic illustration, the dispensing zone ( 120 ) for liquid nitrogen, comprising a tank ( 121 ) with vacuum isolated walls ( 123 ), defining a container ( 122 ) for liquid nitrogen under atmospheric pressure, thanks to an vent ( 125 ) open to atmosphere, located in the cap ( 124 ) covering the entrance of the tank ( 121 ); in the midst of cap and tank, if required, a seal to prevent leaks of nitrogen towards the work zone, where personnel stands, is used. Tank ( 121 ) has a bottom wherein a plurality of holes is located, for the exit of liquid nitrogen; in FIG. 2 b a preferred embodiment with 8 exits, referred by ( 126 a ), ( 126 b ), ( 126 c ), ( 126 d ), ( 126 e ), ( 126 f ), ( 126 g ) and ( 126 h ), is shown, being located in two parallel rows with 4 holes each and being correspondent by pairs.
[0071] Although FIG. 2 b illustrates the preferred embodiment of the equipment, with 8 exits useful for liquid nitrogen, in practice, the equipment can be designed to satisfy the requirements by user, adding or reducing holes or modifying its layout, to adapt to that of the food container to be frozen; it is possible too, as described below, to use just a subset of the total available holes, for a specific application.
[0072] Turning back to FIG. 2 a , underneath the tank ( 121 ) and as a part of the dispensing zone, means ( 130 ) for control of dispensing are located; the area being isolated with high density polyurethane foam inside. It can be seen in the lower part of the Figure, 4 protrusions representing the nozzles ( 131 a ), ( 131 b ), ( 131 c ) and ( 131 d ) which correspond to holes ( 126 a ), ( 126 b ), ( 126 c ) and ( 126 d ), respectively; behind these nozzles there is another identical set corresponding to parallel holes ( 126 e ), ( 126 f ), ( 126 g ) and ( 126 h ). Each nozzle is associated to a solenoid actuated cryogenic needle valve (not showed); each cryogenic valve being controlled by an actuator, preferable of the pneumatic type, ( 132 a ), ( 132 b ), ( 132 c ) and ( 132 d ), respectively, in the illustrated view.
[0073] Control means are complemented with devices for detection, transmission, display and control of other variables, such as a level indicator ( 300 ) for nitrogen inside the tank ( 121 ), liquid nitrogen level regulator ( 310 ), and nitrogen gas flowmeter ( 320 ).
[0074] Feeding of liquid nitrogen into the tank ( 121 ) is carried out from the phase separator ( 110 ) trough the feed hole (128=in the upper zone of the tank ( 121 ).
[0075] Referring now to the phases separator ( 110 ), schematically illustrated in detail in FIG. 3 , it has a liquid nitrogen feed from a storage tank (not illustrated) through a tube header ( 111 ), through a control cryogenic valve ( 112 ) up to a discharge ( 113 ) which permits the liquid nitrogen entry into the chamber ( 114 ) wherein the liquid nitrogen remains at ambient pressure while the vent of gas is permitted through the exit ( 115 ), maintaining an adequate level of liquid nitrogen to be fed, through the inferior duct ( 116 ) to the dispensing section ( 120 ); finally the liquid nitrogen goes to the dispensing zone ( 120 ) through the duct ( 117 ).
[0076] In the dispensing zone ( 120 ), as illustrated in FIG. 4 , the liquid nitrogen is dispensed from the tank at atmospheric pressure ( 121 ) by simple gravity flow of liquid nitrogen through the holes ( 126 ) in the bottom ( 127 ) of the tank ( 121 ), towards the plurality of nozzles ( 131 ) that permit the liquid nitrogen directly pass to the center of the upper surface of each article to be frozen, which in case of food, corresponds to one individual portion. The level of liquid nitrogen in the tank ( 121 ) determines the hydrostatic pressure on the bottom of the tank and so, the amount of liquid nitrogen passing towards the nozzles ( 131 ) from the holes ( 126 ) per time unit; hence the importance to maintain control on said level, as indicated below.
[0077] In order to have an efficient freezing, it is necessary that the dispensing of liquid nitrogen be done in a sufficient quantity to guarantee the food portion freezing; determination of the quantity to be dispensed will depend on the nature and properties of the product to be frozen, which as described above, are critical in case of food, in order to guarantee that its nutritional and organoleptic characteristics are not altered during the process or during the storing in cold chambers. Being extremely critic in this regard, the equipment has been equipped with a very precise control system for quantity of liquid nitrogen that is permitted to reach the article or articles to be frozen; thus, in FIGS. 4 to 7 said control system is illustrated
[0078] With reference to FIG. 4 , illustrating the basic elements of the control system for liquid nitrogen; the elements described are common to each one of the exits of liquid, so they are referred as a whole by its main number, i.e. ( 131 ), without any reference to the letter which differentiates its position, ( 131 a ), ( 131 b ), etc., so, there is a plurality of nozzles ( 131 ) to discharge the liquid nitrogen flowing by action of gravity from the tank ( 121 ) at atmospheric pressure; the nitrogen going out though the holes located in the bottom ( 126 ); the flow of liquid nitrogen up to the nozzles ( 131 ) is stopped by the action of the cryogenic valves ( 135 ) preferably of the type of needle valves, with its active elements made of stainless steel; cryogenic valves are located with its stem horizontally oriented, so the liquid nitrogen flows vertical and downwardly when the cryogenic valve ( 135 ) is operated; each cryogenic valve ( 135 ) is calibrated to discharge a certain quantity of liquid nitrogen per time unit and it is actuated by a pneumatic actuator ( 132 ) with air suppliers ( 134 ) for opening/closing; air supply to the actuators is offered by a 5-ways solenoid valve ( 133 ).
[0079] Operation of 5-ways solenoid valves ( 133 ) is based on successive open/close periods, electrically controlled by a time controller ( 200 ) or timer, in which the operator can select the opening time. FIG. 5 illustrates the electric lines with a double solid line, i.e. the main source ( 210 ) and operation lines ( 220 ) for 5-ways valves; the pneumatic lines ( 136 ) for feeding the solenoid valves ( 133 ) are crossed by oblique lines. Control means further include a general switch ( 230 ) and an actuator ( 240 ) for the cryogenic valve ( 112 ) for feeding of liquid nitrogen from the tube header ( 111 ) coming from a storage tank (referred by number ( 500 ) in FIG. 7 ).
[0080] In a simple embodiment of the equipment, time control ( 200 ) is set by hand and the start of any freezing cycle for a container is made by hand too, once the operator locates said container in position under the set of nozzles ( 131 ). Starting the timer ( 200 ) and therefore discharging the liquid nitrogen is made when the actuator button ( 250 ) is pressed.
[0081] Note that the bottom of the tank ( 121 ) is leveled, so the height of liquid nitrogen is uniform at any point, guaranteeing uniform hydrostatic pressure, as demonstrated in comparative tests performed to determine the potential flow differential done among the eight nozzles in the test equipment. Variations in the level of liquid nitrogen in the tank are maintained at minimum by a level regulator ( 310 ).
[0082] The test consisted in dispensing liquid nitrogen through the eight nozzles, in an arrangement corresponding to the operation of an equipment with food to be frozen confined in a tray type container ( 600 ), such as that in FIG. 8 , described in the International application WO 2007/011199 (Maccise, 2007), with nozzles located on the center of each cavity and numbered according to the template ( 700 ) in FIG. 9 . Results are in Table 1, following:
[0000]
TABLE 1
Test for homogeneity in quantity of nitrogen
dispensed through eight nozzles in the test equipment.
DISPENSED LIQUID NITROGEN
TIME
(kg × 1000) PER NOZZLE
(S)
1
2
3
4
5
6
7
8
1
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
2
10.0
10.0
10.0
9.0
9.0
10.0
10.0
10.0
3
15.0
16.0
16.0
16.0
15.0
15.0
16.0
16.0
4
21.0
21.0
21.0
22.0
22.0
22.0
22.0
22.0
5
30.0
31.0
32.0
29.0
31.0
32.0
32.0
30.0
6
38.0
38.0
38.0
37.0
38.0
39.0
38.0
37.0
7
50.0
51.0
51.0
51.0
52.0
51.0
52.0
53.0
8
59.0
60.0
59.0
60.0
60.0
59.0
60.0
59.0
9
65.0
66.0
66.0
67.0
66.0
67.0
68.0
67.0
10
75.0
75.0
76.0
76.0
76.0
76.0
77.0
77.0
[0083] It is observed in the table 1 that measurements reflect uniformity in dispense; in the graph in FIG. 10 it could be appreciated minimal variations in volumes dispensed.
[0084] The container for transport of articles to be frozen should be conformed in a way to each portion of food (or individual article) be confined in one cavity, narrow enough so as to guarantee that the article is located in the center of each cavity and guarantee therefore that each nozzle is located just on such center. The cavity can have any shape, but preferable must be one in which the article to be frozen be loose accommodated in it.
[0085] To locate the container in position, as illustrated in FIG. 1 , the equipment of the invention is completed with a transporter ( 140 ), i.e. of the kind of rollers, extending from a distance before the body of the equipment, enough to accommodate the container on it; the container is dragged until its position below the nozzles ( 131 ) for freezing, and then it is carried out to the next section of the process of food.
[0086] In a test to determine the profile of temperature produced with the passing through the wall isolated chamber ( 150 ), samples of sushi-rolls were frozen, putting a thermocouple “1” in the center of the roll, and a thermocouple “2” in the interior wall of the most outer layer of the roll. Details are indicated in Table 2, following; it is important to point out that the sampled roll was frozen in a container with other 6 rolls, so the data in Table 2 are values for 7 complete rolls.
[0000]
TABLE 2
Test Parameters for the example
Roll
Test
Temp
w/thermocouple
Time LN2
Thermocouples
Time
Environm
Spicy
25 s
1 center
30 min
7° C.
Surimi
1.650 kgs
2 int. wall
1.4223 m 3
[0087] A predefined dose of liquid nitrogen, suitable for freezing a complete roll with characteristics of the ingredients used to prepare it, is applied for 25 seconds with the results in FIG. 11 ; observing the high impact I temperature and time to take down until temperatures below −170° C. and the increasing time, delayed to reach a −21° C. temperature in a 15 minutes period, exposing the product to a environmental temperature of 7° C., providing time enough to handle the product up to the end of the process without physical changes.
[0088] In the preferred embodiment of the invention, the transporter ( 140 ) is used to produce a wall isolated cold chamber ( 150 ), inside of which it is permitted to produce a nitrogen-rich and oxygen-poor atmosphere, with a temperature low enough so as to permit the liquid nitrogen contacting the processed object to continue cooling it (as a function of the characteristics of the product itself), maintaining the temperature distribution profiles in the frozen article.
[0089] Transporter ( 140 ) has a slot ( 160 ) through which the nitrogen gas, produced by the thermal shock between the liquid leaving the nozzles ( 131 ) and the surrounding air or the surface of the article to be frozen and the container, is drawn; the suction (provided by a extractor connected to the exit duct ( 190 ) of the chamber ( 150 )), produces a curtain at the entrance to the chamber ( 150 ) preventing the diffusion of nitrogen gas to areas occupied by personnel; the nitrogen gas produced, is further guided along the chamber ( 150 ) above and below ( 180 ) of the frozen containers, as indicated by arrows; the cold chamber ( 150 ) is limited in the distal end of the freezing point by a slot ( 170 ) with an equivalent function to the slot ( 160 ) described before. Nitrogen gas is extracted through a duct ( 190 ) connected to an extractor (not illustrated) to be vented to atmosphere.
[0090] FIG. 7 is a schematic diagram illustrating the installation required to operate the equipment ( 100 ) of the invention, including the deposit tank for liquid nitrogen ( 500 ), a valve train ( 510 ) to regulate the flow of liquid nitrogen up to the tube header for feeding ( 111 ) to the phases separator, and the isolation required ( 520 ) to reduce looses of cold by transference to environment. Observe that with the equipment of the invention and an installation as the illustrated, the requirements of liquid nitrogen are diminished, as well as the personnel, premises and space, reducing the associated costs.
[0091] From the functional point of view, the equipment proposed in the invention is comparable in performance, and improves the equipment existing at present in the market, and conventionally used for the same kind of activities, such as equipments based on immersion tubs. In tests carried out to compare performances, there were obtained the results shown in Table 3:
[0000]
TABLE 3
Comparative analysis of the use of liquid
nitrogen for the same basis of processed product.
Equipment of
Immersion tub
the invention
Kg of product
7,500
7,500
net consumption
19,983
15,112
LIN (m3)
rate m3/kgs
2.664
2.015
[0092] Some advantages determined for the equipment of the invention, among others and from the point of view of the food processed are as follows:
It remarkable improves the quality in any frozen food, due to the direct contact between the liquid nitrogen and the food to be frozen. Nutrimental properties in the food remain intact, and because of the low cryogenic temperature and speed of freezing, food stays innocuous at all. Shelf life substantially increases compared to that of any other type of freezing, preserving the original characteristics and properties of the food. It creates ice micro-crystals which not harm the membrane of the food cell, preserving the original characteristics and properties of food. It permits to dispense precise liquid nitrogen doses required by food to be frozen. Due to the ultrafast dosing, freezing of the food considerably reduces to times in the order of few seconds depending on the heat transfer velocity and quantity of food. It permits to establish a steady-state production line, because e the food to be frozen can be contained in its final packing. It offers high security, since there is not risk to direct contact by operators with liquid nitrogen. It significantly reduces loss of product since eliminates the contact once it is frozen within its final packing.
[0102] Some advantages regarding the investment required:
It noticeably reduces the investment since the costs of equipment and installation represent between 30% and 40% of the investment costs in equipments at present. It reduces the size of the operation space to be used up to 80% off from that required by equipments at present.
[0105] Some advantages regarding operation costs:
It reduces freezing cost since the consumption of liquid nitrogen to be used is precisely dosed to avoid an excessive consumption for losses to environment, mainly. It significantly reduces losses of product since it diminishes the handle of it, increases efficiency and productivity in freezing due to exactness in dosing of liquid nitrogen as required.
[0108] The previous description of the invention is based in a preferred embodiment, for illustrative purposes, wherein the equipment includes eight nozzles for dispensing of liquid nitrogen; however, it could be clear for a skilled person in the technical field, that it is possible to carry out modifications to said preferred embodiment in such a way to fit the equipment to specific operation conditions for each particular user. By example, in the illustrated embodiment with eight nozzles, it is possible to temporarily close some of them, to operate a lower number, say 4. In a similar way, an equipment originally fit up for operating a dozen of nozzles could be adapted for a lower number, i.e. 10, 8, 6, 4 or 2 nozzles, without being limitative in a decrease by pairs.
[0109] Since the hydrostatic charge in the bottom of the tank in the dispensing zone is uniform, location of holes and so of the associated nozzles could be modified “from factory” to fulfill particular applications. It is further possible to modify the geometry of the vertical wall of the tank to adopt a cylindrical shape, or a flat-bottom regular prism, without a noticeable effect on the distribution profiles for liquid nitrogen towards the nozzles.
[0110] It is clear too that hand operations described regarding the illustrated equipment in the preferred embodiment, can be replaced for automatic controls, permitting the establishment of high-volume production lines.
[0111] These and other modifications that can be evident to a skilled person in the field should be considered within the scope of the inventions, in the light of the following claims.
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The invention is related to an ultrafast freezing equipment for food contained in a packing with multiple cavities, for public sale, by applying a liquid nitrogen trickle, in an amount enough to produce an ultrafast freezing of food. Liquid nitrogen is dispensed from a container at atmospheric pressure, vacuum isolated, through a plurality of nozzles, by gravity, into the center of the upper surface for each cavity, producing short-time immersion in the individual cavity. Nitrogen gas produced is used to make a practically oxygen-free atmosphere, cold enough to maintain the freezing process after dispensing. The process diminish the amount of liquid nitrogen required as compared to other freezing processes, as well as personnel, facilities and physical space needed for install and operate it, reducing the associated costs.
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This application is a continuation, of application Ser. No. 08/623,430, filed Mar. 28, 1996, now abandoned, which is a continuation-in-part of application Ser. No. 08/324,345, filed Oct. 17, 1994, now U.S. Pat. No. 5,514,503 and a continuation-in-part of U.S. patent application Ser. No. 08/499,982, filed Jul. 10, 1995, now U.S. Pat. No. 5,624,775, and a continuation-in-part of U.S. patent application Ser. No. 08/197,141, filed Feb. 16, 1994, now U.S. Pat. No. 5,544,582, which is a continuation-in-part of Ser. No. 145,155, Nov. 3, 1993, now U.S. Pat. No. 5,535,637, and a continuation-in-part of Ser No. 145,244, Nov. 3, 1993, now U.S. Pat. No. 5,533,447.
FIELD OF THE INVENTION
The invention relates to color filters for flat panel displays and methods for their production.
BACKGROUND OF THE INVENTION
Liquid crystal display (LCD) panels, particularly color LCD panels, are used for flat screen televisions, projection television systems and camcorder view finders, with many more applications anticipated in the future.
The fabrication of an active matrix liquid crystal display involves several steps. In one step, the front glass panel is prepared. This involves deposition of a color filter element onto a suitable substrate, such as glass. Color filter formation typically involves depositing a black matrix pattern and three primary (typically either red, green and blue or yellow, magenta and cyan) color dot or color cell patterns within the spaces outlined by the black matrix. The printed lines which form the black matrix typically are about 15-25 microns wide and about 0.5 to 2 microns thick. The red, green, and blue color cells are typically on the order of about 70-100 microns in width by 200 to 300 microns in length. The color cells are typically printed in films less than about 10 microns thick, and preferably less than 5 microns thick, and must be evenly applied and accurately registered within the pattern formed by the black matrix. The front glass substrate is typically completed by depositing a planarizing layer, a transparent conducting layer, and a polyimide alignment layer over the color filter element. The transparent conducting layer is typically indium tin oxide (ITO), although other materials can also be utilized.
In a second step, a separate (rear) glass panel is used for the formation of thin film transistors (TFT's) or diodes, as well as metal interconnect lines. Each transistor acts as an on-off switch for an individual color pixel in the display panel. The third and final step is the assembly of the two panels, including injection of a liquid crystal material between the two panels to form the liquid crystal panel.
One challenge to making the red, green and blue color pixel dots (also referred to as color cells) of the color filter is preventing the different colored inks from mixing with one another. In the past, this problem has been solved by first forming the black matrix pattern on a glass substrate (such as by photolithography) and then depositing the colors within the black matrix pattern.
It would be desirable to provide alternative methods for making color filters which have good resolution and registration, and which can be obtained easily and at a lower cost than prior art color filter arrays. It would also be desirable to achieve these qualities using a process which takes less steps than current processes.
SUMMARY OF THE INVENTION
In the present invention, a transparent raised pattern is formed on a color filter substrate, and the individual colored ink patterns that make up the color filter are deposited within the recesses formed by the transparent raised pattern. Preferably, the raised pattern is formed using mechanical forming techniques. However, other techniques, such as photolithography, could also be employed. By mechanical forming techniques, it is meant that the raised pattern is formed mechanically, such as by intaglio printing techniques, as opposed to photolithographic and other chemical forming techniques, wherein a portion of material is removed chemically during formation. The raised pattern preferably corresponds to a desired black matrix pattern. The colored ink is then deposited within the raised pattern, preferably utilizing typographic or other ink imaging pins which are smaller than the spaces formed by the raised pattern, to thereby facilitate deposition of the ink within the raised pattern without smearing or mixing the different ink colors.
In one embodiment a liquid transparent material is deposited within the recesses of an intaglio imaging surface, such as an intaglio roll or plate. Preferably, the recessed pattern of the intaglio imaging surface corresponds to a desired black matrix pattern. The transparent ink is hardened (e.g. by curing), preferably prior to or during deposition to the substrate, to precisely duplicate the shape of the intaglio recessed pattern. Ink in intaglio and gravure print plates typically has a negative meniscus, the surface of the ink in the recessed intaglio pattern curving below the print plate surface. Consequently, if necessary, an adhesive may be employed to remove the transparent material and apply it to the substrate. In such cases, the adhesive can be applied either to the transparent material or to the substrate. Alternatively, a positive meniscus can be provided, for example by employing ink jet or other imaging pins to overfill the recesses of the intaglio pattern. Preferably, the transparent material is liquid when it contacts the substrate, and the liquid transparent material is cured or otherwise hardened while in contact with the substrate to thereby remove the material from the recesses of the intaglio pattern.
In an alternative embodiment a transparent liquid material is deposited onto the substrate and the transparent material is contacted with an embossing pattern. The embossing pattern can likewise be provided on a roll or plate. Preferably, the liquid material is cured or hardened while being contacted by the intaglio pattern, so that the transparent material retains the shape of the intaglio pattern. Preferably, the embossing pattern on the roll or plate corresponds to a desired black matrix pattern so that after being embossed by the roller plate, the transparent material is left with a raised pattern corresponding to the black matrix pattern employed in the display.
After formation of the raised pattern, the colored ink which makes up the color filter pattern is deposited within the cells formed by the raised pattern. Ink printing methods are preferably employed to deposit the red, green and blue color cells within the recesses. The transparent raised pattern preferably is about 1 to 10 microns thick, more preferably about 2 to 6 microns thick, and most preferably about 3 to 4 microns thick (above the glass substrate). Preferably, the colored ink is deposited into the cells using ink imaging pins which have a smaller size than the cell size formed by the black matrix pattern.
The liquid transparent material may comprise, for example, polyimides, melamines, epoxides, acrylics, vinyl ethers, polyurethanes, polyesters, and acrylated or methacrylated acrylics, esters, urethane, epoxides and other materials which are conventionally useful as planarizing layers in conventional color filter devices, as well as combinations thereof. Preferably, the transparent material is formed of a radiation curable material so that it may be cured. A preferred material for the transparent material is a radiation curable acrylate material, such as a radiation curable epoxy acrylate.
The methods of the present invention enable the production of extremely accurate transparent raised patterns having well defined square edges. These transparent raised patterns facilitate separation of the materials used to form the color pixels of the color filter.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a cross-section of a raised pattern formed using the method of the present invention.
FIG. 2 illustrates the forming of a raised pattern in accordance with the present invention.
FIG. 3 illustrates an alternative method for forming a raised pattern in accordance with the present invention.
FIG. 4A illustrates the deposition of a colored ink from an imaging roll into the recesses of a raised pattern in accordance with the invention.
FIG. 4B illustrates the deposition of a colored ink from an imaging plate into the recesses of a raised pattern in accordance with the invention.
FIG. 4C is an enlarged partial top view of an imaging pin depositing ink into a raised pattern from an imaging roll or plate as illustrated in FIGS. 4A and 4B.
FIG. 5 is a liquid crystal display employing a raised pattern formed in accordance with the invention.
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, as illustrated in FIG. 1, a transparent or semitransparent raised pattern 10 is formed on a substrate 14, and the individual colored ink patterns are then deposited within the recesses 11 formed by the raised pattern 10 to form a color filter pattern. Preferably, the raised pattern 10 is formed using mechanical forming techniques. By mechanical forming techniques, it is meant that the raised pattern is formed mechanically, such as by embossing or intaglio printing techniques, as opposed to photolithographic and other chemical forming techniques, wherein a portion of material is removed chemically during or after formation. However, the invention is not limited to mechanical forming, and other techniques, including photolithography, could be utilized in some embodiments to make the raised pattern.
Raised pattern 10 can be formed using a variety of techniques. For example, in the embodiment illustrated in FIG. 2, a liquid transparent material 15 is deposited onto a suitable substrate 14, such as glass. The transparent material 15 is then embossed by an embossing means to form an upraised pattern on substrate 14. In FIG. 2, transparent material 15 is contacted by patterned intaglio roller 18 (with no ink thereon) while transparent material 15 is in a deformable state. Patterned intaglio roller 18 has a recessed pattern 20 thereon corresponding to the desired black matrix pattern. As a result, patterned intaglio roller 18 (which could alternatively be an intaglio plate) contacts and embosses the deformable transparent material 15 to form raised pattern 10. In a preferred embodiment, raised pattern 10 corresponds to the desired black matrix pattern to be employed in the display. Transparent material 15 is hardened sufficiently to retain the embossed pattern obtained by contact with roll 18. This can be accomplished by utilizing thermoplastic materials and cooling the transparent material, at the point of contact with roll 18, to set the ink. Alternatively, and more preferably, radiation curable materials are employed, and radiation is emitted from ultraviolet light 24 through substrate 14 to cure the transparent material 15 during the embossing operation.
In an alternative embodiment, illustrated in FIG. 3, transparent material 15 is deposited from roll coater 22 into the recesses 20 of intaglio roll 18. Alternatively, transparent material 15 may be applied using slot coating techniques. After being deposited into recessed pattern 20 of intaglio roll 18, transparent material 15 is cured or otherwise hardened sufficiently so that the shape of recessed pattern 20 is retained by the material 15, and material 15 is transferred to substrate 14. In a preferred embodiment, radiation curable ink is employed for the transparent material 15, and the ink is hardened by curing the ink with radiation prior to or simultaneous with transfer to substrate 14. Most preferably, transparent material 15 is liquid prior to contacting the black matrix pattern, and cured during the transfer of the black matrix pattern to transparent material 15. Such curing may be accomplished by employing ultraviolet radiation curable material to form transparent material 15, and applying radiation, via ultraviolet (UV) light 24, for example, to transparent material 15 during deposition of the transparent material 15. Alternatively, a UV light could be mounted within roll 18, and roll 18 made of UV radiation transparent material to allow the radiation to be emitted therefrom. It should be noted that the radiation employed does not have to be ultraviolet, but could instead be visible, infrared, or other radiation, depending on the photoinitiator employed for the transparent material 15. Alternatively, transparent material 15 could be cured via UV light 24A prior to deposition to the substrate 14, and the deposition step achieved by using adhesives which are applied either to the substrate 14 or the transparent material 15.
After formation of raised pattern 10, the various colored ink patterns are deposited within the recesses 11 formed by raised pattern 10 using a typographic ink imaging pattern, as illustrated in FIGS. 4A and 4B. The typographic ink imaging pattern can be supplied on a pattern roll 50, as illustrated in FIG. 4A, or on a pattern plate 50A, as illustrated in FIG. 4B. In FIGS. 4A and 4B, pattern roll 50 and pattern plate 50A, respectively, comprise a plurality of typographic ink imaging pins 51. However, the invention is not limited to the use of typographic imaging pins, and other imaging pins (e.g., ink jet) can be employed. The imaging pins 51 carry the colored ink 36 and deposit the ink within the recesses 11 formed by raised pattern 10. As can be seen in the illustration, the ink is preferably still fluid after deposition and may extend somewhat above the surface of the black matrix pattern.
FIG. 4C illustrates a top view of the process illustrated in FIG. 4A, showing black matrix pattern 11 and typographic ink imaging pin 51 positioned within a cell formed by black matrix pattern 11 to deposit a color ink 36 therewithin.
Preferably, the colored ink is deposited into the cells using ink imaging pins which have a smaller size than the cell size formed by the black matrix pattern. For example, in a cell having dimensions of approximately 50 by 175 microns, the typographic ink imaging pin should have a dimension in which the width W is between 20 and 40 microns and the length L is between 140 and 160 microns. More preferably, the pin size has a width between 25 and 35 microns and a length between 145 and 155 microns. Most preferably, the pin has a width of about 30 microns and a length of about 150 microns. Thus, the width W of the pin is preferably between 10-30 microns smaller than the black matrix cell width, more preferably 15-25 microns smaller than the cell width and most preferably about 20 microns smaller than the cell width, whereas the length L of the pin should be between about 15-25 microns shorter than the cell length, more preferably about 20-30 microns shorter than the cell length, and most preferably about 25 microns shorter than the cell length. The height of the typographic pin is also important, and is closely related to the thickness of the ink on the inking roll which applies ink to the typographic pin. For example, in one process which utilizes typographic pins to deposit colored ink within black matrix cells having a dimension of about 50 by 175 microns, the inking thickness on the inking roll should be about 24 microns when using a pin approximately 30 microns wide by 150 microns long. Because it is desirable to have the typographic pin longer in height than the thickness of the ink on the inking roll, the height h of the imaging pins in such embodiments should be at least 30 microns, and more preferably at least 35 microns, and most preferably about 40 microns in height. Preferably, the pins are constructed so that the tops of the imaging pins are ink wetting, while the sides of the imaging pins are less or non-wetting to the inks.
In one embodiment, the imaging pins are porous imaging pins, and the ink is forced through the porous imaging pins. The imaging plate or roll could, for example, comprise a reservoir for containing the pixel ink behind the porous imaging plate, and the pixel ink selectively forced through the porous imaging pins of the imaging plate to apply ink to the printing surface of the imaging pins.
If desired, the colored pixel inks 36 and raised pattern 10 can be covered with a planarizing or protective layer 40, as illustrated in FIG. 5. The protective layer could be applied over the inks 36 and clear raised pattern 10 after the formation of these components, utilizing conventional coating techniques.
Forming the color filter pattern on a raised pattern facilitates separation of the different colored inks. This is extremely useful, for example, where it is desirable to employ a black matrix pattern separate from the color filter pattern. For example, in such cases, the colored inks could be employed on one component, and the black matrix pattern employed on a separate substrate, e.g. the other (TFT) glass substrate. If desired, the black matrix pattern can be deposited on top of the thin film transistor. For applications in which the black matrix pattern is deposited on the TFT substrate, it is believed that formation of the raised pattern 10 on transparent material 15 is very desirable, in order to separate and align the various red, green, and blue color cells with the black matrix pattern. By then registering the black matrix pattern 10 to align with raised pattern 10, when one looks down at the resultant liquid crystal display, the color cells will appear to be within the black matrix pattern.
In the embodiment illustrated in FIG. 5, a raised pattern 10 in accordance with the present invention is provided on first glass substrate 14. Raised pattern 10 separates the color pixel inks 36 from one another. Preferably, a planarizing layer 40 is deposited over the color pixels. Such planarizing layer 40 can be deposited using conventional techniques, e.g. roll coating, slot orifice coating, and so forth. An ITO electrode 42 is deposited over planarizing layer 40. On the second glass substrate 14a, a black matrix pattern 46 is provided on thin film transistor pattern 44. In the embodiment illustrated, black matrix pattern 46 comprises grid lines having a larger width than that of the raised pattern 10, thereby hiding the raised pattern 10 from the view of the consumer when the display is completed. However, other relative sizes could also be employed. The liquid crystal display in FIG. 5 is completed by sandwiching a liquid crystal material 48 between the two glass substrates 14 and 14a.
The transparent raised pattern 10 may be formed from, for example, those materials selected from the group consisting of polyimides, epoxides, melamines, acrylics, vinyl ethers, polyurethanes, polyesters, and acrylated or methacrylated acrylics, esters, urethane, or epoxides, and other materials which are conventionally useful as planarizing layers in conventional color filter devices. A preferred material for raised pattern 10 is a radiation curable acrylate material, such as a radiation curable acrylate. A particularly preferred material for raised pattern 10 is a radiation curable acrylate having the following composition (parts by weight):
TABLE I______________________________________dipentaerythrital pentaacrylate 50 neopentyl glycol diacetate 25 isobornyl acrylate 25 cellulose acetate butyrate resin 10 silicone polyacrylate or epoxysilicones 5______________________________________
The silicone polyacrylate is believed to act as a non-wetting agent with respect to the colored pixel inks. This is considered a desired effect. The liquid transparent material 15 is preferably deposited as a thin film, typically less than 10 microns. Preferably, the transparent material is formed of a radiation curable material to facilitate curing.
Preferably, any apparatus used for carrying out the methods of the present invention is mounted on its side (i.e., vertically mounting the rolls). By vertically mounting the apparatus, they may be removed vertically (in an axial direction, relative to the roll) from the printing apparatus, as opposed to conventional horizontally disposed rollers, which must be removed horizontally.
For embodiments in which an ink (black matrix and/or color ink) is cured, the ink is preferably formulated to be radiation curable. By curable, it is meant that the ink cross-links. By radiation curable, it is meant that the ink cross-links when exposed to appropriate radiation. This is regardless of whether the ink also has hot melt thermoplastic properties in the uncured (uncross-linked) state or incorporates a solvent.
Although the invention has been described in detail for the purpose of illustration, it is understood that such detail is solely for that purpose and variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention which is defined by the following claims.
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A method for making color filters for liquid crystal display panels. A raised pattern corresponding to the desired black matrix pattern is formed on a substrate, e.g., by an embossing means. A plurality of colored ink patterns is formed in the appropriate location within the boundaries formed by the raised pattern, thereby forming the multicolor image that will become the color filter.
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BRIEF DESCRIPTION
1. Field of the Invention
This invention relates to the making of composite parts using composite molds and vacuum and/or pressure forming.
2. Background of the Invention
For many years the aircraft industry has had difficulty building molds suitable for producing composite parts using vacuum bag molding techniques. The major difficulty has been in producing molds that will maintain their vacuum integrity at temperatures in excess of 250 degrees F. for extended production runs. At the present time surface coats of heavily filled epoxy resins are generally to provide both a smooth surface finish coat for the laminate mold and the necessary vacuum integrity. So long as the cure temperatures used are 250 degrees F., or less, such molds are acceptable and have a life expectancy that will allow them to be used in the manufacture of several production parts. It has been found, however, that when the cure temperature for composite graphite parts reaches 300 to 350 degrees F. the epoxy in the laminate molds begins to deteriorate at an accelerated rate. This deterioration results in premature crazing of the surface coat and the crystallization of resin within the laminate. Leak paths then develop through the molds. Vacuum integrity is lost and this may result in porosity in any parts formed in the laminate mold. Many parts may be produced before the porosity is observed and often such parts can only be scrapped.
OBJECTS OF THE INVENTION
Principal objects of the present invention are to provide a method of producing composite parts without porosity
Other objects are to provide a mold for making composite parts that will maintain vacuum integrity and a durable surface to produce uniform acceptable parts even when subjected to temperatures of 350 degrees F. or higher.
Another object is to provide a mold that will direct any leakage that may occur to vacuum outwardly of the area in which a composite part is formed.
Still other objects are to provide a method and apparatus that are adaptable to the productions of composite parts of differing configurations and that can be readily used by relatively unskilled persons.
FEATURES OF THE INVENTION
Principal features of the present invention include forming a mold for composite parts by laying up a composite laminate surface having the reverse configuration of the part surface desired; placing a layer of uncured Viton rubber (either as a unitary sheet or as abutting but not over lapping piece) over a back of the laminate surface and to extend outwardly therefrom in all directions; and securing the Viton sheet to the laminate surface using adhesive, temperature and pressure to shape and mold the Viton rubber. Viton rubber is a gas-impervious rubber material and "VITON" is a registered trademark of the DuPont Corporation.
Another principal feature of the invention comprises forming a high pressure laminate surface of a high fiber volume. This is achieved by compacting plies of fabric tightly together and removing excess resin. The surface is resistant to crazing or deterioration, with an underlying membrane of Viton rubber to seal against leak paths developing through the mold in the part area.
In one preferred embodiment the Viton sheet is further mechanically secured to the laminate surface by formation of a composite mold base structure that sandwiches the Viton rubber sheet between said composite mold and the laminate surface and with the edge of the Viton rubber sheet projecting beyond the outermost edge of the laminate surface. An adhesive strip may be provided on a surface of the composite mold base to receive and hold a vacuum bag through which a negative pressure is developed between the bag and the mold.
In another preferred embodiment, the laminate surface is pre-formed and is wrapped with a Viton sheet to prevent vacuum action on the part being formed such that porosity will result in the part. The Viton rubber is then cured with heat and pressure to bond to the lay-up mold. An adhesive bonding strip may be provided on a retainer surface of the laminate that extends fully around the mold, outwardly of the part being produced, to receive and hold the vacuum bag.
Other objects and features of the invention will become apparent from the following detailed description and drawing disclosing what are presently contemplated as being the best modes of the invention.
THE DRAWING
In the drawings
FIG. 1 is a perspective view of a mold constructed according to the method of the invention and arranged to have a composite part formed therein;
FIG. 2, a transverse section, taken on the line 2--2 of FIG. 1, but showing a composite part, in the mold; and
FIG. 3, a view like that of FIG. 2, but showing another embodiment of the mold of the invention.
DETAILED DESCRIPTION
Referring now to the drawings:
The method of the invention is best understood with reference to the preferred embodiments of apparatus shown in FIGS. 1-3.
In the illustrated preferred embodiment of FIGS. 1 and 2, a lay-up mold, shown generally at 10, is adapted to form a composite part such as is shown at 11 in FIG. 2.
The mold is constructed generally by forming a composite laminate mold surface 12. The mold surface 12 is formed on a cathode, not shown, as a reverse shape of the composite mold to be made. Preferably, the mold surface 12 is made as a four ply composite laminate, cured at 350 degrees F. and 90 psi. After the mold surface 12 has cured, uncured Viton rubber 13, is applied to the back of the surface. The Viton rubber fully covers the back of the mold surface 13 and extends outwardly therefrom at 14. A film adhesive may be used to bond the Viton rubber to the back of the mold surface heat and pressure are applied to the rubber to mold it in place and to bond it to the mold.
In the embodiment of FIGS. 1 and 2, a composite mold base structure 15 is formed by generally laying it up over the Viton rubber layer and outwardly beyond the edge of the rubber layer. The mold base structure 15 and the mold surface 12 then clamp the rubber layer between them. A "tacky-tape" double adhesive surface strip 16 may be secured provided therefor the composite mold base and extends fully around the rubber layer. The composite mold base thus cooperates with a vacuum bag (not shown) attached to the strip 16 and thus to the mold base, and overlies the mold surface to permit a negative pressure to be created between the bag and the mold during the formation of composite parts.
As best seen in FIG. 3, a lay-up mold surface 20 may also be wrapped with Viton rubber sheet 21 to provide a suitable mold. While this arrangement is suitable for use with new mold constructions it has also proven very effective as a means of converting previously used molds, whether or not crazing has developed therein, to a mold of the invention.
As shown a retainer 22 is provided around the periphery of the mold surface 20 and the edges of the rubber sheet 21 are secured beneath a lip 23 of the retainer. The rubber sheet is applied in an uncured form and conforms to the configuration of a back side 20a of the mold surface 20, the ends of the mold surface and partially onto a front surface 20b. The rubber sheet is also preferably adhesively bonded to the mold surface and the retainer is adhesively bonded to the mold surface. The bonding agent used is selected to withstand the temperatures involved in the molding process.
In the embodiment of the invention shown in FIGS. 1 and 2, should any crazing or cracking occur in the mold base structure 15 air moving therethrough will engage the rubber sheet and be directed along the sheet to be discharged to the vacuum source outwardly of the article forming portion of the mold.
A typical process of the invention comprises the following steps:
(1) Preparing a cathode (i.e. mold used in the preparation of the lay-up mold and having the configuration of the part to be produced) by cleaning it with methyl ethyl ketone and applying a liquid release agent, such as "Monocoat 91", a product of Chem-Trend, Inc. The release agent is baked to the cathode as instructed by the supplier prevents adhesion of other materials to the surface treated;
(2) Preparing an epoxy impregnated (pre-preg) graphite fabric such as MXG-7620, manufactured by the Fiberite Company by removing selvage from the fabric and cutting the pre-preg into small squares, for example, twenty-four inch squares, maximum size to reduce continuous fiber lengths, thereby reducing effects of resin shrinkage and leakage paths along fibers and then packaging the cut squares to protect them from humidity;
(3) Forming a lay-up mold by marking the perimeter of a four-ply lay-up to be at least two inches beyond the outer trim edge of the part to be formed and then laying up two plies of 2534 fabric pre-impregnated graphite fiber (a fine quality fabric) with zero degree and ninety degree orientation and laying up two additional plies of 2548 fabric (a medium quality fabric) with a plus forty-five degrees and minus forty-five degrees. During and following lay-up of the fabric the materials are de-bulked, as necessary;
(4) Bagging the lay-up to cure it into a lay-up mold. In this bagging process the four-ply lay-up is covered with a "Teflon" coated porous peel ply such as 234-TFP manufactured by Airtech, Inc. trimmed to be even with the edge of the lay-up. "TEFLON" is a registered trademark of the DuPont Corporation. Thermocouples are inserted through the cover material to permit reading of temperatures therein. A cover of hologen release film, such as A- 4000, manufactured by Airtech, Inc. is placed over the porous peel ply with this cover extending approximately one inch beyond the laminate and is perforated eight inches on center. The edges of the film are taped to restrict edge bleed. Additionally, one ply of Airtech, Inc., N-4 (4 ounce bleeder material) net is applied and trimmed to be even with the edges of the laminate, a ply of Airtech, Inc. A-4000 halogen release film perforated on two inch centers is applied to extend one-half inch past the edge of the laminate and a ply of Airtech, Inc. N-10 net (10 ounce breather material) is applied and trimmed even with the edge of the laminate.
Vacuum ports, spaced not more than forty-two inches apart, and with not less than two ports being used are provided and the entire assembly is bagged with Airtech, Inc. DP 1000 bagging film.
(5) Curing the tool by loading it in an autoclave under vacuum. Applying pressure of 90 psi and heating the tool at the rate of three to five degrees F. per minute to 180 degrees F. and holding that temprature for one hour; heating the tool at the rate of three to five degrees per hour to a temperature of 250 degrees F. and holding that temperature for three hours. Thereafter, the temperature of the tool is reduced at the rate of five to ten degrees per minute to 100 degrees F., before releasing the pressure.
(6) All consumables are stripped away, while being careful not to move the laminate.
(7) Viton rubber is applied to the back surface of the laminate by first applying one ply of American Cyanamid Co. FM 400 modified epoxy adhesive film thereto and extending to the edges of the laminate. Thereafter, the surfaces of the Viton rubber pieces are wiped with methyl ethyl ketone and the pieces are applied to the FM 400 layer with adjacent edges of the pieces abutting but not overlapping and with a maximum spacing between pieces of 0.030 inch. The Viton rubber is extended one-fourth inch beyond the edge of the four-ply laminate.
(8) The Viton rubber is covered with one ply of Airtech, Inc. A 4000 release film perforated on six inch centers and extending one inch beyond the edges of the Viton rubber. The release film is covered with one ply of Airtech, Inc. N-4 breather material and the assembly is bagged with Airtech, Inc. DP 1000 bagging film and debulked at 150 degrees F. and 20 psi. Debulking vacuum is maintained until room temperature is obtained, at which time the assembly is debagged. Any gaps in the Viton rubber are then filled with small pieces of Viton rubber bonded in place with methyl ethyl ketone or with a paste made by dissolving Viton rubber in methyl ethyl ketone and applied with a trowel.
(9) A base mold is formed by laying one ply of Fiberite 2534, 0 degree, over the exposed cathode surface and one-fourth inch beyond the edge of Viton rubber. One ninety degree ply of Fiberite 2548 is laid over the entire surface of Viton rubber and 2534 fabric. Eight plies of Fiberite 2577 are applied at 0, 90, +45, -45, +45, 90 and 0 degrees.
(10) If deemed necessary the assembly can be debulked by applying a perforated ply of Airtech, Inc. A-4000 halogen release film, a ply of Airtech, Inc. N-4 breather material, bagging the assembly and debulking for a minimum of four hours at room temperature.
(11) The assembly, including the base mold lay-up is bagged in the same manner described in step (4), except that N-10 bleeder is used rather than the N-4 bleeder used in step 4.
(12) The bagged assembly is cured in an autoclave. The entire assembly is placed in an autoclave in a level position and under vacuum. Pressure of one-hundred psi is applied, with the vacuum being vented at 20 psi. The mold is then heated at a rate of three to five degrees F. per minute to 180 degrees F., at which time the temperature is maintained for one hour. The mold is then heated at a rate of three to five degrees per minute to 250 degrees F., at which it is held for one hour. The mold is then again heated to increase the temperature at a rate of three to five minutes until 300 degrees F. is reached, at which it is held for two hours. Thereafter the mold is again heated to increase in temperature at a rate of three to five degrees per minute until 350 degrees F. is reached. The mold is then maintained at the temperature for one hour before the temperatre is reduced back to 100 degrees F. at the rate of five to ten degrees per minute.
It is to be understood that the foregoing example is of a typical process incorporating the invention and that the processing times, temperatures, particular films used and other materials will vary in accordance with the resin system used and established processes.
Although a preferred form of my invention has been herein disclosed, it is to be understood that the present disclosure is by way of example and that variations are possible without departing from the subject matter coming within the scope of the following claims, which subject matter I regard as my invention.
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A method of and apparatus for forming composite parts comprising producing a composite mold surface having a high fiber volume and that is resistant to crazing, backing the mold surface with Viton rubber extending beyond the outermost peripheries of a part to be formed in the mold surface with heat and pressure and securing the Viton rubber in place, preferably using a composite mold base structure and with the Viton rubber clamped between the mold surface or by other mechanical means such as a composite retainer on the composite mold surface to receive and protect the edge of the Vitonrubber.
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The present invention relates generally to a machine for processing crustaceans such as crawfish and extracting the tailmeat and other edible portions therefrom. The present invention also relates to an automatic air conveyor loading system that delivers the crawfish to the processing machine at a desired orientation and at a predetermined rate.
BACKGROUND OF THE INVENTION
In many cultures the tender tailmeat of crawfish is considered quite a delicacy, and crawfish are an important part of the culinary heritage in many areas. Today, crawfish are an important component of the well known Cajun cuisine, and can be boiled and served whole, or can be peeled for use in more elegant dishes.
Crawfish are quite abundant in low lying swampy areas, such as the bayous of Louisiana's Atchafalaya Basin in the southern United States. For many years crawfish have been trapped in the wild, but more recently rice farmers have begun to raise crawfish in their rice ponds when rice is not being grown. In many regions, a short time after the rice is harvested, the fields are again flooded and the crawfish emerge in quantity and proceed to spawn. The immature crawfish find shelter in the rice plants, and feed off old decaying rice plants, bacteria, and fungi, making crawfish an ideal rotation crop.
In many localized regions, consumers prefer whole, live crawfish. However, in order to be widely commercialized, the crawfish must be peeled and the tailmeat must be extracted. Hand peeling contributes to bacterial contamination, and accordingly the peeling process must conform to governmental regulations. The rice growing belt of the southern United States is capable of producing great quantities of crawfish, and the state of Louisiana alone produces over 100 million pounds of whole crawfish annually. However, due to the lack of a viable mechanical peeling machine, most of the market is confined to localized regions, remote gourmet restaurants, and some overseas markets. Thus, in order for crawfish producers to capture a larger market segment, both in the United States and abroad, the crawfish must be mechanically peeled and the tailmeat extracted.
Although other crustacean processing devices have been proposed, for example U.S. Pat. No. 4,785,502 issued to Howard, U.S. Pat. No. 4,912,810 issued to Laughlin, and U.S. Pat. No. 5,055,085 issued to Thibodeaux, those devices have not found widespread acceptance, and therefore currently the peeling process is primarily manual. Further, most common peeling practices totally ignore the salvage of the "head fat" (actually the hepatopancreas organ) which gives crawfish its distinctive flavor. Accordingly, only those consumers who eat the whole boiled crawfish or those diners who eat carefully peeled crawfish at gourmet restaurants are able to enjoy the full distinct crawfish flavor. Another drawback of hand peeling is that the process is very inefficient and highly labor intensive, coupled with the fact that peeling is a low paying job which makes for an unreliable workforce. In order to process a full supply of cooked crawfish, a producer may require 36 workers, 10 hours per day, six days per week. The work is very tedious and labor intensive, and generally very inefficient, and also forces the crawfish producer to rely on a somewhat unreliable labor market. Frequently, if large portion of the work force fails to show up for work, a large quantity of crawfish waiting to be processed spoils, which obviously increases the producer's costs.
In addition to facing the high cost of hand processing, the domestic crawfish industry also faces commercial competition from both the shrimp industry and from foreign crawfish imports. The majority of imported crawfish come from China and other Asian countries, and the extremely low labor costs in that region make it extremely difficult for domestic producers to compete. However, it is expected that governmental regulations will soon prevent the import of foreign crawfish for lack of compliance with the rules discussed above, which will place an even greater premium on domestically produced crawfish. Domestic producers also have a hard time competing with the shrimp industry, because the shrimp industry has developed large scale mechanical peeling machines that significantly lower the per pound price of processed shrimp meat.
The market for processed crawfish, and thus the very livelihood of crawfish producers, is now in jeopardy. The domestic crawfish industry presently cannot compete with the low labor costs of the imported crawfish or with the low price of mechanically processed shrimp. Furthermore, the crawfish industry has been unable to develop a viable, efficient mechanical peeling machine. Although some have tried to adapt shrimp processing machines to process crawfish, these efforts have failed because the tailmeat on crawfish is much harder to extract due to a tough internal membrane that tends to bind crawfish tailmeat to the internal surface of their shells. Shrimp processing machines either fail to extract enough of the tailmeat to be economical, or they simply waste or destroy most of the edible portion.
There have been prior attempts to develop crawfish processing machines, but most prior art mechanical machines were woefully inefficient. Like the shrimp machines, the prior art crawfish machines simply wasted too much of the precious tailmeat to be economical, or they completely failed to recover the head fat, and thus the distinctive crawfish flavor was lost. Most of the prior art machines simply lopped off the entire tail by shearing the crawfish at the joint between the head and the tail. Thus a portion of the edible meat that extends forward of the tail into the head, which can represent a sizeable percentage of the tailmeat, was lost. Also, none of the prior art machines had any mechanism at all to extract the head fat, which made the processed meat much less competitive in marketplace because of the loss of the distinctive flavor. Finally, none of the prior art machines could reliably and effectively extract the "mud vein" from the tailmeat.
Another serious drawback with even the best of the prior art processing machines is the lack of an automatic loading feature. Without an automatic loading feature, crawfish have to be hand loaded, one by one, into the processing machine. Again, the costs associated with this additional labor component undermines the competitiveness of the processed meat.
Accordingly, there exists a need for an improved crustacean processing machine that quickly and efficiently extracts a very high percentage of the edible meat from crawfish. There also exists a need for an improved crawfish processing machine that extracts and preserves the "head fat" that gives crawfish its distinctive flavor. Such an improved crawfish processing machine must separate the tailmeat from the shell without shearing the crawfish or without simply cutting off the tail, and must be able to process enough crawfish to enable domestic crawfish producers to compete with both the shrimp industry and the imported crawfish industry. Such an improved machine must also be able to extract the tailmeat without severing the mud vein, and should include an automatic loading feature.
SUMMARY OF THE INVENTION
The improved crawfish processing machine of the present invention helps crawfish producers to address each of the problems outlined above. An improved crawfish processing machine according to the present invention enables crawfish producers to process crawfish reliably, quickly and economically. The present invention extracts a much higher percentage of the tailmeat than prior art devices, and preserves the distinctive crawfish flavor by recovering a sizeable percentage of the "head fat." The present invention utilizes a novel impact or "bumping" feature that ruptures the membrane that binds the tailmeat to the shell, and also utilizes a novel separation feature that rips or tears the tail away from the body rather than shearing the crawfish apart. Accordingly, a larger portion of the tailmeat is extracted. Furthermore, the present invention includes a novel "head fat" extraction method, which extracts and preserves the head fat for packaging along with the processed tailmeat, thus preserving the distinctive crawfish flavor and enhancing the marketability of the finished product.
The improved crawfish processing machine of the present invention incorporates an automatic air conveyor loading system that delivers commercial size crawfish to the machine in a desired orientation. The air conveyor system includes a unique orientation chute or slide that delivers the crawfish onto the conveyor in a dorsal side up, tail first orientation. The air flotation conveyor then slowly floats the crawfish towards the pick up point in the machine where the actual processing commences. The air flotation system includes an automatic, air operated centering system that keeps the crawfish in the middle of the conveyor at all times, which ensures the best possible loading position and ensures removal of the mud vein as is discussed below.
The present invention includes an upper processing assembly which includes a head clamp for grasping the head of the crawfish, and also includes a lower processing assembly that includes a tail clamp for grasping the tail of the crawfish. The head clamp is mounted on a reciprocating carriage assembly that allows the head clamp to reciprocate horizontally. The entire carriage is connected to a mechanical counterbalance, which ensures smooth, vibration free operation at all times. A vertically oriented 4 position linear thruster, which has the head clamp assembly mounted thereto, is attached to the carriage of the upper processing assembly. The head clamp itself includes a pair of horizontally opposed gripper arms which clamp onto the crawfish and which are actuated by a horizontal pneumatic cylinder. The head clamp assembly also includes a vacuum cup to assist in the pick up of the crawfish, and a rotary unit to operate the head fat extraction cup as discussed below. Accordingly, the upper processing assembly is capable of grasping the crawfish at the pick up point and transporting the crawfish vertically and horizontally through the machine.
The lower processing assembly includes a main processing station or plate which is mounted to a slide or carriage. The lower processing assembly is driven by a short action linear thruster which allows the lower processing assembly to reciprocate horizontally in order to effectuate the innovative impact or "bumping" technique referred to above, which eases the extraction of the tailmeat from the shell. A flexible tail clamp mounted to a rotary unit is attached to the end of a second linear thruster, which enables the tail clamp to rotate from a retracted position to an extended position over the tail portion of the crawfish. A linear thruster then lowers the clamp onto the tail of the crawfish and clamps the tail firmly against the processing plate. The tail clamp includes an extension that presses against the end of the tail at the terminus of the intestinal tract or "mud vein." A pair of air extraction needles are positioned below the main processing plate, and a third linear thruster drives the needles into the tail of the crawfish to extract the tailmeat at the appropriate moment.
The present invention utilizes an air operated automatic infeed conveyor to sort, orient, and deliver the crawfish to the pick up point. An infeed hopper utilizes vibrating cascade bars to separate the crawfish, which tend to clump together. The hopper empties onto a reciprocating conveyor, which in turn empties the crawfish into a series of collection chutes, each of which empties into a vibrating orientation slide. The orientation slides are lined with artificial grass or similar material, and are shaped to gradually narrow into a trough like shape. The legs and claws of the crawfish catch on the textured artificial grass, so that each crawfish exits the orientation slide in a tail first, dorsal side up orientation. The oriented crawfish are routed onto an air conveyor, consisting of a pressurized air plenum having a perforated surface, which floats the crawfish on a bed of air. Horizontal air jets on each side of the plenum urge the crawfish forward and maintain the crawfish in the center of the air flotation conveyor. Preferably, the conveyor is divided into two segments, each having a desired forward velocity, in order to prevent the crawfish from piling on top of each other.
A cooked and chilled crawfish is delivered to the machine in a desired orientation, preferably upright and with the tail portion folded or curved forward towards the head, either by hand or by the automated conveyor discussed in greater detail below. The head clamp, augmented by the vacuum cup, picks up the crawfish at the delivery point by gripping the back of the crawfish. After clamping onto the crawfish at the pickup station, the head clamp raises the crawfish past the claw choppers, which tear off the claws, and then transports the crawfish horizontally across the main processing plate. In so doing, the tail of the crawfish is dragged across a tail straightening brush that wipes back or straightens the tail so that the ensuing functions can be carried out. The head clamp drops slightly relative to the processing plate, which helps to flatten the tail against the processing plate. The tail clamp then rotates and descends onto the tail of the crawfish, firmly clamping the tail against the processing plate, but in a flexible or resilient fashion that allows the forward portion of the tail structure to flex slightly in a vertical direction within the tail clamp. A resilient diaphragm integrated into the tail clamp allows for this slight amount of vertical flexibility, and avoids a shearing effect at the separation point as will be discussed below. With the head clamp holding the head of the crawfish, and with the tail clamp holding the tail, the lower processing assembly, the main processing plate, the tail clamp, and hence the tail of the crawfish is momentarily impacted or "bumped" toward the stationary head clamp holding the head, which ruptures the bond between the tailmeat and the shell, thus making the tailmeat significantly easier to extract. Immediately thereafter, the head clamp ascends which separates the head from the tail. The resilient diaphragm of the tail clamp allows the forward portion of the tail to flex slightly in the vertical direction, so that the resulting separation is by tearing rather than by a straight shearing effect. As a result, a larger portion of the tailmeat, including a portion of the meat that extends into the head, is extracted from the crawfish and packaged.
After separation, the dual air extraction needles positioned below the main processing plate are driven upward by the linear thruster through two holes in the main processing plate and pierce the underside of the tail, one on each side of the mud vein. A charge of compressed air forces the tailmeat out of the shell and into a recovery hopper or conveyor. The dual needle arrangement in conjunction with the tail clamp promote the removal of the mud vein from the tailmeat by retaining the mud vein within the spent shell. The spent shell is released by the tail clamp assembly, which then returns to its original position. The spent shell is then shoved out of the way when another crawfish is moved onto the main processing plate.
Unlike prior art machines, the present invention preserves the head fat for packaging through the use of a novel head fat extraction method. After separation, the head of the crawfish is still held by the head clamp, and the rotary unit attached to the head clamp actuates to swing the head fat extraction cup into position adjacent the head. A linear thruster drives the vacuum cup into the head, and the vacuum cup sucks out and collects the head fat as the upper processing assembly and the head clamp are returning to their initial starting positions to commence another cycle.
For the sake of simplicity, the foregoing description describes the operation of a single processing head and its associated component parts. In a preferred embodiment, the present invention will typically include four pairs of processing heads totalling eight processing heads. Each pair of processing heads will share a single linear thruster for the head clamp assembly as well as a single linear thruster for bumping the lower processing assembly. A single processing head machine according to the present invention can process crustaceans at a projected rate of 17 crustaceans per processing unit per minute, which is over 1000 crustaceans per hour. A machine incorporating 8 processing units can process crustaceans at a projected rate of approximately 8000 crustaceans per hour, which is roughly equivalent to the output of 32 hand peelers.
The control of the machine is governed by an electronic programmable controller. The controller ensures that each step in the process is carried out in the proper sequence, and the controller can be adjusted to vary the cycle time per crawfish. The controller monitors the input and output of each processing head, and enables any two heads to be shut off for maintenance, etc., while the other units remain in operation. Vacuum operated counters responsive to the vacuum pick up cups track the crawfish infeed and alert the operator to a malfunction. These counters serve to both track the number of crawfish processed, such as for accounting purposes, and also to alert the operator to a potential malfunction if the machine fails to pick up the crawfish. Also, the present invention includes an infrared sensor at the pick up point, which when interrupted by a crawfish initiates the processing cycle.
Accordingly, it is an object of this invention to provide an economical and efficient machine for processing crustaceans, especially crawfish.
It is another object of this invention to provide a crawfish processing machine that interrupts the normal bond between the edible tailmeat of the crustacean and the shell in order to facilitate easier removal of the tailmeat from the shell.
A still further object of this invention is to provide a crawfish processing machine that recovers a higher percentage of the edible meat by tearing the tail away from the body rather than by shearing the tail off the body.
Yet another object of this invention is to provide a crawfish processing machine that recovers the head fat, thus preserving the distinctive crawfish flavor.
A still further object of this invention is to provide a processing machine that can be loaded automatically rather than by hand.
These and other objects of the invention will become evident to those skilled in the art upon a reading of the following description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevational view of the crustacean processing machine of the present invention including an elevational view of the automatic loading system;
FIG. 2 is a fragmentary view in perspective of the crustacean processing machine of the present invention showing the infeed conveyor and the upper and lower processing assemblies;
FIG. 3 is a fragmentary view in perspective similar to that shown in FIG. 2, but with the upper processing assembly shown grasping a crawfish;
FIG. 4 is a fragmentary view in perspective similar to those shown in FIGS. 2 and 3, but with the upper processing assembly shown dragging the tail of a crustacean across the tail straightening element in preparation for the separation and extraction steps;
FIG. 5 is a fragmentary view in perspective similar to those shown in FIGS. 2 through 4, but showing the tail clamp of the lower processing assembly grasping the straightened tail of the crustacean;
FIG. 5a is a fragmentary elevational view showing the head clamp and the tail clamp grasping the head and tail respectively of the crustacean, and further showing the tail clamp and the lower processing assembly being impacted or bumped towards the head clamp to rupture the internal membrane securing the tailmeat to the shell;
FIG. 6 is a fragmentary view in perspective showing the head clamp and the upper processing assembly being drawn upwardly relative to the lower processing assembly in order to separate the crustacean's head from the tail; FIG. 6a is a fragmentary elevational view showing the head portion being separated or torn away from the tail portion;
FIG. 7 is a fragmentary view in perspective showing the dual air injection needles being moved upwardly through the processing plate and injecting air into the tail, thereby extracting the tailmeat;
FIG. 8 is a fragmentary view in perspective of the head fat extraction mechanism shown extracting the head fat as the head clamp returns to its original position;
FIG. 8A is a fragmentary view in perspective of an alternate embodiment for the head fat extraction mechanism shown in FIG. 8, shown with the head fat extraction cup in a retracted position;
FIG. 8B is a fragmentary view in perspective of the head fat extraction mechanism shown in FIG. 8A, shown with the vacuum cup in the lowered position and inserted into the head of the crustacean;
FIG. 9 is a fragmentary view in perspective similar to that shown in FIG. 8 and illustrating the spent head being ejected from the head clamp;
FIG. 10 is a fragmentary view in perspective showing the head clamp preparing to pick up the next crustacean for processing;
FIG. 11 is a fragmentary view in perspective of the automatic crawfish loading unit of the present invention;
FIG. 12 is a front elevational view of one of the orientation chutes shown in FIG. 11;
FIG. 13 is a cross sectional view of the orientation chute taken along lines 13--13 of FIG. 12;
FIG. 14 is a cross sectional view of the orientation chute taken along lines 14--14 of FIG. 12; and
FIG. 15 is a cross sectional view of the orientation chute taken along lines 15--15 of FIG. 12.
DETAILED DESCRIPTION OF THE INVENTION
The embodiment described herein is not intended to limit the scope of the invention to the precise form disclosed. Rather, the embodiment has been chosen and described to explain the principles of the invention and its application and practical use to best enable others skilled in the art to follow its teachings. Although a typical commercial embodiment would incorporate four pairs of processing heads for a total of eight processing heads per machine, for the sake of simplicity, the structure and operation of a single processing unit will be described.
Referring now to the drawings, a crawfish processing machine according to the present invention is generally indicated by the reference numeral 10. Machine 10 includes main processing assembly 12 and automatic loading system 14, which delivers cooked and chilled commercial size crawfish 8 to main processing assembly 12 in a dorsal side up, tail first orientation as is discussed in greater detail below. Automatic loading system 14 delivers crawfish 8 in an infeed direction as indicated by the reference arrow 13. Main processing assembly 12 includes upper processing assembly 16 and lower processing assembly 18, both of which are mounted to frame 11 as is discussed in greater detail below. Each crawfish 8 includes a head portion 6 and a tail portion 7.
Upper processing assembly 16 includes carriage 20. Carriage 20 includes reciprocating drive assembly 22 equipped with one or more pinions 23 that engage rack 41, so that carriage 20 can reciprocate back and forth relative to frame 11 from a first position A as shown in FIG. I to a second position B as shown in dotted lines in FIG. 1, in a direction substantially parallel to the infeed direction 13 of crawfish 8. Preferably, carriage 20 has a horizontal travel of several inches and an adjustable cycle time. Upper processing assembly 16 includes counterweight 17, which weighs the same as carriage 20 and all of the attachments thereto. Carriage 20 is moveable between an A position in which head clamp 24 is centered over the crawfish pick up point as is discussed below, and a B position (shown in dotted lines in FIG. 1) in which carriage 20 is positioned over the main processing plate as is discussed below. Carriage 20 is preferably a device marketed under the brand name Ultran by Bimba Manufacturing. Linkage belt 19 mounted on a plurality of pulleys 15 connects carriage 20 to counterweight 17, so that as carriage 20 moves back and forth between positions A and B, counterweight moves in the opposite direction, which equalizes and balances the inertial forces created when carriage 20 starts and stops its horizontal stroke and which ensures smooth, vibration free operation. Attached to carriage 20 is linear actuator or thruster 21, which includes moveable end 23. Linear thruster 21 is vertically oriented so that it has a substantially vertical stroke. Linear thruster 21 is preferably a four position, air operated device as is commonly employed in the machine industry and marketed by Bimba Manufacturing. Alternatively, a typical pneumatic cylinder as is commonly employed in the machine industry may be used. Movable end 23 of thruster 21 has attached thereto clamp assembly 24. As shown in FIG. 2, clamp assembly 24 includes a pair of gripper arms 26, 27, which are preferably molded or otherwise formed from a stiff rubber material so that clamp assembly 24 can accommodate a variety of crawfish sizes. Gripper arms 26, 27 each include curved surface or indentation 26a, 27a, respectively in order to ensure a firm grip. Gripper arms 26, 27 are mounted to pneumatic gripper 25 which is mounted horizontally at end 23 of thruster 21, so that gripper arms 26, 27 can be shifted horizontally between open position and a closed position clamped around the crawfish upon actuation of gripper 25. Pneumatic gripper 25 is preferably a pneumatically operated Parallel Gripper sold under the brand name PHD by PHD, Inc., of Airport and Piper Drive, Fort Wayne, Ind. Clamp assembly 24 further includes suction cup 28 which is disposed between gripper arms 26, 27 for assisting in the pick up of crawfish 8. Suction cup 28 includes vacuum sensitive counter 29 which is discussed in greater detail below. By virtue of thruster 21, clamp assembly 24 can be moved vertically to four pre-set positions, including the fully retracted position C shown in FIG. 2, the fully extended pickup position D shown in FIG. 3, a first intermediate position E shown in FIG. 4 for travel across the processing plate 30 as discussed below, and a second intermediate position F shown in FIG. 5 for holding the head of the crawfish during the impact or "bumping" step as discussed below. Each of these positions is governed by a Hall effect switch located inside the linear thruster as is common practice in the machine industry, which allow the user to adjust the stroke of the thruster or cylinder as desired. As shown in FIG. 8, head clamp assembly 24 further includes vacuum extraction tube 56 and head ejection air jet 58, both of which are mounted to rotary unit 60, and which are discussed in greater detail below. Rotary unit 60 is preferably a device sold under the trade name Pneu-Turn by Bimba Manufacturing, as are each of the rotary units described herein. Finally, a pair of stationary serrated blades 33 are mounted to frame 11 adjacent the crawfish pick up point, which remove the claws from crawfish 8 as the crawfish is being raised by clamp assembly 24.
Lower processing assembly 18 includes main processing plate 30 mounted to subframe 32. Processing plate 30 includes tail-straightening element 34, which is preferably a continuous run nylon brush or other suitable material which has sufficient surface friction to engage the tail 7 of crawfish 8 as the crawfish is dragged across element 34 by the horizontal motion of head clamp 24, thereby straightening the tail 7. Processing plate 30 includes separation and extraction area 36. Extraction area 36 includes a pair of extraction holes 37, 38. Gap 39 between processing plate 30 and spent shell chute 35 provides clearance for the horizontal motion of lower processing assembly 18 and also provides space for head clamp assembly 24 to lower to its second intermediate position F as shown in FIG. 5a. Second intermediate position F is necessary in order to clamp tail portion 7 firmly to processing plate 30, because the head or body of crawfish 8 is typically thicker than the forward portion of tail 7, and hence the head or body must be held lower than the tail in order for the tail to be clamped firmly as is discussed below. Lower processing assembly 18 further includes tail clamp assembly 40, which is mounted to linear actuator or thruster 42. Linear thruster 42 is preferably vertically oriented and further includes rotary unit 43 to permit tail clamp assembly 42 to rotate about a vertical axis, so that clamp assembly 42 can swing from a retracted position G as shown in FIGS. 2, 3 and 4 to an extended position H as shown in FIGS. 5, 6 and 7 over the tail 7 of crustacean 8 that has been positioned on processing plate 30 by head clamp assembly 24 as discussed above. Linear thruster 42 then actuates to lower clamp assembly 40 onto the tail 7 of crawfish 8, thus clamping the tail 7 firmly against processing plate 30. Tail clamp assembly 40 further includes a pair of clamping arms 44, 45, which are connected by a bendable strap or flexible clamping diaphragm 46. Tail clamp assembly 40 further includes spring loaded pressure pad or tail brace 47 for bracing the end portion of tail 7, thus clamping the terminal end of the intestinal tract, commonly known as the "mud vein."
Lower processing assembly 18 further includes a pair of air extraction needles 48, 49, mounted below subframe 32 of lower processing assembly 18. Air extraction needles 48, 49 are preferably mounted at an angle and each are mounted to a two-position linear thruster 50, enabling air extraction needles to be shiftable between a retracted position and extended position wherein the tips of air extraction needles 48, 49 penetrate extraction holes 37, 38 in processing plate 30, and protrude into the tail 7 of the crustacean 8, straddling the mud vein. Extraction needles 48, 49 are mounted to mounting plate 53, which in turn is mounted to subframe 54 and frame 11. Extraction needles are connected to a high pressure air source 57, which supplies a burst of air through needles 48, 49 when needles 48, 49 are inserted into the tail 7 of crustacean 8, which extracts the tailmeat and shoots the extracted meat into collection chute 55 for direction to collection conveyor (not shown). The tailmeat is processed and packaged in a conventional manner, although the "head fat" may be recovered and packaged along with the meat as is discussed below.
A shown in FIG. 1, subframe 32 of lower processing assembly 18 is movably mounted to frame 11, and two position linear thruster 51 is attached at one end to frame 11 and at the other end to subframe 32. Alternatively, a fixed stroke air cylinder may be used in place of linear thruster 51. Accordingly, linear thruster 51 is able to move subframe 32 of lower processing assembly 18 back and forth in a direction generally parallel to the infeed direction 13 of crawfish 8. When subframe 32 is moved, processing plate 30 also moves as can be seen in FIG. 5a. As subframe 32 and processing plate 30 move, the crawfish 8 which is clamped to processing plate 30 by tail clamp 40 moves horizontally relative to head clamp 24, which is holding the forward portion or head 6 of the crawfish 8 and which remains stationary. Thruster 51 is preferably set for a quick, short action thrust, and includes stiff return spring 52 to almost instantaneously return lower processing assembly 18 to its original position. The resulting impact and release action ruptures an internal membrane (not shown) that binds the tailmeat of the crustacean 8 to the internal surface of the shell or tail 7.
Referring now to FIGS. 1 and 11 through 15, automatic loading system 14 includes hopper 70 having a plurality of vibrating cascade bars 72, which are repeatedly shaken by vibrator 73, so that crawfish 8 drop through hopper 70 onto continuously reciprocating conveyor 74. Conveyor 74 includes fixed rollers 75 and reciprocating rollers 76, 77. Collection chutes 78a, 78b, 78c and 78d are mounted immediately below conveyor 74, and each collection chute feeds into vibrating orientation slide 79a, 79b, 79c and 79d, respectively. Preferably, four chutes and four slides are used in order to achieve proper spacing on conveyor 74, although a single chute and a single slide may be used. Orientation slides 79a-d are mounted at an angle so that crawfish 8 will slide down the slides and onto conveyor 74, assisted by the vibrating action of vibrator 81. As shown in FIGS. 12 through 15, orientation slides 79a through 79d include substantially flat infeed end 95, outfeed end 97 having trough 97a, and curved middle portion 99 having indentation 99a. Orientation slides 79a through 79d are preferably lined with artificial grass pad or lining 98. Alternatively, the chutes 79a-d may be constructed of or lined with a mesh hardware cloth or a similar roughened material. The claws and legs of crawfish 8 tend to catch or drag on the lining 98 as the crawfish slides down the slide, so that a crawfish entering the slide tail first will remain tail first, while a crawfish entering the slide head first will gradually turn around as it slides down the vibrating slide. Also, due to the natural curve of the crawfish in the cooked state, each crawfish will be on its side when it is dropped at substantially flat infeed end 95. The tail 7 of crawfish 8 gradually drops into indentation 99a, and then into trough 97a as the crawfish moves down vibrating slides 79a-d. Accordingly, each crawfish will exit the orientation slides tail first, dorsal side up. As reciprocating roller 77 moves horizontally a distance H, reciprocating roller 76 moves up and down the same distance, so that conveyor 74 sequentially drops a crawfish 8 into chutes 78a-d, thus sequentially dropping a crawfish 8 onto each orientation slide 79a-d.
A shown in FIG. 1, automatic infeed conveyor 80 includes first stage 82 and second stage 84. Each stage 82, 84 includes a pressurized plenum 85, floor 86 having perforations 87, and sidewalls 88. A pair of side jets 89, 90 provide a continuous jet of air, and are mounted to sidewalls 88 at intervals. The oriented crawfish 8 thus float on a bed of air provided through perforations 87, and side jets 89, 90 urge the crawfish along the conveyor 80 towards pick up point 92. Side jets 89, 90 preferably have vertically oriented rectangular orifices 91, so that the air exiting orifices 91 push crawfish 8 forward and also maintain crawfish 8 in the center of conveyor 80, and in a vertical, non-leaning position. The velocity of the crawfish can be controlled by adjusting both the pressure and the angle of side jets 89, 90. Preferably, the forward velocity of crawfish 8 in infeed direction 13 is slightly higher on first stage 82 than on second stage 84. This ensures a constant supply of crawfish at the pick up point, because the crawfish back up but don't override each other. At pick up point 92, sidewalls 88 include apertures 93 to provide clearance for head clamp assembly 24. Infrared sensor 94 is mounted to second stage 84 of conveyor 80 adjacent pick up point 92. Finally, electronic controller 96 monitors the operations of the machine, and may be adjusted to increase or decrease the cycle time as desired.
In operation, a number of commercially sized crawfish 8 are loaded into hopper 70 and separated by the action of vibrating cascade bars 72. The crawfish 8 drop onto reciprocating conveyor 74, and then are distributed sequentially into collection chutes 78a through 78d, which in turn drop the crawfish onto orientation slides 79a-d. Due to the folded tail, the crawfish at this point will naturally be on their sides, either head first or tail first. Once the crawfish come into contact with vibrating slides 79a-d, the legs and claws repeatedly catch on the rough artificial grass lining 98, while the smoother tail does not, which ensures that the crawfish exit slides 79a-d in a tail first, dorsal side up orientation. The crawfish then move along conveyor 80 on a bed of air towards pick up point 92. Side jets 89, 90 maintain crawfish 8 in the center of air conveyor 80. The presence of crawfish 8 at pick up point 92 is detected by infrared sensor 94, which triggers the commencement of the processing cycle. Alternatively, the crawfish 8 may be manually loaded onto conveyor 74 or manually placed at pick up point 92.
Upon commencement of the processing cycle, carriage 20 is in position A, placing upper processing assembly 16 and head clamp head clamp assembly 24 over pick up point 92. Thruster 21 extends clamp assembly 24 from the fully retracted position C to the fully extended position D immediately over the waiting crawfish 8. Vacuum cup 28 contacts crawfish 8 and lifts it slightly, and controller 96 actuates gripper 25, thus closing arms 26, 27 firmly around the crawfish. Thereafter, thruster 21 raises clamp assembly 24 approximately 11/2 inches to the first intermediate position E. In the process, the claws 5 of crawfish 8, which are no longer needed, are ripped off by serrated blades 33. After clamp 24 is raised, carriage 20 begins its horizontal stroke from position A towards position B. In the process, the tail portion is dragged across the tail straightening brush 34, so that by the time the crawfish is in position on main processing area 31 of processing plate 30, the tail is straight. When carriage 20 reaches the end of its horizontal stroke at position B, thruster 21 lowers clamp assembly 24, which positions the tail flat on the processing plate 30.
At this point, rotary unit 43 activates to swing tail clamp assembly 40 approximately ninety degrees into position directly over tail 7, and thruster 42 extends forcing clamp 40 downward, pressing tail 7 firmly against processing plate 30 with flexible diaphragm 46 draped across tail 7 and brace 47 securing the end of the mud vein. Thereafter, linear thruster 51 imparts a brief horizontal force, moving the entire lower processing assembly horizontally approximately 1/4 inch, thus rupturing the internal membrane that bonds the tailmeat to the internal surface of the tail 7. Return spring 52 almost immediately returns lower processing assembly to its original position. Thereafter, thruster 21 retracts to position C, which raises head clamp assembly approximately 23/8 inches, while tail clamp 40 remains stationary. In the process, the head 6 is separated from the tail 7 in a tearing fashion made possible by a bendable strap or flexible diaphragm 46, which allows the forward portion of the tail portion to raise vertically and flex slightly as head clamp 24 raises and separates head 6 from tail 7.
Next, upper processing assembly 16 extracts the head fat, while lower processing assembly 18 simultaneously extracts the tailmeat. After thruster 21 raises clamp assembly 24 to fully retracted position C, carriage 20 begins its horizontal return stroke from position B back to position A. Rotary unit 60 swings approximately ninety degrees forcing vacuum extraction cup 56 into head 6 enabling cup 56 to extract head fat. Preferably, the head fact extraction occurs while carriage 20 is traveling horizontally between positions B and A. Before carriage 20 returns to position A, rotary unit 60 swings vacuum cup back out of head 6, gripper 25 opens arms 26, 27, and air jet 58 shoots a blast of air, which pushes spent head 6 off to the side where it drops onto a waste conveyor (not shown) for disposal.
At the same time, tail 7 is still clamped firmly to processing plate 30 after the head has been separated as discussed above. Linear thruster 50 forces the tips of extraction needles 48, 49 through extraction holes 37, 38 and into tail 7 so that needles 48, 49 penetrate into the tail 7 straddling the mud vein. At this point a charge of air through needles 48, 49 forces the tailmeat inside tail 7 to be discharged with sufficient force that the tailmeat is ejected into collection chute 55 for collection and packaging. Alternatively, a charge of CO 2 gas or other gases or fluids may be used. Brace 47 of clamp assembly 40 retains the mud vein within the spent shell. Thereafter, linear thruster 42 retracts, which raises tail clamp assembly 42 off the spent tail shell, and rotary unit 43 rotates tail clamp 40 approximately ninety degrees back to it's original position. The spent tail shell remains on processing plate 30 until the spent shell is pushed out of the way and into chute 35 by the next incoming crawfish 8.
FIGS. 8A and 8B illustrate a second embodiment for the head fat extraction mechanism of the claimed invention, in which the elements are the same or substantially the same as those in the embodiment discussed above and retain the same reference characters, but increased by 100. Clamp assembly 124 includes a pair of gripper arms 126, 127, which are preferably molded or otherwise formed from a stiff rubber material so that clamp assembly 124 can accommodate a variety of crawfish sizes. Gripper arms 126, 127 each include curved surface or indentation 126a, 127a, respectively in order to ensure a firm grip. Gripper arms 126, 127 are mounted to pneumatic gripper 125, and a rotary unit 103 and a linear thruster 104 are mounted to gripper 125. Gripper arms 126, 127 can be shifted horizontally between open position and a closed position clamped around the crawfish upon actuation of gripper 125. Pneumatic gripper 125 is preferably a pneumatically operated Parallel Gripper sold under the brand name PHD by PHD, Inc., of Airport and Piper Drive, Fort Wayne, Ind. Clamp assembly 124 further includes swing arm 155 having head fat extraction tube 156 mounted at one end. Swing arm 155 is mounted to rotary unit 103 which enables swing arm 155 to shift between a raised or retracted position shown in FIG. 8A and a lowered or extended position shown in FIG. 8B. In the lowered position, head fat extraction tube 156 is positioned adjacent the head 6 of crawfish 8. Swing arm 155 is also mounted to linear thruster 104, which permits swing arm 155 to shift between a first position spaced apart from gripper 125 as shown in FIG. 8A, and a second position nearer gripper 125 as shown in FIG. 8B, thus thrusting extraction tube 156 into the separated head 106 of crawfish 108. Head clamp assembly 124 further includes head ejection air jet 158.
It will be appreciated that the foregoing is presented by way of illustration only, and not by way of any limitation, and that various alternatives and modifications may be made to the illustrated embodiment without departing from the spirit and scope of the invention.
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An apparatus for extracting tailmeat and other edible materials from crustaceans. The apparatus of the present invention includes a pair of clamps movably mounted to a frame which grasp the head and tail portions of the crustacean and then momentarily impact the head portion towards the tail portion, thus rupturing an internal membrane that bonds the tailmeat to the shell of the crustacean thereby greatly easing the extraction of the tailmeat from the shell. After impact, the clamps are separated from each other so as to separate the head portion of the crustacean from the tail portion. The tail clamp allows the tail portion to flex slightly, which avoids a shearing effect and which retains more edible material in the separated tail portion, where it is subsequently extracted. The tail meat extraction means includes a pair of hollow needles for insertion into the tail portion of the crustacean straddling the intestinal tract, and a charge of compressed air forced through the needles into the tail portion forces the tailmeat out of the shell. A brace on the tail clamp grasps the end of the intestinal tract and retains the intestinal tract within the empty shell. Suction means are included for extracting head fat from the separated head of the crustacean, which head fat is collected and preserved for packaging along with the tailmeat.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to apparatus which utilizes the rotary motion imparted to a member as the motive force for a pump.
2. Description of the Prior Art
It is well-known in the art that the magnitude of the pressure differential across a seal between a stationary and a relatively rotatable member increases the forces imposed on the seal and commensurately reduces the operating life thereof. This is especially true in the hydrocarbon drilling environment where seals are typically used on various downhole tools.
U.S. Pat. No. 3,600,109 (Pavlichenko, et al.) relates to an arrangement to seal the shaft of a drilling face machine. U.S. Pat. No. 3,894,818 (Tschirky) relates to an in-hole motor in which thrust bearings are provided with means to lubricate the bearings employing pressure balanced seals.
Other sealing arrangements between a relatively rotating shaft and a stationary housing are those disclosed in U.S. Pat. No. 3,740,057 (Doyle, et al.), U.S. Pat. No. 3,888,495 (Mayer) and U.S. Pat. No. 4,080,115 (Sims, et al.).
U.S. Pat. No. 4,039,229, issued to Ohlberg discloses a roller bearing construction which includes at least one bounding wall fabricated of an elastic material. U.S. Pat. No. 1,892,217, issued to Moineau discloses a gear mechanism adapted for use as a pump, a prime mover or a fluid transmission means.
Until very recently, some downhole tools, more particularly turbodrills, have been used to drill oil wells with thrust bearings constructed from laminations of rubber and steel. Lubrication and cooling were provided by the drilling mud circulating in the well bore. Their poor performance in such environment compelled designers, engineers and operators to shift to standard bearings (balls, rollers, etc.) operating in a clean lubricant. This required sealing off the chamber housing the bearings system from any intrusion of contaminants present in the drilling mud and the mud itself.
The duration of efficient operation depends on the life of the bearings, among other factors, and in turn the life of the bearings depends on the life of the seals separating the clean lubricant from the drilling mud.
A significant factor controlling the life of these seals is the differential pressure across them. Reducing the pressure differential across these seals using a modified roller bearing as prime mover for a pump is considered to be a feature of the present invention.
It would be advantageous to utilize the rotary motion necessarily imparted to a downhole tool as the motive force for a pump. Further, it is believed to be advantageous to provide a seal arrangement for use in the hydrocarbon production environment wherein the motive force generated by the rotation of the shaft is imparted to a bearing member and is utilized to pump lubricating fluid between internal chambers to thereby equalize pressure differences across the shaft sealing members. Also believed advantageous as a consequence of the pumping of lubricating fluid between internally defined chambers is the circulation of the lubricating fluid so that a heat transfer relationship between the fluid and the structural members may be provided to lower bearing operating temperatures. It is also advantageous to generate the higher pressures of the fluid on the "inside" of the seals to insure that any leakage flow tends to be in a direction from the inside to the outside, thus effectively isolating the region between the seals from the region outside the seals.
SUMMARY OF THE INVENTION
This invention relates to an apparatus which utilizes the rotary motion of a downhole member as the motive force for a pump so that a pressure differential may be generated to isolate a component from a particular region. In particular, the invention relates to an apparatus for minimizing the pressure differential across the seals between a housing and a shaft relatively rotatable with respect thereto. The seals define an interior region in which a bearing, as a roller bearing, is disposed for supporting the rotation of the shaft with respect to the housing. The bearing and the first seal cooperate to define an interior chamber within the region. A member, as a floating piston, is disposed between the opposite side of the bearing and the second seal to define second and third chambers within the interior region. Means for communicating the first and third chambers, as a channel defined within the structure of either the shaft or the housing, is provided so that a pressure increase in the first chamber is applied to the fluid in the third chamber. A pressure relief arrangement, biased by a predetermined force, opens to vent the third chamber when the pressure of the fluid in the third chamber exhibits a magnitude which exerts a force exceeding the biasing force. The relief arrangement may take the form of a fluid conduit disposed in the floating piston. The conduit has a valve arrangement disposed therein. The valve may be a check valve biased by a spring toward the closed position.
Mounted on the roller bearing is a suitable pump, as a Moineau pump. Motive force for the pump is provided by the rotation of the shaft. The pump responds to the rotation of the shaft imparted to the roller bearing to pump lubricating fluid from the second chamber into the first chamber to increase the fluid pressure therein. The fluid pressure also increases within the third chamber as a consequence of the disposition of the channel. When the pressure within the first and the third chambers exceeds the predetermined level, the pressure generates a force acting against the biasing force of the check valve. When the force exerted by the pressure of the fluid in the third chamber exceeds the predetermined biasing force imposed on the check valve the valve opens, thus relieving the pressure in the first and third chambers. If the biasing force imposed on the check valve is set slightly below a desired pressure level in the third (and thereby the first) chamber, the pressures in those chambers may be selected and maintained such that a minimum pressure differential is defined across the first and second seal.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be more fully understood from the following detailed description thereof, taken in connection with the accompanying drawings, which form a part of this application and in which:
FIG. 1 is a side elevational view entirely in section illustrating an apparatus for minimizing pressure differential across a shaft seal in accordance with the instant invention.
FIG. 2 is a partial cross-sectional view taken through section lines A--A in FIG. 1.
FIG. 3 is a partial cross-sectional view taken through section lines B--B in FIG. 1.
FIG. 4 is an alternative embodiment of the apparatus depicted in FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1, shown in side elevational view is an arrangement generally indicated by reference character 140 for minimizing the pressure differential across a first upper seal 134U and a second lower seal 134L. The seals 134U and 134L are disposed between a stationary housing 10 and a rotatable shaft 12 relatively rotatable with respect thereto. FIG. 1 illustrates the structure disposed with respect to an axial centerline CL it being understood that the structures defined are symmetrical with respect to that centerline CL and extends circumferentially around the shaft 12.
The shaft 12 may be any relatively rotatable member with respect to a housing 10, as for example, a turbodrill. The first and second seals 134U and 134L, respectively, may be any suitable shaft sealing arrangement utilized in the operating environment and are typically fabricated of suitable resilient material.
The first seal 134U and second seal 134L cooperate to enclose an annular space or interior region 136 between the housing 10 and this shaft 12. Region 136 is shown divided into three (3) sections 136U, 136C, and 136L. The housing 10 (or the shaft 12, or both) may be relieved to define a diametrically enlarged dimension as at 124, for the interior region 136.
Disposed within the interior region 136 is a bearing generally indicated at 127. As seen in FIG. 1 the preferred embodiment of the invention utilizes a roller bearing in which an inner race 129"I" is keyed (as by a key 131A) to the rotatable shaft 12. The outer race 129"O" of the bearing may be keyed (as by key 131B) or otherwise integrally installed as with a press fit into the housing 10. A plurality of roller elements 133 are supported between the inner race 129"I" and the outer race 129"O" in order to define the bearing surfaces on which relative rotation of the shaft 12 with respect to the housing 10 is permitted. To facilitate rotation the entire interior region 136 is provided with a suitable lubricating fluid, as lubricating oil.
Mounted between the housing and shaft in the vicinity of the bearing 127 is a rubber stator 135. The stator 135 and its support ring 142 may be formed integral with outer race 129 "O", see FIG. 1. Suitable seals 141A and 141B, as O-ring seals, may be disposed as shown between the housing and shaft, respectively. The rubber stator 135 is an annular member, see Section "BB" (FIG. 3).
A pump, generally indicated by 143 includes a shaft 147 connected to any one of the roller elements 133. The end of the shaft drives the pump 143. The pump may take the form of a Moineau pump which is received within the rubber stator 135. As will be seen the pump 143 is responsive to the motive force of the shaft 12 imparted to the bearing element 127 to provide a pumping action whereby pressure differentials across the first and second seals 134U and 134L may be minimized.
A first chamber 136U is defined above the bearing 127/pumps 143 and the first seal 134U.
Disposed in the space between the lower surface of the bearing 127 arrangement and the second seal 134L is a member, or floating piston 157. The piston 157 is an annular member provided with inner and outer seal rings 159A and 159B, respectively. The member, or floating piston 157 is operative to subdivide the portion of the interior region between the bearing 127 and the second seal 134L into a second chamber 136C and a third chamber 136L. The chamber 136C is further subdivided into a sub-chamber 136C-1 by the bearing 127. The second chamber 136C communicates with the subchamber 136C-1 defined between the bearing and stator. That is, although the first chamber 136U is isolated from the second chamber 136C, and the second chamber is isolated from the third chamber 136L, the second chamber 136C is to be construed to include the sub-chamber 136C-1 between the bearing 127 and the stator 135.
Means 148 for communicating the first chamber 136U with the third chamber 136L are provided. In the preferred embodiment, the means 148 take the form of a channel 148A provided in the structure of the shaft 12 so that the first chamber 136U and the third chamber 136L are in fluid communication. It is understood that although the channel 148A is shown as disposed within the rotating shaft 12 it may be disposed with equal effect within the housing 10.
A pressure relief arrangement 150 is provided for relieving the pressure in the third (and the first) chambers. The arrangement includes a conduit or bore 152 provided within the floating piston 157 and communicating the second chamber 136C with the third chamber 136L. It is likewise to be appreciated that the pressure relief arrangement may take any form whereby the third chamber (and the first chamber) may be relieved. For example, the channel 148A may be provided within the rotor 12 or the housing 10 in accordance with this invention.
The arrangement 150 includes a valve 158 provided in the conduit or bore 152. The valve element may take the form of a check valve having a ball 158A biased against a seat by a spring 160. The spring 160 exerts a force acting in the direction 162 urging the ball 158A toward the seat 174 to thereby interdict communication between the second and third chambers. As will be seen herein, the magnitude of the force imposed by the spring 160 is selected in accordance to a predetermined pressure magnitude which is desired to be present in the fluid within the first chamber 136U and in the third chamber 136L.
Since the second chamber 136C unrestrictedly communicates with the sub-chamber 136C-1, it may therefore be appreciated that the second chamber 136C serves as a fluid reservoir. Lubricating fluid is introduced into the second chamber 136C through a reservoir inlet port 180. Similarly, fluid is also provided to the third chamber 136L by a second inlet port 182. Air is vented through port 183. In operation, of course, both inlet ports 180 and 182 and vent port 183 are provided with suitable caps.
The operation of the invention may now be discussed. It is advantageous in order to extend the operating life of the seals 134U and 134L for as long a period as possible. To effect this end it is desirable to maintain the pressure in the chamber 136U above the pressure in the region 30 yet to maintain the pressure differential therebetween as low as possible. Similarly, it is desirable to maintain the pressure in the third chamber 136L above but as close as possible to the pressure of the region 20 beyond the second seal 134L so as to minimize the differential thereacross. In accordance with this invention an arrangement is provided whereby the pressure differentials across the first seal 134U and second seal 134L are minimized. Further, an arrangement is provided to positively maintain higher pressure in the first chamber 136U and the third chamber 136L than in the regions beyond the seals 134U and 134L.
Rotational motion of the shaft 12 is imparted to the bearing 127, including the roller elements 133. Consequently, the shaft 147 and thereby the pump 143 are rotated causing fluid to be pumped from the sub-chamber 136C-1 (and, therefore, from the reservoir or second chamber 136C) into the first chamber 136U.
The motive force for the pump is derived from the rotation of the shaft 12 which turns the bearing element 133 which turns the pump shaft. As a result of the pumping action of the Moineau pump the pressure P 136U in the first chamber 136U increases. This pressure increase is also sensed as a result of the channel 148A as an increase in pressure P 136L in the third chamber 136L. It is apparent that the pressure levels in the first chamber 136U and the third chamber 136L are substantially equal but separated only by the pressure drop of the channel 148. If the pressures in the first chamber 136U and therefore the third chamber 136L increase beyond a predetermined magnitude, the fluid in the third chamber 136L exerts a force on the ball 158A opposing the force acting in the biasing direction 162. When the force generated by the fluid in the third chamber 136L exceeds the biasing force, the valve 158 of the pressure relief arrangement opens and the third chamber 136L is in communication with the second chamber 136C. As a result, fluid is vented from the third chamber 136L into the reservoir or second chamber 136C thereby relieving the pressure levels in the third chamber 136L and the first chamber 136U.
By judiciously selecting the magnitude of the biasing force 162 acting on the valve 158 it may be readily understood that the magnitude of the pressures within the third chamber 136L and the first chamber 136U may be controlled. In this manner, the pressure differentials across the first seal 134U and the second seal 134L may be minimized with the attendant advantages in seal life resulting therefrom.
Also as a concomitant advantage it may be appreciated that the pumping of the lubricating fluid from the reservoir 136C and the sub-chamber 136C-1 associated therewith, through the first chamber 136U, the channel 148, the third chamber 136L, the channel 148A and thence back into the second chamber 136C provides a circulation path for the lubricating fluid which acts to decrease the operating temperature in the closed system so defined. Yet further, it is believed that since the seal rings 159A and 159B associated with the piston or member 157 are exposed only to circumferential rotating forces and are thus static in a vertical direction (as viewed in FIG. 1) the useful thereof is also enhanced. Further, by judiciously selecting the pump output, the pressure can be maintained at higher levels in the chambers 136U and 136L than in the regions 20 and 30. By judicious sizing of the chambers, the rate of leakage from the chambers 136U and 136L into the regions 20 and 30 may be accommodated, thus permitting a determination of the duration of safe operation.
It is to be understood, of course, that a reservoir may be disposed elsewhere than the second chamber, so long as the second chamber communicates therewith. Further, the third chamber may be relieved directly into the reservoir so defined and remain within the contemplation of this invention. It is, however, believed advantageous to relieve the third (and first) chambers into the reservoir defined by the second chamber, in the manner discussed above. It is also to be understood that although the bearing is disclosed in the preferred embodiment as a roller bearing and the pump as a Moineau pump, the invention is not to be construed as so limited. It is to be understood that any mechanism whereby the rotation of the shaft is utilized to pump fluid from the reservoir (shown as the chamber 136C) into the first and third chambers 136U and 136L, respectively, lies within the contemplation of this invention such as a gear pump, see Section "BB", Alternative Design, FIG. 4.
In view of the foregoing it may be appreciated that the motive force for a pump derived from the rotation of the shaft may be utilized to circulate lubricating fluid from a reservoir and into the first and third chambers to thereby maintain the pressure differential across the first and second seals as minimal as possible. By judiciously selecting the magnitude of the biasing force imposed on the valve in the second channel it may also be appreciated that the pressure in the first and third chambers may be relieved so that the predetermined pressure levels desired therein may be maintained.
Having described the preferred embodiment of the invention those skilled in the art having benefit of the teachings of the instant invention as set forth hereinabove may effect numerous modifications thereto, which modifications are to be construed as lying within the scope of the invention as defined in the appended claims.
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An arrangement for minimizing the pressure differential across shaft seals is characterized by a pump powered by the rotative force of a shaft to pump a fluid from a reservoir chamber into a chamber next-adjacent to each shaft seal. When the pressures in the chambers adjacent to the seals exceed a predetermined magnitude, a pressure relief arrangement is opened, thus venting the chambers and maintaining the differentials across the seals as minimal as possible.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a National Stage Entry of PCT/IN2011/000858, filed Dec. 15, 2011, which claims priority to Indian Patent Application No. 1589/MUM/2011, filed May 30, 2011.
BACKGROUND
[0002] 1. Filed of Invention
[0003] The present disclosure relates to a process for preparing 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulphinyl pyrazole (Fipronil).
[0004] 2. Discussion of Related Art
[0005] 5-Amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethyl sulphinyl pyrazole [Fipronil] is one of the important fluorine bearing 1-Aryl pyrazole derivatives developed in the recent two decades. It is a novel pesticide characterized by high efficiency, low toxicity and especially low residue. Commercially fipronil is synthesized by oxidation of thiopyrazole with oxidizing agents in presence of suitable solvents. The process makes use of corrosive and expensive chemicals such as trifluoroacetic acid/hydrogen peroxide, m-chloroperbenzoic acid/dichloromethane/chloroform and the like.
[0006] EP 295117 discloses preparation of 5-amino-1-(2,6-dichloro-4-trifluoro methyl phenyl)-3-cyano-4-trifluoromethyl sulphinyl pyrazole by oxidation of
[0007] 5-amino-1(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethyl-thiopyrazole with meta-chloroperbenzoic acid. A problem encountered in the preparation is the co-formation of the corresponding sulfone compound 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfonyl pyrazole, which is difficult to remove from the sulfoxide.
[0008] It has been found that a mixture of trifluoroaceticacid and hydrogen peroxide (trifluoroperaceticacid) gives excellent results in terms of both selectivity and yield. However, the problem associated with the use of trifluoroacetic acid and hydrogen peroxide mixture on large scale is that it leads to corrosion of the glass linings of industrial reaction vessels. This corrosion occurs as a result of the formation of hydrogen fluoride and it prohibits the use of this reagent mixture in such vessels. Further, it was found that the addition of a corrosion inhibiting compound such as boric acid to the reaction mixture inhibits the corrosion process and reduces the speed of corrosion to a level that is typically less than 5 μm/year.
[0009] WO01/30760 describes oxidation of 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethyl thio-pyrazole with trifluoro-acetic acid (TFA)and hydrogen peroxide in presence of boric acid. Boric acid is used to prevent the corrosion of glass/metal equipment. Whilst this may be effective during oxidation, however TFA is a costly chemical and must be recovered due to process economics.
[0010] US20090030211 discloses a process for the preparation of fipronil. The process involves oxidizing 5-amino-3-cyano-1-(2,6-dichloro-4-trifluro methylphenyl)-4-trifluromethylthio pyrazole in a medium comprising an oxidizing agent, trichloroaceticacid and a melting point depressant. The melting point depressant employed in the process is monochloroaceticacid, dichloroaceticacid, methylenedichloride, ethylenedichloride, monochlorobenzene and haloalkane. The process utilizes trichloroacetic acid as a substitute solvent for TFA (trifluoroaceticacid) along with melting point depressant.
[0011] IN183/MUM/2010 discloses a process for the preparation of fipronil which obviates the use of large quantity of TFA. The process utilizes a mixture of solvents which provides selective degree of oxidation as that of trifluoroaceticacid along with a oxidant and a corrosive inhibiting agent. The solvent system used is a mixture of trifluoroaceticacid and chlorobenzene in a ratio of 60:40% w/w to 55:45% w/w.
[0012] CN101250158 discloses a process for the synthesis of fipronil by oxidation of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluromethylphenyl)-4-trifluromethylthio pyrazole in presence of a phase transfer catalyst selected from the group consisting of tetrabutyl ammonium chloride, tetrabutyl ammonium bromide, 4-N, N-dimethyl pyridine, triethylbenzylammonium chloride, sodium dodecyl sulphonate and trimethyl dodecyl ammonium chloride, in a solvent and sulphuric acid medium.
[0013] However, the process disclosed in CN101250158 is expensive process as it utilizes phase transfer catalyst. Further, the process disclosed in CN101250158 involves dissolution of the oxidant in sulphuric acid which causes degradation of oxidant and leads to incomplete oxidation. The process therefore shows inconsistency in the yield and the quality.
[0014] Therefore, there is felt a need to develop a simple and in-expensive method for the synthesis of fipronil which overcomes the drawbacks associated with aforesaid process.
SUMMARY OF THE INVENTION
[0015] Some of the objects of the invention are as follows:
To provide a simple process for the preparation of 5-Amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulphinyl pyrazole which gives consistent yield and quality. To provide a process for the preparation of 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulphinylpyrazole which obviates the use of a phase transfer catalyst. To provide a process for the preparation of 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulphinylpyrazole which is safe, convenient, easy to operate on commercial scale and cost-effective.
[0019] In accordance with the present invention, there is provided a process for preparing fipronil, said process comprising the following steps:
a. oxidizing, in a solvent selected from the group consisting of ethylene dichloride, methylene dichloride, carbon tetrachloride, chloroform, dibromoethane, bromobenzene, chlorobenzene and ortho- dichlorobenzene, a reactant mixture containing a compound 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylthio-pyrazole of formula II and concentrated sulfuric acid having concentration in the range of 75% to 98% w/w, with hydrogen peroxide having concentration in the range 40 to 70% w/w, at a temperature in the range of −10° C. to 40° C. to obtain an oxidized product mixture; b. quenching said product mixture with water at a temperature in the range of 10 to 25° C.; c. heating the quenched product mixture at a temperature in the range of 60 to 70° C. to obtain a biphasic system containing an aqueous phase containing sulphuric acid and an organic phase containing the oxidized product; d. isolating said organic phase by separating the aqueous phase; e. neutralizing the isolated organic phase containing the oxidized product to obtain crude fipronil; and f. crystallizing the crude fipronil to obtain crystallized fipronil.
[0026] Typically, the amount of the hydrogen peroxide used is in the range of 0.9 moles to 1.6 moles per mole of the compound II.
[0027] Typically, the amount of the solvent used is 100 to 7000 ml per mole of the compound II.
[0028] Typically, the amount of the concentrated sulphuric used is 400 gm to 3000 gms per mole of the compound II.
[0029] In a preferred embodiment of the present invention the aqueous phase obtained after separation of the organic phase in step (d) is concentrated to obtain concentrated sulphuric acid having concentration in the range of 75% to 85% w/w.
DETAILED DESCRIPTION OF THE INVENTION
[0030] The present invention provides a process for the preparation of a compound of formula (I) 5-Amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-tri fluoromethylsulphinylpyrazole (Fipronil) by oxidizing a compound 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylthio pyrazole of formula (II)
[0000]
[0031] The process for the preparation of fipronil in accordance with the present invention includes the following steps:
preparing a mixture containing a compound 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoro methyl thio-pyrazole and a solvent, cooling the mixture to a temperature in the range of −10 to 20° C. and adding a mineral acid over a period of about 3 to about 4 hours to obtain a reactant mixture, adding an oxidizing agent to the reactant mixture maintaining the temperature in the range of −10 to 20° C., maintaining the reaction at the temperature in the range of 10° C. to 50° C. for a period of 1 to 8 hours to obtain an oxidized product mixture, quenching the product mixture by slowly adding the mixture to chilled water over a period of about 2 hours, heating the quenched mixture at a temperature of about 60 to 70° C. to obtain a biphasic system containing an aqueous phase and an organic phase containing the oxidized product, isolating said organic phase by separating the aqueous phase, neutralizing the isolated organic phase containing the oxidized product to obtain crude fipronil, and crystallizing the crude fipronil to obtain crystallized fipronil.
[0041] The oxidant can be added simultaneously along with the mineral acid, however care is taken that the oxidant is not added into sulphuric acid as it will degrade the oxidant.
[0042] The mineral acid is concentrated sulphuric acid (H 2 SO 4 ) having concentration in the range of of 75% to 98% w/w. The amount of sulphuric acid (H 2 SO 4 ) quantity used is in the range of 400 gm to 3000 gm per mole of compound II.
[0043] The oxidizing agent is a peroxide compound selected from the group consisting of hydrogen peroxide, t-butyl hydrogen peroxide, benzoyl peroxide and sodium peroxide. Preferably, the oxidizing agent is hydrogen peroxide (H 2 O 2 ) having concentration in the range of 40 to 70% w/w.
[0044] In accordance with one of the embodiments of the present invention the amount of hydrogen peroxide is in the range of 0.9 moles to 1.6 moles per mole of the compound of formula II.
[0045] The solvent is at least one selected from the group consisting of ethylene dichloride, methylene dichloride, carbon tetrachloride, chloroform, dibromoethane, bromobenzene, chlorobenzene and ortho dichlorobenzene. Preferably 100 ml to about 7000 ml of the solvent per mole of the compound of formula II is used in the process.
[0046] The following examples are merely illustrative of the invention and should not be construed as limiting.
EXAMPLE 1
[0047] 1.5 liter of ethylene dichloride & 421.0 gms of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluromethylphenyl)-4-trifluromethylthio pyrazole was charged in a reactor flask with overhead stirring & condenser system. This mass was then cooled to 12-15° C. and 68.0 gms of H 2 O 2 (50.0% w/w) & 500.0 gms of H 2 SO 4 (90.0% w/w) were simultaneously added over a period of 3.0 to 4.0 hours. The reaction temperature was then raised to 28-30° C. & maintained for about 2.0 hours. The reaction mass obtained thereafter was slowly added into 1700 ml of chilled water at 10-20° C. over a period of 2.0 hours. To this mass, 1500 ml of ethylene dichloride was added and the mixture was heated to 60° C. in order to separate the aqueous and organic layers. The obtained organic phase was washed with water & then with 5% NaHCO 3 solution followed by water wash, till a neutral pH was obtained. The crude yield of fipronil after removal of solvent was 425.0 gms. The crude fipronil was crystallized from same solvent after partial evaporation to yield 325 gms of crystalline fipronil with 94.0% purity.
EXAMPLE 2
[0048] 1.5 liter of methylene dichloride & 421.0 gms of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluromethylphenyl)-4-trifluromethylthio pyrazole was charged in a reactor flask with overhead stirring & condenser system. This mass was cooled to 12-15° C. and 68.0 gms of H 2 O 2 (50.0% w/w) & 500.0 gms of H 2 SO 4 (90.0% w/w) were simultaneously added to the mass over a period of 3.0-4.0 hours. The reaction temperature was then raised to 28-30° C. & maintained for about 2.0 hours. The reaction mass obtained thereafter was slowly added into 1700 ml of chilled water at a temperature of about 10-20° C. over a period of 2.0 hours. To this mass, 1500 ml of methylene dichloride was added and the mixture was heated to 60° C. to separate the aqueous and organic layers. The organic phase was washed with water & then with 5% NaHCO 3 solution, followed by water wash, till a neutral pH was obtained. The crude yield obtained was 425.0 gms. The obtained crude fipronil was then crystallized from same solvent after partial evaporation to yield crystalline Fipronil (325 gms) with 94.0% purity.
EXAMPLE 3
[0049] 3.0 liter of ethylene dichloride & 421.0 gms of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluromethylphenyl)-4-trifluromethylthio pyrazole was charged in a reactor flask with overhead stirring & condenser system. This mass was cooled to a temperature of about 5-10° C. 95.0 gms of H 2 O 2 (50.0% w/w) & 2000.0 gms H 2 SO 4 (85.0% w/w) were simultaneously added over a period of 3-4 hours. The reaction temperature was maintained at 12-15° C. for about 2.0 hours with monitoring of reaction conversion. The reaction mass obtained thereafter was slowly added into 800 ml of chilled water at a temperature of about 10-20° C. over a period of 2.0 hours. This mass was heated to a temperature of about 60-65° C. to separate the aqueous and organic layers. The organic phase was washed with water & then with 5% NaHCO 3 , followed by water wash, till a neutral pH was obtained. The crude yield of fipronil after removal of solvent was 435.0 gms. The crude fipronil was then crystallized to yield 350.0 gms of fipronil with 95.50% purity.
EXAMPLE 4
[0050] 3.0 liter of ethylene dichloride solvent & 421.0 gms of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluromethylphenyl)-4-trifluromethylthio pyrazole was charged in a reactor flask with overhead stirring & condenser system. This mass was cooled to a temperature of about 5-10° C. and 2500.0 gms of H 2 SO 4 (85.0% w/w) was added over a period of 3.0 to 4.0 hours. After that, 95.0 gms of H 2 O 2 (50.0% w/w) was added to the aforesaid mass over a period of 3.0 hours at 11-13° C. The reaction temperature was maintained at a temperature of about 12-15° C. for about 2.0 hours with monitoring of reaction conversion. The reaction mass obtained thereafter was slowly added into 1250 ml of chilled water at a 10-20° C. over a period of 2.0 hours. This mass was heated to a temperature of about 60-65° C. to separate the aqueous and organic layers. The organic phase was washed with water & then with 5% NaHCO 3 solution, followed by water wash, till a neutral pH was obtained. The crude yield was 436.0 gms. The crude fipronil was then crystallized from same solvent after partial evaporation to yield 358.0 gms crystalline fipronil of 95.0% purity.
EXAMPLE 5
[0051] 3.0 liter of ethylene dichloride solvent & 421.0 gms of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluromethylphenyl)-4-trifluromethylthio pyrazole was charged into a reactor flask with overhead stirring & condenser system. This mass was cooled to a temperature of about 5-10° C. and 1000.0 gms of H 2 SO 4 (85.0% w/w) was added over a period of 1.5 to 2.0 hours. 61.0 gms of H 2 O 2 (50.0% w/w) was then added to the aforesaid mass over a period of 3.0 hours at 07-13° C. The reaction temperature was maintained at a temperature of about 10-13° C. for about 1.0 hours. The reaction mass obtained thereafter was slowly added into 370 ml of chilled water at a 10-25° C. over a period of 2.0 hours. This mass was treated as in above experiments to yield crystalline fipronil (315.0 gms) of 95.0-96.5% purity.
EXAMPLE 6
[0052] In a reactor flask with overhead stirring system, 2500 gms of 85.0% W/W H 2 SO 4 & 100 ml of ethylene dichloride solvent was charged. This mass was cooled under stirring to 3.0-5.0° C. and then 421.0 gms of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluromethylphenyl)-4-trifluromethylthio pyrazole solid was added over a period 1.0 hour. 95.0 gms of H 2 O 2 (50.0% w/w) was then added to the aforesaid mass over a period of 3.0 hours at 3-8° C. The reaction temperature was maintained at a temperature of about 6-13° C. for about 3.0 hours. The reaction mass obtained thereafter was slowly added into 475-500 ml of chilled water at a 10-25° C. over a period of 2.0 hours. This mass was filtered/centifuged at 30-35° C. and the solid cake was washed with plenty of water to make it free of acidity. The crude cake wasdried and then crystallized in 1000 ml of dichloro ethane solvent to yield 360.0 gms of crystalline fipronil with 94.0-96.0% purity.
EXAMPLE 7
[0053] The aqueous layer was collected from example No. 5, it contained 62% W/W H 2 SO 4 . The aqueous layer was extracted with 200 ml ethylene dichloride solvent to remove dissolved impurities, if any. The extracted aqueous sulphuric acid was then concentrated under reduced pressure of 10-15 mmHg and at 120-130° C. temperature to yield 900 grams of concentrated sulphuric acid having strength of 85-87% W/W.
[0054] Oxidation of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluromethylphenyl)-4-trifluromethyl thio pyrazole (378 gms) was carried out using concentrated sulpuric acid (85-87% W/W) as obtained above in similar manner as described in example No. 5 to yield crystalline fipronil (280 gms) of 95.0-96.5% purity.
[0055] Technical Advancement and Economic Significance:
The process of the present invention obviates the use of a phase transfer catalyst. The process of the present invention prevents degradation of oxidant by avoiding a step of dissolution of oxidant in sulphuric acid. The crude yield of the product (fipronil) is between 97-99%. The spent H 2 SO 4 of 60-70% W/W generated in the process will be recyclable after concentrating back to 85-86% W/W.
[0060] The numerical values mentioned for the various physical parameters, dimensions or quantities are only approximations and it is envisaged that the values higher/lower than the numerical values assigned to the parameters, dimensions or quantities fall within the scope of the invention, unless there is a statement in the specification specific to the contrary.
[0061] While considerable emphasis has been placed herein on the specific steps of the preferred process, it will be appreciated that additional steps can be made and that many changes can be made in the preferred steps without departing from the principles of the invention. These and other changes in the preferred steps of the invention will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the invention and not as a limitation.
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A process for preparation of Fipronil (i.e. 5-amino-1-(2, 6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoro-methylsulphinyl-pyrazole) is provided, which comprises oxidizing 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-tri-fluoromethylthio-pyrazole with sulfuric acid and hydrogen peroxide as oxidizing agent in the presence of a solvent such as ethylene dichloride, chlorobenzene.
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PRIORITY
[0001] This application claims priority to provisional application Ser. No. 60/130,773 filed Apr. 23, 1999.
BACKGROUND
[0002] A well known commercial product in the laundry care industry is the fabric dryer sheet. In use, the consumer typically uses at least one sheet in the drying cycle of the laundering process. The sheets generally include a substrate material, such as a web, wherein the substrate carries one or more ingredients to impart desired benefits to the clothing. These ingredients can include, for example, perfumes, anti-static agents, dye transfer inhibitors, whitening agents, enzymes, stain repellents and wrinkle reducing agents.
[0003] Processes for fabricating these dryer sheets are also well known. In a typical process, a large role of the web material is guided at high speeds through various coating, smoothing and drying/cooling steps wherein one or more ingredients are applied to the web. An example of this process is shown in FIG. 1.
[0004] With reference to FIG. 1, web 5 is preferably a polyester material and provided in rolls 2 . Rolls 2 are typically about 37 inches to about 85 inches in width and have a length between about 8,000 and about 13,000 yards. Web 5 passes through various rollers and rods wherein ingredients are applied to the web. As shown, web 5 is passed over guide roll 12 and onto applicator roll 14 . Applicator roll 14 transfers ingredients 17 from coating pan 15 onto the web. A holding tank (not shown) can be used to supply the ingredients to coating pan 15 . Preferably, automatic controls are used to ensure a proper level and temperature of ingredients 17 in pan 15 .
[0005] As known in the art, ingredients 17 can include perfume material in addition to other fabric treatment agents, particularly those that provide anti-static and fabric softening benefits. These fabric treatment agents can include, for example: cationic compounds, such as quartemary ammonium compounds; nonionic surfactants, such as ethoxylated alcohols; fatty alcohols; fatty acids; alkali metal soaps of fatty acids; carboxylic acids and salts thereof; fatty acid esters; glycerides; waxes; anionic surfactants; water; optical brighteners; fluorescent agents; antioxidants; colorants; germacides; perfumes; bacteriocides; enzymes; dye transfer inhibitors; soil release polymers; skin care benefit agents; perfume carriers (e.g. starch, clyclodextrins); wrinkle reducing agents; and the like. Various preferred non-cationic formulations are disclosed in U.S. patent applications Ser. No. 08/832,887, filed Apr. 4, 1997, the contents of which is incorporated by reference. In prior art processes, perfume has been present from about 2 wt % to about 6 wt % based on total ingredients 17 .
[0006] In a preferred embodiment, the ingredients are maintained at approximately 140-190° F. in both the holding tank and coating pan 15 . At this temperature, one or more ingredients can be lost to the atmosphere due to their volatility or be adversely affected by means of thermal degradation. When the perfume is present, it is estimated that there is a loss of approximately 15 wt. % of the perfume to the atmosphere at this coating step.
[0007] Further on in the process of FIG. 1, after coated in the coating pan, coated web 5 ′ passes over smoothing rod 18 to guide roll 20 . From guide roll 20 , the web passes to heating drum 22 , travels to cooling drums 24 and 26 , which are preferably cooled to below about 100° F. by chilled water. Cooled web 5 ′ then passes to trimming station 28 , wherein the web is rolled and preferably cut into roles 2 ′. Roles 2 ′ are preferably about 12 inches in width. At this point in the process, the roles can be stored for later cutting and packaging. During the process shown in FIG. 1, the web can travel as fast as 1,000 feet per minute. It is estimated that the additional perfume lost after the step of coating can be in the range of approximately 20 wt. % to 30 wt. % from that which was originally present in pan 15 .
[0008] Turning to FIG. 2, final processing of coated web 5 ′ is carried out by passing one or more of the coated roles 2 ′ through a series of guide rollers 32 . The web is then folded by folders 34 , passed to conveyor 36 and cut by knife 38 . After cutting, the folded sheets are tamped down, stacked and accumulated for packaging.
[0009] During the above-described processes, it has been found that a significant amount of volatile agents can be lost prior to final packaging, particularly perfumes. This is generally due to the relatively high volatility of most perfume agents. For example, it has been found that up to 45% of the perfume added in a typical process can be lost by the time the dryer sheet is folded and packaged.
[0010] Therefore, there is a need for an improved fabric dryer sheet manufacturing process wherein the loss of volatile agents during the process of making the fabric sheets is minimized.
[0011] Perfume agents can be classified by their relative volatility. High volatile perfumes are known as “high notes” while relatively unvolatile perfumes are known as “low notes”. Due to their high volatility, high note perfumes are typically more perceptible by humans than low note perfumes. High note perfumes also have a wider range of odors and, therefore, allow for greater flexibility when selecting perfume agents. Unfortunately, when manufacturing dryer sheets, it is the desired high notes that can be lost during processing. This has resulted in a decreased amount of high note perfumes making it into the packaged product and alteration of the perfume profile. Use of high note perfumes have also been reduced or eliminated from perfume formulations due to the above-described process conditions.
[0012] Therefore, there is also a need for fabric sheet manufacturing techniques that would allow for increased usage of high note perfumes, wherein the highly volatile perfumes are retained on the fabric sheet so as to reach the consumer.
SUMMARY
[0013] For simplicity, “perfume” will be used herein to describe a fabric treatment agent that can volatilize or degrade from heat in an undesirable manner. It is within the scope of the present disclosure, however, that other volatile agents or heat sensitive agents can be advantageously applied by the presently disclosed process.
[0014] The present disclosure relates to a process that minimizes the loss of perfume and other volatile agents during the fabrication of dryer sheets. It has been found that it is possible to de-couple the addition of volatile or heat sensitive agents from one or more of the manufacturing process steps, particularly those portions that run at a high speed and/or high temperature.
[0015] In one preferred embodiment, the a selected agent or agents are applied during high speed web movement after high temperature application of other ingredients. In a second preferred embodiment, the selected agent or agents can be applied just prior to folding and packaging.
[0016] It has been found, for example, that by adding the perfume or other volatile agents closer to the step of packaging, i.e. after application of other ingredients in coating pan 15 , there is less loss of ingredients to the atmosphere during the dryer sheet process. In the case of perfumes, this new process has less affect on the perfume profile and, therefore, a wider variety of perfumes can be used. In addition, because ingredients are no longer lost or lost to a lesser extent, less of the ingredient is needed when practicing the present disclosure, resulting in raw material cost savings.
DESCRIPTION OF THE DRAWINGS
[0017] [0017]FIG. 1 illustrates a fabric sheet coating process that is known in the art;
[0018] [0018]FIG. 2 illustrates a fabric sheet cutting and folding process that is known in the art;
[0019] [0019]FIG. 3 illustrates a fabric sheet coating process that generally shows a preferred location of applying fabric treatment agents, subsequent to the main coating operation;
[0020] [0020]FIG. 4 illustrates a fabric sheet cutting and folding process that generally shows preferred locations of applying fabric treatment agents, subsequent to the main coating operation;
[0021] [0021]FIG. 5, illustrates a preferred method and apparatus for applying fabric treatment agents to a substrate material that can be used in the processes shown in FIGS. 3 and 4;
[0022] [0022]FIG. 6 illustrates an alternate, preferred method and apparatus for applying fabric treatment agents to a substrate material that can be used in the processes shown in FIGS. 3 and 4;
[0023] [0023]FIG. 7 illustrates a preferred method of transferring liquid agents to the apparatus of FIG. 6; and
[0024] [0024]FIG. 8 illustrates a fabric sheet cutting and folding process that shows the apparatus of FIG. 6 at preferred locations.
DETAILED DESCRIPTION
[0025] With reference to FIGS. 3 and 4, processes in accordance with the present disclosure are shown. FIG. 3 shows preferred fabric treatment agent application zone A, wherein ingredients can be added to web 5 ′ subsequent to the coating of ingredients 17 . Zone A is located after cooling drums 24 and 26 before cutting station 28 . By applying perfumes and/or other fabric treatment agents at or near zone A, the high temperatures associated with the upstream coating operation are avoided. In addition, because web 5 ′ is rolled-up at trimming station 28 shortly after application zone A, the fabric treatment ingredients become trapped as web 5 ′ winds about itself.
[0026] [0026]FIG. 4 shows an alternate, preferred application zones B. In this embodiment, the fabric treatment agents are applied in prior to final folding and cutting of the substrate. Several zones are shown because the preferred process performs several cutting and folding operations simultaneously. An advantage of waiting to apply certain fabric treatment agents just prior to cutting and folding is that roles 2 ′ can be generic across several brands. More specifically, for example, if the only difference between two or more brands of product is the type or quantity of perfume, rolled stock 2 ′ can be used for each brand as needed.
[0027] Turning to FIG. 5, a preferred apparatus for applying fabric treatment agents to web 5 ′ is shown. Spray assemblies 80 have controllers 81 and air flow modules 82 for controlling the flow and spray pattern of liquid spray 83 emitted from nozzles N. Spray assemblies 80 can be pressure spray assemblies or, more preferably, ultrasonic sprayers as shown. Preferred ultrasonic spray assemblies are available from Sono-Tek Corporation, Milton, N.Y. The Sono-Tek sprayers use ultrasonic power to atomize liquids. The flow of liquid from nozzles N and the flow of air from modules 82 are regulated by controllers 81 . Controllers 81 can be programmed to apply more or less liquid agent and can be coupled to web speed information so as to apply predetermined, uniform quantities of fabric treatment agent. While three spray assemblies or shown, one or more can be used, depending on the width of web 5 ′ and on the width of the spray. Spray assemblies can be used in zones A or B of FIGS. 3 and 4, respectively.
[0028] With reference to FIGS. 6 and 7, an alternate preferred apparatus for applying fabric treatment agents web 5 ′ is shown. In FIG. 6, the perfume applicator generally includes tubular member 50 having a plurality of micro holes 52 . Web 5 ′ is directed past the applicator by one or more guide rolls 54 . The number and configuration of guide rolls 54 is not critical and could even be eliminated.
[0029] Liquid fabric treatment agent is preferable pumped into applicator 50 by means of a metering pump 60 associated with tank 70 . As shown, the liquid passes through tube 58 , into one end of applicators 50 . Most preferably, the liquid is pumped into applicators 50 through a manifold (not shown) that directs the liquid into each end of the applicators 50 . Such a system can provide a more uniform pressure profile within applicator 50 . Applicators 50 are preferably fabricated from a low friction material that can apply the fabric treatment agents to the web as it contacts tubular member/applicator 50 and passes over the micro holes. While two rows of micro holes are shown, various combinations of holes, slits or other orifice that allow the liquid to exit the applicator can be used. Applicators 50 can be used in zones A or B of FIGS. 3 and 4, respectively. FIG. 8 shows several applicators similar to FIG. 6 in use prior to the steps of cutting and folding.
[0030] In a preferred process where one or more of the fabric treatment applicators are used to apply perfume, at least between about 50% to about 75% by weight of the total perfume in the final product is added after the high temperature coating operation. In a most preferred process about 95% to about 100% by weight of the total perfume in the final product is added after the high temperature coating operation.
[0031] By applying certain fabric treatment agents at either or both zone A and zone B, the need for changing and cleaning ingredients 17 in coat pan 15 can be eliminated, allowing for manufacturing efficiencies.
[0032] In practice it was unexpectedly found that the post-added perfume could absorb into the dryer sheet material that was processed as shown in FIG. 1. By absorbing, the sheet remained “non-tacky”, and processing, such as cutting and packaging, were not hindered. See example 2, below.
EXAMPLE 1
[0033] An 11 inch by 6.75 inch polyester substrate was first coated with 1.392 grams of anti-static/softening agent on a bench-top coater. Subsequently, 0.058 grams of perfume (4% by weight, excluding the weight of the substrate) was sprayed onto the coated sheet. This sheet and a typical production sheet were analysed by a HeadSpace GC. The production sheet was produced using the process shown in FIGS. 1 and 2, i.e., without de-coupling the perfume from the coating step. The perfume level in ingredients 17 dosed into coat pan 15 was also initially 4% by weight. The analysis data is shown in the following table.
TABLE 1 Perfume added, Perfume remaining, Sample g g Perfume Loss, % Lab Sample 0.058 0.055 5.0 Production 0.058 0.033 42.5 sheet
[0034] The data indicates that the new process has improved the perfume retention. Therefore, for example, if the final product sold to the consumer only needs 0.033 g of perfume to deliver the expected perfume benefit, the methods disclosed herein allow for the addition of only 0.0347 g of perfume per sheet to deliver the same/expected amount—more than 40% reduction in perfume use.
EXAMPLE 2
[0035] An 11-inch wide dryer sheet roll was coated with anti-static/softening agent and perfume via the production process of FIG. 1. The role was mounted on a pilot scale coater. An applicator device as shown in FIG. 6 was set to contact the web of dryer sheet between unwind and rewind rolls. The roll was unwound and rewound at the speed of 10 ft/min while a pump was pumping perfume with the flow rate of 1.03 g/min onto the coated web. The addition of perfume is equal to extra 4% of perfume added to the sheet. The sheets with the extra 4% perfume made by this method showed a minimal increase of tackiness. Thus, the process was demonstrated.
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A process for applying relatively volatile or heat sensitive ingredients, such as perfume, to fabric dryer sheets minimizes the loss of the ingredients to the atmosphere or through degradation.
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BACKGROUND OF THE INVENTION
1. Field of the Invention.
The present invention relates to crystal growth, and, more particularly, to epitaxial growth of semiconductors.
2. Description of the Related Art.
Epitaxial growth of electronic grade semiconductors such as gallium arsenide (GaAs) relies on methods such as liquid phase epitaxy (LPE), molecular beam epitaxy (MBE), and metalorganic chemical vapor deposition (MOCVD). MBE and MOCVD both provide the ability to grow extremely abrupt p-n junctions and heterojunctions of lattice-matched materials; and such abrupt junctions are required for fabrication of superlattices and quantum well structures. However, both MBE and MOCVD have serious shortcomings, and recently chemical beam epitaxy (CBE) has been proposed as a system to overcome these shortcomings by combining features of MBE and MOCVD; see, W. Tsang, Chemical Beam Epitaxy of InP and GaAs. 45 Appl. Phys. Lett. 1234 (1984).
The CBE system of Tsang (FIG. 1 is a schematic illustration) has the basic structure of an MBE system: a hemispheral vacuum chamber with sources arranged on the curved surface and aimed at the wafer holder located at the chamber center. The sources in MBE systems are effusion cells containing solid or molten elements (for example, growth of layers of Al x Ga 1-x As with various x values and with silicon for n doping requires a cell for each of aluminum, gallium, arsenic, and silicon). Good uniformity across a wafer for MBE grown layers despite the nonuniformity of the elemental fluxes from the effusion cells can be achieved by rotation of the wafer during growth. A wafer is heated typically to 500° to 700° C. for growth to insure sufficient surface mobility of the deposited atoms so they can easily migrate to the appropriate lattice sites. In short, the growth conditions require simultaneous ultrahigh high vacuum, mechanical rotation, and heat for the wafers. These conditions pose a reliability problem for the wafer holders. The CBE system replaces some or all of the conventional elemental effusion cells with cells that are outlets of tanks of metalorganic gasses (for example, trimethylaluminum (TMAl), triethylgallium (TEGa), and trimethylarsine (TMAs)). This substitution solves the MBE problems of effusion cell life and flux drift, and the CBE cells are much simpler than the MBE effusion cells; but the problems of simultaneous high vacuum, mechanical rotation, and heat still remain.
The limited angle of flux produced by an MBE effusion cell or a CBE cell makes multiwafer operation very difficult. Movement of wafers past a stationary bank of MBE or CBE cells is not practical due to the complexity of such an arrangement (and the flux drift of MBE cells). Thus a problem of small throughput exists for both MBE and CBE.
SUMMARY OF THE INVENTION
The present invention provides a chemical beam epitaxy (CBE) system with multiple wafers held in a fixed circular arrangement about an oscillating set of radially aimed chemical beam sources. In preferred embodiments each wafer is mounted on its own individual holder, the heaters for these wafer holders are rigidly attached to the walls of a cylindrical vacuum chamber, the wafer holders are mounted on an assembly which can be rotated to index the various wafer holders in front of a wafer loadlock for loading and unloading, the wafers are stationary during epitaxial growth and are directly opposite the heaters affixed to the chamber walls, the multiple gas sources are mounted along the cylindrical axis of the vacuum chamber with their fluxes directed radially outward toward the heated wafers, the gas sources rotate during growth insuring that each wafer intercepts the same average flux during the course of a growth run, the gas sources also oscillate along the axis to improve uniformity within a wafer, the spent gasses are exhausted at the bottom of the chamber using a symmetrical pumping arrangement, and baffle plates are used to insure that each wafer experiences a similar vacuum environment during growth.
This solves the problems of the known MBE and CBE systems by separating the heating of the wafers from the relative beam motion across the wafers and by simple arrangements for simultaneous epitaxy on multiple wafers.
BRIEF DESCRIPTION OF THE DRAWINGS
The drawings are schematic for clarity.
FIG. 1 illustrates a known CBE system;
FIGS. 2A-B are cutaway perspective and plan views of a first preferred embodiment CBE system; and
FIG. 3 is a detailed view of the gas cells of the first preferred embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A first preferred embodiment CBE system, generally denoted by reference numeral 30, is schematically shown in cutaway perspective and plan views in FIGS. 2A-B and includes ultrahigh vacuum chamber 32 with wafer loadlock 34, baffles 35 and vacuum pump connection 36 leading to vacuum pumps not shown for clarity, wafer holders 38 attached to holder ring 40 which in turn is held on tracks inside of chamber 32 so that ring 40 can be rotated (as indicated by arrow 42) to bring an individual wafer holder 38a to a position for removal through loadlock 34, wafer heaters 42 affixed to the walls of chamber 32, gas cells 44 which oscillate both vertically (as indicated by arrow 46) and rotationally (as indicated by arrow 48), and liquid nitrogen jacketing for chamber 32 which is not shown for clarity. Chamber 32 has an approximately 50 cm inside diameter and 20 cm inside height. Wafer heaters 42 are resistive heaters, and baffles 35 insure each wafer position has the same pumping environment.
An example of the operation of system 30 to grow alternating layers of GaAs and Al x Ga 1-x As on GaAs wafer 52 is as follows. Initially, vacuum pumps attached to connections 36 evacuate chamber 32 to a low pressure such as 10 -10 Torr and hold this low pressure to outgas adsorbed contaminates; after the outgassing is completed, the liquid nitrogen jacket is filled. Next, wafer 52 mounted in a wafer holder 38 and previously cleaned is introduced into chamber 32 through loadlock 34 and attached to holder ring 40 as shown by holder 38a in FIG. 2B. Then holder ring 40 is rotated to bring wafer 52 held in wafer holder 38 to a position adjacent one of the wafer heaters 42, and wafer heater 42 is activated to bring the temperature of wafer 52 up to a growth temperature of about 550° C.
Once wafer 52 is up to growth temperature, beam 50 of triethylgallium (TEGa) and trimethylaluminum (TMAl) molecules mixed with hydrogen as a carrier gas is directed at wafer 52 from one of the gas cells 44. Gas cells 44 have multiple vertical outlets (see FIG. 3 for a detailed illustration of gas cells 44) to cover the height of wafer 52 and, additionally, oscillate vertically (indicated by arrow 46 in FIG. 2A) to insure vertical average uniformity of beam 50. Beam 50 is fairly narrow, so gas cells 44 rotate (indicated by arrow 48 in FIG. 2B) to insure horizontal average uniformity. The rotation may be in a single direction or oscillatory to simplify the sealing. The pressure in chamber 32 during growth is about 10 -4 to 10 -3 Torr, so the mean free path of the molecules in beam 50 is much greater than the distance from gas cells 44 to wafer 52 (about 15 cm) and little scattering occurs to spread beam 50. A TEGa or TMAl molecule from beam 50 that impinges on wafer 52 at growth temperature dissociates, ejecting three alkyl radicals and leaving a Ga or Al atom on wafer 52.
At the same time beam 50 is impinging on wafer 52, beam 54 of arsenic (mostly in the form of dimers As 2 ) mixed with hydrogen as a carrier gas and alkyl radicals is emanating from another of gas cells 44 and will impinge on wafer 52 as gas cells 44 rotate. Gas cells 44 rotate at approximately one revolution per second, so the time interval between beam 50 and beam 54 on wafer 52 is about 170 milliseconds if gas cells 44 consist of six separate cells as indicated in FIG. 2B. The sticking coefficients of Ga and Al on the wafer surface is near unity, so the 170 milisecond interval does not result in evaporation of the Ga and Al prior to the arsenic arrival. The flux of arsenic in beam 54 is greater than the flux of Ga and Al in beam 50, so the epitaxial growth is in the presence of an excess of arsenic. The arsenic in beam 54 derives from cracking trimethylarsine (TMAs) at about 1100° C. just prior to injection into chamber 32; see FIG. 3 schematically illustrating a simplified version of gas cells 44. Note that disk-shaped resistive heaters 45 for the outlets of gas cells 44 can be affixed in chamber 32 by placing a vertical support 47 between the chamber axis and loadlock so that the support does not disrupt the chemical beams when aimed at a wafer. Note that the pressure in chamber 32 is mostly due to the ethyl and methyl radicals and the carrier hydrogen.
The switching from growth of a GaAs layer to growth of an Al x Ga 1-x As layer is simply by opening the valve on the TMAl; the ratio of TMAl to TEGa determines the x value. Thus the growth of alternating layers of GaAs and Al x Ga 1-x As is due to the opening and closing of the TMAl valve.
A ring of shutters may be attached to gas cells 44 mounting so particular cells can be shuttered, and a shutter for each wafer growth location (each heater 42) between gas cells 44 and the wafer can be synchronized with the rotation of gas cells 44 permitting different compounds to be simultaneously grown on different wafers. Shutters generally can be used to overcome transient flow effects arising during valving; this permits very abrupt compositional and doping changes. However, system 30 has the additional capability of stopping the rotation of gas cells 44 with the beams between wafers during valving to avoid transient flow effects. Thus the number of wafer heaters 42 plus the number displaced by loadlock 34 preferably equals the number of radial directions of outlets of gas cells 44; this allows all of the beams to simultaneously impinge of wafers (or the loadlock) or simultaneously be between wafers.
MODIFICATIONS AND ADVANTAGES
Various modifications of the preferred embodiment devices and methods may be made while retaining the features of separating the relative motion of the molecular beams on the wafer from the wafer heating and the multiwafer arrangement such separating provides. For example, the gas cells could include two or more cells aimed in the same direction so there would be no time delay between the chemical beams impinging on the wafer surface. The chamber could be elongated axially so that multiple wafers could be stacked vertically, or could have various cross sectional shapes such as hexagonal or octagonal.
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A chemical beam epitaxy system including a cylindrical vacuum chamber (32) with wafer heaters (42) affixed about the cylindrical wall, a rotatable wafer holder ring (40) with mounted wafer holders (38) adjacent the wafer heaters (42), and a central rotatble set of gas cells (44) for directing chemical beams (50, 54) across wafers (52) in the wafer holders (38).
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BACKGROUND
[0001] The present invention relates generally to integrated circuit memory devices and, more particularly, to a column redundancy system and method for embedded dram (eDRAM) devices with multibanking capability.
[0002] The discarding or scrapping of defective integrated circuits when defects are identified is economically undesirable, particularly if only a small number of circuit elements are actually defective. In addition, relying on a “zero defect” goal in the fabrication of integrated circuits is an unrealistic expectation from a practical standpoint. Accordingly, redundant circuit elements are provided on integrated circuits to reduce the number of discarded integrated circuits. If a primary circuit element is determined to be defective during testing, a redundant circuit element is substituted for the defective primary circuit element. Substantial reductions in scrapped devices may be achieved by using redundant circuit elements without substantially increasing the cost of the integrated circuit.
[0003] One example of a type of integrated circuit device that uses redundant circuit elements is integrated memory circuits, such as dynamic random access memories (DRAMs). These devices typically include millions of individual memory cells arranged in arrays of addressable rows and columns. The rows and columns of memory cells are the primary circuit elements of the integrated memory circuit. By providing redundant circuit elements, either as rows or columns, defective primary rows or columns can be replaced.
[0004] Because the individual primary circuit elements (rows or columns) of an integrated memory circuit are separately addressable, replacing a defective circuit element typically involves blowing fuse-type devices in order to “program” a redundant circuit element to respond to the address of the defective primary circuit element. This process is very effective for permanently replacing defective primary circuit elements. In the case of DRAMs, for example, a particular memory cell is selected by first providing a unique row address corresponding to the row in which the particular memory cell is located and subsequently providing a unique column address corresponding to the column in which the particular memory cell is located. When the address of the defective primary circuit element is presented by the memory customer (user), the redundancy circuitry must recognize this address and thereafter reroute all signals to the redundant circuit element.
[0005] As new and improved memory products are developed (e.g., embedded DRAM with multibanking capability), the speed of a column redundancy system should correspondingly “keep up” with the speed of the new designs. In other words, it is undesirable to have a column redundancy system either negate or limit the performance of a data path as data is moved in and out of a memory array.
BRIEF SUMMARY
[0006] The above discussed and other drawbacks and deficiencies of the prior art are overcome or alleviated by a column redundancy system for a memory array having a page structure organized into columns and data lines. In an exemplary embodiment of the invention, the system includes a steering logic network for coupling a memory input/output (I/O) device to the memory array. A storage register is in communication with the steering logic network, the storage register for storing location information for defective data lines in the memory array. During a memory operation, the location information stored in the storage register is transmitted to the steering logic network, the storage register further having the location information loaded therein prior to the memory operation. Thereby, the steering logic network prevents any of the defective data lines from being coupled to the I/O device.
[0007] In a preferred embodiment, the location information is generated by programming programmable fuse devices included in the memory array, and the defective memory element location is decoded from a binary signal representation to a thermometric signal representation. The steering logic includes a series of multiplexing devices therein, the multiplexing devices capable of selectively routing the data lines in the memory array to corresponding data lines in the I/O device. If a first defective data line is detected in the memory array, then the steering logic prevents the first defective data line from being coupled to its corresponding data line in the I/O device. Furthermore, data lines subsequent to the first defective data line in the memory array are coupled by the steering logic to corresponding data lines in the I/O device in accordance with a one position shift.
[0008] If a second defective data line is detected in the memory array, then the steering logic prevents the second defective data line from being coupled to its corresponding data line in the I/O device. Then, data lines subsequent to the second defective data line in the memory array are coupled to corresponding data lines in the I/O device in accordance with a two position shift.
[0009] The column redundancy system preferably further includes carrying logic coupled with the storage register, the storage register further providing a first switching signal to the steering logic network and the carrying logic providing a second switching signal to the steering logic network. The first and second switching signals determine whether a data line in the memory array is connected in a first, second or third position with respect to a corresponding data line in the I/O device.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] Referring to the exemplary drawings wherein like elements are numbered alike in the several Figures:
[0011] [0011]FIG. 1( a ) is a block diagram of an existing column redundancy system which may be implemented for a block of embedded DRAM (eDRAM);
[0012] [0012]FIG. 1( b ) is a switching diagram illustrating one example of the operation of steering logic used in column redundancy systems;
[0013] [0013]FIG. 1( c ) is a switching diagram illustrating another example of the operation of steering logic used in column redundancy systems;
[0014] [0014]FIG. 2( a ) is a block diagram of a column redundancy system, in accordance with an embodiment of the invention;
[0015] [0015]FIG. 2( b ) is an alternative embodiment of the block diagram of FIG. 2( a );
[0016] [0016]FIG. 3( a ) is a schematic diagram of an exemplary shift register and carry logic associated therewith, as shown in FIGS. 2 ( a ) and 2 ( b );
[0017] [0017]FIG. 3( b ) is a schematic diagram of the shift register and carry logic of FIG. 3( a ), as programmed according to the switching example illustrated in FIG. 1( b ); and
[0018] [0018]FIG. 3( c ) is a schematic diagram of the shift register and carry logic of FIG. 3( a ), as programmed according to the switching example illustrated in FIG. 1( c ).
DETAILED DESCRIPTION
[0019] Referring initially to FIG. 1( a ), there is shown a block diagram of an existing column redundancy system 10 which may be implemented, for example, within a block of embedded DRAM (eDRAM). Within a given 1 Mb eDRAM block, one example of a possible memory page configuration includes 256 datalines each having 8 column addresses. Included within the array structure will be, for example, 8 spare datalines (2 assigned to each of four groups of 64 data lines). If a particular data line in a group is found to be defective, that line will be replaced by one of the 2 spare data lines. In such a case, this information is recorded and accessed by the user, so that the spare data line will be used in read/write operations.
[0020] In the redundancy system of FIG. 1( a ), a series of pre-programmed fuse data storage elements 12 (containing individual latches therein) is associated with remotely located, individual memory array blocks. Thus, for a 4 Mb eDRAM, there may be four individual 1 Mb memory array blocks, each having fuse data associated therewith. The fuse data 12 contains redundancy information (i.e., which if any data lines are to be replaced) for its corresponding memory array block. A multiplexer 14 receives the fuse data and selects the appropriate set of fuse data 12 when a specific memory block is to be accessed. The multiplexed data is then sent to a thermometric decoder 16 for converting binary coded data lines to thermometric code used by steering logic 18 to correctly route the data to and from the memory array blocks. As will be described in greater detail hereinafter, the steering logic 18 is essentially a series of braided, individual 3 to 1 multiplexers (switches) that determine a connection path between a given data line on the array side of the steering logic 18 and one of three possible corresponding data lines on the I/O side of the logic. The specific connection of the three possible connections to an I/O side data line is dependent upon the particular fuse data associated with an array block.
[0021] By way of a simplified example, it will be assumed that a group of data lines for a subject memory array block contains eight normal data lines (numbered 0-7) and two redundant data lines (numbered 8-9). Thus, as shown in the switching diagram of FIG. 1( b ), there can be at most two defective data lines in the array for it to be useable. It will further be assumed that the third data line (number 2) in the array is defective and has been accordingly flagged by an appropriate fuse data device. In this simplified example, therefore, a set of “fuse” bits will be encoded with “0010”, which is the binary representation of data line 2 . (It will be noted that four bits are used for this binary representation since there are ten total data lines in the example.) Because data line 2 in the subject array is defective, it is not connected to corresponding data line 2 from an I/O device. Instead, data line 3 in the array is shifted over one position to connect to data line 2 in the I/O device. As a result, each successive data line in the array must also be shifted over one position. In other words, beginning with data line 3 on the array side of steering logic 18 , each successive data line N on the array side is rerouted to data line N−1 on the I/O side of steering logic 18 . Alternate array data line 8 is thus rerouted to the last data line ( 7 ) on the I/O side of steering logic 18 .
[0022] In order for this switching configuration to be executed by steering logic 18 , the binary fuse data signal (0010) is transmitted (through multiplexer 14 ) to thermometric decoder 16 , where it is converted into the ten-bit thermometric code (0011111111). The thermometric code reflects that array data line 2 is defective and is not connected to is corresponding I/O side data line 2 . Thereafter, the remaining good array data lines are switched over by one (N-1) position with respect to the I/O side data lines. Again, in this simplified example, the thermometric code comprises ten bits, one bit for each data line and redundant data line in the array. In an actual device, a 64-bit data line grouping (with two spare lines) would have a 66-bit thermometric signal as an input to the steering logic 18 . The thermometric code generated by decoder 16 is then sent to steering logic 18 , where the appropriate switching signals generated therein execute the switch configuration shown in FIG. 1( b ). Additional details regarding a three-way data line multiplexer (e.g., possible switch positions N, N−1, N−2) may be found in U.S. Pat. No. 5,796,662, the contents of which are incorporated herein by reference.
[0023] As indicated above, a conventional array block allows for two defective data lines. Thus, there is the possibility that there will be two such defective data lines. An example of this condition is shown in the switching diagram of FIG. 1( c ), where, in addition to data line 2 , data line 5 in the array is also defective.
[0024] Because data line 5 in the array is also defective, it will not be connected to data line 4 on the I/O side of steering logic 18 . Instead, data line 6 in the array is now routed two places over to data line 4 on the I/O side. Therefore, beginning with data line 6 on the array side of steering logic 18 , each successive data line N on the array side is now rerouted to data line N−2 on the I/O side of steering logic 18 . As a result, both alternate data lines 8 and 9 in the array are now used. As is the case with the example of FIG. 1( b ), the steering logic 18 must receive this information (about defective data line 5 ) from the stored fused data. A second stored binary code (0110) is thus multiplexed and sent for thermometric decoding. Although not shown, the system of FIG. 1( a ) actually uses a second thermometric decoder to decode a separate fuse data signal in the event a second defective data line exists. The thermometric output from this second decoder, accordingly, is (0000011111). This time, however, the first “1” in the second thermometric code indicates the location of the second bad data line in the array, and the remaining 1's indicate an N−2 shift for the subsequent good data lines.
[0025] It will be appreciated that the redundancy system of FIG. 1( a ), as illustrated by the simplified examples in FIGS. 1 ( b ) and 1 ( c ), involves a series of signal processing steps which take a certain amount of time to complete. In addition, the fact that these fuse data storage elements 12 are remotely located with respect to the other redundancy system elements further increases the amount of time used to complete an operation. With the above system, a column replacement solution may be completed on the order of about 5 ns. Although such a speed is suitable for some existing memory configurations, certain newer DRAM designs take advantage of multibanking of memory blocks. Unfortunately, however, the time taken to transmit the remotely located fuse data is too long to be implemented with eDRAM having multibanking capability, given a single block of column redundancy logic to be used by all blocks.
[0026] Therefore, a novel system and method is disclosed that improves the speed at which a single column redundancy element services a plurality of memory array blocks. Referring now to FIG. 2( a ), there is shown a block diagram illustrating a column redundancy system 20 , in accordance with an embodiment of the invention. Broadly stated, system 20 (in lieu of remotely extracting fuse data and passing the same through a decoding process and a multiplexing process as part of a read/write operation cycle) employs a register array to store a compressed version of the thermometric output of a pair of thermometric decoders 16 . Thereby, the thermometric code is “pregenerated” and stored for use by the local steering logic so as to eliminate the time otherwise used doing the same during a read/write cycle.
[0027] As shown in FIG. 2( a ), a register array 22 includes a series of individual shift registers 24 along with accompanying carry logic 26 . The carry logic 26 , described in greater detail later, is used in conjunction with shift registers 24 to provide an additional control bit to steering logic 18 for the determination of one of three possible switch positions for a given array data line (or, if bad, than an open circuit connection). Each shift register 24 has thermometrically decoded fuse data bits inputted thereto from a thermometric decoder 28 . In a preferred embodiment, the decoded fuse data bits are serially loaded into (and decoded by) a single decoder 28 , the output of which is serially loaded into shift registers 24 . In the embodiment shown in FIG. 2( a ), device real estate is saved by using a single decoder 28 for all of the fuse data bits.
[0028] Alternatively, as shown in FIG. 2( b ), the fuse data bits may be inputted into individual thermometric decoders 28 for parallel loading into the shift registers 24 . That is, for each memory bank or block within a memory device the data stored in the appropriate fuse structure will be sent to a separate decoder 28 , decoded, and then stored in a corresponding shift register 24 . Although in this embodiment the fuse data loading process (during system power up) is completed in a shorter period of time, the trade off is the amount of device real estate used for the dedication of multiple thermometric decoders 28 .
[0029] Still an alternative possibility is to use a single decoder 28 in conjunction with a multiplexer and counter device (not shown) to load the register array 22 one shift register 24 at a time upon power up of the system. Regardless of which of the above described embodiments are implemented, the thermometric fail data for each array block, once loaded at power up, is readily accessible by steering logic 18 through multiplexer 30 during memory operations.
[0030] Referring now to FIG. 3( a ), there is shown a schematic diagram of an exemplary shift register 24 and carry logic 26 associated therewith, as depicted in FIGS. 2 ( a ) and ( b ). Shift register 24 has a plurality individual storage latches 32 , which receives the inputted thermometric code therein. The carry logic 26 includes a plurality of OR gates 34 corresponding to the number of storage latches. Again, for a memory array having a total of X “normal” data lines and Y redundant data lines, each register 24 will have (X+Y) latches 32 therein and the carry logic 26 will include (X+Y) OR gates 34 therein. In keeping with the example described earlier, it will be assumed that a memory block configuration includes a total of ten array data lines (including 2 redundant data lines). Thus, FIG. 3( a ) illustrates ten latches 32 and ten OR gates 34 .
[0031] Each OR gate 34 has the data stored in a corresponding one of the latches 32 as a first input thereto. Except for the first OR gate, the carry output from the previous OR gate serves as the second input thereto. The outputs of each OR gate are used as one of the two control inputs to the individual MUXs in steering logic 18 . The other control input will be the value of the data stored in each latch 32 .
[0032] The operation of the register 24 and carry logic 26 will be understood with reference to FIGS. 3 ( b ) and 3 ( c ). In FIG. 3( b ), there is shown the specific logic state of register 24 and carry logic 26 that will drive the switching configuration example illustrated in FIG. 1( b ). That is, array data line 2 is bad and the remaining array data lines are shifted N−1 positions to a corresponding I/O data line. It will be noted that the ten register latches 34 in FIG. 3( b ) store the thermometric code therein corresponding to a bad data line 2 , namely (0011111111).
[0033] With only one (or no) bad data lines, the significance of the carry input is not immediately apparent. Obviously, with no bad data lines, the entire register would contain 0's therein, as well as the values of the carry inputs. The switching logic would not execute any shifting, and array data line N would be connected to corresponding I/O data line N, for all values of N. If there is one bad array data line, the location thereof is identified by a transition from 0 to 1 in the register. Thereafter, the remaining l's indicate that each subsequent array data line is shifted by N−1 positions.
[0034] On the other hand, if there are two bad array data lines, then an additional bit (other than the one stored in the latches 34 ) is needed to distinguish the third possible switch position, shift by N−2. This is where the function of the carry logic 26 comes into play. As illustrated in FIG. 3( c ), the register is now loaded with the thermometric data corresponding to the example of FIG. 1( c ), where both data array lines 2 and 5 are bad.
[0035] The carry logic 26 allows a first bad array data line to be identified by a transition from “0” to “1” in the register 24 . A second bad array data line will be identified by a transition from “1” to “0” in the register 24 . However, since the initial transition from “0” to “1” causes a “1” to be propagated through the remainder of the carry logic 26 , the second transition from “1” to “0” is distinguished from no transition at all if no bad data lines exist. In other words, the carry logic 26 allows the steering logic 18 to distinguish between a series of 0's representing no shift from a series of 0's representing a shift by N−2. If the register bit is “0” and the carry bit is “0”, then a good array data line will not be shifted. If the register bit is “1” and the carry bit is “1”, then a good array data line will be shifted by N−1. Finally, if the register bit is “0” and the carry bit is “1”, then a good array data line will be shifted by N−2.
[0036] The carry logic 26 enables the storage of two failing array data lines in a single register, thereby using half as many storage latches as in a conventional redundancy system. However, in lieu of the carry logic, two shift registers could also be used to perform an equivalent function. One register would contain information about a first bad array data line, and another register would contain information about a second bad data line. The multiplexing device in steering logic would still have a two signal input for an array data line.
[0037] Regardless of whether one or two shift registers are used, the key to saving time over a conventional redundancy system is that the shift registers are loaded with the decoded fuse data during power up of the entire system. Although the use of carry logic 26 is a relatively slow procedure, the performance of the column redundancy system 10 is not impacted because the registers are already loaded by the time operations of the memory array are commenced. This is in contrast to the conventional redundancy systems, where time is taken during memory operations to retrieve the fuse data from the remotely located fuse elements, decode the data, and then send it to the steering logic. Under worst case conditions, column redundancy system 10 has been shown to operate as high as 400 MHz (2.5 ns cycle), which allows for the desired multibanking of eDRAM.
[0038] While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
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A column redundancy system is disclosed for a memory array having a page structure organized into columns and data lines. In an exemplary embodiment of the invention, the system includes a steering logic network for coupling a memory input/output (I/O) device to the memory array. A storage register is in communication with the steering logic network, the storage register for storing location information for defective data lines in the memory array. During a memory operation, the location information stored in the storage register is transmitted to the steering logic network, the storage register further having the location information loaded therein prior to the memory operation. Thereby, the steering logic network prevents any of the defective data lines from being coupled to the I/O device.
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This application is a file wrapper continuation-in-part of U.S. patent application Ser. No. 08/286,155, filed on Aug. 8, 1994, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to apparatus and methods for activating electric wireline firing systems in which a firing pin is actuated by pressure, and more particularly, to such apparatus and methods in which the firing pin is not actuated simultaneously with application of electrical voltage to the apparatus.
2. Description of Related Art
Many devices conventionally utilized to complete or work over a subterranean well, such as perforating guns, jet cutters, and chemical cutters, are actuated by applying electrical current of a specified voltage to an electric detonator via a wireline on which the device is suspended from a surface wellhead. Application of the specified electrical voltage via wireline to these devices detonates an electrical blasting cap or detonator which is connected to and in turn detonates the explosive charge of a perforating gun, a jet cutter, a chemical cutter, or a similar system. The electrical current required to detonate the blasting cap or detonator of these devices is relatively low, for example 0.2 amps for a duration of one second or less.
A significant problem associated with detonating such conventional devices via an electric wireline is that the presence of high radio frequencies, stray voltages, or other electrical influences, such as welding or cathodic protection, in the vicinity of the surface location of the wellhead may inadvertently result, via an electrical short in the wireline spool or if the device is not properly grounded, in the premature detonation of the device at the surface or prior to proper placement of the device at a desired location within a subterranean well. Premature detonation can also result from human error of inadvertent supplying sufficient electrical voltage to detonate the firing apparatus. Such premature detonation results in an extremely unsafe operating environment which can result in injuries and even fatalities at or near the wellhead. It is believed that the majority of accidents involving the use of explosives in a subterranean well are a result of such premature detonations.
In an effort to improve the safety of detonation operations using an electric wireline, operators have attempted to eliminate radio frequencies and stray voltages near the wellhead. However, such operations can take a considerable amount of time and be expensive and have not been completely effective, especially in more populous areas where complete elimination of radio frequencies, stray voltages and other electrical influences generated by third parties is often not practical. Thus, a need exists for an electric wireline firing system which can be safely used in conjunction with a conventional downhole explosive device.
Accordingly, it is an object of the present invention to provide a method and apparatus for safely activating electric wireline firing systems.
It is another object of the present invention to provide a method and apparatus in which the firing pin of an electric wireline firing system is not actuated simultaneously with application of electrical voltage to the apparatus.
It is a further object of the present invention to provide a method and apparatus for safely activating the firing pin of an electric wireline firing system which is inexpensive to construct and to operate.
it is a still further object of the present invention to provide a method and apparatus for safely activating the firing pin of an electric wireline firing system which requires that a relatively high voltage be applied to detonate the firing apparatus.
SUMMARY OF THE INVENTION
To achieve the foregoing and other objects, and in accordance with the purposes of the present invention, as embodied and broadly described herein, one characterization of the present invention is a an apparatus for activating electric wireline firing systems is provided which comprises a means for securing a firing pin against movement toward a detonator and a means for releasing the firing pin from the securing means in response to voltage being applied to the releasing means.
In another embodiment of the present invention an apparatus is provided for activating electric wireline firing systems. The apparatus comprises a tubular housing and a motor having a lead screw secured thereto and positioned within the housing. A bushing is positioned upon the lead screw and is capable of axial movement upon the lead screw when the latter is rotated. An elongated rod is positioned within the housing and connected to the bushing. A firing pin is positioned within said housing and secured against movement by the elongated rod.
In yet another embodiment of the present invention, a method is provided for activating an electric wireline firing system which has a firing pin and a detonator. The method comprises releasably securing a firing pin against movement toward a detonator by securing means connected to a motor and applying a voltage to the motor which is sufficient to move the securing means and permit the firing pin to move and strike the detonator.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawing, which is incorporated in and forms a part of the specification, illustrates the embodiments of the present invention and, together with the description, serves to explain the principles of the invention.
In the drawings:
FIGS. 1a, 1b and 1c are a partially cutaway, cross sectional view of one embodiment of the detonating apparatus of the present invention;
FIG. 2 is a cutaway, cross sectional view of an alternative embodiment of the retainer sleeve portion of the retainer rod of the detonating apparatus of the present invention;
FIG. 3 is a laid out arrangement of an automatic I-slot for use in conjunction with the apparatus of the present invention; and
FIGS. 4a, 4b and 4c are a partially cutaway, cross sectional view of another embodiment of the detonating apparatus of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1, the apparatus of the present invention is illustrated generally as 10 and comprises a generally tubular housing 12 having a first section 14 and a second section 16 which are releasably secured together by means of threaded engagement with connection sub 20. Connection sub 20 has a bore 22 therethrough. Second section 16 is provided with at least one port 17 therethrough which may be sealed with any suitable means 19 (FIG. 2), such as wax, gel or metal, which is removed upon being subjected to downhole temperature, pressure, and/or fluid encountered in a well. A plurality of O-rings 24 are positioned between the connection sub 20 and first and second housing sections 14 and 16, respectively, to provide a fluid tight seal therebetween. One end of housing 12 is releasably secured to an electrical connection sub 30 by threaded engagement while the other end of housing 12 is releasably secured to a detonator connection sub 40 by threaded engagement therewith. O-rings 32 are positioned between first housing section 14 and electrical connection sub 30 and O-rings 42 are positioned between second housing section 16 and detonator connection sub 40 to provide for a fluid tight seal therebetween.
Electrical connection sub 30 is provided with a bore 31 therethrough. An insulating sleeve 39 is positioned within bore 31 to electrically insulate component parts which are positioned therein. A contact pin 33 is positioned within bore 31 and sleeve 39 and extends through insulating bushing 34 which is secured within sub 30 by any suitable means, for example snap ring 35. A spring 36 is also positioned within bore 31 and sleeve 39 and contacts pin 33 at one end thereof and contact button 37 at the other end thereof. Contact button 37 mates within one end of insulator cap 51 which is partially positioned within sleeve 39 and which is secured to motor 50 by any suitable means, for example bolts 53. Insulating sleeve 39, insulating bushing 34 and insulator cap 51 are constructed of suitable electrical insulating material, for example phenolic resin.
Electrical connection sub 30 is electrically connected to a D.C. electrical motor 50 by means of wire 38 which is secured to contact button 37. Motor 50 has a shaft 52 extending from one end thereof. A coupling 54 is secured at opposite end thereof to shaft 52 and lead screw 56 by means of pins 53. A bushing or rolled thread nut assembly 60 is positioned around lead screw 56 and has a plurality of ball bearings (not illustrated) positioned within races formed between the interior of bushing 60 and the exterior of lead screw 56. At least one ball feed tube 64 is integrally formed with bushing 60 and protrudes from the external surface thereof. Ball feed tubes 64 function to align bearings within the races. Straps 65 are provided on the exterior of bushing 60 to retain the ball bearings within such tubes and races. As assembled upon lead screw 56, bushing 60 can be moved in either direction along the axis of lead screw 56 depending upon the rotation applied to screw 56 by motor 50.
A guide sleeve 80 is positioned within first section 14 of tubular housing 12 between motor 50 and connection sub 20. Guide sleeve 80 is secured to connection sub 20 by means of set screw 81 and is provided with a slot 82. A guide pin 77 is threadably engaged to and extends from the outer surface of guide coupling 70 so as to be received within slot 82 of guide sleeve 80 and inhibit rotation of guide coupling 70 and therefor bushing 60 and retainer rod 90 during operation of the present invention. A shear pin 83 may be provided in guide coupling 70 and extends into guide sleeve 80 to inhibit movement of bushing 60 along lead screw 56 until a predetermined amount of torque is applied by motor 50. Such shear pin affords the operator of the apparatus a small period of time after application of voltage to motor 50 within which voltage may be terminated prior to movement of any apparatus components which would cause detonation. Guide coupling 70 is releasably secured by threaded engagement to one end of bushing 60 and to one end of a retainer rod 90 by means of separate sets of screw threads as illustrated in FIGS. 1a and 1b. Retainer rod 90 extends through bore 22 in connection sub 20 and terminates in a retainer sleeve portion 94 of a substantially greater diameter and having at least one port 95 therethrough. O-rings 91 are provided around rod 90 to provided a fluid tight seal between rod 90 and connection sub 20. Retainer sleeve portion 94 of rod 90 is positioned within second portion 16 of tubular housing 12 and receives an elongated male portion 44 of detonator connection sub 40. Male portion 44 has at least one port 45 in the sidewall thereof. A firing pin 100 has a groove formed within the outer surface thereof and is positioned within bore 41 through sub 40. Firing pin 100 is releasably secured within male portion 44 by means of at least one ball 46 which is positioned within at least one port 45 and is biased into engagement with firing pin 100 by retainer sleeve portion 94. O-rings 101 are positioned around firing pin 100 to provide for a fluid tight seal with detonator connecting sub 40 as thus assembled.
One end of detonator connecting sub 40 is releasably secured to a detonator sub 110 by threaded engagement. A detonator which is illustrated in FIG. 1c generally as 120 comprises a relatively thin disk 122 constructed of a suitable material, such as copper, a housing 124, and an explosive charge 126. The other end of detonator sub 110 can be provided with a suitable male, female or other coupling to secure the assembly of the present invention to a desired tool, for example perforating gun(s), jet cutter(s), or chemical cutter(s).
As assembled, the contact pin 33 of the firing assembly of the present invention is secured to a casing collar locator which in turn is suspended from the wellhead at the surface by wireline (not illustrated) as will be evident to a skilled artisan. The assembly is lowered into the subterranean well until the tool which is secured thereto is positioned at a desired depth. Once positioned within a well, fluid within the well will be communicated into the interior of second portion 16 of housing 12 via port(s) 17 and the interior of sleeve portion 94 of retainer rod 90 via ports 95. Any means initially blocking port(s) 17 will have been first removed by means of well temperature and/or pressure and/or contact with well fluid. O-rings 24, 42, 91 and 101 cooperate to maintain well fluid within this area of the apparatus. Although fluid pressure is transmitted to motor 50 via retainer rod 90, guide coupling 70, bushing 60 and lead screw 56, the gear ratio of the motor provides sufficient mechanical resistance to prevent lead screw from rotating. Initially firing pin 100 is secured within male portion 44 of connecting sub 40 by means of at least one ball 46 which is positioned within at least one port 45 and is biased into engagement with firing pin 100 by retainer sleeve portion 94. Once a desired subsurface location is reached, electrical current is applied to motor 50 from an electrical source at the surface, such as a power supply, via the wireline, casing collar locator, and electrical connection sub 30. Motor 50 rotates shaft 52 and lead screw 56 causing bushing 60 and in turn guide coupling 70 and retainer rod 90 to move axially upwardly until retainer sleeve portion 94 moves past ball(s) 46. Once sleeve portion 94 no longer biases ball(s) 46 inwardly, the pressure of well fluid on firing pin 100 forces ball(s) 46 outwardly thereby disengaging and permitting downward movement of firing pin 100. Fluid pressure communicated via port(s) 17 and 45 forces firing pin 100 downwardly through subs 40 and 110 and into contact with detonator 120 thereby striking plate 122 and detonating explosive charge 126. Detonation of charge 126 in turn detonates an explosive detonating cord (not illustrated) which activates the tool secured to the assembly.
By utilizing the assembly of the present invention, a significant time delay occurs between when electrical voltage is applied to the apparatus and when detonation occurs. The exact amount of time which will elapse between application of electrical voltage to the apparatus of the present invention and detonation of the explosive charge within the detonator is dependent upon the speed of the motor 50, the pitch of lead screw 56, and the distance that the lead screw has to stroke. Further, the voltage applied to the apparatus of the present invention, i.e. the electrical voltage which is applied to motor 50, is several orders of magnitude greater than that required to electrically activate a conventional detonator. Thus, the possibility of high radio frequencies and/or stray voltages actuating the firing pin is essentially eliminated by use of the present invention.
An alternative embodiment of retainer rod is illustrated in FIG. 2 as 190 and includes a retainer sleeve portion 194 configured and sized to cover port(s) 17 in second portion 16 of housing 12. O-rings 198 and 199 are provided about the periphery of sleeve portion 194 and are positioned on opposite sides of port(s) 17 to prevent communication of well fluid pressure to the interior of second housing portion 16 and sleeve 194. In this manner, fluid pressure does not act upon rod 190 and motor 50 or firing pin 100 until sleeve 194 is moved to a position where port(s) 17 are uncovered and firing pin 100 is released for movement. In this embodiment, port(s) 197 are provided in the top of sleeve 194 to relieve fluid pressure transmitted to motor 50 via rod 190, connector 70, bushing 60 and lead screw 56.
Several other fail safe devices may be included in the apparatus of the present invention to further ensure the safety thereof. For example, a thermal switch 132 (FIG. 1 a) may be used in conjunction with motor 50 so that current can only be applied thereto when the switch is exposed to temperatures, such as those encountered in a subterranean well, for a period of time sufficient to close the switch. A discrete logic circuit relay switch 134 may also be used in conjunction with motor 50 which requires a digital or analog signal to actuate the circuit thereby permitting current flow to motor 50. Firing pin 100 can be further secured to male portion 44 of connecting sub 40 by means of shear pins 96 (FIG. 1c) to guard against premature firing should the locking mechanism described above fail. As illustrated in FIG. 3, slot 82 in guide sleeve 80 may also be configured in the form of a J-slot to provide a further locking mechanism. From the initial position illustrated in FIG. 3, movement of the bushing upon application of a particular current to motor 50 would move pin 77 to position b within slot 82 while application of reversed polarity current to motor 50 would be required to move the bushing as previously described above to position pin at c in FIG. 3 so as to unlock the firing pin. It will be evident to a skilled artisan that the length of retainer sleeve portion 94 or 194 needs to be shortened to permit downward movement of bushing 60, guide coupling 70, and retainer rod 90 during movement of pin 77 to position b. As will be apparent to the skilled artisan, other slot configurations than the J-slot configuration illustrated in FIG. 3 can be utilized to perform an equivalent locking function.
Although male portion 44 is illustrated as having ports 45 into which balls 46 are positioned to secure firing pin 100, other alternative locking mechanisms can be employed to releasably secure firing pin 100 within male portion 44. For example, male portion 44 can be formed as an inwardly extending collet latch which sleeve 94 or 194 biases into engagement with the groove in the exterior surface of firing pin 100. When sleeve 94 or 194 is lifted from male portion 44, the collet retracts outwardly permitting movement of the firing pin. In this embodiment, balls 46 are eliminated.
Referring now to FIGS. 4a-c, another embodiment of the apparatus of the present invention is illustrated generally as 200 and comprises a generally tubular housing 212 having a first section 214 and a second section 216 which are releasably secured together by means of threaded engagement with connection sub 220. Connection sub 220 has a bore 222 therethrough which terminates at one end of sub 220 in an enlarged section 223. A gland nut 227 is threadably secured to and partially positioned within enlarged section 223 of bore 222. Second section 216 is provided with at least one port 217 therethrough. A plurality of O-rings 224 are positioned between the connection sub 220 and first and second housing sections 214 and 216, respectively, to provide a fluid tight seal therebetween. One end of housing 212 is releasably secured to an electrical connection sub 230 by threaded engagement while the other end of housing 212 is releasably secured to a detonator connection sub 240 by threaded engagement therewith. O-rings (not illustrated) are positioned between first housing section 214 and electrical connection sub 230 and O-rings 242 are positioned between second housing section 216 and detonator connection sub 240 to provide a tight seal therebetween.
Electrical connection sub 230 is substantially similar to electrical connection sub 30 which is illustrated in FIG. 1a and described above. Electrical connection sub 230 is electrically connected to a D.C. electrical motor 250 by means of wire 38 which is secured to contact button 37 as illustrated in FIG. 1a. Motor 250 has a shaft 252 extending from one end thereof which terminates in a generally rectangular or blade configuration. The lower end of motor 250 mates with a motor mount 225 which is positioned within first section 214 of housing 212. Motor mount 225 is provided with an inwardly extending, generally annular portion 226. The upper end of drive rod 256 is provided with a slot 258 which is configured to receive and mate with the blade configured end of motor shaft 252. Drive rod 256 is also provided with a generally annular collar 259. A plurality of roller thrust bearings 255 are situated on both sides of collar 259 and are secured between drive rod 256, motor mount 226 and connection sub 220 by means of cap screw(s) 253. Drive rod 256 has a threaded portion 257.
A retainer sleeve 280 is positioned within second section 216 of tubular housing 212 and is provided with a threaded bore 281 through the upper end thereof within which threaded portion 257 of drive rod 256 is engaged. A cap screw or guide pin 277 is threadably engaged to and extends from the outer surface of retainer sleeve 280 so as to be received within slot 219 formed in second section 216. As assembled upon threaded portion 257 of drive rod 256, retainer sleeve 280 can be moved in either direction along threaded portion 257 depending upon the rotation applied to drive rod 256 by motor 250. A shear pin (not illustrated in FIG. 4) may be provided in retainer sleeve 280 and extend into second section 216 to inhibit movement of sleeve 280 along threaded portion 257 of drive rod 256 until a predetermined amount of torque is applied by motor 250. Such shear pin affords the operator of the apparatus a small period of time after application of voltage to motor 250 within which voltage may be terminated prior to movement of any apparatus components which would cause detonation. Drive rod 256 extends through bore 222 in connection sub 220 and has gland nut 227 positioned therearound. O-rings 229 are provided around rod 256 to provided a fluid tight seal between rod 256 and gland nut 227. O-rings 228 are provided around gland nut 227 to provides a fluid tight seal between connection sub 220 and gland nut 227.
As positioned within second section 216 of tubular housing 212, retainer sleeve 280 receives an elongated male portion 244 of detonator connection sub 240. Male portion 244 is formed as an inwardly extending collet latch. A firing pin 300 has a groove formed within the outer surface thereof and is positioned within bore 241 through sub 240. Firing pin 300 is releasably secured within male portion 244 by means of the collet latch configuration of male portion 244 being biased into engagement with firing pin 300 by retainer sleeve 280. O-rings 301 are positioned around firing pin 300 to provide for a fluid tight seal with detonator connecting sub 240 as thus assembled.
One end of detonator connecting sub 240 is releasably secured to a detonator sub 310 by threaded engagement. A detonator which is illustrated in FIG. 4c generally as 320 comprises a relatively thin disk 322 constructed of a suitable material, such as copper, a housing 324, and an explosive charge 326. The other end of detonator sub 310 can be provided with a suitable male, female or other coupling to secure the assembly of the present invention to a desired tool, for example perforating gun(s), jet cutter(s), or chemical cutter(s).
As assembled, the contact pin 233 of the firing assembly of the present invention is secured to a casing collar locator which in turn is suspended from the wellhead at the surface by wireline (not illustrated) as will be evident to a skilled artisan. The assembly is lowered into the subterranean well until the tool which is secured thereto is positioned at a desired depth. Once positioned within a well, fluid within the well will be communicated into the interior of second portion 216 of housing 212 via port(s) 217. O-rings 224, 228, 229 and 242 cooperate to maintain well fluid within this area of the apparatus. Initially firing pin 300 is secured within male portion 244 of connecting sub 240 by means of the collet latch configuration of male portion 244 being biased into engagement with the groove in firing pin 300 by retainer sleeve 280. Once a desired subsurface location is reached, electrical current is applied to motor 250 from an electrical source at the surface, such as a power supply, via the wireline, casing collar locator, and electrical connection sub 230. Motor 250 rotates shaft 252 and drive rod 256 causing retainer sleeve 280 to move axially downwardly until pin 277 which extends from the outer surface of retainer sleeve 280 moves to position b (FIG. 3) within slot 219 of second section 216. Thereafter, application of reverse polarity to motor 250 causes sleeve 280 to move axially upwardly upon threaded section 257 of drive rod 256. Once retainer sleeve 280 moves past male portion 244, the collet latch configuration of male portion 244 is permitted to expand and disengage from firing pin 300. The pressure of well fluid which is communicated via port(s) 217 on firing pin 300 assists the downward movement of firing pin 300 through subs 240 and 310 and into contact with detonator 320 thereby striking plate 322 and detonating explosive charge 326. Detonation of charge 326 in turn detonates an explosive detonating cord (not illustrated) which activates the tool secured to the assembly.
While the foregoing preferred embodiments of the invention have been described and shown, it is understood that the alternatives and modifications, such as those suggested and others, may be made thereto and fall within the scope of the invention.
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A method and apparatus of activating electric wireline firing systems in which a firing pin is restrained against movement toward a detonator until application of sufficient voltage to the apparatus. The firing pin is not permitted to move immediately upon application of voltage to the apparatus thereby providing a period during which voltage may be interrupted to prevent detonation of the system. The requisite voltage which must be applied to the apparatus is relatively high thereby ensuring against premature detonation of the system due to high radio frequencies, stray voltages or other electrical influences.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] Pursuant to 35 U.S.C. § 119(e), this application claims the benefit of U.S. Provisional Application (serial number unknown), (converted from U.S. application Ser. No. 09/567,271, filed May 9, 2000).
BACKGROUND
[0002] The treatment of tumor can be approached by several modes of therapy, including surgery, radiation, chemotherapy, or any combination of any of these treatments. Among them, chemotherapy is indispensable for inoperable or metastatic forms of cancer. Considering the diversity of tumors in terms of cell type, morphology, growth rate, and other cellular characteristics, the U.S. National Cancer Institute (NCI) has developed a “disease-oriented” approach to anti-tumor activity screening. Boyd, M. R. (1989) In Principle of Practice of Oncology Devita , J. T., Hellman, S., and Rosenberg, S. A. (Eds.) Vol. 3, PPO Update, No. 10. This in vitro screening system is based on human tumor cell line panels consisting of approximately 60 cell lines of major human tumors (e.g., leukemia, lung cancer, colon cancer, CNS cancer, melanoma, ovarian cancer, renal cancer, prostate cancer, or breast cancer), and serves as a tool for identifying compounds that possess anti-tumor activities.
[0003] Of particular interest are the anti-tumor compounds that function via one or more of the following four mechanisms: (1) inhibiting G 2 /M progression of the cell cycle, which might eventually induce the apoptosis in tumor cells (Yeung et al. (1999) Biochem. Biophys. Res. Com. 263: 398-404); (2) disturbing tubulin assembly/dissembly, which may inhibit the cell mitosis and induce the cell apoptosis (Panda et al. (1997) Proc. Natl. Acad. Sci. USA 94:10560-10564); (3) inhibiting endothelial cell proliferation and angiogenesis effect (Witte et al. (1998) Cancer Metastasis Rev. 17: 155-161; Prewett et al. (1999) Cancer Res. 59:5209-5218); or (4) regulating Ras protein-dependent signal transduction pathway (Hernandez-Alcoceba et al. (2000) Cell Mol. Life Sci. 57: 65-76; Buolamwini (1999) Cur. Opin. Che. Biol. 3: 500-509).
SUMMARY
[0004] This invention is based in part on the discovery that piperazinedione compounds have anti-tumor activities, identified by NCI screening system, and function via one or more of the above-mentioned four mechanisms.
[0005] An aspect of the present invention relates to piperazinedione compounds of formula:
[0006] Each of and independently, is a single bond or a double bond; A is H or CH(R a R b ) when is a single bond, or C(R a R b ) when is a double bond. Z is R 3 O-(Ar)-B, in which B is CH(R c ) when is a single bond, or C(R c ) when is a double bond; Ar is heteroaryl; R 3 is H, alkyl, aryl, heteroaryl, C(O)R d , C(O)OR d , C(O)NR d R e , or SO 2 R d ; and both B and R 3 O can be substituted at any suitable position on Ar. Each of R 1 and R 2 , independently, is H, C(O)R d , C(O)OR d , C(O)NR d R e , or SO 2 R d ; and each of R a , R b , R c , R d . and R e , independently, is H, alkyl, aryl, heteroaryl, cyclyl, or heterocyclyl. Optionally, R a and R b taken together are cyclyl or heterocyclyl; and, also optionally, R 1 and R a or R 1 and R b taken together are cyclyl or heterocyclyl.
[0007] Referring to the above formula, a subset of the piperazinedione compounds of this invention is featured by that both and are double bonds. In these compounds, Ar is pyridyl linked to B at position 2, R c is H, R 3 O is arylalkoxy linked to position 5 of pyridyl, both R 1 and R 2 are H, one of R a and R b is aryl or heteroaryl, and the other of R a and R b is H. Another subset of the piperazinedione compounds of this invention is featured by that both and are single bonds. In these compounds, Ar is pyridyl linked to B at position 2, R c is H, R 3 O is arylalkoxy linked to position 5 of pyridyl, both R 1 and R 2 are H, one of R a and R b is H, aryl, or heteroaryl, and the other of R a and R b is H.
[0008] Alkyl, aryl, heteroaryl, cyclyl, and heterocyclyl mentioned herein include both substituted and unsubstituted moieties. The term “substituted” refers to one or more substituents (which may be the same or different), each replacing a hydrogen atom. Examples of substituents include, but are not limited to, halogen, hydroxyl, amino, alkylamino, arylamino, dialkylamino, diarylamino, cyano, nitro, mercapto, carbonyl, carbamido, carbamyl, carboxyl, thioureido, thiocyanato, sulfoamido, C 1 ˜C 6 alkyl, C 1 ˜C 6 alkenyl, C 1 ˜C 6 alkoxy, aryl, heteroaryl, cyclyl, heterocyclyl, wherein alkyl, alkenyl, alkoxy, aryl, heteroaryl cyclyl, and heterocyclyl are optionally substituted with C 1 ˜C 6 alkyl, aryl, heteroaryl, halogen, hydroxyl, amino, mercapto, cyano, or nitro. The term “aryl” refers to a hydrocarbon ring system having at least one aromatic ring. Examples of aryl moieties include, but are not limited to, phenyl, naphthyl, and pyrenyl. The term “heteroaryl” refers to a hydrocarbon ring system having at least one aromatic ring which contains at least one heteroatom such as O, N, or S. Examples of heteroaryl moieties include, but are not limited to, furyl, fluorenyl, pyrrolyl, thienyl, oxazolyl, imidazolyl, thiazolyl, pyridinyl, pyrimidinyl, quinazolinyl, and indolyl.
[0009] Another aspect of the present invention relates to a pharmaceutical composition that contains a pharmaceutically acceptable carrier and an effective amount of at least one of the piperazinedione compounds described above.
[0010] A further aspect of this invention relates to a method for treating tumor (e.g., leukemia, lung cancer, colon cancer, CNS cancer, melanoma, ovarian cancer, renal cancer, prostate cancer, or breast cancer). The method includes administering to a subject in need thereof an effective amount of the piperazinedione compound having the formula:
[0011] Each of and , independently, is a single bond or a double bond; A is H or CH(R a R b ) when is a single bond, or C(R a R b ) when is a double bond, Z is CH(R c R d ) when is a single bond, or C(R c R d ) when is a double bond; each of R 1 and R 2 , independently, is H, C(O)R e , C(O)OR e , C(O)NR e R f , or S 2 R e ; and each of R a , R b , R c , R d , R e , and R f , independently, is H, alkyl, aryl, heteroaryl, cyclyl, or heterocyclyl, provided that one of R c and R d is aryl or heteroaryl. If is a double bond, is a single bond, and one of R c and R d is H, then the other of R c and R d is heteroaryl. Optionaly, R a and R b taken together are cyclyl or heterocyclyl; and, also optionally, R 1 and R a or R 1 and R b taken together are cyclyl or heterocyclyl.
[0012] Referring to the above formula, a subset of the just-described piperazinedione compounds is featured by that both and are double bonds. In these compounds, one of R c and R d is 2-pyridyl, the other of R c and R d is H, both R 1 and R 2 are H, one of R a and R b is aryl or heteroaryl, and the other of R a and R b is H. The 2-pyridyl can be further substituted with 5-arylalkoxy. Another subset of the piperazinedione compounds is featured by that both and are single bonds. In these compounds, one of R c and R d is 2-pyridyl, the other of R c and R d is H, both R 1 and R 2 are H, one of R a and R b is H, aryl, or heteroaryl, and the other of R a and R b is H.
[0013] Seven exemplary piperazinedione compounds are 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-phenylmethylidene piperazine-2,5-dione, 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-p-hydroxyphenylmethylidenepiperazine-2,5-dione, 3-[(5- benzyoxypyridin-2-yl)methylidene]-6-p-fluorophenylmethylidenepiperazine-2,5-dione, 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-p-chlorophenylmethylidenepiperazine-2,5-dione, 3-[(5-benzyoxypyridin-2-yl)methylidene]-6- p-phenylmethoxy phenylmethylidenepiperazine-2,5-dione, 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-[(thien-2-yl)methylidene]piperazine-2,5-dione, and 3 ,6-di[(5-phenylmethoxypyridin-2-yl)methyl]piperazine-2,5-dione. Their structures are shown below:
[0014] The piperazinedione compounds described above include the compounds themselves, as well as their salts and their prodrugs, if applicable. Such salts, for example, can be formed between a positively charged substituent (e.g., amino) on a piperazinedione compound and an anion. Suitable anions include, but are not limited to, chloride, bromide, iodide, sulfate, nitrate, phosphate, citrate, methanesulfonate, trifluoroacetate, and acetate. Likewise, a negatively charged substituent (e.g., carboxylate) on a piperazinedione compound can form a salt with a cation. Suitable cations include, but are not limited to, sodium ion, potassium ion, magnesium ion, calcium ion, and an ammonium cation such as teteramethylammonium ion. Examples of prodrugs include esters and other pharmaceutically acceptable derivatives, which, upon administration to a subject, are capable of providing piperazinedione compounds described above.
[0015] Also within the scope of this invention are a composition containing one or more of the piperazinedione compounds described above for use in treating tumor, and the use of such a composition for the manufacture of a medicament for the just-described use.
[0016] Other features or advantages of the present invention will be apparent from the following detailed description of several embodiments, and also from the appending claims.
DETAILED DESCRIPTION
[0017] The piperazinedione compounds described above can be prepared by methods well known in the art, as well as by the synthetic routes disclosed herein. For example, one can react a piperazine-2,5-dione compound with a heteroaryl formaldehyde to produce an intermediate heteroaryl-methylidene-piperazine-2,5-dione. The intermediate can then be reduced to heteroaryl-methyl-piperazine-2,5-dione (a compound of this invention), or reacted with a ketone or another formaldehyde, followed by a base treatment, to produce a mixture of piperazinedione isomers, which are cis- or trans- or E- or Z- double bond isomeric forms. The desired isomeric product can be separated from others by high pressure liquid chromatography (HPLC). If preferred, proper functional groups can be introduced into the heteroaryl ring by further modifications. Alternatively, a desired reduced product can be obtained by reacting the product with a reducing agent.
[0018] Shown below is a scheme that depicts the synthesis of seventeen piperazinedione compounds.
[0019] Details of synthesis of Compounds 1-17 are described in Examples 1-17, respectively. To prepare other piperazinedione compounds, the pyridinyl (shown in the above scheme) can be replaced by an aryl or another heteroaryl (e.g., furyl, pyrrolyl, imidazolyl, pyrimidinyl, or indolyl), and one of the two acetyl groups (Ac) on the piperazinedione ring (also shown in the above scheme) can be replaced by another substituent (e.g., carbonyl, carbamido, carbamyl, or carboxyl).
[0020] Note that the piperazinedione compounds contain at least two double bonds, and may further contain one or more asymmetric centers. Thus, they can occur as racemates and racemic mixtures, single enantiomers, individual diastereomers, diastereomeric mixtures, and cis- or trans- or E- or Z- double bond isomeric forms. All such isomeric forms are contemplated.
[0021] Also within the scope of this invention is a pharmaceutical composition that contains an effective amount of at least one piperazinedione compound of the present invention and a pharmaceutically acceptable carrier. Further, this invention covers a method of administering an effective amount of one or more of the piperazinedione compounds described in the “Summary” section above to a subject in need of tumor treatment. The piperazinedione compounds can function via one or more of the above described action mechanisms, or via any other mechanism. “An effective amount” refers to the amount of the compound which is required to confer a therapeutic effect on the treated subject. The interrelationship of dosages for animals and humans (based on milligrams per meter squared of body surface) is described in Freireich et al., (1966) Cancer Chemother Rep 50: 219. Body surface area may be approximately determined from height and weight of the patient. See, e.g., Scientific Tables, Geigy Pharmaceuticals, Ardley, N.Y., 1970, 537. An effective amount of the piperazinedione compounds can range from about 0.1 mg/Kg to about 50 mg/Kg. Effective doses will also vary, as recognized by those skilled in the art, depending on the types of tumors treated, route of administration, excipient usage, and the possibility of co-usage with other therapeutic treatments such as use of other anti-tumor agents or radiation therapy.
[0022] To practice the method of the present invention, a piperazinedione compound-containing composition can be administered orally, parenterally, by inhalation spray, topically, rectally, nasally, buccally, vaginally or via an implanted reservoir. The term “parenteral” as used herein includes subcutaneous, intracutaneous, intravenous, intramuscular, intraarticular, intraarterial, intrasynovial, intrasternal, intrathecal, intralesional and intracranial injection or infusion techniques.
[0023] A sterile injectable composition, for example, a sterile injectable aqueous or oleaginous suspension, can be formulated according to techniques known in the art using suitable dispersing or wetting agents (such as, for example, Tween 80) and suspending agents. The sterile injectable preparation can also be a sterile injectable solution or suspension in a non-toxic parenterally acceptable diluent or solvent, for example, as a solution in 1,3-butanediol. Among the acceptable vehicles and solvents that can be employed are mannitol, water, Ringer's solution and isotonic sodium chloride solution. In addition, sterile, fixed oils are conventionally employed as a solvent or suspending medium (e.g., synthetic mono- or diglycerides). Fatty acids, such as oleic acid and its glyceride derivatives are useful in the preparation of injectables, as are natural pharmaceutically-acceptable oils, such as olive oil or castor oil, especially in their polyoxyethylated versions. These oil solutions or suspensions can also contain a long-chain alcohol diluent or dispersant, or carboxymethyl cellulose or similar dispersing agents. Other commonly used surfactants such as Tweens or Spans or other similar emulsifying agents or bioavailability enhancers which are commonly used in the manufacture of pharmaceutically acceptable solid, liquid, or other dosage forms can also be used for the purposes of formulation.
[0024] A composition for oral administration can be any orally acceptable dosage form including, but not limited to, capsules, tablets, emulsions and aqueous suspensions, dispersions and solutions. In the case of tablets for oral use, carriers which are commonly used include lactose and corn starch. Lubricating agents, such as magnesium stearate, are also typically added. For oral administration in a capsule form, useful diluents include lactose and dried corn starch. When aqueous suspensions or emulsions are administered orally, the active ingredient can be suspended or dissolved in an oily phase combined with emulsifying or suspending agents. If desired, certain sweetening, flavoring, or coloring agents can be added. A nasal aerosol or inhalation composition can be prepared according to techniques well-known in the art of pharmaceutical formulation and can be prepared as solutions in saline, employing benzyl alcohol or other suitable preservatives, absorption promoters to enhance bioavailability, fluorocarbons, and/or other solubilizing or dispersing agents known in the art. A piperazinedione compound-containing composition can also be administered in the form of suppositories for rectal administration.
[0025] The carrier in the pharmaceutical composition must be “acceptable” in the sense of being compatible with the active ingredient of the formulation (and preferably, capable of stabilizing it) and not deleterious to the subject to be treated. For example, solubilizing agents such as cyclodextrins, which form specific, more soluble complexes with the piperazinedione compounds, or one or more solubilizing agents, can be utilized as pharmaceutical excipients for delivery of the piperazinedione compounds. Examples of other carriers include colloidal silicon dioxide, magnesium stearate, cellulose, sodium lauryl sulfate, and D&C Yellow #10.
[0026] The piperazinedione compounds can be preliminarily screened for their efficacy in treating cancer by one or more of the following in vitro assays.
[0027] One assay is based on the NCI screening system, which consists of approximately 60 cell lines of major human tumors. See Monks, et al. (1991) JNCI, J Natl. Cancer Inst. 83: 757-766; Alley, et al. (1988) Cancer Res. 48: 589-601; Shoemaker, et al. (1988) Prog. Clin. Biol. Res. 276: 265-286; and Stinson, et al. (1989) Proc. Am. Assoc. Cancer Res. 30: 613. Briefly, a cell suspension that is diluted according to the particular cell type and the expected target cell density (5,000-40,000 cells per well based on cell growth characteristics) is added (100 μL) into a 96-well microtiter plate. A pre-incubation is preformed at 37° C. for 24 hr. Dilutions at twice of an intended test concentration are added at time zero in 100 μL aliquots to each well of the microtiter plate. Usually, a test compound is evaluated at five 10-fold dilutions. In a routine testing, the highest concentration of the test compound is 10 −4 M. Incubations are performed for 48 hr in 5% CO 2 atmosphere and 100% humidity. The cells are assayed by using the sulforhodamine B assay described by Rubinstein, et al. (1990, JNCI, J Natl. Cancer Inst. 82: 1113-1118) and Skehan, et al. (1990, JNCI, J. Natl. Cancer Inst. 82: 1107-1112). A plate reader is used to read the optical densities and a microcomputer processes the optical densities into the special concentration parameters. The NCI has renamed an IC 50 value, the concentration that causes 50% growth inhibition, a GI 50 value to emphasize the correction for the cell counted at time zero; thus, the GI 50 measures the growth inhibitory power of the test compound. See Boyd, et al. (1992) In Cytotoxic Anticancer Drugs: Models and Concepts for Drug Discovery and Development; Vleriote , F. A.; Corbett, T. H.; Baker, L. H. (Eds.); Kluwer Academic: Hingham, Mass., pp 11-34.
[0028] In another assay, a piperazinedione compound is tested for its cytotoxicity on PC-3 cells (a prostate cancer cell line). More specifically, cells are incubated with a test compound in a serum-free medium for 24 hr. The cytotoxic effect can be determined using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay method described in Boyd (In Principle of Practice of Oncology Devita, J. T., Hellman, S., and Rosenberg, S. A. (Eds.) Vol. 3, PPO Update, No. 10, 1989).
[0029] Another in vitro assay can be used to evaluate the efficiency of a piperazinedione compound in arresting the cell cycle progression. More specifically, a test piperazinedione compound is added to PC-3 cells in a concentration-dependent manner using propidium iodide-stained flow cytometric assessment. The cell population of sub-G 0 /G 1 , G 0 /G 1 , S, and G 2 /M phase is then determined. In addition, the effect of a piperazinedione compound on the Ras activity can be examined to determine its regulation of Ras protein-dependent signal transduction pathway.
[0030] The anti-tumor activity of a piperazinedione compound can be further assessed by an in vivo animal model. Using SCID mice as the model, PC-3 cells are subcutaneously injected into the mice to develop a prostate tumor. The anti-tumor activity of a piperazinedione compound is determined after treatment. Additionally, the anti-tumor activity of a piperazinedione compound can also be evaluated using in vivo anti-angiogenesis testing. For example, nude mice can be used to test the effect of a piperazinedione compound on bFGF-induced angiogenesis. A matrigel with bFGF or vscular endothelial growth factor (VEGF) is subcutaneously injected into a mouse with concurrent intraperitoneal administration of a piperazinedione compound. After several days of incubation, the matrigel is cut down for examination of angiogenesis.
[0031] Without further elaboration, it is believed that the above description has adequately enabled the present invention. The following specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. All of the publications cited herein are hereby incorporated by reference in their entirety.
EXAMPLE 1
Synthesis of 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-phenylmethylidene piperazine-2,5-dione (Compound 1)
[0032] 1,4-Diacetyl-piperazine-2,5-dione (8.6 g) was added to a solution of 5-benzyoxypyridin-2-yl-formaldehyde (4.0 g) in 5.6 mL of triethylamine and 40 mL of dimethylformamide. The mixture was stirred at room temperature for 16 hr and then cooled at ice bath to produce a yellow precipitate. The precipitate was then collected and washed with ethyl acetate to give 5.4 g (77%) of I-acetyl-3-[(5-benzyoxypyridin-2-yl)methylidene]piperazine-2,5-dione (Compound A).
[0033] mp: 189-191° C.
[0034] [0034] 1 HNMR (400 MHz, DMSO): δ2.52 (s, 3H), δ4.54 (s, 3H), δ4.33 (s, 2H), δ5.25 (s, 2H), δ6.85 (s, 1H), δ7.384˜δ7.488 (m, 5H), aromatic), δ7.499 (d, J=8.8, 1H), 67 7.689 (d, J=8.8, 1H), δ8.533 (s, 1H), and δ12.147 (s, 1H).
[0035] Compound A (3.51 g) was added to a 40 mL of dimethylformamide solution containing equal molar of benzaldehyde and 4 equivalents of triethylamine. The solution was refluxed at 60° C. for 16 hr and cooled at ice bath to produce a yellow precipitate. The precipitate was then collected and washed with ethyl acetate to give 3.3 g (83%) of the desired product 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-phenylmethylidenepiperazine-2,5-dione (Compound 1) as a mixture of isomers. The mixture was predominately the ZZ and EZ isomers.
[0036] mp: 223-225° C.
[0037] [0037] 1 HNMR (400MHz, DMSO): δ5.243 (s, 2H), δ6.695 (s, 1H), δ6.812 (s, 1H), δ7.346˜δ7.634 (m,12H, aromatic), δ8.528 (s, 1H), δ10.245 (s, 1H), and δ12.289 (s, 1H).
EXAMPLE 2
Synthesis of 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-p-hydroxyphenyl methylidenepiperazine-2,5-dione (Compound 2)
[0038] Compound A (3.51 g), obtained from Example 1, was added to a 40 mL of dimethylformamide solution containing 1.5 g of 4-hydroxybenzaldehyde and 4 equivalents of triethylamine. The solution was refluxed at 130° C. for 16 hr and cooled at ice bath to produce a yellow precipitate. The precipitate was then collected and washed with ethyl acetate to give 3.3 g (83%) of the desired 3-[(5-benzyoxypyridin-2-yl) methylidene]-6-p-hydroxyphenylmethylidenepiperazine-2,5-dione (Compound 2).
[0039] mp: 260-263° C.
[0040] [0040] 1 HNMR (400 MHz, DMSO): δ5.244 (s, 2H), δ6.669 (s, 1H), δ6.753 (s, 1H), δ6.798 (s, 1H), 1H, aromatic), δ6.819 (s, 1H, aromatic), δ7.347˜δ7.647 (m, 9H, aromatic), δ9.821 (s, 1H), δ10.064 (s, 1H), and δ12.216 (s, 1H).
EXAMPLE 3
Synthesis of 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-p-methoxyphenyl methylidenepiperazine-2,5-dione (Compound 3)
[0041] Compound A (3.51 g), obtained from Example 1, was added to a 40 mL of dimethylformamide solution containing 1.4 g of 4-methoxybenzaldehyde and 4 equivalents of triethylamine. The solution was reluxed at 130° C. for 16 hr and cooled at ice bath to produce a yellow precipitate. The precipitate was then collected and washed with ethyl acetate to give 3.3 g (83%) of the desired 3-[(5-benzyoxypyridin-2-yl) methylidene]-6-methoxyphenylmethylidenepiperazine-2,5-dione (Compound 3).
[0042] mp: 238-240° C.
[0043] [0043] 1 HNMR (400 MHz, DMSO): δ5.244 (s, 2H), δ6.669 (s, 1H), δ6.753 (s, 1H), δ6.798 (s, 1H, aromatic), δ6.819 (s, 1H, aromatic), δ7.347˜δ7.647 (m, 9H, aromatic), δ9.821 (s, 1H), δ10.064 (s, 1H), and δ12.216 (s, 1H).
EXAMPLE 4
Synthesis of 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-p-fluorophenyl methylidenepiperazine-2,5-dione (Compound 4)
[0044] Compound A (3.51 g), obtained from Example 1, was added to a 40 mL of dimethylformamide solution containing 1.3 g of 4-fluoro benzaldehyde and 4 equivalents of triethylamine. The solution was refluxed at 130° C. for 16 hr and cooled at ice bath to produce a yellow precipitate. The precipitate was then collected and washed with ethyl acetate to give 3.12 g (75%) of the desired 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-p-fluorophenylmethylidenepiperazine-2,5-dione (Compound 4).
[0045] mp: 242-244° C.
[0046] [0046] 1 HNMR (400MHz, DMSO): δ5.237 (s, 2H), δ6.688 (s, 1H), δ6.794 (s, 1H), δ7.209˜δ7.624 (m, 11H, aromatic), δ8.520 (s, 1H), δ10.348 (s, 1H), and δ12.279 (s, 1H).
EXAMPLE 5
Synthesis of 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-p-chlorophenyl methylidenepiperazine-2,5-dione (Compound 5)
[0047] Compound A (3.51 g), obtained from Example 1, was added to a 40 mL of dimethylformamide solution containing 1.3 g of 4-chlorobenzaldehyde and 4 equivalents of triethylamine. The solution was refluxed at 130° C. for 16 hr and cooled at ice bath to produce a yellow precipitate. Then the precipitate was collected and washed with ethyl acetate to give 3.45 g (80%) of the desired 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-p-chlorophenylmethylidenepiperazine-2,5-dione (Compound 5).
[0048] mp: 250-251° C.
EXAMPLE 6
Synthesis of 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-p-benzyoxyphenylmethylidene piperazine-2,5-dione (Compound 6)
[0049] Compound A (3.51 g), obtained from Example 1, was added to a 40 mL of dimethylformamide solution containing 1.45 g of 4-benzyoxybenzaldehyde and 4 equivalents of triethylamine. The solution was refluxed at 130° C. for 16 hr and cooled at ice bath to produce a yellow precipitate. The precipitate was then collected, washed with ethyl acetate, and recrystallized from dimethylformamide to give 3.45 g (80%) of the desired 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-p- benzyoxyphenylmethylidene piperazine-2,5-dione (Compound 6).
[0050] mp: 253-255° C.
[0051] [0051] 1 HNMR (400 MHz, DMSO): δ5.142 (s, 2H), δ5.235 (s, 2H), δ6.672 (s, 1H), δ6.777 (s, 1H), δ7.041˜δ7.639 (m, 16H, aromatic), δ8.520 (s, 1H), δ10.180 (s, 1H), and δ12.235 (s, 1H).
EXAMPLE 7
Synthesis of 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-[(furan-2-yl) methylidene]piperazine-2,5-dione (Compound 7)
[0052] Compound A (2.8 g), obtained from Example 1, was added to a 40 mL of dimethylformamide solution containing 2 mL of furfural and 4 equivalents of triethylamine. The solution was refluxed at 60° C. for 48 hr and cooled at ice bath to produce a yellow precipitate. The precipitate was then collected, washed with ethyl acetate, and recrystallized from dimethylformamide to give 2.5 g (80%) of the desired 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-[(furan-2-yl)methylidene]piperazine-2,5-dione (Compound 7).
[0053] mp: 256-257° C.
[0054] [0054] 1 HNMR (400 MHz, DMSO): δ5.245 (s, 2H), δ6.656 (d, J=1.6, 1H), δ6.664 (d, J=1.6, 1H), δ6.685 (s, 1H), δ6.720 (s, 1H), δ7.349˜δ7.942 (m, 8H, aromatic), δ8.527 (s, 1H), δ9.515 (s, 1H), and δ12.312 (s, 1H).
EXAMPLE 8
Synthesis of 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-[(thien-2-yl) methylidene]piperazine-2,5-dione (Compound 8)
[0055] Compound A (2.8 g), obtained from Example 1, was added to a 40 mL of dimethylformamide solution containing 2 mL of thiophene-2-carbaldehyde and 4 equivalents of triethylamine. The solution was refluxed at 60° C. for 2 days and cooled at ice bath to produce a yellow precipitate. The precipitate was then collected, a washed with ethyl acetate, and recrystallized from dimethylformamide to give 1.9 g (59%) of the desired 3-[(5-benzyoxypyridin-2-yl)methylidene]-6-[(thiophene-2-yl)methylidene] piperazine-2,5-dione (Compound 8).
[0056] mp: 215-217° C.
[0057] [0057] 1 HNMR (400 MHz, DMSO): δ5.245 (s, 2H), δ6.716 (s, 1H), δ6.974 (s, 1H), δ7.186 (s, 1H), δ7.384˜δ7.746 (m, 9H, aromatic), δ8.525 (s, 1H), δ9.753 (s, 1H), and δ12.288 (s, 1H).
EXAMPLE 9
Synthesis of 3-[(5-benzyloxypyridin-2-yl)methylidene]-6-[(2-pyridinyl) methylidene]piperazine-2,5-dione (Compound 9)
[0058] Compound A (2.8 g), obtained from Example 1, was added to a 40 mL of dimethylformamide solution containing 2 mL of pyridine-2-carbaldehyde and 4 equivalents of triethylamine. The solution was refluxed at 60° C. for 2 days and cooled at ice bath to produce a yellow precipitate. The precipitate was then collected, a washed with ethyl acetate, and recrystallized from dimethylformamide to give 2.7 g (85%) of the desired 3-[(5-benzyloxypyridin-2-yl)methylidene]-6-[(2-pyridinyl)methylidene] piperazine-2,5-dione (Compound 9).
[0059] mp: 248-250° C.
[0060] [0060] 1 HNMR (400 MHz, DMSO): δ5.246 (s, 2H), δ6.709 (s, 1H), δ6.788 (s, 1H), δ7.349˜δ7.661 (m, 8H, aromatic), δ7.923 (d, J=8, 1H, aromatic), δ8.473 (d, J=3.6, 1H), δ8.533 (d, J=2.8, 1H), δ8.680 (d, J=2, 1H), δ10.667 (s, 1H), and δ12.324 (s, 1H).
EXAMPLE 10
Synthesis of 3,6-di[(5-phenylmethoxypyridin-2-yl)methylidene]piperazine -2,5-dione (Compound 10)
[0061] Compound A (0.31 g), obtained from Example 1, was added to a 40 mL of dimethylformamide solution containing equal molar of 5-benzyoxypyridin-2-yl-formaldehyde and 4 equivalents of triethylamine. The solution was refluxed at 130° C. overnight and cooled at ice bath to produce a yellow precipitate. The precipitate was then collected and washed with ethyl acetate to give 0.36 g (80%) of the desired 3,6-di[(5-phenylmethoxypyridin-2-yl)methylidene] piperazine-2,5-dione (Compound 10).
[0062] mp: 283-28° C.
[0063] [0063] 1 HNMR (400 MHz, DMSO): δ5.145 (s, 4H), δ6.780 (s, 2H), δ7.240˜δ7.394 (m, 14H, aromatic), δ8.381 (s, 2H), δ10.145 (s, 1H), and δ12.58 (s, 1H).
EXAMPLE 11
Synthesis of 3-[(5-phenylmethoxypyridin-2-yl)methylidene]-6-(2-oxo- 3-indolylidenepiperazine-2,5-dione (Compound 11)
[0064] Compound A (2.8 g), obtained from Example 1, was added to a 40 mL of dimethylformamide solution containing 1.5 g of isatine and 4 equivalent of triethylamine. The solution was refluxed at 130° C. for 2 hr and cooled at ice bath to produce a yellow precipitate. The precipitate was then collected and washed with ethyl acetate to give 3.04 g (87%) of the desired 3-[(5-phenylmethoxypyridin-2-yl)methylidene]-6-(2-oxo- 3-indolylidenepiperazine-2,5-dione (Compound 11).
[0065] mp:>300° C.
EXAMPLE 12
Synthesis of 1-acetyl-3-[(5-benzyoxypyridin-2-yl)methyl]piperazine-2,5-dione (Compound 12)
[0066] A suspension of 3.51 g of 1,4-diacetyl-piperazine-2,5-dione and excess of zinc powder in a mixture of 100 mL of acetic acid and 10 mL of water was stirred and refluxed for 5-10 minutes and cooled. The mixture was filtered. The solid thus obtained was collected and washed with water to give 2.0 g of the desired 1-acetyl-3-[(5-benzyoxypyridin-2-yl)methyl]piperazine-2,5-dione (Compound 12).
[0067] mp: 215-216° C.
EXAMPLE 13
Synthesis of 3,6-di[(5-benzyoxypyridin-2-yl)methyl]piperazine -2,5-dione (Compound 13)
[0068] A suspension of 3,6-di[(5-benzyoxypyridin-2-yl)methylidene]piperazine-2,5-dione (0.2 g) and excess of zinc powder in a mixture of 10 mL of acetic acid and 10 mL of water was stirred and refluxed for 5-10 minutes and filtered while hot. Water was added to dissolve zinc acetate. The filtrate was concentrated and filtered. The solid thus obtained was collected and washed with water to give 80 mg (40%) of the desired 3,6-di[(5-benzyoxypyridin-2-yl)methyl]piperazine-2,5-dione (Compound 13).
[0069] mp: 228-231° C.
EXAMPLE 14
Synthesis of 3-[(5-acetoxypyridin-2-yl)methylidene]-6-(benzylmethylidene) piperazine-2,5-dione (Compound 14)
[0070] 3-[(5-benzyloxypyridin-2-yl)methylidene]-6-(benzylmethylidene)piperazine-2,5-dione (Compound 1, 0.5 g, 1.26 mmol) and NaOH (0.5 g, 12.5 mmol) were dissolved in 100 mL of methanol. The mixture was hydrogenated with 0.5 g palladium/charcoal under 1 atmospheric pressure. After completing the reaction as monitored by TLC, the catalyst was removed by filtration and the filtrate was evaporated in vacuo to produce a reside. The residue was added with 50 mL water and the obtained aqueous solution was adjusted to pH=7. A precipitated was formed and collected to obtain a 0.27 g product of 3-[(5-hydroxypyridin-2-yl)methylidene]-6-(benzylmethylidene)piperazine-2,5-dione (Compound B) (70% yield).
[0071] [0071] 1 HNMR (400 MHz, CDCl 3 ): δ6.758 (s, 1H), δ7.087 (s, 1H), δ7.290˜δ7.580 (m, 7H, aromatic), δ8.328 (s, 1H), and δ12.289 (s, 1H).
[0072] A solution of compound B (0.05 g, 0.16 mmole) in acetic anhydride (50 mL) was refluxed at 150° C. for 24 hrs. The unreacted acetic anhydride and produced acetic acid were removed in vacuo to obtain a residue. The residue was chromatographied using silica gel column with a developing solvent (CH 2 Cl 2 :MeOH=9:1) to give 0.051 g (90%) of Compound 14 as a mixture of isomers. The mixture was predominately the ZZ isomer.
[0073] [0073] 1 HNMR (400 MHz, CDCl 3 ): δ2.377 (s, 3H), δ6.786 (s, 1H), δ7.107 (s, 1H), δ7.368˜δ8.496 (m, 7H, aromatic), δ8.224 (s, 1H), and δ12.498 (s, 1H).
EXAMPLE 15
Synthesis of 3-[(5-benzoyloxypyridin-2-yl)methylidene]-6-(benzylmethylidene)piperazine-2,5-dione (Compound 15)
[0074] A reaction mixture containing compound B (0.05 g, 0.16 mmole; obtained from Example 14), benzoyl chloride (15 ml, 0.16 mmole) and 50 mL of chloroform was heated to 150° C. for 2 hr. Chloroform was removed in vacuo to produce a residue. The residue was chromatographied using silica gel column with a developing solvent (CH 2 Cl 2 ) to give 0.007 g (10%) of Compound 15.
[0075] [0075] 1 HNMR (400 MHz, CDCl 3 ): δ6.786 (s, 1H), δ7.107 (s, 1H), δ7.368˜δ8.496 (m, 13H, aromatic), and δ8.223 (s, 1H).
EXAMPLE 16
Synthesis of 3-[(5-(4-toluenesulfonyl)pyridin-2-yl)methylidene]-6-(benzylmethylidene)piperazine-2,5-dione (Compound 16)
[0076] A reaction mixture of compound B (0.05 g, 0.16 mmole; obtained from Example 14), toluenesulfonyl chloride (0.03 g, 0.16 mmole), and 50 mL of toluene was heated to 150° C. for 2 hr. Toluene was removed in vacuo to produce a residue. The residue was chromatographied using silica gel column with a developing solvent (CH 2 Cl 2 ) to give 0.007 g (10%) of Compound 16.
[0077] [0077] 1 HNMR (400 MHz, CDCl 3 ): δ2.503 (s, 3H), δ6.751 (s, 1H), δ7.102 (s, 1H), δ7.343˜δ8.159 (m, 12H, aromatic), δ8.223 (s, 1H), and δ12.315 (s, 1H).
EXAMPLE 17
Synthesis of 3-[(5-(4-chlorophenylcarbamic)pyridin-2-yl)methylidene]-6-(benzylmethylidene)piperazine-2,5-dione (Compound 17)
[0078] A reaction mixture of compound B (0.05 g, 0.16 mmole; obtained from Example 14), 4-chlorophenylisocyanate (0.024 g, 0.16 mmole), and 50 mL of chloroform was heated to 100° C. for 24 hr. Chloroform was removed in produce a residue. The residue was chromatographied using silica gel column with a developing solvent (CH 2 Cl 2 ) to give 0.01 g (15%) of Compound 17.
EXAMPLE 18
Screening for anti-tumor activities (NCI cell lines).
[0079] The cytotoxic activities of a number of piperazinedione compounds were measured against a panel of 60 different NCI human tumor cell lines.
[0080] All test compounds were found to be active. The least potent compound exhibited GI 50 values <10 −4 M for 4 cell lines. The most potent compound exhibited GI 50 values <10 −4 M for all 60 cell lines, with GI 50 values <10 −8 M for 9 cell lines.
EXAMPLE 19
[0081] Screening for Anti-tumor Activities (A Prostate Cell Line).
[0082] The cytotoxic activities of a number of piperazinedione compounds and taxol (a well-known anti-tumor agent) were tested on PC-3 cells. Cells were incubated in the presence of each compound in a serum-free medium for 24 hr. The cytotoxic activities were determined by the MTT assay. All test compounds are active. Unexpectively, the most potent piperazinedione compound has an EC 50 value around 0.3 microM, >30 times more potent than taxol.
EXAMPLE 20
[0083] In Vitro Assay (Inhibition of G 2 /M Progression of the Cell Cycle).
[0084] PC-3 cells were incubated in the presence of a piperazinedione compound in a serum- free medium and harvested, fixed, and stained with propidium iodide at the 6 th , 12 th , 18 th , and 24 th hr, respectively. The stage of cell cycles was determined based on flow cytometric measurements. The test compound induced an arrest of the cell cycle as entranced by a large number of cells at G 2 /M phase. In addition, a piperazinedione compound had a marked effect on the regulation of Ras activity
EXAMPLE 21
[0085] In Vitro Assay (Disturbance of Tubulin/microtubulin Assembly).
[0086] Tubulin/microtubulin was incubated in the presence of a piperazinedione compound at different concentrations in a solution (0.1 M MES, 1 mM EGTA, 0.5 mM MgCl 2 , 0.1 mM EDTA, and 2.5 M glycerol) at 37° C. Then, GTP was added to induce polymerization of tubulin/microtubulin. Optical density (OD) was measured at 350 nm at various time points to determine the degree of the polymerization. The test compound inhibited the polymerization at 10 −6 −10 −5 M.
EXAMPLE 22
[0087] In Vivo Assay (Inhibition of Tumor Enlargement)
[0088] SCID mice, subcutaneously injected into PC-3 cells, developed a tumor more than 800 mm 3 in volume. A piperazinedione compound significantly diminished the tumor volume after a 14-28 days treatment.
EXAMPLE 23
[0089] In Vivo Assay (Regulation of Angiogenesis Activity)
[0090] After subcutaneous incubation of a bFGF or VEGF-containing matrigel plug (0.5 mL/20 g mouse) for 6 days, a significant angiogenic effect was detected in the plug. Intraperitoneal injection of a piperazinedione compound almost completely diminished the angiogenic effect.
Other Embodiments
[0091] All of the features disclosed in this specification may be combined in any combination. Each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, each feature disclosed is only an example of a generic series of equivalent or similar features.
[0092] From the above description, one skilled in the art can easily ascertain the essential characteristics of the present invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. For example, compounds structurally analogous the piperazinedione compounds of this invention also can be made, screened for their anti-tumor activities, and used to practice this invention. Thus, other embodiments are also within the claims.
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Piperazinedione compounds of the formula:
Each of and , independently, is a single bond or a double bond; A is H or CH(R a R b ) when is a single bond, or C(R a R b ) when is a double bond; Z is R 3 O—(Ar)—B, in which B is CH(R c ) when is a single bond, or C(R c ) when is a double bond; Ar is heteroaryl; and R 3 is H, alkyl, aryl, heteroaryl, C(O)R d , C(O)OR d , C(O)NR d R e , or SO 2 R d ; each of R 1 and R 2 , independently, is H, C(O)R d , C(O)OR d , C(O)NR d R e , or SO 2 R d ; and each of R a , R b , R c , R d , and R e , independently, is H, alkyl, aryl, heteroaryl, cyclyl, or heterocyclyl. Optionally, R a and R b taken together are cyclyl or heterocyclyl; and, also optionally, R 1 and R a or R 1 and R b taken together are cyclyl or heterocyclyl.
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FIELD OF THE INVENTION
The present invention is related to the use of structural testing techniques to speed the testing of a memory array beyond what is possible with conventional functional tests.
ART BACKGROUND
As memory arrays commonly used in many electronic devices become increasingly larger and more densely packed, the test complexity increases exponentially, and so does the time required to thoroughly test the individual cells and other memory array components. As a result, manufacturing test processes take increasing longer to complete, as do efforts to debug the faults that are found.
Common practice within the art is to make use of functional tests wherein various combinations of values are written to and read back from memory cells within a memory array. However, as both the rows and columns of memory cells within memory arrays continue to increase in size, the number of write and read operations required to adequately test the memory cells increases exponentially, and causes a corresponding exponential increase in the amount of time required to carry out such tests. This has prompted questions about engaging in making increasing tradeoffs between manufacturing throughput of parts and thoroughness of test coverage, increasing the likelihood that faulty memory arrays will be passed on to customers.
Such functional tests also do not provide much in the way of information needed to trace the source of the failure. In essence, when it is found that a cell has returned a value other than what was last written to it, this result doesn't not provide an indication as to whether it was an address decoder fault, a data latch fault, a data line fault, a memory cell fault or a driver fault. Therefore, further tests are needed to isolate the fault within the memory array so that subsequent manufacturing yields may be improved, and as memory arrays continue to increase in size, the length of time required to perform these additional tests also increases.
BRIEF DESCRIPTION OF THE DRAWINGS
The objects, features, and advantages of the present invention will be apparent to one skilled in the art in view of the following detailed description in which:
FIG. 1 is a block diagram of one embodiment of the present invention.
FIGS. 2 a and 2 b are block diagrams of another embodiment of the present invention.
FIG. 3 is a block diagram of still another embodiment of the present invention.
FIG. 4 is a flow chart of one embodiment of the present invention.
FIG. 5 is a flow chart of another embodiment of the present invention.
FIG. 6 is a flow chart of still another embodiment of the present invention.
DETAILED DESCRIPTION
In the following description, for purposes of explanation, numerous details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one skilled in the art that these specific details are not required in order to practice the present invention.
The present invention concerns memory arrays in which there exists an array of memory cells organized in rows and columns, wherein the memory cells are dynamically and randomly accessible, as in the case of commonly available DRAM and SRAM ICs. However, as those skilled in the art will appreciate, the present invention is also applicable to arrays of other circuits, including but not limited to, erasable ROM ICs, programmable logic devices and components organized into arrays within microprocessors.
FIG. 1 is a block diagram of one embodiment of the present invention. Memory array 100 is depicted as comprised of top half 110 , bottom half 112 , address decoder 120 connected to both top half 110 and bottom half 112 via a plurality of word lines (including word lines 130 and 132 ), comparator circuit 140 , and latch 142 . Within top half 110 and bottom half 112 are memory cells 160 and 162 , respectively, connected to bit lines 170 and 172 , respectively. Bit lines 170 and 172 are in turn connected to the inputs of comparator circuit 140 , which is in turn connected to latch 142 . For purposes of clarity in discussing of the present invention, only memory cell 160 and bit line 170 are shown in top half 100 , and only memory cell 162 and bit line 172 are shown in bottom half 112 . However, as known by those skilled in the art, a typical memory array will have many bit lines, each of which will have many memory cells connected to it.
During normal operation of memory array 100 , address decoder 120 decodes part of a memory address and turns on appropriate ones of the word lines connecting address decoder 120 with top half 110 and bottom half 112 to enable access to appropriate memory cells within top half 110 and bottom half 112 . Depending on the memory operation being performed, data is either written to or read from memory cells in top half 110 and bottom half 112 via the bit lines to which they are connected. For example, during a write operation to a memory address associated with both memory cells 160 and 162 , address decoder 120 decodes part of the memory address and turns on word lines 130 and 132 to enable access to memory cells 160 and 162 through bit lines 170 and 172 , respectively.
In one embodiment of the present invention, memory cells 160 and 162 are tested by first writing identical data to each of memory cells 160 and 162 through bit lines 170 and 172 , respectively. Bit lines 170 and 172 are then precharged to either a high voltage state or a low voltage state, commonly referred to as Vcc or Vss, respectively. Address decoder 120 then decodes part of a memory address associated with memory cells 160 and 162 . Memory cells 160 and 162 then output their data onto bit lines 170 and 172 , respectively. Comparator circuit 140 is a single comparator that continuously compares the voltages on bit lines 170 and 172 , and continuously generates a signal indicating whether or not the voltages on bit lines 170 and 172 are substantially similar. In one embodiment, latch 142 may be triggered at one or more predetermined times during the test to capture the state of the output of comparator circuit 140 at such times, such as example times t 1 and t 2 during the progress of example waveforms 180 and 182 showing sample high-to-low transitions on bit lines 170 and 172 , respectively. In another embodiment, latch 142 could be implemented as a “sticky latch” that latches and stores any occurrence of a signal from comparator circuit 140 indicating that the voltages on bit lines 170 and 172 became substantially different.
It is common practice when reading memory cells during normal use of a memory array to precharge the bit lines to a high voltage state. Therefore, in one embodiment of the present invention, the testing of the memory cells would be carried out with the bit lines being charged only to a high state when reading the memory cells. However, due to commonly used memory cell designs, limiting precharging to only a high state would result in as much as half of the circuitry of a memory cell not being tested for excessive leakage or other conditions. Therefore, another embodiment of the present invention would entail testing with the bit lines precharged to both high and low states.
The use of comparator circuit 140 to test memory cells 160 and 162 is based on the assumption that identically designed memory cells connected to identically designed bit lines should be able to drive the voltages of their associated bit lines either high or low at a substantially similar rate. In short, the waveforms seen on both bit lines 170 and 172 (such as example waveforms 180 and 182 ) should look substantially similar. This use of a comparator circuit is also based on the assumption of it being highly unlikely that a process variation or other defect in memory array 100 will result in identical faults to both top half 110 and bottom half 112 , and so it is highly unlikely that both memory cells 160 and 162 will be defective in ways similar enough that the resulting errant waveforms seen on bit lines 170 and 172 will look substantially the same. In other words, it is presumed that an impurity, such as a dust particle or a fabrication process error, will not have identical effects on both top half 110 and bottom half 112 such that tests carried out in accordance with the present invention will reveal no differences between any pair of memory cells between top half 110 and bottom half 112 .
Memory array 100 is shown as split into top half 110 and bottom half 112 in accordance with a common practice known to those skilled in the art so that buffers and other associated circuitry may be centrally located, and allowing the bit lines to be kept short to give the bit lines more desirable electrical characteristics. The present invention takes advantage of this common practice to make use of the same central location provided to centrally locate comparator circuits, such as comparator 140 , to compare the electrical characteristics of adjacent bit lines. However, as will also be clear to those skilled in the art, this split of memory array 100 into top half 110 and bottom half 112 is not necessary to the practice of the present invention. The present invention may be practiced with numerous other layouts or placements of the components comprising a memory array.
FIGS. 2 a and 2 b are block diagrams of other embodiments of the present invention. Memory array 200 is substantially similar to memory array 100 of FIG. 1, and items numbered with 2xx numbers in FIGS. 2 a and 2 b are meant to correspond to items numbered with 1xx numbers in FIG. 1 . In a manner corresponding to memory array 100 , memory array 200 is comprised of address decoder 220 , coupled to memory cell 260 within top half 210 by word line 230 , and coupled to memory cell 262 within bottom half 212 by word line 232 .
However, unlike memory cells 160 and 162 , which were each connected to only one bit line, memory cells 260 and 262 are each connected to a pair of bit lines (bit lines 270 and 274 , and bit lines 272 and 276 , respectively). In one embodiment, pairs of bit lines are used with each memory cell to write and read both a bit of data and its compliment to and from each memory cell. In this embodiment, it would be common practice to route each pair of bit lines to a pair of differential inputs on sense amplifiers for reading a bit of data and its compliment. However, in an alternate embodiment, two (or more) bit lines are used to provide two (or more) entirely independent routes by which data may be written to or read from each memory cell. This use of the bit lines in this alternate embodiment would often reflects the way in which a multiple port memory component is often implemented.
Regardless of the purpose for having a pair of bit lines connected to each of memory cells 260 and 262 , in a manner that corresponds to bit lines 170 and 172 of memory array 100 of FIG. 1, in FIG. 2 a , bit lines 270 and 272 are connected to the inputs of comparator circuit 240 , and bit lines 274 and 276 are connected to the inputs of comparator circuit 244 . Also corresponding to FIG. 1, the outputs of comparator circuits 240 and 244 are connected to latches 242 and 246 .
In an embodiment of the present invention where memory cells are written to and read from using pairs of bit lines that carry data and its compliment, memory cells 260 and 262 are tested by first writing identical data to each of memory cells 260 and 262 through bit lines 270 and 274 , and bit lines 272 and 276 , respectively. Bit lines 270 through 276 are then precharged to either a high voltage state or a low voltage state. Address decoder 220 then decodes part of a memory address associated with memory cells 260 and 262 . Memory cells 260 and 262 then output their data onto bit lines 270 and 274 , and bit lines 272 and 276 , respectively. Comparator circuit 240 is a single comparator that continuously compares the voltages on bit lines 270 and 272 , and continuously generates a signal indicating whether or not the voltages on bit lines 270 and 272 are substantially similar. Comparator circuit 244 does the same with the voltages on bit lines 274 and 276 . In one embodiment, latches 242 and 246 may be triggered at one or more predetermined times during the test to capture the state of the output of comparator circuits 240 and 244 at those times. In another embodiment, latches 242 and 246 could each be implemented as a “sticky latch” that latches and stores any occurrence of a signal from the comparator circuits to which they are connected indicating that voltages on their associated bit lines became substantially different.
Furthermore, in an embodiment where memory cells are written to and read from using pairs of bit lines to carry data and its complement and sense amplifiers are used in reading from memory cells, the sense amplifiers could also be configured to serve as the comparators used as the comparator circuits to test the memory cells. This could be accomplished through the use of multiplexers to selectively connect and disconnect different ones of the bit lines as needed to allow the sense amplifiers to perform one or the other of these two functions as depicted by the use of multiplexers 280 and 284 in FIG. 2 b to selectively couple either one or the other of bit lines 270 or 276 to one input on each of comparators 240 and 244 , respectively. Otherwise, in an alternate embodiment, the sense amplifiers and the comparators could remain separate components.
In an alternate embodiment of the present invention where memory cells may be independently written to or read from using either of the bit lines attached to each of the memory cells, as in the case of a multiple port memory, the memory cells are tested in much the same manner just described. However, to ensure that the function of writing memory cells 260 and 262 is free of defects, the testing of each of memory cells 260 and 262 would be carried out twice, first using bit lines 270 and 272 to write identical data to memory cells 260 and 262 , respectively, and then again using bit lines 274 and 276 .
FIG. 3 is a block diagram of yet another embodiment of the present invention. Memory array 300 is substantially similar to memory array 200 of FIGS. 2 a and 2 b , and items numbered with 3xx numbers in FIG. 3 are meant to correspond to items numbered with 2xx numbers in FIGS. 2 a and 2 b , with exception of the comparator circuits and their associated latches. In a manner corresponding to memory array 200 , memory array 300 is comprised of address decoder 320 , coupled to memory cell 360 within top half 310 by word line 330 , and coupled to memory cell 362 within bottom half 312 by word line 332 . Also in a manner corresponding to memory array 200 , memory cell 360 is coupled to bit lines 370 and 374 , and memory cell 362 is coupled to bit lines 372 and 376 .
Unlike the embodiments depicted in FIGS. 2 a and 2 b , the comparator circuits of FIG. 3 are each comprised of a subtracting circuit and a pair of comparators. Bit lines 370 and 372 are connected to the inputs of subtracting circuit 390 . Subtracting circuits 390 subtracts the voltage level of one of bit lines 370 from the voltage level of the other of bit lines 372 , and outputs a voltage that represents the difference resulting from the subtraction, which could be either a positive or negative voltage output. This output of subtracting circuit 390 is, in turn, connected to one of the two inputs on each of comparators 340 and 341 . Correspondingly, bit lines 374 and 376 are connected to the inputs of subtracting circuit 392 , and the output of subtracting circuit 392 is connected to one of the two inputs on each of comparators 344 and 345 . The other input on each of comparators 340 and 344 are connected to a high voltage level reference, +vref, and correspondingly, the other input on each of comparators 341 and 345 are connected to a low voltage reference, −vref. The outputs of comparators 340 , 341 , 344 and 345 are connected to the inputs of latches 342 , 343 , 346 and 347 , respectively.
Regardless of whether the memory cells of memory array 300 are written to and read from with a pair of bit lines, or each of the two bit lines connected to each cell are meant to be used to perform independent read and write operations, the testing of memory cells 360 and 362 of memory array 300 is carried out in much the same way as was described above for memory cells 260 and 262 in FIGS. 2 a and 2 b . However, the configuration of comparator circuits that are each comprised of a subtracting circuit and a pair of comparators as shown in FIG. 3 affords greater ability to control the degree to which the voltages on pairs of bit lines that are being compared may differ from each other. More precisely, by adjusting +vref and −vref, comparators 340 and 344 can be biased to allow the voltage levels on bit lines 370 and 372 to differ to a degree that is adjustable before either comparator 340 or 344 outputs a signal indicating a malfunction. If the difference in voltage levels between bit lines 370 and 372 is such that it rises above +vref, then comparator 340 will output a signal indicating so to latch 342 , and if the difference in voltages levels between bit lines 370 and 372 is such that it drops below −vref, then comparator 344 will output a signal indicating so to latch 346 .
FIG. 4 is a flow chart of one embodiment of the present invention. Starting at 400 , identical values are written to a pair of memory cells in a memory array at 410 . At 420 , corresponding pairs of bit lines from each of the two memory cells are connected to the inputs of a comparator circuit. In one embodiment, where each memory cell is connected to only one bit line, this would mean that each of the two bit lines would be connected to the inputs of a single comparator circuit at 420 . Alternatively, in another embodiment where each memory cell is connected to two bit lines, then each bit line from one memory cell is connected to a comparator circuit along with a corresponding bit line from the other memory cell at 420 .
At 430 , the identical values are read back from each of the pair of memory cells, and each corresponding pair of bit lines connected to a comparator circuit are compared. If the voltage levels differ substantially between a corresponding pair of bit lines, then a failure is found at 460 . However, if there are no substantially differing voltage levels between corresponding pairs of bit lines, then this test of the pair of memory cells and the bit lines to which they are connected passes at 450 .
FIG. 5 is a flow chart of another embodiment of the present invention. The testing of memory cells in a memory array starts at 500 . At 510 , identical values are written to a pair of memory cells in a memory array, and at 520 , corresponding pairs of bit lines coupled to each memory cell in the pair of memory cells are connected to the inputs of a comparator circuit. Then, at 530 , the identical values are read back from the pair of memory cells, and the voltage levels of the corresponding pairs of bit lines are compared. If, at 540 , a substantial difference is found in the voltage levels in a corresponding pair of bit lines, then the fact that a substantial difference was found is latched at 550 , However, regardless of whether such a substantial difference was found at 540 , the test ends if there are no more memory cells to be tested at 560 . Otherwise, the test is repeated for another pair of memory cells at 510 .
By way of one example, referring variously to both FIGS. 1 and 5, at 510 , identical values are written to memory cells 160 and 162 , using bit lines 170 and 172 , respectively. At 520 , bit lines 170 and 172 are connected to the inputs of comparator circuit 140 . At 530 , the identical data written to both memory cells 160 and 162 is read back from memory cells 160 and 162 , using bit lines 170 and 172 , respectively, and the voltage levels on bit lines 170 and 172 are compared using comparator circuit 140 . If comparator circuit 140 detects a substantial difference in voltage between bit lines 170 and 172 , then an indication of this fact is latched by latch 142 . If, at 560 , more memory cells are to be tested, then at 510 , another pair of identical values are written to another pair of memory cells. Alternatively, the test may be repeated for memory cells 160 and 162 , with bit lines 170 and 172 being pre-charged to a high state for one test of reading back the identical data, and then being pre-charged to a low state for another reading back of the identical data.
By way of another example, referring variously to both FIGS. 2 and 5, where memory cells 260 and 262 are written to and read from with pairs of bit lines, and specifically, where bit lines 270 and 272 are used to write and read data, while bit lines 274 and 276 are used to write and read the compliments of the data. At 510 , identical values are written to memory cells 260 and 262 , using bit lines 270 and 272 to write identical data to memory cells 260 and 262 , respectively, while bit lines 274 and 276 are used to write identical compliment data to memory cells 260 and 262 , respectively. At 520 , bit lines 270 and 272 are connected to the inputs of comparator circuit 240 , and bit lines 274 and 276 are connected to the inputs of comparator circuit 244 . At 530 , the identical data and compliments written to both memory cells 260 and 262 is read back using bit lines 270 and 274 to read back from memory cell 260 , and bit lines 272 and 276 to read back from memory cell 262 . If comparator circuit 240 detects a substantial difference in voltage between bit lines 270 and 272 while reading back the data, then an indication of this fact is latched by latch 242 .
Correspondingly, if comparator circuit 244 detects a substantial difference in voltage between bit lines 274 and 276 while reading back compliment data, then an indication of this fact is latched by latch 244 . If, at 560 , more memory cells are to be tested, then at 510 , another pair of identical values are written to another pair of memory cells. Alternatively, the test may be repeated for memory cells 260 and 262 , with bit lines 270 , 272 , 274 and 276 being pre-charged to a high state for one test, and then being pre-charged to a low state for the other test.
FIG. 6 is a flow chart of still another embodiment of the present invention. The testing of memory cells using pairs of bit lines to read and write both bits of data and their compliments in a memory array starts at 600 . At 610 , identical values are written to a pair of memory cells in a memory array, and at 620 , corresponding ones of bit lines for data and complimentary data that are coupled to each memory cell in the pair of memory cells are connected to the inputs of comparator circuits. Then, at 630 , voltage references used by the comparator circuits are set. At 640 , the identical values are read back from the pair of memory cells, and the voltage levels of the corresponding pairs of bit lines for data and their compliments are compared. If, at 650 , a substantial difference is found in the voltage levels in a corresponding pair of bit lines, then the fact that a substantial difference was found is latched at 660 , However, regardless of whether such a substantial difference was found at 650 , the test ends if there are no more memory cells to be tested at 670 . Otherwise, the test is repeated for another pair of memory cells at 610 . Alternatively, the test may also be repeated if it is desired to test the bit lines with both a high and a low pre-charging during the reading back of the identical data.
By way of example, referring variously to both FIGS. 3 and 6, where memory cells 360 and 362 are written to and read from with pairs of bit lines, and specifically, where bit lines 370 and 372 are used to write and read data, while bit lines 374 and 376 are used to write and read the compliments of the data. At 610 , identical values are written to memory cells 360 and 362 , using bit lines 370 and 372 to write identical data to memory cells 360 and 362 , respectively, while bit lines 374 and 376 are used to write identical compliment data to memory cells 360 and 362 , respectively. At 620 , bit lines 370 and 372 are connected to the inputs of subtracting circuit 390 , which together with comparators 340 and 341 , comprise a comparator circuit. Correspondingly, bit lines 374 and 376 are connected to the inputs of subtracting circuit 392 , which together with comparators 344 and 345 , also comprise a comparator circuit. At 630 , voltage reference +vref, which is coupled to inputs of comparators 340 and 341 , and voltage reference −vref, which is coupled to inputs of comparators 344 and 345 , are both set. At 640 , the identical data and compliments of that data earlier written to both memory cells 360 and 362 is read back, using bit lines 370 and 374 to read back from memory cell 360 , and bit lines 372 and 376 to read back from memory cell 262 . At 650 , if a substantial difference was found in the voltage levels of corresponding pairs of bit lines 370 and 372 or bit lines 374 and 376 , then at 660 , the occurrence of this is latched by the appropriate one of latches 342 , 343 , 346 or 347 .
More specifically, subtractor circuit 390 subtracts the voltage on bit line 370 from bit line 372 , and outputs a voltage representing the resulting difference to the inputs of both comparators 340 and 341 . If there is a difference in the voltage levels between bit lines 370 and 372 , then the output of subtractor circuit 390 will be a non-zero voltage level that will be either negative or positive depending on which of bit lines 370 or 372 have the higher voltage level. Comparator 340 compares this output from subtracting circuit 390 , if the voltage level of the output is higher than +vref, then an indication that this is so is latched by latch 342 . Similarly, comparator 341 compares the output from subtracting circuit 390 , and if the voltage level of the output is lower than −vref, then an indication that this is so is latched by latch 343 . Correspondingly, subtracting circuit 392 provides an output representing the difference between the voltage levels of bit lines 374 and 376 to the inputs of comparators 344 and 345 , which in turn, compare this output to +vref and −vref, respectively, and any indication that the voltage level of this output has risen above +vref or dropped below −vref is latched by latches 346 and 347 , respectively.
If, at 670 , more memory cells are to be tested, then at 610 , another pair of identical values are written to another pair of memory cells. Alternatively, the test may be repeated for memory cells 360 and 362 , with bit lines 370 , 372 , 374 and 376 being pre-charged to a high state for one test, and then being precharged to a low state for the other test.
The invention has been described in conjunction with the preferred embodiment. It is evident that numerous alternatives, modifications, variations and uses will be apparent to those skilled in the art in light of the foregoing description. It will be understood by those skilled in the art, that the present invention may be practiced in support of other functions in an electronic device.
The example embodiments of the present invention are described in the context of an array of memory cells accessible, in part, by bit lines. However, the present invention is applicable to a variety of electronic, microelectronic and micromechanical devices.
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An apparatus and method for testing memory cells comprising coupling a first and a second memory cell to a first and a second bit lines, respectively, reading data from the first and second memory cells through the first and second bit lines, and comparing the voltage levels of the first and second bit lines.
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The present application claims priority of Chinese patent application Serial No. 200610171614.1, filed Dec. 31, 2006, the content of which is hereby incorporated by reference in its entirety.
FIELD OF INVENTION
The present invention relates to a gas filtering device, more particularly, to an integrated device, which used in a trace detector for detecting explosives and drugs, to filtrate and buffer the migrated gas and reacted gas.
BACKGROUND OF INVENTION
In conventional arts, a filter used in a trace detector for detecting explosives and drugs only has effects in filtering water, organic substances and absorbable particles in the migrated gas and reacted gas. Filter medium is filled in the whole inner space of the filter. Due to the sucking action from the gas source, the migrated gas in the flow path of the detector passes through the filter before entering into the migrated pipe. Because of the on-way pressure lost and partially pressure lost of the gas flow caused by the filter, as well as the uncertainty of the arrangement of the particle filter medium and the effects of the inner structure of the filter, the flow current and the pressure of the passing gas is fluctuated. Thus, the detecting performance of the detector is affected and the detecting precision is decreased.
SUMMARY OF INVENTION
One object of the present invention is to overcome at least one aspect of the limitation and shortages existing in the arts.
Accordingly, one object of the present invention is to provide a gas filtering-buffering device, which is able to provide filtering function and buffering function to the gas to be processed, thus, the detection precision of a trace detector is improved.
According to one aspect of the present invention, there is provided a gas filtering-buffering device which comprises, at least one gas filtering unit; a gas inlet, the gas to be processed flows into the at least one gas filtering unit from the gas inlet; and a gas outlet, the gas processed by the at least one gas filtering unit is discharged out of the at least one gas filtering unit via the gas outlet, wherein the at least one gas filtering unit comprising: a gas buffering cavity for performing buffering function for the gas, and a gas filtering part for performing filtering function for the gas.
In one embodiment, the at least one gas filtering unit includes: a first gas filtering unit and a second gas filtering unit connected hermetically and in series, wherein the first gas filtering unit including a first gas buffering cavity and a first gas filtering part, and the second gas filtering unit including a second gas buffering cavity and a second gas filtering part.
Preferably, the first gas filtering unit and the second gas filtering unit are connected by a connection unit, the connection unit is provided with a flow passage through which the gas from the first gas filtering unit flows into the second gas filtering unit.
Furthermore, the first gas filtering unit, the connection unit and the second filtering unit may be configured to have a substantial U-shape. Alternatively, the connection unit may be integrated with the first gas filtering unit and the second filtering unit.
In a further embodiment, the first gas buffering cavity is provided at the upstream of the first gas filtering part in a gas flow direction; and the second gas buffering cavity is provided at the downstream of the second gas filtering part in the gas flow direction.
Preferably, the first gas filtering part has a moisture filter medium layer; and the second gas filtering part having an organic substance filter medium layer and an absorbing filter medium.
Preferably, the gas filtering-buffering device further comprises: a first porous filter medium baffle provided between the first gas buffering cavity and the moisture filter medium layer; and a second porous filter medium baffle provided between the second gas buffering cavity and said organic substance filter medium layer and absorbing filter medium layer.
Preferably, the gas filtering-buffering device further comprises: a first precise filtering layer provided between the gas inlet and the first gas buffering cavity; and a second precise filtering layer provided between the gas outlet and the first gas buffering cavity.
Preferably, the gas filtering-buffering device further comprises: a first precise filtering layer baffle provided between the first precise filtering layer and the first gas buffering cavity; and a second precise filtering layer baffle provided between the second precise filtering layer and the second buffering cavity.
Alternatively, the gas filtering-buffering device further comprises: a first adjusting member provided in the first gas buffering cavity for adjusting the precision of the moisture filter medium layer; and a second adjusting member provided in the second gas buffering cavity for adjusting the precision of the organic substance filter medium layer and the absorbing filter medium layer.
Alternatively, the gas filtering-buffering device further comprises: a third adjusting member provided in the first gas buffering cavity for adjusting the filtering precision of the first precise filtering layer; and a forth adjusting member provided in the second gas buffering cavity for adjusting the filtering precision of the second precise filtering layer.
Alternatively, the gas filtering-buffering device further comprises: a first draw bar penetrating through the first filtering unit and connecting the first gas filtering unit and the connection unit; and a second draw bar penetrating through the second filtering unit and connecting the second gas filtering unit and the connection unit.
Alternatively, the first adjusting member is a nut, which is engaged with a first threaded portion provided on the first draw bar and movable along with the first draw bar, so that the filtering precision of the moisture filter medium layer is adjusted by moving the first porous filter medium baffle; and the second adjusting member is a nut, which is engaged with a second threaded portion provided on the second draw bar and movable along with the second draw bar, so that the filtering precision of the organic substance filter medium layer and the absorbing filter medium layer are adjusted by moving the second porous filter medium baffle.
Alternatively, the third and forth adjusting member are nuts, which are engaged with third and forth threaded portions and movable along with the first and second draw bars, respectively, so that the filtering precision of the first and second precise filtering layers are adjusted by moving the first and second precise filtering layer baffle.
In one embodiment, the gas filtering-buffering device further comprises: a first opening and a second opening provided at the first and second gas buffering cavity; and a first cover member and a second cover member movably connected to and closed the first and second openings. Preferably, sealing members are respectively provided between the first and second openings and the first and second cover members.
In an embodiment, each of the first and second gas filtering units may have an integrated structure.
In an embodiment, each of the first and second gas filtering units includes a cartridge filter and a cartridge filter cover connected hermetically with each other, respectively; and each of the first and second gas buffering cavities is provided within the cartridge filter cover, respectively.
The advantage of at least one aspect of one embodiment and the positive effects are:
In the present invention, it is not only provided with a gas filtering part which is able to filter the moisture and organic substance in the gas, but also provided with a gas buffering cavity, which integrate the filtering and buffering functions together. The buffering cavity may expand the capacity and stabilize the pressure of the gas, and balance the concentration, pressure and flow rate of the gas. Also it is advantageous to reduce the on-way pressure lost and partially pressure lost, decrease fluctuation of the flow current and the pressure thus, the detecting performance of the detector is improved.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is front view of the gas filtering-buffering device of the present invention;
FIG. 2 is top view of FIG. 1 ;
FIG. 3 is section view of the gas filtering-buffering device of the present invention;
FIG. 4 is a cross-sectional view taken along with line A-A of FIG. 3 ; and
FIG. 5 is a schematic view of the structure of the precise filtering layer baffle in the present invention.
In drawings, wherein:
1 . gas inlet; 2 . precise filtering layer; 3 . precise filtering layer baffle; 4 . inlet-gas buffering cavity; 5 . adjusting nut; 7 . porous filter medium baffle; 8 . first cartridge filter; 9 . moisture filter medium layer; 10 . central draw bar; 12 . built-in passage end plate; 13 . built-in passage; 15 . absorbing filter medium layer; 16 . organic substance filter medium layer; 17 . second cartridge filter; 20 . porous padding baffle; 21 . outgas buffering cavity; 23 . outlet precise filtering layer baffle; 24 . outlet precise filtering layer; 25 gas outlet; 26 . fixed distance sealing pressure plate; 28 . sealing ring; 29 . locking nut; 30 . sealing ring; 31 . rotary cover; 32 . mounting screw hole; 33 . first filter; 34 . second filter; 36 . first cartridge filter; 37 second cartridge cover.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred embodiments of the present invention will be described hereinafter in detail with reference to the attached drawings, wherein the like reference numerals refer to the like elements throughout the specification. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein; rather, these embodiments are provided so that the present disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.
As shown in FIGS. 1-4 , a gas filtering-buffering device comprises a first filter 33 which serves as the first filtering unit, and the second filter 34 which serves as the second filtering unit, the first filter 33 and the second filter 34 are connected hermetically with each other and in series. The first filter 33 is provided therein with an inlet-gas buffering cavity 4 as a first gas buffering cavity and an inlet-gas filtering part as a first gas filtering part, and the second filter 34 is provided therein with an outgas buffering cavity 21 as a second gas buffering cavity and an outgas filtering part as a second gas filtering part. The gas filtering-buffering device further comprises a gas inlet 1 provided at the one end of the first filter 33 , the gas to be processed flows into the first filter 33 through the gas inlet 1 , and a gas outlet 25 provided at the one end of the second filter 34 , the gas processed by above filter is discharged out of the second filter 34 via the gas outlet 25 . As shown in FIG. 3 , the inlet-gas buffering cavity 4 is provided at the upstream of the first gas filtering part in a gas flow direction, the outgas buffering cavity 21 is provided at the downstream of the second gas filtering part in the gas flow direction. Although in the above embodiment, the gas filtering-buffering device includes the first filter 33 serving as the first filtering unit and the second filter 33 serving as the second filtering unit, the present invention is not limited thereto. Specifically, the gas filtering-buffering device of the present invention also can only have one filter, and a gas inlet and a gas outlet provided at both end of the filter.
Refer to FIG. 3 , the first filter includes a first cartridge filter 8 having a substantially cylindrical shape, a first cartridge cover 36 provided at the left end of the first cartridge filter 8 and hermetically engaged with the first cartridge filter 8 . The second filter includes a second cartridge filter 17 having a substantially cylindrical shape, and the second cartridge cover 37 provided at the left end of the second cartridge filter 17 and hermetically engaged with the second cartridge filter 17 . Although, the first and second cartridge filters in the embodiment have a substantially hollow cylindrical shape, the present invention is not limited thereto, any other desirable shape also can be applied, for example, hollow cube shape. Furthermore, although in the above embodiment, the first filter 33 is structured of two separated parts consisting of the first cartridge filter 8 and the first cartridge cover 36 which are hermetically engaged with each other, the second filter 34 is structured of two separated parts consisting of the second cartridge filter 17 and the second cartridge cover 37 which are hermetically engaged with each other, the present invention is not limited thereto. In particular, the first filter 33 and the second filter 34 also may be formed integrally.
An built-in passage end plate 12 serving as a connection unit is hermetically provided at the right end of the first cartridge filter 8 and the second cartridge filter 17 , an built-in passage 13 is in communication with the first cartridge filter 8 and the second cartridge filter 17 is provided inside the built-in passage end plate 12 . In one embodiment, the built-in passage end plate 12 is configured to be separated parts, as shown in FIG. 1 , which is hermetically connected with the filters 33 , 34 by draw bars 10 , 10 ′. However, the present invention is not limited thereto, for example, the built-in passage end plate 12 also can be configured to have an integrated structure with the first filter 33 and the second filter 34 .
Furthermore, the gas filtering-buffering device further includes a first draw bar 10 penetrating through the first filter 33 and connected with the first filter 33 and the built-in passage end plate 12 , and a second draw bar 10 ′ penetrating through the second filter 34 and connected with the second filter 34 and the built-in passage end plate 12 .
In one embodiment, the first filter 33 is constructed of two separated parts consisting of the first cartridge filter 8 and the first cartridge cover 36 which are hermetically engaged with each other, the central draw bars 10 , 10 ′ are provided separately between the first cartridge cover 36 and the second cartridge cover 37 and the built-in passage end plate 12 . In one embodiment, both two central draw bars 10 , 10 ′ are extended out of the first cartridge cover 36 and the second cartridge cover 37 , and locked by two locking nuts 29 respectively. Apparently, two central draw bars 10 , 10 ′ also can be provided to locate inside of the first filter 33 and second filter 34 so as to connect both inner ends of the first filter 33 and second filter 34 .
As shown in FIG. 2 , in one embodiment, a fixed distance sealing pressure plate 26 is connected at the left end of two central draw bars 10 , 10 ′. The fixed distance sealing pressure plate 26 is pressed at the outside of the first cartridge cover 36 and the second cartridge cover 37 by locking nuts 29 . Sealing rings 28 set on the central draw bars are provided between the fixed distance sealing pressure plate 26 and the first and second cartridge covers 36 , 37 , and all the parts are tightly fitted together by the rotating locking nut 29 tightly to achieve the gas tightness in the flow path.
In the embodiment shown in FIG. 2 , the gas inlet 1 is provided on the first cartridge cover 36 , the inlet-gas buffering cavity 4 is provided inside the first cartridge cover 36 . The inlet-gas filtering part includes a porous filter medium baffle 7 provided at the right side of the inlet-gas buffering cavity 4 and moisture filter medium layer 9 provided inside the first filter 8 . The porous filter medium baffle 7 is used for maintaining and blocking moisture filter medium layer 9 , to prevent it from overflowing into the inlet-gas buffering cavity. The primary function of the moisture filter medium layer 9 is to remove the moisture in the gas, and the main component thereof may be of color silica gel.
In one embodiment, the first filter 33 further includes a precise filtering layer provided at the left side of the inlet-gas buffering cavity 4 , that is, between the inlet-gas buffering cavity 4 and the gas inlet 1 , and a precise filtering layer baffle 3 used for blocking and maintaining a precise filtering layer 2 . The primary purpose of the precise filtering layer 2 is to filter the dust etc. which has entered into the gas filtering-buffering device, and the main component thereof may be absorbent cotton.
In the embodiment shown in FIG. 2 , the gas outlet 25 is provided on the second cartridge cover 37 , the outgas buffering cavity 21 is provided inside the second cartridge cover 37 . The outgas filtering part is constructed by the porous padding baffle 20 at the right side of the outgas buffering cavity 21 , the organic substance filter medium layer 16 and/or absorbing filter medium layer 15 inside the second cartridge filter 17 . The porous padding baffle 20 is used to maintain and block the organic substance filter medium layer 16 and/or absorbing filter medium layer 15 , in order to prevent them from overflowing into the inlet-gas buffering cavity 4 . The primary function of the organic substance filter medium layer 16 and/or absorbing filter medium layer 15 is to absorb the particles, and the essential component thereof may be such as active carbon or molecular sieve.
In an embodiment, the second filter 34 further includes an outgas precise filtering layer and an outgas precise filtering layer baffle provided at the left side of the outgas buffering cavity 21 , that is, a position between the outgas buffering cavity 21 and the gas outlet 25 . The primary purpose of the precise filtering layer 24 is to filter the filtering stuff component etc. mixed into the gas, and the essential component may be such as absorbent cotton.
Refer to FIGS. 1 and 2 , the gas filtering-buffering device further comprises: first and second openings 38 , 38 provided at the first and second gas buffering cavity 4 , 21 ; and first and second rotary covers 31 , 31 movably connected onto and closing the first and second openings 38 , 38 . In the embodiment shown in FIG. 2 , the first cartridge cover 36 and the second cartridge cover 37 are provided with rotary covers 31 , 31 corresponding to the inlet-gas buffering cavity 4 and the outgas buffering cavity 21 , respectively. Sealing rings 30 are provided respectively between two rotary covers 31 , 31 and the first cartridge cover 36 and the second cartridge cover 37 . The rotary covers 31 may be connected with the cartridge covers 36 , 37 by threaded connection. Furthermore, a number of screw holes 32 for fixing and mounting the whole filter are provided respectively on the first cartridge cover 36 , the second cartridge cover 37 , and the built-in passage end plate 12 .
Hereafter, each filter medium baffle according to the embodiment of the present invention will be described in accordance with FIG. 5 . As mentioned in FIG. 5 , the precise filtering layer baffle 3 in the present invention may be a circular-shaped porous baffle, the porous filter medium baffle 7 , the porous padding baffle 20 , the outgas precise filtering layer baffle 23 and the precise filtering layer baffle 3 have a similar structure, these four baffles are freely mounted on the corresponding central draw bars 10 , 10 ′ in series, respectively, wherein nuts 5 , 18 , 22 , and 27 for adjusting their positions are provided within the inlet-gas buffering cavity 4 and outgas buffering cavity 21 . In particular, screw-threads, which incorporate with above nuts 5 , 18 , 22 and 27 , are provided onto a proper location of the central draw bars 10 , 10 ′, so that nuts 5 , 18 , 22 and 27 may be moved along central draw bars 10 , 10 ′, therefore, the filtering precision of each filtering layer may be adjusted by moving each filter medium baffle 3 , 7 , 20 , 23 .
When it is required to adjust the precision of each filtering layer in above, the user opens the rotary cover 31 first, and then wrenches the nuts 5 , 18 , 22 and 27 engaged with the central draw bars 10 , 10 ′, so that each filter medium baffles 3 , 7 , 20 , 20 may be moved along the central draw bars 10 , 10 ′, thus, the filtering precision of precise filtering layers and the capacity of the buffering cavities can be adjusted. Furthermore, the replacement of the filter medium in the first and second filters 33 , 34 also can be achieved through above operation.
More particularly, in the present invention, the filter medium in the moisture removing cavity can be compacted by adjusting the position of the porous filter medium baffle 7 at one side of the moisture filter medium layer 9 . At the same time, the capacity of the inlet-gas buffering cavity is controlled by changing the position of the porous filter medium baffle 7 , and the position of the porous filter medium baffle 7 on the central draw bar 10 may be adjusted by the adjusting nut 5 .
The absorbing filter medium 15 and the organic substance filter medium layer 16 filled inside of the second cartridge filter 17 are organic substance padding, the filter medium in the second cartridge filter 17 is compacted by adjusting the position of the porous padding baffle 20 at one side of the organic substance filter medium. At the same time, the capacity of the outgas buffering cavity is controlled by changing the position of the porous padding baffle 20 , the position of the porous padding baffle 20 on the central draw bar 10 ′ is adjusted by nut 18 .
The inlet-gas precise filtering layer 2 is a fiber filtering layer, and it is closely pasted on an inner wall close to the gas inlet side in the inlet-gas buffering cavity, the inlet-gas precise filtering layer baffle 3 is provided at the outside thereof and mounted on the central draw bar 10 in series, a pretension nut 27 is located at the outside of the inlet-gas precise filtering layer baffle 3 on the central draw bar, the degree of tightness of the inlet-gas precise filtering layer baffle 3 is varied by adjusting the pretension nut 27 , so that the precision of the filtering is changed.
The outgas precise filtering layer 24 is a fiber filtering layer, and it is closed pasted on an inner wall close to the gas outlet 25 side in the outgas buffering cavity, the outgas precise filtering layer baffle 23 is provided at the outside thereof and mounted on the central draw bar 10 ′ in series, a pretension nut 22 is located at the outside of the outgas precise filtrering layer baffle 23 , the degree of tightness of the outgas precise filtering layer baffle 23 is varied by adjusting the pretension nut, so that the precision of the filtering is changed.
In the gas filtering-buffering device of the present invention, there can be three or more gas filtering units as required by the determination of the precision of filtering and so on.
When the gas filtering-buffering device of the present invention operates normally, the gas to be processed is entered into the first filter 33 via the gas inlet 1 . The primary purification is obtained through the primary filtering by the inlet-gas precise filtering layer 2 . When the gas flows into the first filter 33 through the gas inlet with a smaller drift diameter, the flow rate of the gas become extremely fast and it is easy to form turbulent flow. Thus after the gas is purified through the inlet-gas precise filtering layer, first of all, the gas may be processed with expanded capacity, stabilized pressure, and balanced the concentration, the pressure and the rate of the gas in the inlet-gas buffering cavity 4 , then it flows into the first cartridge filter 8 to subject to a moisture removing process by passing through the porous filter medium baffle 7 ; and then, the gas flows into the second filter 34 via the built-in passage 13 , firstly, inside the second cartridge filter 17 , the organic substance in the gas is removed by filtration, and particles in the gas are absorbed, and then, the gas may be processed with expanded capacity, stabilized pressure, and balanced the concentration, the pressure and the rate of the gas by flowing into the outgas buffering cavity 21 through the porous padding baffle, then, the gas is purified by the outgas precise filtering layer 24 and discharged by gas outlet 26 .
It would be appreciated by those skilled in the art that many modifications, alterations and substitutions may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the claims and their equivalents.
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The present invention relates to a gas filtering-buffering device, which comprises at least one gas filtering unit; a gas inlet, the gas to be processed flows into the at least one gas filtering unit from the gas inlet; and a gas outlet, the gas processed by the at least one gas filtering unit is discharged out of the at least one gas filtering unit via the gas outlet, wherein the at least one gas filtering unit comprising: a gas buffering cavity for performing buffering function for the gas, and a gas filtering part for performing filtering function for the gas. In the present invention, it is not only provided with a gas filtering part which is able to filter the moisture and organic substance in the gas, but also provided with a gas buffering cavity, which integrate the filtering and buffering functions together. The buffering cavity may expand the capacity and stabilize the pressure of the gas, and balance the concentration, pressure and flow rate of the gas, it is advantageous to reduce the on-way pressure lost and partially pressure lost, decrease fluctuation of the flow current and the pressure thus, the detecting performance of the detector is improved.
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FIELD
[0001] The present application relates to a process for manufacturing a paperboard from a high consistency pulp slurry of cellulosic fibers containing high levels of intrafiber crosslinked celluosic fibers.
SUMMARY
[0002] This application is directed to a process for manufacturing a paperboard from a high consistency pulp slurry containing high levels of crosslinked cellulosic fibers by dispersing the fibers in a screen with a rotor in the screen and then passing the fibers through the screen basket with a hole diameter of at least 2 mm and forming the cellulosic fibers on a foraminous support. Another slurry of regular cellulosic fibers is deposited on at least one side of the first slurry during the formation process.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003] The foregoing aspects and many of the attendant advantages of this disclosure will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction the accompanying drawings, wherein:
[0004] FIG. 1 is a schematic representation of the equipment components utilized in the present application.
[0005] FIG. 2 is a lobed rotor
[0006] FIG. 3 is a foil rotor
[0007] FIG. 4 is a bump rotor.
[0008] FIG. 5 is a schematic cross-sectional view of a two ply paperboard.
[0009] FIG. 6 shows a wall section of a hot cup container.
DETAILED DESCRIPTION
[0010] High consistency slurries containing high levels of crosslinked cellulosic fibers cannot be used in paperboard machines due to plugging of the screen by the high levels of crosslinked cellulosic fibers in the slurry. A process for using the high consistency slurry containing high levels of crosslinked cellulosic fibers has been discovered which overcomes this problem.
[0011] Referring to FIG. 1 , a high consistency slurry of cellulosic fibers is formed in a dispersion medium, such as water, in a slurry tank, 10 . The resulting slurry is then pumped to a consistency regulator, 12 , where dilution water is added to maintain a fixed consistency. Subsequently the slurry is pumped to the machine chest, 14 , and then into a screen basket, 16 , which may be vertically or horizontally mounted. Various types of rotors may be mounted in the screen basket such as a lobed, foil or bump rotor (see FIGS. 2 , 3 , and 4 ) manufactured by GL&V, Watertown, N.Y. The rotors serve to disperse the fibers in the screen and force acceptable fibers through the screen basket and then to a headbox 18 . Fibers that are rejected pass to a flat screen, 16 a, where they are further separated into rejects which are discarded and acceptable fibers which are returned to the machine chest, 14 . The headbox may be a single ply headbox, a multiply headbox or two or more single ply headboxes arranged to form two or more layers formed by combining one layer from each single ply headbox. From the headbox, the pulp is formed on the wire, 20 , dewatered and dried.
[0012] In one embodiment of the method, at least one high consistency slurry of cellulosic fibers is formed in an aqueous dispersion medium. The cellulosic fibers which are both crosslinked cellulosic fibers and regular cellulosic fibers, are dispersed in a screen by means of a rotor in the screen and then passed through the screen which has a hole diameter of at least 1.5 mm. The cellulosic fibers are formed on a foraminous support. Rotors can be of various types such as lobed, foil, bump, and S; the listing is not meant to limit the types suitable for this application and known by the skilled artisan. In another embodiment the fibers are passed through a screen which has a hole diameter of at least 2 mm. Screen hole sizes up to 6 mm can be used. As used herein, the term “consistency” means the percent solids content of a liquid and solid mixture, for example, a consistency of 2 percent cellulosic fibers means there are two grams of cellulosic fibers in one hundred grams of fiber and liquid. In another embodiment the slurry consistency is at least 2.5 percent and in yet another embodiment the slurry consistency is at least 3 percent. A high consistency slurry means a solid content of 3 to 4 percent, a medium consistency slurry means a solid content of 1 to 2 percent and a low consistency slurry means a solid content of less than 1 percent solids.
[0013] Crosslinked cellulosic fibers can be present in the high consistency slurry at levels of at least 35 percent by weight of the total fibers in the high consistency slurry. In one embodiment they are present at a level of at least 40 percent by weight of the total fiber content in the high consistency slurry. In another embodiment they are present at a level of at least 50 percent by weight of the total fiber content in the high consistency slurry and in yet another embodiment they are present at a level of at least 60 percent by weight of the total fiber in the high consistency slurry.
[0014] The preferred crosslinked cellulosic fibers for use in the application are crosslinked cellulosic fibers. Any one of a number of crosslinking agents and crosslinking catalysts, if necessary, can be used to provide the crosslinked fibers to be included in the layer.
[0015] The following is a representative list of useful crosslinking agents and catalysts. Each of the patents noted below is expressly incorporated herein by reference in its entirety.
[0016] Suitable urea-based crosslinking agents include substituted ureas, such as methylolated ureas, methylolated cyclic ureas, methylolated lower alkyl cyclic ureas, methylolated dihydroxy cyclic ureas, dihydroxy cyclic ureas, and lower alkyl substituted cyclic ureas. Specific urea-based crosslinking agents include dimethyldihydroxy urea (DMDHU, 1,3-dimethyl-4,5-dihydroxy-2-imidazolidinone), dimethyloldihydroxy-ethylene urea (DMDHEU, 1,3-dihydroxymethyl-4,5-dihydroxy-2-imidazolidinone), dimethylol urea (DMU, bis[N-hydroxymethyl]urea), dihydroxyethylene urea (DHEU, 4,5-dihydroxy-2-imidazolidinone), dimethylolethylene urea (DMEU, 1,3-dihydroxymethyl-2-imidazolidinone), and dimethyldihydroxyethylene urea (DMeDHEU or DDI, 4,5-dihydroxy-1,3-dimethyl-2-imidazolidinone).
[0017] Suitable crosslinking agents include dialdehydes such as C 2 -C 8 dialdehydes (e.g., glyoxal), C 2 -C 8 dialdehyde acid analogs having at least one aldehyde group, and oligomers of these aldehyde and dialdehyde acid analogs, as described in U.S. Pat. Nos. 4,822,453; 4,888,093; 4,889,595; 4,889,596; 4,889,597; and 4,898,642. Other suitable dialdehyde crosslinking agents include those described in U.S. Pat. Nos. 4,853,086; 4,900,324; and 5,843,061. Other suitable crosslinking agents include aldehyde and urea-based formaldehyde addition products. See, for example, U.S. Pat. Nos. 3,224,926; 3,241,533; 3,932,209; 4,035,147; 3,756,913; 4,689,118; 4,822,453; 3,440,135; 4,935,022; 3,819,470; and 3,658,613. Suitable crosslinking agents may also include glyoxal adducts of ureas, for example, U.S. Pat. No. 4,968,774, and glyoxal/cyclic urea adducts as described in U.S. Pat. Nos. 4,285,690; 4,332,586; 4,396,391; 4,455,416; and 4,505,712.
[0018] Other suitable crosslinking agents include carboxylic acid crosslinking agents such as polycarboxylic acids. Polycarboxylic acid crosslinking agents (e.g., citric acid, propane tricarboxylic acid, and butane tetracarboxylic acid) and catalysts are described in U.S. Pat. Nos. 3,526,048; 4,820,307; 4,936,865; 4,975,209; and 5,221,285. The use of C 2 -C 9 polycarboxylic acids that contain at least three carboxyl groups (e.g., citric acid and oxydisuccinic acid) as crosslinking agents is described in U.S. Pat. Nos. 5,137,537; 5,183,707; 5,190,563; 5,562,740; and 5,873,979.
[0019] Polymeric polycarboxylic acids are also suitable crosslinking agents. Suitable polymeric polycarboxylic acid crosslinking agents are described in U.S. Pat. Nos. 4,391,878; 4,420,368; 4,431,481; 5,049,235; 5,160,789; 5,442,899; 5,698,074; 5,496,476; 5,496,477; 5,728,771; 5,705,475; and 5,981,739. Polyacrylic acid and related copolymers as crosslinking agents are described U.S. Pat. Nos. 5,549,791 and 5,998,511. Polymaleic acid crosslinking agents are described in U.S. Pat. No. 5,998,511 and U.S. application Ser. No. 09/886,821.
[0020] Specific suitable polycarboxylic acid crosslinking agents include citric acid, tartaric acid, malic acid, succinic acid, glutaric acid, citraconic acid, itaconic acid, tartrate monosuccinic acid, maleic acid, polyacrylic acid, polymethacrylic acid, polymaleic acid, polymethylvinylether-co-maleate copolymer, polymethylvinylether-co-itaconate copolymer, copolymers of acrylic acid, and copolymers of maleic acid. Other suitable crosslinking agents are described in U.S. Pat. Nos. 5,225,047; 5,366,591; 5,556,976; and 5,536,369.
[0021] Suitable crosslinking catalysts can include acidic salts, such as ammonium chloride, ammonium sulfate, aluminum chloride, magnesium chloride, magnesium nitrate, and alkali metal salts of phosphorous-containing acids. In one embodiment, the crosslinking catalyst is sodium hypophosphite.
[0022] The crosslinking agent is applied to the cellulosic fibers as they are being produced in an amount sufficient to effect intrafiber crosslinking. The amount applied to the cellulosic fibers may be from about 1% to about 25% by weight based on the total weight of fibers. In one embodiment, crosslinking agent in an amount from about 4% to about 6% by weight based on the total weight of fibers. Mixtures or blends of crosslinking agents may be used.
[0023] Although available from other sources, noncrosslinked cellulosic cellulosic fibers usable in the present application are derived primarily from wood pulp. Suitable wood pulp fibers for use with the application can be obtained from well-known chemical processes such as the kraft and sulfite processes, with or without subsequent bleaching. Pulp fibers can also be processed by thermomechanical, chemithermomechanical methods, or combinations thereof. The preferred pulp fiber is produced by chemical methods. Groundwood fibers, recycled or secondary wood pulp fibers, and bleached and unbleached wood pulp fibers can be used. Softwoods and hardwoods can be used. Details of the selection of wood pulp fibers are well known to those skilled in the art. These fibers are commercially available from a number of companies, including Weyerhaeuser Company, the assignee of the present invention. For example, suitable cellulose fibers produced from southern pine that are usable with the present application are available from Weyerhaeuser Company under the designations CF416, CF405, NF405, PL416, FR416, FR516, and NB416. Dissolving pulps from northern softwoods include MAC11 Sulfite, M919, WEYCELL and TR978 all of which have an alpha content of 95% and PH which has an alpha content of 91%. High purity mercerized pulps such as HPZ, HPZ111, HPZ4, and HPZ-XS available from Buckeye and Porosonier-J available from Rayonier are also suitable.
[0024] Screen hole diameter can vary. In one embodiment the hole diameter is at least 2 mm, in another embodiment the hole diameter is at least 3 mm. Rotors in the screen used to disperse the fibers and force the fibers through the screen can be lobed, bump or foil rotors. Foil rotors can have from four to ten foils.
[0025] Hot foods, particularly hot liquids, are commonly served and consumed in disposable containers. These containers are made from a variety of materials including paperboard and foamed polymeric sheet material. One of the least expensive sources of paperboard material is cellulose fibers. Cellulose fibers are employed to produce excellent paperboards for the production of hot cups, paper plates, and other food and beverage containers. Conventional paperboard produced from cellulosic fibers, however, is relatively dense, and therefore, transmits heat more readily than, for example, foamed polymeric sheet material. Thus, hot liquids are typically served in double cups or in cups containing multiple plies of conventional paperboard.
[0026] It is desirable to manufacture a paperboard produced from cellulosic material that has good insulating characteristics, that will allow the user to sense that food in the container is warm or hot and at the same time will allow the consumer of the food or beverage in the container to hold the container for a lengthy period of time without the sensation of excessive temperature. It is further desirable to provide a paperboard that can be tailored to provide a variety of insulating characteristics.
[0027] Referring to FIG. 5 , the substrate 50 for the insulating paperboard 52 of the present application is produced in a conventional manner from readily available fibers such as cellulosic fibers. At least one ply, 54 , of the paperboard contains crosslinked fibers. The paperboard of the present application can be made in a single-ply, a two-ply construction, or a multi-ply construction, as desired. While the paperboard of the present application may employ synthetic fibers as set forth above, it is most preferred that paperboard comprise all or substantially all of the cellulosic fibers.
[0028] The distinguishing characteristic of the present application is that at least one ply of the paperboard, whether a single-ply or a multiple-ply structure, contains crosslinked cellulosic fibers. The crosslinked cellulosic fibers increase the bulk density of the paperboard and thus the insulating characteristics. As used herein, crosslinked cellulosic fibers are kinked, twisted, curly, cellulosic fibers. It is preferred, however, that the fibers be produced by intrafiber crosslinking of the cellulosic fibers as described earlier.
[0029] Paperboard of the present application may have a broad set of characteristics. For example, its basis weight can range from 200 gsm to 500 gsm, more preferably, from 250 gsm to 400 gsm. Most preferably, the basis weight of the paperboard is equal to or greater than 250 gsm. To achieve the insulating characteristics of the present invention, it is preferred that the paperboard has a density of less than 0.5 g/cc, more preferably, from 0.3 g/cc to 0.45 g/cc, and most preferably, from 0.35 g/cc to 0.40 g/cc.
[0030] When at least one ply of the paperboard contains crosslinked cellulosic fibers in accordance with the present invention, advantageous temperature drop characteristics can be achieved. These temperature drop characteristics can be achieved by altering the amount of crosslinked cellulosic fiber introduced into the paperboard, by adjusting the basis weight of the paperboard, by adjusting the caliper of the paperboard after it has been produced by running it, for example, through nip rolls, and of course, by varying the number and thickness of additional plies incorporated in the paperboard structure. It is preferred that this paperboard have a caliper greater than or equal to 0.5 mm, a basis weight equal to or greater than 250 gsm, and a density less than 0.5 g/cc defined below. The paperboard of the present application can be a single-ply product. When a single-ply product is employed, the low density characteristics of the paperboard allows the manufacture of a thicker paperboard at a reasonable basis weight. To achieve the same insulating characteristics with a normal paperboard, the normal paperboard thickness would have to be doubled relative to that of the present invention. Using the crosslinked cellulosic fibers of the present invention, an insulating paperboard having the same basis weight as a normal paperboard can be made. This effectively allows the manufacture of insulating paperboard on existing paperboard machines with minor modifications and minor losses in productivity. Moreover, a one-ply paperboard has the advantage that the whole structure is at a low density.
[0031] Alternatively, the paperboard of the application can be multi-ply product, and include two, three, or more plies. Paperboard that includes more than a single-ply can be made by combining the plies either before or after drying. It is preferred, however, that a multi-ply paperboard be made by using multiple headboxes arranged sequentially in a wet-forming process, or by a baffled headbox having the capacity of receiving and then laying multiple pulp furnishes. The individual plies of a multi-ply product can be the same or different.
[0032] The paperboard of the present application can be formed using conventional papermaking machines including, for example, Rotoformer, Fourdrinier, cylinder, inclined wire Delta former, and twin-wire forming machines.
[0033] When a single-ply paperboard is used in accordance with the present invention, it is preferably homogeneous in composition. The single ply, however, may be stratified with respect to composition and have one stratum enriched with crosslinked cellulosic fibers and another stratum enriched with non-crosslinked cellulosic fibers. For example, one surface of the paperboard may be enriched with crosslinked cellulosic fibers to enhance that surface's bulk and the other surface enriched with non-crosslinked fibers to provide a smooth, denser, less porous surface.
[0034] The most economical paperboard to produce is homogeneous in composition. The crosslinked cellulosic fibers are uniformly intermixed with the regular cellulosic fibers. For example, in the headbox furnish it is preferred that the crosslinked cellulosic fibers present in high consistency slurry be present in an amount from about 25% to about 100%, and more preferably from about 30% to about 70%. In one embodiment the crosslinked cellulosic fibers are present at a level of at least 35 percent by weight of the total fiber content. In another embodiment the crosslinked fibers are present at a level of alt least 50 percent by weight of total fiber content. In yet another embodiment the crosslinked fibers are present at a level of at least 60 percent by weight of the total fiber content. In a two-ply structure, for example, the first ply may contain 100% non-crosslinked cellulosic fibers while the second ply may contain from 25% to 100% crosslinked cellulosic fibers or from 30% to 70% crosslinked cellulosic fibers. In a three-ply layer, for example, the bottom and top layers may comprise 100% of non-crosslinked cellulosic fibers while the middle layer contains from about 25% to about 100% and preferably from about 30% to about 70% of crosslinked cellulosic fibers. When crosslinked cellulosic fibers are used in paperboard in accordance with the present invention, it has been found that the paperboard exiting the papermaking machine can be compressed to varying degrees to adjust the temperature drop characteristics across the paperboard. The paperboard once leaving the papermaking machine may be compressed or reduced in caliper by up to 50%, and more preferably, from 15% to 25%. This same result can be achieved by lowering the basis weight of the paperboard.
[0035] The paperboard of the present application can be utilized to make a variety of structures, particularly containers, in which it is desired to have insulating characteristics. One of the most common of these containers is the ubiquitous hot cup utilized for hot beverages such as coffee, tea, and the like. Other insulating containers such as the ordinary paper plate can also incorporate the paperboard of the present invention. Also, carry-out containers conventionally produced of paperboard or of foam material can also employ the paperboard of the present invention. FIG. 6 shows a wall section of a hot cup type container produced which may comprise one or more plies 62 and 64 , one of which, in this instance, 64 , contains crosslinked cellulosic fibers. In this embodiment the crosslinked cellulosic fibers are in the interior ply 64 . A liquid impervious backing is preferably extruded or poly coated to the interior ply coated to the. The backing may comprise, for example, a variety of thermoplastic materials, such as polyethylene. It is preferred that the paperboard used in the bottom of the cup contain no bulky fibers.
EXAMPLES 1-9
[0036] High consistency slurries were prepared at a 3.2 percent consistency containing 50 to 65 percent by weight citric acid crosslinked cellulosic fibers. The crosslinked fiber was deflaked with a standard Beloit Jones refiner with a zero load. Douglas Fir cellulosic fibers were used as the other component in the high consistency slurry. In some cases the Douglas Fir was refined to 650 CSF. A screen hole size of 2 mm was used in all cases. A rotor with six foils, a bump rotor and a lobed rotor, all well known in the art and manufactured by GL&V, Watertown, N.Y., were used in the screen for different trials. Trials were conducted on a pilot screen machine at GL&V, Watertown, N.Y., that allowed stock to be recirculated through the unit back to the screen tank pump. Flow rates ranged from approximately 3785 l/m (1000 gpm) to 5678 l/m (1500 gpm). Fiber reject rates were run at 10 to 13 percent.
[0000] TABLE 1 Screen Trials Condi- Deflaked Basket tion HBA Consistency Doug Fir Hole size, mm Rotor 2 53% 1% non- 2 6 foils refined 1 53% 3.2% non- 2 6 foils refined 3 60% 3.2% non- 2 bump refined 4 60% 3.2% non- 2 lobed refined 5 60% 3.2% non- 2 lobed refined 6 60% 3.2% non- 2 lobed refined 7 60% 3.2% non- 2 lobed refined 8 65% 3.2% 650 CSF 2 lobed 9 65% 3.2% 650 CSF 2 lobed
Condition 2 ran well at 10 percent reject rates and feed rates of 3255 l/m (860 gpm) to 5300 l/m (1400 gpm). Condition 1 ran at a reject rate of 17% but when the reject rate was reduced, the reject line plugged into the center of the screen basket with thick stock.
Condition 3 was run with GL&V's barracuda rotor, a bump rotor, in a random pattern. The run was started with a full reject line but as soon as the accepts line was opened, the flow started to fall off due to stock thickening. The rotor is noted for tendency to fractionate fiber.
[0037] All the remaining runs ran well as follows:
[0000] Condition 4, the run was made with an 11% reject rate, 0.14 kPa (3 lb) differential pressure to the screen and a rotor speed of 900 RPM. Increasing the rotor speed to 1000 RPM had no impact.
Condition 5, the rotor speed was dropped to 800 RPM, at this point the reject flow started to drop off and the rotor speed was returned to 900.
Condition 6 was the same as condition 4.
Condition 7. The inlet pressure was increased 0.48 kPa (10 lb), feed flow increased from 900 GPM to 4164 l/m (1100 GPM) and the differential pressure increased to 0.17 (3.5 lb). This condition ran well.
Condition 8 was run at a reject rate of 15% with a 3123 l/m (825 GPM) feed flow rate.
Condition 9 was run at a at 13% reject rate with a 3785 l/m (1000 GPM) feed flow rate. Theses results indicate that screening at 3.2% consistency and 50% to 65% HBA was successful with a lobed style rotor design.
[0038] Fiber samples were obtained from the feed stock, the accepts line and the reject line and microscopically analyzed for fiber content. The results, shown in Table 2, indicate that, using various rotor and the 2 mm screen hole size, there was no selective fractionation of the crosslinked fiber.
[0000]
TABLE 2
Microstructure - Screen Slush Samples
Bleached Softwood
Rotor Type
Condition
Kraft %
Crosslinked fiber, %
Lobed, F
9
40
60
Lobed, A
9
35
65
Lobed, R
9
38
62
6 Foils, F
1
46
54
6 Foils, A
1
44
56
6 Foils, R
1
45
55
6 Foils, F
2
41
59
6 Foils, A
2
41
59
6 Foils, R
2
46
54
Bump, F
3
39
61
Bump, A
3
39
61
Bump, R
3
38
62
F, feed stock; A, Accepts; R, Rejects
EXAMPLE 10
[0039] A 3 to 3.2 percent high consistency slurry was prepared containing 40 percent by weight crosslinked cellulosic fibers; Douglas Fir wet lap was used as the regular fiber. A screen with a 4 mm hole diameter and a six foil rotor was used prior to the mid ply headbox. A separate slurry containing only Douglas Fir or Pine fibers was refined to 500 CSF and diluted to 0.5 percent consistency prior to pumping the slurry to the outer headboxes. A paperboard was formed on a 500 cm paperboard machine.
EXAMPLE 11
[0040] A 3 to 3.2 percent high consistency slurry is prepared containing 40 percent by weight crosslinked cellulosic fibers; Douglas Fir wet lap is used as the regular fiber. A screen with a 2 mm hole diameter equipped with a lobed rotor is used prior to the mid-ply headbox. A separate slurry containing only Douglas Fir or Pine fibers is refined to 500 CSF and diluted to 0.5 percent consistency prior to pumping the slurry to the outer headboxes. A paperboard is formed on a 500 cm paperboard machine.
EXAMPLE 12
[0041] A 3 to 3.2 percent high consistency slurry is prepared containing 50 percent by weight crosslinked cellulosic fibers; Douglas Fir wet lap is used as the regular fiber. A screen with a 2 mm hole diameter equipped with a lobed rotor is used prior to the mid-ply headbox. A separate slurry containing only Douglas Fir or Pine fibers is refined to 500 CSF and diluted to 0.5 percent consistency prior to pumping the slurry to the outer headboxes. A paperboard is formed on a 500 cm paperboard machine.
EXAMPLE 13
[0042] A 3 to 3.2 percent high consistency slurry is prepared containing 55 percent by weight crosslinked cellulosic fibers; Douglas Fir wet lap is used as the regular fiber. A screen with a 2 mm hole diameter equipped with a lobed rotor is used prior to the mid-ply headbox. A separate slurry containing only Douglas Fir or Pine fibers is refined to 500 CSF and diluted to 0.5 percent consistency prior to pumping the slurry to the outer headboxes. A paperboard is formed on a 500 cm paperboard machine
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A process is described for manufacturing a paperboard from a high consistency slurry containing high levels of crosslinked cellulosic fibers by dispersing the fibers in a screen with a rotor in the screen and then passing the fibers through the screen basket with a hole diameter of at least 2 mm and forming the cellulosic fibers on a foraminous support. Another slurry of regular cellulosic fibers is deposited on at least one side of the first slurry during the formation process. The formed web is dewatered and dried.
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CROSS-REFERENCES TO RELATED APPLICATIONS
This application is a divisional application to the commonly assigned, copending United States Application Ser. No. 06/833,987, filed Feb. 26, 1986, entitled "TREATMENT OF COTTON", now U.S. Pat. No. 4,796,334; this application is related also to the commonly assigned, copending U.S. application Ser. No. 07/207,252, filed June 15, 1988, entitled "TREATMENT OF COTTON", and which application is a continuation application to the aforementioned parent application, namely U.S. application No. 06/833,987.
BACKGROUND OF THE INVENTION
The present invention relates to a new and improved method of processing cotton.
Sticky contaminants, resulting from a variety of insects, and especially from the white fly (Bamessia), for instance, are frequently present on cotton when this is picked. Such contaminants, generally referred to as "honeydew" renders the cotton or cotton fibers sticky, and this causes severe problems, especially during the drawing of cotton slivers: as these pass through the conventional pairs of rollers, the honeydew causes adhesion to these rollers, further cotton fibers become attached and the end-result is a work stoppage and the necessity to clean the rollers. This results in a lack of uniformity of the slivers and yarns which are produced, in serious time losses and increase of production costs with a reduction in the quality of the product.
It is known, for example, from a publication by 0. Elsner, entitled "Der Nachweis von Zuckerablagerungen auf Baumwolle"(The detection of carbohydrate deposits on cotton), published in the journal "Textilbetrieb" in the issue of December 1982, pages 22 through 24, that honeydew containing cotton, when heated in laboratory tests in a stationary manner at 130° C. for about 2 hours, becomes discolored due to honeydew caramelization and assumes a yellow to yellowish brown color.
Although the quantity of such honeydew quantified by the content of reducing sugars contained therein, is generally quite low (of the order of 0.1 to 1.5 per cent by weight), it causes serious problems during the various steps of the processing of cotton or cotton fiber, and especially during a spinning process. The present invention overcomes to a large extent the problems caused by such adhesive substances and renders them harmless.
The contamination of cotton with honeydew or the like causes serious problems in the processing of cotton or cotton fibers at various stages of the processing of such cotton or cotton fibers.
It is clear that the inventive method is applicable at any of the stages of the processing of the cotton or cotton fibers, and an early stage is of course advantageous.
Serious problems are generally encountered with such contaminated cotton or cotton fibers, particularly during the processing of cotton slivers on a draw frame. For the spinning process of cotton, a web is formed on a carding machine. Separation of fiber tufts into individual fibers and forming the web are done on a revolving flat card, which is a particular type of carding machine. After leaving the card, the web is pulled through a funnel-shaped hole and thus there is formed a so-called card sliver. To produce a yarn, the sliver has to be attenuated, possibly combed and finally twisted. Six to eight slivers are fed to a draw frame, and these are drawn into one, and this operation is accompanied by attenuation or drafting.
SUMMARY OF THE INVENTION
Therefore with the foregoing in mind it is a primary object of the present invention to provide a new and improved method of processing cotton and which method permits at least partially eliminating the problems which are caused by the presence of sticky materials like honeydew and the like at the cotton.
Another and more specific object of the present invention is directed to providing a new and improved method of processing cotton and which method permits at least partially removing sticky materials such as honeydew and the like from the cotton.
A further significant object of the present invention is directed to a new and improved method of processing cotton, and which method permits at least partially removing sticky materials like honeydew and the like, and can be readily integrated into existing processes for processing cotton.
Another, still important object of the present invention relates to a new and improved method of processing cotton and which method permits at least partially removing sticky materials like honeydew and the like, and is capable of being integrated at an early stage into existing processes for processing cotton.
Still another significant object of the present invention is directed to the provision of a new and improved method of processing cotton, and which method permits at least partially removing sticky materials like honeydew and the like, and can be carried out in a continuous manner.
Yet, a further significant object of the present invention aims at providing a new and improved method of processing cotton and which method permits at least partially removing sticky materials like honeydew and the like, and is carried out in a relatively simple and extremely economical manner, is highly reliable, not readily subject to breakdown or malfunction and requires a minimum of maintenance and servicing operations.
Now in order to implement these and still further objects of the invention, which will become more readily apparent as the description proceeds, the method of the present development is manifested, among other things, by the features that, cotton is exposed to a heat source having a predetermined temperature and is heated to a preselected maximum temperature during exposure to such heat source. The cotton is exposed to the heat source for a predetermined period of time sufficient for transforming sticky material such as honeydew and the like which is adhered to the cotton, to a hard and brittle, readily removable material.
It has been discovered that by subjecting cotton or cotton fibers to a controlled heating process preferably to a maximum of about 140° C. during a controlled period of time of a maximum of 10 seconds, and advantageously up to about 5 seconds with cotton slivers, honeydew droplets and the like can be rendered brittle and hard losing their adhesive properties without adversely affecting the cotton quality. The heating may be effected at any step of the entire process for processing cotton, but preferably before the drawing of the cotton slivers on the draw frame, as at this stage the most serious problems occur.
A further step of the inventive method may comprise separating the brittle drops from the cotton or cotton fibers.
There are provided simple devices, e.g. comprising a number of rotatory rollers, the surface temperature of which is maintained at a predetermined value, means being provided for passing the cotton sliver over such heated rollers so as to maintain contact for an adequate period of time to convert the sticky material to hard and brittle particles.
The heating process can be effected at any stage of the processing of cotton fibers. It has been found that when the cotton or cotton fibers is heated so as to reach a temperature of about 70° to 140° C., and maintained at such temperature for an adequate period of time, adhering honeydew droplets are converted to hard and brittle particles. The overall heating time of the cotton or cotton fibers is about 1/2 to about 5 seconds for cotton slivers and up to 10 seconds for cotton bales (upper surface), and such heating substantially reduces the stickiness of the fibers or eliminates it altogether.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein throughout the various figures of the drawings, there have been generally used the same reference characters to denote the same or analogous components and wherein:
FIG. 1 is a perspective view of a device used in combination with a conventional drawing frame for carrying out a first exemplary embodiment of the inventive method for processing cotton fiber slivers;
FIG. 2 is a perspective side-view of part of a device of the type as shown in FIG. 1 and containing three heated rollers;
FIG. 3 is a perspective view of three heatable rollers and illustrates exemplary details of the heating means;
FIG. 4 illustrates constructional details of the three-roller system as shown in FIG. 2;
FIG. 5 is an elevational sectional view of a further roller system for carrying out the first exemplary embodiment of the inventive method for processing cotton fiber sliver; and
FIG. 6 is a perspective side-view of a device for carrying out a second exemplary embodiment of the inventive method for processing cotton bales.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Describing now the drawings, it is to be understood that only enough of the construction of a cotton processing device has been shown as needed for those skilled in the art to readily understand the method of treating cotton and the underlying principles and concepts of the present development, while simplifying the showing of the drawings. Turning attention now specifically to FIG. 1 of the drawings, the device illustrated therein by way of example and not limitation will be seen to comprise a device for processing cotton, and containing, for example, the conventional draw frame 17. Precedingly of the conventional draw frame 17, there are arranged six cans 12. Cotton slivers 11 are drawn from the six cans 12 and over a flat surface 13 under a roller 14, through heatable rotatory rollers 15 and 16, and from these to the conventional draw frame 17. The conventional draw frame 17 comprises 4 roller pairs 18, 19, 20 and 22, from which the resulting cotton sliver 23 is drawn into the container 24.
The rollers 15 and 16 are provided with internal electrical heating means which are provided with heat control means, so that the surface temperature of the rollers 15 and 16 can be adjusted to any predetermined value. Various experiments have shown that generally surface temperatures of from about 150° C. and to about 230° C. are satisfactory. When carrying out a first exemplary embodiment of the inventive method, the cotton slivers 11 are pressed or passed over the said rollers 15 and 16 at a speed of about 30 m/min (or 50 cm/sec). The cotton slivers 11 tested were 4 g/m sticky cotton, contaminated with considerable quantities of honeydew. The contact length of the cotton slivers 11 with the rollers was a total of about 55 cm and the cotton slivers 11 were heated during this period of time in such manner that it reached a temperature of about 75° C. The heating to this temperature for the contact time indicated, was adequate to render the adhesive droplets hard and brittle. When the conventional device was used without this attachment, the cotton slivers stuck to the roller pairs and caused serious problems.
When the rollers 15 and 16 are heated to a higher temperature, the time of contact can be decreased.
Details of a three-roller system is shown in FIG. 3 and such three-roller system can be used in conjunction with, for example, a conventional draw frame substantially in the manner as illustrated in FIG. 1 for carrying out the first exemplary embodiment of the inventive method. The rollers 21, 22 and 23 are provided with internal electrical heating coils and with electrical leads for connection with a power source. Heating of the electrical resistance elements results in a predetermined surface temperature of the rollers 21, 22 and 23 and such surface temperature may be automatically maintained within a narrow range by means of a thermostat. The heatable rollers 21, 22 and 23 are followed by a first pair of rollers of which 24 and 25, are shown.
The dimensions of the heatable rollers 21, 22 and 23, and the configuration of these rollers are shown in detail in FIG. 4. The heatable rollers 21, 22 and 23 have each a diameter of 85 mm and the distance between the surfaces of these rollers is 30 mm. The total length of contact from the points A to B, plus C to D and plus E to F, of the heatable rollers 21, 22 and 23 with the cotton sliver 11 moving in the direction designated by the reference character M, is about 55 cm. Heating of the cotton sliver 11 to a minimum temperature of 70° C. at a velocity of 30 m/sec renders the adhering honeydew droplets brittle and hard. When the cotton sliver 11 is moved at a higher velocity there must be used a higher surface temperature and/or a longer path of contact with the heated surfaces.
The further processing of the cotton slivers does not cause any problems. The hard droplets are subsequently crushed to powder or to small particles, and can be sucked off as exemplified by the suction device 100 constituting one possible form of separating means for the hard honeydew droplets. No adverse effect was observed as regards cotton quality or color. It is generally advisable to allow the cotton to attain equilibrium with ambient humidity before further processing.
It should be clear that the aforedescribed rollers also may be heated using hot air or hot liquid and that any combination of heat conduction, convection and radiation may be used in the heating process.
As shown in FIG. 5, there is provided a further roller system for carrying out the first exemplary embodiment of the inventive method. Specifically, the roller system comprises four heatable rollers 51, 52, 53 and 54, each of which is provided with a heating element (not shown) which maintains a predetermined and preselected surface temperature at the rollers 51, 52, 53 and 54 during operation. As shown, the system comprises a support frame 55 on which there are mounted the heatable rollers 53 and 54, whereas the rollers 51 and 52 are mounted on a movable frame 56.
When the movable frame 56 is in the position indicated by the reference character A, the cotton sliver 57, from container 58, passes essentially in contact with half the circumference of each one of the rollers 51 to 54, as shown in FIG. 5, and through roller pairs 59 and 60, which are synchronized with the heatable other rollers 51 to 54. In this arrangement the cotton sliver 57 takes the configuration shown by the full line. When for any reason the process is to be interrupted, for example, in order to prevent overheating, the movable frame 56 is moved towards the right into the position indicated by dashed lines and the reference character A'. The cotton sliver, then, takes the configuration indicated by the further dashed line and such cotton sliver 57' is out of contact with any heated surface. This movement can automatically be actuated whenever the process is to be temporarily interrupted. When treatment of the cotton sliver is to be resumed, the device is actuated and the right-hand-side rollers 51 and 52 move again to the position adjacent to the left-hand rollers 53 and 54, which takes a few seconds. Only after the rollers 51 to 54 have again reached the full-line original position, the movement of the cotton sliver 57 is actuated.
It is, of course, possible to use any number of heatable rollers, from three on upwards, with at least one being located on the right-hand side or movable frame.
In the roller system shown in FIG. 5, the surface temperature of the heatable rollers 51 to 54 does not differ from the surface temperature set out in the other roller system described hereinbefore, and also the period of time during which the cotton sliver 57 is in touch or contact with the heated rollers 51 to 54 is not different.
A further system illustrated in FIG. 6 serves to carry out a second exemplary embodiment of the inventive method for processing cotton bales 63.
Raw cotton is supplied in the form of cotton bales 63, and a movable flock or tuft detaching machine is used in order to gradually remove the cotton in the form of flocks or tufts 62. The flocks or tufts 62 are removed by means of a detaching machine in the form of a wheel 61 during a plurality of passes over the cotton bales 63 which are arranged in line. Thus there is also obtained a homogenous blend from the plurality of cotton bales 63, resulting in a uniform product. The thickness of the cotton layer which is removed during each pass, can be preselected within a rather wide range. The flocks or tufts 62 are sucked or drawn away by a vacuum system (not shown) into a further stage of processing.
The wheel 61 is provided with a plurality of teeth or other structures for plucking the flocks or tufts 62 and rotates so as to remove the flocks or tufts 62 of cotton as the device passes over the bales 63 of cotton, the flock or tufts 62 being sucked by means of the vacuum system into a section 64. According to the invention, there are provided plate-like heating devices 65 and 66 containing heating means adapted to maintain the surface of the plate-like heating devices 65 and 66 in contact with the cotton at a predetermined and preselected temperature as the device moves over the cotton bales 63. When the device moves from left to right, the plate-like heating device 65 is heated, and when the movement is in the opposite direction, the plate-like heating device 66 is heated. The contact of the plate-like heating devices 65 and 66 with the upper layer of the cotton bales 63 is such that it renders the honeydew particles or droplets brittle and hard.
Advantageously, both the plate-like heating devices 65 and 66 are heated to the treatment surface temperature during passage of the flock or tuft detaching machine over the cotton bales 63.
The illustrated flock or tuft detaching machine containing the plate-like heating devices 65 and 66 may be used in addition to the aforedescribed heated-roller devices or may be used, to a large extent, instead of the aforedescribed heated-roller devices.
It should be clear that the inventive method can be effected before the blending of the cotton slivers to a single cotton sliver on a draw frame like, for example, the conventional draw frame 17. However, the inventive method may also be brought into effect at any preceding stage of the processing of the cotton.
It should also be clear that the heating can be effected after ginning, at the ginning stage, at the spinning mill, or any other desired cotton processing stage, particularly to a temperature of above 70° C. by using various heating means such as, for example, hot air, IR heating or the like, as set out above. In fact, the inventive method is intended to encompass any steps adequate to heat-treat cotton or cotton fibers before or during processing at the spinning mill. This heat treatment results in converting or transforming the adhesive sticky honeydew droplets into a hard and brittle form. The devices for heating the upper surfaces of cotton bales can also be provided as separate entities, to be used in conjunction with flock or tuft detaching machines. The hard and brittle droplets are generally crushed to small particles or powder as the cotton slivers pass through the draw frames, or they can be passed through a pair of crushing rollers. Such particles and powder is advantageously removed by a vacuum suction system.
It is clear that various changes and modifications of devices suitable for such heating can be resorted to without departing from the scope and spirit of the present invention.
While there are shown and described present preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto, but may be otherwise variously embodied and practiced within the scope of the following claims.
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The invention relates to a process for rendering harmless sticky material adhering to cotton or cotton fibers, termed "honeydew". According to the process the cotton or cotton fibers is heated for a brief period of time to a temperature adequate to render said honeydew hard and brittle, and this without adversely affecting the cotton or cotton fibers. There are also provided means for effecting such treatment of the cotton fibers in a continuous manner.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention is directed to an X-ray installation of the type having a radiation source and a radiation receiver in the form of a solid state detector, and a central control device.
[0003] 2. Description of the Prior Art
[0004] X-ray installations of the above general type are well known and particularly serve for the implementation of medical examinations. Solid-state detectors for X-ray imaging have been known for a number of years. Such a detector is based on an active read-out matrix, for example, composed of amorphous silicon (a-Si). The image information is converted in an X-ray converter, for example caesium iodide (CsI), and is stored as electrical charge in the photodiodes of the read-out matrix, and is subsequently read out via an active switch element having dedicated electronics and is converted from analog form to digital form. Such solid-state detectors are employed as flat image detectors in, for example, projection radiography mammography and angiography/cardiology.
[0005] For critical-care X-ray diagnostic applications such as, for example, X-ray diagnostic examination of bed-ridden patients, for example to obtain lung exposures, etc., or in the field of trauma diagnostics, film-foil systems and storage foil systems are currently utilized rather than solid-state detectors. This is particularly due to the simple handling of the cassettes. The cassettes are introduced into rack compartments that are arranged under the patient table. A solid-state detector, by contrast, requires a variety of cable connections (data transfer, communication, voltage supply) and therefore has conventionally been considered ill-suited for these applications.
SUMMARY OF THE INVENTION
[0006] An object of the present invention is to provide an X-ray installation having a solid-state detector that is suitable for such critical-care application situations as well:
[0007] This object is inventively achieved in an X-ray installation of the type initially described wherein a transportable radiation receiver communicates for information transmission via a wireless communication link with a mobile control unit.
[0008] The invention thus provides a transportable, small-format and portable radiation receiver which can be positioned independently (i.e., without any mechanical or electrical connections for information transmission) from the other installation components (for example, a C-arm at which the radiation source and the radiation receiver are ordinarily arranged). This radiation receiver thus can be unproblemmatically placed or brought to positions or into positions that could not be assumed if it were a component of a known, rigid system.
[0009] Moreover, in accordance with the invention the radiation receiver wirelessly communicates with the control device, i.e. the signal transmission of the image signals registered with the radiation receiver to the control device, that receives these and processes them in the desired fashion, no longer ensues via cables as in the prior art, but instead, ensues wirelessly. All cable connections, that are complicated and are usually in the way and prevent an arbitrary positioning of the radiation receiver relative to the control device, thus are eliminated. The radiation receiver, consequently, can be moved in space without limitation as to the degrees of freedom, and critical-care and emergency exposure situations can consequently be easily covered. Due to the elimination of the cables, the technician or physician can be positioned and work without impediments. This produces the important advantage that the same digital-generating technology can be employed as in those applications wherein the cables do not represent problems. It is thus no longer necessary to keep specific film-foil systems or storage foil systems as well as the appertaining peripheral devices on hand for these specific applications. This is particularly advantageous for clinical applications since any arbitrary exposure situation can be processed with one system.
[0010] Transmission and reception units for a bidirectional communication are advantageously provided at the radiation receiver and at the control device, respectively. Corresponding control signals for input of an operating status, the implementation of a reset, synchronization with the radiation source, etc., can be provided via the control device to the electronics integrated in the radiation receiver, and the radiation receiver can in turn provide corresponding answerbacks. After the image registration has ensued, the image signals that have been read out and converted are transmitted wirelessly from the radiation receiver to the control device.
[0011] In an embodiment of the invention, the wireless communication is a radio connection, with the transmission and reception units fashioned for the transmission of the signals in the form of blue tooth signals or DECT signals. However, any mobile radio telephone technique is suitable that enables a complete and fast transmission of the relevant signals between the transmission and reception units.
[0012] Alternatively, the transmission and reception units can be fashioned for optical signal transmission. This, for example, can ensue by means of an infrared transmitter and receiver. Any optical transmission technique can be utilized that enables a dependable and fast signal transmission, and thus data transmission.
[0013] It is possible to provide a mains plug cable (power input) or connection receptacle for a mains plug cable at the radiation receiver as the only cable connection. It is preferable, however, to provide an integrated power supply at the radiation receiver, i.e. so that it completely independent from a hard wired supply network. This allows the most complete application and positioning freedom of the radiation receiver. The integrated power supply can be formed by one or more batteries, but accumulators are preferable for economic reasons.
[0014] When accumulators are employed, it is expedient when a charging station is provided to which the radiation receiver can be connected as needed for charging the accumulators. This charging station is expediently provided directly at the X-ray installation, for example, at the central control device. When the accumulators are depleted, which can be indicated by suitable display means at the radiation receiver (for example, light-emitting diodes or sound generators, etc.) or by a corresponding display means at the control device, then the radiation receiver is merely placed in the charging station, where the accumulators are automatically charged.
[0015] Alternatively or additionally, components for the inductive or capacitive feed of the supply voltage can be provided at the radiation receiver. These provide a supply voltage when, for example, an external magnetic field is adjacent thereto, which may be generated by suitable field generation devices.
[0016] In addition to an integrated power supply and/or the components for capacitative or inductive feed, further, a detachable connection for connecting the radiation receiver to a supply network can be provided as warranted. Preferably only one connecting socket is provided at the radiation receiver for this purpose, so that the connection can be unplugged as needed. This has the advantage that the radiation receiver can be unproblemmatically operated via the supply network in situations where a mains cable is not a disturbing factor. This is also possible for application of the radiation receiver with a prone patient, since suitable sockets are usually provided at patient support tables.
[0017] Alternatively, the radiation receiver with an integrated power supply or components for the inductive or capacitative feed can be introduced into a drawer of a Bucky table, i.e. a patient support table equipped with a Bucky drawer, and can be detachably connected to an external power supply upon introduction thereinto. This embodiment of the invention allows known Bucky tables to be employed that have proven to be practical in use, for example for lung exposures of a patient's bed, whereby the radiation receiver is merely introduced into the drawer and is pushed under the patient. When a connection to an external power supply is thereby made at the same time, then it is possible to operate the radiation receiver via the external power supply given this application. When the radiation receiver is taken from the drawer, then it is expedient for it to automatically switch to a mode upon removal wherein, for example, it is supplied via the integrated power supply. A charging station for charging accumulators of the introduced radiation receiver also can be provided in the drawer of the table. These accumulators, however, can be directly charged via the external power supply as an alternative. In any case, a corresponding connection is provided at the radiation receiver for coupling the radiation receiver to the charging station or the external power supply.
DESCRIPTION OF THE DRAWINGS
[0018] [0018]FIG. 1 is a schematic illustration of an inventive X-ray installation in a first embodiment.
[0019] [0019]FIG. 2 is a schematic illustration of a radiation receiver in accordance with the invention.
[0020] [0020]FIG. 3 is a schematic illustration of an inventive X-ray installation in a second embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0021] [0021]FIG. 1 shows an inventive X-ray installation 1 having a central control device 2 as well as a radiation source 4 arranged at a bracket 3 . The radiation source 4 has a transportable radiation receiver 5 that can be positioned remote from the central control device 2 . X-ray images of a patient 6 , who lies on a patient table 7 here, are registered by the radiation receivers in a known way.
[0022] The control device 2 has a transmission and reception unit 8 , and a corresponding transmission and reception unit 9 is provided at the radiation receivers. Both transmission and reception units 8 , 9 are fashioned as radio devices that communicate with one another, preferably bidirectionally, via blue tooth signals or corresponding interfaces.
[0023] When, after positioning of the movable control device 2 and the radiation source 4 shown in the exemplary embodiment, an X-ray beam is applied to the patient 6 , then corresponding, digital electrical signals that are available pixel-by-pixel are obtained in the radiation receiver 5 , which is a known solid state radiation detector. Such solid-state detectors are known and their structure and function therefore need not be discussed in greater detail. The individual pixel-specific signals are then sent with the unit 9 acting as a transmitter to the unit 8 of the control device 2 acting as a receiver, where the signals are received and further-processed.
[0024] No disturbing cables are present since the radiation receiver 5 communicates wirelessly with the control device 2 . As a result, it is unproblemmatically possible to place the radiation receiver 5 under a patient or, as in the example shown in FIG. 1, in a drawer 10 of the patient table 7 fashioned as a Bucky table. In addition (see FIG. 3), arbitrary other employment possibilities are possible. In the example shown in FIG. 3, the radiation receiver 5 is positioned, for example, under the calves; the radiation source 4 arranged at the ceiling is positioned opposite thereto. Here as well, communication ensues between the control device 2 and the radiation receiver 5 via corresponding transmission and reception units 8 , 9 .
[0025] [0025]FIG. 2 shows the radiation receiver 5 in a schematic illustration. In addition to the upper, active region 11 wherein the scintilator, the pixel matrix and the read-out electronics, etc., are provided, the receiver also contains the transmission and reception unit 9 as well as an integrated power supply 12 , which is formed by accumulators in the illustrated exemplary embodiment. These accumulators can be recharged in a charging station 13 at the central control device 2 . When the radiation receiver is not in use, this is simply introduced into the charging station 13 , as illustrated with the radiation receiver 5 indicated with broken lines. Via a suitable connector 14 , an electrical connection is automatically produced between the integrated power supply 12 and the charging station 13 , so that the accumulators are charged.
[0026] Alternatively or in addition, an electrical contact to an external power supply can be produced via the connection means 14 , i.e. a mains cable can be connected as needed to the connector 14 , to supply the supply voltage needed for the operation of the radiation receiver. The receiver can be used with a hard wired voltage supply, for example, as illustrated in FIG. 3. It is also possible to connect the radiation receiver 5 , introduced into the drawer 10 , with a supply terminal provided thereat via the connector 14 in FIG. 1, the radiation receiver 5 being then operated via this supply terminal or the integrated accumulators being able to be charged from this terminal.
[0027] As described, the transmission and reception units 8 , 9 are fashioned as radio units. Expediently, blue tooth signals or DECT signals are employed. As an alternative, the transmission and reception units 8 , 9 can be optical transmission and reception units, for example for the transmission of infrared signals. It is important that a bidirectional signal transfer ensues so that the transmission and reception unit 8 at the control device 2 can provide suitable control instructions to the radiation receiver 5 in order, for example, to activate it or to implement a reset before the image registration, and in order to receive corresponding answerbacks or to enable the image signal transfer to the control device 2 .
[0028] Although modifications and changes may be suggested by those skilled in the art, it is the intention of the inventor to embody within the patent warranted hereon all changes and modifications as reasonably and properly come within the scope of his contribution to the art.
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An X-ray installation has a radiation source and a transportable radiation receiver in the form of a solid state detector, and a mobile central control device, the transportable radiation receiver communicates for information transmission via a wireless communication link.
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This application is a continuation-in-part of U.S. patent application Ser. No. 08/978,759 filed Nov. 26, 1997 now U.S. Pat. No. 5,973,192.
BACKGROUND OF THE INVENTION
The present invention is directed to thioglycerol derivatives and their preparation, the derivatives having utility in optical materials such as lenses.
Plastic lenses for use in eyeglasses and cameras have become widespread in view of their lightweight, durability, dyeability and workability as compared to conventional glass lenses. Resin compositions suitable for the manufacture of optical lenses must possess certain characteristics, including a high refractive index, high surface accuracy, low dispersion properties and good heat resistance, impact resistance and scratch resistance. Diethylene glycol bis(allylcarbonate (DAC) and polycarbonates have conventionally been used for plastic lenses. Lenses made of DAC, however, have lower refractive indices than lenses made of glass of a corresponding overall thickness, and therefore do not perform as well in this regard.
U.S. Pat. Nos. 4,775,733 and 5,191,055 disclose polyurethane lenses made of a polymer between a xylylene diisocyanate compound and a polythiol compound having a higher refractive index than lenses made from DAC. However, such lenses generally suffer from poor heat resistance, hindering the ability to use high temperatures during heat treatment processing steps.
It therefore would be desirable to develop compositions for use in making optical materials that do not suffer from the various drawbacks mentioned above, and that have good machinability and processability.
SUMMARY OF THE INVENTION
The problems of the prior art have been overcome by the present invention, which provides novel thioglycerol derivatives, processes for their manufacture, and optical materials made from such compounds. The thioglycerol derivatives have high concentrations of sulfur relative to compounds conventionally used for optical materials, and thus exhibit high refractive indices without sacrificing important properties such as processability.
DETAILED DESCRIPTION OF THE INVENTION
Thioglycerol (HSCH 2 CH(OH)CH 2 OH) and 1,3-dimercapto-2-propanol are the bases of the compounds of the present invention. They can be conveniently esterified with common mercaptoacids of the formula HS(CH 2 ) n COOH wherein n is from 1 to 5, including thioglycolic acid, 3-mercaptopropionic acid, etc., to form compounds having the following generic formula: ##STR1## wherein X is --SH or X═--SH, ##STR2## and n is from 1 to 5. Those skilled in the art will appreciate that as the chain length of the mercapto acid increases (i.e., as n increases from 1 to 5 and beyond), the percent sulfur in the composition decreases, thereby decreasing the refractive index of the resulting derivative. Accordingly, esterification with thioglycolic acid is especially preferred, in particular with two equivalents of thioglycolic acid, resulting in thioglycerol bismercaptoacetate (TGBMA) having the following formula: ##STR3## In addition, the resulting TGBMA derivative can be further oxidized, such as with peroxide or other suitable oxidizing agents known to those skilled in the art, to give varying degrees of disulfide. Such disulfides, which can include dimers, trimers and oligomers, can be represented by the following generic formula: ##STR4## wherein R 1 , R 2 and R 3 may be the same or different and are independently selected from hydrogen, ##STR5## wherein R' is hydrogen or R 1 . Examples of such disulfides are shown below: ##STR6## The trimers and oligomers are formed by further oxidation of the mercaptans of the dimers. The higher molecular weight materials result in an increase in the refractive index. Moreover, as the reaction medium continues to be heated, the refractive index increases. Accordingly, one can control the refractive index by controlling the heating of the reaction. The resulting product is a complex mixture of any of the foregoing structures.
The esterified product can be washed with a suitable base, preferably ammonia or alkali metal hydroxide, such as sodium or potassium hydroxide, to remove any residual mercaptoacid. The present inventors also have found that limiting the wash step also limits the refractive index of the final product. More specifically, washing the product with base, preferably ammonia, has a drammatic effect on the refractive index. Thus, by limiting the washing step, the refractive index can be kept at a predetermined level (if the refractive index is too high, the product is not compatible with other components).
In an alternative embodiment, thioglycerol is oxidized to the corresponding disulfide with a suitable oxidizing agent: ##STR7## This resulting tetraol can be readily esterified with the aforementioned mercaptoacids to form a highly functionalized mercaptan having a sulfur content slightly higher than thioglycerol bismercaptoacetate: ##STR8##
In a further embodiment of the present invention, 1,3-dimercapto-2-propanol is esterified with thioglycolic acid to produce dimercaptopropanol mercaptoacetate. Disulfides of this mercaptoacetate can be produced by analgous procedures to those above, resulting in the following derivatives: ##STR9##
Optical materials such as lenses can be prepared from the derivatives of the present invention by conventional means. Suitable additives such as surface active agents may be used. The resulting lens may be subjected as necessary to various physical and chemical treatments such as surface polishing, treatment for antistaticity, hard coat treatment, non-reflecting coat treatment, dyeing, treatment for photochromism, etc., all well known to those skilled in the art.
The invention is further illustrated by the following non-limiting examples.
EXAMPLE 1
In a 5 liter, 3 neck roundbottom flask equipped with a magnetic stirrer, thermocouple and a distillation head with vacuum take off, is placed thioglycerol (1994.60 g, 7.78 moles) and thioglycolic acid (2332.96 g, 24.82 moles).
Methane sulfonic acid (14.16 g, 0.15 mole) is added, vacuum applied (5-10 mm Hg) and the reaction heated to 70° C. When the reaction temperature reached about 40° C., water began to distill over. The reaction was heated at 70° C. for 4-5 hours and cooled to room temperature. The reaction is then transferred to a 6 liter Erlenmeyer flask which is equipped with an overhead stirrer.
Aqueous ammonia (4218.00 g, 5%, 12.41 moles) was added and the reaction stirred for 30-45 minutes. An exotherm occurs to approximately 35-40° C. upon addition of the ammonia. This can be controlled by cooling the reaction to 10-15° C. prior to the addition of ammonia. The upper ammonia layer is then removed and the reaction washed with a 3×2 liters of water. After washing is completed, the reaction is stripped water free, either via a vacuum distillation or on the rotary evaporator to yield 1994.6 g, 69%, of TGBMA as a light yellow oil. The refractive index was 1.5825.
EXAMPLE 2
To a 250 ml, three neck flask equipped with a condenser, thermometer, magnetic stirring, and a constant addition funnel was added thioglycerol (42.00 g, 0.39 mole), water (32.40 g, 1.80 mole) and ferrous sulfate (0.02 g, 0.3 mmole). Hydrogen peroxide (42.00 g, 0.30 moles) was added slowly, maintaining a temperature of less than 50° C. Care was taken not to add the hydrogen peroxide too rapidly, thereby avoiding the accumulation of excess peroxide.
The reaction mixture was extracted with methyl isobutyl ketone to remove unreacted thioglycerol. The aqueous portion was concentrated to dryness, after testing for unreacted peroxide, resulting in 41.90 g of the disulfide product (>99% yield). The refractive index was 1.5670.
EXAMPLE 3
Dithioglycerol tetramercaptoacetate was prepared using the procedure described in Example 1 after adjusting the stoichiometry.
EXAMPLE 4
1,3-Dimercapto-2-propanol (12.8 g, 0.1 moles), thioglycolic acid (9.5 g, 0.1 moles) and methane sulfonic acid (0.13 g, 1.30 mmoles) were combined and heated to 70° C. under about 4 mm of vacuum. The reaction mixture was held at this temperature and pressure for 2-3 hours until the water was distilled from the reaction. The reaction completion can be monitored by titration for acid number.
The reaction was washed with a 3.7% aqueous ammonia followed by one or two water washed to remove the excess thioglycolic acid. The final product was stripped to dryness resulting in a 79% yield. The refractive index was 1.6200.
EXAMPLE 5
In a 5 liter, 3 neck round bottom flask equipped with a magnetic stirrer, thermocouple and a distillation head with vacuum take off, is placed thioglycerol (1000.00 g, 9.26 moles), thioglycolic acid (1874.07 g, 20.37 moles) and methane sulfonic acid (11.52 g, 0.12 moles). Vacuum is applied (5-10 mm Hg) and the reaction heated to 70° C. The reaction was heated at 70° C. for 3-4 hours at which time the crude refractive index is 1.5500. After additional heating for 2-3 hours, which raises the crude refractive index to 1.5610, the reaction is cooled and transferred to a 6 liter Erlenmeyer flask equipped with an overhead stirrer.
Aqueous ammonima (2361.3 g, 5%, 6.95 moles) was added to the Erlenmeyer flask and the reaction stirred for 30-60 minutes. An exotherm occurs to approximately 35-40° C. upon addition of ammonia, Cooling the reaction to 10-15° C. prior to ammonia addition can control the exotherm. The upper ammonia layer is then removed and the reaction washed with 3×2 liters of water. After washing is completed, the reaction is stripped water free, either by vacuum distillation or rotary evaporator to yield 1777.9 g, 75% of TGBMA as a light yellow oil. The refractive index has now increased to 1.5825 from the crude refractive index of 1.5610.
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Novel thioglycerol derivatives, processes for their manufacture, and optical materials made from such compounds. The thioglycerol derivatives have high concentrations of sulfur relative to compounds conventionally used for optical materials, and thus exhibit high refractive indices without sacrificing processability.
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BACKGROUND OF THE INVENTION
As urban growth occurs over time, a situation often arises where major arterial routes, especially freeways, become the hub of an infrastructure such that the immediately surrounding land is seen as best suited for developments such as high rise office towers, apartments, shopping centers and other commercial uses. Special zoning is often established for these “preferred development districts”.
Urban planners recognize that the land use in a preferred development district is typically a mix, including many business that have been at the same location for years and that don't require the new infrastructure. Such businesses will be referred to as “land-and-one-story businesses”, because their operation can typically be most economically conducted using land and one story buildings. Although at some point the business owners may realize the benefit from their land value appreciation, the overall land value appreciation in a preferred development district may actually do land-and-one-story business owners more harm than good, for the following reasons. First, it is often difficult to gain approval for improvements to property in a preferred development district. Because everything on a property will typically be leveled when a development project is undertaken, development authorities do not want to authorize nontransferable improvements because they will drive up the cost of property for developers, delaying preferred development. Second, land-and-one-story business owners are often faced with limited or no possibility of expansion at their current location, due both to the high cost of adjacent land, and due to restrictions placed on land use in preferred development districts.
If a land-and-one-story business decides to relocate, the business may find that their current property is of low overall market value, for the following reasons. First, the constraints described above will be faced by any new owner. Second, many people are reluctant to locate a business on property that may be absorbed into a large development project at any time. Third, because the properties of many land-and-one-story businesses have odd, irregular buildings, often built for a specialized purpose, often with a variety of aesthetic, code and regulatory problems, and often with a high percentage of open land, the total rental income such properties can generate is often relatively low, even if rental income per square foot for uses such as warehouse is relatively high. Because redevelopment may not occur for a decade or more, low rental value will significantly depress the market value of a land-and-one-story property.
PURPOSES OF THE INVENTION
One purpose of the building system of the present invention is to reduce the inherent conflict between urban planning authorities and land-and-one-story business owners, by comprising an integrated, modular system for building the basic structure of an inexpensive kind of temporary building that can significantly increase the rental value of land-and-one-story properties without adding significant unrecoverable costs that would delay preferred development.
A second purpose of the building system of the present invention is to comprise an integrated, modular system for building the basic structure of a building that is similar in appearance to conventional permanent concrete block and flat roof buildings, and that has fire resistance properties similar to permanent concrete buildings.
A third purpose of the building system of the present invention is to comprise an integrated, modular building system that can be built in cold climates without a significant unrecoverable investment in a deep foundation.
A fourth purpose of the building system of the present invention is to comprise an integrated, modular building system including engineering design components and architectural design components, for rendering specific buildings having a wide range of floor layout dimensions, such that a construction plan can be quickly prepared from modular elements for a specific building that will fit together with other buildings that are on a specific property, thus providing an increased square footage of rentable warehouse space.
A fifth purpose of the building system of the present invention is to comprise an integrated, modular building system for rendering specific temporary buildings such that if and when the buildings are later taken down, the same building can be erected elsewhere, or individual modules can be reused as parts of multiple other buildings of the present invention, or in other ways, so that most of the material cost of a building of the present invention is recovered if the building is taken down.
A sixth purpose of the building system of the present invention is to render buildings that, although temporary, can remain in service at a location for decades.
A seventh purpose of the building system of the present invention is to standardize a method of disassembling a building of the present invention, such that components are disassembled, staged, loaded and distributed efficiently from the disassembly site for reuse in the construction of other buildings of the present invention and/or for other uses.
SUMMARY OF THE INVENTION
The present invention comprises an integrated, modular system for designing, building, and disassembling the basic structure of an inexpensive kind of temporary building that is similar in appearance to conventional permanent concrete block and flat roof buildings, substantially fireproof, can be erected quickly, can remain in service on a site for decades, and that can then be disassembled such that most of the components can be reused at a different location in the same building, in other buildings of the present invention, or separately.
The wall components of the system of a building of the present invention are of two main block types. The first type comprises a variation of either industry standard sized 7⅝″×7⅝″×15⅝″ two cavity concrete block, or similar blocks with dimensions 7⅝″×7⅝″×18″. In addition to two cavities, each concrete block has one or more block assembly holes positioned such that when the blocks are stacked directly on top of one another without mortar, block assembly rods or block assembly columns, typically of steel and threaded at the top, are then run through the block assembly holes and into the foundation to form an assembly of stacked concrete blocks. The threaded sections at the top of the rods are used to secure roof modules. The second main type of wall block component comprises larger wall modules, typically of concrete, that can be hollow, or that can have an insulation core. These wall modules are also assembled using block assembly rods and/or block assembly columns that are free standing and that run the full height of the wall, through the inside of the wall modules and to the foundation. Such rods and/or columns can vertically support the weight of the roof independent of the wall block modules.
The wall components of the system of a building of the present invention include optional insulation panels that can be placed on either the inside or the outside of the building. These panels typically run the full height of the building, and comprise a layer of insulation board that is vapor sealed, an outer layer typically of finished veneer, and top and bottom flexible panel end sections. The bottom flexible panel end section is placed on the foundation and secured by the wall blocks that are placed subsequently. The top flexible panel end section is placed on the top of the wall blocks and is secured by the weight of the roof. The vapor sealed insulation board side interfaces with the wall blocks, and can be optionally spot glued to the wall blocks.
Wall components of the system of a building of the present invention are joined to roof components using plate modules placed at the top of the wall blocks. These plate modules include roof supporting sections of steel or a similar material, typically span multiple block sections, and have holes to insert the block assembly rods and/or block assembly columns used to assemble the wall blocks. There are two main kinds of plate modules. One has a flat top, and bears roof modules that slope very slightly down to a gutter. The other has a slight rise, to provide a slope to drain the roof.
Door, garage door, and window components of the system of a building of the present invention typically comprise a frame that is sized to fit in the exact area of an array of wall block components, a premanufactured door or window inside the frame, and a lintel sized with respect to the dimensions of wall block components and having holes for the block assembly rods and/or block assembly columns used to assemble the wall blocks.
Three alternative variations comprise the foundation component of the system of a building of the present invention. Each foundation variation typically comprises a level poured concrete base, and each is typically made using a pouring form top section having hollow tubes or solid rods spaced to accommodate the block assembly rods and/or block assembly columns that are placed to assemble the walls after the foundation has hardened.
The first foundation variation comprises pouring concrete directly into a shallow trench or form, or into a form on an existing paved surface, and then leveling.
For cold climates it is desirable to avoid the cost of building a deep foundation for a building that may soon be disassembled and moved. Accordingly, a second alternative variation of the foundation system is used that comprises insulation panels on the ground. The foundation is first constructed identically to the first variation. Ground insulation panels are then secured to the walls at ground level by flexible end panels. Wall blocks are then placed on top of the ground insulation panel end panels. Ground insulation panels can be optionally pinned or weighted to the ground. Ground insulation panels can be used with or without the use of wall insulation panels.
A conventional deep foundation, below the frost line, can be used as a third alternative type of foundation for buildings of the present invention situated in cold climates.
Framing components of the system of a building of the present invention comprise the use of the wall block assemblies including block assembly rods and/or block assembly columns, together with optional major and minor pillars as vertical supporting structure. Framing components also comprise a horizontal structure of one or more optional major beams spanning supporting walls and optionally also spanning supporting pillars, spanning angle iron sections running under the roof modules the full length between opposite walls and secured to the wall block top plates, additional wall perimeter angle irons attached to wall block top plates and running along the inside perimeter of the building, plastic coated steel cable sections secured to roof modules and to the foundation, and vertical angle iron sections secured to both spanning angle irons and to the foundation . These framing components function to join the major components of a building of the present invention into a single structure. Major pillar components of the present invention are optionally used to support major spanning beams, have a square base approximately four feet on each side, and can be pinned to an existing paved surface or to the ground using rods of steel or similar material. Minor pillar components are typically used to support roof modules half way between their span, are typically placed underneath the join between two roof modules, and are typically bolted to a spanning angle iron. Minor pillar components can also be pinned to an existing paved surface or to the ground.
Floor components of the system of a building of the present invention are typically of one of two types. Some buildings are placed on already paved surfaces, and have no floor other than the pavement. Other buildings are on unpaved ground. These buildings have modular floor slabs of molded concrete, that can be optionally pinned to the unpaved ground.
Roof module components of the system of a building of the present invention comprise rectangular assemblies typically with a short roof module end of 3′ in width and with a range of lengths such as 4′, 6′, 12′, 16′, 20′ and the like. These roof modules are placed side by side with adjacent roof modules. The short roof module ends are attached to the threaded rod ends of the block assembly rods and/or block assembly columns that protrude through the flat wall top plates of supporting stacked block assemblies, and/or to a major spanning beam using bolts, and/or to a spanning angle iron using bolts. Roof modules comprise a base that is typically a section of ribbed steel decking, an optional layer of platform panel such as gypsumboard, typically ½ thick″, a layer of insulating material in panel form, such as polyisocyanurate foam, typically 3″ thick, and a layer of rubber membrane, typically of thickness 45 m to 60 m. When the roof modules are in place, rubber membrane sections are glued into place to join adjacent modules. To complete the roof, flashing is added at the top and sloped sides, and gutters are attached to the draining sides.
Building link components of the system of a building of the present invention comprise a connection between an existing building and an adjacent building of the present invention. This typically comprises a previously described garage door opening and lintel in a wall of a building of the present invention that is joined by a short section of wall blocks and wall assembly rods, typically also by a custom roof section, and sometimes by one or more additional custom side panels, to either an existing opening of an existing building, such as a garage door, or to a wall of an existing building, where a corresponding opening is to be cut. Building link components of the system of a building of the present invention can comprise a set of standard designs, but will often include a requirement to fabricate custom components for a specific building.
The system of a building of the present invention includes both standardized engineering parameters, and standardized architectural procedures for rendering blueprints of specific buildings of the present invention that are in some cases designed to fit together with pre-existing buildings. In addition, the system of a building of the present invention can comprise a disassembly plan, that details the order in which components of a building of the present invention will be disassembled, where specific components of a building that is being disassembled are to be sent to be used in construction of other buildings of the present invention or to be used in other ways, and where and when at the disassembly site specific components will be staged and loaded onto trucks.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 —Foundation, stack of concrete blocks, block assembly rods, and block joining panel section, exploded view.
FIG. 2 —Foundation, stack of concrete blocks, wall block, and block assembly rods, exploded view.
FIG. 3 —Enhanced block assembly rod and base, exploded view.
FIG. 4 —Foundation, stack of concrete blocks, top plates, wall block, with enhanced block assembly rods and foundation embedded bases, exploded view.
FIG. 5 —Enhanced block assembly column and base, exploded view.
FIG. 6 —Large ultra-light wall block, top isometric view.
FIG. 7 —Roof module components and roof angle iron frame, exploded view.
FIG. 8 —Assembled roof module, flat wall top plate, roof and foundation joining structure, and concrete block, exploded view.
FIG. 9 —Flat wall top plate sections, wall frame angle iron, and concrete blocks, exploded view.
FIG. 10 —Sloped wall top plate with angle iron mountings, wall section, and spanning angle iron roof framing section, explode view.
FIG. 11 —Sloped wall top plate angle iron mounting, sloped wall top plate base section, spanning angle iron section, bolts, and roof and foundation linking angle iron section, exploded view.
FIG. 12 —Roof module, sloped wall top plates, angle iron mountings, wall section, angle iron roof framing, major supporting beam, major and minor supporting columns, isometric view.
FIG. 13 —Assembled roof module and major spanning beam section, exploded view.
FIG. 14 —Minor supporting pillar, isometric view.
FIG. 15 —Major supporting pillar, isometric view.
FIG. 16 —Wall section, foundation, wall insulation panel, and foundation insulation panel, exploded view.
FIG. 17 —Wall section, door opening, and lintel, isometric view.
FIG. 18 —Floor components, exploded view.
FIG. 19 —Building link components, exploded view.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 illustrates an exploded view of a foundation section, two cement blocks, and block assembly rods of the system of a building of the present invention. The cement blocks are typically of two sizes. One size has dimensions 7⅝″×7⅝″×15⅝″, the U.S. industry standard, allowing in traditional construction for the use of mortar and a resulting final block spacing of 8″ and 16″ on the wall face. The use of this standard block size makes it easier to resell blocks used in a building of the present invention as standard blocks, if the building is later disassembled. The second size has dimensions 7⅝″×7⅝″×18″. Because roof modules are built with ribbed steel decking having industry standards of a 3′ width and 6″ from rib to rib, using cement blocks 18″ wide facilitates placement of a row of roof modules on a building wall of a building of the present invention.
The foundation 1 of FIG. 1 is typically of poured concrete. The foundation concrete can be poured into a shallow trench, or into forms. It can be above or below the frost line depending on the requirements for a specific building. Holes 2 , spaced according to the dimensions of the concrete blocks used, are formed in the foundation 1 of FIG. 1 when the foundation is poured. The holes 2 typically go all the way through the foundation and can go into the underlying ground. If the foundation is on pre-existing pavement, holes are typically drilled in the pavement. If the foundation is on ground, drilling into the ground is typically unnecessary. When the foundation 1 is in place, and the holes 2 have been drilled to ground if needed, block assembly rods 3 are placed in the holes. These block assembly rods 3 are typically made of steel, but can be of other material, including such material as PVC. Pre-cast concrete blocks 4 , having pre-formed holes 5 , are placed such that the block assembly rods 3 run through the pre-formed block holes 5 in the blocks 4 of FIG. 1 . In this way, a stack of pre-cast concrete blocks is assembled, that comprises a section of a wall of a building of the present invention.
As a stack of blocks is commenced, the assembly can begin with shorter block assembly rods, so that blocks are only lifted a maximum of 3′ or 4′ before being placed. When a stack reaches the top of the rods, one is removed and a longer rod is inserted, then the other shorter rod is removed and a longer rod is inserted. When a stack of blocks has reached full height, the final rods may optionally be sized to be driven a short distance of up to a few feet into the ground. The final block assembly rods have threaded heads that are used to bolt on roof modules.
When concrete blocks with standard dimensions 7⅝″×7⅝″×15⅝″ are used, because the industry standard for ribbed steel decking used in roof modules is 3′ wide with ribs spaced every 6″, a liner block approximately 2⅜″ thick is required, to be placed between adjacent stacks of concrete blocks. Such a liner block section is shown as 7 in FIG. 1 . Liner block sections are typically 2′ or 3′ high. The thickness and compressibility of the liner blocks and the spacing of the foundation holes is such that when the concrete blocks are in place, the liner blocks are secured by the concrete blocks. The use of the liner blocks results in the center of each concrete block being approximately 18″ from the center of adjacent blocks in adjacent stacks.
Thus, by repeating the steps for the placement of block assembly rods, pre-formed concrete blocks, and liner blocks when required, a wall is assembled that is sized for subsequent placing of roof modules.
An alternative type of wall of the system of a building of the present invention is comprised of larger wall block sections, such as the section 11 illustrated in FIG. 2 . These larger wall block sections 11 can be of pre-cast solid concrete, or of hollow core concrete, or of concrete with a lightweight core such as of insulating material, or of other material. As with the concrete blocks, the larger wall block sections 11 are placed such that the block assembly rods 3 of FIG. 2 run through the pre-formed wall block holes 12 in the wall blocks 11 of FIG. 2 . The design of larger wall blocks is such that the block dimensions and/or the number and spacing of the wall block holes 12 are determined with respect to the 3′ width and 6″ rib spacing of roof modules. The use of larger wall block sections permits designs of wall block sections with lower density, and improved insulating properties that may in some cases make additional insulation unnecessary.
FIG. 3 illustrates a second alternative and enhanced kind of structure for the use of block assembly rods in the system of a building of the present invention. This enhanced block assembly rod, shown as 21 in FIG. 3, is typically of steel, and comprises a rod shaft 22 having a flat bottom 27 , a top rod plate 26 that is typically of steel and is typically welded to the rod shaft 22 , and a threaded top section 25 . The enhanced block assembly rod 21 is used with a block assembly rod base 28 , typically of steel, comprising a hollow tube structure 23 that is typically welded to a base plate 24 . When the building foundation is formed, block assembly rod bases 28 are cast in the concrete, with the open hole of the tube structure top 29 of FIG. 3 typically even or slightly below the level foundation top.
FIG. 4 illustrates the use of this alternative and enhanced kind of structure for block assembly rods. Block assembly base plates 28 are embedded in the foundation concrete 1 . Concrete blocks 4 or wall blocks 11 are placed on the foundation 1 , with their preformed holes 5 or 12 aligned with the open holes 29 in the block assembly rod base plate tops. Enhanced block assembly rods 21 are then run through the concrete blocks 4 and/or wall blocks 11 , such that the bottom 27 of each enhanced block assembly rod 21 rests on the base plate 24 of a block assembly rod base 28 . At the top of each wall, top plate modules 41 , having holes 42 that align with the enhanced block assembly rod threaded top sections 25 , are placed so that they rest on the top block rod assembly plates 26 . Thus, when the roof is later mounted on the top plate modules 41 , the enhanced block assembly rods 21 function as thin load bearing pillars. The base plate 24 must be of sufficient area so that when base plates 24 are cast in the foundation 1 the base plates and foundation will bear the weight supported by the enhanced block assembly rods 21 .
The enhanced block assembly rods 21 are inhibited from bending by the concrete blocks or wall blocks, but except for this bending prevention, the enhanced block assembly rods 21 can bear the weight of the roof independently of any vertical weight bearing function of the concrete blocks and or wall blocks. This permits the use of concrete blocks and/or wall blocks that can be made primarily with lightweight non-load-bearing material, including insulation. The light weight of such concrete blocks and/or wall blocks makes it more practical to transport buildings of the present invention considerable distances. In addition, through the use of enhanced block assembly rods and ultralight wall blocks comprising insulating material and/or structure, building designs for buildings of the present invention are facilitated that require no additional insulation.
A third alternative and enhanced kind of structure can be used in place of block assembly rods in the system of a building of the present invention. This enhanced structure will be termed a block assembly column. A block assembly column is typically a hollow steel supporting column, similar to commercially available columns, enhanced with top and bottom sections similar to the enhanced block assembly rod of FIG. 3 . Such a block assembly column, shown as 51 in FIG. 5, is typically of steel, and comprises: a hollow steel column 52 that is welded to a flat bottom column plate 61 , that is in turn welded to a solid steel rod section 62 having a flat bottom 57 ; a flat top column plate 56 that is typically of steel and is typically welded to the top of the column 52 , and a threaded top section 55 that is typically welded to the top column plate 56 . The block assembly column 51 is used with a block assembly column base 58 , typically of steel. The block assembly column base 58 comprises a hollow tube structure 53 that is typically welded to a plate 54 . When the building foundation is formed, block assembly column bases 58 are cast in the concrete, with the plate on top of the concrete foundation, and the open hole 59 of the tube structure 53 of FIG. 5 facing up.
FIG. 6 illustrates the structure of a larger ultra-light wall block unit 71 of a design and composition suitable to be used with block assembly columns described above in the system of a building of the present invention. The ultra-light wall block unit 71 comprises an outer shell 72 about 1″ thick of ultra-light concrete, an inner layer 73 about 3″ thick of a light but rigid foam insulating material such as polyisocyanurate foam, hole liners 74 of material such as PVC, and holes 75 that are the inside of the hole liner 74 and that are sized to accommodate block assembly columns. Ultra-light wall block units function together with block assembly columns in a building of the present invention such that when the building is assembled, the columns rest on the foundation, and provide total vertical structural support for the roof of the building. The roof rests on steel top plate modules similar to those illustrated as 41 of FIG. 4 . The weight of the roof is supported from the foundation via the columns, and the columns are inhibited from bending or falling both by the steel rod sections 62 of FIG. 5, and by the encasing structure of the walls. As the building assembly continues, additional framing and wall elements add supporting structure that further enhances the function of the wall blocks 71 in preventing the columns from bending or falling.
FIG. 7 illustrates primary components of a roof module for the system of a building of the present invention. Referring to FIG. 7, a roof module is comprised of up to four main layers: a layer of ribbed steel decking 81 , an optional layer of platform panel 82 that is typically ½″ gypsumboard, a layer of insulation panel 83 that is typically 3″ polyisocyanurate foam, and a layer of a rubber membrane 84 . When the roof module is assembled, bolts 85 are inserted through bolt plates 86 , the layer of insulation panel 83 , the optional layer of platform panel 82 , and the layer of steel decking 81 . There are holes 87 in the layer of insulation panel 83 , holes 88 in the layer of optional platform panel 82 , and holes 89 in the layer of steel decking 81 , all sized and spaced to accommodate arrays of bolts spaced such as to secure the layers together, and to give the resulting assembled panel module added stiffness deriving from the structural properties of the layers. The bolt plates 86 have recessed center sections 90 to accommodate the shape of the bolt head, resulting in a relatively smooth top surface of the bolt head and the bolt plate when the bolts are secured. The bolt plates 86 have center holes 91 to allow the bolt to be inserted, and as a base for the bottoms 92 of the bolt heads. When the roof modules are assembled, some or all of the bolt heads protrude below the lower ribs 93 of the ribbed steel decking 81 , and through holes 96 in a spanning angle iron 94 , a section of which is shown in FIG. 7 . These spanning angle irons 94 run the length of the roof, and are secured to other angle irons that are in turn secured to top plate sections around the inner perimeter of the roof. When the roof modules are bolted to these angle iron sections 94 , this has the effect of both securing the roof module to the building, and indirectly to adjacent roof module sections that are also secured to the angle irons. Thus the roof module sections and the angle irons 94 are structurally an integrated load bearing unit. Although bolting, as shown in FIG. 7, is a preferred way of attaching roof modules to spanning angle irons, it should be understood that other means could be use to attach roof modules to spanning angle irons in the system of a building of the present invention.
FIG. 8 shows an assembled roof module 95 , comprising the layers described with reference to the exploded view of FIG. 7 : the layer of ribbed steel decking 81 , an optional layer of platform panel 82 , a layer of insulation panel 83 , and a layer of a rubber membrane 84 . Continuing to refer to FIG. 8, the exploded view illustrates how the short ends of assembled roof modules of the system of a building of the present invention are attached to walls. The bottom rib sections 93 of the steel decking layer 81 rest on the block top plate 42 , and the block top plate in turn rests either on blocks, such as the concrete block 4 illustrated in FIG. 8, or wall blocks, or a combination thereof, and/or on top rod plate sections 26 of enhanced block assembly rods 21 of FIG. 4 . Referring again to FIG. 8, for some of the block assembly rods 3 , plastic coated steel cables 98 , with a looped end 99 are inserted through a hole 100 in the bottom rib 93 and looped around the block assembly rods 3 . The other end of each cable, also looped, is attached to a protruding bolt precast in the side of the foundation, illustrated as 6 of FIG. 1 . The steel cable is presized according to the height of the building, and is of a length such that it must typically be mechanically stretched to place the bottom loop on the protruding bolt 6 of FIG. 1 .
Referring again to FIG. 8, because the roof modules 95 are bolted to the block assembly rods 3 that run through the top plate holes 42 , cement block holes 5 , and/or wall block holes, and to the foundation, with the steel cables 98 in place, the roof modules, block plates, blocks, and foundation of the system of a building of the present invention all become effectively one assembly.
FIG. 9 illustrates an exploded view of adjacent top plates 41 , a section of angle iron 101 , and the top concrete blocks 4 of two adjacent stacks of concrete blocks of the system of a building of the present invention. Sections of angle iron 101 run the length of each wall, and thus run the entire inside perimeter of a building of the present invention. The inner flange 43 of each top plate section 41 has a bolt or a section of threaded rod 44 welded to it. The angle iron sections 101 have holes 103 that are spaced to align with a row of top plate sections 41 . The angle iron sections 101 are bolted to the top plate flange sections 43 using the bolt or threaded rod sections 44 . In this way the building is further structurally reinforced with respect to any vertical force vector acting on a wall.
FIG. 10 illustrates a sloped wall top module 121 of the system of a building of the present invention. These sloped wall top modules can range in length from about 12′ to about 24′. When roof modules 95 are put in place, they run parallel to the sloped wall top modules, as shown in FIG. 12 . Referring to FIG. 10, the sloped roof top module 121 comprises a triangular shaped frame 122 , having a base plate 123 typically of steel or a similar material, a slight rise section 124 of between about 8″ and 18″, also typically of steel, and a top section 125 also typically of steel. There are holes 126 along the entire length of the base 123 and top section 125 , corresponding to the block assembly rod holes and/or block assembly column holes. The holes 126 in the top section 125 are large enough in diameter to allow a bolt to be placed on the threaded top of a block assembly rod or column, and then to bolt the base plate 123 securely to the block assembly rod or column.
Continuing to refer to FIG. 10, the sloped wall top module 121 has angle iron mountings 127 , typically at one to three points, at which steel angle irons can be attached that run perpendicular to the ribs of the roof modules. A section of one such steel angle iron 94 is shown as ready to be put in place and attached to mounting 128 of the sloped wall top module 121 of FIG. 10 . The sloped wall top module angle iron mountings 127 are typically welded to the base plate 123 , and have holes 130 that are used together with the holes 131 in an angle iron 94 to bolt angle irons 94 to the mountings.
FIG. 11 is a detail view of a mounting 127 on the base plate 123 of a section of a sloped wall top module 121 , and an angle iron 94 ready to be attached to the mounting 127 of the system of a building of the present invention. The angle iron 94 is placed against the mounting 127 , the holes 130 and 131 are aligned, the bolts 132 are inserted, and the angle iron 94 is thus secured to the mounting 127 and thereby to the sloped wall top module 121 . Additional vertical angle irons 133 are also secured to the angle irons 94 using bolts that run through aligned holes 134 and 135 in the angle iron 133 and the spanning angle iron 94 respectively. The other end of the angle iron 133 is bolted to one of the bolts 6 embedded in the foundation 1 as shown in FIG. 1 . In this way, the roof modules, the sloped wall top module, the wall, the block assembly rods and/or columns, and the foundation are all functionally one structure.
FIG. 12 is a view of two sloped wall top module sections 121 , a roof module 95 , a wall section 111 , and primary framing elements of the system of a building of the present invention. The wall top modules are placed such that there is a slope to the roof from the joining point 144 of the two wall top modules, downward to both sides. The joining point 144 of the wall top modules 121 is recessed, allowing the placement of a major spanning beam 141 , a section of which is illustrated in FIG. 12, such that the top 145 of the major spanning beam 141 is level with the sloped top plate sections 123 of the wall top module sections 121 . The major spanning beam 141 is typically a steel I-beam, and spans the length of the building to the opposite wall.
Angle irons 94 are mounted to the mountings on the wall top module sections 121 , as indicated in FIG. 12 . The mounting of the angle irons 94 is not illustrated in FIG. 12, but was illustrated and detailed earlier with reference to FIG. 11 . These angle irons span the length of the building to the opposite wall.
Both major supporting columns 143 and minor supporting columns 142 are used as framing elements in the system of a building of the present invention. These are detailed below with reference to other illustrations. As illustrated in FIG. 12, major supporting columns 143 are typically located under a major spanning beam 141 . Minor supporting columns 142 are typically located under spanning angle irons 94 , but can in some cases also be located under major supporting beams instead of major columns 143 .
When the framing structure is in place, roof modules 95 of the system of the present invention are put in place. These roof modules 95 are secured to angle iron supports 94 , as was described earlier and illustrated by FIG. 7, and one end of each roof module 95 is secured to the walls perpendicular to those with sloped wall top modules 121 , as was described earlier and illustrated by FIG. 8 .
The other end of the roof module 95 may be secured to a major spanning beam 141 , as illustrated in FIG. 13, showing a section of a roof module 95 and a section of a major spanning beam 141 . However, for some smaller buildings and/or sections of buildings of the present invention, both ends of roof modules 95 are secured to walls, and only one sloped wall top module 121 is used. When a major spanning beam is used, the spanning beam 141 has holes 151 , that are spaced to correspond with holes 97 in bottom ribs 93 of the roof module 95 . Bolts 152 are placed in holes 97 of the bottom ribs 93 of the roof module 95 . The roof modules 95 are placed on the roof such that the holes 97 and 151 are aligned, and thus the bolts 152 drop through the holes 151 in the major spanning beam 141 , nuts are placed, and the roof modules 95 are thus secured to the major spanning beam 141 .
FIG. 14 illustrates a minor supporting pillar 142 of the system of a building of the present invention. This typically comprises a hollow steel tube section(s) 159 , an optional pre-cast concrete column section 152 , an optional pre-cast concrete base 153 , and a top assembly further comprising a threaded top plate 154 , a threaded rod section 155 , and a roof supporting top plate 156 . The threaded rod section 155 is used to adjust the overall height of the minor supporting pillar 142 within a range of up to a few inches. The pre-cast concrete base can be pinned to the ground or to existing pavement by running rods of steel or similar material through the preformed holes 157 . The top part of the minor supporting pillar 142 , from the hollow steel tube section(s) 159 up, can be placed in a hole 158 that is pre-cast in the concrete column section 152 , or can be permanently embedded in the concrete column section 152 . The top part of the minor supporting pillar 142 , from the hollow steel tube section(s) 159 up, is commercially available in structures that typically are designed to support about 10,000 lbs.
FIG. 15 illustrates a major supporting pillar 143 of the system of a building of the present invention. This typically comprises a steel tube section 169 , and a pre-cast concrete base 163 . The steel tube section may be hollow, or may be filled with concrete and/or with additional steel reinforcing. The major supporting pillar is sized so that when it is in place its height corresponds to the height of an installed major spanning beam such as the spanning beam section 141 shown in FIG. 12 . The steel tube section 169 may be either permanently mounted in the pre-cast concrete base 163 , or may be placed in a pre-formed hole 168 . An optional steel base plate 167 may be cast in the pre-cast concrete base 163 .
FIG. 16 illustrates an optional wall insulation panel 172 and an optional foundation insulation panel 173 , shown with a wall assembly 171 of the system of a building of the present invention. The foundation and wall insulation panels can be installed together, or separately. The wall insulation panels 172 can be installed on either the inside or the outside of the building. The panels have thin, flexible insulation panel end sections 174 , with block assembly holes 175 that correspond to the pattern of holes 5 in the concrete blocks 4 and/or wall blocks used for the walls. To install wall insulation panels, one insulation panel end section 174 is placed on the foundation, and typically secured by block assembly rods or other rods that run through the block assembly holes. If both wall and foundation insulation panels are used, the end section 174 of the foundation insulation panel 173 is placed on the foundation 1 first, followed by placement of the wall insulation panel 172 end section 174 . The wall block is then installed.
Wall insulation panels such as 172 of FIG. 16 are sized with respect to a standard wall height. When all the wall blocks are in place, installation of the wall insulation panel 172 can be completed. The side of the wall insulation panel 172 can be optionally spot glued with a suitable adhesive, following a standardized pattern of adhesive placement that will facilitate later removal. The wall insulation panel 172 is then pressed or braced firmly against the wall 171 to ensure a permanent adhesive bond. The block assembly rod corresponding to block assembly hole 177 of FIG. 16 is removed if it is in place, and the top insulation panel end section is cut along lines 178 of FIG. 16, so that the top insulation panel end section 174 can be placed flat on the blocks. When the block assembly rod corresponding to the block assembly hole 177 is in place, the top of the insulation panel 172 is thus secured from moving away from the wall.
When foundation insulation 173 is installed, once the end section 174 is secured to the foundation 1 , the panel can optionally be pinned to the ground or to pavement by running securing rods, nails or spikes through holes 176 at the end of the panel section. Alternatively, the foundation insulation panels can be weighted, or secured to the ground in another way that may be preferable due to characteristics of a specific site and building of the present invention.
FIG. 17 illustrates a view of a door opening and lintel assembly for a wall of the system of a building of the present invention. The section of assembled concrete block wall 181 of FIG. 17 has an opening 184 within which a door frame, garage door frame, or window frame, can be placed, as with conventional concrete block or concrete wall buildings. If a window is placed, additional wall block would typically rise from the foundation to the bottom of the window, assembled with shorter block assembly rods. Above the opening 184 is a lintel 182 , typically of reinforced concrete. The lintel 182 has block assembly rod holes 183 that align with the block assembly rod holes 5 in the stacks of blocks that the sides 185 of the lintel are placed in. The block assembly rods run through the lintel as they do through concrete blocks and/or wall blocks. The lintel also has holes 186 that correspond to the holes for block assembly rods that run through the blocks above the lintel, if any. These holes 186 typically run all the way through the lintel, and have enlarged lower ends to allow for shorter block assembly rods to be bolted at both ends to assemble the lintel and blocks above the lintel.
FIG. 18 illustrates a view of a floor module 191 of the system of a building of the present invention, near a section of foundation 1 . Floor modules 191 may be placed on a leveled surface 193 inside the foundation perimeter. They typically adjoin other floor modules and the foundation 1 . Holes 192 are in the floor modules 191 , allowing the floor modules to be pinned to the ground. If the ground is sufficiently leveled, and offers sufficient support, such pinning may be unnecessary. The holes 192 can also be used with cable and other means to easily place the floor modules adjacent to one another. Alternatively, if a building of the present invention is being placed on an already paved surface, floor modules may not be needed.
FIG. 19 illustrates an exploded view of a building link component of the system of a building of the present invention. A building link component is a short passageway from a building of the present invention to a pre-existing adjacent building. A building link may connect with a pre-existing garage door of an adjacent building, or may be placed at a point where it is necessary to cut an opening into the pre-existing building. FIG. 19 illustrates an exploded view of a building link component of a building of the present invention. There is an opening 211 , such as a garage door opening, in a wall section 212 of a building of the present invention. A lintel 201 is above the opening 211 . There are two extensions 202 and 203 to the foundation 1 , adjoining the opening in the pre-existing building. Wall sections 204 and 205 are situated on the foundation extensions 202 and 203 respectively. The sides 207 and 209 of the wall sections 204 and 205 adjoin the wall section 212 . A customized roof module 206 tops the wall sides 204 and 205 , and sits adjacent to the roof modules on the new building, not shown in FIG. 19 . The customized roof module 206 comprises the elements of a standard roof module as described earlier with reference to FIG. 7, but is custom built, and sized to the specific dimensions of a specific building link component. A section of rubber membrane is glued to the main roof modules of the building of the present invention, and to the customized roof module 206 , and gutters and flashing are then added as required to finish the roof.
If the pre-existing building roof is higher than the building roof level of the present invention, then the edge 213 of the customized roof module 206 of the building of the present invention abuts the pre-existing building, and is typically sealed to the pre-existing building wall at the building interface with a waterproof adhesive compound. If the roof level of the building of the present invention is higher than the pre-existing building, an additional custom side section, not shown in FIG. 19, must be attached to the sides 208 and 210 of the wall sections 204 and 205 respectively. Such a side section may be of the same composition of the customized roof module 206 , or may be of a different composition, depending on specifics of the pre-existing building. This element of the building link component of the present invention is not standardized.
The engineering design component of the system of a building of the present invention comprises a set of engineering parameters for combinations of components of a building of the present invention such that any use of a specific combination of components within the set of engineering parameters has been pre-determined to be structurally sound. As an example, it may be determined that for a range of specific floor dimensions, a specific number of parallel spanning roof angle irons, spaced at a specified range of distances, and a spacing of angle iron supporting minor supporting columns of no greater than a specific distance will constitute a specific building design of a building of the present invention that is structurally sound from an engineering point of view. Engineering design parameters may also be defined for a set of standard building link components. The engineering design component of the system of a building of the present invention thus reduces the engineering cost of rendering specific buildings of the present invention.
The architectural design component of the system of a building of the present invention typically comprises a floor and foundation plan and drawing that is unique to the building site, and an additional set of drawings that are modifications of template drawings, and are rendered for a specific project by editing the templates. The template drawings show floors, foundations, walls, roofs, and building links for a building of the present invention. The edited template drawings of a building of the present invention show how specific foundations, walls, doors, windows, framing, roofs, and building links of a building of the present invention are to be rendered. Because the basic structural design for all but the floor plan drawing can typically be prepared by editing templates, the architectural design component of the system of a building of the present invention thus reduces the architectural cost of rendering specific buildings of the present invention. Elements such as wiring, ventilating, heating, air conditioning, plumbing and sprinkler systems are custom designed with respect to the requirements of each building of the present invention, and are beyond the scope of the present invention.
The disassembly plan component of the system of a building of the present invention typically is prepared for each building shortly before the building is to be disassembled. The disassembly plan component specifies where the disassembled components of the specific building are to be sent, and how and where at the site they are to be staged for shipping. The disassembly plan component is prepared with respect to the construction requirements and timetables for other buildings of the present invention that are being assembled using components from the building being disassembled.
Any or all of: electrical, plumbing, heating, air conditioning, and sprinkler systems may be developed as modular systems to be used with buildings of the present invention, or may be installed conventionally once a building of the present invention is in place. Building components such as those enumerated in this paragraph are beyond the scope of the present invention.
While preferred embodiments of the system of a building of the present invention have been described, it should be appreciated that various modifications may be made by those skilled in the art without departing from the spirit and scope of the present invention. Accordingly, reference should be made to the claims to determine the scope of the present invention.
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A building system for the basic structure of a one-story, modular, temporary building, constructed primarily of fire-resistant materials, comprising: a foundation of poured, leveled concrete, having regularly spaced holes for vertical block assembly rods and/or columns; a plurality of wall blocks of standardized size(s) each block having one or more vertical block assembly holes running entirely through the said blocks; a plurality of block assembly rods and/or block assembly columns such that when a column of one or more wall blocks is placed on the foundation with the foundation and block holes aligned one or more block assembly rods and/or columns can be run through the block column and into the foundation thereby rendering an assembly of block(s), rod(s) and foundation that does not require mortar and is easy to disassemble; framing comprised of sloped top plates for a first set of parallel wall sections, spanning angle irons mounted to and perpendicular to the said sloped top plates, an optional steel I-beam major spanning beam(s) parallel to the said spanning angle irons, optional minor supporting pillars, optional major supporting pillars, optional vertical roof and foundation joining elements, optional angle irons assembled around the inside perimeter of the top of the wall sections and being joined to said wall sections; and a plurality of roof modules comprised of standardized lengths of steel ribbed decking, insulating panels, and a membrane; all such that when the aforesaid elements are assembled, the building is functionally one structural unit, can serve for decades, and can be easily disassembled and the components thereof reused. The building system further comprises standardized engineering and architectural techniques and processes such as to efficiently render designs of specific buildings having a floor plan comprised of one or more rectangular sections such that each rectangular section can have a range of dimensions, thereby facilitating specific building designs that can be fitted together with existing one-story buildings of various dimensions with the result of a larger structure that is functionally one building, and is serviceable for uses such as warehousing.
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CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application is a National Stage filing of International Application PCT/EP 2010/000437 filed Jan. 26, 2010, entitled “NEW COMPOUNDS FOR THE TREATMENT OF DISEASES RELATED TO PROTEIN MISFOLDING” claiming priority to PCT/EP2009/007627 filed Oct. 26, 2009. The subject application claims priority to PCT/EP 2010/000437 and to PCT/EP2009/007627, and incorporates all by reference herein, in their entirety.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to the field of protein misfolding diseases and thus to diseases which are associated with or induced by abnormal or pathogenic three-dimensional folding of proteins and/or peptides or which are linked to pathogenic conformational changes of proteins and/or peptides. Especially, the present invention refers to neurodegenerative diseases which are related to or caused by protein misfolding like Alzheimer's disease and the like.
[0003] Especially, the present invention refers to novel specific trimeric pyrazole compounds which exhibit a therapeutic effectiveness in regard to the aforementioned protein misfolding diseases, especially in so far as they are able to suppress or at least to reduce the misfolding of proteins and/or the aggregation of misfolded proteins to layered aggregates, like amyloid plaques. Furthermore, the specific trimeric pyrazole compounds according to the present invention are additionally capable to disassemble already existing misfolded proteins and/or aggregates of misfolded proteins.
[0004] The present invention also relates to novel specific trimeric pyrazole compounds for the prophylactic and/or therapeutic (i.e. curative) treatment of protein misfolding diseases, especially neurodegenerative diseases.
[0005] Furthermore, the present invention refers to the use of at least one trimeric pyrazole compound of the invention for the prophylactic and/or therapeutic (i.e. curative) treatment of protein misfolding diseases, especially neurodegenerative diseases.
[0006] Further, the present invention relates to the use of trimeric pyrazole compounds of the invention for producing a medicament or a pharmaceutical for the prophylactic and/or therapeutic (i.e. curative) treatment of protein misfolding diseases, especially neurodegenerative diseases.
[0007] In addition, the present invention also refers to a medicament and/or pharmaceutic composition comprising at least one trimeric pyrazole compound of the invention for the prophylactic and/or therapeutic (i.e. curative) treatment of protein misfolding diseases, especially neurodegenerative diseases.
[0008] Moreover, the present invention also provides a kit for the inventive uses and treatment methods as described herein, the kit comprising at least one trimeric pyrazole compound of the invention, preferably in a suitable application form.
[0009] Furthermore, the present invention also refers to a method of treatment of protein misfolding diseases, especially neurodegenerative diseases, wherein at least one trimeric pyrazole compound is used and preferably applied to a human or animal suffering from a protein misfolding disease, especially a neurodegenerative disease.
[0010] Finally, the present invention also refers to methods for synthesizing (producing) and/or for the providing of the specific trimeric pyrazole compounds of the invention.
[0011] In physiology, one of the most important processes can be seen in the folding of the translated linear strand of amino acids into a fully functional three-dimensional protein, which represents one of the most complex challenges facing the cellular protein factory. A large amount of physiological tools reveal a tightly regulated assembly line and multiple factors guide nascent proteins to select the correct shape and/or conformation from an almost infinite array of possibilities. Furthermore, in biological systems, specific control mechanisms exist which ensure that misfolded products are targeted for degradation before they cause harm. However, a failure or malfunction of these control systems or the excessive occurrence of protein misfolding, also especially after protein biosynthesis (i.e. the conversion of normally folded protein into pathogenic forms) can result in a huge variety of diseases, which are commonly designated as protein misfolding diseases or diseases related to protein misfolding.
[0012] Among the protein misfolding diseases, Alzheimer's disease, Bovine Spongiforme Encephalopathy (BSE), Creutzfeldt-Jacob's disease (CJD), Huntington's disease, Lewy Body dementia, Parkinson's disease, Diabetes mellitus of type II and Alzheimer's disease (AD) can be mentioned exemplarily.
[0013] With respect to Creutzfeldt-Jacob's disease or CJD, which is the most common among the types of transmissible spongiforme encephalopathies found in humans, this protein misfolding disease is caused by prions and is thus sometimes also designated as a prion disease. The prion that is believed to cause CJD exhibits at least two stable conformations. The native state is water-soluble and present in healthy cells. Its biological function is presumably in transmembrane transport or signaling. The other confirmation state is very poorly water-soluble and readily forms protein aggregates. The CJD prion is dangerous because it promotes refolding of native proteins into the diseased state resulting in β-pleated sheets. The number of misfolded protein molecules thus increases exponentially and the process leads to a large quantity of insoluble prions in affected cells. This mass of misfolded proteins disrupts cell function and causes cell death. The misfolding is characterized by a folding of the dominantly α-helica regions into β-pleated sheets of the CJD prion. There is currently no cure for CJD. The disease is invariably fatal.
[0014] Diabetes mellitus type II also represents a protein misfolding disease. With respect to this disease, the so-called amyloid polypeptide (IAPP or amylin) is commonly found in pancreatic islets of patients suffering from Diabetes mellitus type II or harbouring an insulinoma. Recent results suggest that IAPP can induce apoptotic cell-death in insulin-producing β-cells. IAPP is capable of forming amyloid fibrils in vitro. Within the fibrillization reaction, the earlier prefibrillar structures are extremely toxic to β-cell and insuline producing cells. A later amyloid fiber structures also seems to have some cytotoxic effect on cell cultures. Therefore, IAPP represents an important pharmacological target for the treatment of Diabetes mellitus II diseases.
[0015] Moreover, also Alzheimer's disease has been identified as a protein misfolding disease (proteopathy), caused by accumulation of abnormally folded A-β and tau-proteins in the brain.
[0016] Furthermore, so-called synuclein also represents an interesting pharmacological target. The protein α-synuclein has been found to be mutated in several families with autosomal dominant Parkinson's disease. Mutations in α-synuclein are associated with early-onset of especially familiar Parkinson's disease. The protein aggregates abnormally in Parkinson's disease, Alzheimer's disease, Lewy body disease and other neurodegenerative diseases.
[0017] Thus, previously unrelated diseases, such as Alzheimer's disease, prion diseases and diabetes, share the pathological feature of aggregated misfolded proteins, which especially occur in the form of large deposits in biological systems (e.g. amyloid plaques in Alzheimer's disease). This common principle suggests that these protein misfolding diseases are linked by common principles, which therefore represents common targets for therapeutic intervention and approaches.
[0018] Not at least due to the high impact on the persons concerned, neurodegenerative diseases play an important role among the aforenamed protein misfolding diseases. In general, neurodegenerative diseases can be defined as a condition in which cells of the brain and/or spinal cord are lost, resulting in a decrease of essential functions of the brain, especially with regard to the cognitive and/or motoric function as well as the processing of sensory information. In this context, neurodegenerative diseases are commonly linked with conditions affecting memory and related to dementia but also with conditions causing problems of the control of movements, such as ataxia. Neurodegeneration is often caused by misfolding of proteins, especially in such a way that the misfolded proteins can no longer perform their regular cellular functions and instead trigger equivalent modifications in normal proteins, thus creating a cascade of damage that eventually results in significant neuronal death. Normally, neurodegeneration begins long before the patient experiences any symptoms. It can be months or years before any effect is felt. In general, symptoms are noticed when many cells die or cease to function.
[0019] The most common form of dementia is the so-called Alzheimer's disease (AD), which is synonymously also denoted as Alzheimer disease, Senile Dementia of the Alzheimer Type (SDAT) or simply Alzheimer's. Generally, it is diagnosed in people over 65 years of age, although the less-prevalent early-onset of AD can occur much earlier. As of September 2009, this number is reported to be at least 35 million worldwide. The prevalence of AD is estimated to reach approximately 107 million people by 2050.
[0020] Although the cause of AD is unique for every individual, there are many common symptoms. The earliest observable symptoms are often mistakenly thought to be age-related concerns or manifestations of stress. In the early stages, the most commonly recognized symptom is memory loss, such as difficulty in remembering recently learned facts. As the disease advances, symptoms include confusion, irritability and aggression, mood swings, language breakdown, long-term memory loss and the general withdrawal of the sufferer as the senses of the person concerned decline. Regularly, body functions are lost, ultimately leading to death. AD develops for an indeterminate period of time before coming fully apparent and it can progress undiagnosed for years. The mean life expectancy following diagnosis is approximately seven years. Fewer than three percent of individuals live more than fourteen years after diagnoses.
[0021] Alzheimer's disease is characterized by loss of neurons and synopsis in the cerebral cortex and certain subcortical regions. This loss results in gross atrophy of the affected regions of the brain, including degeneration in the temporal lobe and parietal lobe, and parts of the frontal cortex and cingulat gyrus.
[0022] Alzheimer's represents a protein misfolding disease caused by accumulation of abnormally folded A-β and tau-proteins in the brain. Plaques are made up of small peptides, 39 to 43 amino acids in length, called beta-amyloid (also written as A-β or Aβ or ABeta). Beta-amyloid is a fragment from a larger protein called amyloid precurser protein (APP), a transmembrane protein that penetrates through the neuron's membrane. APP is critical to neuron growth, survival and postinjury repair. In Alzheimer's disease, APP is divided into smaller fragments by enzymes through proteolysis. One of these fragments gives rise to fibrils of beta-amyloid, which forms clumps that are deposited outside of neurons in dense formations known as senile plaques or amyloid plaques.
[0023] Amyloid beta (A-β, Aβ or ABeta) is a peptide of 39 to 43 amino acids that appears to be the main constituent of amyloid plaques in the brains of persons suffering from protein misfolding diseases, like Alzheimer's disease. Similar plaques appear in some variants of Lewy body dementia. The plaques formed by Aβ are composed of a tangle of regularly ordered fibrillar aggregates called amyloid fibers, a protein fold which is also shared by other peptides such as prions associated with other protein misfolding diseases, like CJD. Aβ is formed after sequential cleavage of the amyloid precursor protein, a transmembrane glycoprotein. Aβ protein is generated by successive action of the so-called β- and γ-secretases. The γ-secretase, which produces the C-terminal end of the Aβ-peptide, cleaves within the transmembrane region of APP and can generate a number of isoforms of 39 to 43 amino acid residues in length. The most common isoforms are Aβ 40 and Aβ 42 . The shorter Aβ 40 form is the more common one, wherein Aβ 42 represents the more fibrillogenic isoform of Aβ. Thus, Aβ 42 is the most amyloidogenic form of the peptide.
[0024] The accumulation of beta-amyloid peptides is discussed as the central event triggering neuron degeneration. Accumulation of aggregated amyloid fibrils, which are believed to be the toxic form of the protein and seem to be responsible for disrupting the cell calcium ion homeostasis, induces programmed cell death (apoptosis). It is also known that Aβ selectively builds up in the mitochondria in the cells of Alzheimer's-affected brains and that it also inhibits certain enzyme functions and the utilization of glucose by neurons.
[0025] Alzheimer's disease is also considered as a tauopathy due to abnormal aggregation of the so-called tau-protein. The tau-protein stabilizes the microtubules as a part of the cytoskeleton in the phosphorylated form thereof. Therefore, it is called a microtubule-associated protein. In AD, the tau-protein undergoes chemical changes and becomes hyperphosphorylated. It then begins to pair with other thread, creating neuro-fibrillary tangles and disintegrating the neuron's transport system.
[0026] Furthermore, the degeneration of the muscarinergic cholinerg neurons in AD is associated with a chronic deficiency of the neurotransmitter acetylcholine (ACh), resulting in a significantly decreased signal transmission between the affected neurons.
[0027] Up to now, there is no cure for Alzheimer's disease. Available treatments offer relatively small symptomatic benefit but remain palliative in nature. Current treatments can be divided into pharmaceutical, psychosocial and caregiving. Four medications are currently approved by regulatory agencies to treat the cognitive manifestations of AD. Three of them can be classified as acetylcholine esterase inhibitors and the remaining one is an NMDA receptor antagonist. However, no drug has an indication for delaying or halting the progression of the disease.
[0028] Thus, on the whole, Alzheimer's disease (AD) is a steadily increasing threat, especially for industrialized countries with a growing percentage of old individuals. Research on potential therapies has been going on for several decades now, without producing one single drug which is able to cure Alzheimer's disease. Since AD is accompanied by many diverse symptoms, numerous avenues have been exploited in the search of a therapy. Antiinflammatory, antihypertensive as well as hypolipidemic agents, passive and active immunisation, cholinergic therapies, neuroprotective agents, glutamate receptor antagonists, β- and γ-secretase inhibitors, β-amyloid and tau aggregation inhibitors, metal chelating agents, monoamine oxidase inhibitors, medicinal plants are only a number of the most prominent classes. In recent years passive immunization with Aβ-specific antibodies held most promise for a breakthrough, however, the results of phase II clinical trial revealed only moderate or weak effects with a large percentage of treated patients. As a consequence, the call for small molecules was revived and reinitiated.
[0029] A plethora of small molecules has been screened in the past three decades for their antiaggregation potential against the Alzheimer's peptide. Among these, often colored heterocyclic compounds have been identified, which are in general thought to somehow intercalate between the insoluble cross-β-sheet structure of Aβ fibrils (e.g. congo red, rifampicin, melatonin, cucurmin) Zn— and Cu-chelating agents were thought to lower the aggregation tendency of monomeric Aβ strands (clioquinol). Another prevailing class of compounds are peptides, in some cases taken directly from putative nucleation sites within the Aβ molecule, however, only very few of these compounds stem from rational design with a known structural motif in their complexes with Aβ-monomers, oligomers or fibrils. In this context, a β-sheet breaker LPFFD (iAbeta5) retained the high affinity towards the self-complementary KLVFF region of Aβ, but impaired its β-sheet forming propensity by introducing a proline-kink; the D-peptide LVFFV (PPI-1019) essentially interferes with the aggregation of β-amyloid in the brain and may help to promote its clearance. Furthermore, in prior art, hybrid peptides built from KLVFF and a highly charged KKKKK or EEEEE terminus have been synthesized. Aggregation of toxic Aβ oligomers is promoted because of an increased surface tension.
[0030] Another prominent class are alternating N-methylated and non-methylated peptide amides or esters. These are able to cap growing β-sheets without the ability of crosslinking because their back is blocked for hydrogen bonding due to the sterically demanding N-methyl groups or ester oxygens. These substances have recently been optimized with respect to the antiaggregatory capacity by introduction of three cyclohexylglycine units and reached nanomolar IC 50 values. The compound is also thought to accelerate Aβ self-assembly and thereby deplete the level of neurotoxic Aβ-oligomers. Other examples comprise the small molecule homotaurin, which disrupts complexes between Aβ and glucosaminoglycans. Scyllo-inositol appears to bind oligomers of Aβ 42 , preventing them from damaging synapses. Oligomer-specific Aβ antibodies indicated that scyllo-inositol appears to increase the number of monomers and trimers while reducing the amount of larger oligomeric species, such as 40 mers. A recent approach focuses on Aβ binders from D-peptide libraries by phage display methods.
[0031] However, little knowledge and information is available on the exact mechanism of action for most Aβ complexing agents, even less on structural details. Furthermore, the effectiveness of the substances is not always sufficient and there are also questions arising with regard to the physiological compatibility of the substances.
[0032] Furthermore, a promising approach with regard to the treatment of AD base on the use of aminopyrazoles, which have proven to bind selectively to the backbone of misfolded peptides residing in the β-sheet confirmation.
[0033] In prior art, several aminopyrazoles were synthesized with additional side chains for enhanced water solubility. A combination of two consecutive proteinogenic amino acids, flanked by external aminopyrazolecarboxylate was shown to be complementary to an extended β-sheet. Such derivatives were synthesized and also evaluated on the solid phase. Direct interaction of dimeric and trimeric aminopyrazole derivatives with the mouse prion protein as well as with Aβ(1-42) was shown and characterized by SDS-PAGE (Sodium Dodecyl Sulphate Polyacrylamide Gel Electrophoresis), FCS (Fluorescence Correlation Spectroscopy), AUC (Analytical Ultra Centrifugation), density gradient centrifugation as well as HRMS (High Resolution Mass Spectrometry). The β-sheet recognition as well as the individual strength of all hydrogen bonds involved were also studied in prior art by R2PI spectroscopy on a cooled argon jet stream. It is also known that a trimeric aminopyrazole carboxylate trimer is capable to disassemble preformed Aβ-fibrils in a dose- and time-dependant manner. However, all the aforementioned substances only exhibit a moderate effect with regard to the target structure and are neither optimized with respect to an improved effectiveness in view of an improved compatibility and availability at the pharmacological site of action.
[0034] WO 03/095429 A1 refers to substances having a donor-acceptor/donor-structure on the basis of heterocyclic compounds being linked to specific residues. The donor/acceptor/donor-pattern corresponds to the β-pleated sheet structure of a misfolded protein. The substances described in this document prevent in some respects the aggregation of misfolded proteins into β-amyloid plaques.
[0035] Furthermore, WO 2007/112922 A1 relates to trimeric water-soluble aminopyrazole compounds having a radical at the N-terminal site of the molecule in the form of a straight-chain or branched alkyl group or an amino acid group or a polyamino acid group and having a specific radical at the C-terminal site of the molecule in the form of a NOH, OR 3 or NHR 3 group, in which R 3 is a straight chain or a branched alkyl group or an amino acid group or a polyamino acid group. The molecules described in this document also have a certain effect on the Aβ-protein.
[0036] Although the respective substances named in the above documents have a certain effect on Aβ-protein, there still remains a great need and potential for a further improvement of the effectiveness of substances especially interacting with misfolded proteins, like the Aβ-protein. Furthermore, there also still remains a need to improve the bioavailability of these substances, especially at the place and/or site of pharmacological action, in particular taking into consideration the penetration of the blood/brain-barrier.
[0037] Thus, especially in view of the seriousness of protein misfolding diseases like Alzheimer's disease and the high incidence of these diseases, there is an urgent need for providing new therapeutic approaches and new therapeutic compounds being effective with respect to the treatment of protein misfolding diseases like Alzheimer's disease.
BRIEF SUMMARY OF THE INVENTION
[0038] Therefore, especially in the light of the above-mentioned medical background, it is an object of the present invention to provide a new and effective concept or approach with respect to the prophylactic and/or therapeutic (i.e. curative) treatment of protein misfolding diseases, like Alzheimer's disease, which is to overcome or at least to diminish the aformentioned disadvantages linked to the prior art methods.
[0039] Especially, it is an object of the present invention to provide specific pharmacologically active substances or compounds exhibiting a high effectiveness in the field of the treatment of protein misfolding diseases.
[0040] Furthermore, it is another object of the present invention to provide specific substances having an improved effectiveness with regard to protein misfolding diseases, like Alzheimer's disease, and which also have reduced side-effects if compared to the prior art substances, thereby at the same time being highly effective at the site of pharmacological action, i.e. having improved properties with respect to the uptake and incorporation into the region of the brain, especially in view of an improved penetration capability through the blood/brain-barrier.
[0041] Surprisingly, applicant has found out that the aforedescribed objects can be solved, inter alia, by the subject-matter described herein; further, especially advantageous embodiments are the subject-matter of the respective claims.
[0042] Furthermore, according to another aspect of the present invention, the present invention refers to specific trimeric pyrazole compounds for the prophylactic and/or therapeutic (curative) treatment of a protein misfolding disease described herein. Further, especially advantageous embodiments are the subject-matter of the respective dependent claims.
[0043] Moreover, according to further aspects of the present invention, the present invention also refers to the respective uses of the trimeric pyrazole compound of the invention described herein. Further, especially advantageous embodiments are the subject-matter of the respective claims.
[0044] Furthermore, according to a further aspect of the present invention, the present invention refers to a medicament or a pharmaceutical composition described herein; further, especially advantageous embodiments are the subject-matter of the respective claims.
[0045] The present invention also refers, according to another aspect of the present invention described herein, to a kit, the inventive kit comprising the trimeric pyrazole compounds of the present invention. Further preferably advantageous embodiments are the subject-matter of the respective claims.
[0046] Finally, according to another aspect of the present invention, the present invention refers to a method of treating a human or an animal suffering from a protein misfolding disease described herein. Further, especially advantageous embodiments are the subject-matter of the respective method claims.
[0047] In the following, it has to be noted that explanations, details, examples etc. given with respect to one aspect of the present invention only shall, of course, also refer to all the other aspects of the present invention, even without explicit mentioning of this fact. Thus, it may well be in the following, that specific aspects, explanations, details etc. are only delineated with respect to one specific embodiment only in order to avoid unnecessary repetitions, but they also apply with respect to all the other aspects of the present invention.
[0048] Applicant has now surprisingly found out a new approach for the treatment of protein misfolding diseases thereby using specific trimeric pyrazole compounds.
[0049] Especially, applicant has found out that trimeric pyrazole compounds of the present invention having a nitro group —NO 2 , on its one end (i.e. at the first pyrazole ring), and, on its opposite or other end (i.e. at the third pyrazole ring), specific ligands and/or groups possess outstanding properties with regard to the inhibition or the decrease of protein misfolding, especially with regard to misfolded proteins having beta-sheet structures, like the Aβ-protein, and the respective aggregation thereof.
[0050] With respect to the protein misfolding diseases, besides the Aβ-protein, also the aforenamed amylin (IAPP), synuclein proteins and prion molecules especially associated with CJD may represent the pharmacological target for the inventive trimeric pyrazole compounds. In general, the present invention is not limited to the aforenamed proteins. For, the inventive trimeric pyrazole compounds can be in general tailored with regard to the specific pharmacological target, especially in so far as they are related with or cause protein misfolding diseases and exhibit an abnormal and/or pathogenic β-sheet structure. On the whole, the β-sheet structure of the misfolded protein represents a common basic structure, which is targeted by the inventive concept.
[0051] With regard to the inventive trimeric pyrazole compounds, one central motif thereof has to be seen in the trimeric combination or condensation or linkage of three single pyrazoles, especially wherein two aminopyrazoles and one nitropyrazole are linked to form the trimeric central motif of the inventive compounds.
[0052] For, applicant has shown that the respective inventive aminopyrazoles exhibit a specific donor/acceptor/donor-sequence (DAD-sequence or DAD-structure) which is able to interact with the corresponding sequence of a misfolded protein, especially in the form of a β-sheet. Also for this reason, the inventive trimeric pyrazole compounds act as β-sheet ligands which are able to interact and bind, respectively, with the pharmacological target structure, i.e. the respective misfolded protein structure, especially with the protein in β-pleated form.
[0053] Without being bound to this theory, on the basis of the so-called key/lock-mechanism, the respective molecular target exhibits complementary structures with regard to the hydrogen bond donors and acceptors on the basis of the DAD-sequence of the inventive trimeric pyrazole compounds. In this context, without being bound to this theory, the acceptor-motif of the inventive trimeric pyrazole compound is provided by the respective carbonyl groups (C═O-groups) of the molecule, wherein the donor structures are provided by the respective amide groups (NH-groups) of the molecule. With regard to the interaction of the inventive trimeric pyrazole compound and the target molecule, i.e. the respective misfolded protein, the interaction is generally based on hydrogen bonds. However, the interaction is generally not limited to this intermolecular interaction, but also extends to any other interactions forms, which are as such well known to the skilled practitioner as such.
[0054] With respect to the inventive trimeric pyrazole compounds, applicant has now surprisingly found out that the use of specific ligands on both end sites of the trimeric pyrazole, i.e. a nitro group —NO 2 , on its one end (i.e. at the first pyrazole ring), and specific ligands and/or groups on its opposite or other end (i.e. at the third pyrazole ring), results in an outstanding and surprising improvement of the effectiveness with respect to the interaction of the inventive trimeric pyrazole compounds to target structures, i.e. with respect to the misfolded proteins and/or peptides which reside in the so-called β-sheet-conformation. In this context, the inventive compounds—without being bound to that theory—perfectly fit to the backbone of the misfolded peptides. This results in a strong inhibition of the growing of Aβ-ensembles. Furthermore, the inventive compounds also exhibit a strong interaction with regard to preformed Aβ-fibrills which leads to their disassembly.
[0055] Due to the specific optimization of the terminal groups of the trimeric pyrazole compounds of the invention, a decisive improvement of the interaction between the trimeric pyrazole compound, on the one hand, and the target protein, on the other hand, is realized, resulting in an outstanding complementary fit and thus improved interaction between the trimeric pyrazole compound and the pharmacological target. Thus, the inventive trimeric pyrazole compounds exhibit a high affinity and specifity with regard to the misfolded proteins residing in the β-sheet conformation.
[0056] Thus, on the whole, one central gist of the present invention has to be seen in the fact that on the basis of a specific modification of a pyrazole basic structure with purposefully selected ligands, a significant optimization of the key/lock-mechanism and thus of the specifity and affinity of the trimeric pyrazole compounds of the present invention with regard to the target structure has been realized, resulting in outstanding therapeutic properties of the inventive compounds with regard to diseases basing on protein misfolding, e.g. Alzheimer's disease.
[0057] Thus, according to a first aspect of the present invention, there is provided a trimeric pyrazole compound of the general formula (I)
[0000]
[0058] wherein in the general formula (I) the group Z denotes a group X—Y,
wherein X denotes:
(i) a single bond or (ii) a group of the general formula (II)
[0000]
wherein in the general formula (II) the group R′ denotes a divalent rest selected from C 2 -C 10 -alkylene and n is an integer selected in the range of from 1 to 20, especially 2 to 15, preferably 3 to 10;
wherein Y denotes:
(i) a group —O − or a group —OH; (ii) a carboxylic acid radical or a (poly)amino acid radical or its salts, especially pharmacologically acceptable salts; its esters, especially alkyl or aryl esters; or its amides; (iii) an amine or diamine radical which is optionally protonated.
[0067] Thus, with regard to the generic formula (I) and according to the inventive concept, the trimeric pyrazole compound is provided at its one end (i.e. at the first pyrazole ring; in general also denoted as the N-terminal end or site of the trimeric pyrazole) with a nitro group (NO 2 -group) as delineated on the left end of the molecule as presented in formula (I). Furthermore, the trimeric pyrazole of the present invention exhibits a deprotonized hydroxy group or a specific radical basing on a molecule comprising or consisting of a specific group Z═X—Y on its opposite or other end (i.e. at the third pyrazole ring; in general also denoted as the C-terminal end or site of the trimeric pyrazole) as delineated on the right end of the molecule as presented in formula (I), wherein X may act as a spacer and Y may act as a further interacting part of the molecule especially with regard to the misfolded protein structure. Due to the specific chemical structure of the trimeric pyrazole compounds of the present invention, a highly complementary structure to target proteins, i.e. misfolded proteins and/or peptides residing in the β-sheet structure, is provided, resulting in an outstanding pharmacological effectiveness.
[0068] With regard to the present invention, the trimeric pyrazole motif as given in formula (I) is also abbreviated as “Trimer” and/or “Trim”, so that both abbreviations are synonymously used for the trimeric pyrazole basic structure of the inventive compounds, however, with the proviso that the abbreviation “Trimer” and “Trim” refers to the trimeric pyrazole basic structure as given in formula (I) without the group Z. Thus, “Trimer” and/or “Trim” generally refers to the molecular structure on the basis of formula (I), however, without the group Z as such.
[0069] It is well understood by the skilled practitioner that the above general formula (I) also comprises and refers to all possible tautomeric structures or forms of the above molecule or formula, respectively, such as e.g. all N—NH-tautomers but also others, especially as exemplified by the following formulae or scheme:
[0000]
[0070] According to a preferred embodiment of the present invention, in the above general formula (I) of the trimeric pyrazole compounds of the present invention as defined above:
X denotes:
(i) a single bond or (ii) a group of the general formula (II)
[0000]
wherein in the general formula (II) the group R′ denotes a divalent rest selected from C 2 -C 10 -alkylene and n is an integer selected in the range of from 1 to 20, especially 2 to 15, preferably 3 to 10;
Y denotes:
(i) a group —O − or a group —OH; (ii) a (poly)amino acid radical or its salts, especially pharmacologically acceptable salts; its esters, especially alkyl or aryl esters; or its amides; (iii) an amine or diamine radical which is optionally protonated.
[0079] According to another preferred embodiment of the present invention, in the above general formula (I) of the trimeric pyrazole compounds of the present invention as defined above:
X denotes a single bond if Y denotes a group —O − or a group —OH; or X denotes a single bond or a group of the general formula (II) as defined above if Y denotes (ii) a (poly)amino acid radical or its salts, especially pharmacologically acceptable salts; its esters, especially alkyl or aryl esters; or its amides or (iii) an amine or diamine radical which is optionally protonated.
[0082] According to yet another preferred embodiment of the present invention, in the above general formula (I) of the trimeric pyrazole compounds of the present invention as defined above X denotes a single bond or a group of the general formula (II) as defined above and Y denotes (ii) a (poly)amino acid radical or its salts, especially pharmacologically acceptable salts; its esters, especially alkyl or aryl esters; or its amides or (iii) an amine or diamine radical which is optionally protonated.
[0083] According to a preferred embodiment, X in the aforementioned formula (I) may denote a group of the general formula (III)
[0000]
[0084] wherein in the general formula (III) n is an integer selected in the range of from 1 to 20, especially 2 to 15, preferably 3 to 10.
[0085] According to a further preferred embodiment of the present invention, the group X in the aforementioned formula (I) denotes a group of the general formula (IV)
[0000]
[0086] The aforenamed group of the general formula (IV) is also abbreviated, in the following, as “TEG”.
[0087] With respect to the aforenamed formulae (III) and (IV), this respective molecular structure may act—in a manner of speaking—as a spacer the existence of which further optimizes the effectiveness of the inventive molecule. In this context, applicant has specifically found out that the use of a specific spacer, especially of a TEG-spacer, leads to a further improvement of the suppression of Aβ-fibril formation, especially when combined with further amino acid residues, especially as delineated hereinafter. Without being bound to that specific theory, the TEG-spacer may serve in a dual purpose in so far as it brings recognition units (e.g. the unit Y) close to the U-turn of the fibril and simultaneously protrudes itself into the interior of two parallel Aβ-strands, facilitating further destabilization of the fibrillar structure. The TEG-spacer is in a manner of speaking able to smoothly intercalate between both peptide strands.
[0088] According to a further embodiment of the present invention the (poly)amino acid radical may be derived from α- to ω-amino acids, especially α- and/or β-amino acids, preferably α-amino acids.
[0089] The designation “α- to ω-amino acids” is well known to the skilled practitioner and refers in general to the positioning of the carboxyl group with respect to the amino group of the amino acid.
[0090] According to a further alternative embodiment of the present invention, the (poly)amino acid radical may be derived from proteinogenic or non-proteinogenic amino acids, preferably proteinogenic amino acids.
[0091] According to the present invention, the (poly)amino acid radical may be derived from naturally occurring amino acids.
[0092] In this context, applicant has surprisingly found out that an especial high effectiveness with respect to the interaction to Aβ can be realized under the proviso that the (poly)amino acid radical is derived from the group consisting of lysine, glycine, cyclohexylglycine, leucine, isoleucine, proline, phenylalanine, aspartic acid, amino butyric acids, especially γ-aminobutyric acid, valine and combinations thereof, preferably lysine.
[0093] In this context, especially the use of lysines results in further improved properties of the respective trimeric pyrazole compounds of the invention, especially when combined with a TEG-spacer. In this context, it has been surprisingly found out that the combination of one terminal lysine being bonded to the trimeric pyrazole basic structure via a TEG-spacer results in a very potent compound of the invention with regard to its effectiveness against the respective target structure, especially Aβ. Also multiple lysines result in outstanding properties with regard to the misfolded protein, especially if combined with the TEG-spacer.
[0094] With respect to the inventive trimeric pyrazole compound it is preferred according to the present invention that the (poly)amino acid radical is attached or linked via an amide and/or peptide bond.
[0095] Furthermore, according to another preferred embodiment of the present invention, the polyamino acid radical may comprise or may be composed of at least two or more amino acids attached or linked to each other via an amide and/or peptide bond each.
[0096] The chemical bonding on the basis of amide and/or peptide bonds results in an optimized three-dimensional structure of the inventive compound, further improving the key/lock-mechanism with respect to the interaction with the molecular target structure.
[0097] Furthermore, the trimeric pyrazole compound of the present invention is configured such that the polyamino acid radical comprises or is composed of from 2 to 20 amino acids, especially 2 to 10 amino acids, preferably 2 to 6 amino acids, preferably wherein the amino acids are attached or linked to each other via an amide and/or peptide bond each.
[0098] Furthermore, according to another preferred embodiment of the present invention, the polyamino acid radical may comprise or may be composed of polylysine units optionally combined with at least one amino acid different from lysine and preferably terminally positioned.
[0099] With respect to the abovementioned formula (I) and according to a preferred embodiment of the present invention, the group Z is preferably selected from the group consisting of the following radicals:
[0000]
[0100] With respect to the abovementioned formula (I) and according to yet another preferred embodiment of the present invention, the group Z is preferably selected from the group consisting of the following radicals:
[0000]
[0101] In this context, with regard to the abovementioned specific radicals Z, applicant has surprisingly found out that the specific trimeric pyrazole compounds of the present invention comprising the specific groups have further improved and ameliorated properties with respect to their effectiveness to bind to the respective misfolded proteins or their respective precursors thereof, especially with regard to growing Aβ ensembles and the respective protein aggregates. Furthermore, applicant has surprisingly found out that especially the aforenamed specific trimeric pyrazole compounds of the invention do not only inhibit the growth of the pathogenic protein ensembles, but also leads to the disassembly of already formed or preformed protein aggregates, like preformed Aβ-fibrills. In this context, the aforenamed trimeric pyrazole compounds of the invention exhibit an even more improved and increased effectiveness if compared to the respective compounds of the prior art. This finding is specifically proved by applicant's investigation, as especially presented hereinafter. On the whole, the outstanding performance of the specific trimeric pyrazole compounds of the invention was not at all anticipated and points to their rate impact and potential with regard to the prophylactic and/or therapeutic treatment of the respective protein misfolding diseases, especially Alzheimer's disease (AD). Thus, on the whole, the present invention focuses on the provision of very effective substances on the basis of trimeric pyrazole compounds being able to prevent and inhibit, respectively, the misfolding of proteins, thereby also exhibiting an significant effectiveness with respect to the disassembly of misfolded proteins and/or their respective aggregates. Therefore, the inventive trimeric pyrazole compounds have a decisive impact with regard to neurodegenerative diseases.
[0102] According to a second aspect of the present invention, the present invention refers to the abovedefined trimeric pyrazole compound for the prophylactic and/or therapeutic (curative) treatment of a protein misfolding disease.
[0103] In this context, according to a preferred embodiment of the present invention, the protein misfolding disease is associated with or caused by misfolding of a protein into an abnormal and/or pathogenic β-sheet, especially in combination with a subsequent protein aggregation.
[0104] The protein misfolding disease is preferably selected from the group of neurodegenerative diseases and/or dementia and/or prion diseases, especially Alzheimer's diseases (AD), Parkinson's disease, Creutzfeldt-Jakob disease, Huntington's disease and the like.
[0105] However, the present invention is not limited to the abovenamed diseases. In fact, the inventive concept can be generally applied to any disease being related to or caused by especially conformational changes of proteins from a healthy and/or normal state into an abnormal and/or pathogenic condition. In this context, the inventive trimeric pyrazole compounds can be specifically tailored with regard to the respective target structure, i.e. with regard to the specific protein or protein structure as the molecular target of the inventive trimeric pyrazole compounds.
[0106] With regard to the present invention, the protein misfolding disease is preferably Alzheimer's disease (AD).
[0107] However, the present invention is not limited to neurodegenerative as such. In this context, the inventive trimeric pyrazole compounds also exhibit an effectiveness with regard to other protein misfolding diseases. In this context, the protein misfolding disease may be Diabetes mellitus, especially Diabetes mellitus type II.
[0108] Furthermore, according to a third aspect of the present invention, the present invention also refers to the use of at least one trimeric pyrazole compound as defined above for the prophylactic and/or therapeutic (curative) treatment of a protein misfolding disease.
[0109] Furthermore, according to a fourth aspect of the present invention, the present invention also refers to the use of at least one trimeric pyrazole compound as defined above for producing a medicament or a pharmaceutical composition for the prophylactic and/or therapeutic (curative) treatment of a protein misfolding disease.
[0110] With respect to the inventive uses according to the third and fourth aspect of claimed invention, the protein misfolding disease may be associated with or caused by misfolding of a protein into an abnormal and/or pathogenic β-sheet, especially in combination with a subsequent protein aggregation.
[0111] As delineated above, the protein misfolding disease may be selected from the group of neurodegenerative diseases and/or dementia and/or prion diseases, especially Alzheimer's disease (AD), Parkinson's disease, Creutzfeldt-Jakob disease and Huntington's disease.
[0112] According to a preferred embodiment of these aspects of the present invention, the protein misfolding disease is Alzheimer's disease (AD).
[0113] Furthermore, it is also possible according to the present invention that the protein misfolding disease is Diabetes mellitus, especially Diabetes mellitus type II.
[0114] With regard to the third and fourth aspect of the present invention, the trimeric pyrazole component may be administered in a therapeutically effective amount, i.e. in an amount which provides for an effectiveness with regard to the inhibition and all decrease of the forming of pathogenic protein conformations and/or to provide for an effective disassembly of already formed misfolded proteins or aggregates thereof.
[0115] In this context, the amount an/or concentration of the active agent (i.e. of the trimeric pyrazole compound of the invention with regard to its administration can vary widely and will be in general selected by the skilled practitioner in dependence on the activity of the respective trimeric pyrazole compound, body weight of the person concerned, bioavailability and the side of pharmacological action and the like. In this context, according to a typical embodiment, the dosage of the inventive trimeric pyrazole compound may range from 0.0001 to 100 mg/(kg·day), especially from 0.001 to 50 mg/(kg·day), preferably 0.01 mg/(kg·day) to 10 mg/(kg·day), referred to the body weight of a person concerned.
[0116] According to the present invention, there is also provided—according to a fifth aspect of the present invention—a medicament or a pharmaceutical composition, especially for the prophylactic and/or therapeutic (curative) treatment of protein misfolding diseases, wherein the medicament and/or pharmaceutical composition comprises at least one trimeric pyrazole compound as defined above. In this context, the medicament or pharmaceutical composition may comprise at least one pharmaceutically acceptable excipient. The respective pharmaceutically acceptable excipients are well-known to the skilled practitioner per se and the skilled practitioner is always able to select the respective excipients with regard to their nature and amounts especially in view of the respective inventive trimeric pyrazole compound to be used in the medicament or pharmaceutical composition.
[0117] According to another embodiment of the claimed invention, the medicament or pharmaceutical composition of the invention may be designed as a unit dosage formulation.
[0118] In this context, the medicament or pharmaceutical composition may be formulated to be administered and/or applied intravenously, subcutaneously, intraperitoneally, intrathecally, intravesically, topically, orally, rectally, transdermally, subdurally and/or inhalatively.
[0119] Especially with regard to a systematically administration and/or application of the inventive trimeric pyrazole compounds, it has to be denoted that the inventive compounds exhibits in general also outstanding characteristics with respect to their ability to penetrate and/or to cross the blood/brain-barrier. In this context, the inventive trimeric pyrazole compounds may exhibit specifically optimized physicochemical properties, especially with regard to their lipophylic properties, which allows them to penetrate in a sufficient manner through blood/brain-barrier in order to be present in an effective amount at the side of pharmacological action, i.e. especially in the region of the neuronal cells in the brain for the case of neurodegenerative diseases.
[0120] However, the penetration properties with respect to the blood/brain-barrier may be further enhanced by coadministering the inventive trimeric pyrazole compounds with carrier molecules or the like, which are well-known to the skilled practitioner. For example, the inventive trimeric pyrazole compounds may be administered together with specific peptides, like arginin-rich peptides and/or cationic dendrimers. However, it is also possible to directly administer the inventive trimeric pyrazole compounds to the brain, e.g. via implantation of a specific released system.
[0121] The present invention also refers—according to a sixth aspect of the present invention—to a kit, the kit comprising at least one trimeric pyrazole compound as defined above. In this context, with respect to the kit of the present invention, the trimeric pyrazole compound may be deposited in a storage and/or application unit.
[0122] Furthermore, the kit of the present invention may comprise instruments for formulating and/or administering the trimeric pyrazole compound of the invention. The inventive kit may also comprise a labeling and/or instructional materials, especially for the administration and/or dosage and/or application of the inventive trimeric pyrazole compound.
[0123] Furthermore, with regard to the inventive kit, the kit may also comprise the inventive trimeric pyrazole compound in the form of the medicament or pharmaceutical composition as described above on the basis of the fifth aspect of the present invention.
[0124] With regard to the kit of the present invention, it is also possible that the kit may also comprise at least one agent used in the treatment of protein misfolding diseases, especially of diseases which are associated with or caused by misfolding of a protein into an abnormal and/or pathogenic β-sheet, especially in combination with the subsequent protein aggregation, and/or for the prophylactic and/or therapeutic treatment of neurodegenerative diseases, preferably Alzheimer's disease (AD), the agent being different from the trimeric pyrazole compound of the invention. Thus, the inventive trimeric pyrazole compound may be combined with other active agents which are routinely used for the treatment or prevention of a protein misfolding disease.
[0125] Moreover, according to a seventh aspect of the present invention, the present invention also refers to a method of treating a human or an animal suffering from a protein misfolding disease. The method comprising administering an efficient amount of at least one trimeric pyrazole compound as defined above.
[0126] With regard to the inventive method of treating a human or an animal suffering from a protein misfolding disease, the protein misfolding disease may be associated with or caused by misfolding of a protein into an abnormal and/or pathogenic β-sheet, especially in combination with a subsequent protein aggregation.
[0127] As already delineated above, the protein misfolding disease may be selected from the group of neurodegeneration diseases and/or dementia and/or prion diseases, especially Alzheimer's disease (AD), Parkinson's disease, Creutzfeldt-Jakob disease and Huntington's disease.
[0128] According to a preferred embodiment, also with respect to the method of the invention, the protein misfolding disease is Alzheimer's disease (AD).
[0129] Furthermore, it is also possible according to the inventive concept, that the protein misfolding disease is Diabetes mellitus, especially Diabetes mellitus type II.
[0130] According to the present invention, it is preferable that the trimeric pyrazole compound is administered together with at least one pharmaceutically acceptable excipient.
[0131] Furthermore, the trimeric pyrazole compound is preferably administered in a pharmaceutically effective amount.
[0132] For further explanations, reference is also made to the further aspects of the present invention, which apply accordingly.
[0133] Moreover, according to a eighth aspect of the present invention, the present invention also refers to a method of synthesizing and/or producing the trimeric pyrazole compound of the present invention as defined above.
[0134] For the case that in the above general formula (I) X denotes a single bond and Y denotes a group of —O − or OH the synthesis is effected by ester cleavage and subsequent deprotection reaction of the compound of general formula (Ia′) according to the following reaction scheme:
[0000]
[0135] wherein in the general formula (Ia′) “PMB” denotes the protective group “para-Methoxybenzyl” and “Me” denotes “methyl” (i.e. CH 3 ) and wherein in the general formula (IIa′) “M” denotes hydrogen. The compound of the general formula (Ia′) may be obtained according to WO 03/095429 A1, the whole contents of which is hereby incorporated by reference (see especially Example 4, Molecule 12).
[0136] For all other cases (i.e. especially if X denotes a single bond or a group of the general formula (II) as defined above and if Y denotes (ii) a (poly)amino acid radical or its salts, especially pharmacologically acceptable salts; its esters, especially alkyl or aryl esters; or its amides or (iii) an amine or diamine radical which is optionally protonated) the reaction is performed according the reaction scheme of FIG. 1C and will be delineated hereinafter. Especially, as it may be derived from FIG. 1C , a compound of the general formula (Ia) comprising protective groups “PMB” as defined above is coupled in the presence of an coupling reagent with a species or molecule HN—Z′ (wherein Z′ corresponds to the aforedefined group “Z”, however, without the NH-unit, i.e. Z═—NH—Z′), followed by deprotection reaction. The compound of the general formula (Ia) is e.g. obtained by ester cleavage of the aforedefined compound of the general formula (Ia′).
[0137] Further embodiments, modifications and variations of the present invention are obvious to the skilled practitioner by reading the present specification and/or can be implemented by him without leaving the scope of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0138] FIGS. 1A and 1B display Lewis structures of unprotected aminopyrazole trimer derivatives with appendices Z. Left: small neutral, anionic and cationic moieties, as well as unpolar and TEG-spacered groups. Right: peptidic attachments.
[0139] FIG. 1C shows a synthetic access to the new C-terminally modified aminopyrazole trimers via peptide coupling of various amines onto the PMB-protected trimer and final total deprotection.
[0140] FIGS. 2A and 2B show the kinetics of Aβ aggregation in PBS buffer (pH 7.3) in the absence and presence of selected trimeric pyrazole inhibitors; FIG. 2A : Aβ (1-40), FIG. 2B : Aβ (1-42).
[0141] FIG. 3 discloses the kinetics of Aβ disaggregation effected by addition of a 6-fold excess of trimeric aminopyrazole inhibitors to preformed fibrillar aggregates (33 μM in PBS).
[0142] FIGS. 4A and 4B show the equilibrium of 33 μM Aβ42 aggregation ( FIG. 4A ) vs. disaggregation ( FIG. 4B ) in the absence or presence of trimeric aminopyrazole inhibitors (each at 198 μM); FIG. 4A shows the inhibition of aggregation and FIG. 4B the disaggregation (10 mM PBS, pH 7.3). For each bar, 6 measurements were averaged.
[0143] FIG. 5 displays aMD simulation of the complex between Aβ and the parent aminopyrazole trimer (10 ns).
[0144] FIG. 6A to 6F show the results of sedimentation velocity centrifugation: s-value-distributions of Aβ samples in the presence of Trimer-OH ( FIG. 6A , FIG. 6B , FIG. 6C ) vs. Trim-TEG-OEt ( FIG. 6D , FIG. 6E , FIG. 6F ).
[0145] FIG. 7 shows TEM pictures. A: Aβ(1-42) fibrils. B-F: Aβ(1-42) mixtures (20 μM) with aminopyrazole trimer derivatives (100 μM). B: Trim-OMe; C: Trim-OH, D: Trim-Che; E: Trim-Lys-OMe; F: Trim-TEG-Lys-OMe; G: Trim-TEG-OEt; H: Trim-TEG-OH.
[0146] FIG. 8 displays MD simulations (5 ns) of the complex between Aβ and an aminopyrazole trimer with attached nonpolar binding site; left Trim-Chg-Che; center Trim-Lys-Che; right Trim-TEG-Dodecyl.
[0147] FIG. 9 displays MD simulations of the complexes between Aβ and Trimer-Lys vs. Trim-TEG-Lys.
[0148] FIG. 10A shows a MD simulation of the complex between Aβ and Trimer-TEG-OEt; FIG. 10B shows FCS (Fluorescence Correlation Spectroscopy) measurements at 5 nm Aβ with Trimer-OH in comparison to Trim-TEG-OH/OEt (each at 10 μM).
[0149] FIG. 11A to 11C show typical CD spectra recorded for aggregated Aβ(1-42) alone (curve 5 in FIGS. 11A-11C ) and after addition of aminopyrazole ligand (Type A: Trimer-Lys: FIG. 11A ; Type B: Trimer-KKKKKG: FIG. 11B ; Type C: Trimer-Lys-Che: FIG. 11C ).
[0150] FIG. 12 displays a MD simulation of the complex between Aβ and Trimer-KKKKG.
[0151] FIGS. 13A and 13B display viability assays of PC-12 cells with trimeric aminopyrazoles (100 μM). FIG. 13A shows Aβ lesion control at ˜70%, FIG. 13B at ˜80% viability.
[0152] FIG. 14 shows a dose-response curve for the inhibition of Aβ-induced toxicity in PC-12 cells by Trimer-LPFFD (IC 50 =3.1 mM).
[0153] FIG. 15 shows dose-response curves for the inhibition of Aβ-induced toxicity in PC-12 cells by aminopyrazole trimer derivatives.
DETAILED DESCRIPTION OF THE INVENTION
[0154] The present invention is illustrated on the basis of the following detailed explanations and exemplary embodiments as well as experimental data, which, however, do not limit the present invention in any way.
[0155] In the following, a detailed description of the inventive concept is given on the basis of applicant's studies and investigations, respectively, comprising experimental data which focus on the specific impact of active agents on the basis of inventive trimeric pyrazole compounds on the misfolding of proteins, especially Aβ and the respective aggregation thereof.
[0156] Detailed explanation and exemplification of the present invention:
[0157] Introduction and prior art. As delineated before, Alzheimer's disease (AD) is a steadily increasing threat especially for industrialized countries with a growing percentage of old individuals—today an estimated 5.3 million U.S. citizens are suffering from dementia and the number is predicted to quadruple within the next 50 years. Research on potential therapies has been going on for several decades now, without producing one single drug which is able to cure Alzheimer's disease. Since AD is accompanied by many diverse symptoms, numerous avenues have been exploited in the search for a therapy. Antiinflammatory, antihypertensive as well as hypolipidemic agents, passive and active immunization, cholinergic therapies, neuroprotective agents, glutamate receptor antagonists, β- and γ-secretase inhibitors, β-amyloid and Tau aggregation inhibitors, metal chelating agents, monoamine oxidase inhibitors, medicinal plants are only a number of the most prominent classes (Review: Michael S. Wolfe, Nat. Rev. Drug Disc. 2002, 1, 859-866). In recent years passive immunization with Aβ-specific antibodies held most promise for a breakthrough; however, the results of phase II clinical trials revealed only moderate to weak effects with a large percentage of treated patients. As a consequence, the call for small molecules was revived/reinitiated.
[0158] A plethora of small molecules has been screened in the past 3 decades for their antiaggregation potential against the Alzheimer's peptide (Bisstyrylbenzenes: D. P. Flaherty, S. M. Walsh, T. Kiyota, Y. Dong, T. Ikezu, J. L. Vennerstrom, J. Med. Chem., 2007, 50, 4986-4992). Among these, often colored heterocyclic compounds have been identified, which are in general thought to somehow intercalate between the insoluble cross-β-sheet structure of Aβ fibrils (congo red, rifampicin, melatonin, cucurmin (Yang, F., Lim, G. P., Begum, A. N., Ubeda, O. J., Simmons, M. R., Ambegaokar, S. S., Chen, P. P., Kayed, R., Glabe, C. G., Frautschyj, S. A., and Cole, G. M. (2005) Curcumin inhibits formation of amyloid oligomers and fibrils, binds plaques, and reduces amyloid in vivo, J. Biol. Chem. 280, 5892-5901)) (Hydroxyindoles: T. Cohen, A. Frydman-Marom, M. Rechter, E. Gazit, Biochemistry 2006, 45, 4727-4735). Zn— and Cu-chelating agents were thought to lower the aggregation tendency of monomeric Aβ strands (clioquinol) (Zn and Cu chelators: Cherny R A, Atwood C S, Xilinas M E, Gray D N, Jones W D, McLean C A, Barnham K J, Volitakis I, Fraser F W, and Kim Y, Neuron 2001, 30, 665-676).
[0159] Another prevailing class of compounds are peptides, in some cases taken directly from putative nucleation sites within the Aβ molecule (KLVFF derivatives: a) Tjernberg, L. O., Naslund, J., Lindqvist, F., Johansson, J., Karlstrom, A. R., Thyberg, J., Terenius, L., and Nordstedt, C. (1996) Arrest of β- amyloid fibril formation by a pentapeptide ligand, J. Biol. Chem. 271, 8545-8548; b) B. M. Austen, K. E. Paleologou, S. A. E. Ali, M. M. Qureshi, D. Allsop, O. M. A. El-Agnaf, Biochemistry, 2008, 47, 1984-1992; c) KLVFF aggregation and gelation: M. J. Krysmann, V. Castelletto, A. Kelarakis, I. W. Hamley, R. A. Hule, D. J. Pochan, Biochemistry, 2008, 47, 4597-4605); however only very few of these compounds stem from rational design with a known structural motif in their complexes with Aβ monomers, oligomers or fibrils. Soto presented the β-sheet breaker LPFFD (iAbeta5) (Soto, C., Sigurdsson, E. M., Morelli, L., Kumar, R. A., Castaño, E. M., and Frangione, B. (1998) β- Sheet breaker peptides inhibit fibrillogenesis in a rat brain model of amyloidosis: Implications for Alzheimer's therapy, Nat. Med. 4, 822-826), which retained the high affinity towards the self-complementary LVFFA region, but impaired its β-sheet forming propensity by introducing a proline-kink; the D-peptide MeHN-lvffl-NH 2 (PPI-1019) essentially interferes with the aggregation of β-amyloid in the brain and may help promote its clearance (Praecis). Murphy and Kiessling synthesized hybrid peptides built from KLVFF and a highly charged KKKKK or EEEEE terminus (Ghanta, J., Shen, C. L., Kiessling, L. L., and Murphy, R. M. (1996); A strategy for designing inhibitors of β- amyloid toxicity, J. Biol. Chem. 271, 29525-29528; T. J. Gibson, R. M. Murphy, Biochemistry 2005, 44, 8898-8907). Aggregation of toxic Aβ oligomers is promoted because of increased surface tension.
[0160] Another prominent class are alternating N-methylated and nonmethylated peptide amides or esters, presented by Meredith, Hughes and Kapurniotu (Gordon, D. J., and Meredith, S. C. (2003) Probing the role of backbone hydrogen bonding in β- amyloid fibrils with inhibitor peptides containing ester bonds at alternate positions, Biochemistry 42, 475-485; Hughes, E., Burke, R. M., and Doig, A. J. (2000) Inhibition of toxicity in the β- amyloid peptide fragment β-(25-35) using N - methylated derivatives—A general strategy to prevent amyloid formation, J. Biol. Chem. 275, 25109-25115; Kapurniotu, A., Schmauder, A., and Tenidis, K. (2002) Structurebased design and study of nonamyloidogenic, double N - methylated IAPP amyloid core sequences as inhibitors of IAPP amyloid formation and cytotoxicity, J. Mol. Biol. 315, 339-350). These are able to cap growing β-sheets, without the ability of crosslinking because their back is blocked for hydrogen bonding due to the sterically demanding N-methyl groups or ester oxygens. They have recently been optimized with respect to their antiaggregatory capacity by introduction of 3 cyclohexylglycine units and reached nanomolar IC 50 values. The so far most potent compound is also thought to accelerate Aβ self-assembly and thereby deplete the level of neurotoxic Aβ-oligomers (N. Kokkoni, K. Stott, H. Amijee, J. M. Mason, A. J. Doig, Biochemistry 2006, 45, 9906-9918).
[0161] Other examples comprise the small molecule homotaurin, which disrupts complexes between Aβ and glucosaminoglycans. Scyllo-inositol appears to bind oligomers of Aβ42, preventing them from damaging synapses. Oligomer-specific Aβ antibodies indicated that scyllo-inositol appears to increase the number of monomers and trimers while reducing the amount of larger oligomeric species, such as 40 mers (a) McLaurin, J., Goloumb, R., Jurewicz, A., Antel, J. P. & Fraser, P. E. Inositol stereoisomers stabilize an oligomeric aggregate of Alzheimer amyloid beta peptide and inhibit A β- induced toxicity. J. Biol. Chem. 2000, 275, 18495-18502; b) J. McLaurin, M. E. Kierstead, M. E. Brown, C. A. Hawkes, M. H. L. Lambermon, A. L. Phinney, A. A. Darabie, J. E. Cousins, J. E. French, M. F. Lan, F. Chen, S. S. N. Wong, H. T. J. Mount, P. E. Fraser, D. Westaway, P. St. George-Hyslop; Nat. Med. 2006, 12, 801-808).
[0162] A recent approach comes from Willboldt et al., who selected potent Aβ binders from D-peptide libraries by phage display ( D - peptides by phage display: K. Wiesehan, K. Buder, R. P. Linke, S. Patt, M. Stoldt, E. Unger, B. Schmitt, E. Bucci, D. Willbold, Selection of D - amino - acid peptides that bind to Alzheimer's disease amyloid peptide Abeta (1-42) by mirror image phage display, ChemBioChem 2003, 4, 748-753).
[0163] Surprisingly little knowledge/information, however, is available on the exact mechanism of action for most Aβ complexing agents, even less on structural details. To the best of applicant's knowledge, the only case is Sato's concept of β-sheet packing: peptide inhibitors based on a GxFxGxF framework disrupt sheet-to-sheet packing and inhibit the formation of mature Aβ fibrils (Sato, T, Kienlen-Campard, P., Ahmed, M., Liu, W, Li, H. L., Elliott, J. I., Aimoto, S., Constantinescu, S. N., Octave, J. N, and Smith, S. O. (2006) Inhibitors of amyloid toxicity based on β- sheet packing of A β(1-40) and A β(1-42), Biochemistry 45, 5503-5516). This strategy was developed from inspection of solid state NMR structures of amyloid fibrils and confirmed by 13 C NMR spectroscopy for the best candidate peptide in its direct complex with Aβ1-40. In this context, work by Bitan is also interesting, who identified Met-35 as a structural switch in Aβ aggregation (Bitan, G., Tarus, B., Vollers, S. S., Lashuel, H. A., Condron, M. M., Straub, J. E., and Teplow, D. B. (2003) A molecular switch in amyloid assembly: Met (35) and amyloid β- protein oligomerization, J. Am. Chem. Soc. 125, 15359-15365). A new aspect comes from recent observations, that many small molecules which form colloids inhibit pathological peptide aggregation ( Colloidal inhibition: B. Y. Feng, B. H. Toyama, H. Wille, D. W. Colby, S. R. Collins, B. C. H. May, S. B. Prusiner, J. Weissman, B. K. Shoichet, Nat. Chem. Biol. 2008, 4, 2-3).
[0164] Aminopyrazoles are rationally designed β-sheet ligands with a specific DAD-sequence of hydrogen bond donors and acceptors, complementary to that of a β-sheet (T. Schrader, C. Kirsten, J. Chem. Soc., Chem. Commun. 1996, 2089; T. Schrader, C. N. Kirsten, J. Am. Chem. Soc. 1997, 119, 12061-12068). Derivatives were synthesized and also evaluated on the solid phase (a) P. Rzepecki, M. Wehner, O. Molt, R. Zadmard, T. Schrader, Synthesis 2003, 1815-1826; b) Kate{hacek over (r)}ina {hacek over (C)}ernovskà, Miriam Kemter, Hans-Christoph Gallmeier, Petra Rzepecki, Thomas Schrader and Burkhard König, Org. Biomol. Chem. 2004, 2, 1603-1611; c) P. Rzepecki, H. Gallmeier, N. Geib, Katarina Cernovska, B. König, T. Schrader, J. Org. Chem. 2004, 69, 5168-5178; d) P. Rzepecki, N. Geib, M. Peifer, F. Biesemeier, T. Schrader, J. Org. Chem. 2007, 72, 3614-3624). Direct interaction of dimeric and trimeric aminopyrazole derivatives with the mouse prion protein as well as with Aβ(1-42) was shown and characterized by SDS-PAGE, FCS, AUC, density gradient centrifugation as well as HRMS. β-sheet recognition as well as the individual strength of all hydrogen bonds involved were studied in great detail by R2PI spectroscopy on a cooled argon jet stream (a) P. Rzepecki, L. Nagel-Steger, S. Feuerstein, U. Linne, O. Molt, R. Zadmard, K. Aschermann, M. Wehner, T. Schrader, D. Riesner, J. Biol. Chem. 2004, 279, 47479-47505; b) H. Fricke, A. Funk, T. Schrader, M. Gerhards, J. Am Chem. Soc. 2008, 130, 4692-4698; c) H. Fricke, A. Gerlach, C. Unterberg, M. Wehner, T. Schrader, M. Gerhards, Angew. Chem. 2009, 48, 900-904).
[0165] Results and discussion. In a misfolded extended peptide strand, amino acid sidechains protrude horizontally (orthogonal to) from the vertical peptidic backbone β-sheet; complexed β-sheet ligands will therefore automatically place their recognition sites close to the typical functional groups found in proteinogenic amino acid residues. It was therefore attempted to match the main classes of amino acids with complementary recognition sites on the complexing aminopyrazole trimers, and to vary sizes and distances from their attachment point. Scheme 1 shows an overview about all synthesized derivatives and their classification:
[0166] C-terminal appendices to the trimeric aminopyrazole. 1. Lysine and arginine binders contain carboxylate anions, at varying distances from the heterocyclic core. 2. Aspartate and Glutamate binders were introduced as ammonium cations, placed remote and close to the aminopyrazoles; the pentavalent derivatives are probes for a potential complexation of the glutamate-22 ladder found in the all solid state NMR structures. 3. Polar residues with XH-groups such as serine and tyrosine are able to form multiple hydrogen bonds with ethyleneglycol moieties; the TEG (triethyleneglycol) unit also serves as a water-soluble linker for remote recognition events. 4. Unpolar residues are matched by flexible branched hydrocarbons as found in cyclohexylglycine, already introduced by the Stott group (N. Kokkoni, K. Stott, H. Amijee, J. M. Mason, A. J. Doig, Biochemistry 2006, 45, 9906-9918). 5. Characteristic peptide fragments within the Aβ molecule known for efficient self-recognition were finally introduced as peptidic address labels.
[0167] Synthesis. The trimeric aminopyrazole core structure was elongated with a variety of additional binding sites. To this end, its C-terminal carboxylic acid was connected to the respective amines by way of a peptide bond. Conventional coupling reagents comprised EDC/HOBt, HCTU/Cl-HOBt and Mukaiyama's reagent, which produced the hybrid compounds in high yields. In an economic fashion, all protecting groups of the tether were finally cleaved by TFA together with all PMB-moieties on the aminopyrazole nuclei. Peptidic tethers were first synthesized by manual solid phase peptide synthesis (SPPS) on a Wang resin, followed by covalent attachment at the aminopyrazole trimer (HBTU, DIEA). Final deblocking of all acid-labile protecting groups at 70° C. for ˜3 hrs furnished, after precipitation and recrystallization from ether, analytically pure final products 3a-z. All these new trimeric aminopyrazoles are soluble in DMSO, the most polar even in water. They are listed in Table 1, together with absolute yields and their solubilities.
[0168] FIGS. 1A and 1B display Lewis structures of unprotected aminopyrazole trimer derivatives with appendices Z. Left: small neutral, anionic and cationic moieties, as well as unpolar and TEG-spacered groups. Right: peptidic attachments.
[0169] FIG. 1C shows a synthetic access to the new C-terminally modified aminopyrazole trimers via peptide coupling of various amines onto the PMB-protected trimer and final total deprotection.
[0000]
TABLE 1
Unprotected aminopyrazole trimers for in-vitro aggregation experiments.
Entry
Aminopyrazole
Coupling
Deprotection
Solubility a
milogP
TPSA
1
Trimer-OMe
—
69%
b
−0.26
216.37
2
Trimer-OH
—
93%
b
−0.52
227.37
3
Trimer-diamine
82%
51%
b
−2.09
245.19
4
Trimer-GABA-OMe
57%
76%
b
−0.80
245.47
5
Trimer-GABA-OH
—
78%
b
−1.11
256.47
6
Trimer-Che
83%
82%
b
+1.72
219.17
7
Trimer-Chg-Che
48%
89%
b
+3.10
248.27
8
Trimer-Lys-Che
88%
66%
a
+0.66
274.30
9
Trimer-TEG-OEt
80%
98%
b
−1.08
273.17
10
Trimer-TEG-OH
—
94%
b
−2.07
284.17
11
Trimer-Lys-OMe
63%
96%
a
−1.20
271.50
12
Trimer-TEG-Che
75%
72%
b
+0.41
275.97
13
Trimer-TEG-Dodecyl
75%
70%
b
+3.27
275.97
14
Trimer-TEG-Lys-OMe
82%
91%
a
−2.51
328.30
15
Trimer-LPFFD-OH
SPPS b
>70%*
b
+0.58
389.34
16
Trimer-TEG-KLVFF-OH
SPPS
>70%*
b
−1.83
455.68
17
Trimer-TEG-LPFFD-OH
SPPS
>70%*
b
−3.32
441.10
18
Trimer-KKKKKG-OH
SPPS
>70%*
a
−5.58
532.07
19
Trimer-TEG-KKKKKG-OH
SPPS
>70%*
a
−5.82
588.87
20
Trim-Lys-TEGDA-Lys-Trim
52%
97%
a
−4.10
576.28
a a) water (4.95 mM stock solution); b) DMSO (4.95 mM stock solution), dilutable to 200 μM in water/DMSO (90:10);
b SPPS: solid phase peptide synthesis;
c two steps (mild cleavage from resin followed by PMB deprotection with hot TFA).
[0170] Aggregation studies. The influence of the new β-sheet ligands, based on the aminopyrazole-trimer, on the Aβ self-assembly process was first studied kinetically. Reference curves were obtained independently for both Aβ (1-40) and Aβ (1-42). In a typical experiment, one third (⅓) equivalent of thioflavine T was added to a solution of monomeric Aβ in PBS buffer, prepared in HFIP. The increase in ThT fluorescence was monitored over time, as a measure of the total amount of accumulating aggregates. As expected Aβ (1-42) commenced immediately after dilution with fibril formation, as opposed to Aβ(1-40), which showed the well-known lag phase of ˜24 hrs. Both peptides reached a plateau after ˜3 days, which was set as standard time period for all consecutive aggregation assays.
[0171] Kinetics of Aggregation Inhibition by Trimeric Aminoypyrazoles. Care was taken to eliminate fluorescence changes induced by any other events than the aggregation process; thus each ligand was separately shown to be non-fluorescent and not to alter Tht fluorescence in mixtures. Controls with pure Aβ were identical in peptide concentration as well as buffer and solvent composition. Aβ (1-40): Representative kinetic curves are shown in FIG. 2 . Interestingly, no ligand changes the 24 h lag phase, but instead proceeds with distinctly different velocity before it reaches the aggregation maximum, the trimer prototype being the slowest. Aβ (1-42): Much more impressive is the inhibitory influence of the trimeric ligands on the aggregation kinetics of the full-length Aβ (1-42). The trimer itself is outperformed in its aggregation decelerating effect by the corresponding derivative with a distant lysine, whereas the related compound with a proximal lysine goes to the other extreme and greatly expedites the Aβ aggregation process. Obviously, the location of a single lysine residue on the aminopyrazole ligand has a profound effect on complex formation with and subsequent misfolding of the Alzheimer's peptide.
[0172] FIGS. 2A and 2B show the kinetics of Aβ aggregation in PBS buffer (pH 7.3) in the absence and presence of selected trimeric pyrazole inhibitors; FIG. 2A : Aβ (1-40), FIG. 2B : Aβ (1-42).
[0173] Kinetics of Aβ Disaggregation by Trimeric Aminopyrazoles. Applicant discovered that the parent trimeric aminopyrazole does not only bind to growing Aβ ensembles, but also strongly interacts with preformed Aβ fibrils, and leads to their disassembly. The kinetics of this interesting process reveal a two-phase event, with a rapid disaggregation during the first few minutes, and a slow dissolution within the next 5 days, until the overall equilibrium is reached ( FIG. 3 ). In combination with sedimentation analyses, applicant proposes that the first disaggregation phase involves release of protofibrils from mature fibrils, whereas the second slower disassembly may be characterized by further conformational changes with loss of the well-ordered β-sheets.
[0174] FIG. 3 discloses the kinetics of Aβ disaggregation effected by addition of a 6-fold excess of trimeric aminopyrazole inhibitors to preformed fibrillar aggregates (33 μM in PBS).
[0175] Equilibrium of Aβ Aggregation Inhibited by Trimeric Aminopyrazoles. After 72 h, the aggregation process has reached a maximum in the absence or presence of any trimeric ligand, even for the slow Aβ (1-40) peptide. The respective equilibrium concentration is then indicated by the relative fluorescence intensity reached at the end point. The full series of new aminopyrazole trimer derivatives was subjected to ThT inhibition experiments and the final equilibrium was analyzed by comparison of the respective fluorescence intensities of intercalated dye at 482 nm (exc. at 442 nm). FIG. 4 reveals a significant structure-activity relation for Aβ (1-42): structurally related compounds in general display comparable inhibition properties. Two classes of the modified derivatives surpass the original trimer activity: Trimer-CHE/Trimer-Lys-CHE/Trimer-LPFFD with attached extended lipophilic groups and Trimer-TEG-Lys/Trimer-KKKKG with a distant or multiple lysine residues. Their proposed mechanism of action is discussed within the next chapters together with all the other biophysical, biochemical as well as modeling data.
[0176] Equilibrium of Aβ Disaggregation by Trimeric Aminopyrazoles. Starting from preformed fibrils, the disassembly process was also monitored with the full series of modified trimeric aminopyrazoles. Surprisingly, the inhibition pattern (left) looks quite similar to the disaggregation pattern (right), in several cases, that total percentage of ThT rest fluorescence is identical. In other words, little difference is observed between the end points of aggregation assays, in which the ligand inhibits de novo aggregation starting from monomeric Aβ molecules, and those experiments, which require disaggregation of preformed fibrils by externally added ligand. Experimental evidence is thus provided for the fact, that aminopyrazole ligands operate in a fully reversible fashion, and reach an open equilibrium when the thermodynamically most favorable complex is formed.
[0177] FIGS. 4A and 4B show the equilibrium of 33 μM Aβ42 aggregation ( FIG. 4A ) vs. disaggregation ( FIG. 4B ) in the absence or presence of trimeric aminopyrazole inhibitors (each at 198 μM); FIG. 4A shows the inhibition of aggregation and FIG. 4B the disaggregation (10 mM PBS, pH 7.3). For each bar, 6 measurements were averaged.
[0178] Anchor point for docking experiments. In the past, detailed conformational NMR analyses between aminopyrazole ligands and the model peptide KLVFF, a putative nucleation site in Aβ, furnished strong hints for direct hydrogen bonds between ligand and peptidic backbone (P. Rzepecki, T. Schrader, J. Am. Chem. Soc. 2005, 127, 3016-3025). In addition, upfield shifts of aromatic protons in both phenylalanines indicated π-stacking interactions. Energy-minimizations and subsequent Monte-Carlo simulations in water converged on a complex structure with two consecutive phenylalanines sandwiching an aminopyrazole nucleus, which effectively shielded it from the aqueous solvent. Recent MD simulations between the trimeric aminopyrazole and an Aβ monomer residing in its folded fibril conformation (solid state structure) demonstrated the KLVFF sequence to be superior over all other complexation sites. It was therefore attempted to correlate altered complexation behavior and influence on aggregation of the above-mentioned new series of modified aminopyrazole trimers with specific additional noncovalent interactions predicted from docking experiments of these β-sheet ligands onto the Aβ fibril. Since KLVFF (residues 16-20) represents the starting point of the well ordered part of the Aβ sequence, covalently attached C-terminal appendices of the aminopyrazole trimer will be able to exploit the maximum contact area of the fibril's top face.
[0179] CD measurements of all water-soluble trimeric ligands in 1:1-mixtures with Aβ(1-42) reveal that in most cases, a new CD band evolves at 260-320 nm with a positive maximum at 280 nm, typical for complexes of aromatic moieties (Phe: 260-270 nm; Tyr 270-280 nm; Trp: 290-300 nm). Since at this wavelength aminopyrazole ligands are CD-silent, applicant attributes the new band to tight complex formation between aromatic units in Aβ and ligand, most likely between the two consecutive phenylalanines and the pyrazole nuclei.
[0180] This structural motif offers a unique opportunity for docking experiments, which were hence performed on the hydrogen-bonded complex between aggregated Aβ (Lührs structure) and ligand. Both were involved in backbone recognition, starting from the Phe-Phe pair which locks the first aminopyrazole in a sandwich arrangement.
[0181] Intriguingly, several additional favorable interactions were found, which were typical for each major class of trimer tethers. They will be discussed along with all biophysical experiments conducted for each group of trimers.
[0182] In force-field calculations, the trimer itself forms the characteristic DAD pattern of multiple hydrogen bonds towards the solvent-exposed top face of the KLVFF backbone and simultaneously stacks its pyrazole nuclei with both phenylalanine units in form of a hydrophobic cleft (Trimer-OMe, Trimer-OH, FIG. 5 ).
[0183] FIG. 5 displays aMD simulation of the complex between Aβ and the parent aminopyrazole trimer (10 ns).
[0184] The trimeric aminopyrazole skeleton is able to reduce the total amount of Aβ aggregates (30 μM) to ˜40% at a 6-fold excess, but to <20% at a 10:1 ratio (inhibition 17%, disaggregation: 25%). This corresponds to an estimated dissociation constant of the complex in the low micromolar range (2 μM K d in PBS buffer). Interaction of the new trimeric lead structure and monomeric as well as polymeric Aβ was further studied with fluorescence correlation spectroscopy (FCS), sedimentation analysis (SA, based on analytical ultracentrifugation) and Transmission Electron Microscopy (TEM).
[0185] In a standard FCS experiment a 5 nM Oregon-Green-labeled Aβ solution was prepared in PBS buffer with ˜3% DMSO. Trimer-OMe was added at 100 nM and reduced the peaks x height value to ˜25% of the control. Since the number of peaks remained unchanged, their molecular weight was greatly reduced. Independent confirmation came from sedimentation analyses with Oregon-Green-labeled Aβ: Coefficients for pure Aβ were above 50 S, whereas those for its complex with Trimer-OH continuously decreased in a dose-dependant manner down to 25 S, corresponding to a 50% molecular weight reduction ( FIG. 6 ). It should be noted, that Trimer-OH itself also tends to self-associate; its sharp radial distribution suggests formation of micelles of ˜10 S size. This is not surprising, because it comprises a flat arrangement of unpolar aromatics adorned with polar groups for extensive hydrogen bonding. Finally, TEM pictures were obtained from mature Aβ fibrils (>600 nM) as well as globular particles (3-30 nm) grown in the absence of aminopyrazole ligands. While the diameter of the twisted ribbons from pure Aβ corresponds to 10 nm, thin filaments were produced in the presence of the trimeric ligand (5 nm), and the number of mature fibrils was greatly reduced ( FIG. 7 ). Applicant concludes that the trimer seems to break the mature fibrils into protofilaments by a combination of backbone recognition and hydrophobic interactions. In a preliminary cell culture assay with PC-12 cells, inhibition of Aβ(1-42)-induced toxicity was very moderate (<10% viability increase, FIG. 13 ). Since Trimer-OH/OMe contain only the trimeric aminopyrazole core unit, their interaction profile sets the standard for all other modified derivatives of this investigation.
[0186] FIG. 6A to 6F show the results of sedimentation velocity centrifugation: s-value-distributions of Aβ samples in the presence of Trimer-OH ( FIG. 6A , FIG. 6B , FIG. 6C ) vs. Trim-TEG-OEt ( FIG. 6D , FIG. 6E , FIG. 6F ). FIG. 6A , FIG. 6D : Van-Holde-Weischet distribution plots, G(s), for aggregation mixtures of Aβ(1-42)/Aβ42-OG (17.5 nM/3.5 μM) in 10 mM NaP i , pH 7.4, 4% DMSO with 0 μM (control, circles), 66 μM (triangles), 133 μM (squares), and 200 μM Trimer derivative (diamonds). Samples were incubated slightly agitated at RT for 5 d prior centrifugation at 20,000 rpm, 20° C. FIG. 6B , FIG. 6E : s-value distributions of the control experiments as determined by 2D-SA and Monte Carlo analysis. FIG. 6C , FIG. 6F : s-value distributions of experiments with 200 μM Trimer derivative after 5 d of incubation as determined by 2D-SA and Monte Carlo analysis.
[0187] Small charged extensions at the trimer's C-terminus are too short for specific interactions with other amino acid residues in the neighborhood/vicinity and hardly change the trimer's effect (Trimer-ethylenediamine, Trimer-GABA-OH, Trimer-GABA-OMe). The strong solvation of the tethered ionic group close to the aminopyrazole's hydrogen bonding unit may even hinder its approach to the Aβ peptide backbone. Consequently, all ThT values for inhibition as well as disaggregation lie above the trimer standard. (Both GABA derivatives, however, produce a significant viability increase of up to 30% in the lesion assay; it may be related to the biological response of GABA receptors.)
[0188] FIG. 7 shows TEM pictures. A: Aβ(1-42) fibrils. B-F: Aβ(1-42) mixtures (20 μM) with aminopyrazole trimer derivatives (100 μM). B: Trim-OMe; C: Trim-OH, D: Trim-Che; E: Trim-Lys-OMe; F: Trim-TEG-Lys-OMe; G: Trim-TEG-OEt; H: Trim-TEG-OH.
[0189] By contrast, extended or cyclic unpolar groups align with nonpolar side chains and undergo hydrophobic as well as dispersive interactions (Trimer-CHG-CHE, Trimer Lys-CHE, Trimer-TEG-CHE, Trimer-TEG-DD). Likewise nonpolar peptide fragments derived from Aβ itself and attached to the trimer, may display their well-known self-complementarity and recognize their counterparts in the fibril (Trimer-LPFFD, Trimer-KLVFF). This is especially pronounced if the unpolar appendix is placed at a distance of more than one amino acid from the trimer-C-terminus, pushing the ThT rest fluorescence to values below 30%. According to a conformational search, unpolar binding sites on the ligand prefer the cluster of hydrophobic residues from Ile-31 to Ile-36. A TEG spacer in Trim-TEG-DD allows the attached dodecyl tail to explore the entire Met-35 ladder during MD simulations for extended van-der Waals interactions on the back of the pentameric Lührs fibril. CD spectra of Trim-Lys-Che, Trim-KLVFF and Trim-TEG-DD all feature/display an almost doubled β-sheet band intensity and the total loss of the aromatic signal at 280 nm. A straightforward interpretation suggests a remarkable stabilization of the cross-β-sheet with concomitant withdrawal of the aminopyrazole from its Phe-Phe cleft, resulting in a tight nonpolar lid covering the solvent-exposed unpolar aggregate face ( FIG. 8 ). The related Trim-CHE, which forms thin filaments by itself, displays a remarkable fibril morphology in its complex with Aβ(1-42): very thick screwed fibrils (up to 70 nm) are produced, with a length of at least 600 nm. It thus seems, that fibrillogenesis is not prevented but rather shifted to a much more compact form, which does not accommodate well-ordered fluorescent ThT molecules. Remarkably, three of the eight best candidates in the cell lesion assays contain extended unpolar appendices, either as LPFFD or cyclohexylglycine peptide fragments.
[0190] FIG. 8 displays MD simulations (5 ns) of the complex between Aβ and an aminopyrazole trimer with attached nonpolar binding site; left Trim-Chg-Che; center Trim-Lys-Che; right Trim-TEG-Dodecyl.
[0191] A single C-terminal lysine on the trimer seems to be an exception. After aminopyrazole docking to the KLVFF site, lysine's ε-ammonium ion remains freely solvated during an entire 10 ns MD simulation run ( FIG. 9 left). In this state it could easily form a saltbridge to Glu-22/Asp-23 of an opposing strand, which would according to Tycko support the connection two U strands via their polar interfaces to a fibril (Trimer-Lys-OMe). Contrary to almost all other trimer derivatives, this aminopyrazole accelerates Aβ aggregation (cf. kinetics). The corresponding CD spectrum is also exceptional, because it exhibits the typical additional Cotton effect at the wavelength of aromatic amino acids, but retains the β-sheet. Applicant concludes that docking of the aminopyrazole onto the Phe-Phe motif leads to formation of an intra- or intermolecular salt bridge, which brings two protofibrils in close proximity The exceptionally high aggregation propensity is also well documented in sedimentations, featuring the total loss of amyloid β-peptide during rotor acceleration. TEM pictures of mixtures with Aβ show very thin fibrils (5-10 nm) of 800 nm length, whereas this soluble aminopyrazole does not aggregate by itself.
[0192] In sharp contrast to Trim-Lys, a single lysine separated from the trimeric aminopyrazole core unit by the TEG spacer, leads to the most efficient suppression of Aβ fibril formation of all tested derivatives (20% ThT fluorescence). This structurally closely related pair of aminopyrazole trimers is a striking example for the fact, how strongly the exact placement of binding sites influences the degree and path of Aβ aggregation. Modeling studies reveal a preference for internal ion pair formation with Glu-22, confirmed by extended MD simulations ( FIG. 9 right). Ultracentrifugation and TEM experiments indicate a moderate tendency of the pure compounds to self-assemble into thin filaments, whereas the aggregation process of Aβ is redirected to unstructured material and thin bent filaments—completely different from Aβ fibrils (TEM pictures). In the cell culture experiments, Trim-TEG-Lys provides the most efficient rescue of PC-12 cells from Aβ toxicity (>40%).
[0193] FIG. 9 displays MD simulations of the complexes between Aβ and Trimer-Lys vs. Trim-TEG-Lys.
[0194] The polar triethyleneglycol spacer smoothly intercalates between both peptide strands of the top U and similarly undergoes weak dispersive interactions with amino acids in the vicinity of the β-turn (Trimer-TEG-OEt, Trimer-TEG-OH). In extended MD simulations, the neutral methyl ester (replaced by the related methyl amide) could be observed to intrude into the water-filled canal formed by the stacked β-turns in the solid state structure ( FIG. 10A ). It serves as a linker to remote additional binding sites such as lipophilic or charged peptide fragments. For a better understanding of its influence on the pathologic Aβ self-assembly process, it was independently examined. Compared to the pure trimer prototype, the TEG-elongated aminopyrazole trimer (which is unremarkable/inconspicuous in ThT experiments), does not significantly change the medium aggregate size of aggregated Aβ, but instead produces a moderate amount of very small oligomers (monomers-pentamers), as evidenced by sedimentation analysis ( FIGS. 6A-6F ). For the Trimer standard as well as for both TEG-extensions sedimentation assays prove direct complex formation between the natural and the artificial peptide molecules. At nanomolar Aβ concentrations (as in the human brain) FCS even witnesses the uniform transition to very small oligomers within all Aβ aggregates ( FIG. 10B ). No filaments are formed from pure Trim-TEG-OH or —OMe solutions; in the presence of Aβ, very thin, delicate structures evolve, which show no helical twist. PC-12 cell protection is only very modest, comparable to the Trimer standard. Thus, the TEG spacer could serve a dual purpose: it brings recognition units close to the U-turn auf the fibril and simultaneously protrudes itself into the interior of the two parallel Aβ strands, facilitating further destabilization of the fibrillar structure.
[0195] FIG. 10A shows a MD simulation of the complex between Aβ and Trimer-TEG-OEt; FIG. 10B shows FCS (Fluorescence Correlation Spectroscopy) measurements at 5 nm Aβ with Trimer-OH in comparison to Trim-TEG-OH/OEt (each at 10 μM).
[0196] Remarkably, multiple lysines attached directly or by way of the TEG spacer to the aminopyrazole trimer, in principle allow the formation of multiple chelate complexes with the Glu-ladder beneath the fibril in molecular mechanics calculations (Trimer-KKKKKG, Trimer-TEG-KKKKKG). The modeling picture displays beautiful mutual chelate structures between the multiple glutamate carboxylates and bridging lysine ammonium functionalities. This complexation mode may lead to a significant destabilization of the U-turn structure and eventually dissolve the β-sheet. Together with Trimer-TEG-Lys the above-mentioned are indeed the most potent of all synthesized aminopyrazole derivatives and deplete the ThT fluorescence level down to 20% in inhibition and disaggregation experiments ( FIG. 4 ). The corresponding CD spectrum features the additional CD band at ˜280 nm, typical for aromatic amino acids; however, in this case, the β-sheet band almost completely disappears with time, indicating dissolution of the secondary peptide structure ( FIG. 11A to 11C ).
[0000]
TABLE 2
Classification of CD spectra to three main types
(see also FIG. 11A to 11C).
Type A
Type B
Type C
Trim-Lys-OMe
Trim-KKKKKG
Trim-Lys-Che
Trim-TEG-Lys-OMe
Trim-TEG-KKKKKG
Trim-TEG-KLVFF
Trim-TEG-OH
Trim-Lys-TEGDA-Lys-
Trim-TEG-DD
Trim
[0197] FIG. 11A to 11C show typical CD spectra recorded for aggregated Aβ(1-42) alone (curve 5 in FIGS. 11A-11C ) and after addition of aminopyrazole ligand (Type A: Trimer-Lys: FIG. 11A ; Type B: Trimer-KKKKKG: FIG. 11B ; Type C: Trimer-Lys-Che: FIG. 11C ). Time progresses in the direction of the embedded arrows, indicated by lighter colors (0 h, 1 h, 1 d, 2 d). Test solutions contained 10 μM Aβ(1-42), 5 μM potassium phosphate buffer (pH=7.3), 2% HFIP and 10 μM of the respective aminopyrazole trimer derivative.
[0198] Subsequent MD simulations, however, resulted in successive detachment of the pentalysine tail from the glutamate ladder, until finally all alkylammonium groups pointed into the free solvent and towards the opposite side of the peptide strand. Such an arrangement may also result in far-reaching conformational effects, indicated already be widening of the upper U-turn; these are now proposed to destroy the existing β-sheet ( FIG. 12 ). The high positive charge of all five lysine residues requires the use of PBS with its high ionic strength for sedimentation experiments. Here the positively charged aminopyrazoles alone displayed a considerable self-association, reaching s-values of up to 40 in the absence of a TEG spacer. Admittedly, their structures are somewhat reminiscent of the amphiphilic hybrid peptides (e.g., KLVFF-EEEEE) presented in the nineties for aggregation prevention by surface tension increase. In fact, a similar mechanism could also be functioning in the case of applicant's amphiphilic aminopyrazole-pentalysines.
[0199] FIG. 12 displays a MD simulation of the complex between Aβ and Trimer-KKKKG.
[0200] Inhibition of Aβ-induced toxicity. Initially, all compounds were screened for any toxic effect they might have by adding each compound at 100 μM and measuring the effect on cell viability using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) reduction assay (Datki, Z.; Juhasz, A.; Galli, M.; Soos, K.; Papp, R.; Zadori, D.; Penke, B. Brain Res. Bull. 2003, 62, 223-229) in differentiated rat pheochromocytoma (PC-12) cells (Shearman, M. S. Methods Enzymol. 1999, 309, 716-723). Encouragingly, none of the compounds was toxic to the cells at this concentration. Next, to examine whether the aminopyrazole trimers could protect cell from Aβ42-induced neurotoxicity, cells were treated for 24 h with 10 μM Aβ(1-42), a concentration that produces 30 to 40% decrease in cell viability, in the absence or presence of 100 μM of each compound. The viability of the cells then was assessed using the MTT assay. In both series (with and without TEG spacers) several candidates were found to rescue cell viability significantly.
[0201] Intriguingly, the most efficient inhibition of Aβ toxicity was achieved with 3 lipophilic extensions and Trimer-TEG-Lys-OMe, which were also superior in ThT and related assays. The two GABA derivatives are a surprise—they might potentially interact with GABA receptors and not with the Aβ peptide itself. The above-delineated findings demonstrate that trimeric aminopyrazoles are indeed active against Aβ-induced toxicity in living cells; they also provide experimental evidence for their low toxicity at relatively high doses of 0.1 mM, in spite of, e.g., the presence of an N-terminal nitro group.
[0202] FIGS. 13A and 13B display viability assays of PC-12 cells with trimeric aminopyrazoles (100 μM). FIG. 13A shows Aβ lesion control at ˜70%, FIG. 13B at ˜80% viability.
[0203] Based on this initial screen, applicant evaluated the IC 50 value of compounds that increased the viability of PC-12 cells to ≧90%. The data are summarized in Table 3. To determine the IC 50 value of each of the compounds, dose-dependence MTT experiments were conducted with the aminopyrazole trimers, at a fixed Aβ42 concentration of 10 mM and increasing concentrations of β-sheet ligand (0.3, 1, 3, 10, 30 and 100 μM). IC 50 in this respect is defined as the concentration of the β-sheet ligand (aminopyrazole trimer derivative), at which the inhibition of Aβ toxicity just reaches 50% ( FIG. 14 ).
[0204] FIG. 14 shows a dose-response curve for the inhibition of Aβ-induced toxicity in PC-12 cells by Trimer-LPFFD (IC 50 =3.1 mM).
[0205] Table 3 shows the IC 50 values of the most potent inhibitors of Aβ-induced toxicity.
[0000]
TABLE 3
IC 50 values of the most potent inhibitors of Aβ-induced toxicity.
Inhibitor
IC 50 [μM]
Trim-LPFFD-OH
3.1
Trim-TEG-LPFFD-OH
10.1
Trim-GABA-OH
18.5
Trim-GABA-OMe
20.3
Trim-Lys-TEGDA-Lys-TEGDA
21.5
Trim-TEG-OH
35.3
Trim-TEG-Lys-OMe
52.7
Trim-Chg-Che
81.0
Trim-TEG-KLVFF
>100
Trim-TEG-DD
>100
[0206] With respect to IC 50 values, the two non-polar LPFFD-derivatives were found to be the most effective. Since the Aβ42 concentration was always kept constant at 10 μM, it should be emphasized, that substoichiometric IC 50 values such as that of Trim-LPFFD-OH indicate very high affinity towards the target peptide, even if a 1:1 complex is assumed. It should be kept in mind that, in the brain, Aβ concentrations are in the low nanomolar range, similar to the situation in enzyme assays. Only in such a scenario, IC 50 values can be expected to drop to nanomolar concentrations.
[0207] Conclusions and Outlook. Applicant's investigation provided experimental evidence for the fact that small structural changes in β-sheet ligands have a profound influence on the aggregation behavior of misfolding proteins. Moreover, a common anchor point has been identified for the inventive aminopyrazole trimer derivatives, allowing to perform docking experiments and subsequent MD simulations. Intriguingly, various different types of suitably arranged binding sites correlate well with various kinds of modulated Aβaggregation behavior. CD measurements, on the one hand, as well as ThT aggregation assays, on the other hand, display pronounced continuous changes within more than two hours, which may involve conformational changes which are not yet visible even during extended modeling experiments. A structure activity relation can therefore be suggested, evolving from a synopsis of different biophysical and biochemical and “in silico”-experiments. Two major binding motifs could thus be discovered, which greatly improve the β-sheet breaker ability of the aminopyrazole trimer: remote lipophilic moieties for dispersive interactions with the unpolar cluster of amino acids between Ile-31 to Ile-36, and distant cationic peptide fragments which destabilize Aβ's U-turn. Only the latter, however, effectively destroys the cross-β-sheet. Applicant has confirmed these structure motifs postulated from modeling and aggregation experiments. Direct evidence has been gained from cocrystals of these complexes as well as from 2D solid state NMR experiments.
[0208] Contents:
[0209] 1. General Synthetic Procedures
[0210] 2. Detailed experimental procedures
[0211] 3. Manual Solid Phase Peptide
[0212] 4. Thioflavine T-Assays
[0213] 5. Kinetics of Aβ aggregation and disaggregation
[0214] 6. Equilibrium of Aβ aggregation and disaggregation
[0215] 7. CD spectroscopic measurements
[0216] 8. Fluorescence Correlation Spectroscopy (FCS)
[0217] 9. Sedimentation analysis (SA)
[0218] 10. Transmission Electron Microscopy (TEM)
[0219] 11. Cell Culture/MTT Viability Assays
[0220] 1. General Synthetic Procedures
[0221] General Procedure A (C-Terminal Basic Ester Hydrolysis)
[0222] The N-(p-methoxybenzyl)-pyrazolecarboxylic acid methyl ester derivative was dissolved in a mixture of MeOH (50 ml) and THF (50 ml). Then, aq. lithium hydroxide (2.50 equiv. in 10 ml) was added to the solution and the mixture was stirred at room temperature until the starting material disappeared on the TLC plate. The solvent was removed under reduced pressure. The residue was dissolved in water and acidified with aq 1 M HCl. The precipitate was filtered, washed with aq 1 M HCl and dried in vacuo.
[0223] General Procedure B (Trimer-OH Coupling to C-Terminal Amine Extension with Mukaiyama's Reagent)
[0224] In an argon atmosphere, the N-terminal and PMB-protected pyrazole carboxylic acid compound (1.10 equiv) was suspended in DCM. To this suspension diisopropylethylamine (3.50 equiv) and 2-chloro-1-methylpyridinium iodide (Mukaiyama's reagent, 1.50 equiv) were added. Then the C-terminally and/or side chain-protected amino acid (1.00 equiv) or another coupling partner (1.00 equiv) was added to the reaction mixture. If the C-terminal protected compound was applied as an ammonium salt, another equivalent of diisopropylethylamine (1.00 equiv) was added before for neutralization. The resulting mixture was stirred overnight at room temperature. Subsequently, the organic layer was washed twice with aq 1 M HCl, sat. aq NaHCO 3 and sat. aq NaCl. After drying over MgSO 4 , the solvent was evaporated in vacuo. The crude product was purified by chromatography on silica gel (the eluent is described for each compound in the following detailed procedures).
[0225] General Procedure C (Trimer-OH Coupling to C-Terminal Amine Extension with HCTU)
[0226] Under an inert atmosphere, the N-terminal and PMB-protected pyrazole carboxylic acid compound (1.10 equiv) was dissolved in DCM/DMF (3:1). Cl-HOBt (2.50 equiv), HCTU (1.10 equiv) and 2,6-lutidine (3.00 equiv) were added and stirred for 10 min at 0° C. The C-terminally and/or side chain-protected amino acid (1.00 equiv) or another coupling partner (1.00 equiv) was dissolved in DCM/DMF (3:1) and added to the reaction mixture. If the C-terminal protected compound was applied as an ammonium salt, 2,6-lutidine (1.00 equiv) was added to this solution before for neutralization. The reaction mixture was stirred overnight at room temperature. The mixture was extracted twice with aq 1 M HCl, sat. aq NaHCO 3 and sat. aq NaCl and dried over MgSO 4 . After filtration, the solvent was evaporated until it was dry and the residue was purified by chromatography on a silica column.
[0227] General Procedure D (Trimer-OH Coupling to C-Terminal Amine Extension with EDC)
[0228] In an argon atmosphere, the N-terminal and PMB-protected pyrazole carboxylic acid compound (1.00 equiv) was suspended in DCM and cooled to 0° C. To this suspension HOBt (3.00 equiv) and after ten minutes EDC-HCl (3.00 equiv) were added. The reaction mixture was stirred for another ten minutes and then, the C-terminally protected amine coupling partner was added to the suspension. The mixture was gradually warmed to room temperature and stirred for two more days. Then, the organic layer was washed twice with 1M aq. HCl, sat. aq NaHCO 3 and sat. aq NaCl and dried over MgSO 4 . The solvent was evaporated in vacuo and the crude product was purified by chromatography on silica.
[0229] General Procedure E (PMB-Deprotection)
[0230] In an argon atmosphere the PMB-protected pyrazole compound was heated in anhydrous TFA (2.50 mL/50 μmol) to 70° C. for 5 h. Subsequently, the solution was cooled to 0° C. and treated with ice-cold diethyl ether. The precipitating solid was centrifuged off and washed five times with diethyl ether. Afterwards, the residue was dissolved in DCM and the solvent was removed quickly in vacuo. This procedure was repeated five times and the product was dried in vacuo.
[0231] 1. Detailed Experimental Procedures
3-(3-(3-Amino-1-(4-methoxybenzyl)-1H-pyrazole-5-carboxamido)-1-(4-methoxybenzyl)-1H-pyrazole-5-carboxamido)-1-(4-methoxybenzyl)-1H-pyrazole-5-carboxylic acid methyl ester
[0232] To a solution of the respective nitro precursor (273 mg, 364 μmol) in THF (15 mL) was added methanol (5 mL) and Pd/C (10 mol %). The flask was evacuated and filled with H 2 (general procedure A). The reaction mixture was stirred for 16 h and the catalyst was removed by filtration over celite. The solution was concentrated in vacuo and the product was crystallized over night at 8° C. Yield: 215 mg (299 μmol, 82%); colorless solid.
[0233] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=3.70-3.72 (3s, 9H, CH 3 -PMB), 3.85 (s, 3H, OOCH 3 ), 4.85 (s, 2H, NH 2 ), 5.44 (s, 2H, CH 2 -PMB), 5.58 (s, 2H, CH 2 -PMB), 5.63 (s, 2H, CH 2 -PMB), 6.36 (s, 1H, CH-pyrazole), 6.83-6.90 (m, 6H, CH-arom.), 7.11-7.22 (m, 7H, CH-arom., CH-pyrazole), 7.65 (s, 1H, CH-pyrazole), 10.90 (s, 1H, NH-amide), 11.40 (s, 1H, NH-amide). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=52.1, 52.2, 53.0, 53.2, 54.9, 55.0, 94.8, 101.0, 102.9, 113.5, 113.7, 113.8, 128.5, 128.7, 129.0, 129.6, 130.6, 131.1, 133.8, 134.0, 145.4, 154.1, 157.4, 158.3, 158.6, 158.7, 159.3. Mp.: 182.3-183.1° C. R f : 0.07 n-pentane/ethyl acetate (1:1). HRMS (ESI): calcd for C 37 H 37 N 9 O 7 H: 720.2889; found: 720.2901; calcd for C 37 H 37 N 9 O 7 Na: 742.2708; found: 742.2727.
3-(3-(3-Amino-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxylic acid methyl ester trifluoroacetate (Aminotrimer-OMe)
[0234] A portion of 61 mg (85 μmol, 1.00 equiv) of PMB-protected aminopyrazole trimer synthesized above was treated with hot TFA according to general procedure E to yield the Aminotrimer-OMe as a colorless solid. Yield: 24 mg (51 μmol, 60%).
[0235] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=3.85 (s, 3H, OOCH 3 ), 7.11 (s, 1H, CH-pyrazole), 7.55 (brs, 2H), 11.20 (brs, 1H), 11.25 (brs, 1H), 12.18 (brs, 1H), 13.45 (brs, 1H, NH-pyrazole), 13.67 (brs, 1H, NH-pyrazole), 13.76 (brs, 1H, NH-pyrazole). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=51.9, 98.4, 100.2, 114.5, 116.8, 132.8, 136.6, 145.0, 147.2, 153.9, 154.2, 156.2, 159.2. Mp: decomposition at 272° C. HRMS (ESI): calcd for C 13 H 13 N 9 O 4 H: 360.1163; found: 360.1160; calcd for C 13 H 13 N 9 O 4 Na: 382.0983; found: 382.0988.
1-(4-Methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxylic acid
[0236] A 1.00 g (1.33 mmol, 1.00 equiv) amount of 1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxylic acid methyl ester [O 2 N-Pz(PMB)-Pz(PMB)-Pz(PMB)-OMe] and 81 mg of lithium hydroxide (3.38 mmol, 2.54 equiv) were stirred in a mixture of methanol/THF/water (5:5:1) for 18 h. The crude product is prepared according to general procedure A to yield the compound as a colorless solid. Yield: 0.92 g (1.25 mmol, 94%).
[0237] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=3.70-3.71 (3s, 9H, CH 3 -PMB), 5.60 (s, 2H, CH 2 -PMB), 5.66 (s, 2H, CH 2 -PMB), 5.81 (s, 2H, CH 2 -PMB), 6.86-6.91 (m, 6H, CH-arom.), 7.14-7.20 (m, 5H, CH-arom., CH-pyrazole), 7.25-7.30 (m, 2H, CH-arom.), 7.71 (s, 1H, CH-pyrazole), 7.99 (s, 1H, CH-pyrazole), 11.39 (brs, 1H, NH-amide), 11.53 (brs, 1H, NH-amide). 13 C-NMR (125 MHz, DMSO-d 6 ): δ [ppm]=55.0, 98.9, 103.0, 105.0, 113.8, 114.0, 127.9, 128.7, 128.8, 129.3, 129.5, 134.2, 136.7, 143.6, 144.8, 145.4, 153.5, 155.4, 157.0, 158.7, 159.0, 160.3. Mp: 258.1-260.2° C. HRMS (ESI): calcd for C 36 H 32 N 9 O 9 : 734.2328; found: 734.2323.
3-(3-(3-Nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxylic acid (Trimer-OH)
[0238] 51 mg of compound PMB-protected Trimer precursor (69 μmol, 1.00 equiv) was dissolved in 3 mL trifluoroacetic acid according to general procedure D to yield Trimer-OH as a colorless solid. Yield: 23 mg (64 μmol, 93%).
[0239] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=7.02 (brs, 1H, CH-pyrazole), 7.56 (s, 1H, CH-pyrazole), 7.94 (s, 1H, CH-pyrazole), 11.17 (brs, 1H, NH-amide), 11.42 (s, 1H, NH-amide), 13.51 (brs, 2H, NH-pyrazole), 14.97 (s, 1H, NH-pyrazole). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=98.1, 98.3, 99.9, 102.2, 138.6, 155.0, 155.8, 156.6, 160.4. Mp: decomposition at 313.4° C. HRMS (ESI): calcd for C 12 H 8 N 9 O 6 : 374.0592; found: 374.0611.
2-(1-(4-Methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido-6-(tert-butoxycarbonyl)-lysine methyl ester
[0240] A portion of 200 mg (0.27 mmol, 1.10 eq) of PMB-protected Trimer-OH and 73 mg (0.24 μmol, 1.00 equiv) of N-Amino- ε -(tert-butyloxycarbonyl)-(S)-lysine-carboxylic acid methyl ester hydrochloride were reacted with 95 mg (0.37 mmol, 1.50 equiv) of Mukaiyama's reagent and 0.19 mL (1.11 mmol, 4.50 equiv) of diisopropylethylamine according to general procedure B. The residue was purified by column chromatography on silica gel using n-pentane/ethyl acetate (2:1) to yield the coupling product as a colorless solid. Yield: 153 mg (0.16 μmol, 63%).
[0241] 1 H NMR (500 MHz, CDCl 3 ): δ [ppm]=1.37-1.54 (m, 13H, CH 2 -Lys, (CH 3 ) 3 ), 1.71-1.83 (m, 1H, CH 2 -Lys), 1.88-1.99 (m, 1H, CH 2 -Lys), 3.05-3.14 (m, 2H, CH 2 -Lys), 3.75-3.76 (2s, 9H, CH 3 -PMB), 3.80 (s, 3H, OOCH 3 ), 4.55 (brs, 1H, NH-amide), 4.67-4.75 (m, 1H, α-CH-Lys), 5.54 (d, 2H, 3 J=4.3 Hz, CH 2 -PMB), 5.61 (d, 1H, 3 J=7.5 Hz, CH 2 -PMB), 5.75 (d, 1H, 3 J=7.5 Hz, CH 2 -PMB), 5.81 (s, 2H, CH 2 -PMB), 6.80-6.85 (m, 7H, CH-arom., NH-amide), 7.10 (s, 1H, CH-arom., CH-pyrazole), 7.20-7.26 (m, 5H, CH-pyrazole), 7.33 (brs, 1H, CH-pyrazole), 7.37-7.41 (m, 2H, CH-arom.), 8.40 (brs, 1H, NH-amide), 8.75 (brs, 1H, NH-amide). 13 C NMR (125 MHz, CDCl 3 ): δ [ppm]=13.7, 14.2, 19.1, 21.0, 22.7, 28.4, 29.6, 30.6, 32.0, 40.1, 52.2, 52.8, 53.8, 54.1, 55.2 , 56.0, 64.4, 98.2, 98.8, 103.6, 113.9, 114.1, 127.1, 130.1, 134.6, 135.0, 136.0, 144.7, 154.1, 156.1, 159.2, 159.3, 159.4, 159.8, 172.8. Mp: 94.4° C. R f : 0.10 n-pentane/ethyl acetate (2:1). HRMS (ESI): calcd for C 48 H 55 N 11 O 12 H: 978.4104; found: 978.4144; calcd for C 48 H 55 N 11 O 12 Na: 1000.3924; found: 1000.3942.
6-Amino-2-(-3-(3-(3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido-lysinyl-carboxylic acid methyl ester trifluoroacetate (Trimer-Lys-OMe)
[0242] A portion of 50 mg (51 μmol, 1.00 equiv) of the PMB-protected Trimer-Lys-OMe was treated with hot TFA according to general procedure E to yield the free Trimer-Lys-OMe as a colorless solid. Yield: 37 mg (49 μmol, 96%).
[0243] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=1.38-1.42 (m, 2H, CH 2 -Lys), 1.53-1.59 (m, 2H, CH 2 -Lys), 1.81-1.84 (m, 2H, CH 2 -Lys), 2.78-2.82 (m, 2H, CH 2 -Lys), 3.67 (s, 3H, OOCH 3 ), 4.42-4.45 (m, 1H, α-CH-Lys), 7.41 (s, 1H, CH-pyrazole), 7.61 (s, 1H, CH-pyrazole), 7.65 (bs, 3H, H-8), 7.95 (s, 1H, CH-pyrazole), 8.89 (d, 3 J=6.9 Hz, 1H, NH-amide), 11.16 (s, 1H, NH-amide), 11.42 (s, 1H, NH-amide), 13.28 (s, 1H, NH-pyrazole), 13.45 (s, 1H, NH-pyrazole), 14.97 (s, 1H, NH-pyrazole). 13 C NMR (125 MHz, DMSO-d 6 ): β [ppm]=22.3, 26.3, 29.6, 51.8, 97.5, 98.1, 102.0, 102.5, 154.8, 172.2. Mp: decomposition at 198° C. HRMS (ESI): calcd for C 19 H 23 N 11 O 2 H: 518.1855; found: 518.1860.
2-(1-(4-Methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido-6-(tert-butoxycarbonyl)-lysine
[0244] A 143 mg (146 μmol, 1.00 equiv) amount of 2-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido-6-(tert-butoxycarbonyl)-lysine methyl ester and 9 mg lithium hydroxide (376 μmol, 2.57 equiv) were stirred in a mixture of methanol/THF/water (5:5:1) for 16 h at 65° C. Workup and purification were conducted according to general procedure A to yield the free carboxylic acid as a colorless solid. Yield: 111 mg (115 μmol, 79%).
[0245] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=1.21-1.41 (m, 13H, CH 2 -Lys, (CH 3 ) 3 ), 1.67-1.86 (m, 2H, CH 2 -Lys), 2.87-2.91 (m, 2H, CH 2 -Lys), 3.70-3.71 (3s, 9H, CH 3 -PMB), 4.25 (brs, 1H, α-CH-Lys), 5.59 (s, 2H, CH 2 -PMB), 5.68 (s, 2H, CH 2 -PMB), 5.81 (s, 2H, CH 2 -PMB), 6.77 (t, 3 J=5.3 Hz, 1H, NH), 6.85-6.92 (m, 6H, CH-arom.), 7.17-7.21 (m, 4H, CH-arom.), 7.26-7.29 (m, 2H, CH-arom.), 7.38 (s, 1H, CH-pyrazole), 7.71 (s, 1H, CH-pyrazole), 7.98 (s, 1H, CH-pyrazole), 8.78 (d, 3 J=6.0 Hz, 1H, NH-amide), 11.34 (s, 1H, NH-amide), 11.50 (brs, 1H, NH-amide). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=28.1, 52.6, 54.9, 55.0, 77.2, 100.9, 105.0, 105.1, 105.3, 113.7, 113.8, 113.9, 127.9, 128.7, 129.0, 129.3, 129.5, 129.6, 134.3, 136.7, 144.8, 145.2, 153.5, 158.6, 159.0. Mp: 177.6-180.0° C. HRMS (ESI): calcd for C 47 H 53 N 11 O 12 Na: 986.3767; found: 986.3760; calcd for C 47 H 52 N 11 O 12 : 962.3802; found: 962.3839.
tert-Butyl-6-(1-cyclohexylethylamino)-5-(1-(4-methoxybenzyl)-3-(1-(4-methoxy-benzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido-6-oxo-hexylcarbamate
[0246] A 85 mg (0.88 mmol, 1.10 equiv) amount of PMB-protected Trimer-Lys-OH and 11.76 μL (0.80 mmol, 1.00 equiv) of cyclohexylethylamine were reacted with 34 mg (0.20 mmol, 2.51 equiv) of Cl-HOBt, 36.41 mg (0.88 mmol, 1.10 equiv) of HCTU and 28 μL (1.20 mmol, 3.00 equiv) 2,6-lutidine according to general procedure C. The crude product was purified by column chromatography on silica gel using dichloromethane/ethyl acetate (3:1) to yield compound x as a colorless solid. Yield: 76 mg (71 μmol, 88%).
[0247] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=0.87-0.92 (m, 2H, CH 2 -cyclohexyl), 1.00-1.02 (d, 3H, 3 J=6.8 Hz, CH 3 ), 1.05-1.17 (m, 3H, CH-cyclohexyl, CH 2 -cyclohexyl), 1.24-1.39 (m, 14H, CH 2 -Lys, (CH 3 ) 3 ), 1.52-1.69 (m, 7H, CH 2 -cyclohexyl, CH 2 -Lys), 2.87-2.91 (m, 2H, CH 2 -Lys), 3.59-3.64 (m, 1H, CH), 4.33-4.39 (m, 1H, α-CH-Lys), 5.53-5.63 (m, 2H, CH 2 -PMB), 5.68 (s, 2H, CH 2 -PMB), 5.81 (s, 2H, CH 2 -PMB), 6.75 (t, 1H, 3 J=5.5 Hz, NH), 6.83-6.92 (m, 6H, CH-arom.), 7.17-7.20 (m, 4H, CH-arom.), 7.26-7.29 (m, 2H, CH-arom.), 7.44 (s, 1H, CH-pyrazole), 7.68 (d, 1H, 3 J=8.7 Hz, NH), 7.71 (s, 1H, CH-pyrazole), 7.98 (s, 1H, CH-pyrazole), 8.58 (d, 1H, 3 J=8.1 Hz, NH-amide), 11.33 (s, 1H, NH-amide), 11.50 (s, 1H, NH-amide). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=13.5, 17.6, 18.5, 23.0, 25.6, 25.9, 28.2, 28.6, 28.7, 29.1, 30.1, 33.6, 42.3, 48.5, 55.0, 63.4, 77.2, 99.9, 100.8, 105.0, 113.6, 113.8, 114.0, 127.9, 128.7, 129.0, 129.3, 129.5, 129.7, 134.3, 134.7, 136.7, 144.8, 145.1, 153.5, 155.4, 155.5, 156.8, 158.6, 159.0, 170.5. Mp: 154.2-155.7° C. R f : 0.45 dichlormethane/ethyl acetate (3:1). HRMS (ESI): calcd for C 55 H 68 N 12 O 11 H: 1073.5203; found: 1073.5226; calcd for C 55 H 68 N 12 O 11 Na: 1095.5023; found: 1095.5008.
N-(6-Amino-1-(1-cyclohexylethylamino)-1-oxohexan-2-yl)-3-(3-(3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamide-trifluoro-acetate (Trimer-Lys-Che)
[0248] A portion of 54 mg (50 μmol, 1.00 equiv) of the PMB-protected Trimer-Lys-Che was treated with hot TFA according to the general procedure E to yield the free pyrazole trimer as a light-yellow solid. Yield: 24 mg (33 μmol, 66%).
[0249] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=0.85-1.02 (m, 5H, CH 3 (d, 3 J=6.8 Hz), CH 2 ), 1.06-1.17 (m, 3H, CH, CH 2 ), 1.23-1.40 (m, 3H, CH, CH 2 ), 1.53-1.73 (m, 9H, CH 2 , CH), 2.73-2.81 (m, 2H, CH 2 -Lys), 3.58-3.65 (m, 1H, CH), 4.38-4.45 (m, 1H, α-CH-Lys), 7.38 (bs, 1H, NH-amide), 7.59 (bs, 1H, CH-pyrazole), 7.66 (bs, 3H, NH 2 ), 7.79 (bs, 1H, NH-amide), 7.95 (bs, 1H, CH-pyrazole), 8.54 (bs, 1H, CH-pyrazole), 11.14 (s, 1H, NH-amide), 11.45 (s, 1H, NH-amide), 13.24 (bs, 1H, NH-pyrazole), 13.49 (bs, 1H, NH-pyrazole), 14.98 (bs, 1H, NH-pyrazole). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=17.6, 17.7, 22.5, 25.6, 25.9, 26.6, 28.6, 28.7, 42.3, 48.5, 52.5, 98.1, 102.2, 138.6, 146.4, 155.0, 155.8, 157.7, 157.9, 170.5. Mp: decomposition at 211° C. HRMS (ESI): calcd for C 26 H 36 N 12 O 6 H: 613.2954; found: 613.2971; calcd for C 26 H 35 N 12 O 6 : 611.2808; found: 611.2804.
N-(1-Cyclohexylethyl)-1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamide
[0250] A portion of 150 mg (204 μmol, 1.09 equiv) of PMB-protected Trimer-OH and 27.70 μL (186 μmol, 1.00 equiv) of cyclohexylethylamine were reacted with 57 mg (223 μmol, 1.20 equiv) of Mukaiyama's reagent and 0.10 mL (574 μmol, 3.08 equiv) of diisopropylethylamine according to general procedure B. The crude product was purified by column chromatography on silica gel using n-pentane/ethyl acetate (2:1) to yield the PMB-protected Trimer-Che as a colorless solid. Yield: 131 mg (155 μmol, 83%).
[0251] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=0.85-0.97 (m, 2H, CH 2 -cyclohexyl), 1.09 (d, 3 J=6.8 Hz, 3H, CH 3 ), 1.13-1.19 (m, 2H, CH 2 -cyclohexyl), 1.34-1.41 (m, 1H, CH), 1.59-1.74 (m, 4H, CH 2 -cyclohexyl), 3.70-3.71 (3s, 9H, CH 3 -PMB), 3.76-3.84 (m, 1H, CH), 5.55-5.63 (dd, 3 J=9.0 Hz, 3 J=14.5 Hz, 2H, CH 2 -PMB), 5.68 (s, 2H, CH 2 -PMB), 5.81 (s, 2H, CH 2 -PMB), 6.85-6.91 (m, 6H, CH-arom.), 7.15-7.19 (m, 4H, CH-arom.), 7.25-7.28 (m, 2H, CH-arom.), 7.31 (s, 1H, CH-pyrazole), 7.71 (s, 1H, CH-pyrazole), 7.98 (s, 1H, CH-pyrazole), 8.35 (d, 3 J=8.8 Hz, 1H, NH-amide), 11.33 (s, 1H, NH-amide), 11.50 (s, 1H, NH-amide). 13 C NMR (125 MHz, CDCl 3 ): δ [ppm]=17.5, 25.6, 25.9, 28.9, 29.1, 42.2, 48.8, 52.7, 53.0, 54.9, 55.0, 99.4, 100.9, 105.0, 113.6, 113.8, 114.0, 127.9, 128.6, 128.9, 129.3, 129.5, 129.8, 134.4, 135.4, 136.7, 144.8, 145.0, 153.5, 155.4, 156.8, 158.4, 158.6, 159.0. Mp: 178° C. R f : 0.42 n-pentane/ethyl acetate (2:1). HRMS (ESI): calcd for C 44 H 49 N 10 O 8 H: 845.3729; found: 845.3723; calcd for C 44 H 49 N 10 O 8 Na: 867.3549; found: 867.3552.
N-(1-Cyclohexylethyl)-3-(3-(3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamide (Trimer-Che)
[0252] A portion of 49 mg (58 μmol, 1.00 equiv) of PMB-protected Trimer-Che was treated with hot TFA according to the general procedure E to yield the free pyrazole trimer as a colorless solid. Yield: 23 mg (47 μmol, 82%).
[0253] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=0.90-1.22 (m, 8H, CH 3 , CH 2 -cyclohexyl), 1.37-1.42 (m, 1H, CH), 1.59-1.75 (m, 5H, CH 2 -cyclohexyl), 3.78-3.84 (m, 1H, CH), 7.33 (s, 1H, CH-pyrazole), 7.60 (s, 1H, CH-pyrazole), 7.95 (s, 1H, CH-pyrazole), 8.26 (bs, 1H, NH-amide), 11.12 (s, 1H, NH-amide), 11.43 (s, 1H, NH-amide), 13.15 (s, 1H, NH-pyrazole), 13.46 (s, 1H, NH-pyrazole). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=15.1, 17.6, 25.6, 25.9, 28.9, 29.1, 42.3, 48.7, 64.8, 96.8, 98.1, 102.2, 138.6, 155.0, 155.8, 156.4, 158.1. Mp: decomposition at 265.6° C. HRMS (ESI): calcd for C 20 H 25 N 10 O 5 H: 485.2004; found: 485.1966.
4-(1-(4-Methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)butanoic acid methyl ester
[0254] A portion of 300 mg (0.41 mmol, 1.00 equiv) of PMB-protected Trimer-OH and 63 mg (0.41 μmol, 1.00 equiv) of γ-aminobutanoic acid methyl ester hydrochloride were reacted with 156 mg (0.61 mmol, 1.50 equiv) of Mukaiyama's reagent and 0.32 mL (1.83 mmol, 4.50 equiv) of diisopropylethylamine according to general procedure B. The residue was purified by column chromatography on silica gel using n-pentane/ethyl acetate (2:1) to yield PMB-protected Trimer-GABA-OMe as a colorless solid. Yield: 193 mg (0.23 mmol, 57%).
[0255] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=1.74-1.79 (quin, 3 J=7.1 Hz, 2H, CH 2 ), 2.34 (t, 3 J=7.4 Hz, 2H, CH 2 ), 3.22-3.26 (q, 3 J=6.0 Hz, 3 J=6.6 Hz, 2H, CH 2 ), 3.59 (s, 3H, OOCH 3 ), 3.70-3.71 (3s, 9H, CH 3 -PMB), 5.61 (s, 2H, CH 2 -PMB), 5.67 (s, 2H, CH 2 -PMB), 5.81 (s, 2H, CH 2 -PMB), 6.86-6.91 (m, 6H, CH-arom.), 7.16-7.19 (m, 4H, CH-arom.), 7.25-7.28 (m, 2H, CH-arom.), 7.31 (s, 1H, CH-pyrazole), 7.71 (s, 1H, CH-pyrazole), 7.98 (s, 1H, CH-pyrazole), 8.66 (t, 3 J=5.5 Hz, 1H, NH-amide), 11.34 (s, 1H, NH-amide), 11.50 (s, 1H, NH-amide). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=24.1, 30.6, 37.9, 51.2, 52.6, 53.1, 54.9, 55.0, 59.6, 99.4, 100.8, 105.0, 113.7, 113.8, 113.9, 127.9, 128.6, 128.9, 129.3, 129.5, 129.7, 134.3, 134.9, 136.7, 144.8, 145.1, 153.5, 155.4, 156.8, 158.6, 159.0, 173.0. Mp: 198.8-201.7° C. R f : 0.08 n-pentane/ethyl acetate (2:1). HRMS (ESI): calcd for C 41 H 42 N 10 O 10 H: 835.3158; found: 835.3187; calcd for C 41 H 42 N 10 O 10 Na: 857.2978; found: 857.3001; calcd for C 41 H 42 N 10 O 10 K: 873.2717; found: 873.2751; calcd for C 41 H 41 N 10 O 10 : 833.3013; found: 833.2999.
4-(3-(3-(3-Nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)butanoic acid methyl ester (Trimer-GABA-OMe)
[0256] A portion of 60 mg (72 μmol, 1.00 equiv) of PMB-protected Trimer-GABA-OMe was treated with hot TFA according to the general procedure E to yield the free aminopyrazole as a colorless solid. Yield: 26 mg (55 μmol, 76%).
[0257] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=1.72-1.83 (quin, 3 J=7.1 Hz, 2H, CH 2 ), 2.37 (t, 3 J=7.4 Hz, 2H, CH 2 ), 3.23-3.29 (q, 3 J=6.0 Hz, 3 J=6.9 Hz, 2H, CH 2 ), 3.59 (s, 3H, CH 3 ), 7.16 (bs, 1H, CH-pyrazole), 7.53 (bs, 1H, CH-pyrazole), 7.94 (s, 1H, CH-pyrazole), 8.53 (t, 3 J=5.4 Hz, 1H, NH), 11.08 (bs, 1H, NH-amide), 11.44 (s, 1H, NH-amide). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=24.3, 24.4, 30.6, 31.0, 37.8, 51.2, 87.4, 96.6, 102.2, 155.0, 155.8, 173.0, 174.1. Mp: decomposition at 242° C. HRMS (ESI): calcd for C 17 H 17 N 10 O 7 : 473.1287; found: 473.1317.
4-(1-(4-Methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)butanoic acid
[0258] A 70 mg (84 μmol, 1.00 equiv) amount of PMB-protected Trimer-GABA-OMe and 10 mg lithium hydroxide (418 μmol, 4.98 equiv) were stirred in a mixture of methanol/THF/water (5:5:1) for two days at room temperature. The pure product was prepared according to general procedure A as a colorless solid. Yield: 57 mg (69 μmol, 83%).
[0259] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=1.71-1.77 (quin, 3 J=7.1 Hz, 2H, CH 2 ), 2.34 (t, 3 J=7.4 Hz, 2H, CH 2 ), 3.22-3.26 (q, 3 J=5.8 Hz, 3 J=6.5 Hz, 2H, CH 2 ), 3.70-3.71 (3s, 9H, CH 3 -PMB), 5.61 (s, 2H, CH 2 -PMB), 5.67 (s, 2H, CH 2 -PMB), 5.81 (s, 2H, CH 2 -PMB), 6.86-6.91 (m, 6H, CH-arom.), 7.16-7.20 (m, 4H, CH-arom.), 7.25-7.28 (m, 2H, CH-arom.), 7.32 (s, 1H, CH-pyrazole), 7.71 (s, 1H, CH-pyrazole), 7.98 (s, 1H, CH-pyrazole), 8.66 (t, 3 J=5.7 Hz, 1H, NH-amide), 11.33 (s, 1H, NH-amide), 11.50 (s, 1H, NH-amide). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=24.2, 30.9, 38.1, 52.6, 53.1, 54.9, 55.0, 60.1, 72.2, 99.4, 100.8, 105.0, 113.7, 113.8, 114.0, 127.9, 128.7, 128.9, 129.3, 129.5, 129.7, 134.3, 135.0, 136.7, 144.8, 145.1, 153.5, 155.4, 156.8, 158.6, 159.0, 174.1. Mp: 209.3-211° C. HRMS (ESI): calcd for C 40 H 41 N 10 O 10 Na: 843.2821; found: 843.2849.
4-(3-(3-(3-Nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)butanoic acid (Trimer-GABA-OH)
[0260] A portion of 50 mg (61 μmol, 1.00 equiv) of PMB-protected Trimer-GABA-OH was treated with hot TFA according to general procedure E to yield the free aminopyrazole trimer as a beige solid. Yield: 22 mg (48 μmol, 78%).
[0261] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=1.72-1.78 (quin, 3 J=7.1 Hz, 2H, CH 2 ), 2.28 (t, 3 J=7.4 Hz, 2H, CH 2 ), 3.24-3.28 (q, 3 J=6.0 Hz, 3 J=6.9 Hz, 2H, CH 2 ), 7.20 (bs, 1H, CH-pyrazole), 7.58 (bs, 1H, CH-pyrazole), 7.94 (s, 1H, CH-pyrazole), 8.53 (bs, 1H, H-6), 11.11 (brs, 1H, NH-amide), 11.43 (s, 1H, NH-amide), 13.20 (brs, 1H, NH-pyrazole), 13.49 (brs, 1H, NH-pyrazole), 14.98 (s, 1H, NH-pyrazole). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=24.4, 31.0, 37.9, 96.7, 98.1, 102.2, 138.6, 155.0, 155.8, 174.1. Mp: decomposition at 231° C. HRMS (ESI): calcd for C 16 H 15 N 10 O 7 : 459.1120; found: 459.1143.
tert-Butyl-2-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)ethylcarbamate
[0262] A 146 mg (198 μmol, 1.00 equiv) amount of PMB-protected Trimer-OH was dissolved in 20 mL dichlormethane and cooled to 0° C. To this suspension 80 mg HOBt (592 μmol, 2.98 equiv), 114 mg EDC-HCl (595 μmol, 3.00 equiv) and 64 mg (399 μmol, 2.01 equiv) tert-butyl-2-aminoethylcarbamate were added according to general procedure D. After workup, the crude product was purified by column chromatography on silica gel using n-pentane/ethyl acetate (2:1) to yield the coupled product as a light yellow solid. Yield: 142 mg (162 μmol, 82%).
[0263] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=1.37 (s, 9H, (CH 3 ) 3 ), 3.06-3.12 (m, 2H, CH 2 ), 3.23-3.28 (m, 2H, CH 2 ), 3.70-3.71 (2s, 9H, CH 3 -PMB), 5.61 (s, 2H, CH 2 -PMB), 5.67 (s, 2H, CH 2 -PMB), 5.81 (s, 2H, CH 2 -PMB), 6.86-6.91 (m, 7H, H-4, CH-arom.), 7.16-7.21 (m, 4H, CH-arom.), 7.26-7.29 (m, 2H, CH-arom.), 7.32 (s, 1H, CH-pyrazole), 7.71 (s, 1H, CH-pyrazole), 7.98 (s, 1H, CH-pyrazole), 8.63 (t, 3 J=5.7 Hz, 1H, NH-amide), 11.34 (s, 1H, NH-amide), 11.51 (s, 1H, NH-amide). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=18.5, 20.6, 28.1, 30.1, 52.6, 53.1, 54.9, 55.0, 63.4, 77.6, 99.5, 100.9, 105.0, 113.7, 113.8, 114.0, 127.9, 128.7, 129.0, 129.3, 129.5, 129.7, 134.3, 134.9, 136.7, 144.8, 145.2, 153.5, 155.4, 155.6, 156.8, 158.6, 159.0, 159.1, 170.3, 171.9. Mp: 117.8° C. R f : 0.06 n-pentane/ethyl acetate (2:1). HRMS (ESI): calcd for C 43 H 47 N 11 O 10 H: 878.3580; found: 878.3596; calcd for C 43 H 47 N 11 O 10 Na: 900.3400, found: 900.3420.
N-(2-Aminoethyl)-3-(3-(3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamide (Trimer-diamine)
[0264] A portion of 52 mg (59 μmol, 1.00 equiv) of PMB-protected Trimer-diamine was treated with hot TFA according to general procedure E to yield the free aminopyrazole trimer as a colorless solid. Yield: 16 mg (30 μmol, 51%).
[0265] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=2.99 (bs, 2H, CH 2 ), 3.48 (bs, 2H, CH 2 ), 7.28 (bs, 1H, CH-pyrazole), 7.61 (brs, 1H, CH-pyrazole), 7.78 (bs, 1H, NH 2 ), 7.95 (bs, 1H, CH-pyrazole), 8.68 (bs, 1H, NH-amide), 11.18 (bs, 1H, NH-amide), 11.42 (bs, 1H, NH-amide), 13.31 (bs, 1H, NH-pyrazole), 13.47 (bs, 1H, NH-pyrazole). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=36.5, 102.3, 136.4, 136.5, 138.6, 155.0, 156.3, 159.2. Mp: decomposition at 256° C. HRMS (ESI): calcd for C 14 H 15 N 11 O 5 Na: 440.1150, found: 440.1188.
Ethyl 2-(2-(2-(2-aminoethoxy)ethoxy)ethoxy)acetate
[0266] To a solution of {2-[2-(2-Azido-ethoxy)-ethoxy]-ethoxy}-acetic acid ethyl ester (0.30 g, 1.15 mmol, 1 eq) in ethanol (7 mL) was added 1M HCl (2.30 mL, 2.30 mmol, 2 eq) and 30.0 mg of Pd/C (10%). The flask was then evacuated and filled with H 2 . The mixture was stirred under H 2 atmosphere at room temperature until the starting material disappeared on the TLC plate and in mass spectra. The solution was filtered through celite and concentrated in vacuo to give a pale yellow syrup. The obtained 2-[2-(2-ethoxycarbonylmethoxy-ethoxy)-ethoxy]-ethyl-ammonium chloride can be stored at −18° C. for several months. Work-up to get the free amine should only be performed immediately before the next step. To obtain the free amine 350 mg (1.29 mmol) of the respective hydrochloride were dissolved in chloroform. The organic layer was washed with sat. aq K 2 CO 3 and H 2 O, and the solvent was evaporated in vacuo at room temperature to give a colorless oil. Yield: 210 mg (0.89 mmol, 69%).
[0267] 1 H-NMR (500 MHz, CDCl 3 ): δ [ppm]=1.28 (t, 3H, CH 3 ), 1.85 (brs, 2H, NH 2 ), 2.88 (t, 2H, CH 2 ), 3.53 (t, 2H, CH 2 ), 3.61-3.76 (m, 8H, CH 2 ), 4.15 (s, 2H, CH 2 ), 4.21 (q, 2H, CH 2 ). 13 C-NMR (125.7 MHz, CDCl 3 ): δ [ppm]=14.3, 41.8, 60.9, 68.8, 70.4, 70.6, 70.7, 71.0, 73.2, 170.6. HRMS (ESI): m/z calcd for C 10 H 22 NO 5 : 236.1492; found: 236.1511, calcd for C 10 H 21 NNaO 5 : 258.1312; found: 258.1325.
1-(1-(4-Methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-yl)-1-oxo-5,8,11-trioxa-2-azatridecan-13-oic acid ethyl ester
[0268] A 200 mg (272 μmol, 1.00 equiv) amount of compound PMB-protected Trimer-OH was dissolved in 20 mL dichlormethane and cooled to 0° C. To this suspension 97 mg HOBt (828 μmol, 3.05 equiv), 156 mg EDC-HCl (816 μmol, 3.00 equiv) and 128 mg (544 μmol, 2.00 equiv) ethyl-2-{2-[2-(aminoethoxy)ethoxy]-ethoxy}acetate were added according to the general procedure D. After workup, the crude product was purified by column chromatography on silica gel using dichlormethane/methanol (70:1) to yield the pure coupling product as a colorless solid. Yield: 207 mg (218 μmol, 80%).
[0269] 1 H NMR (500 MHz, CDCl 3 ): δ [ppm]=1.24 (t, 3 J=7.1 Hz, 3H, CH 3 ), 3.58-3.74 (m, 12H, CH 2 ), 3.76-3.77 (2s, 9H, CH 3 -PMB), 4.11 (s, 2H, CH 2 ), 4.13-4.21 (q, 3 J=7.1 Hz, 2H, CH 2 ), 5.63 (s, 4H CH 2 -PMB), 5.80 (s, 2H, CH 2 -PMB), 6.79-6.89 (m, 7H, H-11, CH-arom.), 7.11 (s, 1H, CH-pyrazole), 7.24-7.30 (m, 6H, CH-pyrazole, CH-arom.), 7.37-7.41 (m, 2H, CH-arom.), 8.40 (s, 1H, NH-amide), 8.43 (s, 1H, NH-amide). 13 C NMR (125 MHz, CDCl 3 ): δ [ppm]=14.1, 39.5, 53.7, 53.9, 55.2, 55.9, 60.9, 68.6, 69.5, 70.3, 70.4, 70.5, 70.8, 98.1, 98.9, 103.7, 113.9, 114.1, 127.1, 128.7, 129.2, 130.0, 134.7, 135.7, 136.1, 144.7, 154.1, 155.1, 156.2, 159.2, 159.3, 159.5, 159.7, 170.5. Mp: 78.6° C. R f : 0.18 dichlormethane/methanol (70:1). HRMS (ESI): calcd for C 46 H 52 N 10 O 13 H: 953.3788; found: 953.3766; calcd for C 43 H 47 N 11 O 10 Na: 975.3608, found: 975.3591.
1-(3-(3-(3-Nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-yl)-1-oxo-5,8,11-trioxa-2-azatridecan-13-oic acid ethyl ester (Trimer-TEG-OEt)
[0270] A portion of 49 mg (52 μmol, 1.00 equiv) of PMB-protected Trimer-TEG-OEt was treated with hot TFA according to general procedure E to yield the pure aminopyrazole trimer as a colorless solid. Yield: 30 mg (51 μmol, 98%).
[0271] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=1.18 (t, 3 J=7.1 Hz, 3H, CH 3 ), 3.38-3.42 (m, 2H, CH 2 ), 3.53-3.59 (m, 10H, CH 2 ), 4.08-4.12 (m, 4H, CH 2 ), 7.27 (bs, 1H, CH-pyrazole), 7.59 (s, 1H, CH-pyrazole), 7.95 (s, 1H, CH-pyrazole), 8.40 (s, 1H, NH-amide), 11.12 (bs, 1H, NH-amide), 11.43 (bs, 1H, NH-amide), 13.22 (bs, 1H, NH-pyrazole), 13.48 (bs, 1H, NH-pyrazole), 14.98 (bs, 1H, NH-pyrazole). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=14.0, 60.0, 67.6, 68.7, 69.5, 69.6, 69.9, 98.2, 102.2, 138.6, 146.4, 146.5, 155.0, 155.8, 156.3, 170.0. Mp: decompositon at 264.3° C. HRMS (ESI): calcd for C 22 H 28 N 10 O 10 H: 593.2063; found: 593.2071; calcd for C 22 H 28 N 10 O 10 Na: 615.1882; found: 615.1899.
1-(1-(4-Methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-yl)-1-oxo-5,8,11-trioxa-2-azatridecan-13-oic acid
[0272] A 153 mg (161 μmol, 1.00 equiv) amount of PMB-protected Trimer-TEG-OEt and 14 mg lithium hydroxide (585 μmol, 3.64 equiv) were stirred in a mixture of methanol/THF/water (5:5:1) for two days at room temperature. The pure product was prepared according to general procedure A to yield the free carboxylic acid as a colorless solid. Yield: 137 mg (148 μmol, 92%).
[0273] 1 H NMR (500 MHz, CDCl 3 ): δ [ppm]=3.36-3.40 (m, 2H, CH 2 ), 3.51-3.58 (m, 10H, CH 2 ), 3.70-3.71 (2s, 9H, CH 3 -PMB), 4.00 (s, 2H, CH 2 ), 5.61 (s, 2H, CH 2 -PMB), 5.67 (s, 2H, CH 2 -PMB), 5.81 (s, 2H, CH 2 -PMB), 6.86-6.91 (m, 6H, CH-arom.), 7.16-7.19 (m, 4H, CH-arom.), 7.26-7.28 (m, 6H, CH-arom.), 7.33 (s, 1H, CH-pyrazole), 7.71 (s, 1H, CH-pyrazole), 7.98 (s, 1H, CH-pyrazole), 8.71 (t, 3 J=5.5 Hz, 1H, NH), 11.33 (s, 1H, NH-amide), 11.50 (s, 1H, NH-amide), 12.55 (bs, 1H, H-1). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=52.7, 53.1, 55.0, 67.5, 68.5, 69.4, 69.6, 69.7, 99.5, 100.8, 105.0, 113.7, 113.8, 113.9, 127.9, 128.7, 128.9, 129.3, 129.5, 129.7, 134.3, 134.8, 136.7, 144.8, 145.1, 153.5, 155.4, 156.8, 158.5, 158.6, 159.0, 159.1, 171.5. Mp: 88° C. HRMS (ESI): calcd for C 44 H 48 N 10 O 13 H: 925.3475; found: 925.3445; calcd for C 44 H 48 N 10 O 13 Na: 947.3295; found: 947.3251.
{2-[2-(2-{[5-({5-[(5-Nitro-2H-pyrazole-3-carbonyl)-amino]-2H-pyrazole-3-carbonyl}-amino)-2H-pyrazole-3-carbonyl]-amino}-ethoxy)-ethoxy]-ethoxy}-acetic acid (Trimer-TEG-OH)
[0274] A portion of 53.0 mg (57.4 μmol) of Trimer(PMB)-TEG-OH OMe was treated with hot TFA according to general procedure E to yield Trimer-TEG-OH as a colorless solid. Yield: 30 mg (53.2 μmol, 94%).
[0275] 1 H-NMR (500 MHz, DMSO): δ [ppm]=3.39-3.40 (m, 2H, CH 2 ), 3.52-3.57 (m, 10H, CH 2 ), 4.01 (s, 2H, CH 2 ), 7.16 (brs, 1H, NH-amide), 7.57 (s, 1H, CH-pyrazole), 7.94 (s, 1H, CH-pyrazole), 8.55 (s, 1H, CH-pyrazole), 11.09 (s, 1H, NH-amide), 11.43 (brs, 1H, NH-amide), 12.75 (s, 1H, NH-pyrazole), 13.09 (s, 1H, NH-pyrazole), 13.51 (brs, 1H, CO 2 H), 14.98 (s, 1H, NH-pyrazole). 13 C-NMR (500 MHz, DMSO): δ [ppm]=39.5, 68.4, 69.7, 70.5, 70.56, 70.6, 70.7, 103.2, 139.6, 155.9, 156.8, 172.5. Mp: decomposition at 349° C. HRMS (ESI): m/z calcd for C 20 H 24 N 10 NaO 10 : 587.1569; found: 587.1553; for C 20 H 23 N 10 Na 2 O 10 : 609.1389, found: 609.1388.
N-(13-Cyclohexyl-11-oxo-3,6,9-trioxa-12-azatetradecyl)-1-(4-methoxy-benzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carbox-amido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamide
[0276] A portion of 110 mg (119 μmol, 1.09 equiv) of compound PMB-protected Trimer-TEG-OH and 16 μL (109 μmol, 1.00 equiv) of cyclohexylethylamine were reacted with 41 mg (161 μmol, 1.47 equiv) of Mukaiyama's reagent and 56.50 μL (324 μmol, 2.98 equiv) of diisopropylethylamine according to general procedure B. The residue was purified by column chromatography on silica gel using dichlormethane/methanol (70:1) to yield the coupled product as a colorless solid. Yield: 84 mg (81 μmol, 75%).
[0277] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=0.81-0.92 (m, 2H, CH 2 ), 1.00 (d, 3 J=6.7 Hz, 3H, CH 3 ), 1.04-1.07 (m, 3H, CH, CH 2 ), 1.23-1.28 (m, 1H, CH), 1.55-1.66 (m, 5H, CH, CH 2 ), 3.55-3.71 (m, 21H, CH 2 , CH 3 -PMB), 4.85 (s, 2H, CH 2 ), 5.61 (s, 2H, CH 2 -PMB), 5.66 (s, 2H, CH 2 -PMB), 5.81 (s, 2H, CH 2 -PMB), 6.86-6.91 (m, 6H, CH-arom.), 7.16-7.19 (m, 4H, CH-arom.), 7.24-7.33 (m, 4H, H-7, CH-pyrazole, CH-arom.), 7.70 (s, 1H, CH-pyrazole), 7.97 (s, 1H, CH-pyrazole), 8.70 (t, 3 J=5.2 Hz, 1H, NH), 11.33 (s, 1H, NH-amide), 11.50 (s, 1H, NH-amide). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=17.6, 25.6, 25.9, 28.8, 38.6, 42.2, 48.1, 52.7, 53.1, 55.0, 55.1, 68.6, 69.5, 69.7, 70.2, 99.6, 100.9, 105.0, 113.7, 113.8, 114.0, 127.9, 128.7, 128.9, 129.3, 129.5, 129.7, 134.3, 134.9, 136.7, 144.8, 145.2, 153.5, 155.4, 158.6, 159.0, 159.1, 168.3. Mp: 189.9-191.2° C. R f : 0.35 dichlormethane/methanol (70:1). HRMS (ESI): calcd for C 52 H 63 N 11 O 12 H: 1034.4730; found: 1034.4757; calcd for C 52 H 63 N 11 O 12 Na: 1056.4550; found: 1056.4588.
N-(13-Cyclohexyl-11-oxo-3,6,9-trioxa-12-azatetradecyl)-3-(3-(3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamide (Trimer-TEG-Che)
[0278] A portion of 42 mg (41 μmol, 1.00 equiv) of PMB-protected Trimer-TEG-Che was treated according to general procedure E to yield the free aminopyrazole as a colorless solid. Yield: 20 mg (30 μmol, 72%).
[0279] 1 H NMR (500 MHz, DMDO-d 6 ): δ [ppm]=0.83-1.33 (m, 9H, CH 3 , CH 2 -cyclohexyl), 1.56-1.67 (m, 5H, CH-cyclohexyl, CH 2 -cyclohexyl), 3.39-3.39 (m, 13H, CH, CH 2 ), 3.86 (s, 2H, CH 2 ), 7.26-7.29 (bs, 2H, CH-pyrazole, NH-amide), 7.59 (bs, 1H, CH-pyrazole), 7.95 (s, 1H, CH-pyrazole), 8.64 (bs, 1H, NH-amide), 11.14 (bs, 1H, NH-amide), 11.44 (bs, 1H, NH-amide), 13.22 (bs, 1H, NH-pyrazole), 13.48 (bs, 1H, NH-pyrazole). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=17.6, 25.6, 25.9, 28.7, 28.8, 38.4, 42.1, 48.1, 51.0, 59.9, 60.1, 68.7, 69.5, 69.7, 70.2, 80.5, 102.2, 138.6, 155.0, 155.8, 168.2. Mp: decomposition at 153° C. HRMS (ESI): calcd for C 28 H 39 N 11 O 9 Na: 696.2824; found: 696.2808; calcd for C 28 H 38 N 11 O 9 Na: 672.2859; found: 672.2874.
N-(1-Cyclohexyl-2-(1-cyclohexylethylamino)-2-oxoethyl)-1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamide
[0280] A portion of 200 mg (0.27 mmol, 1.00 equiv) of PMB-protected Trimer-OH and 103 mg (0.27 mmol, 1.00 equiv) of 2-Amino-2-cyclohexyl-N-(1-cyclohexylethyl)acetamide-trifluoroacetate were reacted with 104 mg (0.41 mmol, 1.50 equiv) of Mukaiyama's reagent and 0.21 mL (1.21 mmol, 4.45 equiv) of diisopropylethylamine according to general procedure B. The crude product was purified by column chromatography on silica gel using dichlormethane/ethyl acetate (7:1) to yield the coupled product as a colorless solid. Yield: 128 mg (0.13 mmol, 48%).
[0281] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=0.89-1.18 (m, 13H, CH 3 , CH 2 ), 1.26-1.32 (m, 1H, CH), 1.56-1.80 (m, 11H, CH, CH 2 ), 3.59-3.63 (m, 1H, CH), 3.70-3.71 (2s, 9H, CH 3 -PMB), 4.28 (t, 3 J=8.6 Hz, 1H, CH), 5.53-5.60 (dd, 3 J=14.5 Hz, 3 J=5.7 Hz, 2H, CH 2 -PMB), 5.67 (s, 2H, CH 2 -PMB), 5.81 (s, 2H, CH 2 -PMB), 6.82-6.80 (m, 6H, CH-arom.), 7.16-7.18 (m, 4H, CH-arom.), 7.26-7.28 (m, 2H, CH-arom.), 7.40 (s, 1H, CH-pyrazole), 7.71 (s, 1H, CH-pyrazole), 7.79 (d, 3 J=8.5 Hz, 1H, NH-amide), 7.97 (s, 1H, CH-pyrazole), 8.46 (d, 3 J=8.8 Hz, 1H, NH-amide), 11.32 (s, 1H, NH-amide), 11.50 (s, 1H, NH-amide). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=17.3, 25.6, 25.7, 28.5, 28.6, 28.7, 42.0, 55.0, 68.2, 100.8, 113.6, 113.8, 114.0, 127.9, 128.7, 128.9, 129.3, 129.5, 129.6, 134.8, 136.7, 156.8, 158.6, 158.9, 159.0, 169.2, 169.5. Mp: 216° C. R f : 0.40 dichlormethane/ethyl acetate (7:1). HRMS (ESI): calcd for C 52 H 61 N 11 O 9 H: 984.4726; found: 984.4737; calcd for C 52 H 61 N 11 O 9 Na: 1006.4546, found: 1006.4492.
N-(1-Cyclohexyl-2-(1-cyclohexylethylamino)-2-oxoethyl)-3-(3-(3-nitro-1H-pyrazol-5-carboxamido)-1H-pyrazol-5-carboxamido)-1H-pyrazol-5-carboxamide (Trimer-Chg-Che)
[0282] A portion of 30 mg (30 μmol, 1.00 equiv) of PMB-protected Trimer-Chg-Che was treated according to general procedure E to yield the free aminopyrazole trimer as a colorless solid. Yield: 17 mg (27 μmol, 89%).
[0283] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=0.89-1.21 (m, 13H, OOCH 3 , CH 2 -cyclohexyl), 1.27-1.33 (m, 1H, CH-cyclohexyl), 1.59-1.79 (m, 11H, CH-cyclohexyl, CH 2 -cyclohexyl), 3.60-3.66 (m, 1H, CH), 4.33 (bs, 1H, CH), 7.39 (bs, 1H, CH-pyrazole), 7.60 (bs, 1H, CH-pyrazole), 7.86 (bs, 1H, H-7), 7.96 (s, 1H, CH-pyrazole), 8.35 (bs, 1H, NH), 11.11 (bs, 1H, NH-amide), 11.42 (bs, 1H, NH-amide), 13.23 (bs, 1H, NH-pyrazole), 13.47 (bs, 1H, NH-pyrazole). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=17.2, 25.3, 25.4, 25.6, 25.9, 28.4, 28.5, 28.7, 29.1, 30.3, 42.0, 48.6, 57.6, 98.0, 98.2, 102.2, 136.4, 136.5, 138.6, 146.5, 146.4, 146.6, 155.0, 155.2, 155.8, 169.6. Mp: decomposition at 248.6° C. HRMS (ESI): calcd for C 28 H 36 N 11 O 6 : 622.2856; found: 622.2878.
Methyl 15-(4-(tert-butoxycarbonylamino)butyl)-1-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyra-zole-5-carboxamido)-1H-pyrazol-5-yl)-1,13-dioxo-5,8,11-trioxa-2,14-diazahexa-decan-16-oate [Trimer(PMB)-TEG-Lys(Boc)-OMe]
[0284] In an argon atmosphere 105 mg (0.11 mmol, 1 eq) of PMB-protected Trimer-TEG-OH, 39 μL (35 mg, 0.34 mmol, 3 eq) of PYBOP, 39 μL (35 mg, 0.34 mmol, 3 eq) of N-methylmorpholine (NMM) and 60 mg (0.20 mmol, 1.8 eq) N-ε-tert.-butyloxycarbonyl-(S)-lysine methyl ester were dissolved in dry dichloromethane (30 mL) and the solution was heated to 40° C. for 4 days. Dichloromethane was evaporated and the remaining residue was purified over a silica gel column, eluting with dichloromethane/methanol (50:1) to yield the product as a colorless solid. Yield 108 mg (82%, 0.11 mmol).
[0285] 1 H-NMR (500 MHz, CDCl 3 ): δ [ppm]=1.25-1.41 (m, 13H, CH 2 , CH 3 -boc), 1.58-1.83 (m, 2H, CH 2 ), 3.00 (brs, 2H, CH 2 ), 3.56-3.58 (m, 2H, CH 2 ), 3.61-3.67 (m, 13H, CH 2 , CH 3 ), 3.72-3.76 (3s, 9H, CH 3 -PMB), 4.02 (s, 2H, CH 2 ), 4.61-4.65 (m, 1H, CH), 5.60-5.79 (2s, 6H, CH 2 -PMB), 6.76-6.81 (m, 6H, CH-arom), 7.09-7.40 (m, 11H, CH-arom, CH-pyrazole, NH-amide), 8.68 (s, 1H, NH-amide), 9.25 (s, 1H, NH-amide). 13 C-NMR (125.7 MHz, CDCl 3 ): δ [ppm]=22.8, 28.6, 29.6, 32.2, 39.6, 40.3, 51.5, 52.5, 53.9, 54.0, 55.4, 56.1, 69.7, 70.3, 70.4, 70.5, 70.6, 71.0, 98.4, 99.3, 104.0, 114.0, 114.1, 114.2, 127.4, 129.0, 129.3, 129.4, 129.5, 130.2, 134.9, 135.8, 136.4, 114.9, 154.3, 155.4, 156.2, 156.5, 159.3, 159.4, 159.7, 159.9, 170.3, 172.9. Rf: 0.16 in dichlormethane/methanol (50:1). Mp: 79° C. HRMS (ESI): m/z calcd for C 56 H 71 N 12 NaO 16 : 1167.5106; found: 1167.5169; calcd for C 56 H 20 N 12 NaO 16 : 1189.4925, found: 1189.4979.
Trifluoro-acetate5-methoxycarbonyl-5-(2-{2-[2-(2-{[5-({5-[(5-nitro-2H-pyrazole-3-carbonyl)-amino]-2H-pyrazole-3-carbonyl}-amino)-2H-pyrazole-3-carbonyl]-amino}-ethoxy)-ethoxy]ethoxy}-acetylamino)-pentyl-ammonium (Trimer-TEG-Lys-OMe)
[0286] In an argon atmosphere 50.0 mg (42.9 μmol) of Trimer(PMB)TEG-Lys(Boc)-OMe were heated in anhydrous TFA (3 mL) to 70° C. for 5 h. After adding cold Et 2 O, the product precipitated. The precipitate was filtered, washed with Et 2 O and dried in vacuo; Yield: 32.0 mg (39.0 μmol, 91%), colorless solid.
[0287] 1 H-NMR (500 MHz, DMSO-d 6 ): δ [ppm]=1.30-1.36 (m, 2H, CH 2 ), 1.50-1.57 (m, 2H, CH 2 ), 1.62-1.80 (m, 2H, CH 2 ), 2.77 (brs, 2H, CH 2 ), 3.40-3.44 (m, 2H, CH 2 ), 3.54-3.60 (m, 10H, CH 2 ), 3.64 (s, 3H, CH 3 ), 3.95 (s, 2H, CH 2 ), 4.31-4.34 (m, 1H, CH), 7.28 (s, 1H, H—CH-pyrazole), 7.60-7.63 (m, 4H, H-33, CH-pyrazole), 7.95-7.98 (m, 2H, H-27, CH-pyrazole), 8.64 (brs, 1H, NH-amide), 11.13 (s, 1H, N—NH-amide), 11.41 (s, 1H, NH-amide), 13.24 (s, 1H, NHpyrazole), 13.47 (s, 1H, NHpyrazole), 14.97 (s, 1H, NHpyrazole). 13 C-NMR (125.7 MHz, DMSO-d 6 ): δ [ppm]=22.3, 26.5, 30.2, 38.6, 51.1, 52.0, 68.8, 69.5, 69.7, 70.2, 97.2, 98.4, 102.2, 146.7, 158.6, 169.6, 172.2. Mp: decomposition at 360° C. HRMS (ESI): calcd for C 27 H 39 N 12 H 11 : 707.2856; found: 707.2851; calcd for C 27 H 38 N 12 NaO 11 : 729.2675; found: 729.2670.
1-(4-Methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-N-(11-oxo-3,6,9-trioxa-12-azatetracosyl)-1H-pyrazole-5-carboxamide (Trimer(PMB)-TEG-dodecyl)
[0288] A 50.0 mg (54.1 μmol, 1.00 equiv) amount of Tri(PMB)-TEG-OH and 20.0 mg (0.11 mmol, 2.00 equiv) of dodecylamine were reacted with 19.0 mg (0.16 mmol, 3.00 equiv) of HOBt and 31.0 mg (0.16 mmol, 3.00 equiv) of EDC*HCl according to general procedure D. The residue was purified by column chromatography on silica gel using dichloromethane/methanol (50:1). Yield: 44.3 mg (40.6 μmol, 75%), pale yellow solid.
[0289] 1 H-NMR (500 MHz, CDCl 3 ): δ [ppm]=0.86 (t, 3H, CH 3 ), 1.22 (brs, 18H, CH 2 ), 1.42-1.50 (m, 2H, CH 2 ), 3.20-3.26 (m, 2H, CH 2 ), 3.56-3.64 (m, 10H, CH 2 ), 3.72-3.75 (3s, 9H, CH 3 -PMB), 4.00 (s, 2H, CH 2 ), 5.59-5.78 (2s, 6H, CH 2 -PMB), 6.75-6.81 (m, 6H, CH-arom), 6.88 (t, 1H, NH-amide), 6.97 (t, 1H, NH-amide), 7.11 (s, 1H, CH-pyrazole), 7.17-7.26 (m, 5H, CH-arom, CH-pyrazole), 7.34-7.38 (m, 3H, CH-arom, CH-pyrazole), 8.62 (s, 1H, NH-amide), 9.13 (s, 1H, NH-amide). 13 C-NMR (125.7 MHz, CDCl 3 ): δ [ppm]=14.2, 22.8, 27.9, 29.4, 29.5, 29.6, 29.7, 29.8, 29.9, 32.0, 39.1, 39.6, 53.9, 54.0, 55.4, 56.1, 69.8, 70.4, 70.5, 70.6, 70.7,70.8, 98.2, 99.1, 103.9, 114.0, 114.1, 114.2, 127.3, 128.9, 129.3, 129.4, 129.5, 130.2, 134.8, 135.8, 136.4, 144.9, 154.2, 155.3, 156.5, 159.3, 159.5, 159.6, 159.9, 170.1. Mp: 105° C. R f : 0.27 in dichloromethane/methanol (50:1). HRMS (ESI): m/z calcd for C 56 H 74 N 11 O 12 : 1092.5513; found: 1092.5521; calcd for C 56 H 73 N 11 NaO 12 : 1114.5332; found: 1114.5345.
3-Nitro-N-(5-(5-(11-oxo-3,6,9-trioxa-12-azatetracosylcarbamoyl)-1H-pyrazol-3-ylcarbamoyl)-1H-pyrazol-3-yl)-1H-pyrazole-5-carboxamide (Trimer-TEG-dodecyl)
[0290] In an argon atmosphere 20.0 mg (18.3 μmol) of Tri(PMB)-TEG-dodecyl were heated in anhydrous TFA (2 mL) to 70° C. for 5 h. After adding cold Et 2 O, the product precipitated. The precipitate was filtered, washed with Et 2 O and dried in vacuo; Yield: 9.50 mg (12.7 μmol, 70%), colorless solid.
[0291] 1 H-NMR (500 MHz, DMSO-d 6 ): δ [ppm]=0.83 (t, 3H, CH 3 ), 1.21 (brs, 18H, CH 2 ), 1.39 (m, 2H, CH 2 ), 3.05-3.09 (m, 2H, CH 2 ), 3.31-3.43 (brs, 2H, CH 2 ), 3.56 (brs, 10H, CH 2 ), 3.85 (s, 2H, CH 2 ), 7.26 (brs, 1H, CH-pyrazole, NH-amide), 7.59-7.63 (m, 2H, CH-pyrazole, NH-amide), 7.95 (s, 1H, CH-pyrazole), 8.62 (brs, 1H, CH-Pyrazol, NH-amide), 11.12 (brs, 1H, NH-amide), 11.43 (brs, 1H, NH-amide), 13.22 (brs, 1H, NH-pyrazole), 13.47 (brs, 1H, NH-pyrazole). 13 C-NMR (125.7 MHz, DMSO-d 6 ): δ [ppm]=13.9, 22.1, 26.4, 28.7, 29.0, 29.1, 31.3, 38.1, 68.8, 69.5, 69.6, 69.7, 69.9, 70.2, 98.2, 102.3, 155.1, 156.0, 169.1. Mp: decomposition at 348° C. HRMS (ESI): m/z calcd for C 32 H 49 N 11 NaO 9 : 754.3607; found: 754.3646; calcd for C 32 H 48 N 11 Na 2 O 9 : 776.3426; found: 776.3449.
Bis(N-benzyloxycarbonyl-N ε -tert-butyloxycarbonyl-(S)-lysinyl)- 4,7,10-trioxa-1,13-tri-decanediamine
[0292] In an argon atmosphere 0.50 g (1.31 mol, 1.00 eq) of Z-Lys(Boc)-OH), 32.0 mg (0.26 mmol, 0.20 eq) of 4-dimethylaminopyridine (DMAP), 250 mg (307 μL, 1.97 mmol, 1.5 eq) of diisopropylcarbodiimide (DIC) and 72 mg (72 μL, 0.33 mmol, 0.25 eq) of 4,7,10-trioxa-1,13-tridecandiamine were dissolved in dry dichloromethane (15 mL) and the solution was stirred at room temperature for 24 h. After filtration of the precipitated urea, dichloromethane was evaporated and the remaining residue was purified over silica gel column, eluting with dichloromethane/methanol (30:1) to yield the product as a colorless oil. Yield 250 mg (0.26 mmol, 79%).
[0293] 1 H-NMR (300 MHz, CDCl 3 ): δ [ppm]=1.31-1.49 (m, 13H, CH 3 , CH 2 ), 1.59-1.85 (m, 4H, CH 2 ), 3.07 (brs, 2H, CH 2 ), 3.26-3.40 (m, 2H, CH 2 ), 3.52-3.61 (m, 6H, CH 2 ), 4.11-4.16 (m, 1H, CH), 4.74 (brs, 1H, NH), 5.08 (s, 2H, CH 2 ), 5.77 (brs, 1H, NH), 6.89 (brs, 1H, NH), 7.28-7.34 (m, 5H, CH-arom). R f : 0.07 in dichloromethan/methanol 30:1. HRMS (ESI): m/z calcd for C 48 H 77 N 6 O 13 : 945.5612; found: 945.5612; calcd for C 48 H 76 N 6 NaO 13 : 967.5363; found: 967.5431.
Bis(amino-N ε -tert-butyloxycarbonyl-(S)-lysinyl)-4,7,10-trioxa-1,13-tri-decandiamine
[0294] To a solution of bis(N-benzyloxycarbonyl-N ε -tert-butyloxycarbonyl-(S)-lysinyl)-4,7,10-trioxa-1,13-tridecandiamine (250 mg, 0.26 mmol) in THF (50 mL) was added 30 mg of Pd—C (10%). The resulting solution was stirred vigorously under H 2 atmosphere at room temperature until the starting material disappeared on the TLC plate and in mass spectra. The solution was filtered through celite and concentrated in vacuo to give a pale yellow oil. Yield: 166 mg (0.25 mmol, 96%).
[0295] 1 H-NMR (500 MHz, CDCl 3 ): δ [ppm]=1.33-1.55 (m, 13H, CH 2 , CH 3 ), 1.77-1.80 (m, 6H, NH 2 , CH 2 ), 3.09-2.12 (m, 2H, CH 2 ), 3.29-3.38 (m, 3H, CH, CH 2 ), 3.52-3.64 (m, 6H, CH 2 ), 4.71 (brs, 1H, NH), 7.54 (brs, 1H, NH). 13 C-NMR (125.7 MHz, CDCl 3 ): δ [ppm]=23.1, 28.6, 29.4, 30.0, 30.5, 34.5, 34.9, 37.3, 40.3, 55.3, 62.6, 69.9, 70.4, 70.7, 79.2, 156.3, 175.3. HRMS (ESI): m/z calcd for C 32 H 65 N 6 O 9 : 677.4808; found: 677.4797; calcd for C 32 H 64 N 6 NaO 9 : 699.4627; found: 699.4616.
t-Butyl(10S,28S)-10,28-bis(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-(1-(4-methoxybenzyl)-3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-2,2-dimethyl-4,11,27-trioxo-16,19,22-trioxa-5,12,26-triazadotriacontan-32-ylcarbamate (Trimer-lys(boc)) 2 -TEGDA
[0296] In an inert atmosphere 26.0 mg (85.2 μmol, 2.50 eq) of PMB-protected Trimer-OH, 59.0 mg (114 μmol, 3.00 eq) of PYBOP, 46.0 mg, 50.0 μL (0.46 mmol, 12.0 eq) of N-methylmorpholine, and 26.0 mg (38.1 μmol, 1.00 eq) of bis(amino-N ε -tert-butyloxycarbonyl-(S)-lysinyl)-4,7,10-trioxa-1,13-tridecanediamine were dissolved in dry dichloromethane (20 mL) and the solution was heated to 40° C. for 4 days. Dichloromethane was evaporated and the remaining residue was purified over silica gel column, eluting with dichloromethane/methanol (30:1) to yield the product as a colorless solid. Yield: 42.0 mg (19.9 μmol, 52%).
[0297] 1 H-NMR (500 MHz, CDCl 3 , 333 K): δ [ppm]=1.33-1.42 (m, 13H,CH 3 , CH 2 ), 1.75-1.93 (m, 4H, CH 2 ), 3.00-3.05 (m, 2H, CH 2 ), 3.32-3.49 (m, 2H, CH 2 ), 3.54-3.65 (m, 6H, CH 2 ), 3.68-3.71 (3s, 9H, CH 3 -PMB), 4.47-4.51 (m, 1H, CH), 4.67 (brs, 1H, NH), 5.39-5.87 (m, 6H, CH2-PMB), 6.71-6.80 (m, 6H, CH-arom), 6.90 (brs, 2H, NH, CH-pyrazole), 7.10-7.17 (m, 4H, CH-arom), 7.25 (s, 1H, CH-pyrazole), 7.33-7.53 (m, 2H, CH-arom), 7.49-7.53 (brs, 2H, NH, CH-pyrazole), 8.48 (s, 1H, NH), 9.73 (s, 1H, NH). 13 C-NMR (125.7 MHz, CDCl 3 ): δ [ppm]=23.4, 28.8, 29.4, 30.1, 32.7, 38.7, 42.7, 54.0, 54.6, 55.6, 56.4, 70.1, 70.6, 70.8, 98.9, 99.9, 104.7, 114.4, 114.5, 114.6, 127.9, 129.4, 129.5, 129.6, 130.3, 135.3, 135.8, 136.8, 145.2, 145.7, 154.6, 156.2, 156.5, 159.7, 159.8, 160.1, 160.2, 172.2. Rf: 0.20 in dichloromethan/methanol (30:1). Mp: 157.3° C. HRMS (ESI): m/z calcd for C 104 H 126 N 24 NaO 25 : 2134.9248; found: 2134.9258.
N,N′-((5S,23S)-1,27-diamino-6,22-dioxo-11,14,17-trioxa-7,21-diazaheptacosane-5,23-diyl)bis(3-(3-(3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamide) (Trimer-Lys) 2 -TEGDA
[0298] A portion of 40.0 mg (18.9 μmol, 1.00 eq) of PMB-protected (Trimer-lys(Boc)) 2 -TEGDA OMe was treated with hot TFA according to general procedure E to yield (Trimer-Lys) 2 -TEGDA as a colorless solid. Yield: 26.0 mg (18.3 μmol, 97%).
[0299] 1 H-NMR (500 MHz, DMSO-d 6 ): δ [ppm]=1.41-1.48 (m, 2H, CH 2 ), 1.62-1.88 (m, 6H, CH 2 ), 2.84 (t, 2H, CH 2 ), 3.18.3.22 (m, 2H, CH 2 ), 3.46-3.59 (m, 6H, CH 2 ), 4.44-4.48 (m, 1H, CH), 6.96 (brs, 1H, CH-pyrazole), 7.21 (brs, 1H, CH-pyrazole), 7.54-7.56 (brs, 1H, H-21), 7.77 (s, 1H, CH-pyrazole), 7.88 (brs, 1H, NH), 10.45 (brs, 1H, NH), 10.98 (brs, 1H, NH). 13 C-NMR (125.7 MHz, DMSO-d 6 ): δ [ppm]=22.6, 26.7, 27.1, 29.3, 31.2, 35.9, 36.8, 38.7, 52.6, 67.3, 68.0, 69.4, 69.5, 69.6, 69.7, 102.3, 138.6, 155.1, 155.9, 157.8, 158.1, 171.3. Mp: 200° C. HRMS (ESI): m/z calcd for C 46 H 63 N 24 O 15 : 1191.4899; found: 1191.4879; calcd for C 46 H 62 N 24 NaO 15 : 1213.4719; found: 1213.4693.
[0300] 3. Manual Solid Phase Peptide Synthesis
3-(3-(3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido-(S)-lysinyl-(S)-lysinyl-(S)-lysinyl-(S)-lysinyl-(S)-lysinyl-(S)-glycine (Trimer-KKKKKG-OH)
[0301] A Wang-resin, preloaded with Fmoc-glycine and an average loading of 0.78 mmol/g, was used as a polymeric carrier. Prior to the first coupling step, the resin was swollen in DMF for 80 min. The coupling of Fmoc-protected amino acids was accomplished by using HBTU and diisopropylethylamine according to the following method: For each coupling step, Fmoc-Lys(Boc)-OH (8.00 equiv), HBTU (7.62 equiv) and diisopropyletylamine (16.00 equiv) were used in a DMF solution. Removal of the Fmoc-protecting group was carried out with 20% piperidine in DMF (1×3 min, 1×7 min) Each coupling and deprotecting step was followed by washing the resin with DMF. The completeness of each coupling step was checked with NF31- and Kaiser-test. [x] The fourth coupling was repeated. After five cycles, the resin was coupled with the PMB-protected Trimer-OH (3.00 equiv), HBTU (3.30 equiv) and diisopropyletylamine (6.00 equiv) in DMF solution for 6 h.
[0302] The pyrazole-peptide compound was cleaved off the resin concomitant with deprotection of lysine's ε-amino-Boc groups by means of an acidic cleavage cocktail (93% TFA, 5% TIS and 2% water) during 3 h. The solution was then cooled to 0° C. and the PMB-protected pyrazole-peptide was precipitated and washed with cold diethyl ether. The colorless solid was dried in vacuo.
[0303] To cleave the PMB-protecting goups on the pyrazole nucleus, the colorless solid was heated under argon in dry TFA for 5 h to 70° C. The solution was again cooled to 0° C. and treated according to general procedure E to yield the pure Trimer-peptide.
[0304] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=1.23-1.33 (m, 12H), 1.51-1.56 (m, 14H), 1.63-1.74 (m, 6H), 2.75 (bs, 11H), 4.20-4.31 (m, 4H), 4.41-4.45 (m, 1H), 7.76 (bs, 16H), 7.94-7.99 (m, 2H), 8.02-8.18 (m, 3H), 8.26-8.28 (m, 1H), 11.47 (bs, 1H), 14.97 (bs, 1H). 13 C NMR (125 MHz, CD 3 OD): δ [ppm]=22.0, 22.2, 26.4, 30.6, 39.2, 53.6, 53.7, 115.3, 117.7, 120.0, 162.6, 163.1, 163.4, 173.3, 173.5, 174.0. Mp: decomposition at 138° C. HRMS (ESI): calcd for C 44 H 72 N 20 O 12 : 1073.5711; found: 1073.5747, calcd for (½ M) 2+ : 537.2913; found: 537.2910, calcd for (⅓ M) 3+ : 358.5302; found: 358.5303.
1-(3-(3-(3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carbox-amido)-1H-pyrazol-5-yl)-1-oxo-5,8,11-trioxa-2-azatridecan-13-carboxamido-(S)-lysinyl-(S)-lysinyl-(S)-lysinyl-(S)-lysinyl-(S)-lysinyl-(S)-glycine (Trimer-TEG-KKKKKG-OH)
[0305] Trimer-TEG-KKKKKG-OH was synthesized using the same procedure as the previous (Trimer-LPFFD-OH). Trimer-TEG-OH (3.00 equiv) was used instead of Trimer-OH in this case.
[0306] 1 H-NMR (500 MHz, CDCl 3 ): δ [ppm]=1.31 (brs, 10H, CH 2 ), 1.49-1.65 (m, 20H, CH 2 ), 2.76 (brs, 10H, H-29), 3.39-3.42 (m, 2H, CH 2 ), 3.52-3.61 (m, 10H, CH 2 ), 3.69-3.84 (m, 2H, CH 2 ), 3.93 (s, 2H, CH 2 ), 4.20-4.33 (m, 5H, CH), 7.58 (brs, 15H), 7.93-8.01 (m, 4H), 8.11 (d, 1H, 3 J=7.26 Hz), 8.26 (t, 1H, 3 J=7.26 Hz), 8.68 (brs, 1H), 11.14 (s, 1H), 11.44 (s, 1H), 12.77 (brs, 1H), 13.19 (brs, 1H), 13.50 (brs, 1H), 14.96 (brs, 1H). 13 C-NMR (125.7 MHz, CDCl 3 ): δ [ppm]=22.0, 22.1, 22.2, 22.3, 26.5, 26.6, 26.7, 31.3, 31.4, 31.5, 38.6, 38.7, 51.8, 52.1, 52.2, 52.3, 68.8, 69.5, 69.6, 69.7, 70.2, 102.4, 116.0, 118.4, 157.8, 158.1, 158.3, 158.6, 169.4, 171.1, 171.2, 171.3, 171.4, 171.5, 171.7. HRMS (ESI): [M+2H] 2+ =m/z calcd for C 52 H 89 N 21 O 16 : 631.8393; found: 631.8493, [M+3H] 3+ =m/z calcd for C 52 H 90 N 21 O 16 : 421.5619; found: 421.5656.
3-(3-(3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carboxamido-(S)-leucinyl-(S)-prolinyl-(S)-phenylalaninyl-(S)-phenylalaninyl-(S)-aspartic acid (Trimer-LPFFD-OH)
[0307] A Wang-resin was used as a polymer support, preloaded with Fmoc-Asp(O t Bu) and an average loading of 0.65 mmol/g. Prior to the first coupling step, the resin was swollen in DMF for 80 min. The coupling of Fmoc-protected amino acids was accomplished by using HBTU and diisopropyletylamine according to the following method: For each coupling step, 9-Fluorenyl-methoxycarbonylamino acid (8.00 equiv), HBTU (7.62 equiv) and diisopropyletylamine (16.00 equiv) were used in a DMF solution. Removal of the Fmoc-protecting group was carried out with 20% piperidine in DMF (1×3 min, 1×7 min). Each coupling and deprotecting step was followed by washing the resin with DMF. The completeness of each coupling step was checked with NF31- and Kaiser-test and the Fmoc-protected amino acid proline with the chloranil-test. [x] After four cycles, the resin was coupled with PMB-protected Trimer-OH (6.00 equiv), HBTU (6.60 equiv) and diisopropyletylamine (12.00 equiv) in DMF solution for 16 h.
[0308] The pyrazole-peptide compound was cleaved off the resin concomitant with deprotection of the tert-butyl group by means of an acidic cleavage cocktail (93% TFA, 5% TIS and 2% water) for 3 h. The solution was then cooled to 0° C. and the PMB-protected pyrazole-peptide was precipitated and washed with cold diethyl ether. The colorless solid was dried in vacuo.
[0309] To cleave the PMB-protecting groups on the pyrazole nucleus, the colorless solid was heated under argon in dry TFA for 5 h to 70° C. The solution was cooled to 0° C. and treated according to general procedure E to yield the pure Trimer-peptide.
[0310] 1 H NMR (500 MHz, DMSO-d 6 ): δ [ppm]=0.83-0.92 (m, 7H), 1.23 (s, 1H), 1.40-1.45 (m, 1H), 1.65-1.95 (m, 6H), 2.56-2.61 (m, 1H), 2.68-2.84 (m, 3H), 2.93-3.06 (m, 2H), 3.48-3.52 (m, 1H), 3.68-3.72 (m, 1H), 4.32-4.43 (m, 2H), 4.53-4.58 (m, 2H), 4.68-4.73 (m, 1H), 7.15-7.29 (m, 12H), 7.54 (bs, 1H), 7.78 (d, 1H), 7.94 (s, 1H), 8.03 (d, 1H), 8.36 (d, 1H), 8.64 (bs, 1H), 11.07 (bs, 1H), 11.43 (s, 1H), 14.98 (s, 1H). 13 C NMR (125 MHz, DMSO-d 6 ): δ [ppm]=21.2, 23.1, 24.1, 24.3, 28.6, 35.9, 37.2, 37.5, 46.6, 48.5, 48.8, 56.4, 53.6, 59.2, 102.2, 126.0, 126.1, 127.9, 129.1, 129.2, 137.5, 138.6, 155.0, 170.4, 170.5, 107.6, 171.0, 171.5, 172.1. Mp: decomposition at 198° C. HRMS (ESI, neg.): calcd for C 45 H 49 N 14 O 13 : 993.3609; found: 993.3588, (½ M) 2− : calcd for C 45 H 49 N 14 O 13 : 496.1762; found: 496.1767, (⅓ M) 3− : calcd for C 45 H 49 N 14 O 13 : 330.4482; found: 330.4488.
1-(3-(3-(3-nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carbox-amido)-1H-pyrazol-5-yl)-1-oxo-5,8,11-trioxa-2-azatridecan-13-carboxamido-(S)-leucinyl-(S)-prolinyl-(S)-phenylalaninyl-(S)-phenylalaninyl-(S)-aspartic acid (Trimer-TEG-LPFFD-OH)
[0311] Trimer-TEG-LPFFD-OH was synthesized using the same procedure as the previous (Trimer-LPFFD-OH). Trimer-TEG-OH (3.00 equiv) was used instead of Trimer-OH in this case.
[0312] 1 H-NMR (500 MHz, CDCl 3 ): δ [ppm]=0.85-0.88 (m, 6H), 1.34-1.93 (m, 7H), 2.54-3.07 (m, 6H), 3.37-3.42 (m, 4H), 3.51-3.59 (m, 10H), 3.90 (s, 2H), 4.30-4.32 (m, 1H), 4.37-4.42 (m, 1H), 4.52-4.62 (m, 2H), 7.16-7.24, 7.53 (brs, 1H), 7.65 (d, 1H), 7.77 (d, 1H), 7.93 (s, 1H), 8.00 (d, 1H), 8.35 (d, 1H), 8.52 (brs, 1H), 11.07 (s, 1H), 11.43 (s, 1H), 12.81 (brs, 2H), 13.48 (brs, 1H), 14.98 (s, 1H). 13 C-NMR (125.7 MHz, CDCl 3 ): δ [ppm]=21.3, 23.2, 23.3, 24.0, 24.2, 28.7, 36.0, 37.2, 37.6, 38.5, 40.3, 46.6, 48.0, 48.6, 53.4, 53.8, 59.2, 68.7, 69.5, 69.7, 70.2, 94.6, 96.7, 98.1, 102.3, 126.1, 126.2, 127.8, 127.9, 129.1, 129.2, 137.4, 137.5, 138.6, 155.0, 155.8, 168.9, 170.2, 170.5, 170.7, 171.1, 171.6, 172.1. HRMS (ESI): [M-H] − =m/z calcd for C 53 H 63 N 15 O 17 : 590.7269; found: 590.7397.
1-(3-(3-(3-Nitro-1H-pyrazole-5-carboxamido)-1H-pyrazole-5-carbox-amido)-1H-pyrazol-5-yl)-1-oxo-5,8,11-trioxa-2-azatridecan-13-carboxamido-(S)-lysinyl-(S)-leucinyl-(S)-valinyl-(S)-phenylalaninyl-(S)-phenylalanine (Tri-TEG-KLVFF)
[0313] A Wang-resin was used as a polymer support, preloaded with Fmoc-Phe and an average loading of 0.65 mmol/g. Prior to the first coupling step, the resin was swollen in DMF for 80 min. The coupling of Fmoc-protected amino acids was accomplished by using HBTU and diisopropyletylamine according to the following method: For each coupling step, 9-Fluorenyl-methoxycarbonylamino acid (8.00 equiv), HBTU (7.62 equiv) and diisopropyletylamine (16.00 equiv) were used in a DMF solution. Removal of the Fmoc-protecting group was carried out with 20% piperidine in DMF (1×3 min, 1×7 min). Each coupling and deprotecting step was followed by washing the resin with DMF. The completeness of each coupling step was checked with NF31- and Kaiser-test. After four cycles, the resin was coupled with PMB-protected Trimer-TEG-OH (3.00 equiv), HBTU (3.30 equiv) and diisopropyletylamine (6.00 equiv) in DMF solution for 16 h.
[0314] The pyrazole-TEG-peptide compound was cleaved off the resin concomitant with deprotection of the tert-butyl group by means of an acidic cleavage cocktail (93% TFA, 5% TIS and 2% water) for 3 h. The solution was then cooled to 0° C. and the PMB-protected pyrazole-peptide was precipitated and washed with cold diethyl ether. The colorless solid was dried in vacuo.
[0315] To cleave the PMB-protecting groups on the pyrazole nucleus, the colorless solid was heated under argon in dry TFA for 5 h to 70° C. The solution was cooled to 0° C. and treated according to general procedure E to yield the pure Trimer-TEG-peptide.
[0316] 1 H-NMR (500 MHz, CDCl 3 ): δ [ppm]=0.69-0.70 (m, 6H), 0.79-0.85 (m, 6H), 1.23-1.68 (m, 9H), 1.82-1.89 (m, 1H), 2.68-3.09 (m, 6H), 3.51-3.59 (m, 12H), 3.91 (s, 2H), 4.07-4.10 (m, 1H), 4.29-4.38 (m, 2H), 4.42-4.47 (m, 1H), 4.54-4.58 (m, 1H), 7.14-7.27 (m, 10H), 7.62-7.63 (m, 4H), 7.69-7.70 (d, 1H), 7.92-7.93 (brs, 2H), 8.1-8.12 (d, 1H), 8.23-8.8.24 (d, 1H), 8.55 (brs, 1H), 11.10 (brs, 1H), 11.34 (s, 1H), 13.21 (brs, 1H), 13.49 ((brs, 1H), 14.98 (brs, 1H). 13 C-NMR (125.7 MHz, CDCl 3 ): δ [ppm]=18.0, 19.2, 21.6, 22.0, 23.1, 24.2, 26.7, 30.8, 31.9, 36.7, 37.6, 38.6, 38.8, 51.0, 51.4, 53.3, 53.4, 57.5, 68.8, 69.6, 69.8, 70.3, 102.3, 126.2, 126.5, 128.0, 128.2, 129.1, 137.3, 137.5, 155.1, 155.9, 169.0, 170.4, 170.9, 171.0, 171.6, 172.6.
[0317] 4. Thioflavin T Fluorescence Assay
[0318] The Aβ(1-40) peptide (Bachem, Bubendorf, Germany) was dissolved in DMSO and stored as (4 μL)-aliquots at −20° C. until use. Aβ(1-42)-peptide (Bachem, Bubendorf, Germany) was prepared in HFIP (hexafluoroisopropanol), lyophilized, redissolved in DMSO and stored as (4 μL)-aliquots at −20° C. The ligands were dissolved in 100% DMSO as 4.95 mM stock solutions and were stored at −20° C.
[0319] Thioflavin T (ThT) measurements were carried out in a 384-well plate (Nunc GmbH, Wiesbaden, Germany) in an InfiniTe 200 plate reader (Tecan GmbH, Crailsheim, Germany). Fluorescence intensity was measured at 37° C., 446 nm excitation wavelength (bandwidth 9 nm) and 490 nm emission wavelength with a bandwidth of 20 nm. Each data point was averaged over 40 lamp flashes. Each measurement cycle was started by shaking the sample carrier orbitally for 30 s at medium intensity to avoid settling of larger aggregates. The 384-well plate was covered with a transparent and DMSO-stable film (Nunc GmbH, Wiesbaden, Germany). Each single sample was composed of 33 μM Aβ(1-40) or rather Aβ(1-42) in 10 mM PBS (phosphate buffered saline), 10.7% DMSO, 10 μM ThT and 198 μM of the test compound. For graph representation emission values of fourfold samples were averaged. Each test compound was measured separately, both in 10 mM PBS and 10 mM PBS with ThT to exclude any potential interactions between ligand and ThT.
[0320] 5. Kinetics of Aβ Aggregation and Disaggregation
[0321] ThT Aggregation Assay
[0322] To an aliquot of 4 μL Aβ(1-42)-peptide (495 μM stock solution) was first added 2.4 μL of the test compound (4.95 mM stock solution). Then, a mixture of 9.5 μL ThT (62.7 μM stock solution), 6 μL PBS and 38.1 μL water (bidest.) was pipetted. Afterwards the mixture was vortexed and briefly centrifugated. Sixty μL of aggregation mixtures were pipetted in a 384-well plate and the fluorescence intensity (exc. at 446 nm, em. at 490 nm) was measured every hour at 37° C. The 384-well sample carrier was agitated 30 s before each measurement. Each point is the average of quadruplication.
[0323] ThT Disaggregation Assay
[0324] A mixture of 4 μL Aβ(1-42)-peptide (495 μM stock solution), 9.5 μL ThT (62.7 μM stock solution), 6 μL PBS and 38.1 μL water (bidest.) was incubated for 24 h in a 384-well plate at 37° C. The fluorescence intensity was measured every hour and the 384-well sample carrier was agitated 30 s before each measurement. After 24 h, 2.4 μL of the test compound (4.95 mM stock solution) was added to the solution. The fluorescence measurements were observed/monitored every hour within 5 days and each measurement cycle was started by shaking the sample carrier orbitally for 30 s. For graph representation emission values of fourfold samples were averaged.
[0325] 6. Equilibrium of Aβ Aggregation and Disaggregation
[0326] Inhibition Assay
[0327] A mixture of 4 μL Aβ(1-42)-peptide (495 μM stock solution), 2.4 μL of the test compound (4.95 mM stock solution), 9.5 μL ThT (62.7 μM stock solution), 6 μL PBS and 38.1 μL water (bidest.) was incubated in a thermo mixer (600 rpm) at 37° C. for 72 h. The ThT assay solution was briefly centrifugated and it was pipetted in a 384-well plate. The ThT fluorescence was measured at λ Ex =446 nm and λ Em =490 nm. Each point is the average of quadruplication.
[0328] Disaggregation Assay
[0329] To obtain preformed fibrils, a mixture of 4 μL Aβ(1-42)-peptide (495 μM stock solution), 6 μL PBS and 38.1 μL water (bidest.) was incubated in a thermo mixer (600 rpm) at 37° C. for 72 h. Then, the test compound (2.4 μL of a 4.95 mM stock solution) was added and the solution was incubated for further five days. After that, 9.5 μL ThT (62.7 μM stock solution) was pipetted and the assay solution was briefly centrifugated. The ThT fluorescence was measured at λ Ex =446 nm and λ Em =490 nm. For graph representation emission values of fourfold samples were averaged.
[0330] 7. Circular-Dichroism-Spectroscopy
[0331] Aβ(1-42)-peptide (Bachem, Bubendorf, Germany) was prepared in HFIP (hexafluoroisopropanol), lyophilized, dissolved in DMSO and stored at −20° C. Aβ(1-42) was dissolved in HFIP to a concentration of 500 μM. This solution was diluted with 5 μM potassium phosphate buffer (pH 7.3) to a final peptide concentration of 10 μM. The single sample was composed of 10 μM Aβ(1-42), 5 μM potassium phosphate buffer (pH 7.3), 2% HFIP and 10 μM of the test compound. The samples were transferred to a 10 mm pathlength cuvette immediately after mixing and circular dichroism spectra were recorded on a J-810 spectropolarimeter (Jasco). Measurement range: 190 nm-400 nm. Data pitch: 1 nm. Response: 1 s. Sensitivity: standard. Scanning speed: 100 nm/min. Accumulation: 1. Temperature: 22° C.
[0332] 8. Fluorescence Correlation Spectroscopy (FCS)
[0333] A Confocor I instrument (Zeiss, Evotec) was equipped with an Argon ion laser. A 24 well sample carrier was covered with tesafilm to avoid evaporation. Experiments were carried out at ambient temperature. Rhodamine 6G calibration was ensured before each measurement. Measurement time was 30 s, in a 20 μl total volume. Data evaluation involved determination of the number and height of peaks measured above a threshold given by 5 times the standard deviation of the fluorescence fluctuation. All solutions were sterile filtered before use through 0.22 μm filters.
[0334] Measurements were performed with the ConfoCor I instrument (Zeiss, Jena, Evotec, Hamburg, Germany) equipped with an argon laser. The pinhole diameter was 45 μm, and the focus was set 200 μm above the cover glass. Adjustment of diffusion times was achieved by comparing with rhodamine 6G. Measurements were made on Lab-Tek chambered borosilicate cover glasses (Nalge Nunc Int. Corp., Naperville, Ill.) used as sample carriers. The fluorescent probe Aβ(1-42) was synthesized in solid phase using Fmoc chemistry and labeled directly at the N-terminus with OregonGreen™ (Molecular Probes, Leiden, The Netherlands). The peptide was purified by reverse-phase HPLC. Purity was >95% as estimated by reversed phase HPLC and mass spectrometric analysis (Dr. P. Henklein, Institute of Biochemistry, Charité Berlin, Germany). The stock solution contained 500 nM labeled peptide in 5% water-free DMSO, 10 mM sodium phosphate, pH 7.2, and was filtered through 0.45 μm pore nylon filters. Although originally chosen for combination with unlabeled Aβ(1-42) it proved to be more advantageous to use this probe with the less aggressively aggregating Aβ(1-40). The unlabeled Aβ(1-40) (Sigma) was dissolved at 500 μM in 100% water-free DMSO. Comparative measurements with different ligands were performed with trifluoroacetate salts of the ligands, which rendered the sample preparation more convenient because of their higher solubility. The ligands were dissolved at a concentration of 5.4 mM in 100% DMSO. The final incubation assay contained 20 μM Aβ(1-40), 10 nM OregonGreen™-labeled Aβ(1-42), with or without 100 μM ligand in 10 mM sodium phosphate and 6% DMSO in a 50 μl final volume. All solutions were sterile filtered except the Aβ(1-40) stock solution. For each sample the fluorescence intensities were recorded 10 times for 60 s directly after mixing and again after 1 day of incubation at room temperature. It should be noted that the sample holder of the instrument is not thermostated, so experiments were performed at ambient temperature.
[0335] The concentration dependence was analyzed by repeated measurement cycles beginning after 2 h of incubation at room temperature and lasting for 8 h. In each cycle fluorescence fluctuations for each sample position were measured 20 times for 30 s with a resolution of 16.7 data points/s. All samples contained 10 mM sodium phosphate, pH 7.2, 50 mM NaCl, 33 μM Aβ(1-40) (Bachem Biochemica, Heidelberg, Germany), 8% DMSO, and 5.6 nM OregonGreen™-labeled Aβ(1-42). The concentration of the ligand varied from 1.35 to 108 μM.
[0336] 9. Sedimentation Analysis (SA)
[0337] Sedimentation velocity centrifugation was performed in an XLA (BeckmanCoulter, Palo Alto, USA) equipped with absorption optics and a four hole titanium rotor. Prior to the centrifugation the solutions were incubated slightly agitated at room temperature for different incubation times. Sample volumes ranging from 300 to 400 μl were filled into standard double sector aluminum center pieces and spun at 20,000 rpm, 20° C. after thermal calibration. Radial scans were recorded at a resolution of 0.002 cm. Detection wavelength was chosen at 493 nm to observe endlabeled FITC or Oregon Green™ and to avoid background absorbance from the test compound.
[0338] Data analysis: Sedimentation data were analyzed with UltraScan 9.4 (http://www.ultrascan.uthscsa.edu). After timeinvariant noise subtraction, s-value distributions were determined model independently using the enhanced van HoldeWeischet method in the UltraScan software ( Demeler and van Holde 2004, van Holde and Weischet 1978). Molecular weight and frictional ratios were determined with two-dimensional spectrum analysis (Brookes et al. 2006) and the genetic algorithm optimization method ( Brookes and Demeler 2006, 2007). Hydrodynamic corrections for buffer conditions were made according to data published by Laue et al. (1992) as implemented in UltraScan. The partial specific volume of the Aβ42, v=0.7377 cm 3 /g was calculated on the basis of its amino acid content by a routine implemented in UltraScan. Experimental intensity data were timeinvariant noise corrected using the 2DSA analysis. The van HoldeWeischet analysis was used to initialize the svalue range in the 2DSA from 1150 S. The frictional ratio range was initialized between 110. 2DSA analyses were performed with 24 grid movings with a 10 point resolution in both dimensions, resulting in a final svalue resolution of 0.625 S and 0.042 f/f 0 units. The 2DSA results were used to initialize the GA analysis, and parsimoniously regularized GA distributions were used to initialize the GA Monte Carlo analysis. Data were analyzed on the Bioinformatics Core Facility cluster (University of Texas, Health Science Center, San Antonio, Tex., USA) and on the Lonestar cluster at the Texas Advanced Computing Center (Austin, Tex., USA). The hydrodynamic behavior of a molecule sedimenting in a sector shaped cell is fully described by the Lamm equation ( Lamm 1929). In the case of polydisperse samples the shape of the sedimentation boundary and its evolution over time contains information about size, shape and partial concentration of the sedimenting species. To extract the information a linear combination of solutions of the Lamm equation is fitted to the experimental data. The simulated solutes represented in the linear combination of Lamm equations covers both the sedimentation coefficient range as well as the frictional ratio range of solutes present in the experimental data.
[0339] 10. Transmission Electron Microscopy (TEM)
[0340] Transmission electron microscopy (TEM): TEM experiments were performed with a Phillips CM 200 FEG instrument. After absorbing 5 μl of a tenfold diluted sample of the solution used for analytical ultracentrifugation to the holey carbon film coated copper grids (Plano, Wetzlar, Germany) the samples were washed twice with 0.1 and 0.01 mM ammonium acetate and then negatively stained with 2% (w/v) ammonium molybdate solution for 90 s.
[0341] 11. Cell Culture
[0342] MTT viability assays. Cell viability assays were performed as described in Fradinger et al. (Fradinger et al., PNAS, 2008). Rat pheochromocytoma (PC-12) cells were maintained in F-12 nutrient mixture with Kaighn's modification (F-12K) (Gibco BRL, Carlsbad, Calif.) with 15% heat-inactivated horse serum and 2.5% FBS at 37° C. in an atmosphere of 5% CO 2 . For cell viability assays, cells were plated in 96-well plates at a density of 25,000 cells per well in differentiation media (F-12K, 0.5% FBS, 100 mM nerve growth factor) and maintained for 48 h. Aβ42 was solubilized in a minimal amount of DMSO (Sigma) and then diluted in the F-12K media in the absence or presence of the compounds and then added to cells and incubated for 48 h at 37° C. The final Aβ42 concentration was always kept constant at 10 μM. The stock solutions of the compounds were prepared at 10 mM in DMSO and diluted in the F-12K media at the required concentration. Negative controls included DMSO at the same concentration as in the peptide solutions and media alone. A positive control was 1 mM staurosporine as lethal dose which represented 100% reduction in cell viability, based on which the percentage viability of all of the experimental conditions was calculated. Cell viability was assessed quantitatively by the CellTiter 96 Non-Radioactive Cell Proliferation Assay (Promega). Briefly, 15 μl of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetra-zolium bromide (MTT) dye solution was incubated with the cells for 3 h. Then 100 μl of solubilization/stop solution was added and the plates were incubated overnight in the dark to ensure complete solubilization. Plates were read by using a Synergy HT microplate reader (BioTek), and the absorbance at 570 nm (formazan product) minus the absorbance at 630 nm (background) was recorded. Corrected absorbance was used to calculate the percent cell viability from the experimental change (Amedia-Aexperimental) over the dynamic range (Amedia-Astaurosporine). At least three independent experiments with six replicates (n≧18) were carried out, and the results were averaged.
[0343] To determine the IC 50 value of each of the compounds, dose-dependence MTT experiments with the compounds were conducted. Aβ42 was used at 10 μM and the compounds were used at 100, 30, 10, 3, 1 and 0.3 μM. Three independent experiments with six replicates (n≧18) were carried out, and results were averaged. The data for each compound was fitted to the following equation to get the IC50 values.
[0000] y =Bottom+((Top−Bottom)/(1+10 (x−log(I/C 50 )) ))
[0344] Top: the y value at which the top of the sigmoidal curve becomes parallel to the X-axis; Bottom: the y value at which the bottom of the sigmoidal curve becomes parallel to the X-axis. IC 50 in this respect is defined as the concentration of the β-sheet ligand (aminopyrazole trimer derivative), at which the inhibition of Aβ toxicity just reaches 50%.
[0345] FIG. 15 shows dose-response curves for the inhibition of Aβ-induced toxicity in PC-12 cells by aminopyrazole trimer derivatives.
[0346] Also, MTT viability assays were run with differentiated PC-12 cells. Healthy cells (viability 100%) were lesioned on day 1 with 10 μM Aβ(1-42) and simultaneously protected by 100 μM solutions of aminopyrazoles. After 8 days, the living cells were counted and compared to the untreated control (70%/80%). In both series (with and without TEG spacers) several candidates rescued cell viability significantly, the most impressive results stemming from the TEG-spacered derivatives ( FIGS. 13A and 13B ). Intriguingly, the most efficient inhibition of Aβ toxicity was achieved with 3 lipophilic extensions and Trimer-TEG-Lys, which were also superior in ThT and related assays. The two GABA derivatives are a surprise—they might potentially interact with GABA receptors and not with the Aβ peptide itself. The above-delineated findings demonstrate, that trimeric aminopyrazoles are indeed active against Aβ-induced toxicity in living cells; they also provide experimental evidence for their low toxicity at relatively high doses of 0.1 mM, in spite of, e.g., the presence of an N-terminal nitro group.
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The present invention relates to the field of protein misfolding diseases and thus to diseases which are associated with or induced by abnormal or pathogenic three-dimensional folding of proteins and/or peptides or which are linked to pathogenic conformational changes of proteins and/or peptides, such as Alzheimer's disease. Particularly, the present invention provides novel trimeric pyrazole compounds, which exhibit a therapeutic effectiveness in regard to the aforementioned protein misfolding diseases, and refers to their use for the treatment of such protein misfolding diseases, especially neurodegenerative diseases as well as to medicaments or pharmaceutical compositions comprising these compounds.
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This invention relates to a process for preparing amide esters of dibasic acids. More particularly this invention is directed to a process for reacting a dibasic acid with an alkyl amine in a distillation column to selectively provide the mono amido ester and avoid making large amounts of the diamide. These compounds are useful as precursors in the manufacture of detergent bleach ingredients.
BACKGROUND OF THE INVENTION
The discovery of highly stable organic peracid molecules is critical to the commercialization of detergent formulations containing peracid bleaches. Such peracids have recently been discovered which are highly crystalline and have relatively high melting points. Also, it is highly important for highly stable bleaches to be prepared in a manner which eliminates, or at least minimizes contamination from metals. Metals or metal ions are particularly deleterious to peracids because they catalyze the decomposition of the peroxygen group.
Consequently, the detergent industry requires peracids which are highly stable, have high melting points and are conveniently manufactured in high volume. Because of their high melting points both the peracids and their precursors are typically purified by precipitation or crystallization techniques. Metal ions typically present in the crystallization media become trapped in the peracid crystals and become impurities which reduce the stability of the peracid. The amount of metal ion contamination is directly related to stability of the peracid.
A recent patent, U.S. Pat. No. 4,634,551 to Burns et al describes novel, relatively stable and high melting crystalline amide peracids. Generally, the precursors to these amide peracids, that is, the amido acids, were reported to have been prepared by the reaction of the appropriate acid chloride with the appropriate amine followed by precipitation of the resulting amido acid. Stability of the ultimate amide peracids generated via this method are affected not only by metal contamination but also by the chloride impurity. Attempts to purify the peracid has proven inadequate to economically remove metals and chlorides. Even purification of the amine precurser is not adequate to provide an economical product of sufficient purity for use in preparing the peracid.
The peroxyacids found in U.S. Pat. No. 4,634,551 are represented by the the formula ##STR1## where in R 1 is selected from the groups consisting of alkyl, aryl or alkaryl radicals containing from about 1 to about 14 carbon atoms, R 2 is an alkylene group containing from 2 to 14 carbon atoms and R 3 is H or an alkyl, aryl or alkaryl group containing from 1 to about 10 carbon atoms, the total number of carbon atoms being from about 10 to about 20.
There is needed a process for the manufacture of large quantities of alkyl mono amido esters with a high degree of selectivity so as to minimize the simultaneous production of diamido compounds. In one effort to minimize the amount of diamido ester, a large excess of the diester is employed. This requires the movement and handling of large amounts of material because the mole ratio of diester to amine needed for improved selectivity to produce the desired mono amido ester is from 5:1 to 10:1.
The reaction of an alkyl amine with, for example, the diester of adipic acid is well known as in U.S. Pat. No. 3,417,114 to Kueski. It is noted therein that esters of mono-, di, tri, or tetracarboxlyic acids may be employed wherein the resulting amide may contain one or more ester groups, depending on the extent to which the ester groups are converted to amide groups. However, no indication is given as to how to provide a selective reaction to produce a mono amido ester of a dibasic acid.
The production of amides by reaction in a column is described in U.S. Pat. No. 3,324,179 to Scholz et al. This patent discloses the reaction of four carbon fatty acids with alkylamines wherein the amine reactant is in excess or at least in stoichiometric amounts. Reflux ratios in the range of 2:1 to 30:1 are disclosed.
The production of methyl formamide by the reaction of ammonia and methyl formate in a reaction column is disclosed in U.S. Pat. No. 4,659,866 to Kaspar et al. It is reported that virtually quantitative conversion to the amide is provided in a continuous process.
Diamides are prepared in high purity according to U.S. Pat. No. 3,296,303 to Nemec et al by the reaction of a secondary amine with a diacid or diester wherein the diester is derived from selected ethylene or propylene glycols. The amidation step is conducted by employing the amine in a ratio with the ester or acid of at least 2:1. The process seeks to avoid the production of a mixture containing mono ester amides.
Amides are also produced in the presence of water at relatively low temperatures by employing catalysts according to U.K.1,108,395. There is reference to conducting such reactions in a column. Amides are prepared at temperature of less than 30° C. with ion exchange resins, either strongly basic or strongly acid.
Although considerable work has been done in the art of preparing amides, the provision of a selective reaction of an amine with a dibasic acid to provide a high proportion of mono amido esters of such dibasic acids has not heretofore been discovered. In the production of large quantities of such material it is vital to reduce the amount of unwanted production of diamides to provide an environmentally sound mass production process.
Attempts to provide the mono amido ester of dicarboxylic acids has resulted in a relatively low yield of the desired product. The above mentioned patent to Kuceski indicates, recovery from a catalyzed reaction of about 40% by weight of the mono amido ester of adipic acid, based upon the weight of the original starting material. Other attempts to provide such product from dimethyl adipate improved over the result of Kuceski only by employing large excess of diester in the reaction mixture. Excess diester, on a molar basis, of up to 10:1 over the amine reactant in a typical batch type reaction was required to obtain up to 93% recovery of the mono amido methyl ester of adipic acid. However it is desirable to use more economical processes than can be achieved with such a large excess of starting material.
BRIEF DESCRIPTION OF THE INVENTION
In accordance with this invention there is provided a process for the preparation of a mono amido ester of a dibasic acid represented by the formula ##STR2## wherein R 1 is an alkyl group having from 4 to 12 carbon atoms, R 2 is an alkylene group containing from 2 to 6 carbon atoms and R 3 is an alkyl radical having from 1 to 4 carbon atoms which comprises the steps of introducing into a reaction column in which there is sufficient retention to provide for reaction of the amine and a diester represented by the formula ##STR3## wherein R 2 and R 3 have the same meaning as above, and an amine of the formula
R.sup.1 NH.sup.2
wherein R 1 has the same meaning as above, in a ratio of said ester to said amine of about 2:1, wherein the mono amido ester is removed from the column as it is produced and whereby in excess of about 95% of the amine converted to an amido compound is converted to an mono amido ester. It has been discovered that the selectivity of the reaction with respect to the production of mono amido ester is very high even though a molar ratio of ester to amine in the reaction mixture is relatively low.
DETAILED DESCRIPTION OF THE INVENTION
In the practice of this invention a trayed column is employed with a reboiler and the usual temperature control means. In continuous operation the column is operated to remove overhead low boilers produced in the reaction and to remove product from the reboiler portion of the column. Typical reflux condenser is employed to return a portion of the low boilers being removed overhead. The diester is introduced into the column at about five trays below the top of the column while the amine is introduced into the column about 20 trays from the top. A typical dibasic acid is adipic acid and it is most convenient to employ the dimethyl ester in the reaction with an amine to produce the mono amido methyl ester. In such an operation, the column is operated so as to maintain a temperature in the reboiler in the range of from about 200° C. to about 225° C. while the top is maintained in the range of from about 45° C. to about 55° C. Suitable adjustment of these temperatures can be made to provide for compounds of different molecular weight within the scope of this invention.
A continuous process is preferred wherein the product is continuously removed from the bottom of the column and the alcohol by-product removed continuously overhead. Small amounts of the diamide are also removed from the bottom of the column along with the mono amido ester which is easily separated in a subsequent step.
It has been found that optimum conversion to the mono amido ester is achieved at a reactant ratio of diester to amine of about 2:1. Higher ratios may be employed but the need to handle larger amounts of reactants is not accompanied by corresponding increase in conversion to the mono amido ester.
While not operating the process in an anhydrous mode, it has been found that too much water in the column drastically decreases the yield of desired product and causes hydrolysis of the amide to produce an acid. Therefore, the amount of water allowed in the system is in the range of about 0.05% to about 0.25% of the total weight of the diester in the column. Water produced in the manufacture of the diester must be reduced to a very low level prior to introduction into the process of this invention.
Typical dibasic acids include those having from 2 to 6 carbon atoms between the carboxyl groups. Preferably, the dibasic acids useful in this invention contain from about 3 to 5 carbon atoms between the carboxyl groups and are aliphatic, straight chained. Included are adipic acid, glutaric acid, succinic acid, pimelic acid and suberic acid.
Amines employed in the process of this invention are primary amines containing either straight or branched chain alkyl groups. Typically the amine contains from 4 to 12 carbon atom. Such amines are commercially available. Typical amines include octylamine, nonylamine and decylamine. The linear straight chain alkyl amines are preferred because the final amido acid has higher melting points than branched chained amido acids.
As noted above the reactants, diester and amine are introduced into a reaction column at the above noted areas of the column and allowed to react in the column while the alcohol by-product and desired mono amido ester are continuously removed. By sizing the column and adjusting the flow rates of reactants the reaction time or holding time in the column is regulated. It has been found that an adequate amount of reaction time in the column is essential to providing high conversion of the amine to the mono amino ester. The reaction time is controlled by the retention in the column particularly in the area between the feed trays. Retention time is controlled by regulating the feed rate and the reflux ratio. Reaction times in the range of from about 20 to about 60 minutes has been found to be adequate and a reaction time of about 40 minutes is preferred. Such times refer to the retention time in the area of the column between the feed trays.
From the above, it can be seen that it is important to maintain the reactants in the column while allowing the alcohol produced in the reaction to leave the column relatively quickly. For this reason the amine of the formula R 1 NH 2 is chosen so as to have a lower boiling point than the diester and also to have a higher boiling point than the resultant alcohol produced in the reaction. These choices can be made by the choice of alkyl or alkylene groups in the respective reactants. A reasonable spread of boiling points is desirable such that ordinary distillation equipment may be employed to achieve both the desired retention of reactants for the purpose of reaction as well as efficient separation of product and by-product from the reaction mixture in the column.
To provide adequate separation of the desired product from the column, it is preferred to operate the process of this invention at a reflux ratio in the range of from about 20 to 1 to about 60 to 1 and more preferably in the range of from about 35 to 1 to about 40 to 1. Of course, the reaction producing the desired mono amido ester is provided at any reflux ratio which maintains the desired retention time in the column and the reflux ratio noted above provides the desired degree of product separation.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
EXAMPLE 1
To demonstrate the process of this invention an Oldershaw column having a diameter of 2.54 centimeters and containing 30 trays was employed. A feed tray for the dimethyl adipate feed was provided between the 25th and 26th trays from the bottom and a feed tray for the nonylamine feed was provided between the 10th and 11th trays from the bottom. Pressure at the top of the column was maintained at 300 mm Hg absolute. Dimethyl adipate at ambient temperature was fed to the column at 58 gram/hr, and nonylamine at ambient temperature was fed to the column at 21.8 gram/hr. Heat input to the reboiler was maintained at a level sufficient to distill off the methanol evolved from the reaction at a reflux ratio of 36/1. Enough liquid was maintained in the column to give a retention time in the column of 44 minutes based on total feed to the column. The overflow from the reboiler contained the product nonyl amido methyl adipate, by product dinonyl adipate and excess dimethyl adipate. Analysis of this overflow allowed calculation of selectivity for nonyl amido adipate. For nonyl amine this was about 95% and for dimethyl adipate about 97% where selectivity is defined as the percentage of reactant producing nonyl amido methyl adipate versus that producing said product plus dinonyl adipate.
EXAMPLE 2
Employing the apparatus as described in Example 1, dimethyl adipate at ambient temperature was fed to the column at 81.3 gram/hr and nonyl amine at ambient temperature was fed to the column at 34.6 gram/hr. Heat input to the reboiler was maintained at a level sufficient to distill off the evolved methanol at a reflux ratio of 6/1. Enough liquid was maintained in the column to give a retention time in the column of about 5.4 minutes based on total feed to the column. In this case selectivity was considerably lower than in Example 1. Selectivity of nonyl amine was about 65% and for dimethyl adipate about 78%. This experiment shows the importance of retention time in the column to achieve maximum conversion and selectivity of the amine to produce mono amido methyl adipate.
Although the invention has been described in terms of specific embodiments which are set forth in considerable detail, it should be understood that this description is by way of illustration only and that the invention is not necessarily limited thereto since alternative embodiments and operating techniques will become apparent to those skilled in the art in view of this disclosure. Accordingly, modification are contemplated which can be made without departing from the spirit of the described invention.
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A process for preparing precursors for amido containing organic peracids is disclosed wherein a diester of a dibasic acid is reacted with an amine to provide a mono amido carboxylic acid ester. The reaction is conducted in a reaction column to provide a highly selective reaction which limits the amount of diamide produced. The selective reaction is conducted with a moderate excess of diester and may be conveniently operated on a continuous basis.
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TECHNICAL FIELD
The present invention relates to the flushing method of toilet and the apparatus therefor.
BACKGROUND TECHNOLOGY
The sealing between the outlet of conventional toilet bowl and the sewer generally adopts a Z-shaped trap. The function of the trap is the sealing of water and prevention of escape of unpleasant odour from the sewer. The higher the trap is situated, the more water is stored and the tighter is the sealing. The egesta in the trap and the flushing water are to be discharged by means of the principle of siphon. The more water stored in the trap, the more difficult is the flushing and the more water is consumed. Moreover, the existing toilet is generally provided with a watertank, so the water source with a constant pressure provided by the converter pump or the water reservoir in high building can not be directly used. And as the components in the watertank of the toilet are subject to worn-out and damage, the phenomena of spilling and leaking would frequently occur, and also the toilet bowl is difficult to be cleanly flushed and the drain conduit is apt to be blocked up and form dirt.
SUMMARY OF INVENTION
The object of the present invention is to provide a flushing method of toilet which has auxiliary discharging and cleaning units in the trap. Another object of the present invention is to provide the toilet for carrying out the above-mentioned method.
A further object of the present invention is to provide the components for improving the existing toilet.
The flushing method of toilet of the present invention comprises the steps of spraying the high-pressure flush water that is provided by a flow pipe along the baffle of the toilet bowl in the bottom of the trap of the toilet bowl, spraying the flush water for washing the toilet bowl in said toilet bowl, and after said high-pressure efflux has discharged the egesta with the sealing water and the flushing water, supplying the sealing water to the trap.
The toilet of the present invention comprises a toilet bowl and a trap, a nozzle for producing a high-pressure efflux being provided at the bottom of the trap of the toilet near the juncture of the rear side-wall of the toilet bowl and the baffle, the orientation of this high pressure efflux being generally parallel to the extending direction of the baffle, the nozzle being in communication with a flushing control valve through an efflux communing pipe, the flushing control valve being in communication with a flow pipe, a water supply tank being in communication with the efflux communicating pipe and at least one nozzle for flushing the bowl being provided in the bowl, the nozzle being in communication with the flushing control valve through a flushing communicating pipe.
The toilet components of the present invention comprise an efflux nozzle for producing the high pressure efflux provided at the bottom of the trap of the toilet near the juncture of the rear side-wall of the toilet bowl and the baffle, the orientation of the high pressure efflux being generally parallel to the extending direction of the baffle; at least one flushing nozzle provided in the bowl for the use of flushing the bowl; a water intake pipe passing through the mounting hole on the bowl, said water intake pipe being in communication with the flushing control valve, said efflux nozzle and the flushing nozzle, said control valve being in communication with a flow pipe and a water supply tank communicating with the water intake pipe.
The further solution of the present invention is as follows:
The water supply tank has an air escape check valve;
The water supply tank is connected with a toilet cleaning agent charging unit. The charging unit has a toilet cleaning agent valve controlled by the pressure of the water supply tank to make the sealing water added to the trap containing toilet cleaning agent.
The efflux nozzle and the flushing nozzle are both connected to a base in which are provided an upper water supply passage and a lower water supply passage. A downward facing fan-shaped slot is provided at the front end of the base perpendicular to the direction of the axis of the base. The fan-shaped slot is in communication with the upper water supply passage and forms a fan-shaped nozzle for flushing the rear part of the bowl. An inclined jet orifice is provided behind the fan-shaped slot. The jet orifice is in communication with the lower water supply passage and forms a dashing nozzle for dashing away the egesta. The flushing nozzles are symmetrically disposed on the base. The flushing nozzles are in communication with the upper water supply passage and form a nozzle for flushing the two lateral sides and the front portion of the bowl. A water volume adjusting device is provided in the upper water supply passage.
The toilet components also include a decorative shield for the purpose of covering.
According to the present invention, a nozzle is provided in the trap to produce a high pressure efflux supplied by the flow pipe to quickly crush the egesta and discharge them into the sewer so to raise the flushing efficiency and reduce the water consumption. The volume of the flushing water is only one fifth of the normal consumption. The crushed egesta will not be susceptible to adhering to the drain conduit so blocking up will rarely occur. As the water tank is dispensed with and the number of components is reduced, the phenomena of spilling and leaking caused by damage of the water tank components will be put an end to and much of the space in the toilet room can be saved. This saved space can be used for installing an armchair or a cabinet etc. Since the consumption of the supplying water is scanty, so is the toilet cleaning agent added to the supplying water for eliminating dirts and odour.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a partial cutaway plan view of the toilet of the present invention.
FIG. 2 is a sectional view taken along line I—I in FIG. 1 .
FIG. 3 is a sectional view taken along line II—II in FIG. 1 .
FIGS. 4 and 5 are schematic views showing the operation states of the air escape chick valve employed in the water supply tank according to the present invention respectively.
FIG. 6 is a perspective view of the water supply tank with a toilet cleaning agent charging unit according to the present invention.
FIG. 7 is a sectional view of the water supply tank and the toilet cleaning agent charging unit.
FIG. 8 is a plan view of FIG. 6 .
FIG. 9 is an enlarged sectional view of the toilet cleaning agent shown in FIG. 7 .
FIG. 10 is an enlarged sectional view of an alternative embodiment of the charging unit shown in FIG. 9 .
FIG. 11 is a side view of a nozzle employed by the present invention.
FIG. 12 is a front sectional view of the nozzle shown in FIG. 11 .
FIG. 13 is a sectional view of a toilet with the toilet components of the present invention.
FIG. 14 is a sectional view taken along the line III—III in FIG. 13 .
FIG. 15 is a sectional view of the toilet components of the present invention.
FIG. 16 is a right view of the toilet shown in FIG. 15 .
FIG. 17 is a left view of the toilet shown in FIG. 15 .
FIG. 18 is sectional view of a toilet with another kind of toilet components of the present invention.
FIG. 19 is a sectional view taken along the line IV—IV in FIG. 18 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIGS. 1 and 2, the toilet of the present invention comprises a toilet bowl 1 and a trap 12 . Trap 12 is constituted of rear side-wall 15 of bowl 1 , baffle 16 and the front side-wall 14 of the bowl. The baffle 16 and the bottom board 17 of the toilet constitute the drain passage 13 . The drain passage 13 is connected with a drain conduit (not shown). A nozzle 7 producing a high pressure efflux is provided at the bottom of the trap 12 of the toilet near the juncture of the rear side-wall 15 of the toilet bowl 1 and the baffle 16 , and the orientation of the high pressure efflux is generally parallel to the extending direction of the baffle 16 . The nozzle 7 being in communication with a flushing control valve 3 through an efflux communicating pipe 8 , the flushing control valve 3 being in communication with a flow pipe 2 . In the tank body 11 is provided a water supply tank 4 the volume of which is equivalent to the volume of water being stored in the trap 12 and generally less than {fraction (1/10)} of the volume of a conventional toilet water tank. The water supply tank 4 has an inlet 19 , which is in communication with the efflux communicating pipe 8 . In bowl 1 is provided a flushing nozzle 5 for flushing bowl 1 , the mounting angle of which is adjustable to be adjusted according to different water pressure. Said nozzle 5 can be any nozzle which can adjust the direction of the flushing water. In the present embodiment, there are two nozzles 5 , one provided at the front end and the other at the rear end, flushing nozzle 5 being in communication with the flushing control valve 3 through a flushing communicating pipe 6 . The flushing communicating pipe 6 is mounted within the circulating conduit 10 , which is formed around the upper rim of bowl 1 . The control valve 3 and the water supply tank 4 are installed in the tank body 11 , which is in communication with the circulating conduit 10 . The control valve 3 might be a valve with one inlet and two outlets, that is, it has one inlet communicating with flow pipe 2 and two outlets which communicate respectively with the flushing communicating pipe 6 and the efflux communicating pipe 8 . The control valve 3 might also be a valve with one inlet and one outlet, that is, it has one inlet communicating with flow pipe 2 and one outlet communicating with both the flushing communicating pipe 6 and the efflux communicating pipe 8 . A rotating handle 9 is used for controlling the opening and closing of the flushing control valve 3 .
Referring to FIGS. 3-5, the water supply tank 4 has an air escape check valve 18 mounted on the top of the water supply tank 4 . This valve 18 has a sleeve 20 . A fluid inlet 21 is provided at the bottom of the sleeve 20 which is connected with the housing of the water supply tank 4 . A valve seat 25 which has a through hole 26 is mounted in the sleeve 20 . A valve core 22 which is connected with a guide-bar 23 passing through the through hole 26 is also provided in the sleeve 20 . The guide-bar is fitted over by a spring 24 . One end for the spring 24 is connected to the valve seat 25 and the other end is connected to the guide bar 23 . The valve core 22 can close the through hole 26 . FIG. 4 shows the state that the valve core 22 has closed the through hole 26 when the water supply tank 4 is full of water and FIG. 5 shows the state when the through hole 26 is opened.
Referring to FIGS. 6-8, the water supply tank 4 of the present invention has a toilet cleaning agent charging unit 30 . The charging unit 30 has a toilet cleaning agent valve 31 controlled by the pressure in the water supply tank 4 to make the sealing water supplied to the trap containing toilet cleaning agent. The charging unit 30 is installed in the storage tank 27 .
Referring to FIG. 7, in the embodiment shown in FIG. 7, the air escape check valve 18 has a sleeve 20 at the bottom of which is provided a fluid inlet 21 . The sleeve 20 is connected to the housing of the water supply tank. A valve seat 28 is mounted in the sleeve 20 . A through hole 26 is provided in the valve seat 28 . A floating ball 29 for closing the through hole 26 is provided in the sleeve 20 .
Referring to FIG. 9, the toilet cleaning agent valve 31 mounted in the shell body 33 of the charging unit 30 has a guide pipe 32 and a cylinder body 36 . One end of the guide pipe 32 is in communication with the water supply tank 4 and the other end by which the guide pipe 32 is connected to the shell body 33 has a vertically upward pipe segment 34 .
A partition board 35 having a through hole 46 is provided between the pipe segment 34 and cylinder body 36 . A stop block 38 with a hole is provided on the top of the cylinder body 36 and an inlet 37 for the toilet cleaning agent is provided at the bottom of the cylinder body 36 . A bolt 42 is inserted into the pipe segment 34 through the hole on the stop block 38 and the through hole 46 on the partition board 35 . A piston piece 40 , a sealing gasket 41 and a spring 39 is mounted on the bolt 42 disposed in the cylinder body 36 . A piston piece 44 , a sealing gasket 43 and a nut 45 is mounted on the bolt 42 disposed in the pipe segment 34 .
FIG. 10 shows an alternative embodiment of the charging unit of FIG. 9 . In this embodiment, the same parts as shown in FIG. 9 are indicated by the same reference numerals. The difference between this embodiment and the embodiment shown in FIG. 9 is that the bolt 42 is replaced by a screw rod 47 . The upper and lower ends of screw rod 47 are respectively connected with spherical pistons 48 and 49 , and recesses to engage with the spherical pistons 48 and 49 are provided on the partition board 35 .
FIGS. 11 and 12 show a flushing nozzle 5 employed by the present invention. This flushing nozzle 5 has a three-way base 50 which has one inlet and two outlets. Each of the outlets is fitted with a flushing pipe 51 . Flushing orifices are opened lengthwise on the pipes 51 , and the ends of the pipes 51 are crushed to form narrow slit nozzles 52 . Female thread is provided in the two outlets of the base 50 and male thread is provided on the pipes 51 . Nuts 54 are provided on pipes 51 , and the pipe 51 is fixed in the base 50 by the nuts 54 .
FIGS. 13 and 14 are schematic views showing the assemblage of the toilet components of the present invention to improve the prior art toilet. The toilet bowl 1 shown in the drawing is a bowl of the conventional type. The same reference numerals in the drawings indicate the same parts or similar locations.
In the embodiment shown in FIGS. 13 and 14, the toilet components 60 of the present invention comprise: an efflux nozzle 64 producing the high pressure efflux provided at the bottom of the trap of the toilet near the juncture of the rear sidewall of the toilet bowl 1 and the baffle 16 , the orientation of the high pressure efflux being generally parallel to the extending direction of the baffle 16 ; two flushing nozzles 65 for flushing the bowl provided in the bowl 1 ; a base 61 for connecting the efflux nozzle 64 and with the flushing nozzle 65 ; a water intake pipe 72 passing through the mounting hole 73 on the bowl, one end of the water intake pipe 72 communicating with the flushing control valve 3 and the other end communicating with the base 61 , the control valve 3 communicating with a flow pipe 2 ; and a water supply tank 4 communicating with the water intake pipe 72 , which the water supply tank 4 can be the water supply tank described above and employ corresponding accessories.
The toilet components also include a decorative shield 69 for the purpose of covering. It is employed to cover over the whole bowl 1 except the portion where the nozzle orifice should be exposed.
In the conventional toilet bowl, some of the baffles 16 have depression 76 at the lower end. The function of such depression is to retain more water. However, this depression is disadvantageous to the flow of the efflux, hampering the discharge of the egesta. For this reason, a water deflecting plate 70 is provided by the present invention, which can be put over the deppression 76 by means of adhesives or the like.
Referring to FIGS. 15-17, an upper water supply passage 62 and a lower water supply passage 63 are provided in the base 61 . A downward facing fan-shaped slot 66 is provided at the front end of the base perpendicular to the direction of the axis of the base. The fan-shaped slot 66 is in communication with the upper water supply passage 62 , and form a fan-shaped nozzle 66 for flushing the rear part of the bowl. An inclined jet orifice 67 is provided behind the fan-shaped slot 66 . The jet orifice 67 is in communication with the lower water supply passage 63 , and form a dashing nozzle 67 for dashing the egesta out. Two symmetrically arranged flushing nozzles 65 are also provided on the base 61 . The flushing nozzles 65 are in communication with the upper water supply passage 62 , and form nozzles for flushing two lateral sides and the front part of the bowl. A water volume adjusting device 68 is provided in the upper water supply passage 62 .
What is described in FIGS. 18 and 19 is an alternative embodiment of the components for improved toilet of the present invention, the parts identical with those of the above embodiment are indicated by the same reference numericals. The different between the present embodiment and the embodiment shown in FIGS. 13-17 is the structure and layout of the flushing nozzle. In this embodiment, the efflux communicating pipe 72 is inserted in the refitted hole opened on bowl 1 . A communicating base 81 is mounted on the end portion of the efflux communicating pipe 72 . On the communicating base 81 is fitted a nozzle 80 for flushing the bottom of the bowl and the trap 12 . An efflux nozzle 65 is in communication with the communicating base 81 . The mounting pattern of this nozzle 65 is the same as that shown in FIGS. 13 and 14. A decorative shield 69 covers over the nozzle 65 and the communicating base 81 . Obviously, the shield 69 should not hamper the orifice of the nozzle. The efflux communicating pipe 72 also communicates with water supply tank 4 and flushing communicating pipe 6 . The flushing communicating pipe 6 is inserted in the circulating conduit 10 formed around the upper rim of bowl 1 . Openings are provided at appropriate locations on the conduit 10 and nozzles 5 whose mounting angles are adjustable are mounted on the flushing communicating pipe 6 through the openings. The efflux communicating pipe 72 communicates with the flow pipe 2 by way of the flushing control valve 3 .
The following is a description of the process of operation of the present invention.
Referring to FIGS. 1-3, when bowel movement or urination is finished, a man turns the rotating handle 9 to open the flushing control valve 3 , so shat water under pressure rushes respectively into the efflux communicating pipe 8 and flushing communicating pipe 6 , then from communicating pipes 6 and 8 to nozzles 5 and 7 and water supply tank 4 as well. As the pressurized water entering the water supply tank 4 meets with the least resistance, water first enters the water supply tank 4 . When water rises to a certain height, it will enter the sleeve 20 through the inlet 21 and push the valve core 22 upward until it blocks the through hole 26 , and at the same time, the pressurized water is sprayed out from nozzles 5 and 7 . The nozzle 5 is used for flushing the interior of the bowl 1 , which nozzle 7 produces the flushing water with high spraying speed.
At a static state, the water in the trap cuts the toilet off from the sewer, achieving good effect of sealing and odour cut off. When the trap is in the working state, the efflux from nozzle 7 washes the egesta in the trap to the entrance 13 of the sewer. Under the high speed spray of flushing water, the negative pressure in the trap caused by the efflux pulls the egesta along with water rapidly into the sewer. When the control valve 3 is closed, the water in the water supply tank 4 flows out from the opening 19 and enters the trap 12 to form a water seal.
When using the toilet cleaning agent charging unit 30 shown in FIGS. 6-8 and the water supply tank 4 is stored with water, the pressurized water pushes forward the piston for allowing the toilet cleaning agent in the toilet cleaning agent charging unit 30 flow into the pipe segment 34 . When the control valve 3 is closed, the water in the water supply tank 4 flows out from the opening 19 and enters the trap 12 along with the toilet cleaning agent to form a water seal with toilet cleanit agent. So achieve the object of eliminating the filth and odour in the trap.
The working principle of other embodiments of the present invention is essentially the same as the above-stated principle, so it is unnecessary to go into details.
The basic principle of the present invention has been described above by way of embodiments, yet those skilled in the art will clearly understand that various modifications may be made without departing from the inventive conception of the present invention; all these modifications should be within the scope of the conception of the present invention.
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A toilet flushing method causes high-pressure flush water, provided by a flow pipe, to spray along the baffle in the bottom of the trap of a toilet bowl and causes the flush water used for washing the toilet bowl to spray into the toilet bowl. The high-pressure flush water discharges the egesta with water in order to supply sealing water to the trap. A toilet, which uses components for improving the prior art toilet, carries out the flushing method.
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CROSS REFERENCES TO RELATED APPLICATIONS
This application claims priority from and is related to commonly owned U.S. Provisional Patent Application Ser. No. 60/460,932, filed Apr. 7, 2003, entitled: A Method and Apparatus for Process Control in Time Division Multiplexed (TDM) Etch Processes, this Provisional Patent Application incorporated by reference herein.
FIELD OF THE INVENTION
The present invention generally relates to the field of semiconductor wafer processing. More particularly, the present invention is directed to a method and apparatus for controlling the reaction chamber pressure during a time division multiplexed etching and deposition process.
BACKGROUND OF THE INVENTION
The fabrication of high aspect ratio features in silicon is used extensively in the manufacture of micro-electro-mechanical (MEMS) devices. Such features frequently have depths ranging from tens to hundreds of micrometers. To ensure manufacturability, the etching processes must operate at high etch rates to maintain reasonable throughputs, along with other performance requirements such as smooth etch profiles.
Conventional, single step, plasma etch processes cannot simultaneously meet these needs, and time division multiplex etch processes have been developed. Time division multiplexed (TDM) approaches for etching silicon have been described by Suzuki et al. (U.S. Pat. No. 4,579,623), Kawasaki et al. (U.S. Pat. No. 4,795,529) and Laermer et al. (U.S. Pat. No. 5,501,893). TDM etch processes typically employ alternating etching and deposition steps. For example, in etching a silicon (Si) substrate, sulfur hexafluoride (SF 6 ) is used as the etch gas and octofluorocyclobutane (C 4 F 8 ) as the deposition gas. In an etch step, SF 6 facilitates spontaneous and isotropic etching of silicon (Si); in a deposition step, C 4 F 8 facilitates protective polymer passivation onto the sidewalls as well as the bottom of the etched structures. In the subsequent etching step, upon energetic and directional ion bombardment, the polymer film coated in the bottom of etched structures from the preceding deposition step will be removed to expose the silicon surface for further etching. The polymer film on the sidewall will remain, inhibiting lateral etching. TDM processes cyclically alternate between etch and deposition process steps to enable high aspect ratio structures to be defined into a masked silicon substrate at high etch rates.
In each process step, gases (for example, SF 6 and C 4 F 8 ) are introduced into the reaction chamber through a gas inlet at flow rates specified in the process recipe. TDM etch process are typically performed in high density plasma reactors (e.g., inductively coupled plasma (ICP), electron cyclotron resonance (ECR), etc.).
TDM process recipes consist of a series of process loop(s) and steps. Each loop consists of two or more process steps controlling the process variables (e.g., gas flow rates, chamber pressure, RF powers, process step times, chamber temperature, wafer temperature, etc.). The steps within a loop are repeated a number of times before executing the next step or loop in the overall process recipe. It is known to make changes to the process step parameters as a loop repeats to improve etch performance, this is known in the art as process morphing (see Teixeira et al. U.S. Pat. No. 6,417,013).
Pressure control is an important component of etching and deposition processes. The flow rate and pressure of the process gases present in the chamber must be carefully controlled to provide the desired deposition and etch characteristics for a repeatable manufacturing process.
A TDM plasma reactor evacuation system typically comprises a turbo pump separated from the reaction chamber by a throttle valve. A pressure controller uses reactor chamber pressure data from a manometer to control a throttle valve. The controller opens or closes the throttle valve to increase or decrease the vacuum supplied from the turbo pump to the reaction chamber. In this manner, the controller maintains the desired pressure in the reaction chamber. During the TDM process chamber pressure set points and gas flow rates cyclically alternate within the process loops. The gas flows can be either single component or mixtures of multiple components. The pressure controller must adjust the throttle valve position to compensate for these changing flow and pressure conditions. Ideally, the pressure controller adjusts the throttle valve position to instantly achieve the pressure set point without pressure set point overshoot or undershoot.
Throttle valves and controllers, currently available, typically operate in either Pressure Control mode or Position Control mode. In the Pressure Control mode the controller monitors the pressure in the reaction chamber and maintains the set point pressure by adjusting the position of the throttle valve (i.e., closed loop pressure control). In position control mode the controller positions the throttle valve to a set point position without monitoring the chamber pressure (i.e., open loop pressure control).
A number of groups have looked at means for process control in plasma chambers. Kessel et al. (U.S. Pat. No. 4,253,480) describes a pressure regulator that employs an adjustable solenoid valve to control pressure. Kessel teaches the fundamental mechanism dictating the operations of many throttle valves used in vacuum chambers. The actual pressure in a container is measured and converted to electrical signals. A comparator generates a regulation signal that represents the difference between the actual pressure and a command pressure. A regulator uses the regulation signal to direct the valve in such a manner that the valve member is adjustable between intermediate positions within a range between the open and closed positions of the valve. In fact, the throttle valves used in TDM process tools are operated following such principles. However, as described earlier, the inability to control pressure during the transition of the constantly alternating TDM process steps is the real issue, and cannot be addressed by Kessel's technique.
Kaveh et al. (U.S. Pat. No. 5,758,680) and McMillin et al. (U.S. Pat. No. 6,142,163) describe the use of a ballast port for inserting gas into the evacuation system to compensate the pressure fluctuations in the reaction chamber so as to minimize throttle valve movement between different process steps. They further disclose a method to reduce the time for gas stabilization in a vacuum chamber. A throttle valve is first pre-positioned to the desired position. The desired position is estimated using pre-determined estimation curves. Then for a specified period of time, proportional and derivative (PD) control is enabled to control throttle valve movement. Then proportional, integral and derivative (PID) control is enabled to regulate throttle valve movement. The examples taught in the disclosure show that the time period for pressure stabilization is reduced from ˜20 seconds to at least 3–5 seconds. While Kaveh and McMillin contemplate the change of gas flow rates and pressures when process steps change from one to the next, the use in cyclical and alternating TDM processes is not taught. Additionally, many TDM processes employ alternating process steps which last only a few seconds or shorter, which makes pressure control impractical using the disclosed technique.
Brown et al. (U.S. Pat. No. 6,119,710) describes the use of adjustable gas flow into the reaction chamber to compensate the pressure variations in the chamber. However, in many TDM processes, changing process gas flow rate during a process step is undesirable.
Beyer et al. (U.S. Pat. No. 5,944,049) describes regulating chamber pressure by controlling either the exhaust pressure at the exhaust side of a vacuum pump or the internal pressure at a compression stage of the first vacuum pump. Adjustments on vacuum pumping speed or injection of inert gas into the exhaust side or the compression stage of a vacuum pump are used to control reaction chamber pressure. Beyer does not teach how to use this technique in TDM processes.
Puech (U.S. patent application Ser. No. 20020168467) describes a way to control pressure by injecting passive control gas at a complementary flow rate into an area near the evacuation port. The flow rate of the controlled passive gas is regulated so as to maintain the total gas flow into the vacuum enclosure at a substantially constant rate. While Puech teaches the control of pressure in the TDM processes that employ process steps on the order of one second, the method does not teach the use of actively regulating throttle valve in pressure control.
The current methods of pressure control for TDM processes, Pressure Control and Position Control, have limitations. One problem with pressure control mode in a TDM process is that, in practice, there is typically a trade off between achieving fast pressure response time while minimizing set point deviations. Fast response times are possible at the expense of a period of pressure set point overshoot. Optimizing available Pressure Control mode algorithms to minimize set point overshoot results in slow response times. As the TDM step durations decrease, the time spent trying to reach the recipe specified set point becomes a significant fraction of the processing time.
A problem with the current method of Position Control mode in a TDM process is unacceptably long pressure response times. While position mode minimizes process overshoot, the slower response times result in the chamber pressure spending a large fraction of the process time approaching the requested set point value (i.e., out of compliance with the recipe specified set point).
Another problem with the position control mode method is that it is an open loop pressure control algorithm. Therefore, there is not any correction for perturbations in gas flow or pumping efficiency. These perturbations tend to cause the process pressure, and subsequent process performance, to vary with time.
Therefore, there is a need for a pressure control means for TDM processes, preferably for those processes that employ process steps that are a few seconds or less in duration.
Nothing in the prior art provides the benefits attendant with the present invention.
Therefore, it is an object of the present invention to provide an improvement which overcomes the inadequacies of the prior art devices and which is a significant contribution to the advancement of the semiconductor processing art.
Another object of the present invention is to provide a method for anisotropically etching a feature in a substrate comprising the steps of: subjecting the substrate to an alternating cyclical process within a plasma chamber, said alternating cyclical process having an etching step and a deposition step; introducing into said plasma chamber a first process gas for depositing a film onto the substrate during the deposition step of said alternating cyclical process; introducing into said plasma chamber a second process gas for etching the substrate during the etching step of said alternating cyclical process; regulating pressure of said plasma chamber by setting a throttle valve at a predetermined position set point for a predetermined period of time during at least one step of said alternating cyclical process; igniting a plasma for a recipe period of time for the deposition step of said alternating cyclical process and the etching step of said alternating cyclical process; enabling a closed loop pressure control algorithm after said predetermined period of time expires; and controlling pressure at a recipe specified pressure set point in said plasma chamber through a closed loop pressure control for a period that lasts the remaining time of the step.
Yet another object of the present invention is to provide a method of pressure control in a time division multiplex process comprising the steps of: regulating a process pressure in a vacuum chamber in at least one step of the time division multiplex process by setting a throttle valve at a predetermined position set point for a predetermined period of time; introducing into said vacuum chamber at least one process gas; enabling a closed loop pressure control algorithm after said predetermined period of time expires; and controlling pressure at a recipe specified pressure set point through a closed loop pressure control for a period that lasts the remaining time of said step of the time division multiplex process.
Still yet another object of the present invention is to provide a method for controlling pressure in a vacuum chamber, the method comprising the steps of: regulating a process pressure in the vacuum chamber by setting a throttle valve at a predetermined position set point for a predetermined period of time; introducing into said vacuum chamber a gas; enabling a closed loop pressure control algorithm after said predetermined period of time expires; and controlling pressure at a recipe specified pressure set point in said vacuum chamber through a closed loop pressure control.
The foregoing has outlined some of the pertinent objects of the present invention. These objects should be construed to be merely illustrative of some of the more prominent features and applications of the intended invention. Many other beneficial results can be attained by applying the disclosed invention in a different manner or modifying the invention within the scope of the disclosure. Accordingly, other objects and a fuller understanding of the invention may be had by referring to the summary of the invention and the detailed description of the preferred embodiment in addition to the scope of the invention defined by the claims taken in conjunction with the accompanying drawings.
SUMMARY OF THE INVENTION
For the purpose of summarizing this invention, this invention comprises a method and an apparatus for controlling the pressure in a vacuum chamber during a TDM process.
A feature of the present invention is to provide a method for anisotropically etching a feature in a substrate. The method comprising the following steps. The substrate is placed within a plasma chamber and subjected to an alternating cyclical process having an etching step and a deposition step. The pressure of the plasma chamber is regulated by setting a throttle valve at a predetermined position set point for a predetermined period of time to ensure that the chamber pressure does not overshoot or undershoot the desired operating level while minimizing the time required to reach the set point value. A first process gas, such as octofluorocyclobutane, is introduced into the plasma chamber for depositing a film onto the substrate during the deposition step of the alternating cyclical process. A plasma is ignited for a recipe period of time for the deposition step of the alternating cyclical process. A closed loop pressure control algorithm is enabled after the predetermined period of time expires. Then, the pressure of the plasma chamber is controlled at a recipe specified pressure set point through a closed loop pressure control for the remaining time of the deposition step. Next, the pressure of the plasma chamber is again regulated by setting the throttle valve at a predetermined position set point for a predetermined period of time to ensure that the chamber pressure does not overshoot or undershoot the desired operating level while minimizing the time required to reach the set point value. A second process gas, such as sulfur hexafluoride is introduced into the plasma chamber for etching the substrate during the etching step of the alternating cyclical process. A plasma is ignited for a recipe period of time for the etching step of the alternating cyclical process. A closed loop pressure control algorithm is enabled after the predetermined period of time expires. Then, the pressure of the plasma chamber is controlled at a recipe specified pressure set point through a closed loop pressure control for the remaining time of the etching step.
The predetermined position set point can either be set or derived from the following:
1. A throttle valve position of a preceding like step of the alternating cyclical process;
2. An average valve position of a plurality of preceding like steps of the alternating cyclical process; or
3. Prior calibration experiments.
The predetermined position set point can be adjusted by an offset from about 0.5 to 2 of the throttle valve position of the preceding like step of the alternating cyclical process. The predetermined position set point can change using a predefined function for the duration of the predetermined period of time. The predetermined position set point can be modified based on pressure performance of a preceding like step of the alternating cyclical process such as minimizing the time to reach the recipe specified pressure set point or minimizing the deviation from the recipe specified pressure set point.
The predetermined period of time is about 0.05 to 0.5 seconds long. The predetermined period of time can be modified based on pressure performance of a preceding like step of the alternating cyclical process such as minimizing the time to reach the recipe specified pressure set point or minimizing the deviation from the recipe specified pressure set point.
Yet another feature of the present invention is to provide a method of pressure control in a time division multiplex process. The method comprising the following steps. The process pressure in a vacuum chamber is regulated in at least one step of the time division multiplex process by setting a throttle valve at a predetermined position set point for a predetermined period of time to ensure that the chamber pressure does not overshoot or undershoot the desired operating level while minimizing the time required to reach the set point value. At least one process gas is introduced into the vacuum chamber for processing a substrate according to the time division multiplex process. A closed loop pressure control algorithm is enabled after the predetermined period of time expires. Then, the pressure of the vacuum chamber is controlled at a recipe specified pressure set point through a closed loop pressure control for a period that lasts the remaining time of the processing step of the time division multiplex process.
Still yet another feature of the present invention is to provide a method for controlling pressure in a vacuum chamber. The method comprising the following steps. The process pressure of the vacuum chamber is regulated by setting a throttle valve at a predetermined position set point for a predetermined period of time to ensure that the chamber pressure does not overshoot or undershoot the desired operating level while minimizing the time required to reach the set point value. A gas is introduced into the vacuum chamber. A closed loop pressure control algorithm is enabled after the predetermined period of time expires. Then, the pressure is controlled at a recipe specified pressure set point in the vacuum chamber through a closed loop pressure control.
The foregoing has outlined rather broadly the more pertinent and important features of the present invention in order that the detailed description of the invention that follows may be better understood so that the present contribution to the art can be more fully appreciated. Additional features of the invention will be described hereinafter which form the subject of the claims of the invention. It should be appreciated by those skilled in the art that the conception and the specific embodiment disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view showing the major assemblies of a plasma processing machine;
FIG. 2 is a graph of the desired pressure versus time response for a two step TDM process operated in pressure control mode;
FIG. 3 is a graph of the prior art pressure versus time response for a two step TDM process operated in a pressure control mode;
FIG. 4 is a graph of the prior art pressure versus time response for a TDM process operated in position control mode;
FIG. 5 is a graph of the prior art pressure versus time response for a TDM process operated in position control mode over longer time scales;
FIG. 6 is a graph explaining the control system of an embodiment of the present invention;
FIG. 7 a is a block diagram explaining the control system of an embodiment of the present invention;
FIG. 7 b is a continuation of the block diagram of FIG. 7 a explaining the control system of an embodiment of the present invention;
FIG. 8 is a graph of pressure versus time for experimental examples when the process control method of the present invention is implemented for various input values;
FIG. 9 is a graph showing optimization of one of the input values of the present invention;
FIG. 10 is a graph of pressure versus time for experimental examples when the process control method of the present invention is implemented for various input values; and
FIG. 11 is a graph of pressure versus time for experimental examples when the process control method of the present invention is implemented where etch hold times are held at 0.25 seconds and deposition hold times are held at 0.40 seconds with a constant position offset for the etch step of α=0.88 and a constant position offset for the deposition step of β=1.25.
Similar reference characters refer to similar parts throughout the several views of the drawings.
DETAILED DESCRIPTION OF THE INVENTION
We disclose a means of controlling pressure in a TDM, or any alternating step process, through a “Hold and Release” method. A throttle valve is pre-positioned when a process step is switched to the next process step. A control system is implemented to automatically set the position value at which the throttle valve is pre-positioned. The set position is derived from the throttle valve position in the preceding process steps of the same type. For a pre-determined period of time the throttle valve is held at the set position. After the holding period, the throttle valve is released, and a closed loop feedback control algorithm (e.g., PID loop) is enabled for the throttle valve to regulate the pressure in a vacuum chamber in the pressure control mode. The control system and method are disclosed.
A plasma etching system according to the present invention is shown in FIG. 1 . In an ICP reactor, a RF generator 100 delivers power to a coil 105 in the upper part of a reaction chamber 110 . This power is transmitted into one or more process gases that are introduced through a gas inlet (not shown) in order to ionize the process gas or gases and form a plasma 120 . A second RF generator 115 delivers power to a wafer support 130 so as to induce a DC bias on a wafer 125 , thereby controlling the direction and energy of ion bombardment to the surface of the wafer 125 . An evacuation system continuously removes the gaseous species (i.e., unreacted gases, volatile by-products, etc.) from the reaction chamber 110 through an exhaust manifold 150 . The pressure in the reaction chamber 110 is regulated through a throttle valve 145 . The throttle valve 145 is operated by a throttle valve controller 140 . The reaction chamber 110 pressure is measured by a manometer 135 . The output signal of the manometer 135 is fed as an input to the throttle valve controller 140 .
FIG. 2 illustrates the desired pressure response 200 of multiple loops 225 for a two step TDM process. The pressure set point 230 for the first step 205 requires a different throttle valve position than the pressure set point 235 for the second step 210 . A quick pressure response is desired in a TDM process due to the rapid rise time 215 between steps in conjunction with minimal deviation from set point 220 during the process steps.
FIG. 3 graphically illustrates a prior art solution with the throttle valve controller in pressure control mode. This figure shows a plot of pressure response 300 versus time with a corresponding throttle valve position 305 for a two step TDM process. During a TDM process, this control method results in pressure overshoot 325 from the recipe specified set point 320 . The pressure control performance degrades further as the TDM step 310 duration decreases. In addition, the corresponding throttle valve position 315 never realizes a steady state position.
FIG. 4 graphically illustrates an alternative prior art solution with the throttle valve controller in position control mode. This figure shows a plot of pressure response 400 versus time with a corresponding throttle valve position 405 for a two step TDM process. This control method uses throttle valve position set points 410 & 415 to drive the throttle valve to set positions during the TDM process. In this example, a delay in pressure response 420 relative to position set point change is noticed and the desired pressure 402 is never achieved.
FIG. 5 graphically illustrates yet another problem encountered when position control mode is used to control reaction chamber pressure. This figure shows a plot of pressure response versus time for a two step TDM process with a fixed throttle valve position using two different gas flows in the corresponding steps. Pressure drift 500 over a long process run (100's of iterations) is observed. This pressure drift 500 may be due to the temperature increase in the reaction chamber wall. Consequently, additional measures must be taken in order to maintain process performance reliability and repeatability.
FIG. 6 shows a graph of a pressure response 605 versus time with a corresponding throttle valve position 600 for a two step TDM process. As demonstrated earlier, pressure control during the transition between process steps has proven to be difficult as pressure overshoot may occur. According to one embodiment of the present invention, position control mode is applied in the first segment 630 of a step 610 . The throttle valve is pre-positioned and held at a set position 635 that is derived from the throttle valve position 620 from the previous execution of the step. After the first segment 630 , the throttle valve is released from the position control mode. At that point a closed loop feed back control algorithm is enabled so that pressure control mode is applied for the remainder of the step 610 .
After the step 610 is completed, the process step is switched to a next step 615 . During the first segment 650 of this step 615 the throttle valve is switched to position mode. The throttle valve is held at another set position 655 that is derived from the known throttle valve position 640 of the previous execution of that step. Position control mode is applied for a set period 650 and the throttle valve is held at the set position 655 for this entire period. After the holding period 650 is expired, the throttle valve is released and a pressure control mode is applied for the remainder of the step 615 by enabling a closed loop pressure feedback control algorithm for the throttle valve. Alternatively, in the step described above, the throttle valve can be pre-positioned at a position that is derived from the average value of the throttle valve position measured in a number of previous steps of the same kind. This has the advantage of smoothing out step to step variations.
In many TDM processes, it is beneficial to assign different time lengths for the holding periods 630 , 650 (see FIG. 6 ). It is also beneficial to adjust the pre-positions 635 , 655 flexibly—not just taking the throttle valve's last position from the previous process steps. According to another embodiment of the invention, the holding periods in the deposition step and the etch step are independently determined, and the pre-position values for the throttle valve in the holding periods are independently adjusted. One method of deriving an adjusted value for the pre-positions 635 , 655 is to apply a multiplier to the throttle valve's last position from the previous execution of that step. As shown in FIG. 6 , this multiplier will result in an offset 625 , 645 of the pre-position values 635 , 655 from the previous step value position 620 , 640 . In this manner, the pre-positioned throttle valve position can be offset either greater than or less than the position from the previous step.
A block diagram illustration for this embodiment is shown in FIGS. 7 a and 7 b for a two-step TDM silicon etch process. In FIG. 7 a , the holding period is denoted as “t etch hold ” 630 and as “t dep hold ” 650 . The step time periods are denoted as “t etch ” 610 and as “t dep ” 615 . These time lengths can be part of the process recipe at the beginning of the execution of the process. Further more, the throttle valve position from the previous step is denoted as “Etch Position” 620 and as “Dep Position” 640 . The pre-position for holding the throttle valve in the etch period 630 is taken from a preceding etch step and adjusted by a factor of α. Likewise, the pre-position for holding the throttle valve in the deposition period 650 is taken from a preceding deposition step and adjusted by a factor of β. The values of α and β can be set manually in the process recipe or automatically by a feedback control loop (e.g., PID) that measures the pressure and uses that information to adjust the pre-position value to minimize overshoot and minimize the time to reach setpoint as the process proceeds. The parameters α and β typically have a value between 0.5 and 2.0 which translate to 50 percent to 200 percent of the prior position. For example, in the case where α and β are set to 1.0, the invention will use the throttle valve position value 620 from the previous execution of the etch step as the pre-position value during the etch hold period.
It will be obvious to one skilled in the art that the pressure control scheme need not be applied to all steps within a TDM process loop. Setting the values of the etch hold length period 630 to zero allows the method to revert to the prior art method of closed loop pressure feedback control. Similarly, in the case where α and β are set to unity and the length of the etch hold period 630 is set to the etch step time 610 allowing the method to revert to the prior art method of position control mode (open loop pressure control mode).
PRESSURE CONTROL EXAMPLES
For any step in a TDM process using the current invention, two parameters need to be specified for the throttle valve; i.e., the duration of the hold time, and the magnitude of the offset.
FIG. 8 graphically exhibits experimental examples when the process control method of the present invention is implemented. The effect of various length of etch holding periods are displayed. As can be seen, if the etch holding period is less than about 0.1 seconds long, the pressure overshoot occurs during the deposition-to-etch transition. If the holding period is about 0.2 to 0.3 seconds long the overshoot is nearly eliminated and the deviation from the pressure set point 805 is minimized. As the etch holding time gets longer, the pressure overshoot reappears in the scope of the experiment. This result demonstrates that the hold and release method of the present invention indeed improves pressure control capability significantly.
In another embodiment of the invention, the pre-position hold time can be automatically adjusted as the process proceeds to minimize set point overshoot. FIG. 9 graphs the pressure set point overshoot versus the pre-position hold time from the data of FIG. 8 for a two step TDM silicon etch process. A feedback control loop (e.g., PID) that measures the pressure overshoot uses that information to adjust the pre-position hold time to minimize overshoot as the process proceeds. Likewise a feedback control loop (e.g., PID) that measures the time to reach setpoint can use that information to adjust the pre-position hold time so that the time to reach setpoint is minimized as the process proceeds.
FIG. 10 graphically exhibits experimental examples when the process control method of the present invention is implemented. The effect of various values of pre-positioning offsets for a fixed duration are displayed. At a negative 5% etch hold position adjust (α=0.95) the pressure overshoot is minimized. This result demonstrates that the hold and release method of the present invention indeed improves pressure control capability significantly.
It will be apparent to one skilled in the art that the described embodiments can be applied to multi-step looping processes that contain two or more process steps per loop. The invention can also be applied to looped processes where the pressure set-point or other recipe specified step parameters are changed within a loop during the course of the process, (e.g., morphed TDM processes).
It is important to note that the invention does not require a hold time and position offset for each step type within the alternating process. Another embodiment of the invention would include introducing a position hold time for at least one of the step types within a TDM process.
FIG. 11 graphically presents an example in which optimized control of pressure in a two step TDM silicon etch process is attempted. In FIG. 11 , “t etch hold ” is 0.25 seconds, “t dep hold ” is 0.4 seconds, α=0.88 and β=1.25. Compared with previous examples (see FIGS. 3 , 4 and 5 ), the resultant pressure profile during the cyclical TDM process operation is significantly improved as it is nearly “squared”. The pressure approaches the set point values more rapidly and pressure overshoot and undershoot are almost eliminated.
The present disclosure includes that contained in the appended claims, as well as that of the foregoing description. Although this invention has been described in its preferred form with a certain degree of particularity, it is understood that the present disclosure of the preferred form has been made only by way of example and that numerous changes in the details of construction and the combination and arrangement of parts may be resorted to without departing from the spirit and scope of the invention.
Now that the invention has been described,
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The present invention provides a method for controlling pressure in a vacuum chamber during a time division multiplexed process. A throttle valve is pre-positioned and held for a predetermined period of time. A process gas is introduced into the vacuum chamber during the associated plasma step (deposition or etching) of the silicon wafer. At the end of the predetermined period of time, the process gas continues to flow with the throttle valve being released from the set position. At this point, the throttle valve is regulated through a proportional derivative and integral control for a period that lasts the remaining time of the associated plasma step.
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CROSS-REFERENCE TO RELATED APPLICATION
This is a continuation of International Application No. PCT/US98/21236 filed Oct. 8, 1998 designating the United States, which claims the benefit of the filing date of U.S. Provisional Patent Application No. 60/061,773 filed Oct. 10, 1997.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a ram cylinder and piston construction which includes an electronics enclosure compartment.
2. Discussion of the Prior Art
Hydro-pneumatic vehicle suspension systems are well known. Typically, one or more single or double acting hydraulic rams are provided at each wheel to support the vehicle, with hydraulic circuits interconnecting the rams. A gas-charged accumulator is typically used to pressurize the hydraulic circuits and therefore, provide resilient displacement of the rams and consequently springing of the vehicle.
One hydro-pneumatic vehicle suspension system has come to be known as the “X” type. In such a system, the rams of diagonally opposite wheels of a vehicle are connected with discrete hydraulic circuits, each circuit connecting the bore side of one of the rams with the rod side of the diagonally opposite ram. Such an X-system is known, for example, from patents such as French Patent No. 1,535,641 and U.S. Pat. Nos. 4,270,771; 5,447,332; 5,562,305; 5,601,306; and 5,601,307.
Central to the design are the rams which support the vehicle body on the wheels and react to the hydraulic system. Another important aspect of the design are hydraulic accumulators which essentially act as springs to pressurize the rams so as to desirably support the body over the wheels.
Each ram may mount an accumulator assembly, which poses special problems not normally associated with shock absorbers, struts or common hydraulic cylinders. The wheel suspension rams must not only mount the accumulator assembly, but must also do so in a small and certain space or “envelope”, being closely adjacent to the body, the wheel, and other suspension components, while permitting electrical and hydraulic connections to be made to the cylinder/accumulator assembly. Each ram must fit within the permitted envelope and be lightweight and strong, since it is pressurized to an extent to bear the weight of the vehicle and dynamic loading.
In addition, each ram may also include electronics, for example for an internal linear displacement transducer, to provide an input of the displacement of the cylinder to an onboard computer so that the controller has that information to determine adjustments that should be made to the system to deliver the desired ride characteristics. The present invention relates to such a ram, which has an electronics enclosure integrated into it.
SUMMARY OF THE INVENTION
The invention provides a fluid power ram in which the electronic components of the ram are contained within a chamber of a compartment which is positioned at an end of the ram. The compartment is intersected by the longitudinal axis of the ram and includes a ram mounting attachment outside of the chamber for mounting the end of the ram. Thereby, electronics of the ram are protected within a structurally sound, clean and dry compartment within the ram, without increasing the radial envelope required by the ram, and in a manner which facilitates service access to the ram.
In a preferred form, the compartment includes first and second clam shells with a parting line between them which is generally perpendicular to the longitudinal axis of the cylinder. In this form, the first and second clam shells are preferably bolted together with bolts that have their axes parallel to the longitudinal axis of the ram. The bolts may also usefully fix the first and second clam shells to the end of the cylinder. The ram mounting attachment can be formed as part of an outer one of the clam shells. In this manner, service access to the ram is provided by unbolting the clam shells.
In another useful aspect of the invention, an opening is formed in the inner one of the clam shells, the opening being axially aligned with the longitudinal axis of the ram. A pressure tube is sealed to the opening and the pressure tube extends axially within the ram along the longitudinal axis. A sensor extends within the pressure tube from the compartment. Thereby, the invention can be practiced to house long, axially extending electronic components inside the ram.
These and other objects and advantages of the invention will be apparent from the detailed description and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a longitudinal cross-sectional view of a ram according to the invention, shown together with a nitrogen charged accumulator assembly;
FIG. 2 is a perspective view of an inner tube of the ram of FIG. 1;
FIG. 3 is a perspective view of an upper clamshell of the ram of FIG. 1; and
FIG. 4 is a perspective view of a lower clamshell of the ram of FIG. 1 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 illustrates a ram 10 of the invention for incorporation into a vehicle suspension system of the above-described type. The ram 10 is illustrated with an accumulator assembly 12 attached to it, which establishes fluid communication between the ram 10 and a nitrogen charged accumulator 13 . The assembly 12 has a goose neck fitting 14 which is sealed and affixed to the upper outer tube 18 by welding or other suitable means. The goose neck 14 provides communication between the upper reservoir 20 inside the tube 18 and the accumulator 13 , and has a bleed fitting 15 for bleeding air from the hydraulic circuit.
Preferably, a disc valve pack 17 is provided in the goose neck 14 in the fluid stream between the reservoir 20 and the accumulator 13 , so as to damp the resilience provided by the accumulator 13 . An on/off or proportional solenoid operated valve may also be provided, for remotely varying the damping of fluid communication with the accumulator 13 . However, the invention need not be practiced with any type of accumulator or valve, or any particular hydraulic circuit or suspension system, and no such accumulator, valve circuit or system forms any part of the present invention.
The ram 10 has a cylinder 22 which includes an outer tube 24 and an inner tube 26 . The outer tube 24 includes the upper tube 18 , and a lower tube 28 . The upper tube 18 , lower tube 28 , and inner tube 26 are all welded together by seam weld 30 . In addition, the lower end of outer tube 24 is welded to the inner tube 26 by seam weld 32 at the gland end of the cylinder. The upper and lower tubes 18 and 28 are generally tubular. The inner tube 26 , on the other hand, has an outer surface which is contoured with circumferentially spaced, axially running ribs 34 , best shown in FIG. 2 . The ribs 34 define between them passageways for fluid flow between the inner tube 26 and the outer tube 24 , while permitting free flow from one passageway to another, by providing a break at 35 and at 37 in each rib. A lower port 38 is provided for supplying and exhausting fluid from the lower reservoir 40 , which is defined between the lower tube 28 and the inner tube 26 . An upper port 42 is provided for supplying and exhausting fluid from the upper reservoir 20 . Thus, port 38 provides communication with reservoir 40 and port 42 provides communication with reservoir 20 . It is noted that reservoir 20 is in communication with the bore side or upper chamber 36 (passageways not shown) and that the reservoir 40 is in communication with rod side or lower chamber 44 , via holes 46 which are formed in the inner tube 26 .
Chamber 44 is the volume which is at the lower, gland end 48 , below piston 52 , which is bordered on the outside by inner tube 26 and is bordered on its inner diameter by piston rod 50 . Piston 52 is secured to the top of rod 50 and establishes a sliding seal with the inner tube 26 . Bore side chamber 36 is capped off by clam shell compartment 54 and includes the volume above piston 52 and extends down inside the piston rod 50 . The inner diameter of chamber 36 is defined by pressure tube 56 . Pressure tube 56 is sealed at its lower end by a pressure tube cap 58 and at its upper end is joined and sealed, such as by welding, to the clam shell compartment 54 . A position sensor 60 extends down inside the pressure tube 56 , which keeps the sensor 60 dry, and a magnet 62 is affixed inside the piston 52 by a magnet carrier sleeve 64 so that the sensor 60 can sense the axial position of the magnet 62 . Sensor 60 may be any type of linear displacement transducer, although in the embodiment disclosed it is a magneto-strictive type of sensor.
The sensor 60 is supported inside the pressure tube 56 by a printed circuit board 66 which itself is encased in a protective housing 68 . The circuit board 66 and housing 68 are captured between a lower or inner clam shell 70 and an upper or outer clam shell 72 , which make up the clam shell compartment 54 . The shells 70 , 72 define a side opening 71 (FIG. 4) at the parting line between them to permit wires (not shown) to enter the compartment created by the shells, to make electrical connections to the electronic circuitry contained therein. The lower clam shell 70 is sealed to the upper outer tube 18 and the upper clam shell 72 has upper mounting stud 74 extending from it, for connection to the vehicle chassis. The stud 74 is one type of ram mounting attachment, it being possible to practice the invention with other types of ram mounting attachments, another common type being a ball joint, for example. The upper clam shell 72 has spaced holes 76 and the lower clam shell 70 has spaced holes 78 in registration with the holes 76 so that the clam shell assembly 54 can be bolted to the upper end of the upper outer tube 18 . The printed circuit board 66 may also have a similar pattern of holes for securing it in the compartment 54 using the bolts (not shown).
As mentioned above, the gland 48 is formed by the lower end of the inner tube 26 . Gland 48 has formed in it an axial generally cylindrical hole through which the piston rod 50 extends and in which annular grooves are formed for containing sliding seals 49 and 51 so as to establish a fluid-tight sliding seal with the piston rod 50 . At the lower end of piston rod 50 , compression disc 78 is screwed into the piston rod 50 with a fluid-tight seal 79 between the disc 78 and the rod 50 . Mounting stud 80 extends from the disc 78 for mounting the lower end of the cylinder 10 to a wheel support wishbone, or other wheel support suspension structure. A bellows 82 has its lower end attached to the disc 78 and its upper end attached around the outer tube 24 so as to help keep the piston rod 50 clean.
The chamber 44 extends upwardly from the gland 48 for a distance before encountering the holes 46 which establish communication between the chamber 44 and the reservoir 40 . Thus, when the piston 52 reaches the lower limit of its stroke, its bottom corner first passes the holes 46 so as to trap a volume of hydraulic fluid between its bottom end and the gland 48 , which provides a hydraulic cushion. However, since the piston seals are provided higher up on the piston 52 , there must be a very close fit between the piston 52 and the lower end of the chamber 44 . Thus, the lower end of the chamber 44 is slightly smaller in diameter than the chamber 44 above the holes 46 , as can be seen in FIG. 1 . Because of the extremely accurate concentricity required to establish a small enough clearance between the piston 52 and the bore at the lower end of the chamber 44 to provide a hydraulic cushion, the gland 48 and the inner tube 26 which defines the bore of chamber 44 are made in one piece.
Also as mentioned above, the inner tube 26 has the raised ribs 34 which define between them axial and circumferential flow passages. The raised ribs 34 also serve to reinforce the inner tube 26 because of the increased thickness of material in the area of the ribs 34 . However, in addition, the outer surfaces of the ribs 34 are in close proximity to the inner surface of outer tube 24 as shown in FIG. 1 . Thus, as inner tube 26 flexes outwardly, the ribs 34 contact the outer tube 24 and outer tube 24 helps restrain the inner tube 26 from flexing further outwardly. Thus, there is structural sharing between the inner tube 26 and the outer tube 24 of the loads which are placed on the inner tube 26 .
Thus, at least three aspects of the cylinder 10 are believed to be unique. One is providing the clam shell compartment 54 for housing the electronics associated with the sensor 60 . Another is providing for structural sharing between the inner tube 26 and the outer tube 24 , more specifically by providing the ribs 34 , and the third is forming the gland 48 and the inner tube 26 in a single piece.
Many modifications and variations to the preferred embodiment described will be apparent to those skilled in the art, which will still incorporate aspects of the invention. Therefore, the invention should not be limited to the embodiment described but should be defined by the claims which follow.
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A ram ( 10 ) with a hydraulic cylinder ( 22 ) and piston ( 52 ) has an electronics enclosure compartment ( 54 ) integrated within it at one end. The compartment ( 54 ) is formed by two clam shells ( 70, 72 ) which are bolted to the end of the cylinder ( 22 ) so as to create a chamber for housing the electronics ( 66 ). The outer clam shell ( 72 ) has an axially aligned ram mounting attachment ( 74 ) integrally formed on it, and the inner clam shell ( 70 ) has an axial opening to which is sealed a hollow tube ( 56 ) which extends axially within the ram ( 10 ) so as to enclose a sensor ( 60 ) which is associated with the electronics ( 66 ) in the compartment ( 54 ).
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a semiconductor laser device having a diffraction grating for producing feedback of laser light, which attains laser oscillation in a single longitudinal mode.
2. Description of the Prior Art
Semiconductor laser devices used as a light source in optical information processing systems, optical measuring systems, or other systems employing optical fibers are required to have operating characteristics that can provide laser oscillation in a single longitudinal mode. The semiconductor laser devices that can attain laser oscillation in a single longitudinal mode, that is, can emit laser light of a single wavelength, include distributed feedback (DFB) laser devices and distributed Bragg reflection (DBR) laser devices, which have a diffraction grading with a periodic corrugation formed in an active region and in the area adjacent to the active region, respectively, and emit laser light of a given wavelength.
For example, a conventional distributed feedback laser device comprises a diffraction grating with a periodic corrugation disposed on the surface of an n-type InP substrate, and an n-type InGaAs optical waveguide layer and an InGaAs active layer, both of which are disposed thereon, wherein laser light goes back and forth in the diffraction grating, resulting in laser oscillation.
In order to obtain the oscillation of laser light in the diffraction grating with a periodicity Λ, the following relation is required to hold:
Λ=(N/2)·(λ/n.sub.o) (I)
where λ is the oscillation wavelength, n o is an equivalent refractive index, and N is a natural number, which denotes the order of the diffraction grating. For example, when λ=1.3 to 1.5 μm, n o =3.3, and N=1, Λ is in the range of 1970 to 2350 Å. That is, the periodicity of the first-order diffraction grating is in the range of 1970 to 2350 Å.
On the other hand, for a distributed feedback semiconductor laser device comprising a GaAlAs layer, as an active layer, formed on the GaAs substrate, which can provide an oscillation wavelength of 8900 Å or less, when λ≧8900 Å, n o =3.4, and N=1, Λ is equal to or less than 1310 Å. That is, the periodicity of the first-order diffraction grating is 1310 Å or less. Moreover, as can be seen from Equation I, by increasing the order of the diffraction grating, the periodicity Λ of the diffraction grating increases by a factor of that order.
To form such a diffraction grating, a holographic exposing system is employed that uses a He-Cd laser (wavelength λ o =3250 Å). That is, a photoresist layer is formed on the substrate, and then exposed with an interference fringe pattern of the He-Cd laser, after which the photoresist layer thus exposed is developed to form a striped photoresist mask with a given periodicity. Using this photoresist mask, a diffraction grating with a periodic corrugation is formed on the substrate by a chemical etching technique.
The coupling efficiency of the diffraction grating increases by increasing the depth of the diffraction grating. When a diffraction grating of lower order is the same in shape and depth as a diffraction grating of higher order, the diffraction grating of the lower order has a coupling efficiency greater than that of the diffraction grating of the higher order. However, it is technically impossible to form a diffraction grating of the first order, which can be used for short wavelength AlGaAs DFB laser devices, with the conventional holographic exposing system (light source: He-Cd laser, wavelength λ o 3250 Å).
Accordingly, a second-order diffraction grating with a periodic triangular shaped corrugation formed in the [011] direction. However, it is very difficult to form such a second-order triangular shaped diffraction grating because its periodicity Λ is extremely small. Moreover, because the depth of the diffraction grating is small, it is difficult to form a diffraction grating with high accuracy and to obtain a high coupling efficiency.
For these reasons, the order of the diffraction grating is taken as the third order to form the diffraction grating with high accuracy, and the periodic corrugation of rectangular shape is formed in the [011] direction to obtain high coupling efficiency as compared to the periodic corrugation of triangular shape. However, even with such a rectangular shaped diffraction grating, there is a problem of how to obtain a high coupling efficiency.
SUMMARY OF THE INVENTION
The semiconductor laser device with a resonator containing an active region of this invention, which overcomes the above-discussed and numerous other disadvantages and deficiencies of the prior art, comprises a third-order diffraction grating with a periodic corrugation for producing feedback of laser light, said corrugation being of substantially rectangular shape, wherein the ratio of the width of each convex portion of said corrugation to the periodicity of said corrugation is in the range of 0.20 to 0.25, 0.40 to 0.60, or 0.70 to 0.95.
In a preferred embodiment, the diffraction grating is positioned in said active region to produce the distributed feedback of laser light.
In a preferred embodiment, the diffraction grating is positioned in the area adjacent to said active region to produce the distributed Bragg reflection of laser light.
Alternatively, another preferred semiconductor laser device of this invention comprises an active layer positioned between a first cladding layer and a second cladding layer, and an optical guiding layer positioned between said active layer and one of said cladding layers, said optical guiding layer having a third-order diffraction grating with a periodic corrugation of substantially rectangular shape, wherein the ratio of the width of each convex portion of said corrugation to the periodicity of said corrugation is in the range of 0.20 to 0.25, 0.40 to 0.60, or 0.70 to 0.95.
In a preferred embodiment, a carrier barrier layer of the same conductivity type as one of the cladding layers is positioned between said active layer and said optical guiding layer.
In a preferred embodiment, the periodic corrugation of said diffraction grating is formed in the [011] direction.
In a preferred embodiment, the first cladding layer is disposed on a current blocking layer and said current blocking layer is disposed on a substrate, wherein said current blocking layer contains a V-shaped channel that reaches said substrate and wherein an electric current is injected into said active layer through said V-shaped channel.
Thus, the invention described herein makes possible the objectives of (1) providing a semiconductor laser device having a third-order diffraction grating with high coupling efficiency, which can attain stable laser oscillation in a single longitudinal mode; (2) providing a semiconductor laser device having a third-order diffraction grating, in which the diffraction grating has a periodicity greater than that of conventional second-order diffraction gratings, thereby attaining its high accuracy; and (3) providing a semiconductor laser device having a third-order diffraction grating, in which the diffraction grating has a periodic corrugation of substantially rectangular shape, thereby attaining its high coupling efficiency.
BRIEF DESCRIPTION OF THE DRAWINGS
This 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 drawings as follows:
FIG. 1 is a perspective view showing a semiconductor laser device of this invention.
FIG. 2 is a longitudinal sectional view, taken at the center plane along the [011] direction, showing the semiconductor laser device of FIG. 1.
FIG. 3 is a perspective view showing another semiconductor laser device of this invention.
FIG. 4 is a longitudinal sectional view, taken at the center plane along the [011] direction, showing the semiconductor laser device of FIG. 3.
FIG. 5 is a schematic diagram showing a process of forming a diffraction grating of this invention.
FIG. 6 is a schematic diagram showing the parameters of a diffraction grating of this invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
This invention is realized on the basis of the findings by the present inventors that the coupling efficiency of a diffraction grating varies significantly depending on the ratio of the width of each convex portion of the diffraction grating to the periodicity Λ of the diffraction grating. For example, in a third-order diffraction grating with a rectangular shaped corrugation, when the ratio of the width of each convex portion to the periodicity of the diffraction grating is set at around 3:1 or around 3:2, the coupling efficiency amounts to approximately 0 cm -1 , thereby making it impossible to obtain satisfactory effect of the diffraction grating. On the other hand, when the ratio of the width of each convex portion to the periodicity of the diffraction grating is in the range of 0.20 to 0.25, 0.40 to 0.60, or 0.70 to 0.95, the coupling efficiency is extremely higher than that obtained in the diffraction grating with a conventional structure. Therefore, when the corrugation of the diffraction grating is formed into a shape which gives a ratio falling within these ranges, a semiconductor laser device with high coupling efficiency can be obtained.
EXAMPLES
FIG. 1 shows a distributed feedback V-channeled substrate inner stripe (DFB-VSIS) laser device of this invention. FIG. 2 is a sectional view, taken at the center plane parallel to the direction of the propagation of laser light, showing the DFB-VSIS laser device of FIG. 1. This laser device is produced as follows:
As shown in FIG. 1, on a p-type GaAs substrate 1, an n-type GaAs current blocking layer 2, a p-type Al 0 .5 Ga 0 .5 As cladding layer 3, a p-type Al 0 .13 Ga 0 .87 As active layer 4 (the thickness thereof being 0.10 μm), an n-type Al 0 .5 Ga 0 .5 As carrier barrier layer 5 (the thickness thereof being 0.05 μm), an n-type Al 0 .25 Ga 0 .75 As optical guiding layer 6 (the thickness thereof being 0.15 μm), an n-type Al 0 .5 Ga 0 .5 As or n-type Al 0 .75 Ga 0 .25 As cladding layer 7, and an n-type GaAs cap layer 8 are successively grown by an appropriate growth method and an Au/Zn electrode 9 and an Au/Ge/Ni electrode 10 are formed on the back surface of the p-type GaAs substrate 1 and the upper surface of the cap layer 8, respectively.
In the n-type current blocking layer 2, a V-shaped channel 11 having sufficient depth to reach the p-type substrate 1, is formed in the [011] direction, and an electric current is injected into the p-type active layer 4 through the region of this V-shaped channel 11.
At the interface between the n-type optical guiding layer 6 and the n-type cladding layer 7, a periodic corrugation is formed to constitute a diffraction grating 12. The periodic corrugation of the diffraction grating 12 is repeated in the [011] direction, and the grooves formed by the periodic corrugation extend in the [011] direction. The periodicity of the corrugation is set so that the diffraction grating 12 is of the third order. The corrugation of the diffraction grating 12 is of substantially rectangular shape, as shown in FIG. 2.
FIG. 3 shows another DFB-VSIS laser device of this invention. FIG. 4 is a sectional view, taken at the center plane parallel to the direction of the propagation of laser light, showing the DFB-VSIS laser device of FIG. 3. This laser device is produced as follows:
As shown in FIG. 3, on a p-type GaAs substrate 1, an n-type GaAs current blocking layer 2, a p-type Al 0 .5 Ga 0 .5 As cladding layer 3, a p-type Al 0 .13 Ga 0 .87 As active layer 4 (the thickness thereof being 0.10 μm), an n-type InGaAsP optical guiding layer 6a (the thickness thereof being 0.20 μm), an n-type Al 0 .75 Ga 0 .25 As cladding layer 7 (the thickness thereof being 0.5 μm), and an n-type GaAs cap layer 8 are successively grown by an appropriate growth method. In the same manner as the first example, in the n-type current blocking layer 2, a V-shaped channel 11 having sufficient depth to reach the p-type substrate 1 is formed in the [011] direction. Through the region of this V-shaped channel 11, an electric current is injected into the p-type active layer 4. Furthermore, at the interface between the n-type light guiding layer 6a and the n-type cladding layer 7, a periodic corrugation is formed to constitute a diffraction grating 12.
In the above-mentioned semiconductor laser devices, laser light goes back and forth within the diffraction grating 12 so as to resonate. The refractive index of the p-type active layer 4 is set greater than that of the p-type cladding layer 3 and n-type cladding layer 7. Accordingly, the laser light is mainly confined in the p-type active layer 4, whereas the n-type optical guiding layers 6 and 6a in which an optical waveguide is formed, serve as a buffer layer between the diffraction grating 12 and the p-type active layer 4, and also have the function of leading to laser light leaks from the p-type active layer 4 to the diffraction grating 12.
Next, the production of the diffraction grating 12 in these semiconductor laser devices will be explained below. First, a photoresist layer is formed on the surface of the n-type optical guiding layers 6 and 6a, and then exposed into a striped pattern along the [011] direction by a holographic technique. The photoresist layer thus exposed is developed to form a photoresist mask. Using this photoresist mask, the surface region of the n-type optical guiding layers 6 and 6a is etched with an etchant (a mixed solution of bromine water, phosphoric acid, and water) to form a corrugation with a given periodicity in the [011] direction, resulting in a diffraction grating 12 of the third order.
As in the above-mentioned example, when the periodic pattern of the diffraction grating 12 is formed so as to be repeated in the [011] direction, a striped photoresist mask 20 is used which is formed periodically in the [011] direction as shown in FIG. 5. The etching proceeds both in the horizontal direction 21 and the vertical direction 22 by the side etching effect. As a result, the diffraction grating 12 has a corrugation of substantially rectangular shape. The ratio of the degree of progress of this etching in the horizontal direction and in the vertical direction depends on the crystallographic plane orientation of the n-type optical guiding layers 6 and 6a as well as the composition of the etchant used.
The dependence of the coupling efficiency on the shape of the diffraction grating thus formed will be discussed below.
For each of the third-order rectangular shaped diffraction gratings 12 of the above-mentioned semiconductor laser devices, the coupling efficiency was theoretically evaluated. The results are shown in Table 1 (for the first example) and in Table 2 (for the second example). In this evaluation, the coupling efficiency was calculated with varying duty ratios (W/Λ) when the periodicity of the diffraction grating 12 is denoted by the symbol "Λ" and the width of each convex portion 12a of the diffraction grating is denoted by the symbol "W" as shown in FIG. 6. The periodicity of the diffraction grating 12 was set to 3000 Å. The height H of the diffraction grating 12 was set to 1000 Å. In Tables 1 and 2, the mark "O" means that the diffraction gratings marked can be applied to semiconductor laser devices, whereas the mark "×" means that the diffraction gratings marked cannot be applied to semiconductor laser devices. In both examples, the coupling efficiency was approximately 0 cm -1 at the duty ratio of either 0.33 or 0.66.
TABLE 1______________________________________ Applicability toDuty ratio Coupling efficiency semiconductor(W/ ) (cm.sup.-1) laser devices______________________________________0.05 7.9 X0.10 28.8 X0.15 58.4 X0.20 78.1 O0.25 78.4 O0.30 42.8 X0.35 26.9 X0.40 120.0 O0.45 216.5 O0.50 278.9 O0.55 286.9 O0.60 212.5 O0.65 63.9 X0.70 139.3 O0.75 353.9 O0.80 518.1 O0.85 589.1 O0.90 519.4 O0.95 315.3 O______________________________________
TABLE 2______________________________________ Applicability toDuty ratio Coupling efficiency semiconductor(W/ ) (cm.sup.-1) laser devices______________________________________0.05 74.23 X0.10 145.75 O0.15 195.86 O0.20 207.24 O0.25 168.96 O0.30 80.77 O0.35 44.61 X0.40 182.38 O0.45 299.89 O0.50 363.97 O0.55 349.60 O0.60 247.84 O0.65 70.65 X0.70 149.03 O0.75 362.69 O0.80 517.91 O0.85 568.77 O0.90 491.05 O0.95 289.49 O______________________________________
From these theoretical evaluations, it was found that when the diffraction grating 12 is formed so as to have a duty ratio (W/Λ) in the neighborhood of 0.20, 0.50, or 0.80, coupling efficiency enough for the purpose of application to semiconductor laser devices can be obtained even in the third-order rectangular shaped diffraction grating.
Actually, DFB laser devices with the respective structures of the above-mentioned two examples were produced by taking the duty ratio (W/Λ) as 0.2, the periodicity as 3500 Å, and the height H as 1500 Å. Both the DFB laser devices attained stable laser oscillation in a single longitudinal mode. The temperature range ΔT for attaining laser oscillation in a single longitudinal mode was 80° C. for the AlGaAs DFB laser device (in the first example), and 110° C. for the AlGaAs DFB laser device having an InGaAsP optical guiding layer (in the second example). Thus, extremely excellent results were obtained.
Although the above-mentioned examples only disclose two types of AlGaAs DFB laser devices, this invention is widely applicable to semiconductor laser devices made of other compound semiconductor materials, such as AlGaInP DFB laser devices capable of emitting visible light and the like. Moreover, this invention is not limited to distributed feedback (DFB) laser devices, but is also applicable to distributed Bragg reflection (DBR) laser devices.
Although the above-mentioned examples only disclose, as a method of forming the third-order rectangular shaped diffraction grating, a chemical etching technique that uses an anisotropy in the plane orientation of wafers, such a diffraction grating can also be formed by any other technique. For example, the rectangular shaped diffraction grating can be formed by a dry etching technique so as to have a duty ratio in the neighborhood of 0.20, 0.50, or 0.80. Moreover, the diffraction grating can be readily formed because the periodicity Λ thereof can be set greater when compared with conventional second-order diffraction gratings.
It is understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the scope and spirit of this invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the description as set forth herein, but rather that the claims be construed as encompassing all the features of patentable novelty that reside in the present invention, including all features that would be treated as equivalents thereof by those skilled in the art to which this invention pertains.
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A semiconductor laser device with a resonator containing an active region for laser oscillating operation is disclosed which comprises a third-order diffraction grating with a periodic corrugation for producing feedback of laser light, the corrugation being of substantially rectangular shape, wherein the ratio of the width of each convex portion of the corrugation to the periodicity of the corrugation is in the range of 0.20 to 0.25, 0.40 to 0.60, or 0.70 to 0.95.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of application Ser. No. 13/110,037, filed May 18, 2011, entitled “Apparatus and Method to Improve Toddler's Steps and Mobility” which is invented by all of the inventors as the present application and is incorporated herein by reference in their entireties.
BACKGROUND OF THE INVENTION
Any child that transitions from a crawling position to one towering on two feet is beginning to understand the art of walking. Children start to learn how to walk anywhere between 8 to 14 months. In the process of this learning, the walking is unsteady and the child toddles. A toddler is a young child ranging in age from 10 months to 24 months.
The transition from crawling to walking is filled with mishaps, errors, poor judgment and poor foot placement that cause the toddler to fall onto the ground. At the same time, the transition must be exciting and exhilarating since the toddler never gives up in their determination to walk. There is a driving sprit in the toddler to master the art of walking.
A number of the toddlers require a “grip” to hold onto while they are learning to stand erect and walk. A grip is defined as a physical structure that has characteristics that allow the small hands of a toddler to grab, hold, or support themselves before they have a chance to fall. The toddlers begin to start taking steps and use this grip to maintain their balance as they begin mastering the art of walking.
One grip can be the finger of a parent. The toddler wraps their fingers around the finger of a parent to stand erect. This is probably the best loving grip for the toddler to use while learning to walk. As the toddler moves, the grip moves with the toddler. The toddler develops a strong dependence that the grip is always going to be there, allowing the toddler to concentrate more on the art of walking.
A recent report printed 20 Jan. 2010 in the Journal Of Neurophysiology entitled “Kinematic Strategies in Newly Walking Toddlers Stepping Over Different Support Surfaces”, by Dominici et al. indicates that “ . . . in each toddler we tried to implement unsupported stepping over an obstacle in such a way that an experimenter initially held the toddler by hand and tried to leave the toddler's hand while approaching the obstacle. In all such trials, toddlers stopped before the obstacle or attempted to touch and held again the hand of the experimenter. Thus since unsupported stepping was never successful in situations with obstacles, . . . ” The studies of toddlers stepping over obstacles is very limited. The study attempted to have the toddler step unsupported over obstacles without success since the child require support. The experimenters were required to hold the toddler by one hand to negotiate the obstacles.
Often, the toddler will also experiment independently and seek to develop the art of walking on their own by using local stable inanimate objects that appear to have sufficient height. After crawling to the object, the toddlers hand seeks the “grips” of this local object. Some examples of inanimate objects that can provide a grip include a wall, a table edge and top, a chair seat and back, a sofa, a piece of folded fabric of their parent's pants and a bed.
An object that provides a grip for a long horizontal run at an appropriate constant height from the ground is extremely beneficial and is called a horizontal grip (for example, the top surface of a coffee table). Such a grip is advantageously useful for the toddler when learning to walk because the toddler can then began to take steps either knowing that the grip is readily available in case the toddler faults in their steps or if the toddler always requires the support of the grip while taking their first steps. The height from the ground for the location of the grip is anywhere between the hip and the shoulder height of the toddler.
Another important aspect to develop in the art of walking is determining what to do with obstacles in the path. One option is to go around the obstacle if it is too large; however, if the obstacle is relatively small maybe the toddler will attempt to raise their foot over the obstacle. Succeeding the ability to step over obstacles brings the toddler that much closer to mastering the art of walking.
BRIEF SUMMARY OF THE INVENTION
Toddlers are very inquisitive and seek out new challenges and objects to study as they move around the home. A first embodiment of the invention provides an apparatus and process for toddlers that include in its structure easily accessible grips. This embodiment uses a rectangular coffee table or any small table with legs that can be easily flipped with its top flat surface against the floor. The table in this inverted position exposes legs pointing into the air. In addition, the horizontal cross-support beams attached to the legs providing additional stability. The height of these cross-support beams from the floor can occur at various levels. To a toddler, the new object appears to now look like an inviting structure. The table in the upside down mode can be viewed as a “toddler gym” since a toddler could practice balancing, walking or stepping. Soon the toddler will experience that by using the toddler gym, with grips and obstacles incorporated into the structure, a determined toddler will use the toddler gym as it self learning tool. Moving between the legs on the shorter side of the rectangle provides a first grip from where the short trip starts and second grip to terminate the short trip and support the toddler if necessary. This short trip comprises at least one step taken independently and supported not by grips but the toddler themselves. This is an important step that the toddler can practice until they become confident bringing them closer to mastering the art of walking. Note that the toddler is not requiring the support of experimenters as mentioned in the earlier study, instead, the toddler is self-driven to perform these tasks independently.
Another embodiment of the invention provides an apparatus and process for toddlers that includes in its structure both easily accessible grips and obstacles. In a first attempt, the toddler attempted to step over a horizontal bar about 3 inches high unaided and failed. The toddler then proceeded to use the grip and while holding the grip, begins stepping over the obstacle until the toddle steps easily over the 3 inch obstacle. Then, the toddler proceeds to attempt an unaided step over the obstacle and succeeds.
The obstacle can be for instance, a horizontal cross support beam for the toddler to step over, or a movable step that can snap onto the horizontal cross support beam for the toddler to learn how to step up and step down from a step. The movable step is typically attached to the bottom surface of the top table surface. Once the table is placed in the upside down mode, this movable step is easily detached from the bottom surface of the table and snapped onto a horizontal cross support beam.
A yet further embodiment of the invention is a toddler table that can be used as a table while in the right side up mode and as a “toddler gym” while in the upside down mode. This toddler table will have the ability to adjust the height of the grips, of a horizontal grip and of the horizontal bar that will behave as an obstacle. In this embodiment, the horizontal bar can be an obstacle if positioned low (less than knee height) or a horizontal grip if positioned greater than hip height. Once the use of the toddler gym ceases, the toddler gym can be flipped to serve its second purpose of a table. The additional benefit is that the legs can be adjusted in height so that the table top elevation can be adjusted as the toddler grows.
A yet additional embodiment of the invention is placing motors and integrated circuit chips into key positions within the table. The integrated circuits can be used to form systems for controlling the structure of the toddler gym by adjusting the height of the grips and horizontal bar using voice control, keyboard control or by a touch pad.
An apparatus operated in one of two modes comprising: a right side up mode where the apparatus operates as a table; an upside down mode where the apparatus provides a grip and an obstacle, a toddler can hold the grip and repetitively step over the obstacle, whereby the toddler learns to successfully step over the obstacle without holding the grip, a plurality of legs, a plurality of cross support beams, at least one leg with the grip, at least one cross support beam being the obstacle, a protective foam covering exposed surfaces in the upside down mode, at least one cross support beam is adjustable in height, a beam clamping means to secure the cross support beam, the cross support beam at a height greater than a hip of the toddler, whereby the cross support beam provides a horizontal grip for the toddler and, a positional step that snaps onto the obstacle, whereby the toddler can practice stepping up and stepping down the positional step. The apparatus, further comprising: at least one leg is telescopic in length, and a leg clamping means to secure the telescopic leg.
A method of training a toddler to step over an obstacle, comprising the steps of flipping a table upside down, locating a grip and an obstacle in the upside down table, holding the grip so a toddler steadies themselves, locating the obstacle substantially equal to a height of a toddler's step, stepping over the obstacle until the toddler's step consistently clears the obstacle, whereby the toddler releases the grip and successfully steps over the obstacle, covering exposed surfaces of the upside down table with a protective foam, telescoping a length of at least one leg, securing the telescopic leg with a clamp, adjusting at least one cross support beam in height, securing the at least one cross support beam to a given height and, adjusting the given height greater than the hip of the toddler, whereby the cross support beam provides a horizontal grip for the toddler. The method further comprising the steps of snapping a positional step on the obstacle, whereby the toddler can practice stepping up and stepping down the positional step.
An apparatus with two modes comprising, an upside down mode where the apparatus provides a grip, a horizontal grip and an obstacle, a protective foam covers exposed surfaces hi the upside down mode, telescopic legs adjustable in length, cross support beams adjustable in height and a right side up mode where the apparatus presents a table with a flat surface at a slope, whereby the slope of the flat surface is dependent on a length distribution of the telescopic legs, whereby a toddler uses the upside down mode to learn how to step over the obstacle, whereby a toddler uses the upside down mode to practice assisted walking by holding the horizontal grip.
BRIEF DESCRIPTION OF THE DRAWINGS
Please note that the drawings shown in this specification may not be drawn to scale and the relative dimensions of various elements in the diagrams are depicted schematically and not necessary to scale.
FIG. 1 a shows a conventional coffee table with its top surface upright called the right side up mode.
FIG. 1 b depicts the conventional coffee table in the upside down mode with its top surface upside down on the surface of the floor and a toddler attempting to step over a horizontal bar illustrating this inventive technique.
FIG. 2 illustrates a failed attempt in independently stepping over a horizontal bar illustrating this inventive technique.
FIG. 3 shows the toddler preparing to step over the horizontal bar illustrating this inventive technique.
FIG. 4 depicts the toddler using the “grip” of the leg to support the toddler while stepping right leg over the horizontal bar illustrating this inventive technique.
FIG. 5 illustrates the toddler successfully stepping over the horizontal bar illustrating this inventive technique.
FIG. 6 shows the toddler stepping over the horizontal bar while holding onto a grip of the leg illustrating this inventive technique.
FIG. 7 depicts the toddler successfully stepping over the horizontal bar illustrating this inventive technique.
FIG. 8 illustrates the toddler attempting to independently step over a horizontal bar (without the use of a grip) illustrating this inventive technique.
FIG. 9 shows the toddler independently stepping over the horizontal bar illustrating this inventive technique.
FIG. 10 depicts the toddler successfully stepping over the horizontal bar without the aid of a grip illustrating this inventive technique.
FIG. 11 illustrates the toddler attempting to independently step over a horizontal bar (without the use of a grip) illustrating this inventive technique.
FIG. 12 a shows the toddler successfully stepping over the horizontal bar without the use of a grip illustrating this inventive technique.
FIG. 12 b shows the toddler standing next to the table in the right side up mode after being flipped right side up again.
FIG. 13 a depicts a toddler gym with a height adjusting horizontal bar illustrating this inventive technique.
FIG. 13 b illustrates perforated holes in the body of the leg illustrating this inventive technique.
FIG. 13 c shows the horizontal bar coupled to the leg illustrating this inventive technique.
FIG. 13 d depicts movements to latch and unlatch the horizontal bar illustrating this inventive technique.
FIG. 14 a illustrates the horizontal bar coupled to the leg illustrating this inventive technique.
FIG. 14 b depicts the belt and screw to adjust the friction of the horizontal bar illustrating this inventive technique.
FIG. 14 c illustrates a bolt adjusting mechanism to adjust the height of the horizontal bar illustrating this inventive technique.
FIG. 14 d shows a side view of the leg with vertical slots illustrating this inventive technique.
FIG. 14 e depicts movements to latch and unlatch the horizontal bar illustrating this inventive technique.
FIG. 14 f illustrates a clamp and lock to adjust the horizontal bar illustrating this inventive technique.
FIG. 15 shows a 3-d perspective of another toddler gym with 6 legs illustrating this inventive technique.
FIG. 16 a depicts telescoping legs illustrating this inventive technique.
FIG. 16 b illustrates a twist lock for the telescoping leg illustrating this inventive technique.
FIG. 16 c shows a snap lock for the telescoping leg illustrating this inventive technique.
FIG. 16 d depicts leg extension segments illustrating this inventive technique.
FIG. 16 e illustrates the placement of the leg extension on a leg illustrating this inventive technique.
FIG. 17 shows a 3-d perspective of another toddler gym with 6 legs and without the top surface of a table and a step illustrating this inventive technique.
FIG. 18 a depicts the coupling of the table top support to the leg illustrating this inventive technique.
FIG. 18 b illustrates a coupling of the table top support to the leg using a different connector illustrating this inventive technique.
FIG. 19 shows a 3-d perspective of the table after the toddler gym in FIG. 15 is flipped in the right side up mode illustrating this inventive technique.
DETAILED DESCRIPTION OF THE INVENTION
This inventive embodiment uses a common everyday object and converted the object into a useful learning tool. The tool helps toddlers master the art of walking. This occurs since a horizontal bar can be repositioned at any level from the floor. In one case, providing an obstacle to step over, and in another case, providing a horizontal grip that the toddler can use to practice walking. In addition, the vertical grips can be adjusted in height to address the growth of the toddler.
FIG. 1 a illustrates a coffee table 1 - 1 . This is a typical coffee table with a rectangular top surface 1 - 2 of 5 by 1.5 feet standing 13.5 inches high. The table has 4 legs and cross support beams to hold the legs in place.
FIG. 1 b illustrates the invention where the table in FIG. 1 a has been flipped into the upside down mode 1 - 3 with the top surface 1 - 2 of the table in contact with the floor. The table was flipped to expose the legs and cross support beams. This structure exposes the legs 1 - 4 to 1 - 7 and cross support beams 1 - 8 to 1 - 11 . Two of the cross support beams 1 - 8 and 1 - 10 are 3 inches in height measured from the bottom surface of the table top 1 - 12 . The remaining two cross support beams 1 - 9 and 1 - 11 are 6 inches from the bottom surface of the table top. The flipped table was in the presence of a toddler 1 - 13 who became intrigued with the new structure. The toddler 1 - 13 approached the structure and attempted to step over the cross support beam 1 - 8 unaided. FIG. 2 illustrates that the toddler 1 - 13 has failed to step over the cross support beam 1 - 8 and instead collapsed on their own legs.
However, as FIG. 3 illustrates, the toddler 1 - 13 refuses to give up and this time approached one of the legs 1 - 4 in the drawing 3 - 1 . The toddler grips onto the leg 1 - 4 and uses this leg as a support to cross over the cross support beam 1 - 8 as illustrated in the drawing 4 - 1 in FIG. 4 . This time the toddler was successful and now was within the area corralled by the cross support beams as depicted in the drawing 5 - 1 in FIG. 5 .
In FIG. 6 , the drawing 6 - 1 illustrates that the toddler 1 - 13 now uses the leg 1 - 5 as a grip to step over the cross support beam 1 - 10 and support the toddler. As the drawing 7 - 1 in FIG. 7 shows, the toddler 1 - 13 is again successful. The toddler continued to repeat the process of stepping over the cross support beam using the legs as grips. Each attempt showed improvement and the toddler continued playing with the table in the upside down mode until the toddler developed the confidence to attempt an independent stepping of the cross support beam again.
FIG. 8 illustrates the toddler preparing to perform an independent step over the cross support beam 1 - 8 as depicted in 8 - 1 . FIG. 9 depicts the toddler 1 - 13 stepping their right foot over the cross support beam 1 - 8 unaided as indicated in 9 - 1 . FIG. 10 shows the drawing 10 - 1 where the toddler has successfully stepped over the cross support beam. FIG. 11 illustrates the toddler 1 - 13 stepping their right foot over the cross support beam 1 - 10 while the drawing in 12 - 1 of FIG. 12 a shows that the toddler 1 - 13 has successfully negotiated the cross support beams at a height of 3 inches. FIG. 12 b illustrates the table 1 - 1 being flipped 180° into the right side up mode and positioned next to the toddler 1 - 13 .
Interestingly, the table in the upside down mode presents itself as an inviting structure to the toddler which further enticed the toddler to seek further investigation. Their first attempt of the toddler was to step over the cross support beam unaided, but ended up being unsuccessful. The legs appearing as “grips” provided support to the toddler while stepping over the cross support beams that were 3 inches high. The support that the grip gave to the toddler allowed the toddler to practice stepping over the cross support beam until the toddle developed the ability to step independently over the beam. Once the toddler mastered this stepping, the table can be flipped right side up into the right side up mode and serve as the useful function of a coffee table.
One embodiment of the invention is that a table can be flipped upside down into the upside down mode and serve as a tool to improve the kinematic of the leg movement of a toddler who is just learning to step over obstacles. Once the step at the given height is mastered, the table can be flipped right side up into the right side up mode and used as a table again.
Another embodiment is to introduce height adjustment the cross support beams into the table 13 - 1 . FIG. 13 a illustrates the table in the upside down mode where the cross support beam 13 - 6 can be positioned over the range of various heights 13 - 14 . This structure exposes the legs 13 - 2 to 13 - 5 and cross support beams 13 - 6 to 13 - 9 . Three of the legs show a ball-like addition 13 - 10 to 13 - 12 added to the end of the leg (not shown on the last leg to simplify drawing). These serve to provide an easy grip for the toddler as well as providing a soft protection against the point of the leg if the toddler falls. In addition, the exposed components can be covered with protective foam so that a falling toddler would not hit any hard surfaces. The junction between a proposed cross support beam 13 - 13 and the leg 13 - 2 is highlighted by the dotted oval 13 - 15 . Several possibilities are provided for the view 13 - 16 provided in FIG. 13 a.
The first possibility is illustrated using FIG. 13 b through FIG. 13 d that presents one way of adjusting the height of the cross support beam 13 - 13 . FIG. 13 b presents one possibility of what can be inside the view 13 - 16 of FIG. 13 a which shows the leg 13 - 2 a with perforated holes 13 - 17 . FIG. 13 c illustrates the view 13 - 15 demonstrating the coupling of the leg 13 - 2 a with the cross support beam 13 - 13 a . A collar 13 - 19 that slides on the outside diameter of the leg 13 - 2 a couples the cross support beam 13 - 13 a to the leg. A sleeve 13 - 18 that moves back and forth as illustrated is used to adjust the height of the cross support beam 13 - 13 a . The detail of the mechanism is further depicted in FIG. 13 d which shows the sleeve 13 - 18 pushed to the left by a spring loaded assemble (not shown) inside the sleeve 13 - 18 . This exposes the pin 13 - 21 which is inserted into one of the holes 13 - 17 in the leg 13 - 2 a . To adjust the cross support beam 13 - 13 a , the sleeve is pulled to the right against the spring loaded assembly causing the pin 13 - 21 to be withdrawn within the cross support beam 13 - 13 a thereby allowing the cross support beam 13 - 13 a to move vertically.
The view of 13 - 15 of FIG. 13 a as applied to another apparatus that can be used to adjust the height of the cross support beams is illustrated in FIG. 14 a . The leg 13 - 2 b is coupled to the beam 13 - 13 b by the coupling unit 14 - 3 and adjusted by the sleeve 14 - 2 . The sleeve rotates clockwise to loosen and counter clockwise to tighten the cross support beam to the leg. The view 14 - 4 along the length of the leg is further illustrated in FIG. 14 b . The sleeve 14 - 2 has a thread on the inside diameter that matches the thread 14 - 5 associated with the belt 14 - 6 . As the sleeve is turned counter clockwise the belt 14 - 6 tightens around the leg 13 - 2 b and develops a friction that prevents the vertical movement of the cross support beam 13 - 13 b . A pin or clamp 14 - 7 is used to hold the belt to the beam 13 - 13 b.
Another embodiment of cross support beam adjustment apparatus 14 - 8 is illustrated in FIG. 14 c . The leg 13 - 2 c supports a bolt 14 - 9 (exposed portion can be rubber coated) whose shaft 14 - 10 has threads and connected to a nut 14 - 11 that is secured to the cross support beam 13 - 13 c . As the bolt is turned clockwise, the cross support beam 13 - 13 c is lifted. Similarly, when turned counter clockwise, the beam 13 - 13 c lowers.
A vertical slot assembly apparatus is illustrated in FIG. 14 d and FIG. 14 e . The view 13 - 16 of the leg in FIG. 13 a for this additional embodiment is depicted in FIG. 14 d as the drawing 14 - 13 . FIG. 14 e illustrates the leg 13 - 2 d with the cross support beam 13 - 13 d having a hook structure 14 - 14 that engages into the slots illustrated in FIG. 14 d . The height of the cross support beam is adjusted by positioning the beam 13 - 13 d into another slot of the leg 13 - 2 .
A yet additional apparatus to attach the cross support beam 13 - 13 e to the leg 13 - 2 e is depicted in FIG. 14 f . The cross support beam 13 - 13 e is coupled to a clamp that holds onto the leg 13 - 2 e . The clamp comprises a lower portion 14 - 15 that fits half way around the leg 13 - 2 e and is connected to a pin 14 - 16 . The pin 14 - 16 allows the upper portion 14 - 17 of the clamp to rotate around the pin 14 - 16 to form the clamp. A pin or screw 14 - 18 is used to tighten the upper portion of the clamp to the lower portion of the clamp so that the cross support beam is firmly coupled to the leg 13 - 2 e.
Another apparatus of a table flipped upside down 15 - 1 is illustrated in FIG. 15 . The number of legs and cross support beams that are used can vary depending on the cost of the final product, the exercise that the apparatus is targeting in the toddler, and the area displaced by the table. The legs are 15 - 2 to 15 - 7 where each has a telescopic leg extension 15 - 8 to 15 - 11 . The leg extensions for legs 15 - 5 and 15 - 6 are not illustrated. Each leg has a grip 15 - 12 to 15 - 17 . The cross support beams 15 - 18 to 15 - 24 can be adjusted by using one of the earlier presented adjustable assemblies. A toddler interactive electronic device 15 - 25 can be hung from one of the beams and provide a reward to the toddler if the toddler enters different segmented sections of the surface 15 - 26 . Each of the cross support beams can be individually adjustable in height so that the toddler can be challenged as they master stepping over each obstacle or beam. Once the cross support beams have a height that greater than the hip of the toddler, the cross support beam becomes a horizontal grip that the toddler can use to hold and either practice walking or master horizontal grip holding.
A first embodiment of the telescoping leg is illustrated in FIG. 16 a . The leg 15 - 7 has a sliding telescopic leg extension 15 - 11 that can be adjusted 16 - 2 by sliding the leg into the cavity and adjusting the length of the extension 16 - 3 .
FIG. 16 b illustrates a collar 16 - 4 that tightens the extension when rotated in the direction as shown. Another apparatus to hold the extension is provided in FIG. 16 c . The collar 16 - 5 is snapped tightened by the assembly 16 - 6 . Once snapped, the collar immobilizes the extension to the leg.
Another apparatus for leg height adjustments is to screw extensions 16 - 7 to 16 - 11 onto the end of the legs. An example is illustrated in FIG. 16 e which shows a short extension 16 - 11 screwed onto the end of the leg 15 - 7 .
FIG. 17 depicts the table 17 - 1 in the upside down mode having flat strips 17 - 2 to 17 - 8 coupling the tops of the legs together to provide additional strength. The table top is not shown for simplicity. A movable or positional step 17 - 10 is illustrated snapped to the horizontal beam 15 - 19 and can be used by the toddler to learn how to step up and to step down the positional step. The toddler can hold onto the grip 15 - 13 while learning the step movements. The positional step can be stored to a clip on the bottom surface of the table top.
A 3-D perspective view 17 - 9 of the corner of the table edge is presented is presented in FIG. 18 a and FIG. 18 b . The flat strips 17 - 4 and 17 - 3 have slots that accept the other. An attachment (rivet, screw, bolt) 18 - 1 in FIG. 18 a couples both flat strips 17 - 4 and 17 - 3 to the leg 15 - 3 . A press fitted assembly 18 - 2 with a lip 18 - 3 is presented in FIG. 18 b . The entire assemble can be press fitted together until the lip of the assembly snaps into place within the leg 15 - 3 .
The upside down table in FIG. 15 can be flipped right side up as shown by 19 - 1 and as illustrated in FIG. 19 and stood on the legs to provide a table surface 15 - 26 for the toddler. Note that the height of the table can be adjusted as the toddler grows. Besides adjusting all legs to the same height, the legs can be adjusted to make a slanting table to allow the toddler to draw pictures where the toddler's back is less curved. The table with a flat surface in the right side up mode and a slope of the flat surface can be adjusted by varying the length distribution of the telescopic legs
Finally, it is understood that the above description is only illustrative of the principles of the current invention. It is understood that the various embodiments of the invention, although different, are not mutually exclusive. In accordance with these principles, those skilled in the art may devise numerous modifications without departing from the spirit and scope of the invention. The toddler gym can use electronic motors to turn any screws in the supports such that the length of the legs or height of the cross support beams can be adjusted by mechanical gears drive by electronic motors. The toddler gym can have at least one processor comprising a CPU (Central Processing Unit), microprocessor, multi-core-processor, DSP, a front end processor, or a co-processor. All of the supporting elements to operate these processors (memory, disks, monitors, keyboards, power supplies, etc), although not necessarily shown, are known by those skilled in the art for the operation of the entire system.
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An apparatus which can be operated in one of two modes. The apparatus has a plurality of legs, a processor, at least one electronic motor controlled by the processor, a plurality of mechanical gears coupled to the at least one electronic motor, the plurality of mechanical gears are configured to adjust a length of the at least one leg wherein a point on a surface of the apparatus can be adjusted in height. The plurality of legs can be adjusted in length to slant the surface of the apparatus at an angle or to vary a height of the surface of the apparatus. The two modes may include an upside down mode wherein the apparatus is configured to operate as a toddler gym or a right side up mode where the apparatus is configured to operates as the table.
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CROSS-REFERENCES TO RELATED APPLICATIONS
This is a continuation-in-part of application Ser. No. 08/595,035, filed Jan. 31, 1996, now U.S. Pat. No. 5,789,008.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable
REFERENCE TO "MICROFICHE APPENDIX" (SEE 37 CFR 1.96)
Not applicable
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an ice cream sandwich and method for making the same.
More particularly, the invention relates to an ice cream sandwich cookie which maintains its crispness after being contacted by ice cream, which can withstand temperatures of 120 degrees F. to 130 degrees F. during shipment, and which complements the edible texture and flavor of an ice cream sandwich.
2. Description of the Related Art including Information Disclosed Under 37 CFR 1.97 and 1.98
Conventional oblong or rectangular ice cream sandwiches comprise a slab of vanilla ice cream between a pair of rectangular chocolate cookies. The chocolate cookies absorb moisture from the ice cream and, as a result, the cookies become soft and moist and tend to stick to the fingers of a person holding and eating the ice cream sandwich. The migration of moisture from ice cream to the cookies is one reason that the crispy brown wafer "cookie" material used to make ice cream cones can not be utilized in an ice cream sandwich. The crispy wafer material would absorb moisture from the ice cream and become soft and mushy. The wafer material (or the ice cream) can be sealed by completely coating the wafer material with chocolate in order to block the migration of moisture from the ice cream to the wafer material. A chocolate coating is messy and tends to stick to the fingers of a person consuming the ice cream sandwich. Further, many individuals are either allergic to or simply do not like chocolate. And, many ice cream flavors do not combine favorably with chocolate. Another disadvantage of chocolate is that it tends to melt at temperatures in excess of 100 degrees F. During shipment to plants which manufacture ice cream sandwiches, wafers can encounter temperatures of 120 to 130 degrees F. Such temperatures cause many chocolate compositions to melt and, as a consequence, cause wafers coated with chocolate to stick to one another. In order to counter this problem, "high-temperature" chocolate compositions have been prepared which resist melting at high temperatures. However, many of these high temperature chocolate compositions can have an unfavorable waxy texture when frozen.
Another solution to the problem of moisture absorption is to saturate with oil the cookies in an ice cream sandwich. Saturating cookies with oil makes them sticky and gooey and can cause portions of the cookies to stick to the fmgers of an individual consuming the ice cream sandwich.
Making an ice cream sandwich with chocolate cookies, wafer material, or other baked or cooked food compositions which are firm and crispy is advantageous because consumers like the combination of ice cream and crispy cookie materials. This is why ice cream cones are popular.
Another disadvantage of many wafer and cookie materials is that they are too weak to be utilized on machinery which produces an ice cream sandwich by injecting soft ice cream between a pair of spaced apart cookies and by then indexing the cookies to "wipe" excess ice cream off the nozzle which injected the ice cream.
Accordingly, it would be highly desirable to provide an improved ice cream sandwich which would include ice cream sandwiched between a pair of crispy crunchy cookies.
It would also be high desirable to provide a cookie which could be utilized for an ice cream sandwich and which would resist or prevent the migration of moisture from the ice cream into the cookie through the cookie-ice cream interface.
Further, it would be highly desirable to provide improved ice cream sandwich cookies of the type described which could be shipped at high temperatures without experiencing a degradation in quality and without adhering to one another, and which could be utilized on equipment which produces ice cream sandwiches at a high rate of speed by using a pair of cookies to receive soft ice cream and to then "wipe" the ice cream from the nozzle dispensing the ice cream.
Therefore, it is a principal object of the invention to provide an improved ice cream sandwich and method for producing the same.
A further object of the invention is to provide an ice cream sandwich including a slab of ice cream sandwiched intermediate a pair of crispy, crunchy cookies.
Another object of the invention is to provide a laminate cookie which can contact ice cream for an extended period of time without permitting moisture to migrate from the ice cream across the ice cream-cookie interface and into the cookie.
Still a further object of the invention is to provide a laminate cookie which includes a moisture barrier which resists degradation when the cookie is subjected to temperatures in the range of -40 degrees F. to 130 degrees F.
Yet another object of the invention is to provide an food laminate which can enhance the edibility and taste of an ice cream sandwich.
And, a further object of the invention is to provide an ice cream sandwich cookie which need not be saturated with oil to prevent the absorption of moisture by the cookie.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS(S)
These and other, further and more specific objects and advantages of the invention will be apparent to those skilled in the art from the following detailed description thereof, taken in conjunction with the drawings, in which:
FIG. 1 is a perspective view of an ice cream sandwich constructed in accordance with the principles of the invention; and,
FIG. 2 is a section view of a portion of the ice cream sandwich of FIG. 1 illustrating further structural details of the top cookie thereof and taken along section line 2--2 thereof.
BRIEF SUMMARY OF THE INVENTION
Briefly, in accordance with my invention I provide an improved ice cream sandwich. The ice cream sandwich includes at least one layer of ice cream; at least one cookie having an inner support surface facing said layer of ice cream; an oil on said inner support surface; and, a membrane covering said oil and said inner support surface and comprised of an edible food, said membrane contacting said layer of ice cream. The oil is liquid at a temperature in the range of 65 to 140 degrees F. The cookie can be crispy.
In another embodiment of the invention, I provide an article of manufacture comprising a laminate for an ice cream sandwich. The ice cream sandwich includes ice cream contacting the laminate. The laminate includes a cookie having an inner support surface which faces the ice cream in said ice cream sandwich; a hydrophobic food substance on the inner support surface; and, a membrane covering the food substance and the inner support surface and comprised of an edible food.
In a further embodiment of the invention, I provide a method of producing a laminate for an ice cream sandwich. The ice cream sandwich includes ice cream contacting the laminate. The method includes the steps of providing a cookie having an inner support surface which faces and is adjacent said ice cream in said ice cream sandwich; and, contacting the support surface with a hydrophobic food substance and with a membrane comprised of an edible food.
DETAILED DESCRIPTION OF THE INVENTION
The cookies utilized in the practice of the invention are presently preferably the rectangular chocolate cookies used in conventional ice cream sandwiches or are cookies made from the crispy brown wafer material which includes a grid pattern. The crispy brown wafer material (hereafter "wafer material") typically comprises the cone into which ice cream is dispensed, either from a soft serve machine or manually with a scoop. Some wafer material is light and quite porous. Other wafer material is heavier or denser; for example, the heavier denser dark brown wafer material which comprises the cone of a DRUM STICK (Trademark) ice cream cone. Either type of wafer material can be utilized in the practice of the invention. The cookies utilized in the invention can be baked or made from any desired edible food material other than the cookie materials described above. As utilized herein, the term cookie includes any small cake. Such cakes are usually, but not necessarily, sweet. A cake is any of a variety of breads which are baked or otherwise cooked.
In the automated "wipe" machines which produce an ice cream sandwich by injecting through a nozzle ice cream between a pair of spaced apart opposed cookies and by indexing the sandwich away from the nozzle so that one of the cookies "wipes" ice cream off the nozzle, when wafer material comprises the cookies, it is preferred that a heavier denser wafer material (like the wafer material in a DRUM STICK) be utilized to prevent the wafer from breaking.
While the cookies utilized in the ice cream sandwich of the invention can take on any desired shape and dimension, it is presently preferred that they be rectangular (like the chocolate cookies currently utilized in conventional ice cream sandwiches) or be circular.
If ice cream is dispensed between a pair of opposing rectangular cookies and the resulting ice cream sandwich is immediately eaten, then each cookie need not be particularly resistant to absorbing moisture from the ice cream which is contacting the cookie. If, however, ice cream is dispensed on one or more cookies and the resulting ice cream sandwich is stored frozen for a period of time prior to being eaten, then it is desirable that the cookies not absorb moisture from the ice cream in the sandwich.
I have discovered a food laminate which slows or prevents the migration of moisture from ice cream through the laminate-ice cream contact interface and into the laminate. The laminate includes a cookie, preferably (but not necessarily) a crispy crunchy cookie of the type described above. A liquid layer of an edible oil is sprayed or otherwise applied over the surface of the cookie which normally would contact the ice cream in an ice cream sandwich. The edible oil is preferably applied relatively uniformly over the entire surface of the cookie, or at least over the portion(s) of the surface of the cookie which would, if the oil were not applied, be contacted by the ice cream in the ice cream sandwich . After the oil is sprayed or otherwise spread onto the cookie a sheet of an edible membrane is pressed against the oil. The oil is preferably in liquid form, but may be semi-liquid-semi-solid or solid. As used herein, the term oil includes any of numerous edible hydrophobic mineral, vegetable, and synthetic substances, including animal and vegetable fats, that are generally slippery, viscous, liquid or liquefiable at or above room temperature (preferably at temperatures in excess of 95 degrees F.), soluble in various organic solvents (such as ether), but not soluble in water. Edible means suitable by nature for use as food for human beings. Examples of oils include, without limitation, milk butter, fractions of butter, high melting point fractions of butter, low melting point fractions of butter, olive oil, coconut oil, cocoa butter, CRISCO, corn oil, sunflower seed oil, chocolate including white chocolate, canola oil, hydrogenated and partially hydrogenated oils such as partially hydrogenated canola or soybean oil.
The membrane is preferably coextensive with the cookie surface, but should at least cover the area of the cookie surface which would be contacted by the ice cream in the ice cream sandwich if the oil and membrane were not applied to the cookie. When the membrane is pressed against the cookie, the oil helps the membrane adhere to the cookie. Most cookie surfaces are not extremely smooth. The conforming of the paper to high and low points on the cookie surface can also facilitate adherence of the membrane to the cookie. Food compositions other than oil can be utilized to adhere the membrane to the cookie.
The membrane can, if desired, be porous and absorb excess oil on the cookie. More than one layer of membrane can be utilized. The thickness of the membrane and of the membrane layer can vary as desired. Soft thin membranes with the consistency of soft, pliable tracing paper can be utilized as can thicker membranes having the thickness of twenty pound copy paper, of construction paper, or of various cardboards. The softness, porosity, absorbency, and pliability of the membrane can also vary. However, a thin, porous, pliable, soft membrane of rice starch paper is presently preferred. The rice starch paper absorbs excess oil from the cookie. Potato starch paper, paper made from pasta starch, paper made from the protein casein, or any other sheet of edible membrane can be utilized in the practice of the invention. The rice starch paper and other starch membranes noted above ordinarily are comprised substantially of starch, but include small amounts of protein, include binders, etc. Such membranes comprised of starch are readily available in commerce. The membrane utilized need not be porous as long as the oil or other food composition helps adhere the paper to the cookie surface.
The combination of hydrophobic oil and membrane is important. If only the oil is utilized, then high temperatures encountered during shipment of the laminate food of the invention can make the oil less viscous and cause it to be absorbed into the cookie. The membrane helps to retain the oil in the desired position adjacent and contacting the membrane, or, when the membrane is porous and/or absorbent, retains oil in the membrane. The membrane stabilizes the oil. The oil also stabilizes the membrane. One reason that it is preferable that the membrane be porous and/or absorbent and at least partially absorb oil is that the oil makes the membrane water resistant and helps prevent the starch in the membrane from being dissolved by water in ice cream contacting the ice cream. Ordinarily, at least portions of the membrane resist the migration of moisture from the ice cream into the cookie portion of the laminate food. Together, the hydrophobic oil and membrane form an effective barrier for significantly slowing or preventing the migration of moisture from ice cream contacting the paper. Flavoring, vitamins, minerals, trace elements, preservatives, and other components can, if desired, be added to the membrane, the oil, and the cookies used in the ice cream sandwich of the invention.
In an alternate embodiment of the invention, oil is applied to or absorbed into the membrane before the membrane is applied to the cookie. This procedure may be desirable because it reduces the number of applications which must be made on the surface of the cookie which will be adjacent the ice cream in an ice cream sandwich. The oil and membrane can be applied to any surface(s) or all surfaces of the cookie.
In still another embodiment of the invention, the oil and membrane are applied to the surface of a first cookie, after which a second cookie is applied over the membrane, to sandwich the edible membrane and oil between a pair of cookies. Additional quantities of oil or other food compositions can be utilized to secure the second cookie layer to the edible membrane. The second cookie ordinarily, but not necessarily, is coextensive with the first cookie and is the same size as the first cookie. The resulting food laminate includes the first cookie, an oil layer, at least one layer of edible membrane, a second oil layer, and the second cookie. In this embodiment of the invention, the second cookie layer directly contacts the ice cream in an ice cream sandwich. Moisture migrates from the ice cream sandwich into the second cookie, but the edible membrane-oil layers prevent the moisture from migrating into the first cookie.
In yet another embodiment of the invention, cookie batter is placed on a layer of edible membrane impregnated with oil. When the batter and paper are baked, the membrane adheres to the resulting cookie. Or, the membrane is adhered to the cookie after it is baked or cooked. Applying the membrane to a baked cookie while it is still warm facilitates the adhering of the membrane to the cookie.
The amount of oil applied to the surface of a cookie can vary as desired, but it is presently preferred that the amount of oil be minimized to insure that at least the outer portion of the cookie does not become saturated with oil and loose its crispy texture. The outer portion of the cookie is the portion which is not contacted by ice cream and which ordinarily is contacted by the fingers of an individual holding and eating an ice cream sandwich which includes the cookie. As noted in the Examples below, only a relatively small amount of oil ordinarily is required.
The following examples depict the presently preferred embodiments of the invention for the purpose of illustrating the practice thereof and not by way of limitation of the scope of the invention.
EXAMPLE 1
Waffle batter is prepared. The following ingredients are utilized:
13/4 cups sifted all-purpose flour
3 teaspoons baking powder
1/2 teaspoon salt
2 beaten egg yolks
13/4 cups milk
1/2 cup salad oil or melted shortening
2 stiffly beaten egg whites
The dry ingredients are sifted together. The yolks, milk and oil are combined and stirred into the dry ingredients. The whites are folded in, leaving a few fluffs. The resulting waffle batter makes three ten inch waffles.
EXAMPLE 2
A waffle iron is provided. The iron includes a lower flat circular metal griddle or plate surface and an upper hinged indented circular metal griddle or plate that impresses a grid pattern into waffle batter as it bakes. Each of the griddles is ten inches in diameter. The upper griddle is turned about its hinge to a position adjacent the lower griddle. The upper and lower griddle are heated to temperatures utilized to produce waffles from batter poured on the griddles. The upper heated griddle is turned about its hinge to a position spaced apart from the lower heated griddle. About one-third of the batter of Example 1 is poured on the lower griddle. The upper griddle is turned about its hinge to a position in which it contacts the batter and is near the lower griddle. The batter is cooked between the upper and lower griddles for several minutes or until the batter is cooked and a crispy brown waffle is produced. The upper griddle is then turned about its hinge away from the lower griddle and the cooked crispy waffle is removed. The cooked waffle has a lower flat surface and an upper surface which has grid pattern. The cooked waffle is about one-half inch thick.
EXAMPLE 3
A pair of circular waffle cookies 13, 18 (FIG. 1) about three and a half inches in diameter are cut from the waffle produced in Example 2. Each of the circular waffle cookies has a lower flat surface 15 and an upper surface which has a grid pattern 16.
Thin porous rice starch paper is obtained. The starch paper has a thickness comparable to that of tracing paper. Two circular pieces 17, 19 each having a diameter of about three and a half inches are cut from the rice paper.
An aerosol can of PAM cooking oil is provided. The aerosol can of PAM is distributed by American Home Food Products,Inc. of Madison, N.J. 07940. PAM cooking oil includes canola oil, grain alcohol from corn (added for clarity), lecithin from soybeans (prevents sticking), and propellant. A one second spray from the aerosol can of PAM covers a 10" skillet at 6 to 12 inches away. PAM cooking oil is 100% natural.
The aerosol can of PAM, the circular waffle cookies 13 and 18, and the circular pieces of edible rice starch paper 17 and 19 are utilized in the following manner to produce a pair of food laminates.
First, the aerosol can of PAM is held about six inches away from the lower substantially flat surface 15 of one 13 of the circular waffle cookies. The valve-nozzle of the aerosol can of PAM is manually operated to open the valve-nozzle for one second to cause PAM cooking oil spray to contact the lower flat surface 15 of the waffle cookie 13. A layer 14 of PAM oil is produced on the lower surface 15.
Second, a membrane comprising one of the circular pieces 17 of rice starch paper is pressed against the lower flat surface 15 of the waffle cookie 13. The PAM oil 14 on the lower surface causes the porous membrane 17 to adhere to the lower surface. The membrane 17 absorbs some of the PAM oil 14 from the lower surface of the cookies.
The foregoing two steps are utilized on the remaining waffle cookie 18 to produce a food laminate, i.e., the bottom flat surface of the remaining circular waffle cookie 18 is sprayed with PAM oil for one second, after which a membrane comprising the remaining circular piece of rice starch paper 19 is pressed against the lower flat surface of the remaining waffle cookie 18. The food laminate with the cookie 18 is substantially identical to the food laminate with the cookie 13.
After each of the waffle cookies has been treated with PAM oil and a membrane, a pair of food laminates 10 and 11 are produced. Each food laminate includes a waffle cookie 13 or 18, a layer 14 of PAM oil, and a membrane 17 or 19 of rice starch paper.
EXAMPLE 4
The pair of food laminates of Example 3 are stacked such that the membrane 17 on the bottom of the top food laminate 10 sets on, is in registry with, and contacts the top surface of the bottom laminate 11, i.e. the membrane 17 on the top food laminate 10 does not contact the membrane 19 on the bottom food laminate 11, but instead directly contacts the cookie 18 in the bottom food laminate 11.
The pair of stacked food laminates 10, 11 are placed in an oven and heated to 130 degrees F. for one hour. The food laminates are removed and cooled.
The top food laminate 10 is lifted from the bottom food laminate 11. Laminate 10 does not stick to laminate 11.
EXAMPLE 5
Example 4 is repeated, except that the stacked food laminates are left in the oven for twelve hours. Similar results are obtained. The top food laminate 10 does not stick to the bottom food laminate 11.
EXAMPLE 6
Example 4 is repeated, except that the stacked food laminates 10, 11 are left in the oven for forty-eight hours. Similar results are obtained. The top food laminate 10 does not stick to the bottom food laminate 11.
EXAMPLE 7
A three-quarter inch layer 12 of soft serve vanilla ice cream is dispensed between the food laminates 10 and 11 of Example 3 to form the ice cream sandwich illustrated in FIG. 1. The ice cream contacts only the membrane-lined surfaces of laminates 10 and 11. The circular spaced apart food laminates 10 and 11 are parallel to one another. The ice cream sandwich is stored in the freezer of a General Electric refrigerator for one month. After one month the sandwich is removed and the cookies 13 and 18 are evaluated for crispness. Cookies 13 and 18 are as crisp as they were prior to making and freezing the ice cream sandwich. Moisture from the ice cream has not penetrated the cookies 13 and 18, or, if moisture from the ice cream has penetrated the cookies 13 and 18, it is not noticeable and is negligible.
EXAMPLE 8
Example 7 is repeated, except that the cookies 13 and 18 from Example 3 are utilized without applying a layer of PAM oil and of membrane to each cookie. Consequently, the ice cream sandwich of Example 7 consists only of cookies 13 and 18 directly contacting the ice cream 12 without a barrier of PAM oil and rice starch paper intermediate ice cream 12 and cookies 13 and 18. After one month, the ice cream sandwich is removed from the freezer and the cookies 13, 18 are evaluated for crispness. Cookies 13 and 18 have absorbed moisture from ice cream 12 and are no longer crisp.
EXAMPLE 9
Examples 3 to 8 are repeated, except that olive oil and membranes comprised of thin sheets of potato starch paper are utilized in place of the PAM oil and of the membranes comprised of rice starch paper. Similar results are obtained.
EXAMPLE 10
Examples 3 to 8 are repeated, except that a one-quarter inch thick crispy crunchy chocolate cookies are utilized in place of each of the waffle cookies 13 and 18. Each of the pair of chocolate cookies is about three and a half inches in diameter. The chocolate cookies have a consistency similar in make-up to the round chocolate cookies used to make OREO brand chocolate cookies with the white filling. Similar results are obtained. In particular, in Example 7, the chocolate cookies are crisp after the ice cream sandwich is removed from the freezer after one month. In Example 8, the chocolate cookies are not crisp and have absorbed moisture from the ice cream in the ice cream sandwich.
EXAMPLE 11
Example 10 is repeated, except that membranes comprised of thin pasta starch paper are utilized in place of the rice starch paper membranes and corn oil is utilized in place of the PAM oil. Similar results are obtained.
EXAMPLE 12
Examples 1 to 8 are repeated, except that the waffles produced in Example 2 are each about 0.085 inch thick. Although the thickness of each waffle can vary as desired, it is presently preferred that the thickness of the waffles be in the range of about 0.07 inch to 0.10 inch.
EXAMPLE 13
Examples 1 to 8 are repeated, except that:
1. The waffles produced in Example 2 are each about 0.085 inch thick instead of one-half inch thick.
2. When the waffles produced in Example 2 are removed from the waffle iron they are moist and pliable and become crisp and rigid in about five to fifteen seconds.
3. Before the waffles produced in Example 2 become crisp and rigid, they are each turned around a separate conical metal mandrel to form a waffle cones for receiving ice cream. After each waffle cone becomes crisp and rigid it is removed from its mandrel.
4. In Example 3, conical food laminates are produced by spraying PAM oil against the inner conical surface of each of the waffle cones, and each piece of rice starch paper membrane is wrapped in a conical shape and inserted in one of the cones and pressed against the inner conical surface of the cone. Each piece of membrane adheres to the inner conical surface of one of the waffle cones. Consequently, in Example 3 a pair of PAM oil-membrane lined waffle cone laminates are produced instead of food laminates 10 and 11.
5. In Examples 4, 5, and 6, one waffle cone laminate is stacked inside the other waffle cone laminate such that the membrane in one cone laminate contacts the outer waffle surface of the other cone laminate. The stacked pair of waffle cone laminates is placed in the oven instead of the stacked food laminates 10 and 11. The results in Examples 4, 5, and 6 are similar, i.e., one cone laminate does not stick to the other cone laminate after the stacked cone laminates are heated in the oven at 130 degrees F. for one, twelve, and forty-eight hours, respectively.
6. In Example 7, each of the waffle cone laminates is filled with soft serve vanilla ice cream instead of dispensing the ice cream between laminates 10 and 11. The ice cream only contacts the membrane lined inner surface of each cone laminate. Each cone laminate comprises an ice cream sandwich because the ice cream in the cone is contacting at least one cookie laminate (i.e., a waffle cone lined with PAM oil-membrane) and/or because the ice cream is also intermediate a pair of opposing cookie laminate surfaces (i.e., the ice cream is between opposing sides of the cone). The results in Example 7 are similar, i.e., after the waffle cone laminates containing the vanilla ice cream are stored in the freezer of a refrigerator for one month, the waffle cone portions of the cone laminates are still crisp.
7. In Example 8, the waffle cones are utilized without applying a layer of PAM oil and of membrane to the inside of each cone. The results are similar, i.e., after being stored in the freezer for a month, the waffle cones have absorbed moisture and are no longer crisp.
The ingredients utilized to produce the cookies of the invention can vary widely as desired. Many recipes for producing cookies are well known in the art. For example, the ingredients of a powder mixture utilized to make sugar waffle cones include, in order of descending proportion, wheat flour, sugar, vegetable shortening (containing partially hydrogenated soybean oil), dextrose, whole, egg, lecithin, and artifical flavoring.
EXAMPLE 14
One thousand grams of zein is obtained. Zein is a water-insoluble prolamine protein of corn gluten. The zein is food grade F-4000 zein powder produced by Freeman Industries, L.L.C. of 100 Marbledale Road, Tuckahoe, N.Y. 10707-0415. The zein is a straw-to-yellow colored granular powder which has a bland taste and a molecular weight of about 35,000. The bulk density range of the zein is 1.25 to 2.1 gm/10 ml. The zein is insoluble in water, and is soluble in 80% alcohol. The zein comprises on a dry basis about 88 to 96% protein. One hundred percent of the zein powder passes through a U.S. 20 mesh screen. The total bacterial count of the zein does not exceed 1000 per gram. Tests carried out on the zein for Escherichia coli and Salmonella indicate that these bacteria are not present.
Zein includes alanine, asparagine, glutamic acid and glutamine, isoleucine, leucine, phenylalanine, proline, serine, tyrosine and other amino acids. Alcohol partially solubilizes the fat layer; promoting intermingling.
EXAMPLE 15
The 1000 grams of zein powder of Example 14 is mixed with 9000 grams of a 90% isopropyl alcohol solution to produce a zein-alcohol solution. The 90% isopropyl alcohol solution includes 90% by weight isopropyl alcohol and 10% by weight water. The zein-alcohol solution is stirred for about five to ten minutes, or until the zein is completely dissolved. The resulting zein-alcohol solution is somewhat viscous, has a pH of 7.0 (the pH is typically in the range of 6.5 to 7.0) and has a light amber color. Fifteen grams of stearic acid is admixed in the zein-alcohol solution to promote intermingling, interlocking, adsorption, and binding with and by a fat layer which is adjacent and contacts a layer of the zein-alcohol solution.
If desired ethanol can be utilized in place of isopropyl alcohol in the alcohol solution which is admixed with zein. The alcohol solution can include from about 75% to 95% by weight alcohol (either isopropyl alcohol or ethanol), but preferably includes from about 80 to 90% by weight alcohol. When the amount of water in the alcohol solution is reduced, the drying time is reduced. When the amount of water in the alcohol solution is increased, the cost of supplying alcohol is reduced and the alcohol solution is less flammable.
Plasticizers can be utilized to replace about 0.05% to 2.0% by weight of the water in the alcohol solution and to act as a partial solvent. Examples of plasticizers which can be utilized with zein include stearic acid, oleic acid, casein, (polyvinyl pryolidone) acetylated glycerides, propylene glycol, and glycerine. Such plasticizers slightly increase the solubility of a film made with the zein-alcohol solution and also produce a film which is more flexible. The addition of propylene glycol and other plasticizers typically slightly increases the drying time. Plasticizers assist in the layering of a zein-alcohol solution over a fat layer because plasticizers ordinarily (and, in the practice of the invention, preferably) are to at least some extent fat soluble as well as alcohol soluble. If casein is utilized, the alcohol content ordinarily must be reduced to less than 10% by weight of the zein alcohol solution to prevent the protein from denaturing.
Surfactants can be utilized to replace about 0.001% to 3.0% by weight, preferably 0.1% to 1.5% by weight, of the water in the alcohol solution. Examples of such surfactants are sodium laurel sulfate or food grade silicon wetting agents. Such surfactants assist the spreading of a zein-alcohol solution over a fat layer. When zein is admixed with alcohol, a surfactant ordinarily is not required. If, however, whey or some other protein is utilized which is dissolved primarily in water, then a surfactant is desirable to prevent the aqueous protein solution from beading on the fat layer.
A solution of zein can also, if desired, be made without utilizing any alcohol. In such a case, zein is admixed with propylene glycol and ammonia to produce a zein-glycol-ammonia solution. The strong odor of ammonia is one disadvantage of a zein-glycol-ammonia solution. When, however, the zein film is dry, there is no residual ammonia in the film. The zein-glycol-ammonia solution can include plasticizers, surfactants, and emulsifiers.
A water soluble protein like whey can be utilized in place of zein, in which case a stabilizer like lethicin can be utilized.
The weight percent of zein in the zein-alcohol solution is in the range of 1% to 20%.
EXAMPLE 16
EXAMPLE 3 is repeated except that the circular pieces 17 of rice starch paper are not utilized. Instead, after PAM is used to form a layer 14 of PAM oil on lower surface 13, a quantity of the zein-alcohol solution of EXAMPLE 15 of sprayed onto layer 14 to form a thin layer of zein-alcohol solution extending over and co-extant with layer 14. The zein-alcohol layer dries to form a circular film having a diameter equivalent to each of the circular pieces 17 of rice starch paper which was utilized in EXAMPLE 3, which pieces 17 are not utilized in this EXAMPLE 16. Similarly, after PAM oil is sprayed on the bottom flat surface of cookie 18, a layer of zein-alcohol solution is sprayed onto the oil covering the bottom flat surface of cookie 18. Stearic acid from the zein-alcohol solution is adsorbed by fat is layer 14. Fat from layer 14 is adsorbed by alcohol in the zein-alcohol solution. The zein-alcohol solution dries to form a circular film having a diameter equivalent to each of the circular pieces 17 of rice starch paper utilized in EXAMPLE 3, which pieces 17 are not utilized in this EXAMPLE 16.
After each of the waffle cookies has been treated with PAM oil and the zein-alcohol solution, a pair of food laminates are produced. Each food laminate includes a waffle cookie 13 or 18, a layer 14 of PAM oil, and a dried zein film covering and contacting the layer 14 of PAM oil.
The dried zein film is from 80% to 99.999%, preferably 90% to 99%, by weight zein protein.
EXAMPLE 17
Examples 3 to 8 are repeated, except that the food laminates prepared in EXAMPLE 16 are utilized instead of the food laminates prepared in EXAMPLE 3. Similar results are obtained.
EXAMPLE 18
Example 10 is repeated except that the one-quarter inch thick crispy crunchy chocolate cookies are laminated utilizing the process described in EXAMPLE 16, i.e., the chocolate cookies are laminated by applying a layer of PAM and by then applying a layer of zein-alcohol solution. Similar results are obtained.
EXAMPLE 19
Example 13 is repeated except that in Step 4 of Example 13, rice starch paper is not utilized. Instead, after PAM oil is sprayed against the inner conical surface of each of the waffle cones to form a layer of PAM oil, the zein-alcohol solution of Example 15 is sprayed on the PAM oil covering the inner conical surface. The zein-alcohol solution is permitted to dry to form a zein film covering the PAM oil and the inner conical surface of the waffle cones. Similar results are obtained.
EXAMPLE 20
Example 16 is repeated except that a pair of crispy, crunchy, corn flakes of the type utilized in KELLOG'S CORN FLAKES and other similar corn flakes breakfast cereals is utilized in place of the circular waffle cookies 13, 18, i.e., each corn flake is sealed with a laminate layer by first spraying and completely coating it with PAM oil and then spraying and completely coating it with the zein-alcohol solution of Example 15. The zein-alcohol solution dries to form a zein film completely covering and sealing each corn flake.
EXAMPLE 21
The pair of laminate corn flakes of EXAMPLE 20 are placed in a bowl of milk along with ordinary corn flakes not laminated with the PAM oil and zein film. The laminate corn flakes retain their crispiness longer than corn flakes not laminated with PAM oil and the zein film.
EXAMPLE 22
Twenty-five grams of lethicin and eleven grams of 9WR food grade potassium stearate (Sold by WITCO Company) is admixed with 7854 grams of 95% ethanol (95% ethanol is comprised of 95% by weight ethanol and 5% by weight water) to form an ethanol-stearate solution. Ten grams of sodium laurel sulfate (NF grade) is mixed with eleven hundred grams of water to form an aqueous sulfate solution. The aqueous sulfate solution is mixed with the ethanol-stearate solution to form an ethanol-stearate-sulfate solution. The 1000 grams of zein powder of Example 1 is mixed with the ethanol-stearate-sulfate solution to produce ten thousand grams of a zein-alcohol solution. 9000 grams of a 90% isopropyl alcohol solution to produce a zein-alcohol solution. The zein-alcohol solution is stirred for about five to ten minutes, or until the zein is completely dissolved. The resulting zein-alcohol solution is somewhat viscous, has a pH of 6.8 (the pH is typically in the range of 6.5 to 7.0) and has a light amber color.
EXAMPLE 23
Example 16 is repeated, except that the zein-alcohol solution of Example 22 is utilized in place of the zein-alcohol solution of Example 15. Similar results are obtained.
EXAMPLE 24
Examples 3 to 8 are repeated, except that the food laminates prepared in EXAMPLE 23 are utilized instead of the food laminates prepared in EXAMPLE 16. Similar results are obtained.
EXAMPLE 25
Example 23 and 24 are repeated, except that chocolate with a melting point of 92 degrees is utilized in place of the PAM oil. Similar results are obtained.
EXAMPLE 26
Example 23 and 24 are repeated, except that chocolate with a melting point of 72 degrees is utilized in place of the PAM oil. Similar results are obtained.
EXAMPLE 27
Example 23 and 24 are repeated, except that chocolate with a melting point of 100 degrees is utilized in place of the PAM oil. Similar results are obtained.
EXAMPLE 28
Ten grams of sodium laurel sulfate (NF grade) is mixed with eleven hundred grams of water to form an aqueous sulfate solution. The aqueous sulfate solution is mixed with 7989 grams of ethanol to form an ethanol-sulfate solution. One thousand grams of food grade casein powder is mixed with the ethanol-sulfate solution to produce ten thousand grams of an aqueous casein solution. The aqueous casein solution is stirred for about five to ten minutes, or until the zein is completely dissolved. The resulting aqueous casein solution is somewhat viscous, has a pH of 7.0 (the pH is typically in the range of 6.5 to 7.0) and has a light amber color. The weight percent of casein in the aqueous casein solution is in the range of 1% to 20%.
EXAMPLE 29
Example 16 is repeated, except that the aqueous casein solution of Example 28 is utilized in place of the zein-alcohol solution of Example 15. The aqueous casein solution is applied in a fine mist at an elevated temperature of 90 degrees F. to form only a thin film to facilitate drying of the solution. The dried casein film includes from 80% to 99.99% by weight casein, preferably 90 to 99% by weight casein. Otherwise similar results are obtained.
EXAMPLE 30
Example 29 is repeated, except that (1) chocolate with a melting point of 92 degrees is utilized in place of the PAM oil, (2) the chocolate solidifies and cools to a room temperature of 76 degrees F before the aqueous casein solution is sprayed onto the chocolate dries. Similar results are obtained.
EXAMPLE 31
The waffle cookies prepared in Example 30 are shipped. During shipping, the temperature of the cookies rises from 76 degrees F. to 95 degrees F. for a short while and then cools to 80 degrees F. The chocolate melts when the temperature exceeds 92 degrees F. When the chocolate melts, a portion of the chocolate is absorbed by the casein film.
EXAMPLE 32
Example 29 is repeated, except that (1) chocolate with a melting point of 72 degrees is utilized in place of the PAM oil, (2) the chocolate is liquid when the aqueous casein solution is sprayed onto the chocolate, and (3) the chocolate solidifies while the casein solution simultaneously dries to form a casein film over the chocolate. The simultaneous drying of the chocolate and the casein solution facilitates adsorption of portions of the chocolate into the casein film and facilitates adsorption of portions of the aqueous casein solution into the chocolate. Otherwise similar results are obtained.
As would be appreciated by those of skill in the art, the laminating processes of the invention can, if desired, be utilized on any type of cookie, cereal, bread, bagel, cracker, muffin, or other baked goods, regardless of whether such baked goods are utilized in an ice cream sandwich.
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A baked good includes a laminate. The laminate includes a layer of fat and a protein layer which adsorbs a portion of the fat layer. The laminate prevents moisture from penetrating the baked good.
CROSS-REFERENCES TO RELATED APPLICATIONS
This is a continuation-in-part of application Ser. No. 08/595,035, filed Jan. 31, 1996, now U.S. Pat. No. 5,789,008.
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TECHNICAL FIELD
[0001] The present invention relates to a benzimidazole-2-piperazine heterocyclic compound, a preparation method, a pharmaceutical composition containing the same, and use thereof as a therapeutic agent and a poly(ADP-ribose)polymerase (PARP) inhibitor.
RELATED ART
[0002] Chemotherapeutics and ionizing radiation are two ways commonly used in the treatment of cancers. The two therapies both cause DNA single strand and/or double strand break, and thus exert a cytotoxic effect, resulting in the death of target tumor cells due to chromosome damage. In response to DNA damage, an important consequence is the activation of cell cycle checkpoint signaling for the purpose of protecting the cells against mitosis in case of DNA damage, thereby avoiding cell damage. In most cases, the tumor cells have a high proliferation rate while exhibiting deficiency in cell cycle checkpoint signaling. Therefore, it can be inferred that a specific mechanism of DNA repair exists in the tumor cells, which may rapidly respond to and repair the chromosome damage associated with proliferation regulation, such that the tumor cells survive the cytotoxic effect of some therapeutic agent.
[0003] In clinical use, the concentration of the chemotherapeutic agent or the intensity of the radiation is effective for counteracting the mechanism of DNA repair, to ensure the killing effect on target tumor cells. However, resistance to treatment may be developed in the tumor cells through a strengthened mechanism of DNA damage repair, such that the tumor cells survive the fatal DNA damage. To overcome the resistance development, the dose of the therapeutic agent or the intensity of the radiation is generally required to be enhanced. This has a detrimental effect on normal tissues around the lesion, whereby serious adverse effects are implicated during treatment, and the treatment risk is increased. Meanwhile, the therapeutic effect is decreased with increasing resistance. Therefore, it can be inferred that the cytotoxic effect of a DNA damaging agent may be improved in a tumor cell-specific manner by regulating the DNA damage signaling and repair mechanism.
[0004] Poly(ADP-ribose)polymerases (PARPs) characterized by poly(ADP-ribosyl)ation activity constitute a super family of 18 intranuclear and cytoplasmic enzymes. Through this poly(ADP-ribosyl)ation, the catalytic activity of target proteins and the protein-protein interactions may be modulated, and some fundamental biological processes are regulated, including DNA repair, and cell death. Moreover, the genomic stability also correlates with the poly(ADP-ribosyl)ation.
[0005] PARP-1 activity accounts for about 80% of the total PARP activity in the cells. PARP-1 and PARP-2 closest thereto are members in the PARP family that have an ability to repair the DNA damage. As a sensor and signaling protein of DNA damage, PARP-1 can quickly detect and directly bind to the site of DNA damage, followed by inducing the aggregation of numerous proteins required for DNA repair, such that the DNA damage is repaired. When PARP-1 is deficient in the cells, PARP-2 is able to repair the DNA damage in place of PARP-1. Studies show that compared with normal cells, PARPs are expressed at a generally increased level in solid tumors. Furthermore, cancers (e.g. breast and ovary cancer) which are deficient in DNA repair-related genes (e.g. BRCA-1 or BRCA-2) are extremely sensitive to the PARP-1 inhibitor, indicating that the PARP inhibitor, as a single therapeutic agent, is potentially useful in the treatment of triple negative breast cancer. Moreover, since the mechanism of DNA damage repair is a principal mechanism through which resistance is developed in the tumor cells counteracting the chemotherapeutic agent and ionizing radiation. Accordingly, PARP-1 is considered to be a target of interest in seeking a new method for treating cancers.
[0006] The PARP inhibitors that are developed and designed previously are analogues developed with nicotinamide of NAD that is a substrate for PARP as a template. These inhibitors are competitive inhibitors of NAD, which compete with NAD for the catalytic sites of PARP, thereby hindering the synthesis of poly(ADP-ribose) chain. Without the modification with poly(ADP-ribosyl)ation, PARP cannot be cleaved from the site of DNA damage, such that other proteins involved in repair cannot access the site of damage and thus the repair process cannot be performed. Therefore, under attack of cytotoxic agents or radiation, the presence of the PARP inhibitor ultimately leads to the death of tumor cells with impaired DNA.
[0007] In addition, NAD, consumed as a substrate for PARP, is essential to the synthesis of ATP in cells. At a high level of PARP activity, the intracellular NAD level decreases dramatically, thus affecting the ATP level in cells. Due to the inadequate content of ATP in the cells, the cells are failed in ATP-dependent programmed cell death, and have to turn to necrosis, a special apoptosis process. During necrosis, a large amount of inflammatory factors are released, causing a toxic effect to other organs and tissues. Therefore, the PARP inhibitor may find use in the treatment of many diseases associated with such a mechanism, including neurodegenerative diseases (for example, senile dementia, Huntington's disease, and Parkinson's disease), diabetes, ischemia or complications during ischemic reperfusion, for example, myocardial infarction and acute renal failure, diseases of circulatory system, for example, septic shock, and inflammatory diseases such as chronic rheumatism.
SUMMARY
[0008] An objective of the present invention is to provide a new benzimidazole-2-piperazine heterocyclic compound and a derivative thereof, as well as their tautomers, enantiomers, diastereomers, racemates, pharmaceutically acceptable salts, metabolites and metabolic precursors or prodrugs.
[0009] Another objective of the present invention is to provide a pharmaceutical composition comprising the benzimidazole-2-piperazine heterocyclic compound as an active ingredient.
[0010] A further objective of the present invention is to provide a method for preparing the benzimidazole-2-piperazine heterocyclic compound.
[0011] A still further objective of the present invention is to provide use of the benzimidazole-2-piperazine heterocyclic compound in the preparation of drugs.
[0012] In a first aspect of the present invention, a benzimidazole-2-piperazine heterocyclic compound of general Formula (I) is provided:
[0000]
[0013] where in general Formula (I), R is hydrogen or halo;
[0014] one of X, Y, and Z is nitrogen, and the others are CH or X, Y, and Z are all CH;
[0015] R 1 is hydrogen, C 1 -C 6 alkyl, methoxy, trifluoromethyl, halo, nitro, cyano, CONR 2 R 3 , and NR 2 R 3 ;
[0016] R 2 is hydrogen, or C 1 -C 6 alkyl; and
[0017] R 3 is hydrogen, C 1 -C 6 alkyl, or C 3 -C 6 cycloalkyl, or NR 2 R 3 are cyclized to form morpholinyl, tetrahydropyrrolyl, and piperidinyl.
[0018] Further preferably, in the compound of general Formula (I) provided in the present invention, R is hydrogen or fluoro;
[0019] one of X, Y, and Z is nitrogen, and the others are CH, or X, Y, and Z are all CH;
[0020] R 1 is hydrogen, C 1 -C 4 alkyl, methoxy, trifluoromethyl, fluoro, nitro, cyano, CONR 2 R 3 , and NR 2 R 3 ;
[0021] R 2 is hydrogen, or C 1 -C 4 alkyl; and
[0022] R 3 is hydrogen, C 1 -C 4 alkyl, or C 3 -C 6 cycloalkyl, or NR 2 R 3 are cyclized to form morpholinyl, and tetrahydropyrrolyl.
[0023] Most preferably, the compound of general Formula (I) according to the present invention is Compounds (1)-(37) below:
[0000]
[0024] The compound of general Formula (I) is any one of an enantiomer, a diastereoisomer, and a conformer, or a mixture of two or more thereof.
[0025] The compound of general Formula (I) is a pharmaceutically acceptable derivative.
[0026] The compound of general Formula (I) according to the present invention may exist as a pharmaceutically acceptable salt.
[0027] The pharmaceutically acceptable salt according to the present invention is a hydrochloride, a sulfate, a phosphate, an acetate, a trifluoroacetate, a methanesulfonate, a trifluoromethanesulfonate, a p-toluenesulfonate, a tartrate, a maleate, a fumarate, a succinate or a malate of the compound of general Formula (I).
[0028] In a preferred embodiment of the present invention, the benzimidazole-2-piperazine heterocyclic compound of general Formula (I) is a 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide compound and a pharmaceutically acceptable salt thereof.
[0029] In a second aspect of the present invention, a method for preparing the compound of general Formula (I) is provided. The reaction scheme is as follows:
[0000]
[0030] where R and R 1 are as defined above. The method comprises specifically:
[0031] Step 1): cyclizing substituted methyl 2,3-diaminobenzoate with carbonyldiimidazole, to obtain substituted methyl 2-oxo-2,3-dihydro-1H-benzimidazole-4-carboxylate (II);
[0032] Step 2): chlorinating the substituted methyl 2-oxo-2,3-dihydro-1H-benzimidazole-4-carboxylate (II) obtained in Step 1) through reaction with phosphorus oxychloride, to obtain substituted methyl 2-chloro-1H-benzimidazole-4-carboxylate (III);
[0033] Step 3): subjecting the substituted methyl 2-chloro-1H-benzimidazole-4-carboxylate (III) obtained in Step 2) to nucleophilic substitution with piperazine in the presence of a base, to obtain substituted methyl 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxylate (IV);
[0034] Step 4): aminolyzing the ester group of the substituted methyl 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxylate (IV) obtained in Step 3) in a methanolic ammonia solution, to obtain substituted 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide (V); and
[0035] Step 5): coupling the substituted 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide (V) obtained in Step 4) with an acid, or reductively aminating the substituted 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide (V) obtained in Step 4) with an aldehyde, to generate the compound of general Formula (I).
[0036] In a third aspect, a pharmaceutical composition is provided, which comprises a therapeutically effective amount of the compound of general Formula (I) as the active ingredient and one or more pharmaceutically acceptable carriers and/or diluents, or comprises a therapeutically effective amount of the compound of general Formula (I) as the active ingredient and a pharmaceutically acceptable carrier, excipient, or diluent.
[0037] In the third aspect, a pharmaceutical composition is provided, which comprises a therapeutically effective amount of a pharmaceutically acceptable derivative of the compound of general Formula (I) as the active ingredient and one or more pharmaceutically acceptable carriers and/or diluents, or comprises a therapeutically effective amount of a pharmaceutically acceptable derivative of the compound of general Formula (I) as the active ingredient and a pharmaceutically acceptable carrier, excipient, or diluent.
[0038] In the third aspect, a pharmaceutical composition is provided, which comprises a therapeutically effective amount of a pharmaceutically acceptable salt of the compound of general Formula (I) as the active ingredient and one or more pharmaceutically acceptable carriers and/or diluents, or comprises a therapeutically effective amount of a pharmaceutically acceptable salt of the compound of general Formula (I) as the active ingredient and a pharmaceutically acceptable carrier, excipient or diluent.
[0039] The pharmaceutical composition may be prepared into tablets, capsules, an aqueous suspension, an oily suspension, a dispersible powder, granules, lozenges, an emulsion, a syrup, a cream, an ointment, a suppository or an injection.
[0040] In the pharmaceutical composition, the compound of general Formula (I) may exist in free form.
[0041] In a fourth aspect of the present invention, use of the compound of general Formula (I) in the preparation of drugs for treating diseases that are ameliorated through inhibition of the PARP activity is provided.
[0042] In the fourth aspect of the present invention, use of a pharmaceutically acceptable derivative of the compound of general Formula (I) in the preparation of drugs for treating diseases that are ameliorated through inhibition of the PARP activity is provided.
[0043] In the fourth aspect of the present invention, use of a pharmaceutically acceptable salt of the compound of general Formula (I) in the preparation of drugs for treating diseases that are ameliorated through inhibition of the PARP activity is provided.
[0044] In the fourth aspect of the present invention, use of the pharmaceutical composition in the preparation of drugs for treating diseases that are ameliorated through inhibition of the PARP activity is provided.
[0045] The diseases that are ameliorated through inhibition of the PARP activity include vascular diseases, septic shock, ischemic damage, neurotoxic symptoms, hemorrhagic shock, inflammatory disease or multiple sclerosis.
[0046] In the fourth aspect of the present invention, use of the compound of general Formula (I) in the preparation of adjuvant drugs for treating tumors is provided.
[0047] In the fourth aspect of the present invention, use of a pharmaceutically acceptable derivative of the compound of general Formula (I) in the preparation of adjuvant drugs for treating tumors is provided.
[0048] In the fourth aspect of the present invention, use of a pharmaceutically acceptable salt of the compound of general Formula (I) in the preparation of adjuvant drugs for treating tumors is provided.
[0049] In the fourth aspect of the present invention, use of the pharmaceutical composition in the preparation of adjuvant drugs for treating tumors is provided.
[0050] In the fourth aspect of the present invention, use of the compound of general Formula (I) in the preparation of drugs for boosting tumor radiotherapy is provided.
[0051] In the fourth aspect of the present invention, use of a pharmaceutically acceptable derivative of the compound of general Formula (I) in the preparation of drugs for boosting tumor radiotherapy is provided.
[0052] In the fourth aspect of the present invention, use of a pharmaceutically acceptable salt of the compound of general Formula (I) in the preparation of drugs for boosting tumor radiotherapy is provided.
[0053] In the fourth aspect of the present invention, use of the pharmaceutical composition in the preparation of drugs for boosting tumor radiotherapy is provided.
[0054] In the fourth aspect of the present invention, use of the compound of general Formula (I) in the preparation of chemotherapeutic agents for tumors is provided.
[0055] In the fourth aspect of the present invention, use of a pharmaceutically acceptable derivative of the compound of general Formula (I) in the preparation of chemotherapeutic agents for tumors is provided.
[0056] In the fourth aspect of the present invention, use of a pharmaceutically acceptable salt of the compound of general Formula (I) in the preparation of chemotherapeutic agents for tumors is provided.
[0057] In the fourth aspect of the present invention, use of the pharmaceutical composition in the preparation of chemotherapeutic agents for tumors is provided.
[0058] In the fourth aspect of the present invention, use of the compound of general Formula (I) in the preparation of drugs for treating an individual with a cancer which is deficient in Homologous Recombination (HR) dependent DNA double strand break (DSB) repair is provided.
[0059] In the fourth aspect of the present invention, use of a pharmaceutically acceptable derivative of the compound of general Formula (I) in the preparation of drugs for treating an individual with a cancer which is deficient in Homologous Recombination (HR) dependent DNA double strand break (DSB) repair is provided.
[0060] In the fourth aspect of the present invention, use of a pharmaceutically acceptable salt of the compound of general Formula (I) in the preparation of drugs for treating an individual with a cancer which is deficient in Homologous Recombination (HR) dependent DNA double strand break (DSB) repair is provided.
[0061] In the fourth aspect of the present invention, use of the pharmaceutical composition in the preparation of drugs for treating an individual with a cancer which is deficient in Homologous Recombination (HR) dependent DNA double strand break (DSB) repair is provided.
[0062] Preferably, the cancer comprises one or more cancer cells having a reduced or abrogated ability to repair DNA DSB by HR relative to normal cells.
[0063] Preferably, the cancer has a BRCA-1 or BRCA-2 deficient mutant phenotype.
[0064] Preferably, the cancer is breast, ovary, pancreas or prostate cancer.
[0065] To examine the degree of inhibition of the compounds provided in the present invention on the PARP enzyme, the activity of the compounds of the present invention for PARP enzyme are determined through biological enzyme activity assay.
[0066] PARP is an enzyme responsible for post-translational modification, which may be activated by means of DNA damage. The process catalyzed by PARP in vivo is mainly NAD-dependent poly(ADP-ribosyl)ation, in which the substrates are mainly some nuclear proteins including PARP, one example of which is histone. In the present invention, the PARP activity is assayed by determining the poly(ADP-ribosyl)ation degree of histone coated in a 96-well plate in the presence of NAD, and the PARP activity under the action of a PARP inhibitor is correspondingly assayed, thereby evaluating the degree of inhibition of the compounds on PARP activity.
DETAILED DESCRIPTION
[0067] The terms used in the description and claims have the following meanings, unless stated otherwise.
[0068] In the present invention, the term “C 1 -C 6 alkyl” refers to a saturated linear or branched monovalent hydrocarbyl group having 1 to 6 carbon atoms. Examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, and t-butyl.
[0069] The term “halogen” and “halo” refer to F, Cl, Br, and I.
[0070] “Pharmaceutically acceptable salt” refers to a salt that retains the biological effectiveness and properties of the parent compound. The salt includes:
[0071] (1) acid addition salts, obtainable through reaction of the parent compound as a free base with an inorganic acid including hydrochloric, hydrobromic, nitric, phosphoric, metaphosphoric, sulfuric, sulfurous, perchloric acid and the like; or an organic acid including acetic, propionic, acrylic, oxalic, (d) or (L)-malic, fumaric, maleic, hydroxybenzoic, γ-hydroxybutyric, methoxybenzoic, phthalic, methanesulfonic, ethanesulfonic, naphthalene-1-sulfonic, naphthalene-2-sulfonic, p-toluenesulfonic, salicylic, tartaric, citric, lactic, mandelic, succinic or malonic acid; or
[0072] (2) salts formed by replacing the acidic proton present in the parent compound with a metal ion, for example, alkali metal ion, alkaline earth metal ion or aluminum ion; or through coordination with an organic base, for example, ethanolamine, diethanolamine, triethanolamine, tromethamine, N-methyl glucosamine, and the like.
[0073] “Pharmaceutical composition” refers to a mixture of one or more of the compound according to the present invention or a pharmaceutically acceptable salt, solvate, hydrate or prodrug thereof with other chemical ingredients, for example, a pharmaceutically acceptable carrier. The pharmaceutical composition is provided for the purpose of promoting the administration of the drug to an animal.
[0074] “Pharmaceutically acceptable carrier” refers to an inactive ingredient in the pharmaceutical composition that does not cause significant irritation to an organism and does not interfere with the biological activity and properties of the administered compound, for example, but not limited to: calcium carbonate, calcium phosphate, various carbohydrates (e.g. lactose, and mannitol), starch, cyclodextrin, magnesium stearate, cellulose, magnesium carbonate, acrylic polymers or methacrylic polymers, gel, water, polyethylene glycol, propylene glycol, ethylene glycol, castor oil, hydrogenated castor oil or polyethoxyhydrogenated castor oil, sesame oil, corn oil, and peanut oil.
[0075] In addition to the pharmaceutically acceptable carrier, the pharmaceutical composition may further comprises pharmaceutically acceptable adjuvants, for example antibacterial agents, antifungal agents, antimicrobial agents, preservatives, colorants, solubilizers, thickeners, surfactants, chelating agents, proteins, amino acids, lipids, carbohydrates, vitamins, minerals, trace elements, sweeteners, pigments, fragrances or a combination thereof.
[0076] In the present invention, a compound and use of the compound as a poly(ADP-ribose)polymerase inhibitor are provided. The process parameters may be appropriately adapted by those skilled in the art based on the disclosures herein. It should be particularly noted that all equivalent replacements and modifications are apparent to those skilled in the art, and contemplated by the present invention. The method and use of the present invention have been described with reference to preferred examples, and it is apparent that the invention may be implemented and applied by persons of skill in the art through modification, or appropriate alternation and combination made to the method and use of the present invention without departing from the disclosures, spirits and scope of the present invention.
[0077] Hereinafter, the present invention is further described with reference to examples.
PREPARATION EXAMPLES
Example 1
Preparation of Compound (1)
2-(4-(pyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide. The reaction scheme was specifically as follows
[0078]
Step 1: Preparation of methyl 2-oxo-2,3-dihydro-1H-benzimidazole-4-carboxylate
[0079] To a solution of methyl 2,3-diaminobenzoate (0.8 g, 4.8 mmol) dissolved in anhydrous tetrahydrofuran (20 mL), carbonyldiimidazole (1.56 g, 9.6 mmol) was added, warmed to reflux, and reacted for 8 hrs. After cooling, the solvent was removed under reduced pressure, and the residue was separated by flash column chromatography (petroleum ether:ethyl acetate=5:1) to obtain Compound a: methyl 2-oxo-2,3-dihydro-1H-benzimidazole-4-carboxylate as a light solid (0.3 g, yield 33%). MS (ESI) m/z: [M+H] + =193.
Step 2: Preparation of methyl 2-chloro-1H-benzimidazole-4-carboxylate
[0080] Compound a: methyl 2-oxo-2,3-dihydro-1H-benzimidazole-4-carboxylate (1.1 g, 5.7 mmol) was added to phosphorus oxychloride (8 mL), warmed to reflux, and reacted for 8 hrs. After cooling, the solvent was removed under reduced pressure, and the residue was separated by flash column chromatography (petroleum ether:ethyl acetate=5:1) to obtain Compound b: methyl 2-chloro-1H-benzimidazole-4-carboxylate as a white solid (1.5 g, yield 100%). MS (ESI) m/z: [M+H] + =211.
Step 3: Preparation of methyl 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxylate
[0081] To Compound b: methyl 2-chloro-1H-benzimidazole-4-carboxylate (59 mg, 0.28 mmol) dissolved in dimethylformamide (5 mL), piperazine (110 mg, 1.12 mmol) was added, warmed to 100° C., and reacted for 8 hrs. After cooling, the solvent was removed under reduced pressure, and the residue was separated by flash column chromatography (dichloromethane:methanol=10:1) to obtain Compound c: methyl 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxylate as a white solid (100 mg, yield 100%). MS (ESI) m/z: [M+H] + =261.
Step 4: Preparation of 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0082] To a solution of Compound c: methyl 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxylate (100 mg, 0.28 mmol) dissolved in tetrahydrofuran (5 mL), aqueous ammonia (5 mL) was added, warmed to 70° C., sealed, and reacted for 8 hrs. After cooling, the solvent was removed under reduced pressure, and the residue was separated by flash column chromatography (dichloromethane:methanol=10:1) to obtain Compound d: 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide as a white solid (20 mg, yield 28%). MS (ESI) m/z: [M+H] + =246.
Step 5: Preparation of 2-(4-(pyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0083] To Compound d: 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide (74 mg, 0.3 mmol) dissolved in dimethylformamide (5 mL), 2-chloropyrimidine (34 mg, 0.3 mmol) and triethylamine (30 mg, 0.3 mmol) were added, warmed to 100° C., and reacted for 8 hrs. After cooling, the solvent was removed under reduced pressure, and the residue was separated by flash column chromatography (dichloromethane:methanol=10:1) to obtain Compound (1): 2-(4-(pyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (32 mg, yield 33%). LC-MS (ESI): m/z 324 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.10 (br, 1H), 9.16 (br, 1H), 8.44-8.38 (m, 2H), 7.62-7.54 (m, 2H), 7.36-7.32 (m, 1H), 7.01-6.95 (m, 1H), 6.70-6.63 (m, 1H), 3.89 (br, 4H), 3.67 (br, 4H).
Example 2
Preparation of Compound (2)
2-(4-(5-fluoropyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0084]
[0085] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound d: 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 2-chloro-5-fluoropyrimidine, to obtain Compound (2): 2-(4-(5-fluoropyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (30 mg, yield 72%). LC-MS (ESI): m/z 342 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 11.92 (br, 1H), 9.13 (br, 1H), 8.50 (s, 2H), 7.60 (d, 1H, J=7.8 Hz), 7.52 (br, 1H), 7.32 (d, 1H, J=7.8 Hz), 6.98 (t, 1H, J=7.8 Hz), 3.87-3.83 (m, 4H), 3.67-3.64 (m, 4H).
Example 3
Preparation of Compound (3)
2-(4-(5-ethylaminopyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0086]
[0087] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound d: 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 2-chloro-5-ethylaminopyrimidine, to obtain Compound (3): 2-(4-(5-ethylaminopyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (23 mg, yield 42%). LC-MS (ESI): m/z 367 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 9.08 (br, 1H), 7.92 (s, 2H), 7.78-7.72 (m, 2H), 7.66-7.60 (m, 2H), 7.22-7.16 (m, 1H), 4.71-4.67 (m, 2H), 4.19-4.15 (m, 2H), 3.73-3.70 (m, 4H), 2.65-2.60 (m, 2H), 1.37 (t, 3H, J=4.5 Hz).
Example 4
Preparation of Compound (4)
2-(4-(5-acetamidopyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0088]
[0089] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound d: 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 2-chloro-5-acetamidopyrimidine, to obtain Compound (4): 2-(4-(5-acetamidopyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (12 mg, yield 22%). LC-MS (ESI): m/z 381 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 11.85 (br, 1H), 9.89 (br, 1H), 9.14 (s, 1H), 8.54 (s, 2H), 7.60 (d, 1H, J=7.5 Hz), 7.51 (br, 1H), 7.31 (d, 1H, J=7.5 Hz), 6.98 (t, 1H, J=7.5 Hz), 3.84-3.65 (m, 8H), 2.00 (s, 3H).
Example 5
Preparation of Compound (5)
2-(4-(5-methoxypyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0090]
[0091] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound d: 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 2-chloro-5-methoxypyrimidine, to obtain Compound (5): 2-(4-(5-methoxypyrimidin-2-yl)piperazin-1-yl) 1H-benzimidazole-4-carboxamide (17 mg, yield 41%). LC-MS (ESI): m/z 354 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 11.86 (br, 1H), 9.15 (br, 1H), 8.25 (s, 2H), 7.60 (d, 1H, J=7.5 Hz), 7.51 (br, 1H), 7.31 (d, 1H, J=7.5 Hz), 6.98 (t, 1H, J=7.5 Hz), 3.77 (br, 7H), 3.64 (br, 4H).
Example 6
Preparation of Compound (6)
2-(4-(5-aminopyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0092]
[0093] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound d: 2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 2-chloro-5-aminopyrimidine, to obtain Compound (6): 2-(4-(5-aminopyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (190 mg, yield 83%). LC-MS (ESI): m/z 339 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 9.12 (br, 1H), 7.60-7.25 (m, 7H), 7.00-6.95 (m, 1H), 3.67 (br, 8H).
Example 7
Preparation of Compound (7)
2-(4-(pyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0094]
[0095] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound d: 2-(4-(pyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 4-chloropyrimidine, to obtain Compound (7): 2-(4-(pyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (25 mg, yield 65%). LC-MS (ESI): m/z 324 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 11.85 (br, 1H), 9.09 (br, 1H), 8.53 (s, 1H), 8.22 (d, 1H, J=8.1 Hz), 7.60 (d, 1H, J=7.5 Hz), 7.50 (br, 1H), 7.33 (d, 1H, J=7.5 Hz), 6.99 (t, 1H, J=7.5 Hz), 6.91 (d, 1H, J=8.1 Hz), 3.80-3.79 (m, 4H), 3.68-3.66 (m, 4H).
Example 8
Preparation of Compound (8)
2-(4-(3-ethylaminopyridin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0096]
[0097] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound d: 2-(4-(pyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 2-chloro-3-ethylaminopyridine, to obtain Compound (8): 2-(4-(3-ethylaminopyridin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (13 mg, yield 36%). LC-MS (ESI): m/z 366 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.02 (br, 1H), 9.18 (br, 1H), 7.62-7.50 (m, 4H), 7.34-7.31 (m, 1H), 7.00-6.89 (m, 3H), 3.77-3.74 (m, 4H), 3.14-3.10 (m, 4H), 2.00-1.93 (m, 2H), 0.85-0.80 (m, 3H).
Example 9
Preparation of Compound (9)
2-(4-(4-trifluoromethylpyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0098]
[0099] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound d: 2-(4-(pyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 2-chloro-4-trifluoromethylpyrimidine, to obtain Compound (9): 2-(4-(4-trifluoromethylpyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (36 mg, yield 55%). LC-MS (ESI): m/z 392 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 11.87 (br, 1H), 9.13 (br, 1H), 8.72 (d, 1H, J=4.8 Hz), 7.61 (d, 1H, J=7.8 Hz), 7.53 (br, 1H), 7.33 (d, 1H, J=7.8 Hz), 7.07 (d, 1H, J=4.8 Hz), 6.99 (t, 1H, J=7.8 Hz), 3.94 (br, 4H), 3.69 (br, 4H).
Example 10
Preparation of Compound (10)
2-(4-(6-trifluoromethylpyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0100]
[0101] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound d: 2-(4-(pyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 6-chloro-4-trifluoromethylpyrimidine, to obtain Compound (10): 2-(4-(6-trifluoromethylpyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (40 mg, yield 61%). LC-MS (ESI): m/z 392 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 11.88 (br, 1H), 9.12 (br, 1H), 8.66 (s, 1H), 7.61 (d, 1H, J=7.5 Hz), 7.53 (br, 1H), 7.35 (s, 1H), 7.33 (d, 1H, J=7.5 Hz), 6.99 (t, 1H, J=7.5 Hz), 3.92 (br, 4H), 3.69 (br, 4H).
Example 11
Preparation of Compound (11)
2-(4-(5-methylcarbamoylpyridin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0102]
[0103] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound d: 2-(4-(pyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 6-chloro-3-methylcarbamoylpyridine, to obtain Compound (11): 2-(4-(5-methylcarbamoylpyridin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (15 mg, yield 24%). LC-MS (ESI): m/z 380 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 11.86 (br, 1H), 9.14 (br, 1H), 8.6 (s, 1H), 8.24 (br, 1H), 7.96 (d, 1H, J=9.6 Hz), 7.61 (d, 1H, J=7.8 Hz), 7.52 (br, 1H), 7.32 (d, 1H, J=7.8 Hz), 7.01-6.92 (m, 2H), 3.77 (br, 4H), 3.67 (br, 4H), 2.74 (d, 3H, d=4.2 Hz).
Example 12
Preparation of Compound (12)
2-(4-(5-carbamoylpyridin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0104]
[0105] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound d: 2-(4-(pyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 6-chloro-3-carbamoylpyridine, to obtain Compound (12): 2-(4-(5-carbamoylpyridin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (25 mg, yield 41%). LC-MS (ESI): m/z 366 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 11.86 (br, 1H), 9.14 (br, 1H), 8.64 (s, 1H), 7.99 (d, 1H, J=7.8 Hz), 7.79 (br, 1H), 7.60 (d, 1H, J=9.0 Hz), 7.51 (br, 1H), 7.32 (d, 1H, J=7.8 Hz), 7.17 (br, 1H), 7.01-6.91 (m, 2H), 3.78 (br, 4H), 3.67 (br, 4H).
Example 13
Preparation of Compound (13)
2-(4-(2-trifluoromethylpyridin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0106]
[0107] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound d: 2-(4-(pyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 4-chloro-2-trifluoromethylpyridine, to obtain Compound (13): 2-(4-(2-trifluoromethylpyridin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (7 mg, yield 13%). LC-MS (ESI): m/z 391 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 11.88 (br, 1H), 9.13 (br, 1H), 8.34-8.29 (m, 1H), 7.63-7.60 (m, 1H), 7.53 (br, 1H), 7.35-7.30 (m, 2H), 7.12-7.09 (m, 1H), 7.03-6.97 (m, 1H), 3.70-3.64 (m, 8H).
Example 14
Preparation of Compound (14)
2-(4-(5-cyanopyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0108]
[0109] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound d: 2-(4-(pyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 2-chloro-5-cyanopyrimidine, to obtain Compound (14): 2-(4-(5-cyanopyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (40 mg, yield 71%). LC-MS (ESI): m/z 349 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 11.88 (br, 1H), 9.09 (br, 1H), 8.80 (s, 2H), 7.60 (d, 1H, J=7.2 Hz), 7.53 (br, 1H), 7.33 (d, 1H, J=7.2 Hz), 6.99 (t, 1H, J=7.2 Hz), 4.01 (br, 4H), 3.69 (br, 4H).
Example 15
Preparation of Compound (15)
2-(4-(5-dimethylcarbamoylpyridin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0110]
[0111] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound d: 2-(4-(pyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 6-chloro-3-dimethylcarbamoylpyridine, to obtain Compound (15): 2-(4-(5-dimethylcarbamoylpyridin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (35 mg, yield 44%). LC-MS (ESI): m/z 394 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.11 (br, 1H), 9.19 (br, 1H), 8.24 (s, 1H), 7.66-7.59 (m, 2H), 7.53 (br, 1H), 7.34-7.31 (m, 1H), 7.00-6.91 (m, 2H), 3.73-3.70 (m, 8H), 2.96 (s, 6H).
Example 16
[0112] Preparation of Compound (16) 6-fluoro-2-(4-(pyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide. The reaction scheme was specifically as follows
[0000]
Step 1: Preparation of 5-fluoro-3-nitro-2-(2,2,2-trifluoroacetamido)benzoic acid
[0113] 2-trifluoroacetamido-5-fluoro-benzoic acid (2.5 g, 10 mmol) was slowly added to fuming nitric acid (14 mL) while in an ice bath. The reaction was continued for 1 hr with stirring while in the ice bath, then poured into ice-water, and filtered, to obtain Compound e: 5-fluoro-3-nitro-2-(2,2,2-trifluoroacetamido)benzoic acid as a white solid (1.9 g, yield 65%). MS (ESI) m/z: [M−H] − =295.
Step 2: Preparation of 2-amino-5-fluoro-3-nitrobenzoic acid
[0114] A 10% aqueous sodium hydroxide solution (20 mL) was added to a solution of Compound e: 5-fluoro-3-nitro-2-(2,2,2-trifluoroacetamido)benzoic acid (1.18 g, 4 mmol) dissolved in ethanol (20 mL). The reaction was warmed to 80° C. and stirred for 3 hrs. Ethanol was removed under reduced pressure, and the residue was adjusted to pH 4 with hydrochloric acid and filtered, to obtain Compound f: 2-amino-5-fluoro-3-nitrobenzoic acid as a yellow solid (0.72 g, yield 90%). MS (ESI) m/z: [M−H] − =199.
Step 3: Preparation of methyl 2-amino-5-fluoro-3-nitrobenzoate
[0115] Thionyl chloride (2.38 g) was slowly added dropwise into a solution of Compound f: 2-amino-5-fluoro-3-nitrobenzoic acid (0.8 g, 4 mmol) dissolved in methanol (20 mL) while in an ice bath, warmed to reflux, and reacted for 8 hrs. After cooling, the solvent was removed under reduced pressure, and the residue was separated by flash column chromatography (petroleum ether:ethyl acetate=5:1) to obtain Compound g: methyl 2-amino-5-fluoro-3-nitrobenzoate as a yellow solid (0.5 g, yield 58%). MS (ESI) m/z: [M+H] + =215.
Step 4: Preparation of methyl 2,3-diamino-5-fluorobenzoate
[0116] 10% palladium on carbon (0.7 g) was added to a solution of Compound g: methyl 2-amino-5-fluoro-3-nitrobenzoate (7 g, 32.7 mmol) dissolved in methanol (50 mL), hydrogenated for 7 hrs at room temperature, and filtered. The residue was separated by flash column chromatography (petroleum ether:ethyl acetate=5:1) to obtain Compound h: methyl 2,3-diamino-5-fluorobenzoate as a yellow solid (2.16 g, yield 36%). MS (ESI) m/z: [M+H] + =185.
Step 5: Preparation of methyl 6-fluoro-2-oxo-2,3-dihydro-1H-benzimidazole-4-carboxylate
[0117] Analogous to the process in Step 1 in Preparation of Compound (1) in Example 1, Compound h: methyl 2,3-diamino-5-fluorobenzoate was cyclized with carbonyldiimidazole (CDI), to obtain Compound i: methyl 6-fluoro-2-oxo-2,3-dihydro-1H-benzimidazole-4-carboxylate (711 mg, yield 37%). MS (ESI) m/z: [M+H] + =211.
Step 6: Preparation of methyl 2-chloro-6-fluoro-1H-benzimidazole-4-carboxylate
[0118] Analogous to the process in Step 2 in Preparation of Compound (1) in Example 1, Compound i: methyl 6-fluoro-2-oxo-2,3-dihydro-1H-benzimidazole-4-carboxylate was chlorinated with phosphorus oxychloride, to obtain Compound j: methyl 2-chloro-6-fluoro-1H-benzimidazole-4-carboxylate (681 mg, yield 94%). MS (ESI) m/z: [M+H] + =229.
Step 7: Preparation of methyl 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxylate
[0119] Analogous to the process in Step 3 in Preparation of Compound (1) in Example 1, Compound j: methyl 2-chloro-6-fluoro-1H-benzimidazole-4-carboxylate was subjected to nucleophilic substitution with piperazine, to obtain Compound k: methyl 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxylate (430 mg, yield 65%). MS (ESI) m/z: [M+H] + =279.
Step 8: Preparation of 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0120] To a solution of Compound k: methyl 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxylate (100 mg, 0.28 mmol) dissolved in tetrahydrofuran (5 mL), aqueous ammonia (5 mL) was added, warmed to 70° C., sealed, and reacted for 8 hrs. After cooling, the solvent was removed under reduced pressure, and the residue was separated by flash column chromatography (dichloromethane:methanol=10:1) to obtain Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide as a white solid (20 mg, yield 28%). MS (ESI) m/z: [M+H] + =246.
Step 9: Preparation of 6-fluoro-2-(4-(pyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0121] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 4-chloropyrimidine, to obtain Compound (16): 6-fluoro-2-(4-(pyrimidin-4-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (21 mg, yield 48%). LC-MS (ESI): m/z 342 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.04 (br, 1H), 9.10 (br, 1H), 8.52 (s, 1H), 8.22 (d, 1H, J=7.2 Hz), 7.71 (br, 1H), 7.33-7.2 (m, 1H), 7.19-7.17 (m, 1H), 6.90 (d, 1H, J=7.2 Hz), 3.80 (br, 4H), 3.66 (br, 4H).
Example 17
Preparation of Compound (17)
6-fluoro-2-(4-(5-fluoropyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0122]
[0123] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 2-chloro-5-fluoropyrimidine, to obtain Compound (17): 6-fluoro-2-(4-(5-fluoropyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (27 mg, yield 87%). LC-MS (ESI): m/z 360 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 9.11 (br, 1H), 8.49 (s, 2H), 7.71-7.69 (m, 1H), 7.31-7.28 (m, 1H), 7.18-7.15 (m, 1H), 3.84-3.82 (m, 4H), 3.68-3.65 (m, 4H).
Example 18
Preparation of Compound (18)
2-(4-(5-(dimethylcarbamoyl)pyridin-2-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide
[0124]
[0125] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 6-chloro-3-dimethylcarbamoylpyridine, to obtain Compound (18): 2-(4-(5-(dimethylcarbamoyl)pyridin-2-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-car boxamide (14 mg, yield 18%). LC-MS (ESI): m/z 412 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.57 (br, 1H), 9.12 (br, 1H), 8.23 (s, 1H), 7.70-7.63 (m, 2H), 7.31-7.27 (m, 1H), 7.18-7.14 (m, 1H), 6.94-6.91 (m, 1H), 3.72 (br, 8H), 2.95 (s, 6H).
Example 19
Preparation of Compound (19)
2-(4-(5-cyanopyrimidin-2-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide
[0126]
[0127] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 2-chloro-5-cyanopyrimidine, to obtain Compound (19): 2-(4-(5-cyanopyrimidin-2-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide (43 mg, yield 77%). LC-MS (ESI): m/z 367 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.11 (br, 1H), 9.07 (br, 1H), 8.80 (s, 2H), 7.72 (br, 1H), 7.33-7.29 (m, 1H), 7.20-7.16 (m, 1H), 4.00 (br, 4H), 3.69 (br, 4H).
Example 20
Preparation of Compound (20)
6-fluoro-2-(4-(3-methylcarbamoylpyridin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0128]
[0129] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 2-chloro-N-methylnicotinamide, to obtain Compound (20): 6-fluoro-2-(4-(3-methylcarbamoylpyridin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (28 mg, yield 52%). LC-MS (ESI): m/z 398 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.21 (br, 1H), 9.10 (br, 1H), 8.41 (br, 1H), 8.26-8.25 (m, 1H), 7.75-7.72 (m, 1H), 7.68 (br, 1H), 7.32-7.28 (m, 1H), 7.18-7.15 (m, 1H), 6.96-6.92 (m, 1H), 3.69 (br, 8H), 2.79 (s, 3H).
Example 21
Preparation of Compound (21)
6-fluoro-2-(4-(5-trifluoromethylpyridin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0130]
[0131] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 2-chloro-5-trifluoromethylpyridine, to obtain Compound (21): 6-fluoro-2-(4-(5-trifluoromethylpyridin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (23 mg, yield 52%). LC-MS (ESI): m/z 409 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.32 (br, 1H), 9.10 (br, 1H), 8.44 (s, 1H), 7.85-7.81 (m, 1H), 7.70 (br, 1H), 7.32-7.28 (m, 1H), 7.19-7.15 (m, 1H), 7.06-7.02 (m, 1H), 3.81 (br, 4H), 3.70 (br, 4H).
Example 22
Preparation of Compound (22)
6-fluoro-2-(4-(5-methylcarbamoylpyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0132]
[0133] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 2-chloro-N-methylpyrimidine-5-carboxamide, to obtain Compound (22): 6-fluoro-2-(4-(5-methylcarbamoylpyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carb oxamide (17 mg, yield 29%). LC-MS (ESI): m/z 399 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.01 (br, 1H), 9.08 (br, 1H), 8.78 (s, 2H), 8.37 (br, 1H), 7.73 (br, 1H), 7.34-7.27 (m, 1H), 7.19-7.13 (m, 1H), 3.98 (br, 4H), 3.67 (br, 4H), 2.75 (s, 3H).
Example 23
Preparation of Compound (23)
6-fluoro-2-(4-(6-methylcarbamoylpyridazin-3-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0134]
[0135] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 6-chloro-N-methylpyridazin-3-carboxamide, to obtain Compound (23): 6-fluoro-2-(4-(6-methylcarbamoylpyridazin-3-yl)piperazin-1-yl)-1H-benzimidazole-4-carb oxamide (20 mg, yield 27%). LC-MS (ESI): m/z 399 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.05 (br, 1H), 9.11 (br, 1H), 8.84 (br, 1H), 7.87 (d, 1H, J=10.5 Hz), 7.74 (br, 1H), 7.44-7.41 (m, 1H), 7.31 (d, 1H, J=10.5 Hz), 7.20-7.17 (m, 1H), 3.90 (br, 4H), 3.72 (br, 4H), 2.80 (s, 3H).
Example 24
Preparation of Compound (24)
6-fluoro-2-(4-(5-methylcarbamoylpyridin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0136]
[0137] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 6-chloro-N-methylnicotinamide, to obtain Compound (24): 6-fluoro-2-(4-(5-methylcarbamoylpyridin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (6 mg, yield 13%). LC-MS (ESI): m/z 398 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.58 (br, 1H), 9.12 (br, 1H), 8.62 (s, 1H), 8.04-7.98 (m, 1H), 7.72 (s, 1H), 7.32-7.26 (m, 2H), 7.17-7.15 (m, 1H), 6.98-6.92 (m, 1H), 3.75-3.69 (m, 8H), 2.73 (s, 3H).
Example 25
Preparation of Compound (25)
6-fluoro-2-(4-(5-methylcarbamoylpyrazin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0138]
[0139] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 5-chloro-N-methylpyrazin-2-carboxamide, to obtain Compound (25): 6-fluoro-2-(4-(5-methylcarbamoylpyrazin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (38 mg, yield 64%). LC-MS (ESI): m/z 399 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.05 (br, 1H), 9.09 (br, 1H), 8.62 (s, 1H), 8.39 (br, 1H), 8.34 (s, 1H), 7.72 (br, 1H), 7.33-7.29 (m, 1H), 7.19-7.17 (m, 1H), 3.88 (br, 4H), 3.70 (br, 4H), 2.77 (s, 3H).
Example 26
Preparation of Compound (26)
2-(4-(5-ethylcarbamoylpyrazin-2-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide
[0140]
[0141] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 5-chloro-N-ethylpyrazin-2-carboxamide, to obtain Compound (26): 2-(4-(5-ethylcarbamoylpyrazin-2-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide (19 mg, yield 31%). LC-MS (ESI): m/z 413 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.09 (br, 1H), 9.11 (br, 1H), 8.63 (s, 1H), 8.44-8.42 (m, 1H), 8.34 (s, 1H), 7.73 (br, 1H), 7.33-7.29 (m, 1H), 7.20-7.17 (m, 1H), 3.87 (br, 4H), 3.71 (br, 4H), 3.28 (q, 2H, J=6.9 Hz), 1.09 (t, 3H, J=6.9 Hz).
Example 27
Preparation of Compound (27)
6-fluoro-2-(4-(5-isopropylcarbamoylpyrazin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0142]
[0143] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 5-chloro-N-isopropylpyrazin-2-carboxamide, to obtain Compound (27): 6-fluoro-2-(4-(5-isopropylcarbamoylpyrazin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carb oxamide (22 mg, yield 28%). LC-MS (ESI): m/z 427 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.04 (br, 1H), 9.09 (br, 1H), 8.63 (s, 1H), 8.32 (s, 1H), 8.05-8.00 (m, 1H), 7.70 (br, 1H), 7.34-7.29 (m, 1H), 7.20-7.16 (m, 1H), 4.09 (sep, 1H, J=6.6 Hz), 3.88 (br, 4H), 3.71 (br, 4H), 1.15 (d, 6H, J=6.6 Hz).
Example 28
Preparation of Compound (28)
2-(4-(5-t-butylcarbamoylpyrazin-2-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide
[0144]
[0145] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 5-chloro-N-t-butylpyrazin-2-carboxamide, to obtain Compound (28): 2-(4-(5-t-butylcarbamoylpyrazin-2-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide (29 mg, yield 35%). LC-MS (ESI): m/z 441 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.04 (br, 1H), 9.09 (br, 1H), 8.62 (s, 1H), 8.31 (s, 1H), 7.71 (br, 1H), 7.53 (br, 1H), 7.33-7.29 (m, 1H), 7.20-7.16 (m, 1H), 3.86 (br, 4H), 3.71 (br, 4H), 1.37 (s, 9H).
Example 29
Preparation of Compound (29)
6-fluoro-2-(4-(5-(pyrrolin-1-acyl)pyrazin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0146]
[0147] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with (5-chloropyrazin-2-yl)(pyrrolin-1-yl)methanone, to obtain Compound (29): 6-fluoro-2-(4-(5-(pyrrolin-1-acyl)pyrazin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (14 mg, yield 17%). LC-MS (ESI): m/z 441 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.04 (br, 1H), 9.08 (br, 1H), 8.51 (s, 1H), 8.34 (s, 1H), 7.71 (br, 1H), 7.33-7.29 (m, 1H), 7.19-7.16 (m, 1H), 3.86 (br, 4H), 3.70 (br, 4H), 3.47-3.45 (m, 4H), 1.86-1.83 (m, 4H).
Example 30
Preparation of Compound (30)
6-fluoro-2-(4-(5-(morpholin-4-acyl)pyrazin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0148]
[0149] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with (5-chloropyrazin-2-yl)(morpholin-2-yl)methanone, to obtain Compound (30): 6-fluoro-2-(4-(5-(pyrrolin-1-acyl)pyrazin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (32 mg, yield 37%). LC-MS (ESI): m/z 455 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.04 (br, 1H), 9.09 (br, 1H), 8.41 (s, 1H), 8.35 (s, 1H), 7.71 (br, 1H), 7.34-7.30 (m, 1H), 7.20-7.16 (m, 1H), 3.85 (br, 6H), 3.70 (br, 4H), 3.62 (br, 6H).
Example 31
Preparation of Compound (31)
6-fluoro-2-(4-(6-trifluoromethylpyridazin-3-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0150]
[0151] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 3-chloro-6-trifluoromethylpyridazine, to obtain Compound (31): 6-fluoro-2-(4-(6-trifluoromethylpyridazin-3-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (15 mg, yield 20%). LC-MS (ESI): m/z 410 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.05 (br, 1H), 9.10 (br, 1H), 7.94-7.85 (m, 1H), 7.71 (br, 1H), 7.51-7.47 (m, 1H), 7.34-7.30 (m, 1H), 7.21-7.17 (m, 1H), 3.93 (br, 4H), 3.72 (br, 4H).
Example 32
Preparation of Compound (32)
6-fluoro-2-(4-(6-trifluoromethylpyridine-3-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0152]
[0153] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 5-bromo-2-trifluoromethylpyridine, to obtain Compound (32): 6-fluoro-2-(4-(6-trifluoromethylpyridine-3-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (23 mg, yield 19%). LC-MS (ESI): m/z 409 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 9.09 (br, 1H), 8.50 (s, 1H), 7.72-7.66 (m, 2H), 7.52-7.48 (m, 1H), 7.33-7.28 (m, 1H), 7.20-7.16 (m, 1H), 3.72 (br, 4H), 3.54 (br, 4H).
Example 33
Preparation of Compound (33)
6-fluoro-2-(4-(2-trifluoromethylpyrimidin-5-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0154]
[0155] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 5-bromo-2-trifluoromethylpyrimidine, to obtain Compound (33): 6-fluoro-2-(4-(2-trifluoromethylpyrimidin-5-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (12 mg, yield 16%). LC-MS (ESI): m/z 410 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.04 (br, 1H), 9.09 (br, 1H), 8.69 (s, 2H), 7.71 (br, 1H), 7.32-7.29 (m, 1H), 7.20-7.17 (m, 1H), 3.73 (br, 4H), 3.62 (br, 4H).
Example 34
Preparation of Compound (34)
6-fluoro-2-(4-(5-trifluoromethylpyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0156]
[0157] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 2-chloro-5-trifluoromethylpyrimidine, to obtain Compound (34): 6-fluoro-2-(4-(5-trifluoromethylpyrimidin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (8 mg, yield 14%). LC-MS (ESI): m/z 410 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.02 (br, 1H), 9.09 (br, 1H), 8.75 (s, 2H), 7.72 (br, 1H), 7.33-7.29 (m, 1H), 7.20-7.17 (m, 1H), 4.00 (br, 4H), 3.69 (br, 4H).
Example 35
Preparation of Compound (35)
6-fluoro-2-(4-(5-trifluoromethylpyrazin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide
[0158]
[0159] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 2-chloro-5-trifluoromethylpyrazine, to obtain Compound (35): 6-fluoro-2-(4-(5-trifluoromethylpyrazin-2-yl)piperazin-1-yl)-1H-benzimidazole-4-carboxamide (60 mg, yield 90%). LC-MS (ESI): m/z 410 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.04 (br, 1H), 9.09 (br, 1H), 8.51 (s, 1H), 8.50 (s, 1H), 7.71 (br, 1H), 7.33-7.30 (m, 1H), 7.20-7.17 (m, 1H), 3.89 (br, 4H), 3.71 (br, 4H).
Example 36
Preparation of Compound (36)
2-(4-(5-dimethylcarbamoylpyrazin-2-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide
[0160]
[0161] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 5-chloro-N,N-dimethylpyrazin-2-carboxamide, to obtain Compound (36): 2-(4-(5-dimethylcarbamoylpyrazin-2-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carb oxamide (29 mg, yield 37%). LC-MS (ESI): m/z 413 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.02 (br, 1H), 9.09 (br, 1H), 8.37 (s, 1H), 8.34 (s, 1H), 7.71 (br, 1H), 7.33-7.30 (m, 1H), 7.20-7.16 (m, 1H), 3.83 (br, 4H), 3.73 (br, 1H), 3.07 (s, 3H), 2.98 (s, 3H).
Example 37
Preparation of Compound (37)
2-(4-(5-cyanopyrazin-2-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide
[0162]
[0163] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 5-chloro-2-cyanopyrazine, to obtain Compound (37): 2-(4-(5-cyanopyrazin-2-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide (40 mg, yield 58%). LC-MS (ESI): m/z 367 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.05 (br, 1H), 9.07 (br, 1H), 8.59 (s, 1H), 8.49 (s, 1H), 7.69 (s, 1H), 7.33-7.29 (m, 1H), 7.20-7.16 (m, 1H), 3.93 (br, 4H), 3.71 (br, 4H).
Example 38
Preparation of Compound (38)
2-(4-(2-cyanopyrimidin-5-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide
[0164]
[0165] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 5-bromo-2-cyanopyrimidine, to obtain Compound (38): 2-(4-(2-cyanopyrimidin-5-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide (18 mg, yield 26%). LC-MS (ESI): m/z 367 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.03 (br, 1H), 9.08 (br, 1H), 8.63 (s, 2H), 7.73-7.65 (m, 1H), 7.33-7.29 (m, 1H), 7.22-7.17 (m, 1H), 3.73-3.69 (m, 8H).
Example 39
Preparation of Compound (39)
6-fluoro-2-(4-(2-methylcarbamoylpyrimidin-2-yl)piperazin-5-yl)-1H-benzimidazole-4-carboxamide
[0166]
[0167] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 5-bromo-N-methylpyrimidine-2-carboxamide, to obtain Compound (39): 6-fluoro-2-(4-(2-methylcarbamoylpyrimidin-2-yl)piperazine-5-yl)-1H-benzimidazole-4-carboxamide (16 mg, yield 29%). LC-MS (ESI): m/z 399 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.02 (br, 1H), 9.08 (br, 1H), 8.67 (s, 2H), 8.34 (br, 1H), 7.71 (br, 1H), 7.33-7.27 (m, 1H), 7.19-7.12 (m, 1H), 3.99 (br, 4H), 3.68 (br, 4H), 2.72 (s, 3H).
Example 40
Preparation of Compound (40)
2-(4-(2-ethylcarbamoylpyrimidin-5-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide
[0168]
[0169] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 5-bromo-N-ethylpyrimidine-2-carboxamide, to obtain Compound (40): 2-(4-(2-ethylcarbamoylpyrimidin-5-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide (17 mg, yield 23%). LC-MS (ESI): m/z 413 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.01 (br, 1H), 9.09 (br, 1H), 8.64 (s, 2H), 8.31 (br, 1H), 7.72 (br, 1H), 7.34-7.27 (m, 1H), 7.19-7.13 (m, 1H), 3.96 (br, 4H), 3.65 (br, 4H), 3.26 (q, 2H, J=6.9 Hz), 1.07 (t, 3H, J=6.9 Hz).
Example 41
Preparation of Compound (41)
2-(4-(2-dimethylcarbamoylpyrimidin-5-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide
[0170]
[0171] Analogous to the process in Step 5 in Preparation of Compound (1) in Example 1, Compound 1: 6-fluoro-2-(piperazin-1-yl)-1H-benzimidazole-4-carboxamide was subjected to aromatic nucleophilic substitution with 5-bromo-N-dimethylpyrimidin-2-carboxamide, to obtain Compound (41): 2-(4-(2-dimethylcarbamoylpyrimidin-5-yl)piperazin-1-yl)-6-fluoro-1H-benzimidazole-4-carboxamide (19 mg, yield 26%). LC-MS (ESI): m/z 413 (M+1) + . 1 H NMR (300 MHz, DMSO-d6): δ 12.03 (br, 1H), 9.07 (br, 1H), 8.63 (s, 2H), 8.32 (br, 1H), 7.72 (br, 1H), 7.31-7.26 (m, 1H), 7.18-7.13 (m, 1H), 3.97 (br, 4H), 3.67 (br, 4H), 3.08 (s, 3H), 2.97 (s, 3H).
[0172] Biological Evaluation
[0173] Experimental Principle:
[0174] Poly(ADP-ribosyl)ation of nuclear proteins is a post-translational modification occurred in response to DNA damage. PARP is the abbreviation of poly(ADP-ribose)polymerase, which catalyzes the attachment of poly(ADP-ribose) to an adjacent nuclear protein in the presence of NAD, thus eliciting a mechanism of DNA repair through base excision repair pathway. The level of biotin-labeled ADP-ribose binding to histone can be detected by using the HT Universal Chemiluminescent PARP Assay Kit commercially available from Trevigen Corp.
[0175] Reagents and Materials
[0176] 1. HT Universal Chemiluminescent PARP Assay Kit with Histone-coated Strip Wells, commercially available from Trevigen (US), Catalog #: 4676-096-K.
[0177] 2. Plate reader: EnVision Multilabel Plate Reader available from Perkin Elmer (US).
[0178] Solutions and Buffers
[0179] 1. Washing buffer: 0.1% Triton X-100 in PBS.
[0180] 2. 20×PARP buffer—It was 1:20 diluted in deionized water to obtain a 1× buffer, which was used for diluting the recombinant PARP enzyme, PARP Cocktails, and test compounds.
[0181] 3. 10×PARP Cocktail was formulated into a 1×PARP Cocktail by mixing 10×PARP Cocktail 2.5 μl/well, 10× activated DNA 2.5 μl/well, and 1×PARP buffer 20 μl/well.
[0182] 4. The PARP enzyme was carefully diluted with the 1×PARP buffer just before use, the diluted enzyme solution should be used as quickly as possible and the remaining solution should be discarded.
[0183] 5. Strep-HRP was 1:500 diluted with the 1× Strep diluent just before use to obtain a 1× solution.
[0184] 6. The chemiluminescent substrate was prepared just before use, by uniformly mixing equal volume of PeroxyGlow A and B to obtain a substrate for horseradish peroxidase.
[0185] Experimental Method
[0186] Formulation of Compound Solutions
[0187] 1. 10 mM stock solution of each test compound was diluted to 10 μM, and 1 μM in DMSO.
[0188] 2. Just before experiment, the solution at various concentration gradients of each compound dissolved in DMSO was 1:20 diluted in the 1×PARP buffer, to obtain a 5× compound solution for test. The positive and negative control wells contained the 1×PARP buffer (containing 5% DMSO).
[0189] Experimental Procedures
[0190] 1. 50 μl of 1×PARP buffer per well was added to infiltrate the histone, and the plate was incubated for 30 min at room temperature. Then the 1×PARP buffer in each well was aspirated, and the remaining liquid was tapped dry on paper towels.
[0191] 2. The diluted 5× solutions of Compounds (1) to (37) were added to respective wells (10 μl per well). The positive and negative control wells contained the 1×PARP buffer (containing 5% DMSO).
[0192] 3. The PARP enzyme was diluted in the 1×PARP buffer to give a concentration of 0.5 Unit per 15 μl, and then 15 μl of the enzyme solution was added to each well except that the negative control well was added exclusively with the 1×PARP buffer. The plate was incubated for 10 min at room temperature.
[0193] 4. 25 μl of the 1×PARP Cocktail was sequentially added to each well.
[0194] 5. The plate was incubated for 60 min at 27° C.
[0195] 6. After incubation, the reaction solution was aspirated from the wells, and the remaining liquid was tapped dry on paper towels. Then, the plate was washed 4 times with 0.1% Triton X-100 in PBS (200 μl per well per wash), and the remaining liquid was tapped dry on paper towels.
[0196] 7. Subsequently, the diluted 1× Strep-HRP solution was added to each well, and then the plate was incubated for 60 min at 27° C.
[0197] 8. After incubation, the reaction solution was aspirated from the wells, and the remaining liquid was tapped dry on paper towels. Then, the plate was washed 4 times with 0.1% Triton X-100 in PBS (200 μl per well per wash), and the remaining liquid was tapped dry on paper towels.
[0198] 9. After washing, equal volume of the PeroxyGlow A and B solutions were uniformly mixed, 100 μl of the solution was added to each well, and the chemiluminescent signals were recorded on a plate reader immediately.
[0199] Data Processing
[0200] The readout of each well is converted into the percent inhibition. The percent inhibition of the compounds may be calculated by an equation below:
[0000]
Inhibition
(
%
)
=
Readout
of
positive
control
well
-
X
Readout
of
positive
control
well
-
Readout
of
negative
control
well
×
100
%
[0201] Note: the readout of the positive control well is designated as 100% enzyme activity; the readout of the negative control well is designated as 0% enzyme activity; and the activity X refers to the readout from respective concentration of each sample.
[0000]
TABLE 1
Inhibition of the compounds on PARP-1 enzyme
Compound
Inhibition
Inhibition
No
(%) at 100 nM
(%) at 30 nM
IC 50
(1)
76
59
48
nM
(2)
69
42
49
nM
(3)
13
6
3579
nM
(4)
53
27
106
nM
(5)
60
32
74
nM
(6)
54
26
98
nM
(7)
85
73
17
nM
(8)
16
8
928
nM
(9)
31
16
217
nM
(10)
64
38
55
nM
(11)
78
59
25
nM
(12)
77
57
25
nM
(13)
69
43
49
nM
(14)
78
57
28
nM
(15)
70
44
54
nM
(16)
91
78
9
nM
(17)
78
56
26
nM
(18)
77
56
30
nM
(19)
93
77
9
nM
(20)
67
39
48
nM
(21)
60
32
68
nM
(22)
93
71
10
nM
(23)
89
78
12
nM
(24)
65
45
45
nM
(25)
92
79
7
nM
(26)
94
80
7
nM
(27)
86
66
14
nM
(28)
78
53
25
nM
(29)
88
71
12
nM
(30)
92
78
9
nM
(31)
95
80
8
nM
(32)
84
66
15
nM
(33)
98
88
5
nM
(34)
60
36
56
nM
(35)
91
76
9
nM
(36)
92
83
8
nM
(37)
98
87
3
nM
(38)
95
84
6
nM
(39)
92
78
9
nM
(40)
93
77
9
nM
(41)
92
75
8
nM
[0202] The data given in Table 1 fully suggests that the compounds of the present invention are all PARP-1 inhibitors. As indicated in the examples, the IC 50 value of Compounds (1), (2), (5), (6), (7), (10), (11), (12), (13), (14), (15), (16), (17), (18), (19), (20), (21), (22), (23), (24), (25), (26), (27), (28), (29), (30), (31), (32), (33), (34), (35), (36), (37), (38), (39), (40), and (41) is not greater than 100 nM, and the IC 50 value of Compounds (16), (19), (25), (26), (30), (31), (33), (35), (36), (37), (38), (39), (40), and (41) is further not greater than 10 nM.
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The present invention relates to a class of benzimidazole-2-piperazine heterocyclic derivatives, a preparation method and medical use thereof. Specifically, the present invention relates to a new benzimidazole-2-piperazine heterocyclic derivative of general Formula (I), a preparation method, a pharmaceutical composition containing the same, and use thereof as a therapeutic agent and especially as a poly(ADP-ribose)polymerase (PARP) inhibitor.
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BACKGROUND OF THE INVENTION
This invention relates to intumescent compositions and more particularly to intumescent compositions comprising a bicyclic phosphate compound and a compound of nitrogen. The intumescent compositions of this invention impart flame retardant and intumescent character to polymers.
Intumescent compositions may be generally described as those compounds and mixtures which swell upon heating to produce a voluminous char or residue. A familiar example of such compositions is mercuric thiocyanate or "pharaoh's serpents" which, when ignited, forms a voluminous ash that resembles a moving serpent. Other compositions have been formulated which combust to form adherent, tough insulating foams that resist further burning and act to insulate and protect the underlying substrate. These formulations have found wide commercial use in fire retardant paints and mastics.
More recently, additives have been incorporated into molding resins which render them intumescent and flame retardant. In U.S. Pat. Nos. 3,936,416 and 4,201,705 there are described polyolefin compositions containing melammonium polyphosphates and phosphate esters which are flame retarded. Upon combustion, a tough, insulating char forms at the surface of the molded article which resists further burning and acts to protect the bulk of the polyolefin resin from further burning.
As is well known in the art, the behavior of flame retardant additives in resin formulations varies greatly with the nature of polymeric substrate. This is particularly true with intumescent compositions since the rapid formation of the protective char layer is highly dependent upon such factors as the combustion temperature and the viscosity of the melt formed by the burning substrate. Other considerations that may also come into play even where the intumescent behavior is optimum include the effect of the additive on the physical properties, color and molding characteristics of the base resin. The development of intumescent additives for use in flame retarding resins thus remains a highly empirical art wherein predictability of behavior is rare to non-existent, and the art has largely concentrated on the development of highly specific additive combinations for particular resins and end-uses.
The development of an intumescent additive combination which exhibits a greater latitude in dispersability and char-forming character and thus capable of being formulated for use in a wider variety of dissimilar resins would thus be a useful advance in the flame retardant art.
SUMMARY OF THE INVENTION
The present invention is an intumescent additive combination comprising a bicyclic phosphate compound and a compound of nitrogen. More particularly, the invention is an intumescent composition comprising 2,6,7-trioxa-1-phosphabicyclo[2.2.2.]octane-4-methanol-1-oxide (PEPA) and a compound of nitrogen. The composition may be formulated to impart a degree of flame retardant and intumescent character to a variety of polymers.
DETAILED DESCRIPTION OF THE INVENTION
The bicyclic phosphate compound, PEPA, which may be represented by the formula: ##STR1## is a known phosphate compound and may readily be prepared by conventional processes as is disclosed in U.S. Pat. No. 3,293,327. PEPA has been disclosed for use as a flame retardant in polyesters and particularly in polyester fibers as is set forth in U.S. Pat. No. 3,873,496, however PEPA alone is not an intumescent additive for polyesters and is described by the patentee as a thermally stable flame retardant and unreactive with molten polyesters.
The bicyclic phosphate compound PEPA is used with a nitrogen compound to provide an intumescent composition. A wide variety of nitrogen compounds are effective when used with PEPA for producing intumescent properties, and particularly useful are ammonium compounds and derivatives of ammonia including amines, ureas, guanidines, guanamines, s-triazines such as melamine and ammeline, amino acids and peptides, as well as salts and derivatives thereof. More preferable are the amino-s-triazines such as melamine, ammeline and benzoguanamine and salts thereof, urea, guanidine and salts thereof and ammonium salts including ammonium phosphate and ammonium polyphosphate.
The intumescent compositions of this invention comprise mixtures of from 5 to 95 wt. % PEPA and from 95-5 wt. % of the nitrogen compound. The specific ratio employed will depend in part upon the particular nitrogen compound employed, in as much as the various nitrogen compounds are not equally effective in producing intumescent behavior.
The intumescent compositions of this invention, when further compounded with a polymeric resin will impart flame retardant and intumescent character. Polymers which exhibit intumescent behavior when compounded with a sufficient amount of an intumescent composition of this invention include polyolefins, polyvinylaromatic resins such as polystyrene and styreneacrylonitrile copolymers, ABS graft copolymers, polycarbonate resins such as bisphenol-A polycarbonate, polyacrylate resins such as polymethyl methacrylate polyamides such as Nylon 6, and polyvinylchloride, as well as blends and alloys of these resins. As would be expected, not every intumescent combination of PEPA and nitrogen compound is effective in producing a desirable level of intumescence in every polymeric resin, and one skilled in the art will recognize the need for evaluating and selecting particular combinations for particular end uses. In general when employed at levels above about 20 parts by weight of intumescent composition per hundred parts by weight of resin, intumescent characteristics will be present. The degree of intumescence will increase with increased levels of intumescent additive compositions, and for some purposes, the including of as much as 60 parts by weight of intumescent composition per hundred parts by weight of resin may be preferred.
The compounding of the polymer with the intumescent composition may be accomplished by any of the conventional compounding processes including powder blending, Banbury mixing, melt extrusion and the like. Those skilled in the art will recognize that the particular intumescent composition selected for use with a particular resin will necessarily be stable at the processing temperature when melt processing is to be carried out. Where it is desired to use compositions which decompose at or near the melt temperature of the resin, powder blending and compression molding may be employed to minimize premature decomposition and intumescing.
The preparation of the intumescent compositions of this invention and the use of such compositions in flame retardant resins will be better understood by consideration of the following examples, which are provided to further illustrate the practice of this invention and not by way of limitation.
The Limiting Oxygen Index (LOI) test is employed to determine the minimum concentration of oxygen, in percent, which will support combustion of a test sample. The test is more fully described in ASTM-D-2863-70.
The UL-94 flame test is a standard test for rating the vertical burn characteristics of a test sample.
EXAMPLES 1-16
In the following Examples, 1:1 mixtures of PEPA and the indicated nitrogen compound were prepared by simple mixing of the powdered and/or liquid compounds. The mixtures were tested for intumescent behavior by placing a sample on the tip of a laboratory spoon and exposing the sample to a bunsen burner flame for 5 to 10 sec. The compositions of the mixtures and their respective intumescent behavior are summarized in Table I.
TABLE I______________________________________Intumescent Character of 1:1 PEPA/NitrogenCompound MixturesExample IntumescentNo. Nitrogen Compound Behavior______________________________________1 Melamine +2 Melamine, Acetic Acid Salt +3 Melamine HBr +4 Bis-melammonium pentate.sup.(1) +5 Melamine-formaldehyde resin +6 Benzoguanamine +7 Benzoguanamine phosphate +8 Ammeline +9 Cyanuric Acid +10 Glycine +11 Ammonium polyphosphate +12 Cyanamide +13 Urea +14 Guanidine HCl +15 Cyanoguanidine +16 Thiourea +______________________________________ Notes: .sup.(1) dipentaerythritol diphosphate salt of melamine; see U.S. Pat. No 4,154,930
It will be apparent that mixtures of PEPA with a variety of nitrogen compounds are intumescent.
EXAMPLES 17-39
In the following Examples, compositions containing PEPA:Nitrogen Compound:Resin in a ratio of 1:1:1 were similarly prepared by simple mixing of the powdered resin with the PEPA/nitrogen composition. Testing for intumescent behavior was again accomplished by placing a sample on the tip of a laboratory spoon and holding the sample on a bunsen burner flame for 5-10 sec. The compositions and intumescent behavior of these mixtures are summarized in Table II.
TABLE II______________________________________Intumescent Behavior of PEPA/NitrogenCompound/Resin (1:1:1) BlendsExample Nitrogen Intumescent.sup.(2)No. Compound Resin.sup.(1) Behavior______________________________________17 Melamine ABS +18 Melamine SAN Slight19 Melamine PolyCarbonate +20 Melamine PVC +21 Melamine PP +22 Melamine PE +23 Ammonium ABS + Polyphosphate24 Ammonium SAN Slight Polyphosphate25 Ammonium PolyCarbonate + Polyphosphate26 Ammonium PVC + Polyphosphate27 Ammonium PP + Polyphosphate28 Ammonium PE + Polyphosphate29 Guanidine ABS +30 " SAN +31 " PolyCarbonate +32 " PVC +33 " PP +34 " PE +35 Glycine ABS V. Slight36 " PP Slight37 " PE Slight______________________________________ Notes: .sup.(1) ABS = StyreneArylonitrile-butadine graft copolymer; SAN = StyreneAcrylonitrile copolymer; Polycarbonate = bisphenolA polycarbonate resin; PVC = polyvinyl chloride; PP = polypropylene; PE = polyethylene. .sup.(2) + = substantial char remains after burning; slight = only sligh amount of char formation.
The variation of char forming character with resin type and nitrogen compound will be apparent from these data. Although PEPA/melamine and PEPA/ammonium polyphosphate mixtures are effective char formers in a variety of resins including polypropylene (Examples 21 and 27) and PVC (Examples 20 and 26), the same combinations produced only slight char formation in SAN (Examples 18 and 24). A mixture of PEPA and guanidine, however, was an effective char former in SAN (Example 30). Similarly, a PEPA/glycine mixture, in itself an effective intumescent was only slightly effective as a char-former when compounded with resins at this level (Examples 35-37).
EXAMPLES 38-48
In the following Examples, the flame retardant behavior of representative resin compositions containing mixtures of PEPA and nitrogen compounds as intumescent additives at various levels was measured by the UL-94 and LOI methods. The resin compositions were prepared by compounding the indicated resin in the mixing head of a Brabender extruder, then extruding the composition. The resin composition was then chopped and compression molded to form specimens for testing. The compositions and the UL-94 and LOI test results are summarized in Table III.
TABLE III__________________________________________________________________________PEPA/Nitrogen Compounds as Flame RetardantsExample P/N.sup.(1) Loading.sup.(3) UL94No. N-Compound Ratio Resin.sup.(2) phr Test LOI Intumescent__________________________________________________________________________38 Melamine 2.9/1 PP 30 V-0 29.3 +39 " 3.6/1 PP 30 V-0 31.5 +40 " 4/1 PP 22 V-0 31.1 +41 " 4/1 PP 20 V-1 30.1 +42 " 4/1 Nylon 6 26 V-0 27.5 +43 Melamine 1.6/1 PP 20 V-0 29.8 +Phosphate44 Melamine 1.5/1 Styrene 50 V-0 29.7 +Phosphate45 Melamine .8/1 " 45 NVE 22.3 V. LightPhosphate46 Ammonium 1.5/1 PP 30 V-0 29.5 +Polyphosphate47 Benzoguanamine 1.5/1 PP 30 V-2 26.8 +Phosphate48 MelamineCyanurate 1.7/1 PP 30 NVE 30.6 +49 Melamine 1.5/1 PMMA 50 V-0 36.5 +Phosphate50 Melamine 1/1 ABS/Nylon 27.7 V-0 29.6 +Phosphate__________________________________________________________________________ Notes: .sup.(1) P/N ratio = weight ratio of PEPA to nitrogen compound .sup.(2) PP = polypropylene; ABS/Nylon = 100 pbw ABS, 30 pbw Nylon 6 allo .sup.(3) Loading = parts by weight of PEPA/N compound per hundred parts resin
The ability of the intumescent compositions of this invention to impart intumescent and flame retardant character to resins is apparent from these data. Not all compositions produce flame retardant V-O character to all resins. Thus, although compositions of Examples 41, 45, 47 and 48 exhibit intumescence and high LOI values, these resins were not rendered V-O. As will be apparent from a comparison of Examples 44 and 45, intumescent and flame retardant character is affected by the ratio of PEPA to nitrogen compound. Although some intumescent behavior will be seen in resins at some loading level for all P/N ratios, generally ratios of 1:1 and greater will be preferred.
The invention will thus be seen to be intumescent compositions comprising PEPA and a nitrogen compound which may be adapted to render polymeric resins intumescent and flame retardant.
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Compositions comprising 2,6,7-trioxa-1-phosphobicyclo [2.2.2.] octane -4-methanol-1-oxide and a nitrogen compound selected from the group melamine, ammeline, benzoguanidine, guanidine, urea and salts thereof, are intumescent and are readily adapted to flame retard a variety of dissimilar resins including polyolefins, polyvinylaromatic resins, polycarbonates, polyacrylates, polyamides, PVC and blends thereof.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to glass fiber mats which include an improved binder, particularly for application in roofing and flooring products.
2. Description of the Prior Art
Glass fiber mats are composed of glass fibers held together by a binder material. Typical binders used in the industry are urea-formaldehyde resins, phenolic resins, bone glue, polyvinyl alcohols, acrylic resins and polyvinyl acetates. These binder materials are impregnated directly into the fibrous mat and set or cured to provide the desired integrity for the glass fibers.
Unfortunately, the binder materials of the prior art are deficient in one or more respects for glass fiber mats. In particular, such binder materials provide glass fiber mats which exhibit only acceptable tensile strengths at room temperature or at elevated temperatures. Furthermore, the tensile strengths of such mats deteriorate appreciably when the mats are subjected to wet conditions, which can be encountered in their use in roofing and flooring products. In addition, these prior art mats have relatively poor flexibility resulting in buckling, creasing or cracking of the mats during use as a base in asphalt roofing shingles, or as a backing felt or base support for sheet vinyl flooring.
Accordingly, it is an object of this invention to provide glass fiber mats which include an improved binder therefor, and, particularly, glass mats having properties which are desirable for use in roofing and flooring products.
A feature of the invention is the provision of glass fiber mats with an improved binder therewith which exhibits, in combination, excellent tensile strengths at both room and elevated temperatures, and also under wet conditions, and which shows a high degree of flexibility in commercial use in the roofing and flooring industries.
SUMMARY OF THE INVENTION
The above stated objects and features of the invention are accomplished herein by providing a glass fiber mat composed of a plurality of glass fibers held together by an improved binder comprising about 25% to 90% by weight of urea-formaldehyde resin and about 10% to 75% by weight of a styrene-butadiene latex copolymer containing about 0.1% to 5% by weight of acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, or mixtures thereof.
The glass mats of the invention are made by applying the binder composition to the wet glass mat, drying and curing the binder at elevated temperatures. The finished glass mat product contains about 70% to 90% by weight glass fibers and about 10% to 30% by weight of binder.
In the best mode of the invention, the binder is comprised of about 80% by weight of urea-formaldehyde and about 20% by weight of styrene and butadiene latex copolymer containing about 40% by weight styrene and 60% by weight butadiene, modified with about 2% to 4% by weight of the acrylamide type monomer. The fibrous material is present in an amount of about 80% by weight and the binder about 20% by weight of the mat.
The urea-formaldehyde component of the binder preferably is a modified resin containing methylol type groups which can be cured to form methylene or ether type linkages in the binder.
DETAILED DESCRIPTION OF THE INVENTION
The following detailed description of the invention will be made with particular reference to a wet-laid process for preparing glass fiber mats, although it will be understood that other processes known in the art, such as a dry-laid process, may be used as well. Furthermore, the description is made using chopped bundles of glass fibers, although other forms of glass fibers such as continuous strands, also may be used.
The process of forming glass fiber mats according to the invention begins with chopped bundles of glass fibers of suitable length and diameter. Generally, fibers having a length of about 1/4 inch to 3 inches and a diameter of about 3 to 20 microns are used. Each bundle may contain from about 20 to 300, or more, of such fibers, which may be sized or unsized, wet or dry, as long as they can be suitably dispersed in an aqueous dispersant medium. The bundles are added to the dispersant medium to form an aqueous slurry. Any suitable dispersant known in the art may be used. The fiber slurry then is agitated to form a workable dispersion at a suitable consistency. The dispersion then is passed to a mat-forming machine. En route to the screen, the dispersion usually is diluted with water to a lower fiber concentration.
The fibers are collected at the wire screen in the form of a wet fiber mat and the excess water is removed by vacuum in the usual manner. The wet mat now is ready for application of the binder composition thereto, which is accomplished by soaking the mat in an excess of binder solution and dewatering under vacuum, to remove excess binder solution. The mat then is dried and the binder composition is cured in an oven at elevated temperatures, generally at least at about 400° F. This heat treatment alone will effect curing; alternatively, but less desirable, catalytic curing may be used, such as with an acid catalyst, e.g. ammonium chloride or p-toluene sulfonic acid.
The binder composition of the invention is prepared by blending a urea-formaldehyde resin with a styrene-butadiene latex copolymer containing about 0.1% to 5% of an acrylamide type monomer, for example, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, or mixtures thereof. Suitably, the binder composition comprises about 25% to 90% by weight of the urea-formaldehye resin and about 10% to 75% by weight of the modified styrene-butadiene latex copolymer. Preferably, it consists of about 50% to 85% of the urea-formaldehyde and about 15% to 50% of the particular styrene-butadiene latex copolymer. In the optimum mode of the invention, the ratio is about 80% of the resin and about 20% of the latex copolymer.
The styrene-butadiene latex copolymer component of the binder composition suitably may contain about 10% to 90% by weight of styrene and 90% to 10% by weight of butadiene, modified by said 0.1% to 5% by weight thereof of said acrylamide type monomer. Small amounts of other monomers, such as carboxylic acids, e.g. methacrylic, fumaric or itaconic acid, also may be present, if desired, in the styrene-butadiene copolymer.
Preferably, about 30% to 70% styrene and 70% to 30% butadiene is used; optimally the ratio is about 40% styrene to about 60% butadiene.
The acrylamide monomer preferably is present in an amount of about 1% to 4% of the styrene-butadiene content of the latex copolymer, and, optimally about 2% to 3%. The acrylamide material may be used individually or as mixtures thereof, e.g. acrylamide and N-methylolacrylamide, may be used, generally in about equal proportions.
A preferred commercial source of styrene-butadiene latex copolymer is "6200-SBR", sold by the GAF Corporation, Chattanooga, Tennessee.
The urea-formaldehyde resins of the binder composition also are commercially available materials, for example, urea-formaldehyde resins such as "S-3701-C" sold by Pacific Resins and Chemicals, Inc., Tacoma, Washington, and "PR-913-23", sold by Borden Chemical, Columbus, Ohio, may be used. These resins generally are modified with methylol groups which upon curing form methylene or ether linkages. Such methylols may include N,N'-dimethylol; dihydroxymethylolethylene; N,N'-bis(methoxymethyl), N,N'-dimethylolpropylene; 5,5-dimethyl-N,N'-dimethylolpropylene; N,N'-dimethylolethylene; N,N'-dimethylolethylene and the like.
The resin and latex copolymer components of the binder composition are quite compatible. Accordingly, they are intimately admixed in aqueous solution to form a stable emulsion which does not become gummy, or gel, even after prolonged storage, e.g. for periods of a week or longer, which is advantageous in practical commercial use of the composition.
The following examples will illustrate the invention with more particularity, but are not to be construed as limiting thereof.
EXAMPLE 1
In a typical run, about 2.7 g. (dry basis) of chopped bundles of glass fibers having a length of 1 inch and a diameter of 13 microns was dispersed with agitation in water containing 20 ppm of "Aromox DMHT," Armak Co., McCook, Illinois, at a fiber consistency of 0.02% by weight of fibers in the aqueous slurry. The dispersion then was formed into a wet glass mat by passing it onto a wire mesh with vacuum applied to remove excess water. The moisture content of the wet mat was about 40%.
A binder composition was prepared by mixing 135 g. of styrene-butadiene latex copolymer emulsion containing 2% by weight N-methylolacrylamide ("6200-SBR" GAF Corp-45% solids) and 440 g. of urea-formaldehyde resin ("S-3701-C" Pacific Resin and Chemical, Inc.-55% solids), and diluting with water to a 20% by weight solids content solution, i.e. about 4% styrene-butadiene and 16% urea-formaldehyde. The pH of the composition was 7.3.
The wet glass mat, suspended on the wire mesh, then was soaked into the thus-prepared binder composition, and excess binder removed by reapplying vacuum. The resultant wet glass mat, with binder applied, contained about 34% by weight glass fibers, 9% binder and 57% water.
The wet glass mat then was dried and cured for about 5 minutes at about 400° F. The resultant dry glass mat contained about 20% by weight binder; its basis weight was 100 g./m 2 .
The physical properties of the finished glass mat are given below:
______________________________________Tensile Strength* N/50mm______________________________________(a) at room temp. 430(b) at 400° F. 356(c) under wet conditions 260Flexibility** mm______________________________________mandrel diameter 100______________________________________ *Instron Tensile Tester 50 mm side mat strips with crosshead speed of 13 mm/min. and jaw span of 170 mm. **A strip of mat was wrapped around mandrels of different diameters. The onset of creasing or buckling of the sample was noted at the given diameter of the mandrel.
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A glass fiber mat having excellent tensile strength and flexibility is provided herein. The mat includes a plurality of glass fibers and a binder therefor which is characterized by comprising about 25% to 90% by weight of a urea-formaldehyde resin and about 10% to 75% by weight of a styrene-butadiene latex copolymer containing about 0.1% to 5% by weight of an acrylamide type monomer.
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FIELD OF THE INVENTION
The present invention relates to a process for reducing the level of chloride in a chlorosilane direct process residue hydrolyzed substrate. Particularly, the invention relates to a process for reducing the level of chloride to less than 0.5% by weight on a dry basis.
BACKGROUND OF THE INVENTION
The manufacture of silicone products generates residue that can present serious problems in its safe and environmentally acceptable disposal. A variety of methods are known for treating chlorosilane direct process residue. However, there is a persistent high level of chloride in the treated chlorosilane residue.
Methods for reducing the level of chloride in chlorosilane residue are also known. However, the chloride level of treated residue is still too high limiting or preventing the use of residue in cement kilns. Additionally, smelter operations impose financial penalties for chlorosilane residues with chloride levels above 0.1%.
SUMMARY OF THE INVENTION
In accordance with one aspect of the invention, there is provided a process for providing a low-chloride hydrolyzate comprising contacting an acid or base hydrolyzed substrate of a chlorosilane direct process residue with nitric acid to provide a hydrolysate with a chloride content of less than about 1.8% by weight. In certain embodiment, the process of the present invention effectively reduces the level of chloride to less than 0.5% by weight. The treated chlorosilane direct process residue hydrolyzed substrate of the present invention is especially useful in cement kilns and smelter operation.
BRIEF DESCRIPTION OF THE FIGURE
FIG. 1 is a flowchart of the use of a chlorosilane direct process stream and the subsequent treatments of the chlorosilane direct process residue.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention provides a process to effectively reduce the level of chloride in the chlorosilane residue to offer an economical and environmentally sound utilization of the residue stream.
In the specification and claims herein, the following terms and expressions are to be understood as indicated herein below.
It will also be understood that any numerical range recited herein is intended to include all sub-ranges within that range and any combination of end points of said ranges or sub-ranges.
All methods described herein may be performed in any suitable order unless otherwise indicated or clearly contrary to context. The use herein of any and all examples or exemplification language (for example, such as), is intended merely to better illustrate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
It will be further understood that any compound, material or substance which is expressly or implicitly disclosed in the specification and/or recited in a claim as belonging to a group of structurally, compositionally and/or functionally related compounds, materials or substances includes individual representatives of the group and all combinations thereof.
Referring to FIG. 1 , chlorosilane direct process residue (i) can be obtained from what is commonly called the “direct process” where silicon metalloid is reacted with organochloride to produce chlorosilane direct process stream (ii) and byproduct chlorosilane direct process residue (i). For example, an organochloride such as methyl chloride is reacted with silicon metalloid to form organochlorosilanes. Chlorosilane direct process residue (i) has little or no commercial value.
Chlorosilane direct process residue (i) can include, for example, high-boiling liquids (>75° C.), distillation residues, chlorosilanes, suspended silicon powder, elevated levels of copper, zinc and tin, as well as a variety of other metals.
The major components of chlorosilane direct process residue (i) are summarized in Table 1. These compositions are considered typical for by-product streams, but considerable batch to batch variation can exist. The liquid portion of the residue may include numerous high boiling multi-functional alkylchlorosilanes, alkylchlorocarbosilanes, alkylchlorosiloxanes and alkylchlorooligosilanes, where the alkyl substituent is predominantly methyl, although others such as ethyl, propyl, may be present. Hydrocarbons and other species may also be present in varying concentrations, but usually at low levels.
TABLE 1
Major Components of Chlorosilane
Direct Process Residue (i)
Components
1,1,2-trichloro-1,2,2-trimethyldisilane
1,2-dimethyl-1,1,2,2-tetrachlorodisilane
1,2-dichloro-1,1,2,2-tetramethyldisilane
chloropentamethyldisilane
1,3-dichloro-1,1,3,3-tetramethylcarbodisilane
1,1,3-trichloro-1,3,3-trimethylcarbodisilane
1,3-dimethyl-1,1,3,3-tetrachlorocarbodisilane
1,3-dimethyl-1,1,3,3-tetrachlorodisiloxane
1,3-dichloro-1,1,3,3-tetramethyldisiloxane
1,1,3-trichloro-1,3,3-trimethyldisiloxane
dichlorodimethylsilane
methyltrichlorosilane
dichloroethylmethylsilane
R(CH 3 )SiCl 2 + R(CH 3 ) 2 SiCl, wherein R is
ethyl, propyl, butyl, pentyl or hexyl
Solids
Al
Fe
Zn
Cu
Cl
The hydrolysis of chlorosilane direct process residue (i) can be carried out in an acidic or basic medium to produce chlorosilane direct process residue hydrolyzed substrate (iii).
In one embodiment, the acidic aqueous medium comprises an acid selected from HCl and/or HNO 3 .
In another embodiment, the basic aqueous medium comprises a base selected from the group consisting of calcium hydroxide, calcium oxide, sodium oxide, sodium hydroxide, potassium oxide, potassium hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium bicarbonate, sodium carbonate, sodium bicarbonate, magnesium carbonate, magnesium bicarbonate and combinations thereof.
In one specific embodiment, the process of reducing the level of chloride in chlorosilane direct process residue hydrolyzed substrate (iii) comprises contacting substrate (iii) with nitric acid for a time sufficient to reduce the chloride content to less than 1.8% by weight.
The amount of nitric acid to substrate (iii) is in the range of from 0.1:1 to 10:1 by weight to chlorosilane direct process residue hydrolyzed substrate (iii) on a dry basis, more specifically of from 1:1 to 10:1 by weight to chlorosilane direct process residue hydrolyzed substrate and most specifically of from 1:1 to 6:1 by weight to chlorosilane direct process residue hydrolyzed substrate (iii). The concentration of nitric acid is in the range of from 0.1% to 30% by weight, more specifically of from 1% to 20% by weight, and most specifically of from 1% to 10% by weight. Percent of dry solids is determined by placing a one gram sample of wet substrate (iii) in a 150° C. oven for 0.75 hours and comparing, the weight remaining after heating. The water content is typically about 50% for the total weight of the substrates.
The nitric acid is in contact with chlorosilane direct process residue hydrolyzed substrate (iii) for 1 to 6 hours, more specifically of from 1-3 hours, and most specifically of from 1-1.5 hours. The nitric acid is in contact with chlorosilane direct process residue hydrolyzed substrate (iii) at the temperature in the range of from 70 to 110° C., more specifically of from 80 to 100° C., and most specifically of from 80 to 90° C.
In certain embodiments, the process further comprises washing the acid or base hydrolyzed substrate with water to provide a hydrolyzate with an about 40% reduction in the level of chloride prior to contacting with nitric acid.
The amount of water employed is in the range of from 1:1 to 1000:1 by weight to chlorosilane direct process residue hydrolyzed substrate more specifically of from 1:1 to 500:1 by weight to chlorosilane direct process residue hydrolyzed substrate (iii), and most specifically of from 10:1 to 100:1 by weight to chlorosilane direct process residue hydrolyzed substrate (iii).
Without being bound by theory, it is believed that the nitric acid oxidizes the silicon-containing backbone of chlorosilane direct process residue hydrolyzed substrate (iii), thereby exposing the residual chemically-bound or physically-constrained chloride to water to aid in a more complete hydrolysis. Evidence of NO 2 and other reduced forms of HNO 3 as byproducts indicates that the oxidation reaction is occurring.
Various features of the invention are illustrated by the examples presented below.
Examples 1-15
Base hydrolyzed chlorosilane direct process residue substrates #1-#4 (BHS #1-#4) and acid hydrolyzed chlorosilane direct process residue substrates #1 and #2 (AHS #1 and #2) that contain different initial amounts of chloride are tested. The substrates were washed by stirring the wet hydrolyzed product with 100-fold weight of deionized water for one hour, filtering and an drying.
Example 1
A 100-mL 2-necked round bottom flask equipped with a magnetic stirbar, condenser, and thermocouple was charged with 9.2 grams of wet (50.5% solids; 4.6 grams of dry) (washed) base hydrolyzed substrate (BHS #1) and 46 grams of 10% nitric acid. The contents of the flask were heated to reflux (101° C.). At 48° C. the solids appeared to have foamed to twice the original size and at 87° C. a brown vapor of NO 2 was seen in the flask and condenser. Within 1½ hrs the NO 2 had dissipated and the reaction was cooled. The solid was filtered and the filtrate collected for chloride analysis. The solid was then washed with water until the pH of the filtrate was 7. The chloride level of the dried solid was measured by a sodium/potassium carbonate fusion followed by a silver nitrate titration and was found to be 0.29% (83% decrease) from the original value.
Examples 2-5
Examples 2-5 are conducted in similar manner as example 1 using base hydrolyzed substrate (BHS #1) and different treating conditions.
Example 6
A 100-mL 2-necked round bottom flask equipped with a magnetic stirbar, condenser, and thermocouple was charged with 4.88 grams of wet (50.5% solids; 2.46 grams of dry) (washed) base hydrolyzed substrate (BIB #1), 0.92 grams of CaCl 2 .H 2 O (0.24 grams chloride) and 24.6 grams of 10% nitric acid. The chloride of the substrate was now 13.0%, consistent with many unwashed substrates. The contents of the flask were heated to 91° C. At 87° C. a brown vapor of NO 2 was seen in the flask and condenser. Within 2 hrs the NO 2 had dissipated and the reaction was cooled. The solid was filtered and the filtrate collected for chloride analysis. The solid was then washed with water until the pH of the filtrate was 7. The chloride level of the dried solid was measured by a sodium/potassium carbonate fusion followed by a silver nitrate titration and was found to be 1.03% (92% decrease) from the original value.
Examples 7-15
Examples 7-15 are conducted in similar manner as example 1 using different starting substrate and/or treating conditions. Table 2 summarizes the conditions and results of chloride reduction treatment.
TABLE 2
Results of Post Treatments
Chloride
Chloride
Post
Chloride
Water
Water:
post-
Nitric Acid
Acid:
HNO 3
Example
Substrate
Initial
Wash
Substrate
wash
Concentration
Substrate
Treatment
1
BHS #1
9.7%
1 hour
3.5:1
3.2%
10%
1:1
0.29%
2
BHS #1
9.7%
1 hour
3.5:1
3.2%
10%
6:1
0.13%
3
BHS #1
9.7%
1 hour
3.5:1
3.2%
10%
0.5:1
0.61%
4
BHS #1
9.7%
1 hour
3.5:1
3.2%
1%
0.5:1
0.61%
5
BHS #1
9.7%
1 hour
3.5:1
3.2%
1%
0.3:1
0.65%
6
BHS #1 +
9.7%
n/a
n/a
13.0%
10%
1:1
1.00%
CaCl 2
7
BHS #2
8.8%
1 hour
100:1
5.2%
10%
1:1
0.91%
no fines
8
BHS #3
12.0%
not
not
12.0%
10%
1:1
1.00%
washed
washed
9
BHS #4
1.0%
10%
6:1
0.14%
10
BHS #4
5.6%
1 hour
100:1
1.0%
10%
3:1
0.16%
11
BHS #4
5.6%
1 hour
100:1
1.0%
10%
1:1
0.21%
12
BHS #4
5.6%
1 hour
100:1
1.0%
10%
0.5:1
0.25%
13
BHS #4
5.6%
1 hour
100:1
1.0%
1%
0.1:1
0.49%
14
AHS #1-
13.1%
1 hour
100:1
7.8%
10%
1:1
1.8%
no fines
15
AHS #2-
—
15 min
400:1
—
10%
1:1
0.7%
no fines
As can be seen from Table 2, the levels of chloride in the treated substrates are significantly reduced, mostly to less than 0.5%, even to less than 0.25%.
Headspace Analysis: In a separate experiment several hydrolyzed substrates were treated with 10% HO in 20 mL crimped-top vials suitable for headspace GC analysis. They were heated to 90° C. for one hour. Injection onto an Agilent GS-GASPRO (60 m×0.32 mm) GC column with electron ionization (70 eV) detection indicated the presence of NO, N 2 O and CO 2 for the substrates heated in the presence of an inert (nitrogen) environment. In an air environment, NO was not seen presumably due to oxidation to NO 2 which followed the same fate as in the experiments run in a nitrogen environment. The lack of NO 2 was explained by the immediate conversion of NO 2 to HNO 3 in the presence of water. Chlorine (Cl 2 ) was not observed.
Treatment of Model Compounds with HNO 3 : Three compounds containing possible moieties in the hydrolyzed substrate were treated at 90° C. with 10% HNO 3 for one hour. The treated compounds and the headspace were analyzed by gas chromatography-mass spectral analysis spectrometry. The headspace analysis showed different results for the three compounds. N 2 O and CO 2 were observed for both the bis(trimethylsilyl)methane and hexamethyldisilane indicative of reduction of the nitric acid and oxidation (with bond breakage) of a carbon moiety. Bis(trimethylsilyl)methane had lower levels of N 2 O and CO 2 in the headspace than the hexamethyldisilane (250× and 30× lower respectively). GCMS analysis of the oxidized products corroborates the carbon-silicon and silicon-silicon bond breakage with the evidence of siloxanes for both substrates. There was no evidence of the nitric acid removing the chloromethyl group in either the head space or in the substrate analysis. These data indicate the possible mechanism by which nitric acid oxidizes the hydrolyzate backbone to expose unreacted chlorosilane. Table 3 shows the results of the experiments with model compounds.
TABLE 3
GC Results of Nitric Acid Treatment of Model Compounds
Headspace
Model Compound
GC Analysis
GCMS of Substrate
Chloromethylpentmethyl-
no measurable
loss of MM; composed
disiloxane
peaks
of M′ and MM′ from SM
Bis(trimethylsilyl)methane
very low levels of
MM, Hexamethyldisilane,
N 2 O and CO 2
Bis(trimethylsilyl)ethane
Hexamethyldisilane
N 2 O and CO 2
MM, MDM, MD 2 M,
TMSO-pentamethyldisilane
As a comparative example, washed BHS #1 was also treated with sulfuric acid, instead of nitric acid. The level of chloride was only reduced to 1.3% after the treatment.
TABLE 4
Comparison of Nitric Acid and Sulfuric Acid
Chloride
Chloride
Post
Chloride
Water
Water:
post-
Nitric Acid
Acid:
HNO3
Substrate
Initial
Wash
Substrate
wash
Concentration
Substrate
Treatment
Example 1
BHS #1
9.7%
1 hour
3.5:1
3.2%
10% HNO 3
6:1
0.13%
Comparson 1
BHS #1
9.7%
1 how
3.5:1
3.2%
0% HNO 3
6:1
1.3%
These examples are to be construed as exemplary in nature only and are not intended in any way to limit the appended claims. It is contemplated that a person having ordinary skill in the art would be able to produce obvious variations of the subject matter and disclosures herein contained that would be by reason of such ordinary skill within the literal or equitable scope of the appended claims.
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The present invention relates to a process for providing a low-chloride hydrolyzate comprising contacting an acid or base hydrolyzed substrate of a chlorosilane direct process residue with nitric acid to provide a hydrolyzate with a chloride content of less than about 1.8% by weight. The process of present invention is especially useful in cement kilns and smelter operation.
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RELATED APPLICATIONS
[0001] This application is a Continuation-in Part Application of U.S. application Ser. No. 09/253,983, filed Nov. 18, 1998, which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] This invention relates generally to an axially oriented optical system and more particularly to a system using a radial rotating light beam for scanning a medium mounted on a fixed cylindrical member.
BACKGROUND OF THE INVENTION
[0003] Previously, scanners of X-ray exposed phosphor plates performed their function on a flat-bed or the external surface of a rotating drum. These systems have problems that increase the cost and reduce the quality of the X-ray image. The undesirable results obtained with a flat-bed or rotating drum system are caused by the continuous changing of the angles and distances of the light beam paths used for stimulating the phosphor of the X-ray exposed phosphor plates. Also, the collection of the stimulated light is performed with a different path and angle for each position on the phosphor plate, thereby requiring complicated, expensive compensation with a resultant reduction in quality. Additionally, the complications with attendant increases in cost are exacerbated when existing systems for supporting the phosphor plates do not maintain a fixed positioning during the scanning procedure.
[0004] Apparatus for radiation image read-out are known and are described, for example, in U.S. Pat. Nos. 4,886,968 and 5,396,081.
[0005] An optical system for an internal drum readout apparatus using a radial rotating light beam, which provides for minimizing distortion together with a reduction of cost and complexity cannot be found in the art.
[0006] Neither the prior art devices nor contemplated solutions for their deficiencies are capable of resulting in a digitizer apparatus providing a combination of reduction in cost with an increase in accuracy and quality.
SUMMARY OF THE INVENTION
[0007] In view of the aforementioned drawbacks of the conventional scanner systems, this invention provides a scanning system with a novel on-axis optical system to minimize distortion and avoid complex compensation introduced by currently used arrangements, while at the same time achieving cost reduction.
[0008] In addition, a light beam scanning system for digitizing X-ray exposed phosphor plates for storage and/or image display is provided.
[0009] There is thus provided, in accordance with a preferred embodiment of the present invention, a scanning apparatus, which includes a medium attached to a surface of a fixed, hollow cylindrical segment, the fixed, hollow cylindrical segment having a first longitudinal axis, a rotational radial laser beam rotating around the first longitudinal axis and arranged to scan said medium, and a light sensitive detector having a light acceptance direction along a second axis coinciding with the first longitudinal axis of the cylindrical segment.
[0010] Further, in accordance with a preferred embodiment of the present invention, the apparatus further includes at least one reflector for directing the beam towards the medium. The apparatus further includes transport apparatus for rotating and translating the laser beam.
[0011] Further, in accordance with a preferred embodiment of the present invention, the medium is a phosphor plate.
[0012] Further, in accordance with a preferred embodiment of the present invention, the reflecting unit may be a slanted mirror fixedly mounted for movement with the transport apparatus. A hole may be formed in the center of the slanted mirror for directing the laser beam therethrough. Furthermore, in accordance with a preferred embodiment of the present invention, the slanted mirror forms an angle in the range of 30-60 degrees relative to the longitudinal axis. The slanted mirror may be concave.
[0013] Further, in accordance with a preferred embodiment of the present invention, the apparatus further includes a rotating shaft, the laser beam being attached to the rotating shaft, wherein power is directed via slip rings attached to the rotating shaft.
[0014] Further, in accordance with a preferred embodiment of the present invention, the apparatus further includes a hollow shaft providing a beam path from the light source to the hole, and a mirror fixedly mounted in the hole for movement with the transport and rotated with the shaft for presentation of the beam along a radial from the axis to the medium.
[0015] Also, in accordance with a preferred embodiment of the present invention, the apparatus further includes a Fresnel lens mounted within the hollow cylindrical segment and proximate to the concave interior of the hollow cylindrical segment. The Fresnel lens has a longitudinal axis perpendicular to the longitudinal axis of the hollow cylindrical segment and the Fresnel lens has a hole formed in the center thereof to allow the beam and the receiving light emanating from the medium to pass through undisturbed.
[0016] Further, in accordance with a preferred embodiment of the present invention, the light emanating from the medium is refracted by the Fresnel lens the refracted light being reflected by the slanted mirror through the detector.
[0017] In addition, in accordance with a preferred embodiment of the present invention, there is also provided a scanning method. The method includes:
[0018] attaching a medium to a surface of a fixed, hollow cylindrical segment, having a first longitudinal axis;
[0019] arranging a rotational radial laser to rotate around the first longitudinal axis beam to scan the medium; and
[0020] detecting the rays reflected from the medium along a second axis, said second axis coinciding with the first longitudinal axis.
[0021] These and other advantages, features and objects will become more apparent from the following description taken in connection with the illustrative embodiments in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] An axially oriented optical system in accordance with the present invention will be described infra with respect to the accompanying drawings, which are not drawn to scale, of which:
[0023] [0023]FIG. 1 is a schematic representation of one embodiment or arrangement of the optical system of this invention;
[0024] [0024]FIG. 2 is a schematic representation of an alternative arrangement of the optical system of this invention;
[0025] [0025]FIG. 3 is a schematic view of the embodiment of FIG. 2 with a rotative drive and encoding system that is applicable to all embodiments;
[0026] [0026]FIGS. 4A and 4B are schematic representations of a phosphor plate or film with a representation of the scan pattern thereon and a representation of a system for axial movement of the optical system, respectively;
[0027] [0027]FIG. 5 is a block diagram of the control system for the operation of the optical system of this invention;
[0028] [0028]FIG. 6 is an isometric view of the optical system of a scanning apparatus constructed and operative in accordance with a further embodiment of the invention;
[0029] [0029]FIG. 7 is a schematic representation of the arrangement of the optical system of FIG. 6;
[0030] [0030]FIG. 8 is a detailed schematic representation of the Fresnel lens arrangement used in the embodiment of FIG. 6 and
[0031] [0031]FIG. 9 which is a schematic representation of an alternative arrangement of the optical system of this invention.
DESCRIPTION OF EMBODIMENTS
[0032] Reference is now made to FIG. 1, which illustrates an embodiment of the present invention in which a system for scanning a medium mounted on a fixed cylindrical member is shown The scanning apparatus 10 comprises a hollow cylinder 12 on the internal face of which is mounted a scanning medium 14 . The light beam for scanning is rotated, as will be described hereinbelow, against the fixed hollow cylinder 12 .
[0033] [0033]FIG. 1 shows a portion or segment of hollow cylinder 12 for shaping a medium, such as a phosphor plate 14 , on the internal face of the cylinder for a scanning procedure. The longitudinal, central axis 16 of the portion of the cylinder 12 forms the main axis of the optical system of the scanning apparatus 10 . Thus, when the phosphor plate 14 is located against and conforms to the internal cylindrical shape of the hollow, cylinder segment 12 , the axis of the phosphor plate 14 is collinear with axis 16 . As is usual with apparatus of this type, the phosphor plate is required to be enclosed to eliminate light other than that required for its function. Since the enclosure is not part of the inventive concept of this invention, it is not shown in the interest of clarity.
[0034] The optical system of the scanning apparatus 10 includes a focused laser light source 18 having its peak wavelength at a suitable level (preferably approximately 635 nm) in order to stimulate the phosphor plate 14 and a light sensitive detector 20 , for example, a photomultiplier tube for converting the stimulated light with a peak wavelength of 390 nm emitted from the phosphor plate 14 into electric signals. The laser beam is directed, as shown by the arrowed line, at a small mirror 22 located and affixed at the center of the detector 20 , for example, by gluing it to a filter 24 of the Schott type that blocks the laser beam wavelength and allows only passage of the 390 nm stimulated light emitted from the phosphor plate 14 . The small mirror 22 directs the laser light source beam 90 degrees along the axis 16 of the cylinder segment 12 to the center of a rotating mirror 26 , whose rotation is about the axis 16 , and is angled with respect to axis 16 to direct the laser beam along the radius from axis 16 to the phosphor plate 14 on the interior of cylinder 12 . Of course, if small lasers were used, they could be mounted on the filter 24 in place of small mirror 22 . The optimal angle of the rotating mirror 26 depends on the type of mirror being used. For example, for a flat rotating mirror shown in the embodiment of FIG. 1, having the dual function of reflecting both the stimulating light and stimulated light, the angle should be preferably be 45 degrees.
[0035] The light source 18 , filter 24 with small mirror 22 and detector 20 remain fixed against rotation, while angled or slanted mirror 26 and its shaft 28 are rotated together. At the point of stimulation of the phosphor plate 14 , the stimulated light at 390 nm is directed, as shown by the arrowed beam lines, back toward the slanted, rotating mirror 26 for passage through the filter 24 to the detector 20 for conversion to an electronic signal for digitalization, as will later be described.
[0036] The optical items 18 through 28 are to be moved in translation so that the beam from the light source traverses the fixed phosphor plate 14 , for example, in the direction of the arrows below the figure while the focused beam either creates arcs of circles or, if desired, a helix during the traverse.
[0037] [0037]FIG. 2 illustrates a further embodiment of the present invention. FIG. 2 schematically represents an alternative arrangement whereby the light source 18 lies on axis 16 of shaft 28 , which is collinear with the hollow cylinder portion 12 , which forms the support for phosphor plate 14 . In this application the shaft is hollow to allow the passage of the beam therethrough, and the angled rotating mirror 26 has a hole 30 at its center for allowing the passage of the beam to small mirror 22 , which is mounted within the hole. Mirror 22 need not be the exact shape as illustrated. For example, it could be a penta prism or other optic arrangement that will perform the same result as the small mirror 22 .
[0038] In this embodiment, the angle of the rotating mirror 26 may be adjusted to suit the type of mirror being used. For instance, if rotating mirror is flat, the mirror may be angled at any suitable angle depending on the size of the mirror and preferably is within the range of 30-60 degrees. Alternatively, rotating mirror 26 may be an alternative shape, such as concave.
[0039] [0039]FIG. 3A illustrates the embodiment of FIG. 2 with the addition of a conventional motor mechanism comprising rotor 32 , mounted for rotation with shaft 28 , and a fixed stator 34 . In the embodiments of FIGS. 1, 2 and 3 the filter 24 and detector 20 do not rotate. A conventional on-axis optical encoder system 36 is also mounted with respect to the motor for providing feedback pulses to stabilize rotation speed and for determining the beam positioning.
[0040] Reference is now made to FIG. 3B which illustrates a further embodiment of the present invention, which is similar to the embodiments of FIGS. 2 and 3A, except that mirror 26 is omitted. In this embodiment, the beam passes through the hollow shaft 28 to the small mirror 22 , which is mounted, as shown in FIG. 3A, at the end of the chamfered hollow shaft. The beam is reflected (B 1 ) at right angles towards the scanning medium 14 . Some of the stimulated light, illustrated by the angle between beams B 2 and B 3 , is directed back towards the detector 20 (via filter 24 ). By altering the size of the detector the amount of collected light may be varied.
[0041] In a further alternative embodiment, at least one reflector may be optionally added, as illustrated, for exemplary purposes only, by curved reflectors 152 . As will be appreciated by persons knowledgeable in the art, the shape, size and number of reflectors may be altered so as to direct the desired pre-determined amount of light towards detector 20 .
[0042] [0042]FIGS. 4A and 4B are illustrations of a phosphor plate film 14 and the mechanism for traversing the film, respectively, during scanning whereby the rotation of the optical system 10 produces a scan path indicated by the parallel lines of FIG. 4A.
[0043] It is an advantage of the present invention that by using a fixed cylinder, the scanning medium can be mechanically fed, in contrast to scanning systems using rotating drums which require the manual attachment of the scanning medium to the face of the drum.
[0044] [0044]FIG. 4A additionally utilizes the parallel lines for depicting a chosen distance, in this case 100 micron spacing, from the previous scan. FIG. 4B illustrates the film 14 of FIG. 4A in its position in the apparatus with the hollow, cylindrical portion 12 removed for clarity. The parallel lines of the film 14 in FIG. 4B are illustrative only of the cylindrical shape of the film 14 when it is within the cylinder 12 .
[0045] Schematically illustrated in FIG. 4B is the means for effecting the axial path spacing of the optical system as disclosed in FIGS. 2 and 3. A support structure or transport 38 , as seen in FIG. 4B is provided with bearings, not shown, for those parts of the optical system 10 , which are required to be rotated, as is conventional in the field of mechanical design. The means for movement of the optical system of this invention along its axis 16 can be selected from a variety of options, only one of which is illustrated. The support structure 38 has a pair of rods 40 for stabilization, guidance and maintenance of direction of the transport 38 in a straight line. A threaded member 42 , fixed with respect to any axial movement, is engaged with mating threads in the support structure 38 for its axial movement in order to obtain the traversing for scanning of the focused spot with respect to the film 14 . A linear stepping motor 44 , schematically shown, provides the rotation of the threaded member to accurately space the separate scans across film 14 . Although the light source 18 is only schematically depicted, it is shown as attached to the support structure 38 .
[0046] [0046]FIG. 5 is a block diagram illustrating the control of the apparatus thus far described. The DC motor 32 , 34 the encoder 36 and the 45 degree angled mirror 26 are connected for simultaneous rotary operation as shown in FIG. 3, since they all are on the same shaft 28 . The DC motor has a rotation motor control 46 , which in turn is connected for cooperation with encoder 36 . The stepper motor 44 of FIG. 4B has a linear stepper control 50 , which is also connected with the output from encoder 36 . The output from the detector, photomultiplier (PMT) 20 and that of encoder 36 provide input to the analog processing unit 48 , which provides its output to an analog to digital converter 52 for connection with a PC computer 54 .
[0047] Operation
[0048] Operation of the apparatus of this invention as a readout device involves the presentation of an X-ray exposed phosphor plate or film 14 to the interior of a fixed portion of a hollow cylinder 12 to which the phosphor plate is pressed firmly to conform to the circular configuration of the cylindrical portion without any motion ensuing while the scanning or reading is being effected. Apparatus for this purpose is well known.
[0049] The scanning operation involves the mounting of a light source such as a 635 nm laser 18 and a spinning mirror surface 26 that is angled at a suitable angle (depending on the type of rotating mirror used, as described hereinabove with respect to FIGS. 1 - 4 ) with respect to its axis of rotation 16 , which is collinear with the central axis of the film 14 and its support 12 . In order to bend the light beam 90 degrees and to rotate it with the mirror, the beam has to be reflected from the center of rotation of the mirror 26 . The beam then forms a rotating spot on the film that follows a path of a portion of a circle on the phosphor plate 14 . When the laser beam starts from between the rotating mirror 26 and the filter 24 , no hole in the rotating mirror 26 is required. Whereas the laser 18 , when it is behind the rotating mirror 26 , requires a hole in its center with a small mirror 22 therein to supply the directing of the beam perpendicular to a spot on the film.
[0050] The support structure or transport 38 contains an optical system which includes light source 18 , spinning mirror 26 and small mirror 22 , when required, and its movement to traverse the phosphor plate 14 is coordinated with the rotative movement of the spot such that, when the spot reaches the end of the film 14 , the cart then moves the distance of one pixel for the next scan. The spot is chosen to be, for example, 100 micron in diameter thereby forming a circular line 100 micron wide; therefore the transport 38 moves the optic system a distance of 100 micron for the next scan.
[0051] More specifically as a readout device, using phosphor plates, the following operation is effected.
[0052] Readout of a previously X-ray exposed phosphor plate is obtained by the 635 nm laser 18 stimulating the crystal layer of the phosphor plate causing it to radiate light at 390 nm as the beam spot on the film makes its scan. The rotating mirror 26 receive the emitted light around its outer periphery for reflection onto the Schott type filter 24 which is transparent to 390 nm while absorbing 635 nm light. The light passing through filter 24 is applied to detector photomultiplier tube 20 , which converts the light to an electric signal that is amplified, gated to represent one pixel on the circular scan and converted to a digital number representing the brightness of the pixel. The filter 24 and detector 20 are also mounted on the transport 38 .
[0053] The encoder 36 stabilizes the motor 32 , 34 by feed back pulses which also control the gating of the output of the detector photomultiplier 20 to define time samples equivalent to 100 micro-meters in distance. The pulses are also used for defining, at any point in time during the scan, the angular position of rotating mirror 26 and the angle of the stimulated emission from the phosphor plate in order to activate the stepper motor for the next parallel scan. If a helical scan is required, the change would be within the skill of an ordinary technician.
[0054] Since the paths of the stimulating light and the stimulated light for all points are identical, and since the hitting and emitting angles for all scan points are perpendicular and identical, and since the scanning speed is constant and easy to maintain, there is no need for correction algorithms or compensation. Digitization resulting from the scanning action results in the ability to replicate and/or store the data from the film.
[0055] Although the invention has been illustrated in the accompanying drawings and described in the foregoing specification in terms of preferred embodiments, the invention is not limited to these embodiments. It will be apparent to those skilled in this art that certain changes, modifications and substitutions can be made without departing from the true spirit and scope of the appended claims. For example, the laser light source 18 could be mounted on the filter 24 thereby eliminating the need for small mirror 22 . Furthermore, the teachings of this invention are applicable to other than a phosphor plate medium.
[0056] Reference is now made to FIGS. 6 - 8 which illustrate a further embodiment of the scanning apparatus, generally designated 100 , constructed and operative in accordance therewith. FIG. 6 shows a portion or segment of a hollow cylinder 102 (similar to hollow cylinder 12 described hereinabove). FIG. 7 is a schematic representation of the arrangement of the optical system 100 and FIG. 8 is a detailed representation of the optical arrangement.
[0057] The optical system 100 is similar to the optical system of scanning apparatus 10 described hereinabove with respect to FIGS. 1 - 5 . Elements having similar functions as previous embodiments are similarly designated and will not be further described.
[0058] The optical system 100 comprises a hollow cylinder 102 for shaping the phosphor plate medium 14 (or similar) to be scanned on the internal face of the cylinder and the optical system shown in FIG. 3. The optical system includes a light source 18 which lies on the axis 16 of a hollow shaft 28 . The hollow shaft, which is collinear with the hollow cylinder portion 102 , allows the beam to pass through The angled mirror 26 has a hole 30 at its center with a small mirror 22 mounted within the hole.
[0059] In addition, optical system 100 further comprises a Fresnel lens 104 , which is inserted on the coaxial cylinder 102 , as shown in FIG. 8. The cylinder 102 is connected to the slanted mirror system and rotates with it, The Fresnel lens 104 is placed on the cylinder so that its longitudinal axis 106 is parallel with the central axis 16 of the laser beam.
[0060] As previously described with respect to the embodiments of FIGS. 1 - 5 (that is without the Fresnel lens 104 ), the light collection is based on a cone of stimulated light with its source at the impinging point 105 of the laser. The base of the cone is defined by the angled mirror 26 which is reflected into the detector photomultiplier (PMT) tube 20 . Alternatively, the stimulated light may be directly aimed to the PMT tube 20
[0061] In order to not to obstruct the bean of light and prevent distortions, a hole 108 is drilled through the center of the Fresnel lens 104 . The diameter of the hole 108 is configured so as to allow the same amount of stimulated light to pass through to the mirror and PMT as the previously described embodiments not having a lens, that is the lens 104 does obstruct the passage of any light. As best seen in FIG. 7, the impinging ray 110 is returned as rays 112 and 114 , which are reflected by mirror 26 as rays 116 and 118 , respectively, through filter 24 into PMT 20 .
[0062] The addition of the Fresnel lens 104 expands the angle of the cone from the impinging point 105 to the rim of the Fresnel lens 104 . As best seen in FIG. 8, the angle of stimulated light is increased from “A” to “A+2B”. Thus, additional rays, such 120 and 122 , are refracted through the rim of the Fresnel lens 104 and then reflected by mirror 26 as rays 124 and 126 , respectively, through filter 24 into PMT 20 .
[0063] Thus, in this embodiment, an additional amount of light enters the PMT 20 , the amount of light being proportional to the expanded angle (“A+2B”). The Fresnel lens 104 concentrates (or bends) the light reflected into its “ring” to the mirror. In other words, the addition of the Fresnel lens 104 allows an increased amount (2B) of light to be collected thereby improving the light collection efficiency of the system.
[0064] It will be appreciated that the invention is not limited to the use of a Fresnel lens but may be used with any other type of light collecting device.
[0065] Reference is now made to FIG. 9, which is a schematic representation of a further embodiment of the present invention. This embodiment is similar to the embodiment of FIG. 2. Elements having similar functions as previous embodiments are similarly designated and will not be further described.
[0066] In the embodiment of FIG. 9, the laser source is attached to the rotating shaft 28 via slip rings 132 (known in the art) enabling power to be fed to the light source (modulator) 18 . The laser beam is then directed through the hole 130 in mirror 26 . The rays are reflected through filter 24 into PMT 20 .
[0067] It will be further appreciated that the present invention is not limited by what has been described hereinabove and that numerous modifications, all of which fall within the scope of the present invention, exist. Rather the scope of the invention is defined by the claims, which follow:
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A scanning apparatus is provided, which includes a medium attached to a surface of a fixed, hollow cylindrical segment, the fixed, hollow cylindrical segment having a first longitudinal axis, a rotational radial laser beam rotating around the first longitudinal axis and arranged to scan said medium, and a light sensitive detector having a light acceptance direction along a second axis coinciding with the first longitudinal axis of the cylindrical segment.
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BACKGROUND OF THE INVENTION
This invention relates to fluid supplying devices equipped with peristaltic pumps, and more particularly to a fluid supplying pump by which a desired amount of fluid can be obtained.
A peristaltic pump has been extensively employed for blending or supplying reaction raw material, catalyst, coloring agent, photosensitive agent, ink, paint, paste material, resin material, oil, flux, lubricant, cosmetic material, adhesive, food material, etc., because it needs no operating pumping section in the path of fluid. Therefore, the fluid is never brought into contact with such a pumping section, which maintains the characteristic of the fluid unchanged.
In the case where only a peristaltic pump is used, an amount of fluid per unitary time delivered under pressure can be determined. However, it is difficult to discharge a desired amount of fluid.
In order to overcome this difficulty, several fluid supplying devices provided with peristaltic pumps which can discharge a desired amount of fluid have been proposed in the art.
For instance, such a device has been disclosed by Japanese Patent Application Laid-Open No. 41903/1974. In this device, a cam plate having cam sections is mounted on the drive shaft of a peristaltic pump connected to an electric motor and the cam sections are detected by a detector so that the number of cam sections thus detected is applied to a counter. When the count value of the counter reaches a value preset in a manual preset device, a switch connected to the electric motor is opened to stop the motor. As a result a predetermined amount of fluid is delivered; that is, a necessary amount of fluid can be delivered without monitoring it.
Furthermore, U.S. Pat. No. 3,277,356 discloses a fluid supplying device in which a relay is connected to an electric motor operating a peristaltic pump so that the operation (drive and stop) of the peristaltic pump is controlled by the on-off operation of the relay. Swinging pins are connected to the drive shaft which connects the peristaltic pump to the electric motor in such a manner that the pins are rotated for a predetermined distance according to the rotation of the drive shaft. In addition, a pull switch operating the relay is disposed at the position of passage of the pins in such a manner that the position of contact between the switch and the pins can be changed. Thus, a desired amount of fluid is discharged.
In a fluid supplying device disclosed in British Pat. No. 1,216,327, at least three rollers adapted to depress an elastic tube are rotated around one axis by an electric motor. A plurality of stationary contacts arranged in circular form are disposed at the positions of passage of a group of electrical sliding contacts rotated with the rollers so that the sliding contacts can easily slide. Operating signals forming binary codes are supplied to the stationary contacts and are read by the sliding contacts. The code thus read is compared with a code set in a manual digital switch. When both are coincident with each other, the motor is stopped, and a desired amount of fluid has been discharged.
However, these conventional fluid supplying devices are still disadvantageous in that it is impossible to obtain different amounts of fluid successively by a single adjustment of the setting of the device.
SUMMARY OF THE INVENTION
Accordingly, an object of this invention is to provide a fluid supplying device which has eliminated the above-described drawbacks accompanying a conventional fluid supplying device.
It is another object of this invention to provide a device simple in construction, that can discharge not only different amounts of fluid but also a predetermined amount of fluid by adjusting the setting of the device only once, and can change the amount of fluid to be discharged as desired.
A fluid supplying device according to this invention comprises: a peristaltic pump having a depression and delivery system which includes an elastic tube for receiving fluid and an assembly of depressing members for alternately constricting and relaxing the elastic tube. A drive shaft connects the depression and delivery system to an electric motor. A rotary member is provided on the drive shaft to rotate with the drive shaft and a plurality of discharge-amount transmitting devices are provided on the rotary member in such a manner that the distances between the discharge-amount transmitting device can be changed as desired. A detector is disposed at the position of passage of the discharge-amount transmitting devices for detecting the discharge-amount transmitting devices. A switch is connected between the detector and the electric motor to deenergize the motor.
An important feature of the fluid supplying device according to the invention is that the rotary member is connected to the drive shaft of the peristaltic pump to rotate with the drive shaft, a plurality of discharge-amount transmitting devices are provided on the rotary member in such a manner that the distances between the discharge-amount transmitting devices can be changed as desired. A detector for detecting the discharge-amount transmitting devices is provided at the position of passage of the discharge-amount transmitting devices and a switch is connected between the detector and the electric motor to switch off the motor.
The fluid supplying device of the invention is constructed as described above. Accordingly, if the discharge-amount transmitting devices are arranged at equal intervals and then the distance between adjacent discharge-amount transmitting device is increased to an integer multiple of the previous one, then the amount of fluid discharged is increased to an integer multiple by this single adjustment. Furthermore, if the distances are made irregular, then different amounts of fluid are discharged successively by the adjustment. The rotary member employed in the fluid supplying device may be a circular, elliptic, triangular, polygonal, rectangular or trapezoid plate, or a rectangular paralleopiped or regular hexahedron block. Furthermore, the rotary member may be opaque or transparent.
The discharge-amount transmitting devices may be screws screwed into holes in the rotary member, or rods or plates engaged with holes such as through-holes, blind holes or groove-shaped slots formed in the rotary member. The distances between the discharge-amount transmitting devices can be changed by installing them on the rotary member or removing them therefrom or by putting them in the rotary member or putting them out of the rotary member. Furthermore, if the rotary member is optically transparent, the distances can be changed as desired by placing light shielding materials on the rotary member or removing them therefrom. If the rotary member is a disk, the discharge-amount transmitting devices may be provided on the circumferential surface or the side of the rotary member. If the rotary member is not a disk, it is suitable to place the discharge-amount transmitting devices on the side thereof.
The detector of the fluid supplying device should be selected according to the type of discharge-amount transmitting device employed. For instance, a microswitch, a limit switch, a pressure-sensitive switch, a photo sensor comprising a light emission element and a photoelectric element, or a read switch can be selectively employed as the detector.
The peristaltic pump employed in the invention may be one in which constriction and relaxation of the elastic tube are alternately carried out by the up and down movement of at least three depressing members provided in the depression and delivery system thereof. Alternatively, it may be one in which the depression and delivery system has at least two rollers which are arranged to rotate along a circular path to depress the elastic tube inserted between the circular path and the rollers. Also, it may be one in which the elastic tube is placed on a flat surface and the tube is cyclically depressed at least two roller-shaped depressing members of the depression and delivery system which are disposed along the tube.
The size and material of the elastic tube and the number of elastic tubes can be selected as required. However, in the case of pumping liquid, it is desirable to use a capillary tube 0.1 to 3.0 mm in inside diameter so that, when the electric motor is stopped, the liquid remaining between the depression and delivery system and the discharge end of the elastic tube will not flow out.
The elastic tube may be preferably made of polyethylene, polypropylene, vinyl chloride, nylon, polyester, fluoro-resin rubber, silicon rubber, or a like material.
The fluid supplying device according to the invention can be used to discharge (or pump) ink, paint such as vinyl paint, paste material, resin material, oil, flux, lubricant, cosmetic material such as manicure paint, vinyl adhesive, adhesive such as cyanoacrylate, food material such as vanilla essence, or the like.
The electric motor employed in this invention may be provided with an electronic circuit for momentarily stopping the motor.
According to another aspect of this invention, a fluid supplying device is provided in which a preset counter is connected to the above-described detector, and a switch is connected between the counter and the electric motor to switch off the motor.
In the situation where, as was described herein, the discharge-amount transmitting devices arranged at equal intervals or at irregular intervals are combined with the detector connected through the switch to the motor, an amount of fluid is discharged in correspondence to the distances between the discharge-amount transmitting devices thus adjusted. Conversely, in the case where the present counter is combined with the discharge-amount transmitting devices, an amount of fluid corresponding to the sum of the distances between the discharge-amount transmitting device, which is equal to the number preset therein, is obtained. Accordingly, it is unnecessary to increase the size of the rotary member and this results in a compact fluid supplying device. The use of the preset counter is advantageous in the case where it is required to discharge different amounts of fluid by making the distances between the discharge-amount transmitting devices non-uniform. For instance, if the number of discharge-amount transmitting devices is set to three (3) so that the first and second discharge-amount transmitting devices are separated by 60°, the second and third ones by 120°, and the third and first ones by 180°, and if it is assumed that 0.01 cc is discharged for every 60°, then with the preset counter set to "4", 0.07 cc is discharged in the first cycle, 0.08 cc is dischargd in the second cycle, 0.09 cc is discharged in the third cycle and so on when the count value of the preset counter reaches "4".
Furthermore, according to another aspect of the invention, a fluid supplying device is provided in which a preset counter is connected to the detector. A switch is connected between the preset counter and the electric motor to switch off the latter, and a preset counter change-over switch connecting the aforementioned switch to the detector is provided.
In this fluid supplying device, an amount of fluid corresponding to the distances between the discharge-amount transmitting devices or corresponding to the sum of the distances between the discharge-amount transmitting devices, which is equal to the number preset therein can be discharged by operating the change-over switch.
In addition, according to another aspect of the invention, a fluid supplying device is provided in which a preset counter is connected to the aforementioned detector. A switch is connected between the counter and the motor to switch off the latter, and a change-over switch is provided between an electric source and a circuit including a preset counter change-over switch connecting the first mentioned switch and the detector, to switch off the electric source.
With this fluid supplying device, when the change-over switch is switched to one side, the fluid is continuously discharged. When the change-over switch is switched to the other side, an amount of fluid corresponding to the distances between the discharge-amount transmitting device or corresponding to the sum of the distances between the discharge-amount transmitting devices, which is equal to the number preset therein, can be discharged.
The novel features which are considered characteristic of this invention are set forth in the appended claims. This invention itself, however, as well as other objects and advantages thereof will be best understood by reference to the following detailed description of illustrative embodiments, when read in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
FIG. 1 is a perspective view showing one example of a fluid supplying device according to this invention;
FIG. 2 is a sectional view showing the essential components of the fluid supplying device shown in FIG. 1;
FIG. 3 is a sectional view taken along line A--A in FIG. 1;
FIG. 4 shows an electrical circuit of the device shown in FIGS. 1 through 3;
FIGS. 5 through 14 are perspective views and sectional views showing various examples of a rotary member employed in the invention, on which discharge-amount transmitting devices are provided;
FIG. 15 is a perspective view showing another example of the fluid supplying device according to the invention;
FIG. 16 is a partial circuit diagram of the device shown in FIG. 15; and
FIGS. 17 and 18 are partial circuit diagrams which are to be connected to terminals T 1 and T 2 of the circuit in FIG. 15.
DESCRIPTION OF THE PREFERRED EMBODIMENT
A first example of a fluid supplying device according to this invention is as shown in FIGS. 1 through 6. In this device, a circular opening 2, an indication lamp 3 and a toggle switch 4 to power the device are provided on the front plate of a housing 1. In addition, a foot switch 5 is connected to a circuit (described later) provided in the housing 1. An annular case 6 is fitted into the circular opening 2 and a frame 7 is disposed inside the housing 1 in such a manner that it surrounds the peripheral edge of the bottom of the annular case 6.
The upper portion of the frame 7 is provided with a slit 8 (FIG. 2) and a protrusion 9 extended therefrom. The lower portion or bottom of the frame is fixedly secured to the bottom wall of the housing 1 with screws. The openings of the annular case 6 are covered with a bottom plate 11 with a hole, and a cover plate 12 with a hole, respectively. Blades 11 and 12 serve as bearings of a drive shaft 10.
A disk 13 is mounted on the drive shaft 10 pivotally supported by the bottom plate 11 and the cover plate 12. The disk 13 has six pins 14 embedded at equal intervals on the coaxial circle of the drive shaft 10. Six depressing members 15, or cylindrical rollers, are mounted on the pins 14 so that they are rotable without making contact with one another.
Furthermore, the depressing members 15 are arranged so that they revolve around the drive shaft 10 when the disk 13 is rotated. Tube holding holes 16 are provided at diametrically opposite portions of the annular case 6. An elastic tube 17 larger in diameter than the tube holding holes 16 is inserted into the tube holding holes 16 under pressure in such a manner that it is press-fitted between the depressing member 15 and the inner wall of the annular case 6. One of both end portions of the elastic tube 17 is employed as a fluid receiving end 18, while the other end portion is employed as a fluid discharging end 19. A gear 20 is mounted on the drive shaft 10, and a disk-shaped rotary member 21 is secured to the gear 20 with screws. As a result, the drive shaft 10, the gear 20 and the rotary member 21 form one unit.
Six discharge-amount transmitting devices 22 (FIG. 3) are provided at equal intervals on the circumferential surface of the rotary member 21, which is coaxial circle of the drive shaft 10. A detector 23 which comprises a microswitch and operates in association with the discharge-amount transmitting devices is fixedly secured to a side of the protrusion 9 in the frame 7. It is secured so that it protrudes through the slit 8 and it can be brought into contact with the discharge-amount transmitting devices 22. The gear 20 is engaged with a gear 26 which is connected to the drive shaft of a gear head 25 connected to an electric motor 24.
The indication lamp 3, the toggle switch 4, the foot switch 5, the detector 23, and the motor 24 are connected as shown in FIG. 4. A relay RA has contact means ra-1 and ra-2. Relay RA and the contact means ra-1 and ra-2 form a switch 40.
The discharge-amount transmitting devices 22 can be obtained by inserting small elements 28, such as screws, into holes 27 provided in the circumferential surface of the disk as shown in FIGS. 5 and 6. Accordingly, the number of discharge-amount transmitting devices can be adjusted by the installation or removal of the small elements 28.
In the case where a fluid is discharged, first the number of discharge-amount transmitting devices 22 is set, and the detector 23 is brought into contact with one small element 28. Then, the toggle switch 4 is closed. As a result, the relay RA is self-held to open the contact means ra-2. Thereafter, the foot switch 5 is depressed and as a result the self-holding operation of the relay RA is released to close the contact means ra-2. The motor 24 is therefore energized to rotate the drive shaft 10.
As the drive shaft 10 is rotated, the disk 13 secured to the drive shaft 10 is rotated, and the depressing members 15 provided on the pins 14 on the disk 13 revolve around the drive shaft 10. As the depressing members 15 revolve, the elastic tube 17 inserted between the assembly of the depressing members 15 and the inner wall of the annular case 6 is depressed and alternately released. Hence, the fluid is introduced into the fluid receiving end 18 of the tube. In this example, the motor 24 is stopped whenever the detector 23 detects each small element 28 of the rotary member 21. Accordingly, it is necessary to depress the foot switch 5 until the entire tube 17 is filled with the fluid.
When the foot switch 5 is depressed after the entire elastic tube 17 has been filled with the fluid, the detector 23 in contact with one small element 28 is brought into contact with the following small element 28 to stop the motor 14. In this operation, an amount of fluid corresponding to the distance between the first and the second small elements 28 is delivered under pressure to the fluid discharging end 19. That is, the amount of fluid mentioned is discharged out of the fluid discharging end 19. When the detector 23 makes contact with the small element 28, the relay RA is operated to close the contact means ra-1 to self-hold the relay RA. As a result, contact ra-2 is opened to stop the motor 24.
When the foot switch 5 is depressed again, the self-holding state of the relay RA is released and the contact means ra-2 is closed to operate the motor 24. Thus, similarly as in the above-described case, the fluid is discharged. If the foot switch 5 is depressed after each other small element 28 is removed from the rotary member--three small element 28 are removed therefrom--, then an amount of discharge is increased to twice that in the above-described case.
Other examples of the discharge-amount transmitting device 22 are shown in FIGS. 7 through 14. In the discharge-amount transmitting device shown in FIGS. 7 and 8, slots 29 are formed in the circumferential surface of the rotary member 21. Mating plate-shaped small elements 30 are inserted into the slots 29 thus formed. The number of small elements 30 may be obtained as desired by installing or removing them.
In the discharge-amount transmitting device shown in FIGS. 9 and 10, threaded through-holes 31 are cut in the rotary member 21, and mating small elements 32 such as threaded rods are screwed into the through-holes 31. The number of small pieces 32 can be changed by installing or removing them or by screwing the small elements 32 in or out of the threaded through-holes 31. In this case, a photo sensor is suitable as a detector to detect the through-holes from which the elements 32 have been removed.
In the discharge-amount transmitting device shown in FIGS. 11 and 12, through-holes 33 are cut in the rotary member 21 in such a manner that one opening of each through-hole 33 is larger in diameter than the other opening thereof. This is best illustrated in FIG. 12, and shouldered small pieces 34 similar in configuration to the through-holes 33 are inserted into the through-holes 33. The number of discharge-amount transmitting devices can be changed by removing the small elements 34 and by inserting them into the through-holes in a direction opposite to the previous direction.
In the example shown in FIGS. 13 and 14, a disk-shaped rotary member 21 is made of optically transparent material such as glass or transparent plastic, and small pieces 35 of adhesive tape are stuck on the surface of the rotary member 21. The number of discharge-amount transmitting devices can be changed by sticking the small pieces 35 onto the rotary member 21 or removing them therefrom. In this case, a photo sensor is employed as the detector. The small pieces 35 should be stuck on the rotary member 21 by utilizing the guide lines 36 marked thereon.
A second example of the fluid supplying device according to the invention is shown in FIGS. 15 through 18. This device is different from the first example in that a preset counter 37 is provided. In other words, in the device, the preset counter 37 typically a "Digital Counter", Type H7A-2D, manufactured by Tateishi Denki Co. is connected to a detector 23, and a switch 40 is connected between the counter and an electric motor 24. The switch 40 comprises a relay RA and its contact means ra-1, ra-2 and ra-3. A preset count change-over switch 43 (not shown in FIG. 15) is provided to connect the switch 40 to the detector 23 and a toggle switch or change-over switch 39 is provided.
The change-over switch 39 comprises switch sections 41 and 42, and the switch section 41 has its movable contact or armature connected to the motor 24. The switch section 42 functions as a power switch to a momentary operation circuit comprising a foot switch 5 and a relay RB (FIG. 17) and to a circuit comprising the preset counter 37, the detector 23, a self-holding circuit having the relay RA, and the preset counter change-over switch 43 (FIG. 18). The relay RB has its contact means rb-1 and rb-2.
(a) If a switch member 44 is turned on to trip the armatures of the change-over switch 39 to the upper contacts of T 1 and T 2 (as viewed in FIG. 16) contacts, then the fluid can be continuously discharged.
(b) If the armatures of the switch 39 are caused to trip to the lower contacts to thereby trip the armatures of the preset counter change-over switch 43 to the upper (as viewed in FIG. 18) contacts, then as in the above-described example, the fluid can be discharged intermittently by using only the foot switch 5. If the continuous fluid discharge is carried out before the intermittent fluid discharge, the discharge-amount transmitting devices 22 will not make contact with the detector 23. In this case, the detector 23 is open and the relay RA is therefore not operated. Accordingly, the armatures of the contact ra-2 and ra-3 are in contact with the lower (as viewed in FIG. 16) contacts to energize the motor 24. As a result, the drive shaft 10 is rotated as much as one discharge-amount transmitting device 22, and is then stopped by means of the detector 23.
Upon depression of the foot switch 5, the relay RB is operated momentarily, whereupon the contact means rb-1 and rb-2 are opened. As a result, the self-holding operation of the relay RA is released, and accordingly the armatures of the contact means ra-2 and ra-3 are tripped to the lower (as viewed in the figure) contacts to operate the motor 24. The drive shaft 10 is rotated and it is thereafter stopped by the detector 23.
(c) Now, the case where the preset counter 37 is used will be described.
First, the armatures of the change-over switch 39 are brought into contact with the lower contacts and the armatures of the preset counter change-over switch 43 are brought into contact with the lower contacts, respectively. Then, a manual digital switch of the preset count 37 is set to a desired number, whereupon the motor 24 begins to operate. The detector 23 is brought in contact with the discharge-amount transmitting device 22 by the operation of the motor 24. As a result, the detector 23 transmits a signal to the preset counter 37, and the signal is counted. When the count value of the preset counter 37 reaches the predetermined value, the contact output of the preset counter 37 is closed. As a result, the relay RA is self-held to cause the armatures of the contacts ra-2 and ra-3 to trip over to the upper contacts, respectively, to stop the motor 24. If the manual digital switch is set to the same number again and the foot switch 5 is depressed, the same amount of fluid is discharged again. That is, the relay RB is momentarily operated to open the contact means rb-1 and rb-2. When the relay contact means rb-1 is opened, the self-holding state of the relay RA is released, and accordingly the armatures of the relay contact means ra-2 and ra-3 are tripped over to the lower contacts to operate the motor 24. When the relay contact means rb-2 is opened, the counting section of the preset counter 37 is reset to zero (0).
In the above-described example, the discharge-amount transmitting devices 22 are disposed at equal intervals. However, it is apparent that if the devices 22 are arranged at irregular intervals, different amounts of fluid are discharged.
Furthermore, in the above-described example, the rotary member 21 is secured to the gear 20 with screws. However, if the construction and arrangement of the relevant parts are somewhat changed, the rotary member 21 can be secured to the drive shaft extended from the gear head 25.
As is apparent from the above description, the fluid supplying device according to the invention is designed so that the number of discharge-amount transmitting devices can be changed as desired. Accordingly, the user can discharge the desired amount of fluid. The fluid supplying device according to the invention is simple in construction and operation, and can be manufactured at low cost.
It is apparent that other modifications can be made without departing from the scope of this invention.
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A fluid supplying device having a peristaltic pump with a depression and delivery system that includes an elastic tube (17) for receiving fluid and an assembly of depressing members (15) for alternately constricting and relaxing the elastic tube. A drive shaft (10) connects the depression and delivery systems to an electric motor (24). A rotary member (21) is provided on the drive shaft to rotate with the drive shaft and a plurality of discharge-amount transmitting devices (22) are provided on the rotary member in such a manner that the distances between the discharge-amount transmitting devices can be changed as desired. A detector (23) is disposed at the position of passage of the discharge-amount transmitting devices for detecting the discharge-amount transmitting devices and a switch (40) is connected between the detector and the electric motor to deenergize the electric motor.
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The present invention relates to a camshaft adjusting device.
BACKGROUND
Camshaft adjusting devices are generally used in valve train assemblies of internal combustion engines to vary the valve opening and closing times, whereby the consumption values of the internal combustion engine and the operating behavior in general may be improved.
One specific embodiment of the camshaft adjusting device, which has been proven and tested in practice, includes a vane adjuster having a stator and a rotor, which delimit an annular space, which is divided into multiple working chambers by projections and vanes. A pressure medium may be optionally applied to the working chambers, which is supplied to the working chambers on one side of the vanes of the rotor from a pressure medium reservoir in a pressure medium circuit via a pressure medium pump, and which is fed back into the pressure medium reservoir from the working chambers on the particular other side of the vanes. The working chambers whose volume is increased have an operating direction which is opposite to the operating direction of the working chambers whose volume is reduced. As a result, the operating direction means that an application of pressure medium to the particular group of working chambers induces a rotation of the rotor relative to the stator either in the clockwise or the counterclockwise direction. The control of the pressure medium flow, and thus the adjusting movement of the camshaft adjusting device, takes place, e.g., with the aid of a central valve having a complex structure of flow-through openings and control edges, and a valve body, which is movable within the central valve and which closes or unblocks the flow-through openings as a function of its position.
One problem with a camshaft adjusting device of this type is that the camshaft adjusting device is not yet completely filled with pressure medium in a start phase or may even have been emptied, so that, due to the alternating torques applied by the camshaft, the rotor may execute uncontrolled movements relative to the stator, which may result in increased wear and an undesirable noise development. To avoid this problem, it is known to provide a locking device between the rotor and the stator, which locks the rotor when the internal combustion engine is turned off in a rotation angle position with respect to the stator which is favorable for startup. In exceptional cases, for example if the internal combustion engine is stalled, it is possible, however, that the locking device does not properly lock the rotor, and the camshaft adjuster must be operated with an unlocked rotor in the subsequent start phase. However, since some internal combustion engines have a very poor start behavior if the rotor is not locked in the central position, the rotor must then be automatically rotated into the central locking position and locked in the start phase.
Such an automatic rotation and locking of the rotor with respect to the stator are known, for example, from DE 10 2008 011 915 A1 and from DE 10 2008 011 916 A1. Both locking devices described therein include a plurality of spring-loaded locking pins, which successively lock into locking gates provided on the sealing cover or the stator when the rotor rotates and which each permit a rotation of the rotor in the direction of the central locking position before reaching the central locking position while blocking a rotation of the rotor in the opposite direction. After the internal combustion engine has warmed up and/or the camshaft adjuster has been completely filled with pressure medium, the locking pins are forced out of the locking gates, actuated by the pressure medium, so that the rotor is subsequently able to properly rotate with respect to the stator to adjust the rotation angle position of the camshaft.
One disadvantage of this approach is that the locking of the rotor may be accomplished only with the aid of multiple successively locking locking pins, which results in higher costs. In addition, the locking procedure requires that the locking pins lock successively in a fail-safe manner. If one of the locking pins does not lock, the locking procedure may be interrupted, since the rotor is thus not locked in the intermediate position on one side and is able to rotate back.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a camshaft adjuster which has a fail-safe and cost-effective central lock of the rotor.
The present invention provides at least two pressure medium lines are provided together in one or multiple of the vanes, which fluidically connect two working chambers of different operating directions to each other, check valves of different operating directions being provided in each of the pressure medium lines, which facilitate an overflow of the pressure medium between the working chambers in one direction and prevent it in the other direction, as a function of the rotation direction of the rotor with respect to the stator, and a first switchable valve device, which facilitates an overflow of the pressure medium between the working chambers of different operating directions in one switching position, being provided in the particular other vanes, in which no check valve is provided.
Due to the proposed approach, the rotor may be rotated out of the stop positions into the central locking position solely by utilizing the active camshaft alternating torques, since the check valve device deliberately facilitates only an overflow of the pressure medium. As a result, the rotor rotates jerkily from the direction of the stop positions in the direction of the central locking position during the active camshaft alternating torques until it locks in the central locking position. The camshaft alternating torques are deliberately used to adjust the rotor only in one direction, since a flow of the pressure medium back through the check valve device is simultaneously prevented. Since, according to the present invention, a first switchable valve device, which facilitates the overflow of the pressure medium, is provided in the other vanes, in which no check valve is provided, the automatic adjusting movement is not blocked by the pressure medium present in the working chambers.
It is furthermore proposed that a second switchable valve device is provided in each of the vanes with the check valves, with the aid of which the flow of the pressure medium to the check valves is facilitated in a first switching position and prevented in a second switching position. Due to the proposed approach, the overflow of the pressure medium may be actively prevented, so that the camshaft adjusting device may be operated with the desired accuracy during the normal, actively controlled adjustment procedure.
It is furthermore proposed that a third switchable valve device is provided, which, in a first switching position, fluidically connects the working chamber into which the pressure medium flows via the check valve to a working chamber of the same operating direction which abuts another vane with a check valve situated therein and fluidically separates it in a second switching position. Since an automatic adjusting movement from the two “advance” and “retard” stop directions should be possible, two check valves of a different operating direction must be provided. If these check valves are provided in two different vanes, an overflow of the pressure medium only between two working chambers is provided with the aid of one check valve provided in the vane, while the overflow of the pressure medium between the working chambers is not possible via a vane which includes an oppositely acting check valve. Due to the proposed approach, in one switching position of the third valve device, the pressure medium is able to flow out of the working chamber having the reducing volume, from which the pressure medium is unable to overflow via the check valve and, via the third switchable valve device, into the working chamber from which the pressure medium is further able to overflow into the working chamber of the opposite operating direction on the other side of the vane via the check valve. In a second switching position of the third valve device, the working chamber is then deliberately separated from the other working chamber, so that the rotor is able to be supported on the stator via the pressure medium present in the working chamber during the automatic adjusting movement, and the automatic adjusting movement in this position of the third valve device is possible only in one rotation direction of the rotor.
It is furthermore proposed that a pressure medium may be applied jointly to the first, second and third valve devices with the aid of a multi-way switching valve. Due to the proposed approach, all three valve devices together may be transferred to a switching position, in which the pressure medium flow between the working chambers of different operating directions is prevented, and thus the automatic adjusting movement made possible according to the present invention is practically deactivated, and the camshaft adjusting device may be operated in the conventional way solely by the active application of pressure medium to the working chambers.
In particular, it is proposed that the working chambers into which the pressure medium flows via the check valves are fluidically connected to a pressure medium line which connects at least two working chambers of the same operating direction via one pressure medium line and to the third switchable valve device via another pressure medium line. As a result, two pressure medium lines, which are separated from each other, empty into the working chamber. One of the pressure medium lines then connects the working chamber to the pressure medium line which permanently connects the working chambers of the same operating direction, e.g., a ring line, for the purpose of actively applying pressure medium to the working chamber during the controlled adjusting movement. The other pressure medium line then connects the working chamber to the working chamber of the same operating direction at the vane which includes the check valve of the opposite operating direction and may be interrupted or opened by the third valve device, whereby the pressure medium flow described above for supporting the rotor or for the overflow of the pressure medium is achieved for the automatic adjusting movement.
It is furthermore proposed that at least one vane, including a first switchable valve device, is provided between the vanes which include the check valves in the circumferential direction. Due to the proposed approach, the available installation space in the rotor may be much better utilized for situating the pressure medium lines. This is advantageous, in particular, since two pressure medium lines empty into one of the working chambers which abut the vanes having the check valves, i.e., one pressure medium line emptying into the ring line and one pressure medium line leading to the third valve device, which run separately in at least one section.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is explained in greater detail below on the basis of one preferred exemplary embodiment. The following are shown in detail in the figures:
FIG. 1 : shows a schematic representation of a camshaft adjusting device according to the present invention, including a circuit diagram of a pressure medium circuit in the position during an adjusting movement of the rotor from the “retard” direction into the central locking position;
FIG. 2 : shows a schematic representation of a camshaft adjusting device according to the present invention, including a circuit diagram of a pressure medium circuit in the position during an adjusting movement of the rotor from the “advance” direction into the central locking position;
FIG. 3 : shows a schematic representation of a camshaft adjusting device according to the present invention, including a circuit diagram of a pressure medium circuit during the adjusting movement in normal operation; and
FIG. 4 : shows an alternative specific embodiment of the camshaft adjusting device according to the present invention.
DETAILED DESCRIPTION
A camshaft adjusting device having a known basic structure with a schematically illustrated vane adjuster as a basic component is apparent from FIGS. 1 through 3 , which includes a stator 16 , drivable by a crankshaft which is not illustrated, and a rotor 17 , which is rotatably fixedly connectable to a camshaft, also not illustrated, and which includes a rotor hub 36 and multiple vanes 11 , 12 and 13 extending radially outwardly. In the upper representation, the vane adjuster is apparent in the developed view, while a detail of rotor hub 36 of rotor 17 , which includes a central locking device 33 , is schematically apparent at the bottom left, and a multi-way switching valve 21 for controlling the pressure medium flow is schematically apparent at the bottom right.
A pressure medium circuit is also apparent, which includes a large number of pressure medium lines 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 23 , 37 , 38 , 39 and 40 , which are optionally fluidically connectable to a pressure medium pump P or a pressure medium reservoir T, whereby, after the pressure medium has been fed back to pressure medium reservoir T via multi-way switching valve 21 , pressure medium pump P conveys it from there and back into the pressure medium circuit.
Stator 16 includes a plurality of stator webs, which divide an annular space provided between stator 16 and rotor 17 into multiple pressure chambers 29 , 30 and 31 . Pressure chambers 29 , 30 and 31 , in turn, are divided by vanes 11 , 12 and 13 of rotor 17 into working chambers 24 , 25 , 26 , 27 , 28 and 32 , into which pressure medium lines 1 , 3 , 4 , 6 , 7 , 8 , 39 and 40 empty. Central locking device 33 includes two locking pins 18 and 19 , which lock into a stator-fixed locking gate 22 for the purpose of locking rotor 17 with respect to stator 16 . Locking gate 22 may be situated, for example, in a sealing cover screwed to stator 16 .
In principle, the rotation angle of the camshaft with respect to the crankshaft during normal operation, i.e., in the “advance” direction, is adjusted by the fact that pressure medium is applied to working chambers 24 , 32 and 27 , thereby increasing their volume, while the pressure medium is simultaneously forced out of working chambers 25 , 26 and 28 , which reduces their volume. Working chambers 24 , 25 , 26 , 27 , 28 and 32 , whose volume is increased in groups during this adjusting movement, are referred to, within the meaning of the present invention, as working chambers 24 , 25 , 26 , 27 , 28 and 32 of one operating direction, while working chambers 24 , 25 , 26 , 27 , 28 and 32 , whose volume is simultaneously decreased, are referred to as working chambers 24 , 25 , 26 , 27 , 28 and 32 of the opposite operating direction. The change in volume of working chambers 24 , 25 , 26 , 27 , 28 and 32 then results in the fact that rotor 17 , including vanes 11 , 12 and 13 , is rotated with respect to stator 16 . In the top representation in FIG. 3 , the volume of working chambers 25 , 26 and 28 is increased by applying pressure medium via the B port of multi-way switching valve 21 , while the volume of working chambers 24 , 32 and 27 is simultaneously decreased by the back-flow of the pressure medium via the A port of multi-way switching valve 21 . This change in volume then results in a rotation of rotor 17 with respect to stator 16 , which results in a shifting of vanes 11 , 12 and 13 to the left in the direction of the arrow in the developed view. To enable rotor 17 to be adjusted with respect to stator 16 , central locking device 33 is first released by applying pressure medium to locking gate 22 via pressure medium lines 2 and 23 from the C port of multi-way switching valve 21 with the aid of pump P. By applying pressure medium to locking gate 22 , locking pins 18 and 19 are forced out of locking gate 22 , so that rotor 17 is able to subsequently rotate freely with respect to stator 16 . To this extent, the camshaft adjusting device corresponds to the prior art.
According to the approach according to the present invention, pressure medium lines 34 and 35 are provided in vanes 11 and 12 and include check valves 9 and 10 situated therein, which facilitate an overflow of the pressure medium out of working chamber 25 into working chamber 24 and out of working chamber 32 into working chamber 26 . The flow of the pressure medium through pressure medium lines 34 and 35 may furthermore be blocked or facilitated by a second switchable valve device, formed by a spring-loaded, movable valve body 14 and 15 . For this purpose, valve bodies 14 and 15 have two switching positions, in which the flow-through is either released or blocked. Pressure medium may be applied to each of the switchable second valve devices via a pressure medium line 2 and 5 , and these second valve devices are transferred from a first to a second switching position, which is apparent in FIG. 3 , upon the application of pressure medium with the aid of a shifting of valve bodies 14 and 15 against the active spring force. In the second switching position, the flow through pressure medium lines 34 and 35 is blocked, so that working chambers 24 and 25 or 32 and 26 are to be viewed as separate from each other, and the camshaft adjusting device may be operated with a correspondingly high degree of adjusting accuracy without an overflow of the pressure medium between working chambers 24 , 25 , 32 and 26 .
Central locking device 33 furthermore includes a third valve device, formed by two locking pins 18 and 19 in rotor hub 36 . Locking pins 18 and 19 are designed as spring-loaded valve bodies, including corresponding grooves or bores, which are movable from a first switching position into a second switching position by applying pressure to locking gate 22 via pressure medium line 23 against the active spring force. Locking pins 18 and 19 are in the first switching position when they engage with locking gate 22 and the springs are relaxed.
The bores or grooves in locking pins 18 and 19 are situated in such a way that a flow of the pressure medium in the first switching position of locking pin 18 is blocked between pressure medium line 1 and pressure medium line 39 and pressure medium lines 40 and 6 with an unloaded spring, as is apparent in the positions in FIG. 1 and in FIG. 2 . One of these positions illustrated in FIG. 1 or FIG. 2 is present if rotor 17 is not locked in the central locking position upon starting the internal combustion engine, and is rotated with respect to stator 16 either in the direction of the “retard” stop position or in the direction of the “advance” stop position. In the illustration, the “retard” stop position is identified by an S and the “advance” stop position by an F.
In both positions of rotor 17 , one of locking pins 18 or 19 does not engage with locking gate 22 and is thus displaced into the second switching position against the spring force. The bores or grooves in locking pins 18 and 19 are situated in such a way that locking pins 18 and 19 facilitate a flow of the pressure medium between pressure medium lines 6 and 40 or 1 and 39 in the second switching position, while the flow through locking pin 18 or 19 engaging with locking gate 22 in the first switching position is blocked.
Pressure medium lines 6 and 40 or 1 and 39 are fluidically connected to working chambers 25 and 26 or 24 and 32 , which are short-circuited thereby with the aid of locking pins 18 and 19 present in the second switching position. Pressure medium lines 3 and 8 empty into a partially annular or annular, shared pressure medium line 38 on rotor hub 36 , which, in turn, is fluidically connectable to pressure medium pump “P” or pressure medium reservoir “T” via the B port of multi-way switching valve 21 . With the aid of partial annular or annular pressure medium line 38 , pressure medium may be jointly applied to working chambers 25 and 28 of an operating direction, or these working chambers may be connected to pressure medium reservoir “T.” Pressure medium line 37 has the same function, via which pressure medium may be applied to working chambers 32 and 27 via the A port of multi-way switching valve 21 , or these working chambers are connectable to pressure medium reservoir “T.” Locking pins 18 and 19 separate each of pressure medium lines 1 and 39 or 6 and 40 , in the locking position, in which they engage with locking gate 22 , so that rotor 17 may be hydraulically supported, with active camshaft alternating torques, via working chamber 24 or working chamber 26 in the direction of the “advance” or “retard”: adjusting direction.
Furthermore, a first switching valve device, formed by a spring-loaded, movable valve pin 20 , is provided in vanes 13 in which no check valve 9 or 10 is provided. Valve pin 20 has a pressure medium line 41 , e.g., in the form of a circumferential groove, through which working chambers 27 and 28 of different operating directions may be short-circuited on the side surfaces of vane 13 in a first switching position of the third valve device.
In the event that the camshaft adjusting device is not locked in the central locking position upon starting the internal combustion engine, and instead is rotated with respect to stator 16 in the direction of the “retard” stop position, rotor 17 is automatically rotated out of this rotated position, as is apparent in FIG. 1 , from the direction of the “retard” (S) stop position in the direction of the central locking position in the direction of the arrow, in that the alternating torques acting upon the camshaft (CTA—Camshaft Torque Actuated) are used to allow the pressure medium to flow out of working chamber 25 through pressure medium line 35 into working chamber 24 via check valve 9 . Since the other working chambers 27 and 28 , which are separated from each other by vanes 13 , each having one valve pin 20 , are short-circuited in this position of valve pin 20 via pressure medium line 41 , the pressure medium may overflow between these working chambers 27 and 28 . Since the pressure medium is furthermore unable to flow out of working chamber 24 , due to the locked position of locking pin 18 , and it is also unable to flow back into working chamber 25 via check valve 9 , rotor 17 is simultaneously unable to rotate back in the direction of the “retard” (S) stop position. Furthermore, working chamber 25 , out of which the pressure medium flows via check valve 9 , is fluidically connected via pressure medium line 40 and locking pin 19 , situated in the unlocked position, to working chamber 26 of the same operating direction, which is also separated from a working chamber 32 of the opposite operating direction by a vane 12 which includes a check valve 10 , so that the pressure medium is able to flow out of this working chamber 26 into working chamber 25 and finally into working chamber 24 via check valve 9 or out of working chamber 25 and into working chamber 28 via pressure medium lines 3 , 38 and 8 , and from there into working chamber 27 via pressure medium line 41 .
Due to the proposed circuit, rotor 17 is practically supported on the pressure medium present in working chamber 24 , the volume of working chamber 24 being increased by the pressure medium flowing in a pulsating manner via check valve 9 , and rotor 17 is rotated thereby with respect to stator 16 . Check valve 9 thus forms a freewheel, together with the correspondingly blocked or released pressure medium lines 1 , 3 , 4 , 6 , 7 , 8 , 39 and 40 , with the aid of which rotor 17 is rotated with respect to stator 16 on one side in the direction of the central locking position, utilizing the alternating torques acting upon the camshaft, until locking pin 19 engages with locking gate 22 or until locking pin 18 comes into contact laterally with a stop of locking gate 22 . Due to the engagement of locking pin 19 with locking gate 22 , the latter automatically enters the first switching position, due to the active spring force, in which the previously released flow connection between pressure medium lines 40 and 6 is blocked and the short circuit produced thereby is released. As a result, another rotational movement of rotor 17 with respect to stator 16 is prevented, and rotor 17 is locked in the central locking position. It is particularly important for the functionality of the freewheel that working chambers 25 and 26 of pressure chambers 29 and 30 having the decreasing volume during the automatic adjusting movement are fluidically connected via the groove or the bore in locking pin 19 , so that the pressure medium is able to flow out of working chamber 26 and does not impede the adjusting movement.
The reverse adjusting procedure from the direction of the “advance” (F) stop position in the direction of the central locking position is apparent in FIG. 2 . The principle of the adjusting movement is identical. In this case, locking pin 18 is in the second switching position and thereby establishes a flow connection between pressure medium lines 1 and 39 , so that working chambers 24 and 32 are fluidically connected to each other. Furthermore, locking pin 19 is in the first switching position and thereby blocks a flow of the pressure medium from working chamber 26 to working chamber 25 , so that working chamber 26 is decoupled from the pressure medium circuit. In this case, when alternating torques occur during the start phase of the internal combustion engine, the pressure medium flows out of working chamber 32 via pressure medium line 34 and check valve 10 present therein into working chamber 26 and thereby increases its volume, since the outflow of the pressure medium is simultaneously prevented by blocked pressure medium line 6 . At the same time, the pressure medium is unable to overflow from working chamber 24 into working chamber 25 due to the orientation of check valve 9 . In order that the pressure medium present in working chamber 24 does not impede the adjusting movement, working chamber 24 is fluidically connected to working chamber 32 of pressure chamber 30 of the same operating direction via locking pin 18 , which is in the second switching position, so that the pressure medium is able to flow out of working chamber 24 via pressure medium lines 1 and 39 into working chamber 32 and onward via check valve 10 . During this adjusting movement, rotor 17 is supported on stator 16 via the pressure medium present in working chamber 26 .
During the adjusting movement illustrated in both FIG. 1 and FIG. 2 , multi-way switching valve 21 is in a basic position in which it is spring-loaded. During the shutdown of the internal combustion engine, multi-way switching valve 21 is automatically moved into the basic position, in which the C port is connected to pressure medium reservoir “T.” The C port is connected to locking gate 22 via pressure medium line 23 and to valve bodies 14 and 15 and to valve pin 20 via pressure medium lines 2 , 5 and 42 , so that pressure medium is not applied to the first, second and third valve devices. If rotor 17 is not locked in the central locking position, the valve devices are either in the position shown in FIG. 1 or in FIG. 2 , and rotor 17 is automatically rotated in the direction of the central locking position upon startup according to the operating principle described above. For the purpose of the active, controlled rotation of rotor 17 , multi-way switching valve 21 is actuated and thereby displaced into a position in which pressure medium is applied to the C port and the B port via pressure medium pump “P,” and the A port is connected to pressure medium reservoir “T.” As a result, pressure medium is applied jointly to the valve devices, which are displaced into the second switching position against the active spring force, as is apparent in FIG. 3 . As a result, valve bodies 14 and 15 and valve pin 20 are moved into a position in which the pressure medium is unable to overflow via vanes 11 , 12 and 13 . At the same time, locking pins 18 and 19 are displaced into a position in which pressure medium lines 1 and 39 or 40 and 6 are fluidically connected to each other, so that working chambers 24 and 32 or 25 and 26 are also fluidically connected to each other. To adjust rotor 17 in the illustrated position in the direction of the “retard” (S) stop position, pressure medium is applied to working chambers 25 and 28 via shared pressure medium line 38 and pressure medium lines 8 and 3 branching therefrom, while the pressure medium flows out of working chambers 27 and 32 and back into pressure medium reservoir “T” via pressure medium lines 7 and 4 and via shared pressure medium line 37 with the aid of the A port. Since working chambers 24 and 26 are simultaneously fluidically connected to working chambers 32 and 25 via locking pins 18 and 19 , the pressure medium is also introduced into working chamber 26 and is removed from working chamber 24 .
It is furthermore particularly important for the present invention that working chambers 24 , 25 , 26 , 27 , 28 and 32 of different operating directions, which are not part of the presently active freewheel, are each short-circuited via a valve pin 20 , so that the automatic adjusting movement is not impeded by the pressure medium present in working chambers 24 , 25 , 26 , 27 , 28 and 32 . It is particularly advantageous that valve pins 20 are situated in vanes 13 themselves, since this makes it possible to facilitate the overflow of the pressure medium directly without additional pressure medium lines.
A further developed specific embodiment of the camshaft adjusting device according to the present invention is apparent in FIG. 4 , in which pressure chambers 29 and 30 , including vanes 11 and 12 with check valves 9 and 10 , are not situated adjacent to each other, but instead encompass between them another pressure chamber 31 , including a vane 13 with a pressure medium line 41 short-circuiting working chambers 27 and 28 . Due to this refinement, the pressure medium lines, which are provided in rotor 17 by bores and grooves, may be situated in a much simpler manner. This is particularly advantageous because the available installation space for accommodating the pressure medium lines in rotor 17 is limited, and the pressure medium lines generally should not be allowed to cross, except for certain nodes. If rotor 17 includes four vanes 11 , 12 and 13 , for example, vanes 11 and 12 , including check valves 9 and 10 , or vane 13 , including the first valve devices, are situated opposite to each other. The course of the pressure medium lines may be simplified thereby, it being possible, in particular, to make much better use of the material of rotor 17 for accommodating the pressure medium lines.
LIST OF REFERENCE NUMERALS
1 pressure medium line
2 pressure medium line
3 pressure medium line
4 pressure medium line
5 pressure medium line
6 pressure medium line
7 pressure medium line
8 pressure medium line
9 check valve
10 check valve
11 vane
12 vane
13 vane
14 valve body
15 valve body
16 stator
17 rotor
18 locking pin
19 locking pin
20 valve pin
21 multi-way switching valve
22 locking gate
23 pressure medium line
24 working chamber
25 working chamber
26 working chamber
27 working chamber
28 working chamber
29 pressure chamber
30 pressure chamber
31 pressure chamber
32 working chamber
33 central locking device
34 pressure medium line
35 pressure medium line
36 rotor hub
37 pressure medium line
38 pressure medium line
39 pressure medium line
40 pressure medium line
41 pressure medium line
42 pressure medium line
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A camshaft adjusting device including a vane cell adjuster with a stator which can be connected to a crankshaft of an internal combustion engine and with a rotor which is rotatably mounted in the stator and can be connected to a camshaft. The camshaft adjusting device also includes a central locking device for locking the rotor in a central locking position relative to the stator. In one or more of the vanes together: at least two pressure medium lines are provided, each of which fluidically connects two working chambers with different working directions to each other. Non-return valves with different working directions are provided in each pressure medium line, each non-return valve allowing a flow of the pressure medium between the working chambers in one direction and preventing the flow in the respective other direction depending on the rotational direction of the rotor relative to the stator. A first switchable valve device is provided in the respective other vanes which are not provided with non-return valves, the valve device allowing a flow of the pressure medium between the working chambers with different working directions in one switch position.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority from European patent application No. 10 163 520.9-2213 filed on May 21, 2010, all of which is incorporated herein by reference in its entirety for all purposes.
FIELD OF THE INVENTION
[0002] The present invention relates to a floating noise reduction system for moving and/or falling fluids, the process for manufacturing of such system and the use of such system.
BACKGROUND OF THE INVENTION
[0003] Falling or dropping and flowing fluid, especially water, is known to create significant noise that becomes a health and safety concern for work personnel and a nuisance for nearby residents. A prominent case is in cooling towers of power plants where costly measures have to be taken to reduce the noise. The conditions in cooling towers are among the worst for any sound dampening installation, as there is a permanent high water impact like from a waterfall moving round in circles. The resulting force can cause severe damage or at least accelerated fatigue to installations of any kind. Additionally, there has to be appropriate, i.e. highly efficient, drainage as any sound damping installation of course has to work above the water surface situation at the base of the tower. Thus, if a system can work under cooling tower conditions it is likely to work everywhere, e.g. also when applied on flowing fluids.
[0004] Some scope in sound attenuating systems has been put on cooling tower noise reduction for a.m. reasons. As the most widespread method, a noise protection wall around the base of the cooling tower is 1. costly and 2. only will reduce the noise emitted at ground level but not the noise escaping through the top opening, other measures had been examined. One approach consists in applying grid-like or mesh-like systems that should disperse the water flow and the noise, subsequently, such as in CN 200972335, CN 100533033, CN 2341088 and CN 2453381. The claimed noise reduction of 15-30 dB of the latter could not be reproduced during our examinations. Honeycombs as damping elements are mentioned in CN 2823955 and CN 1862206, but honeycombs or hollow systems in general are notorious for creating resonance sound, or “drumming”, of course. All the a.m. systems are mainly based on metalwork and/or rigid plastics and thus do not possess material immanent dampening properties. To improve that situation, JP 8200986 claims the use of a combination of water permeable and non-permeable synthetic resin mats, however, also those materials are rather rigid and the drainage properties—despite the claimed drainage ridges—are poor, leading to water agglomeration on top of the mat which will increase the noise level again. CN 2169107 mentions damping mats and particles; however, the claimed system is not able to provide sufficient structural integrity for the application. Another approach is focussing on plate systems where the plates themselves are supported by a damping device and also disperse water, such as in CN 201003910, CN 201302391, CN 201302392, CN 201302393, CN 201184670, CN 1945190 (all describing combinations of rotating and fixed plates, partially combined with pipe systems), CN 201311202 (microporous plates), CN 2821500 (plates, rings and surface structures as known from acoustic indoor systems), JP 56049898 (complex metalwork with damping inlays). Other systems described in the literature are: CN 2447710 and CN 2438075 (use of floating balls) and CH 451216, DE 3009193, DE 1501391, DE 2508122, EP 1500891, SU 989292. The latter documents, as well as a publication (M. Krus et al: Latest developments on noise reduction of industrial induced draft cooling towers, Veenendaal, 2001, pp 33-38) all mainly refer to systems consisting of floating devices which are supporting or carrying the damping system, consisting of mat-like structures, means, some elasticity or flexibility has been acknowledged to be beneficial for sound dampening; JP 58033621 at last mentions that “soft cover” may reduce falling water noise (for sluice doors). However, those systems are not consequently using the potential of elastic dampening and exhibit deficiencies in floating properties as well as in drainage performance; and some systems again are sensitive to mechanical impact.
SUMMARY OF THE INVENTION
[0005] A major object of the present invention thus is to provide a floating noise reduction system or material combination not showing the above mentioned deficiencies but exhibiting a significant and sustainable level of noise reduction over all concerned frequencies and showing an additional drainage effect and high mechanical wear resistance.
[0006] Surprisingly, it is found that such system or material not showing the above mentioned disadvantages can be made from a combination of expanded elastic material with a floating mechanical support made from expanded polymer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] In the accompanying drawings,
[0008] FIG. 1 schematically illustrates the composition of claimed system,
[0009] FIG. 2 schematically illustrates the skeleton (reticulated) structure,
[0010] FIG. 3 schematically illustrates the damping of flowing or falling fluid or waves,
[0011] FIG. 4 schematically illustrates the possible surface structures for drainage and absorption for layers (A) and (B),
[0012] FIG. 5 schematically illustrates the test layout for falling water noise detection, and
[0013] FIG. 6 shows the frequencies being damped by claimed materials: ⅓ octave band spectra resulting from falling water test.
DETAILED DESCRIPTION OF THE INVENTION
[0014] The claimed material comprises at least one layer (A) of expanded polymer based material with open cell (open porosity) structure ( FIG. 1 ). The polymer based material of (A) can be expanded from an elastomer and/or thermoplastic elastomer (TPE) and/or thermoplastic and/or thermoset based polymer mixture, or combinations thereof, and can optionally be crosslinked to improve mechanical (e.g. compression set) and wear properties. Preferred are polymer based materials providing elasticity to (A), either by elastic properties provided by the polymer itself (e.g. for elastomers and TPEs) or by respectively thin, thus flexible expanded structures, or by a combination of both. The polymer based material is expanded by physical and/or chemical expansion agents to an open cell sponge or reticulated (skeleton) structure, depending on the required damping and drainage properties. Preferred is a reticulated (skeleton) structure where the polymer based cell walls are reduced to columns showing a diameter thinner than the average cell diameter (see FIG. 2 ). The polymer based material can be a mixture or compound that may contain fillers, such as oxides, carbonates, hydroxides, carbon blacks, recycled (ground) rubber, other recycled polymer materials, fibres etc., and additives, such as flame retardants, biocides, plasticizers, stabilizers, colours etc., of any kind in any ratio. The polymer base mixture may be crosslinked by any applicable mean of crosslinking, such as sulphur, peroxide, radiation, bisphenolics, metal oxides, polycondensation etc. (A) can show various densities, preferred are densities lower than typical fluids, e.g. lower than 700 kg/m3, to prevent sinking even when fully soaked. Especially preferred are densities lower than 300 kg/m3. It is easily feasible to use various combinations of polymer based compounds and various combinations of layers (A) made thereof. (A) will quickly absorb the falling or flowing fluid, disperse its impulse into smaller drops and in parallel will disperse the resulting impact energy transversally into the matrix of (A). This dispersion will continue through the open cell structure and into layer (B) and finally will lead to noise absorption within the claimed material and transmission of remaining noise into the fluid underneath when damping falling fluid, or into the medium above or outside when damping flowing fluid, or into a lateral medium when damping e.g. waves (see FIG. 3 ). Meanwhile the absorbed fluid itself will be silently drained through (A) and (B) to the fluid underneath or into the medium above or drained laterally. Layer (B) thus not only acts as floating and draining part of the system, but supports the noise reduction by interaction with (A) and by providing further potential for damping additional frequencies. (A) can be of flat surface to the falling fluid, or it can be structured to alter the absorption/dispersion properties, and it can be equipped with e.g. pin holes for better drainage. (A) can also be structured on its face to (B) for same reason, e.g. for drainage or sound decoupling purposes (see FIG. 4 ). Preferred materials for the manufacturing of (A) are elastomers, such as NR, IR, SBR, NBR, CR, IIR, EPM, EPDM, Q, etc., thermoplastic elastomers, such as TPP, TPV, TPU, SAN, SEBS etc., PIR/PUR or polyurethanes, especially reticulated polyurethanes, polyesters, phenolic and melamine based compounds.
[0015] The claimed system comprises at least one layer (B) of expanded polymer based material different or same as for (A) with either open or closed cell structure ( FIG. 1 ). The polymer based material of (B) can be expanded from an elastomer and/or thermoplastic elastomer (TPE) and/or thermoplastic and/or thermoset based polymer mixture, or combinations thereof, and can optionally be crosslinked to improve mechanical (e.g. impact strength) and wear properties. Preferred are polymer based materials providing structural integrity to (B) to prevent breaking or warping of the system. The polymer based material is expanded by physical and/or chemical expansion agents to an open cell sponge or closed cell foam, depending on the required mechanical, damping and drainage properties. Preferred is a minimum 50% closed cell structure, especially preferred are at least 70% closed cells to prevent soaking and saturation with fluid. The polymer based material can be a mixture or compound that may contain fillers, such as oxides, carbonates, hydroxides, carbon blacks, recycled (ground) rubber, other recycled polymer materials, fibres etc., and additives, such as flame retardants, biocides, plasticizers, stabilizers, colours etc., of any kind in any ratio. The polymer base mixture may be crosslinked by any applicable mean of crosslinking, such as sulphur, peroxide, radiation, bisphenolics, metal oxides, polycondensation etc. (B) can show various densities, preferred are densities significantly lower than typical fluids, e.g. lower than 500 kg/m3, especially preferred are densities lower than 200 kg/m3. It is easily feasible to use various combinations of polymer based compounds and various combinations of layers (B) made thereof. (B) comprises a structure to ensure good drainage properties as (B) is responsible to draw the fluid away from (A) into the fluid underneath. This structure can comprise pin holes that can be applied in a wide variety of size and pattern and combinations. The structure can also comprise ridges of any shape in any combination (e.g. triangular, sinus-like, rectangular, trapezoidal etc.) that can be applied on one or both surfaces of (B) (see FIG. 4 ). (B) can be fixed to (A) by mechanical means, or chemically by bonding, or by a combination of both. Layers (A) and (B)—and optionally (C)—can be brought together directly by co-forming, e.g. by co-extrusion and/or co-moulding and/or lamination, and/or can be connected after giving shape to them. The connection can be achieved by adhesives, e.g. one or two part silicone, polyurethane, acrylate, chloroprene, contact adhesives or hot melts or any combination thereof. Or the connection can be achieved by direct melting or welding the two materials together, such as by UHF welding or the like. The preferred final form is a mat or tile like multilayer compound system. The tiles can easily be cut and shaped to fit any geometry of the fluid basin or fluid track to float on. Preferred materials for the manufacturing of (B) are elastomers, such as NR, IR, SBR, NBR, CR, IIR, EPM, EPDM, Q, etc., thermoplastic elastomers, such as TPP, TPV, TPU, SAN, SEBS etc., PIR/PUR or polyurethanes, polyesters, phenolic and melamine based compounds. Especially preferred are compounds providing high impact strength, such as polyalkylidene terephthalates.
[0016] The claimed material furthermore may comprise one or more additional layers (C) within and/or between layers (A) and/or (B) that may provide additional drainage and/or damping and/or other properties, such as preferably reinforcement, impact resistance etc. The layers (C) can e.g. comprise fibres, e.g. as mesh, or nonwoven, wire mesh, resin sheet etc. of any kind; see FIG. 1 .
[0017] The claimed material furthermore may comprise a link system (D) that connects individual pieces, e.g. tiles, comprising layers (A), (B), and optionally (C) together, but still leaving room to move and float. (D) can comprise metalwork, woven bands, elastic links etc., or a combination thereof. (D) is fixed either into layer (B)/(C)—as the structurally toughest ones—or into the system, i.e. (B), from underneath or above or by a combination of both methods. Care has to be taken that (D) will not negatively influence the floating properties (weight) and the flexibility of the whole system. Cardan joints or axle bearing based links or other flexible linking methods are therefore preferred. An accordingly strong layer (C) between (A) and (B) can also take the part of (D) if the pieces of (A) and (B) are connected onto (C) keeping some distance between the respective tiles. However, a connection system (D) is preferred where individual tiles can be easily exchanged, e.g. for maintenance purposes.
[0018] It is a prominent advantage of the claimed material that it is providing excellent damping together with draining effect due to its composition and structure and that it additionally shows built-in anti-fatigue properties due to its composition, allowing long-term use even under harsh conditions.
[0019] A further advantage of the claimed material is the possibility to adapt its properties to the desired property profile (concerning mechanics, damping/absorption, fluid intake, hydrophilic or hydrophobic character, porosity etc.) This can be achieved by modifying the expansion agent(s), the expansion process and the polymer base material composition, as well as the density, and, if required, the crosslinking system(s). The material thus can be altered to damp/absorb from high to low frequencies or frequency bands (see FIG. 6 ), and it can be used in contact with a broad variety of fluids, including aggressive and/or hot or cold ones.
[0020] Another basic advantage of the claimed material is the fact that its noise reduction properties are very constant over a wide temperature range leading to the fact that its performance remains unchanged no matter if it is used in summer or wintertime.
[0021] It is a further important advantage of the claimed material that it will reduce both the ground level noise as well as the top level noise at cooling towers (see table 1 and FIG. 6 ), rendering noise protection walls obsolete.
[0022] It is another important advantage of the claimed material that it can be applied for noise reduction both of falling/dropping and flowing fluids.
[0023] It is another advantage of the claimed material that it is environmental friendly as it does not comprise or release harmful substances, does not affect water or soil or nature in general and as it is recyclable by separating the layers and then grinding or melting them individually.
[0024] A resulting advantage of the material is the fact that it can be blended or filled with or can contain scrapped or recycled material of the same kind to a very high extent not losing relevant properties significantly, which is especially the case for (B) and (C).
[0025] It is another advantage of the claimed material that its expanded structure provides insulation properties, thus, it can be beneficial for keeping fluids warm or cold in addition to the damping properties.
[0026] It is a prominent advantage of the claimed material that it can be produced in an economic way in automatic or semi-automatic shaping process, e.g. by moulding, extrusion and other shaping methods. It shows versatility in possibilities of manufacturing and application. It can be extruded, co-extruded, laminated, moulded, co-moulded etc. as single item or multilayer already and thus it can be applied in almost unrestricted form.
[0027] It is a further advantage of the claimed material that it can be transformed and given shape by standard methods being widespread in the industry and that it does not require specialized equipment.
[0028] It is another advantage of the claimed material for the application that it is long-lasting and durable, however, easy to change in case of maintenance and thus will reduce running costs for the user.
EXAMPLES
[0029] Preparation of Test Samples
[0030] 1. Floating layer (B): an extruded, expanded and cut PET board of 25 mm thickness and 1000×1000 mm width (ArmaStruct®, Armacell, Münster, Germany) was coated with a silicone adhesive layer (ELASTOSIL® R plus 4700, Wacker Chemie, München, Germany) to give the floating part of the system. A sinus shape ridge structure (distance peak to peak of 35 mm) was applied to one surface by thermoforming embossing and pin holes of 20 mm diameter were drilled into the board in a distance of 80 mm.
[0031] 2. Sponge like open cell absorbing layer (A): A rubber compound (Armaprene® N H, Armacell, Münster, Germany) was extruded, expanded and cut to an open cell foam mat of 25 mm thickness and 1000×1000 mm width and then laminated onto the plain surface of (B) as single or double layer by heating the composite up to 120° C. in a hot air oven, using the a.m. adhesive.
[0032] 3. Skeleton structure open cell absorbing layer (A): A reticulated polyurethane foam mat of the type 80 poles per inch (SIF®, United Foam, Grand Rapids, U.S.A.) of 25 mm thickness and 1000×1000 mm width was laminated onto the plain surface of (B) as single or double layer by heating the composite up to 120° C. in a hot air oven, using the a.m. adhesive.
[0033] Experimental Setup
[0034] The experiments were carried out on test equipment proposed and developed by the University of Bradford, UK (Prof K. Horoshenkov). The setup (see FIG. 5 ) comprised of a large underfloor concrete water tank. The tank was 2.5 m deep, 1.8 m wide and 2.35 m long and was able to hold approximately 8 m3 of water. The water was discharged onto the underfloor tank from a perforated water tank mounted above. The perforated water tank was made of PVC and its dimensions were 0.55 m wide×0.55 m long×0.2 m deep. In order to simulate the discharge typical to that measured in a cooling tower the perforated water tank had 243 holes all 1 mm diameter wide drilled in a 5 mm thick base, the spacing between the perforations was approximately 26 mm. The size of the perforations was chosen in accordance with the ISO 140, Part 18 (2006) and corresponds to that required to generate heavy rain. The perforated water tank was calibrated to deliver 5 m3/m2/hr discharge. This required a water supply at the rate of 20.8 litres per min. The calibration was carried out by using a standard flow meter and by weighing the amount of water discharged from the hose pipe over 15 sec intervals. It required the PVC water tank to be filled with 180 mm of water to achieve the equilibrium between the water pick-up and runoff.
[0035] The absorber foam samples (A) were tested in single and double layer configurations placed on top of the floating layer (B) by adhesion as described above. The distance between the top surface of the top foam layer and the bottom of the perforated water tank was kept 2 m in all the experiments to ensure the same terminal velocity of the water droplets. The following items of equipment were used for sound recording and analysis:
[0036] (i) one PC with WinMLS 2004 build 1.07E data acquisition and spectrum analysis software and 8-channel Marc-8 professional sound card.
[0037] (ii) four calibrated Bruel and Kjaer microphones, ½″ type 4188.
[0038] (iii) one 4-channel B & K Nexus conditioning amplifier type-2693 set at 1V/Pa.
[0039] The audio channels were calibrated to 94 dB using a standard B&K microphone calibrator (Type 4230, no: 1670589). The ⅓-octave sound pressure level spectra were measured on the four channels and used to calculate the mean ⅓-otave level spectrum and the broadband sound pressure level (see FIG. 6 ). The lateral positions of the four microphones in the underfloor water tank are shown in FIG. 5 . The microphones were suspended on cables 0.8 m below the bottom of the perforated water tank. The level of ambient noise in the laboratory was very low and signal to noise ratio of better than 20 dB was ensured throughout the tests.
[0040] Results
[0041] Table 1 shows the good damping properties of already a standard sponge structure open cell material. The noise reduction effect even gets much better when very open cell (“skeleton structure”) material is applied. Another incremental improvement can be found in a combination of both.
[0000]
TABLE 1
Falling water test: noise reduction of open cell materials (A) -
SpC = Sponge-like open cell structure; SkC = Skeleton-like
open cell structure - in 25 and 50 mm thickness applied on
a given layer of (B) in comparison with the unarmed water surface
(all innovative examples).
Avg. sound pressure
Type of layer (A)
level (dB)
Noise reduction by dB
SpC foam 25 mm
68.4
8.2
SpC foam 50 mm
67.6
9.0
SkC foam 25 mm
54.5
22.1
SkC foam 50 mm
54.5
22.1
SkC + SpC (25 + 25 mm)
52.6
24.0
No damping
76.6
n.a.
[0042] The frequencies being damped or absorbed also give an indication about the performance of the materials and material combinations. FIG. 6 shows the ⅓ octave band spectra for the materials of table 1 and proves that the skeleton like structure also has advantages in damping a broader range of frequencies (the sponge like structure tends to boom at low frequencies), however, it can be found, too, that a combination of both materials is performing slightly better.
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The present invention relates to a floating noise reduction system for moving and/or falling fluids, the process for manufacturing of such system and the use of such system.
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FIELD OF THE INVENTION
[0001] The present invention pertains mostly to the petrochemical sector. It relates to systems and methods for contaminant reduction in hydrocarbons and biofuels, mainly focused on the significant reduction of sulphur, and metals embedded in the fuel molecules, therefor improving fuel characteristics in the process.
BACKGROUND OF THE INVENTION
[0002] With decreasing reserves of light crude oil we have been led to extract lower quality crudes (sour crudes) which are high in sulphur and metals. The costs associated with de-contaminating, or elevating this crude to International fuel standards is much higher, requiring in some cases the purchase of lighter crudes to reduce contaminants in general due to a lack of cost effective technologies to completely eliminate or significantly reduce these contaminants. The petroleum industry is always looking for more economical ways to crack, distil, refine and improve on fuel characteristics. Recent environmental requirements for fuels to exceed EPA standards, and having the rest of the World focusing on the reduction of these contaminants as well, have prompted the industry to explore new methods to reduce these non-desired elements or substances in the least expensive manner.
[0003] The conventional process used in the petroleum industry for Sulphur reduction is known as hydrolysis. The hydrocarbon is reacted in one or more vessels, incorporating a hydrolysis catalyst and an absorption stage to trap the reacted sulphur. This occurs under high temperature and pressure conditions with sophisticated equipment and requires extensive footprint and energy resources.
[0004] Also, hydrocracking is a process used in the oil industry to convert low quality raw materials into higher-value fuel. This process is the best way to obtain a diesel fuel with lower sulphur content and aromatics. Normally the hydrocracking process is carried out using two suspended bed catalytic packed reactors that operate at high pressure and temperature. In the first reactor the molecule is ruptured, releasing sulfur and nitrogen, then the liquid fraction enters the second reactor where it is hydroisomerized and cracked. The hydrocracking process allows a variety of liquid fuels with certain undesirable characteristics to conform to existing environmental requirements.
[0005] These conventional processes have a high demand in energy and require large spaces for the process to take place, aside from the use of catalysts and other consumables which require periodical exchange or replacement. All this represents an added cost for the industry, especially now that we have to work with heavier fractions of sour crude oil.
SUMMARY OF THE INVENTION
[0006] The present invention provides a novel system and method for sulphur and metal removal from crude oil and all liquid fuel fractions.
[0007] According to an aspect of the invention, the system is a lower energy/power/heat consumption system.
[0008] According to another aspect of the invention, the method removes sulphur, zinc and silica by reacting with sodium methylate.
[0009] According to another aspect of the invention, the method removes sulphur, zinc and silica by reacting with potassium methylate.
[0010] According to another aspect of the invention, the method removes heavy metals by reacting with water.
[0011] According to still another aspect of the invention, the method improves the API index.
[0012] According to yet another aspect of the invention, the method creates cleaner fuels.
[0013] According to another aspect of the invention, the method can be applied to biofuels as well as hydrocarbon fuels.
[0014] According to yet another aspect of the invention, the method reduces associated system maintenance due to a cleaner combustion process.
[0015] According to yet another aspect of the invention, the method increases the volume of the treated fuel.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Further features and advantages of the invention will become apparent from the following detailed description taken in conjunction with the accompanying figures showing illustrative embodiments of the invention, in which:
[0017] FIG. 1 illustrates the sulfur and heavy metal removal system, according to an embodiment of the present invention.
[0018] FIG. 2 illustrates a dosing, mixing and cavitation configuration, according to an embodiment of the present invention.
[0019] FIG. 3 illustrates an isometric view of the sulfur and heavy metal removal system, according to an embodiment of the present invention.
[0020] FIG. 4 illustrates a hydrodynamic cavitation reactor system, according to a preferred embodiment of the invention.
[0021] FIG. 5 illustrates an isometric view of water and methylate tank system, according to an embodiment of the present invention.
[0022] FIG. 6 illustrates a treated fuel pressure release tank, according to an embodiment of the present invention.
[0023] FIG. 7 illustrates a heat exchanger, according to an embodiment of the present invention.
[0024] FIG. 8 illustrates a dosing and mixing unit, according to an embodiment of the present invention.
[0025] Throughout the figures, the same reference numbers and characters, unless otherwise stated, are used to denote like elements, components, portions or features of the illustrated embodiments. The subject invention will be described in detail in conjunction with the accompanying figures, in view of the illustrative embodiments.
DETAILED DESCRIPTION OF THE INVENTION
[0026] The method of the present invention, is based on the use of a mixing and dosing station, followed by an ultrasonic cavitation reactor coupled with a 300 atm. high pressure system in the presence of 5% Sodium or Potassium Methylate additives in one stage to react with the sulfur, zinc, and silica content in the fuel producing sulfates and salts that are collected in their solid form in a centrifuge filter station, and 20% water with 0.5% fluoride, on a secondary stage, that reacts with certain metals (Mercury Hg, Cadmium Cd, Lead Pb, and Vanadium) which are bonded to the fluoride molecules and removed in their solid form via centrifuge filtering station, ostensibly improving overall physical-chemical characteristics of the fuel during the process. Regardless of the fuel enhanced by the method, the resulting fuel will also have better characteristics, since polymeric molecules are broken and rearranged due to ultrasound enhanced chemical reactions, so that characteristics such as, for example, API in the case of crude oil, and flash point, Cetane level, and heating value in the case of diesel are substantially improved, among other treated fuels and improvements.
[0027] An ultrasonic cavitation reactor is a device which reproduces the cavitation phenomenon or cavitation bubbles in the liquid; here a fluid is subjected to a strong change of pressure with the aim of achieving a phase shift among other functions. In the reactor, pressure reached is equal to the vapor pressure of the fluid, causing the formation of cavitation bubbles known as cavities. These reactors provide the formation of cavities, which in turn implode generating high frequency pulses (ultrasonic waves) that shock the fluid causing the rupture and reorganization of the polymer chains in the fuel therefore allowing for new bonds to be attained with the introduced additives.
[0028] During the process of the present invention, the molecular rupture of the polymer chains forms what we call a “temporary active binding center”, also known as radical, which is ready to combine chemically with the methylate molecules in the first stage and fluoride in the second stage. These active binding sites are joined with the desired molecules to react with the contaminant in the fuel, therefore disrupting the original bonds within the fuel before it is treated.
[0029] Any polymer chain fluid that is submitted to this strong pressure change suffers rupture and reorganization of its molecules. When the rupture occurs, unstable molecular “active” sites are formed and become available to be combined in situ with other molecules (additives). The formation of these active sites is what makes possible the reorganization and recombination of the fuel's molecules therefore improving the fuel's overall quality and characteristics, as well as the removal of unwanted contaminants.
[0030] Molecular rupture caused by the process of the present invention is used to liberate the undesired contaminating molecules and reacting them with methylate and fluoride to create new bonds that are easily removed from the stream. Since we must dilute fluoride in water, the excess H2O forms a new polymer chain in the fuel containing hydrogen and oxygen within its final structure. This process improves the treated fuels, increasing the volume of the finished product by the determined percentage, enhancing features and characteristics while remaining molecularly_stable.
[0031] The physics and chemistry behind the process of the present invention is based on studies of the induced sono-chemical reactions on inorganic and organic material after being submitted to ultrasound. In the process of the present invention, the ultrasound energy is supplied by the formation of cavities in the fluid due to the change in pressure induced by the ultrasonic cavitation reactor. The high inlet pressure is violently reduced inside the reactor, causing a thermodynamic change which is used to aid in the formation of cavities within the fluid (cavitation bubbles). When the fluid returns to its initial conditions the cavities then collapse and release a large amount of energy which is absorbed by the fluid rupturing its molecular structure and reorganizing the molecules in a more orderly and stable form for combustion. The intensity in which we create the cavities or cavitation bubbles within the fluid is a function of the system's pressure which also determines the frequency and the intensity of the shock wave that causes the molecular rupture.
[0032] During the phenomenon of creation and subsequent collapse of cavities or cavitation bubbles, the process of the present invention reaches up to 500 atmospheres of localized pressure and hundreds of degrees in temperature, which rupture all polymer chain liquid fluid molecules. This same energy is used to form new polymer chains that are more stable, allow us to remove undesired elements or compounds in the fuel and also results in a fuel with better properties for combustion.
[0033] Based on the above explanation, it is clear that the reactions happen due to a local increase in the temperature, pressure and the formation of molecular radicals. All of these chemical and physical changes are due to the rupture of the fluid molecular links caused by the collapse of the cavitation bubbles created during the process of cavitation. Depending on the nature of the liquid being cavitated, different effects can be obtained such as: radical creation, depolymerization, Lysis, liquid emulsions, rupture of solid particles, and acceleration of chemical reactions, among others.
[0034] FIG. 1 illustrates an embodiment of the present invention used to remove fuel contaminants such as sulfur, zinc, silica, mercury, lead, among others, as well as fuel volume increase. The system improves fuels to produce less polluting fuels as well as increasing its final volume. The system comprises a first stage dosing, mixing, and ultrasonic cavitation station 110 , a centrifuge filtering system 112 , and a heat exchanger 109 . The dosing and mixing station receives fuel from fuel tank 101 which is preheated by a heater 109 , as well as methylate from storage tank 102 by means of pumps 141 , 142 . Before arriving at the station 110 the various liquids travel through a check valve 121 , 122 and each flow is controlled by volume through an adjustable control flow valve 131 , 132 . At the dosing and mixing station in 110 liquids are kept for ten minutes (10 min.) while a micro emulsion is obtained. After this, the mixture passes through a high-pressure pump where the fluid reaches a high pressure of 300 atmospheres. At this high pressure, the fluid enters the ultrasonic cavitation reactor in 110 where cavitation bubbles form and the depolymerization and the desired reactions take place. After the mixture has been cavitated under the mentioned pre-established pressure, the treated fuel is stored in the insulated storage tank 103 for pressure release. The treated fuel is then pumped through pump 111 and filtered through the centrifuge 112 to remove the resulting solids. The fuel is then ready to move to the second stage for metal removal. The second stage system comprises a dosing, mixing, and ultrasonic cavitation station 113 , a centrifuge filtering system 115 , and a heat exchanger 106 . The dosing and mixing station receives fuel from fuel tank 103 which has been treated at the first stage, as well water/fluoride from storage tank 104 by means of pumps 143 , 144 . Before arriving at the station 113 the various liquids travel through a check valve 123 , 124 and each flow is controlled by volume through an adjustable control flow valve 133 , 134 . At the dosing and mixing station in 113 liquids are kept for ten minutes (10 min.) while a micro emulsion is obtained. After this, the mixture passes through a high-pressure pump where the fluid reaches a high pressure of 300 atmospheres. At this high pressure, the fluid enters the ultrasonic cavitation reactor in 113 where cavitation bubbles form and the depolymerization and the desired reactions take place. After the mixture has been cavitated under the mentioned pre-established pressure, the treated fuel is stored in the insulated storage tank 105 for pressure release. The treated fuel is then pumped through pump 114 and filtered through the centrifuge 115 to remove the resulting solids. The final clean fuel goes through a heat exchanger 106 , before exiting through outlet 107 , to remove the temperature increase that results from the cavitation by means of the recycling of the closed loop system 108 .
[0035] FIG. 2 illustrates the dosing, mixing, and cavitation station 110 , 113 from FIG. 1 comprising two mixing tanks 221 , 222 , which receive water/fluoride or methylate through pipe 201 , and preheated fuel from pipe 202 . The mixing that takes place in the tanks 221 , 222 occurs by recirculating with a high pressure pump 231 , 232 . Mixing takes place for a pre-determined amount of time as stated above, at such time a computer-controlled valve 241 , 242 is opened, allowing the mixed fluid to enter the ultrasonic cavitation reactor 261 . After the mixture has been cavitated under pre-established pressure, the chemically treated fuel is sent through a pipe 270 to the insulated storage tank.
[0036] The illustration shown in FIG. 3 is an isometric representation for the embodiment of the present invention used to remove fuel contaminants such as sulfur, zinc, silica, mercury, lead, among others, as well as fuel volume increase. The system improves fuels to produce less polluting fuels as well as increasing its final volume. The system comprises a first stage dosing and, mixing station 310 and an ultrasonic cavitation reactor 310 a, a centrifuge filtering system 312 , and a heat exchanger 309 . The dosing and mixing station receives fuel from fuel tank 301 which is preheated by a heater 309 , as well as methylate from storage tank 302 by means of pumps 341 , 342 . At the dosing and mixing station 310 liquids are kept for ten minutes (10 min.) while a micro emulsion is obtained. After this, the mixture passes through a high-pressure pump where the fluid reaches a high pressure of 300 atmospheres. At this high pressure, the fluid enters the ultrasonic cavitation reactor 310 a where cavitation bubbles form and the depolymerization and the desired reactions take place. After the mixture has been cavitated under the mentioned pre-established pressure, the treated fuel is stored in the insulated storage tank 303 for pressure release. The treated fuel is then pumped through pump 311 and filtered through the centrifuge 312 to remove the resulting solids. The fuel is then ready to move to the second stage for metal removal. The second stage system comprises a dosing and mixing station 313 , an ultrasonic cavitation reactor 313 a, a centrifuge filtering system 315 , and a heat exchanger 306 . The dosing and mixing station receives fuel from fuel tank 303 which has been treated at the first stage, as well water/fluoride from storage tank 304 by means of pumps 343 , 344 . At the dosing and mixing station 313 liquids are kept for ten minutes (10 min.) while a micro emulsion is obtained. After this, the mixture passes through a high-pressure pump where the fluid reaches a high pressure of 300 atmospheres. At this high pressure, the fluid enters the ultrasonic cavitation reactor 313 a where cavitation bubbles form and the depolymerization and the desired reactions take place. After the mixture has been cavitated under the mentioned pre-established pressure, the treated fuel is stored in the insulated storage tank 305 for pressure release. The treated fuel is then pumped through pump 314 and filtered through the centrifuge 315 to remove the resulting solids. The final clean fuel goes through a heat exchanger 306 , before exiting through outlet 307 .
[0037] FIG. 4 illustrates an ultrasonic cavitation reactor of the present invention. In a preferred embodiment the hydrodynamic cavitation reactor is made from stainless steel. The system comprises a high pressure pump 401 set at 300 atmospheres, a cavitation valve 402 , a Schedule 40 SS 1″ diameter pipe 403 , all contained in one module, specifically the valve 402 contains the following zones; liquid entrance zone 404 , a cavitation bubble formation zone 405 , and a shock zone 406 where the molecular rupture and reorganization occurs.
[0038] FIG. 5 illustrates a water/fluoride and methylate storage tank of the present invention. In a preferred embodiment the water and methylate storage tank is made from stainless steel. The system comprises an entrance pipe connector 501 , a cylindrical tank, among other shapes 502 , an exit pipe connector 503 , and a support frame 504 when deemed necessary.
[0039] FIG. 6 illustrates a fuel storage tank of the present invention. In a preferred embodiment the fuel storage tank is made from stainless steel. The system comprises an entrance pipe connector 601 , a cylindrical tank, among other shapes 604 , an exit pipe connector 605 , and a support frame when deemed necessary.
[0040] In a preferred embodiment the heat exchanger is a shell and tube type heat exchanger as illustrated in FIG. 7 . In a preferred embodiment the heat exchanger is made from stainless steel. The system comprises a cooling liquid entrance pipe connector 701 , a temperature sensor 702 , a treated fuel entrance pipe connector 703 , a cooling liquid exit pipe connector 704 , a treated fuel exit pipe connector 705 , and four baffles 706 to ensure proper heat exchange between fluids.
[0041] FIG. 8 illustrates the dosing and mixing station of the present invention. In a preferred embodiment the dosing and mixing station is made from stainless steel. The system comprises a water or methylate entrance pipe connector 801 , a fuel entrance pipe connector 802 , and an extra connector 803 which is used for cleaning, a cylindrical tank, among other available shapes 805 , a mixed fuel/water or fuel/methylate emulsion exit pipe connector 804 , all held together with a steel frame.
[0042] Although the present invention has been described herein with reference to the foregoing exemplary embodiment, this embodiment does not serve to limit the scope of the present invention. Accordingly, those skilled in the art to which the present invention pertains will appreciate that various modifications are possible, without departing from the technical spirit of the present invention.
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The present invention provides a novel system and method for sulphur and metal removal from crude oil and all liquid fuel fractions to biofuels by means of ultrasonic cavitation to enhance chemical reactions of said contaminants with sodium or potassium methylate and a water/fluoride mix in separate stages obtaining a solid form which is filtered out by the use of a centrifuge system. The resulting fuel is molecularly stable and cleaner than regular fuels.
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BACKGROUND OF THE INVENTION
[0001] The present invention relates to an ink cartridge detector operable to detect whether or not an ink cartridge is properly mounted on a cartridge holder. The invention also relates to an ink jet printer provided with the above mentioned ink cartridge detector, and to the ink cartridge to be employed in the above mentioned ink cartridge detector.
[0002] There has been widely used an ink jet printer of a type that prints characters and images on a printing medium by discharging ink which is supplied from an ink tank onto the printing medium through a print head. In the ink jet printer of this type, the ink tank of a cartridge system (hereinafter referred to as an “ink cartridge”) has been widely employed so as to facilitate supply of the ink.
[0003] In the above described ink jet printer, it has been required to detect an amount of remaining ink in the ink cartridge and a mounting condition of the ink cartridge for the purpose of preventing defective printing due to shortage of the remaining ink in the ink cartridge or incomplete mounting of the ink cartridge, or for the purpose of issuing an alarm indicating the shortage or the incomplete mounting. For this reason, there have been proposed mechanisms for enabling the amount of the remaining ink and the incomplete mounting of the ink cartridge to be detected by a single optical sensor of the reflective type (disclosed in Japanese Patent Publications Nos. 10-230616A and 9-174877A, for example).
[0004] In the above described detectors, a light beam is emitted from the optical sensor onto two reflectors (prisms) which are provided in a bottom of the ink cartridge, and the amount of the remaining ink and the mounting condition are detected on the basis of amounts of reflective light beams received from the reflectors. Specifically, the reflector for detecting the amount of the remaining ink is transparent so that reflectivity (intensity of reflected light) may vary according to the amount of the remaining ink, while the reflector for detecting the mounting condition is mirror-finished so that the light can be reflected irrespective of the amount of the remaining ink.
[0005] However, in the above described related-art ink jet printer, there have been such problems as described below.
[0006] i) It has been necessary for the ink cartridge to be provided with two reflectors which are formed of separate members, and hence, the number of components and production steps are increased, creating a high cost for the ink cartridge.
[0007] ii) Because the reflectors of the ink cartridge are exposed inside the printer even when a printing operation is performed, there has been such a possibility that spots such as ink splashed during the printing operation might adhere to the reflectors to make the detection by the optical sensor unstable.
[0008] iii) When the optical sensor has received the reflective light, it is decided that the ink cartridge has been properly mounted. Therefore, when the optical sensor has received an exterior turbulent light, it has been liable to be decided that the ink cartridge has been properly mounted, even though the ink cartridge has not yet been mounted As such, the printing operation might be commenced without proper mounting of the ink cartridge.
SUMMARY OF THE INVENTION
[0009] It is an object of the invention to provide an ink cartridge detector, in which necessity for providing an ink cartridge with a reflector for detecting the mounting condition can be eliminated although the mounting condition of the ink cartridge is detected by an optical sensor of reflective type, whereby not only reduction of cost for the ink cartridge can be attained, but also an erroneous recognition of the mounting condition due to soils or ink splash on the reflector or an exterior turbulent light can be prevented.
[0010] It is also an object of the invention to provide an ink jet printer incorporating such an ink cartridge detector, and an ink cartridge detected by such an ink cartridge detector.
[0011] In order to achieve the above objects, according to the invention, there is provided an ink cartridge detector, comprising:
[0012] an ink cartridge;
[0013] a cartridge holder, on which the ink cartridge is detachably mounted;
[0014] at least one first reflector, provided in the cartridge holder;
[0015] a reflective-type optical sensor, including a light emitter and a light receiver, the optical sensor operable to form an optical path originated from the light emitter to the light receiver via the first reflector; and
[0016] a shading member, provided in the ink cartridge operable to shade the optical path when the ink cartridge is mounted on the cartridge holder.
[0017] The first reflector may be integrally fixed on a bottom portion of the cartridge holder. In such a configuration, not only the structure can be simplified, but also reliability of detecting the mounting condition of the ink cartridge can be enhanced, in comparison with a case where the reflector is provided as a movable member.
[0018] Further, the shading member may be integrally formed with the ink cartridge at a lower portion thereof (a downstream portion with regard to an inserting direction of the ink cartridge with respect to the cartridge holder). In such a configuration, the number of components and production steps of the ink cartridge can be reduced.
[0019] The ink cartridge may be formed with a recess which covers the first reflector when the ink cartridge is mounted on the cartridge holder, so that at least one of side walls forming the recess serves as the shading member. In such a configuration, because the first reflector is covered when the ink cartridge has been mounted, soils or ink splash on the first reflector caused by a printing operation can be reliably prevented.
[0020] The shading member may not shade the optical path when the ink cartridge is provisionally mounted on the cartridge holder. In such a configuration, such an inconvenience that the printing operation is conducted in a provisionally mounted state of the ink cartridge can be avoided.
[0021] The ink cartridge detector may further comprise a first engagement member provided in the ink cartridge, and a second engagement member provided in the cartridge holder. The first engagement member may come into contact with the second engagement member such that the ink cartridge is retained at a first position in which the shading member does not shade the optical path. In addition, the first engagement member may engage with the second engagement member such that the ink cartridge is retained at a second position in which the shading member shades the optical path.
[0022] In one embodiment, the first engagement member is provided as a convex portion formed on the ink cartridge, the second engagement member is provided in a free end portion of an elastic member which is supported by the cartridge holder in a cantilevered manner; the second engagement member is a V-shaped member including a first slope portion and a second slope portion so as to convex toward the ink cartridge; the convex portion is brought into contact with the first slope portion when the ink cartridge is retained at the first position; and the convex potion is retained by the second slope portion when the ink cartridge is retained at the second position.
[0023] Preferably, the optical sensor and the cartridge holder are movable relative to each other. Here, it is preferable that a plurality of first reflectors are arranged in a direction of relative movement between the optical sensor and the cartridge holder. In such a configuration, it is possible to detect the mounting conditions of a plurality of the ink cartridges by the same optical sensor.
[0024] Also, the ink cartridge detector may further comprise a second reflector, provided in the ink cartridge, which reflects light emitted from the light emitter and varies an intensity thereof in accordance with an ink amount remaining in the ink cartridge. Here, the second reflector may be operable to form a part of an optical path originated from the light emitter to the light receiver, when the ink cartridge is mounted on the cartridge holder. In such a configuration, it is possible to detect both the mounting condition of the ink cartridge and the amount of the remaining ink by the same optical sensor.
[0025] According to the invention, there is also provided an ink jet printer comprising the above ink cartridge detector.
[0026] Further, according to the invention, there is also provided an ink cartridge, operable to be detachably attached to a cartridge holder provided with a first reflector capable of forming a part of an optical path originated from a light emitter of an external optical sensor to a light receiver of the optical sensor, the ink cartridge comprising:
[0027] an ink reservoir, storing ink therein,
[0028] a second reflector, which reflects light emitted from the light emitter and varies an intensity thereof in accordance with an ink amount remaining in the ink reservoir, the second reflector operable to form a part of an optical path originated from the light emitter to the light receiver; and
[0029] a shading member, which shades the optical path, which has been formed by the first reflector and the optical sensor, when the ink cartridge is mounted on the cartridge holder.
[0030] Preferably, the shading member shades the first reflector from the light emitted from the light emitter, when the ink cartridge is mounted on the cartridge holder.
[0031] Here, a recess may be formed so as to cover the first reflector when the ink cartridge is mounted on the cartridge holder, so that at least one of side walls forming the recess serves as the shading member. The recess may be shaped as to surround an outer periphery of the first reflector.
[0032] Also, it is preferable that the recess is formed on a face opposing to the cartridge holder.
[0033] The ink cartridge may further comprise a first engagement member. In one embodiment, the first engagement member comes into contact with a second engagement member provided in the cartridge holder, such that the ink cartridge is retained at a first position in which the shading member does not shade the optical path. The first engagement member engages with the second engagement member such that the ink cartridge is retained at a second position in which the shading member shades the optical path.
[0034] Preferably, the second reflector and the shading member are juxtaposed in a direction in which the cartridge holder and the optical sensor are to be moved relative to each other.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] The above objects and advantages of the present invention will become more apparent by describing in detail preferred exemplary embodiments thereof with reference to the accompanying drawings, wherein:
[0036] [0036]FIG. 1 is a side view schematically showing an interior structure of a printer;
[0037] [0037]FIG. 2 is a plan view schematically showing the interior structure of the printer;
[0038] [0038]FIG. 3 is a perspective view of a carriage on which a print head is mounted;
[0039] [0039]FIG. 4 is a front view of an ink supply section showing a state in which ink cartridges are not mounted.
[0040] [0040]FIG. 5 is a front view of the ink supply section showing a state in which the ink cartridges are mounted;
[0041] [0041]FIG. 6 is a perspective view of the ink supply section showing the state in which the ink cartridges are not mounted;
[0042] [0042]FIG. 7 is a perspective view of the ink supply section showing the state in which the ink cartridges are mounted;
[0043] [0043]FIG. 8 is a perspective view of the ink cartridge as viewed from a bottom thereof;
[0044] [0044]FIGS. 9A to 9 C are explanatory views showing detection of mounting condition and detection of an amount of remaining ink;
[0045] [0045]FIG. 10 is a sectional view of the ink supply section taken along a line X-X in FIG. 7, showing a state where the ink cartridge is plenarily mounted; and
[0046] [0046]FIG. 11 is a sectional view of the ink supply section taken along a line Y-Y in FIG. 7, showing a state where the ink cartridge is provisionally mounted
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0047] One embodiment of the invention will be described referring to the accompanying drawings. As shown in FIG. 1, an inlet 11 for inserting paper P by hand is provided on a front face of a printer 10 . An outlet 12 for discharging the paper P after printing is provided on an upper face of the printer 10 . Inside the printer 10 , there is formed a paper feeding path 13 in a V-shape in a side view extending from the inlet 11 to the outlet 12 , and a paper feeding roller unit 14 and a print head 15 are arranged on the paper feeding path 13 . The paper feeding roller unit 14 includes a paper feeding roller 16 and a paper holding roller 17 which are opposed to each other on both sides of the paper feeding path 13 , and adapted to clamp and transport the paper P in accordance with driving rotation of the paper feeding roller 16 .
[0048] The print head 15 is mounted on a carriage 18 which reciprocates in a lateral direction of the paper feeding path 13 (in a direction from the left to the right in FIG. 2), and adapted to perform dot matrix printing on the paper P. The position of the paper P is regulated by a platen 19 . The printing system of the print head 15 is an ink jet system in which characters or images are printed on the paper P by discharging ink, and the ink used for printing is supplied to the print head 15 from an ink supply section 20 which is provided in a rear area of the printer 10 .
[0049] The carriage 18 is supported by a pair of front and rear guide shafts 21 , 22 so as to move from the left to the right, and is forcibly moved in accordance with driving motion of a carriage driving mechanism 23 . The carriage driving mechanism 23 includes a cam shaft 24 which is arranged below the front guide shaft 21 in parallel thereto, and a carriage motor 26 for actuating the cam shaft 24 to rotate by way of a reduction gear train 25 (FIG. 2). On an outer peripheral face of the cam shaft 24 , there is formed a cam groove in a spiral shape (not shown), with which a cam follower 27 extending from the carriage 18 is adapted to be engaged. When the cam shaft 24 is rotated in accordance with the driving motion of the carriage motor 26 , the cam follower 27 is shifted in an axial direction with spiral shifting action of the cam groove. In this manner, it will be possible to reciprocate the carriage 18 from the left to the right in accordance with normal and reverse drives of the carriage motor 26 .
[0050] As shown in FIG. 3, the print head 15 is mounted on an upper part of the carriage 18 . A flat cable 28 and ink tubes 29 having flexibility are drawn from a side area of the print head 15 , and the ink is supplied to the print head 15 from the ink supply section 20 by way of the ink tubes 29 . The carriage 18 has a sensor mounting part 18 a which is extended downwardly from its rear part, and an optical sensor 30 of a reflective type which includes a light emitting element 30 a for emitting a light beam to the rear and a light receiving element 30 b for receiving a reflective light beam is attached to a back face of the sensor mounting part 18 a.
[0051] As shown in FIG. 4, the ink supply section 20 includes a cartridge holder 31 which is provided in a rear area inside the printer 10 , and two ink cartridges 32 A, 32 B which are detachably mounted on the cartridge holder 31 from the above. As shown in FIG. 8, an ink reservoir 34 A is partitioned inside the ink cartridge 32 A to store secondary ink (for example, colored ink such as cyan, magenta, yellow, red, green, blue). The secondary ink is appropriately discharged from an ink outlet 33 A formed in a bottom of the ink cartridge 32 A. A waste ink reservoir 36 is also partitioned inside the ink cartridge 32 A to store waste ink supplied from a recovery inlet 35 formed in the bottom. When the ink cartridge 32 A has been mounted at a predetermined (specific) position on the cartridge holder 31 , the ink outlet 33 A and the recovery inlet 35 are communicated with connecting ports 37 A, 38 which are formed in a bottom of the cartridge holder 31 , thus permitting supply of the secondary ink and recovery of the waste ink.
[0052] On the other hand, inside the ink cartridge 32 B, there are partitioned an ink reservoir 34 B which stores primary ink (for example, black ink) and appropriately discharges the primary ink from an ink outlet 33 B in a bottom of the ink cartridge 32 B. When the ink cartridge 32 B has been mounted at a predetermined (specific) position on the cartridge holder 31 , the ink outlet 33 B is communicated with a connecting port 37 B which is formed in the bottom of the cartridge holder 31 , thus permitting supply of the primary ink.
[0053] The ink cartridges 32 A, 32 B are arranged in a row along a moving direction of the carriage 18 (the optical sensor 30 ). The ink cartridges 32 A, 328 are respectively provided, at positions opposed to a moving path L (see FIG. 5) of the optical sensor 30 on their front faces, with reflectors (reflectors for detecting an amount of remaining ink) 39 A, 39 B in a shape of prism having transparency. The reflectors 39 A, 39 B have a shape of a right triangle prism, and two prism reflective faces S 1 , S 2 which are at a right angle with respect to each other are protruded into the ink reservoirs 34 A, 34 B. As shown in FIG. 9B, when the optical sensor 30 is moved to a position opposed to the reflector 39 A and a light is emitted thereto, the emitted light is reflected at the prism reflective faces S 1 , S 2 sequentially while passing interiors of the reflector 39 A, and received by the light receiving element 30 b . When the optical sensor 30 is moved to a position opposed to the reflector 39 B and a light is emitted thereto, the emitted light is reflected at the prism reflective faces S 1 , S 2 sequentially while passing interiors of the reflector 398 , and received by the light receiving element 30 b.
[0054] Reflectivity (refraction index) of the prism reflective faces S 1 , S 2 is low in the case where levels of the remaining ink in the ink reservoirs 34 A, 34 B are higher than the prism reflective faces S 1 , S 2 , and is high in the case where the levels of the remaining ink are lower than the prism reflective faces S 1 , S 2 . In short, in a state where the prism reflective faces S 1 , S 2 are in contact with the ink as shown in FIG. 9A, an emitted light beam of the optical sensor 30 is absorbed by the ink to have a low reflectivity (the intensity of reflected light is made low), and in a state where the prism reflective faces S 1 , S 2 are in contact with air as shown in FIG. 9B, the light beam is not absorbed by the ink to have a high reflectivity (the intensity of reflected light is made high). In this manner, it will be possible to detect the amount of the remaining ink (presence or absence of the ink at the predetermined level) in the ink cartridges 32 A, 32 B on the basis of a value detected by the light receiving element 30 b of the optical sensor 30 .
[0055] As shown in FIGS. 4 and 6, on the bottom of the cartridge holder 31 , two reflectors (reflectors for detecting mounting condition) 40 A, 40 B are fixed in a row along the moving direction of the carriage 18 (the moving path L of the optical sensor 30 ), in an upwardly protruding posture. Each of the reflectors 40 A, 40 B has a prism part 40 a in a shape of a right triangle prism, and reflective light paths of the optical sensor 30 are formed by two prism reflective faces S 3 , S 4 which are at a right angle with respect to each other, in the same manner as the reflectors 39 A, 39 B for detecting the amount of the remaining ink. On the other hand, recesses (hollowed parts) 41 A, 41 B are integrally formed in respective lower portions of the ink cartridges 32 A, 32 B. When the ink cartridges 32 A, 32 B have been mounted at the predetermined positions of the cartridge holder 31 , the reflectors 40 A, 40 B are inserted into the recesses 41 A, 41 B, and the surroundings are covered. On this occasion, shield parts 42 A, 42 B which are integrally formed on one side faces of the recesses 41 A, 41 B (wall portions opposed to the optical sensor) are interposed between the optical sensor 30 and the reflectors 40 A, 40 B, so as to shield light paths (irradiation paths and reflective paths) between the optical sensor 30 and the reflectors 40 A, 40 B.
[0056] As shown in FIGS. 4 and 9C, in the state where the ink cartridges 32 A, 32 B are not mounted on the cartridge holder 31 , the reflectors 40 A, 40 B are exposed. When the optical sensor 30 is moved to a position opposed to the reflector 40 A in this state, the emitted light is sequentially reflected at the reflective faces S 3 , S 4 while passing the interior of the reflector 40 A, and will enter the light receiving element 30 b . When the optical sensor 30 is moved to a position opposed to the reflector 40 B in this state, the emitted light is sequentially reflected at the reflective faces S 3 , S 4 while passing the interior of the reflector 40 B, and will enter the light receiving element 30 b . On the other hand, as shown in FIGS. 9A and 9B, in the state where the ink cartridges 32 A, 32 B have been mounted on the cartridge holder 31 , front areas of the reflectors 40 A, 40 B are covered with the shield parts 42 A, 42 B. When the optical sensor 30 is moved to the position opposed to the reflector 40 A in this state, the emitted light is shielded by the shield part 42 A, and will not reach the reflector 40 A nor the light receiving element 30 b of the optical sensor 30 . When the optical sensor 30 is moved to the position opposed to the reflector 40 B in this state, the emitted light is shielded by the shield part 42 B, and will not reach the reflector 40 B nor the light receiving element 30 b of the optical sensor 30 .
[0057] In this manner, it is possible to detect the mounting condition of the ink cartridges 32 A, 32 B by the optical sensor 30 , without providing the ink cartridges 32 A, 32 B with the reflectors for detecting the mounting condition. Moreover, in the state where the ink cartridges 32 A, 32 B are not mounted on the cartridge holder 31 as described above, since the light receiving element 30 b is always subjected to the light emission, an exterior turbulent light will not influence detection results of the mounting condition of the ink cartridges 32 A, 32 B, even though the exterior turbulent light is emitted to the light receiving element 30 b . Further, in the state where the ink cartridges 32 A, 32 B have been mounted on the cartridge holder 31 , since the reflectors 40 A, 40 B are covered with the recesses 41 A, 41 B, the ink will not adhere to the reflectors 40 A, 40 B, even though the ink is splashed during the printing operation. As a result, it is possible to prevent an erroneous detection caused by ink adhering to the reflectors 40 A, 40 B.
[0058] [0058]FIG. 10 is a sectional view of the ink supply section taken along a line X-X in FIG. 7, showing a state where the ink cartridge is plenarily mounted, and FIG. 11 is a sectional view of the ink supply section taken along a line Y-Y in FIG. 7, showing a state where the ink cartridge has been provisionally mounted. As shown in these drawings, there are provided, in a rear part of the cartridge holder 31 , two lock plates 43 A, 438 in an upright manner. The lock plates 43 A, 43 B are elastic plate members formed with V-shaped locking portions 44 A, 44 B in their upper end portions. When the ink cartridges 32 A, 328 have been mounted on the cartridge holder 31 from above, convex portions 45 A, 45 B projected from back faces of the ink cartridges 32 A, 32 B lie on the lock portions 44 A, 44 B of the lock plates 43 A, 43 B, as shown in FIG. 11, to hold the ink cartridges 32 A, 32 B in a provisionally mounted state. On this occasion, the shield parts 42 A, 42 B of the ink cartridges 32 A, 32 B are located above the prism parts 40 a of the reflectors 40 A, 40 B, and the light paths between the optical sensor 30 and the reflectors 40 A, 40 B will not be shielded.
[0059] Further, in the above described provisionally mounted state, when the ink cartridges 32 A, 32 B are pushed downward, the lock plates 43 A, 43 B are pressed by the convex portions 45 A, 45 B to be tilted so as to once retreat backward, and then, ride over the convex portions 45 A, 45 b to be tilted so as to be returned forward. After the lock plates 43 A, 43 B have been tilted to be returned, the locking portions 44 A, 44 B are engaged with upper parts of the convex portions 45 A. 45 B as shown in FIG. 10, and the ink cartridges 32 A, 32 B are held (locked) in their mounting positions. On this occasion, the shield parts 42 A, 42 B of the ink cartridges 32 A, 32 B are interposed between the prism parts 40 a of the reflectors 40 A, 40 B and the optical sensor 30 to shield the light path of the optical sensor 30 .
[0060] As described above, according to this embodiment, the printer 10 is constructed by including the optical sensor 30 of a reflective type which projects the light to the cartridge holder 31 to detect the mounting conditions of the ink cartridges 32 A, 32 B on the basis of the reflective light, the reflectors 40 A, 40 B which are provided on the cartridge holder 31 to form the reflective light path of the optical sensor 30 , and the shield parts 42 A, 42 B which are provided in the ink cartridges 32 A, 32 B, and adapted to shield the light path of the optical sensor 30 when the ink cartridges 32 A, 32 B have been mounted on the cartridge holder 31 . In short, although the mounting condition of the ink cartridges 32 A, 32 B is detected by the optical sensor 30 of the reflective type, necessity for providing the ink cartridges 32 A, 32 B with the reflectors for detecting the mounting condition can be eliminated. Therefore, not only reduction of the cost for the ink cartridges 32 A, 32 B can be attained, but also, an erroneous recognition of the mounting condition due to soils such as ink splash on the reflectors or an exterior turbulent light can be prevented.
[0061] Moreover, because the reflectors 40 A, 40 B are fixed members which are integrally provided in the bottom of the cartridge holder 31 , as compared with the reflectors 40 A, 40 B formed of movable members, not only the structure can be simplified, but also reliability of detecting the mounting condition can be enhanced.
[0062] Further, because the shield parts 42 A, 42 B are integrally formed in the lower parts of the ink cartridges 32 A, 32 B, the number of the components and the production steps of the ink cartridges 32 A, 32 B can be decreased.
[0063] Still further, because the ink cartridges 32 A, 32 B have the recesses 41 A, 41 B which cover the reflectors 40 A, 40 B when they have been mounted on the cartridge holder 31 , and the shield parts 42 A, 42 B are formed at the one side faces of the recesses 41 A, 41 B, the reflectors 40 A, 40 B can be protected when the ink cartridges have been mounted, and defective detection due to soils such as ink splash or damage of the reflectors 40 A, 40 B can be prevented.
[0064] Furthermore, the shield parts 42 A, 42 B will not shield the light path of the optical sensor 30 when the ink cartridges 32 A, 32 B are provisionally mounted on the cartridge holder 31 , and therefore, problems such as conducting the printing operation in the provisionally mounted state of the ink cartridges 32 A, 32 B can be avoided.
[0065] Still further, because the cartridge holder 31 and the optical sensor 30 are relatively movable with respect to each other, it is possible to detect the mounting conditions of a plurality of the ink cartridges 32 A, 32 B, and to detect the amount of the remaining ink in the ink cartridges 32 A, 32 B by the same optical sensor 30 .
[0066] Still further, the cartridge holder 31 is provided with a plurality of the reflectors 40 A, 40 B which are arranged in a row along the direction of the relative movement of the optical sensor 30 (along the line L shown in FIGS. 4 and 5), and accordingly, the same optical sensor 30 can detect the mounting conditions of the plurality of the ink cartridges 32 A, 328 .
[0067] In addition, the ink cartridges 32 A, 32 B are provided with the reflectors 39 A, 39 B for detecting the amount of the remaining ink, enabling the amount of the remaining ink to be detected by the optical sensor 30 , and accordingly, the same optical sensor 30 can detect the amounts of the remaining ink as well as the mounting conditions of the ink cartridges 32 A, 328 .
[0068] Although one of the embodiments according to the invention has been described heretofore, the present invention is not limited to those matters shown in the above described embodiment, but may include such a scope as those skilled in the art can make modification and application of the invention, on the basis of the description in the claims and in the detailed description of the invention, and the well known art.
[0069] For example, although in the above described embodiment, the shield part is formed on one side face of the recess which is integrally formed in the ink cartridge, the shield part may be in any shape, provided that it can shield the light path of the optical sensor 30 when the ink cartridge has been mounted on the cartridge holder. For example, the shield part may be formed in a hook-like shape (L-shape) on the one side face of the ink cartridge.
[0070] Moreover, although in the above described embodiment, the ink cartridges are mounted on the printer body, the invention can be realized in the printer in which the ink cartridges are mounted on the carriage. Specifically, by providing the reflectors on the cartridge holder which is mounted on the carriage, and detecting them by the optical sensor which is provided on the printer body, similar function and advantageous effects to those in the above described embodiment can be obtained.
[0071] According to the present invention as has been herein before described, although the mounting condition of the ink cartridge is detected by the optical sensor of a reflective type, necessity for providing the ink cartridge with the reflectors for detecting the mounting condition is eliminated, and not only reduction of the cost for the ink cartridge can be attained, but also, an erroneous recognition of the mounting condition due to soils such as ink splash on the reflectors or an exterior turbulent light can be prevented.
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An ink cartridge is detachably mounted on a cartridge holder. At least one first reflector is provided in the cartridge holder. A reflective-type optical sensor includes a light emitter and a light receiver. The optical sensor is operable to form an optical path originated from the light emitter to the light receiver via the first reflector. A shading member is provided in the ink cartridge operable to shade the optical path when the ink cartridge is mounted on the cartridge holder. A second reflector is provided in the ink cartridge. The second reflector reflects light emitted from the light emitter and varies an intensity thereof in accordance with an ink amount remaining in the ink cartridge.
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FIELD OF THE INVENTION
The present invention relates to foam pigs of the type used to test pipelines for obstructions or damage, and in particular to such a pig that is instrumented.
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is the National Phase of International Application PCT/GB2010/051988 filed 30 Nov. 2010 which designated the U.S. That International Application was published in English under PCT Article 21(2) on 3 Jun. 2011 as International Publication Number WO 2011/064603 A1. PCT/GB2010/051988 claims priority to U.K. Application No. 0920900.8, filed 30 Nov. 2009. Thus, the subject nonprovisional application also claims priority to U.K. Application No. 0920900.8, filed 30 Nov. 2009. The disclosures of both applications are incorporated herein by reference.
BACKGROUND OF THE INVENTION
Pipelines used for the transmission of oil and gas (and other fluids) need to be inspected. This may be immediately after construction or at periodic intervals thereafter. During the construction phase an obstruction in a pipeline may occur for any number of reasons. The pipeline may have received a blow externally from a machine for example, producing a dent extending into the pipe, a tool may have been left inside the pipe by a worker, excess sealant used at pipe joints may not have been properly removed, etc.
Pipelines are usually subjected to detailed gauge mapping before they are commissioned. However, a pig of this type is constructed with a metal body which may become stuck if it encounters an obstruction in the pipeline. To avoid the gauge pig becoming stuck, it is common practice to send a flexible foam pig through the pipeline first which can squeeze past obstructions much more easily. The foam pig is usually propelled through the pipeline by water. If the pig encounters an obstruction, the pig will in general be forced past the obstruction with and be damaged. If the foam pig exits the pipeline in a damaged condition, the operators know that it is not safe to deploy a (gauge) pig. Instead they would deploy further foam pigs to attempt to clean the line and remove obstructions until the foam pigs emerge from the line undamaged.
Pipelines are used to transport many different types of fluids including oil, gas, water, chemicals, slurries and food products. In order to operate efficiently, it is important that the bore of the pipeline does not become restricted either due to mechanical damage to the pipe wall or due to deposits building up on the inside of the pipeline. Even relatively small reductions in the bore, caused by deposits spread along the length of a pipeline, may have a significant effect on the flow of the product and the pumping efficiency. For this reason, cleaning pigs are used to remove deposits from the line. The pigs are in the form of a plug and they are pushed through the line by the product flow. The pig scrapes the deposits from the pipe wall and the particles are entrained by the flow of the product and pushed along by the pig to the end of the pipeline where they are removed by filters. In some pipelines, the cleaning process is carried out on a routine basis (say every week) and in others the operator will only use a cleaning pig when there is a noticeable fall in the pumping efficiency of the line. Typically, pigs are run through the line repeatedly until the product runs clean with no particles in the flow ahead of the pig. In all cases, the pipe is considered to be clean when this condition is reached.
Different types of pigs may be used during the cleaning process in order to avoid the possibility of a pig getting stuck. On the first run of a pig in the line, the degree of blockage of the line may be unknown and, therefore, early runs are carried out using very flexible foam pigs which are able to get through severe restrictions in the line. Once foam pigs are able to get through the line without damage or without too great a pumping pressure being required, then it is assumed that there are no major restrictions in the line and/or the quantity of deposits is not too great. At this point metal bodied pigs with plastic drive discs are used, which are more aggressive in removing deposits from the pipe wall. Finally, metal bodied pigs with brushes or metal scrapers may be used depending on the hardness and adhesion of the deposits.
In the oil and gas industry, the cleaning of pipelines is normally carried out ‘blind’ with no measurements being carried out to determine the nature and location of the blockage in the line or the thickness and the distribution of the deposits. As a result, the cleaning process must be carried out in a very cautious way, with multiple runs of foam pigs and a gradual progression to metal bodied pigs, with increasingly aggressive configurations. This approach can lead to significant inefficiencies in the cleaning process, with large numbers of cleaning runs being required and many of them possibly being unnecessary. It is proposed that a pig which can be used to measure the pipe bore, both at the start and during the cleaning process, could provide information to optimise the selection of the appropriate type of pig to be run in the line, at each stage in the process.
Instrumented pigs, which can measure and gauge the internal bore of a pipeline, are available and are commonly used in the oil and gas industry. These pigs have arrangements of sensors, transducers, and electronics to measure the internal bore of the pipeline and, by calibrating the systems, they are able to identify and measure changes in the pipe diameter. They also identify and measure features such as dents, ovality, and buckles, which may affect the integrity and operating performance of the pipeline. Typically, the product flow is used to push the pigs along and measurements are taken at frequent intervals, as the pigs are transported down the line. Measurement data are captured using recording devices on the pig and, at the end of the run, the data can be downloaded from the pig for viewing and analysis. However, all instrumented bore measurement pigs are hard bodied and are considered to be too great a risk for running in a pipeline at the early stages of cleaning. This patent proposes a bore measurement pig, which has a foam pig body, with the sensing system integrated into the foam matrix. This ensures that the device can be used with minimum risk, at any stage in the cleaning process, and will provide the operator with detailed information on the nature and location of blockages, and the thickness and distribution of deposits in the line.
It is known to instrument a foam pig. U.S. Pat. No. 5,659,142 describes a foam pig instrumented with pressure sensors. As the pig is caused to move along the pipeline a pressure log is recorded by a pressure sensor, which is housed in a cavity at the centre of the pig. The pressure sensor is part of a sealed unit also comprising a processor, a memory and a power source.
Whilst measuring pressure allows the position of an obstruction to be identified, relying on the measurement of pressure does not yield a great deal of information about the nature of the blockage. Also, some pipeline features, such as ovality, may not affect pressure. If the cross-sectional shape changes, without the cross-sectional area changing, there will be little effect on fluid pressure.
Ultrasonic sensing of pipeline geometry is known in the prior art. It has been shown to work very well as long as it is in a medium, e.g. water or other liquids, that have a predictable effect on the transmitted and reflected signal. In liquids that contain solids, gasses, or badly mixed phases, the transference of the signal through the medium can be unpredictable. This can cause confusion of the signal and severe measurement errors.
It would therefore be desirable to provide an instrumented foam pig that is capable not of not only measuring the position of obstructions, but also the position of changes in the shape of the pipeline, and also to yield more detailed information about the nature of obstructions and the size and shape of defects in the pipeline.
SUMMARY OF THE INVENTION
According to the invention there is provided an instrumented pig comprising a foam body having an outer surface and an inner cavity in which, in use, is located a sealed unit housing at least a part of a parameter measurement apparatus configured to measure at least one parameter from which the extent of deflection of the outer surface of the foam body may be derived, the sealed unit including at least one sensor configured to generate an output signal representative of the at least one measured parameter.
Preferably, the parameter measurement apparatus includes at least one magnet situated within the foam of the foam body and spaced apart from the sealed body, and wherein the sensor is a magnetic flux sensor, preferably a Hall effect sensor. With this sensor arrangement as the pig passes through a pipeline, any perturbation in the shape of the pipeline, be that through the pipeline itself being mis-shaped, or there being a foreign body attached to the inner surface of the pipeline, the outer surface of the foam body is caused to deflect. This deflection of the outer surface of the foam body causes compression of the foam body, with the result that a magnet mounted within the foam body moves towards the sensor as the perturbation is encountered by the pig, and away from the sensor as the perturbation is passed, thereby allowing the internal shape of the pipeline to be mapped. By a process of calibration, the distance moved by outer surface of the foam body away from its position of natural repose can be derived by establishing the distance moved by the magnet towards the sensor.
Advantageously, the centre axis of the sealed unit is substantially aligned with the centre line of the foam body.
The foam body may comprise foam cast into the shape of a cylinder. The foam may be open cell foam.
The foam body may comprise two different types of foam, each of differing densities. In a preferred embodiment of the invention the foam body comprises a first foam element of a first density and a second foam element of a second density, said first foam element including a cavity in which the second foam element is inserted, and the second foam element including a cavity in which the sealed unit is housed. Advantageously, the at least one magnet is situated between the first and second foam elements. Preferably, the second foam element is less dense than the first foam element. This provides the advantage that upon encountering a perturbation in the shape of the inner surface of the pipeline, the second foam element will be compressed more than the first foam element. This means that for a given size of perturbation of the pipeline shape, the magnet will move further towards the magnetic flux sensor than if the foam body were comprised of a foam of a single density, because in that embodiment, the foam located between the magnet and the outer surface would be compressed comparatively more than if the foam to the outside of the magnet were more dense than the foam to the inside thereof.
In a preferred embodiment of the invention the at least one magnet is arranged in the foam with its magnetic axis aligned to the radial axis of the foam body, and the corresponding at least one magnetic sensor is aligned such that its sensitive axis is also aligned to the radial axis of the foam body. The lines of magnetic flux pass from the north pole of the magnet around the edges of the magnet to the south pole. In a small area in the centre of the magnet the flux lines are perpendicular to the face of the magnet and aligned to the sensitive axis of the sensors. This arrangement can be used with two sensor magnet pairs or it can be used with multiple magnet sensor pairs. Radial compression of the foam due to a bore reduction will result in radial movement of the magnet towards the sensor resulting in an increased field strength at the sensor and hence increased output signal from the sensor.
In a preferred embodiment of the invention the magnetic North/South axes of magnets are aligned with the longitudinal axis of the foam body and the sensitive axes of sensors and are also aligned with the longitudinal axis of the foam body. In this arrangement, the sensitive axis of the sensor is aligned to the direction of the magnetic lines of flux passing from the North Pole of the magnet to the South Pole ensuring maximum coupling of the magnetic field to the sensor in each sensor/magnet pair. In the radial direction, the lines of flux become more dense the closer the sensor is to the magnet. Hence, radial compression of the foam due to a bore reduction will result in radial movement of the magnet towards the sensor resulting in an increased field strength at the sensor and hence increased output signal from the sensor.
In one embodiment of the invention the magnets are of a length comparable to the expected extent of longitudinal distortion of the foam body in use. By so specifying the length of the magnets, the length of the small area in the centre of the magnet over which the magnetic flux lines are aligned perpendicular to the face of the magnet and parallel to the sensor axis is increased and provided that the longitudinal movement of the magnet is not greater than the length of this area, then the output from the sensor will not change due to longitudinal distortion of the foam body and no error, or no significant error will be observed.
In an alternative embodiment of the invention a pair of sensors is associated with each magnet, wherein each sensor of the pair is positioned such that its sensitive axis is aligned asymmetrically with the sensitive axis of the other, and preferably substantially perpendicular to each other, advantageously, one in the plane of the longitudinal axis and one in the radial axis of the foam body.
By adding the sensor outputs from the sensor pair, the resultant field can be measured which eliminates the error due to the misalignment of the field and sensor.
In an alternative embodiment of the invention a group of at least three sensors is associated with each magnet. Preferaby, each sensor in the group is positioned such that its sensitive axis is aligned asymmetrically with the sensitive axis of the other sensors in the group and preferably perpendicular to each other. Advantageously, one sensor is positioned with its sensitive axis in the plane of the longitudinal axis, one sensor is positioned with its sensitive axis in the radial axis of the foam body and one sensor is positioned with its sensitive axis aligned to a tangent to any circle having its centre of origin on the axis of the pig body and that circle being aligned so that the alignment between the centre of origin of the circle and any point on the circumference of the circle is parallel to the plane of the radial axis of the foam body.
The sensors of the group of at least three sensors may be positioned with their sensitive axes at any angle relative to each other and/or the major axes of the pig that prove through calculation or trial and error that ameliorate a parameter of the signal received by the sensors, for example the amplitude of the signal, or the noise associated with the signal.
In another case embodiment, the sensitive axis of one sensor of the group is aligned with respect to one of the major axes of the foam body while the sensitive axes of other sensors are rotated away from the remaining axes.
In another embodiment of the invention the sensor is an ultra sound sensor. In this embodiment, the sealed unit includes at least one ultrasound transmitter and at least one ultrasound sensor. Advantageously, the sealed unit includes a plurality of ultrasound sensors. In this embodiment the time taken for an emitted ultrasound signal to be reflected is measured. The foam of the foam body provides a predictable medium through which the ultrasound signal is transmitted, even though the signal would be attenuated somewhat.
An advantage of using the time taken for an ultrasound signal to be reflected as the sensed parameter is that any axial deflection of the foam body should not affect the recorded time, whereas in the case of magnets and magnetic flux sensors, axial deflection of the foam body may result in mis-alignment of the magnet with respect to the magnetic flux sensor, which may introduce an error into the measured parameter.
In order to ensure that the ultrasound signal is transmitted through a medium having fixed and known properties, radial guides may be situated in the foam body. The radial guides lead the ultrasonic signal from the centre of the pig to the outer surface of the foam body and back again.
The radial guides may comprise a chamber. The radial guides may be fluid or gel filled. The chamber may be a flexible plastic, such as polythene.
The sealed unit may also include sensors configured to sense other parameters, for example, temperature and pressure. By sensing these parameters as the pig is passed through a pipeline, if the magnitude of any parameter is affected by temperature and/or pressure, with the information recorded a calibration correction can be made.
According to another aspect of the invention there is provided a process of acquiring information representative of the internal shape of a pipeline comprising the steps of passing an instrumented pig according to the invention through a pipeline and recording the distortion of the foam body of the pig during passage of said pig through the pipeline.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings, which illustrate preferred embodiments of a foam pig according to the invention and are by way of example:
FIG. 1 is a schematic representation of a foam pig according to a first embodiment of the invention;
FIG. 2 a is a schematic representation of the foam pig illustrated in FIG. 1 in a pipeline;
FIG. 2 b is a schematic representation of the foam pig illustrated in FIG. 2 a passing through a constriction in a pipeline;
FIG. 3 is an end view of the foam pig illustrated in FIG. 1 ;
FIG. 4 is a schematic representation of the foam pig illustrated in FIG. 1 showing one arrangement of magnets and magnetic sensors;
FIG. 5 is a schematic representation of the foam pig illustrated in FIG. 1 showing another arrangement of magnets and magnetic sensors;
FIG. 6 is a schematic representation of the foam pig illustrated in FIG. 1 showing another arrangement of magnets and magnetic sensors;
FIG. 7 is a schematic representation of the foam pig illustrated in FIG. 1 showing another arrangement of magnets and magnetic sensors;
FIG. 8 is a schematic representation of a foam pig according to another aspect of the invention;
FIG. 9 is a schematic representation of an alternative embodiment of the invention with the pig travelling through a pipeline, which is in good condition;
FIG. 10 shows the pig illustrated in FIG. 9 continuing to travel forward;
FIG. 11 shows the pig illustrated in FIGS. 9 and 10 when it encounters a dent in a pipeline; and
FIG. 12 shows the pig illustrated in FIG. 11 continuing to travel forwards after first encountering the dent illustrated in FIG. 11 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The first arrangement shown in FIG. 1 is suitable for measuring changes in the bore of the pipe where the changes are uniform such as changes in pipe wall thickness. FIG. 1 shows a pig comprising a foam body ( 1 ) of a typical design for use in cleaning and swabbing oil and gas pipelines. These pigs are commonly manufactured in sizes from 4″ to 48″ although other sizes can be produced. The foam body comprises open cell polyurethane foam cast into the shape of a cylinder with a conical nose cone. The outside diameter of the foam body (DF) is typically designed to be equal to the internal diameter of the pipeline. The direction of travel in the pipeline is shown by the arrow ( 2 ). Embedded in the foam matrix are two diametrically opposed magnets ( 3 ) & ( 4 ) equi-spaced about the axial centre line of the pig. The magnets are cast into the foam matrix in such a way that they move with the foam when the material is compressed or elongated.
Also moulded into the foam is a cylindrical housing ( 5 ), which is positioned so that the axial centre line of the housing is aligned with the axial centre line of the foam body. The housing is a pressure sealed container which is designed to protect the contents against the chemical and pressure effects of the product in the pipeline. The housing contains two magnetic sensors, ( 6 ) & ( 7 ) which are capable of detecting the magnetic field from the magnets embedded in the foam. The sensors are positioned diametrically opposite each other, close to the inner wall of the housing and in line with the magnets ( 3 ) & ( 4 ). Also contained in the housing but not shown are electronic circuits to capture and store the data from the sensors; and batteries to power the sensors and circuits.
FIG. 2 a shows the pig running in a normal bore pipe with no restrictions where the internal pipe diameter D 1 is equal to the outside diameter of the foam body DF. The foam is uncompressed and the separation of the magnets ( 3 ) from the sensor ( 6 ) and the separation of the magnets ( 4 ) from the sensor ( 7 ) is the same and equal to X1.
FIG. 2 b shows the pig in a restricted pipe bore where the internal diameter D 2 of the pipe is less than the outside diameter DF of the foam body. In order to pass through this bore, the foam body must compress so that the outside diameter of the foam equals the inside diameter D 2 of the smaller pipe. The foam is a compressible matrix and compression of the outside diameter of the foam results in compression of the matrix throughout the volume of the foam body. On compression of the outer surface of the foam, the polyurethane matrix is displaced inwards towards the centre line and the magnets embedded in the foam will move with the matrix. In the compressed state, the magnets ( 3 ) and ( 4 ) will be at a distance of X2 which is closer to the sensors ( 6 ) and ( 7 ) respectively than in the uncompressed state. The magnetic sensors ( 6 ) and ( 7 ) measure the strength of the field from the magnets and as the magnets move closer to the sensors the strength of the field increases and the output from the sensors will also increase.
For a given section of homogeneous foam, the displacement of points in that foam, when the whole section is compressed, is uniform throughout its thickness. The amount of radial displacement, at any point within the foam, being a function f(x) of its distance X from the point of minimum displacement relative to the point at which the compression is applied. In the instance of a foam pig body, the maximum displacement occurs on the outer surface and the minimum displacement on the axial centreline of the body. The amount of displacement at any point between the centre line and the outer surface will be dependent on many factors including, the formulation of the polyurethane material, the size and distribution of any voids, and the manufacturing processes used to make the pig. However, once a pig has been moulded, these relationships will be fixed and, for a specific pig, the function f(x) can be measured by calibration. Thus, for a given displacement of the outer surface of the foam body 1 , the magnet positioned beneath that point on the surface will be radially displaced by an amount defined by the function f(x) resulting in a measurable change in output from the sensor. Thus a second function f′(x) can be determined relating the output from a sensor to the compression of the foam pig at a point on the outer surface, in-line with the sensor.
Once f′(x) has been determined for each sensor and magnet combination, then a calibration algorithm can be produced which enables the compression of the outer surface of the pig to be determined by measurement of the output from the sensor resulting from the displacement of the magnet embedded in the matrix.
FIGS. 1 & 2 show an arrangement with two diametrically opposite magnets and sensors to measure the pipe bore. This arrangement is suitable for measuring uniform changes in the bore such as those which might result from changes in thickness of pipe wall material. In practice, many bore changes are non-uniform such as those resulting from mechanical damage to the pipeline (dents, ovality, buckles) or from the laying down of deposits on the pipe wall where more material may be deposited on the bottom of the pipe than on the top. For measurement of non-uniform bore changes, more measurement points are required and an arrangement with four magnets and four sensors as shown in FIG. 3 can be used. Additional magnet and sensor pairs can be added at intermediate angular positions to increase the circumferential resolution of the measurements.
In the arrangements shown in FIGS. 1 , 2 and 3 , the magnets embedded in the foam matrix can have rectangular or circular cross sections and the magnetised axis can be aligned to the longitudinal axis of the foam pig or aligned to the radial axis of the pig. The magnet sensors mounted adjacent to the magnet must be capable of measuring the static magnetic field from the magnet. These sensors would typically be Hall Effect sensors. Hall Effect sensors have a sensitive axis which, when aligned to the direction of the magnetic field, gives the maximum output and when aligned perpendicular to the magnetic field gives the minimum output. By aligning the sensitive axis of the sensor to the direction of the magnetic field, optimum coupling of the field to the sensor is achieved.
The preferred arrangement shown in FIG. 4 uses magnets ( 8 ) & ( 9 ) with the magnetic axis aligned to the radial axis of the pig ( 10 ), and magnetic sensors ( 11 & ( 12 ) with the sensitive axis aligned in the same orientation ( 10 ). The lines of magnetic flux pass from the north pole of the magnet around the edges of the magnet to the south pole. In a small area in the centre of the magnet the flux lines are perpendicular to the face of the magnet and aligned to the sensitive axis of the sensors. This arrangement can be used with two sensor magnet pairs as shown in FIG. 4 or it can be used with multiple magnet sensor pairs. Radial compression of the foam due to a bore reduction will result in radial movement of the magnet towards the sensor resulting in an increased field strength at the sensor and hence increased output signal from the sensor.
An alternative arrangement is shown in FIG. 5 where the magnetic North/South axes of magnets ( 13 ) & ( 14 ) are aligned with the longitudinal axis ( 15 ) of the pig and the sensitive axes of sensors ( 16 ) and ( 17 ) are also aligned with the longitudinal axis ( 15 ) of the pig. In this arrangement, the sensitive axis of the sensor is aligned to the direction of the magnetic lines of flux passing from the North Pole of the magnet to the South Pole ensuring maximum coupling of the magnetic field to the sensor in each sensor/magnet pair. In the radial direction, the lines of flux become more dense, the closer the sensor is to the magnet. Hence, radial compression of the foam due to a bore reduction will result in radial movement of the magnet towards the sensor resulting in an increased field strength at the sensor and hence increased output signal from the sensor.
In the ideal case, when the pig enters a reduced bore, the foam compresses in a radial direction, moving the magnet closer to the sensor and producing a greater output. This relationship can be calibrated allowing bore reductions to be estimated by measuring sensor outputs. However, in practice, the foam can be distorted in the longitudinal direction as it encounters larger bore reductions. This results from the mechanical forces acting on the pig as it is driven through the restriction in the bore. FIG. 6 shows the forces acting on the foam pig when being driven through a pipeline. The driving force is provided by the pressure ( 18 ), on the rear face of the pig, arising from the flow of the product in the line. Reacting against this is the frictional drag force ( 19 ) on the outer surface of the pig where it contacts the pipe wall. The two forces acting in opposition tend to generate a shear action resulting in the centre section of the pig being pushed forward and the outer surface being dragged backwards.
In small bore reductions, the shearing action is small and the foam compresses in a radial direction with very little distortion in the longitudinal direction. However, in large bore reductions, the drag forces on the outer skin of the foam against the pipe wall are much higher and the longitudinal distortion of the foam is greater. The effect of this is that in a large bore reduction the magnets ( 20 ) & ( 21 ) will move in a longitudinal direction relative to the sensors ( 22 ) & ( 23 ), moving the sensors away from the centre of the magnets. In the centre of the magnet, the field is aligned with the sensitive axis of the sensors but away from the centre of the magnet, the direction of the field changes and the coupling of the field to the sensor is reduced. This has the effect of reducing the sensor output, which counteracts the increase in sensor output due to the radial movement of the magnet, introducing errors in the measurement of the pipe bore.
One solution to this is to increase the longitudinal length of the magnets which increases the length of the small area in the centre of the magnet over which the magnetic flux lines are aligned perpendicular to the face of the magnet and parallel to the sensor axis. Providing the longitudinal movement of the magnet is not greater than the length of this area, then the output from the sensor will not change and no error will be observed.
Another solution shown in FIG. 7 is to replace the single sensors ( 22 , 23 ) in FIG. 6 , by sensor pairs ( 24 , 25 ) aligned with sensitive axes at 90 degrees to each other in the plane of the longitudinal axis and the radial axis of the pig. By adding the sensor outputs from the sensor pair, the resultant field can be measured, which eliminates the error due to the misalignment of the field and sensor.
FIG. 8 illustrates an alternative form of pig, where the foam body is formed of first and second elements 31 , 32 . The first element 31 is formed of dense foam, whereas the second element 32 is formed of a less dense and hence softer foam. The magnets 33 , 34 are located between the first and second elements 31 , 32 . By fabricating the foam body in first and second elements, a measurement with greater sensitivity may be made. As mentioned above, the compression of the foam is not uniform through the thickness of the body, the amount of compression being a function f(x) of the radial distance X from the centre line of the pig body. Maximum compression occurs on the outer surface of the body and minimum compression on the axial centre line of the body. By forming the second element of a less dense foam than the first element the second element is compressed comparatively more than the first element, and hence the magnet moves through a greater distance resulting in an output from the magnet sensor of greater magnitude.
In the housing 5 are situated a data logger 35 , magnetic sensors 36 and batteries 37 . At one end of the housing 5 there is mounted a plug 38 , which is sealed against ingress of fluid. A further plug 39 may be attached to the plug 38 to export data from the housing 5 .
The housing 5 contains a data logger, power source, and control circuitry to process the outputs from the magnetic sensors. This electronics package would run continuously, recording sensor values in non-volatile digital memory, e.g. a Flash card. Data could be off-loaded via a USB, or similar, interface.
FIGS. 9 to 12 illustrate an alternative embodiment of the invention, in which the deflection of the outer surface of the foam body is detected by measuring the time taken for an ultrasound wave to be reflected from the inner wall of the pipeline.
In FIG. 9 a pig 40 is shown travelling in a direction through a pipeline, which is in good condition. The pig 40 comprises a foam body 41 in which is mounted a cylindrical housing 42 . An ultrasonic transmitter 43 is mounted in the housing 42 and is shown sending out a pulse represented by the arrow 45 towards the pipe-wall 46 .
FIG. 10 shows the pig continuing to travel forwards and, this time, the attenuated signal, represented by the broken line 47 , is bouncing back towards the array of receivers 44
FIGS. 11 and 12 show the same operation taking place as illustrated in FIGS. 9 and 10 , only this time there is a dent 48 in the upper part of the pipe-wall 46 . In the region of the dent 48 the time taken for the ultrasound pulse to reach the pipe-wall 46 and be reflected back to the ultrasonic receivers 44 is reduced.
An advantage of embedding an ultrasonic measurement system in a foam pig is that the foam attenuates the ultrasonic signal, to some extent, but the environment inside the pig is much more predictable than that of the pipeline medium. The mass of the foam is the same, whether or not it is compressed, and the major reflection should come from the inside of the pipe-wall.
The housing 42 contains a data logger, power source, and control circuitry to control the ultrasonic system and to process the outputs from the sensors. This electronics package would run continuously in a predetermined sequence of transmitting and receiving pulses and recording sensor values in non-volatile digital memory, e.g. a Flash card. Data could be off-loaded via a USB, or similar, interface.
The pigs illustrated in FIGS. 1 to 12 may also include sensors for sensing other variables, such as temperature and pressure. These variables would be stored in the data logger for subsequent use in correction during data analysis.
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An instrumented pig comprises a foam body having an outer surface and an inner cavity in which, in use, is located a sealed unit housing at least a part of a parameter measurement apparatus configured to measure at least one parameter from which the extent of deflection of the outer surface of the foam body may be derived, the sealed unit including at least one sensor configured to generate an output signal representative of the at least one measured parameter.
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FIELD OF THE INVENTION
[0001] This invention is in the field of Voice over Internet Protocol (VoIP) communications and, more particularly, in the field of systems and methods of interfacing a standard telephone to a VoIP compatible communication network over an existing wireless network.
BACKGROUND OF THE INVENTION
[0002] VoIP is a technology that allows the systems and transmission channels that connect computer networks to act as an alternative to phone lines, delivering real-time voice to both standard telephones and personal computers (PCs). VoIP allows an individual to utilize a network connection to transmit voice encapsulated data packets over available local communication lines, such as the Internet. This is typically facilitated by the use of an Analog Telephone Adapter (ATA) which emulates some functions of a phone company's central office and connects via a wired interface to a network like the Internet.
[0003] In a VoIP system, the analog voice signal is typically picked up by a microphone and sent to an audio processor within a personal computer. In the computer, either a software or hardware CODEC performs analog-to-digital conversion and compression. Considerable research has been devoted to voice compression schemes that are well know to those skilled in the art. The nominal bandwidth required for telephone-type voice ranges from 2.9 Kbps (RT24 by Voxware) to 13 Kbps (GSM cellular standard).
[0004] In placing the CODEC output into packets, there is a trade-off between bandwidth and latency. CODECs do not operate continuously. Instead, they sample the voice over a short period of time, known as a frame. These frames are like little bursts of data. One or more frames can be placed in a single IP datagram or packet, and then the packet payload is wrapped in the necessary packet headers and trailers. This packet overhead is at least 20 bytes for IP and 8 bytes for the User Datagram Protocol (UDP). Layer 2 protocols add even more overhead. Waiting longer to fill the IP datagram reduces overall overhead, which in turn reduces the true bandwidth needed to send the digitized voice. However, this waiting creates latency at the source, and too much total latency makes for a difficult conversation.
[0005] The total network latency and jitter (changes in the latency) have a degrading effect upon voice quality. Therefore, real-time voice quality is difficult to maintain over a large wide-area packet network without priority handling. As previously mentioned, VoIP converts standard telephone voice signals into compressed data packets that can be sent locally over an Ethernet or globally via an ISP's data networks rather than traditional phone lines. One of the main difficulties with VoIP connections is that the communication network supporting a VoIP platform must be able to recognize that VoIP data packets contain voice signals, and be “smart” enough to know that the communication network has to move the data packets quickly.
[0006] Presently, most VoIP voice traffic does not use the public Internet but runs on private IP-based global networks that can deliver voice data with minimal congestion. As such, transmission of voice signals over private data networks offers businesses some great advantages. For ISPs, merging voice and data on one single network allows them to expand their services beyond simple information access and into the realm of voice, fax, and virtual private networking. For businesses, the benefit is big savings on long-distance service. The Internet right now is a free medium on many networks. If businesses can send voice over a computer network, businesses can conceivably make long-distance or international calls for the cost of a local call. VoIP further facilitates electronic commerce by allowing a customer service representative using one data line to answer telephone questions while simultaneously placing a customer's order online, perusing the company's web site, browsing an online information/product database, or sending an E-mail. Similarly, VoIP also creates new possibilities for remote workers, who for the cost of a local call can log in remotely, retrieve voice mail from their laptop PCs, and keep their E-mail and web applications running while conducting multiple voice and data calls over one phone line. Presently, this type of expanded VoIP functionality is exclusively limited to those with access to private IP based networks, such as business users and not the typical household user.
[0007] In fact, most household computer users are generally limited to the congested public Internet and cannot implement the VoIP standard effectively. If latency and jitter are too high, or the cost of reducing them is excessive, one alternative is to buffer the CODEC data at the receiver. A large buffer can be filled irregularly but emptied at a uniform rate. This permits good quality reproduction of voice. Such a buffering technique is known as audio streaming, and it is a very practical approach for recorded voice or audio. Unfortunately, excessive buffering of the audio signals leads to generally unacceptable one-sided telephone conversations, where one party dominates the transmissions.
[0008] Traditionally, the operating environment for a household user with a VoIP connection is either a laptop or desktop general-purpose computer. The recording and transmission or interpretation of the VoIP packets takes place in the sound system or modem DSP found on the laptop or desktop. As such, the desktop system has a minor advantage over the laptop, because the desktop sound system traditionally provides stereo surround speakers and an accurate microphone. Thus, the desktop system can more accurately capture an individual's voice for retransmission of these voice signals to the user on the other end of the connection. VoIP telephone software buffering and control structures help improve the connection, but even though the audio signal has been accurately sampled, the processor delays and transmission latency associated with the desktop VoIP connection over the public Internet tends to result in a barely audible VoIP call. One of the main difficulties with using VoIP in a household system is that the ATA has to be connected to the network access device via a wired connection and thus limits the placement of the phone.
[0009] The present invention solves these and other problems involved in the current state of the art, as will be explained below.
SUMMARY OF THE INVENTION
[0010] The systems and methods disclosed herein also solve the other problems alluded to above by allowing the network adapters to connect to a wireless network and thereby to a VoIP carrier via a signaling protocol. The limitations of the prior art are thus overcome and additional freedom and functionality are provided the user, as described in more detail below.
[0011] Optionally, the network adapter can also be configured to transmit information over a broadband cellular link, such as EV-DO or other similar types of networks.
[0012] The disclosed network adapter may also include software which allows the user to overcome problems associated with making emergency calls on a VoIP communications network. The central processing unit in the network adapter can also include the ability to route emergency calls to a commercial mobile radio service (“CMRS” or cellular) transmitter over a CMRS network.
[0013] Additional objects, advantages and novel features of this invention will be set forth in part in the description that follows, and in part will become apparent to those skilled in the art upon examination of the following, or may be learned by practicing the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] In the accompanying drawings that form a part of the specification and are to be read in conjunction therewith, the present invention is illustrated by way of example and not limitation, with like reference numerals referring to like elements, wherein:
[0015] FIG. 1 illustrates a network adapter, according to an embodiment of the invention;
[0016] FIG. 2 ( a ) illustrates a communications network, according to an embodiment of the invention;
[0017] FIG. 2 ( b ) illustrates a communications network, according to another embodiment of the invention;
[0018] FIG. 3 ( a ) is a flow chart illustrating the process of making an out-bound call, according to an embodiment of the invention;
[0019] FIG. 3 ( b ) is a continuation of a flow chart illustrating the process of making an out-bound call, according to an embodiment of the invention;
[0020] FIG. 4 is a flow chart illustrating the conclusion of a VoIP voice call, according to an embodiment of the invention;
[0021] FIG. 5 is a flow chart illustrating the beginning of a VoIP voice call, according to an embodiment of the invention;
[0022] FIG. 6 is a flow chart illustrating the beginning of a PSTN voice call, according to an embodiment of the invention; and
[0023] FIG. 7 is a flow chart illustrating the process of making an emergency call, according to an embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0024] In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the invention. In other instances, well known structures, interfaces, and processes have not been shown in detail in order not to unneccessarily obscure the invention. However, it will be apparent to one of ordinary skill in the art that those specific details disclosed herein need not be used to practice the invention and do not represent a limitation on the scope of the invention, except as recited in the claims. It is intended that no part of this specification be construed to effect a disavowal of any part of the full scope of the invention.
[0025] FIG. 1 illustrates the components of a particular device, which is a network adapter 100 , according to an embodiment of the invention.
[0026] The network adapter 100 includes a central processing unit 135 connected to the relay 160 via the SLIC 140 and the DAA 145 . The relay 160 is used to isolate and bridge an analog telephone handset ( 165 ) to a public switched telephone network (PSTN).
[0027] As stated above, the network adapter 100 includes a subscriber line interface (SLIC) 140 and a data access arrangement (DAA) circuit 145 . The SLIC 140 is responsible for emulating a central office. It generates a ring current, detects on-hook and off-hook transition and notifies the central processing unit (CPU) 135 of any signal transition. The SLIC 140 also performs A/D conversion on input voice signal and D/A conversion on voice signal to be processed by the telephone handset ( 165 ). The DAA 145 detects a ring current and notifies the CPU 135 of the presence of a ring current. The DAA 145 also creates off-hook and on-hook transactions in order to emulate a telephone handset back to the phone company's central office, and it also performs A/D and D/A conversion on signals transmitting to and from the central office (not shown).
[0028] The CPU 135 controls the network adapter 100 via programmable software. The CPU 135 is a microprocessor, of a kind that is well known to one of ordinary skill in the art. Integrated into the CPU 135 is a digital signal processor software (not shown) which processes voice signal data in real time.
[0029] Connected to the CPU 135 are several memory devices, flash memory 110 and SDRAM 115 . The flash memory 110 is used as a working storage for the CPU 135 during operation. The SDRAM 115 is used to store information permanently, such as configuration information and program code, when the network adapter 100 is turned off.
[0030] The MPEG-4/H.264 decoder 120 is an integrated circuit that is responsible for producing video output from the CPU 135 to the LCD Display 105 . The MPEG-4/H.264 decoder 120 decodes streaming video information received via the wide area network connection 155 via the CPU 135 . One of ordinary skill in the art can appreciate that any kind of MPEG-4/H.264 decoder can used to decode the video output.
[0031] The LCD Display 105 is used to display information about the incoming call and diagnostic and status information of the network adapter 100 . The LCD Display 105 can also be used to display and present advertising and entertainment to the user. In an alternative embodiment of the invention, the CPU 135 includes circuity which monitors the signal strength of the wireless network (not shown) employed by the network adapter 100 . The signal strength monitoring circuity is well known to one of ordinary skill in the art. The MPEG-4/H.264 decoder 120 receives this information from the CPU 135 in real-time and transfers this information to the LCD Display 105 . The LCD Display 105 receives the signal strength information and displays it to the user in a known manner. Accordingly, the user can monitor the signal strength as displayed on the LCD Display 105 to manually adjust the location of the network interface 100 in order to maximize the signal strength.
[0032] A wireless network card 125 is connected to the CPU 135 . The wireless network card 125 is connected to the CPU 135 via a mini-PCI connector (not shown). The wireless network card 125 allows the network adapter 100 to access any one of available wireless networks. The wireless network card can transmit the information to the network by implementing a variation of the IEEE 802.11 standard, however, one of ordinary skill can appreciate that other methods can be employed as well. The wireless network card 125 is built into the network adapter via a replaceable module via a known standard such as PCI, PCMIA or USB. By employing a particular wireless card, a user can have access to any number of wireless networks such as Wi-Fi, Wi-Max, EV-DO, HSPDA and any other wireless network for which a mini-PCI card has been developed.
[0033] One of ordinary skill in the art can appreciate that the network adapter 100 requires AC or DC power in order to operate. As way of example and not limitation, the network adapter can be powered from an AC electrical outlet or DC power source, such as the cigarette lighter in an automobile or a DC battery.
[0034] In yet another embodiment of the invention, the network adapter 100 can be adapted to include multiple wireless network cards. The multiple wireless network cards feature would allow the user flexiblity to employ different types of wireless network services, such as Wi-Fi and cellular broadband wireless. One of ordinary skill can appreciate that many different services can be employed and the example is used for illustration and not as a way of limitation. The circuitry would be adapted to include a mini-PCI card and another mini-PCI card or other replaceable module, such as PCMIA, USB or PCI. The CPU 135 would include software which would allow the network interface to adaptively switch between using the wireless network cards to transmit a voice signal and allow a user to replace wireless network cards during the operation of the network adapter 100 . For example, when the network adapter 100 is not in range of the router 235 via Wi-Fi or other wireless network, the network adapter 100 would transmit the packetized voice signal from the phone via a broadband cellular network like EV-DO or other applicable cellular broadband network to which the user has a subscription.
[0035] The network adapter 100 has the capability to be attached to a local area network 150 to communicate with users on laptop or desktop personal computers and a wide area/broadband network 155 for communicating over a packet switched network, such as the Internet. Typically, the network adapter has one or more RJ-11 jacks to connect with a telephone, and at least one RJ-45 connection to a 10/100BaseT Ethernet Hub or switch to connect to the local area network 150 .
[0036] Also, connected to the CPU 135 is a cellular chip 130 implementing a transceiver which allows the network adapter 100 to access a cellular network. The cellular chip 130 receives voice data from the CPU and modulates and transmits the data in a known way as to communicate with another user on the celluar network. The cellular chip 130 functions in a duplex manner as to allow voice conversations over the cellular network.
[0037] FIG. 2 ( a ) illustrates a communications network 200 , according to an embodiment of the invention. The communications network 200 includes a telephone 205 , cellular network 210 , network adapter 100 , local area network (LAN) 220 , laptop computer 225 , personal computer 230 , router 235 , a broadband modem 240 , Internet 245 , end-user 250 , and public safety answering point (PSAP) 255 .
[0038] According to an embodiment of the invention, the network adapter 100 includes a wireless network card 125 which allows the analog phone adapter 100 to wirelessly connect to a wide area network, such as the Internet 245 . As shown in FIG. 2 , the network adapter 100 would transmit digitized voice signals to a router 235 . The router 235 is of a kind well known by those of ordinary skill in the art, such as 802.11g routers. The router 235 would receive the voice signal and convert it into a packet format for transmission over the Internet 245 . Accordingly, the network adapter 100 need not be physically connected to the router 235 and therefore does not have to be in close physical proximity to the router 235 .
[0039] The network adapter can receive voice inputs from a telephone 205 , or from a laptop computer 225 or personal computer 230 via a LAN 220 .
[0040] As stated above and with reference to FIG. 1 , the network adapter 100 includes a wireless network card 125 . The wireless network card 125 is of a kind known to one of ordinary skill in the art, such 802.11b and 802.11g PCI cards. The wireless network card 125 in the network adapter 100 can be configured to transmit the digitized voice data across several different networks. One of ordinary skill in the art can appreciate that there are numerous types of wireless PCI cards allowing access to numerous networks, such as Wi-Fi, Wi-Max, EV-DO and HSPDA and others.
[0041] The router 235 transmits the digitized voice signal to the broadband modem 240 . Devices such as routers act as access points, or portals, to a packet switched network, such as the Internet. The broadband modem 240 encodes and transmits the digitized voice signal across a packet switched network such as the Internet 245 . The broadband modem 240 can be cable modem, DSL modem, or satellite or other wireless broadband link. One of ordinary skill in the art can appreciate that the router 235 could be a stand-alone router for a home user or a server in an enterprise setting.
[0042] The transmitted digitized voice signals are received and decoded and converted to analog voice signals by end user 250 at the far-end.
[0043] The network adapter 100 also includes a cellular chip 130 which is used for diverting emergency 911 calls from the VoIP system. When the network adapter 100 detects an emergency call, the CPU 135 diverts the call to the cellular chip 130 for transmission over a cellular network. The PSAP 255 receives the call and processes the call.
[0044] The embodiment shown in FIG. 2 is provided for illustration purposes and not by way of limitation. It will be apparent to one of ordinary skill in the art that the elements that make up the communications network can vary and be optimized for different applications.
[0045] FIG. 2 ( b ) illustrates a communications network 201 , according to an embodiment of the invention. The communications network 201 includes a telephone 205 , network adapter 100 , local area network (LAN) 220 , laptop computer 225 , personal computer 230 , broadband cellular link 265 and end-user 250 . According to one embodiment of the invention, the network adapter 100 is being employed in a broadband communications network such as Evolution Data Optimized (EV-DO) and other similar systems. One of ordinary skill in the art can appreciate that the description is for illustrative purposes and not for limitation.
[0046] The network adapter 100 allows a user either via a telephone 205 or a laptop computer 225 or desktop computer 230 via the LAN 220 to transmit wireless data via a broadband cellular network. The digitized voice signal is applied to the wireless network card 125 via the CPU 135 . The wireless network card 125 would be of a type which would allow access to a broadband cellular network. The wireless network card 125 would transmit the voice data in data packets using a code division multiple access (CDMA) scheme, or whatever packet data communications protocol is being used on that broadband network. The voice signal data would be transmitted along a broadband celluar link 265 to the end-user 250 .
[0047] FIG. 3 illustrates a flow diagram of method 300 of the call flow of a user making an outbound telephone call, in accordance with an embodiment of the invention. The method 300 is described with respect to the network adapter 100 shown in FIG. 1 , but may be applied to other systems.
[0048] In step 305 , the SLIC 140 detects an off-hook condition and notifies the CPU 135 . In step 310 , the DSP (not shown) in the CPU 135 awaits the receipt of the first dual-tone multi-frequency (DTMF) digit from the handset. In step 315 , if the CPU 135 determines from the first digit that the call is to be placed over the relay 160 , then the CPU 135 instructs the DAA 145 to go off-hook, as shown in step 320 .
[0049] In step 325 , the DSP software in the CPU 135 handles the DTMF digits differently depending on whether the call is a VoIP or PSTN call. The routing number path is changed based on whether the call is a VoIP or PSTN call.
[0050] In step 330 , the method 300 determines if the call should be routed to the PSTN. In step 335 , if the DSP software determines the call to be a VoIP call, then the digits are obtained in a loop or stored into the flash memory buffer 110 . In step 340 , if the DSP software determines the call to be a PSTN call, then the digits are obtained in a loop and transferred to the DAA 145 and then transferred to the central office of the local telephone company (not shown).
[0051] In step 345 , the next DTMF digit is received and the method receives the DTMF digits until the last digit has been received in step 350 , which is determined either by a timeout value exceeded while awaiting the digit or by the user pressing the pound key. In step 355 , the method 300 determines whether the last digit has been routed to the PSTN. In the case of a PSTN call, the DAA 145 processes the real time conversion of the analog and digital signal and the call is considered up. In the case of a VoIP voice call, the CPU 135 generates and receives the appropriate messages via WAN 155 based on whatever protocol is used to place the VoIP call. Based on which status message is generated by the far-end analog telephone adapter or VoIP phone (not shown), the CPU 135 produce the appropriate tones to emulate a ringing tone, a busy tone, network congestion tone, etc.
[0052] FIG. 4 illustrates a flow diagram of method 400 of the end of a VoIP call, in accordance with an embodiment of the invention. The method 400 is described with respect to the network adapter 100 shown in FIG. 1 , but may be applied to other systems.
[0053] In step 405 , the CPU 135 is waiting to detect that the SLIC 140 has detected a hang-up (on-hook) status from the handset or a termination message from the far-end. If as in step 410 , the CPU 135 receives a hang-up acknowledgement from the SLIC 140 , then it sends a termination message to the far-end and waits for the far-end to acknowledge it. In step 415 , once the far-end acknowledges the termination, the call is considered ended and the voice session ends.
[0054] If as in step 420 , a hang-up signal is not detected from the far-end handset, the CPU 135 checks whether a termination has been received from the far-end. In step 425 , if the CPU received a hang-up signal from the called party, then the CPU 135 waits to detect a notification from SLIC 140 that the far-end handset has gone off-hook. Upon notification of the hang-up signal from the SLIC 140 , the call is considered over and the voice session ends.
[0055] In step 430 , after waiting a predetermined amount of time for the hang-up signal, the DSP in the CPU 135 will generate a re-order tone and transmit the tone to the SLIC 140 . The re-order tone is to notify the user that the call has been terminated by the far-end and he needs to hang up the handset. In step 435 , the CPU is waiting to detect a notification signal from SLIC 140 that the far-end handset has gone off-hook. In step 440 , once the CPU 135 gets notification that the user went off-hook, the CPU 135 stops the re-order tone and the call is considered over and the voice session ends.
[0056] FIG. 5 illustrates a flow diagram of method 500 of the call flow of the beginnning of a VoIP call, in accordance with an embodiment of the invention. The method 500 is described with respect to the network adapter 100 shown in FIG. 1 , but may be applied to other systems.
[0057] In step 510 , the CPU 135 receives RING signals from voice services. The analog telephone adapter receives a message via the broadband modem 240 from a far-end user indicating that they wanted to initiate a call. In step 515 , the CPU 135 instructs the DSP to generate ring tone to the SLIC 140 which generates ring current to be sent to the handset (not shown). In step 520 , the SLIC 140 waits for the handset to go off-hook. In step 525 , once the handset is determined to be off-hook, the CPU 135 sends a notification message to the far-end. In step 530 , the CPU awaits the acknowledgement from voice services on the far-end. Upon receiving the acknowledgement, the internet voice session begins and both parties can begin to stream voice.
[0058] FIG. 6 illustrates a flow diagram of method 600 of the call flow of a call initated by the PSTN, in accordance with an embodiment of the invention. The method 600 is described with respect to the network adapter 100 shown in FIG. 1 , but may be applied to other systems.
[0059] In step 605 , the network adapter 100 via the DAA 145 receives a message via the broadband modem 240 indicating that someone desires to initiate a call. In step 610 , the CPU 135 instructs the DSP to generate a ring tone to the SLIC 140 which causes ring current to be sent to the handset. In step 615 , the CPU 135 waits for the handset to go off-hook. Once the handset goes off-hook the CPU sends a notification message to the far-end and both parties can begin to stream voice and the PSTN voice session begins.
[0060] In another embodiment of the invention, the network adapter 100 is used to make an emergency call. In prior art systems, there were numerous difficulties in making a 911 call or other emergency call using VoIP technology. For example, the VoIP service did not connect to the 911 service. Moreover, emergency calls made with VoIP service would not include caller-id information indicating the location of the caller, an often important piece of information in an emergency situation. In order to overcome the above stated difficulties, the network adapter can be configured to transfer an emergency call to the PSTN server in order to circumvent the problems associated with using the VoIP server.
[0061] FIG. 7 illustrates a flow diagram of method 700 of the call flow of an emergency call, in accordance with an embodiment of the invention. The method 700 is described with respect to the network adapter 100 shown in FIG. 1 , but may be applied to other systems.
[0062] In step 705 , the SLIC 140 detects an off-hook condition and notifies the CPU 135 . The DSP (not shown) embedded in the CPU 135 awaits the receipt of the first DTMF digit from the handset. In step 710 , the CPU 135 determines that the call is to be an emergency call. This is determined by the user inputting known DTMF digits according to emergency services, such as 911 call, 311 call and other services known to one of ordinary skill in the art.
[0063] In step 715 , the CPU 135 routes the call to a cellular chip 130 which transmits the call to a receiver via a celluar network 210 . The cellular network circuit acts to modulate the voice signal in a manner which allows it to be transmitted over a cellular network. It will be apparent to one of ordinary skill in the art that there are numerous ways to implement a cellular network, such as GSM, CDMA, UMTS and the embodiment provided is not meant to limit the scope of the invention.
[0064] In step 720 , the cellular network transmits the emergency call to the appropriate public safety answering point (PSAP) in a way known to one of ordinary skill in the art. Once the call has been connected to the PSAP, the emergency call begins over the PSTN and cellular network.
[0065] What has been described and illustrated herein is a preferred embodiment of the invention along with some of its variations. The terms, descriptions and figures used herein are set forth by way of illustration only and are not meant as limitations. Those skilled in the art will recognize that many variations are possible within the spirit and scope of the invention, which is intended to be defined by the following claims, in which all terms are meant in their broadest reasonable sense unless otherwise indicated therein.
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The claimed invention consists of integrating a wireless client with a network adapter in a single device which allows a telephone to connect to a network access point for the purpose of establishing Voice over IP (VoIP) calls. The user can attach his telephone to the network adapter and place it anywhere within range of a wireless network and not be required to connect to a wired network via a cable. This allows the end user to place the network adapter and phone in a place without the restrictions of wires. Also, the network adapter could be used to transmit voice data over a broadband link and to transmit emergency calls over a cellular network.
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This invention relates to a process for the recovery of 2,2-bis(4-hydroxyphenyl)propane, also known as bisphenol-A, substantially in the form of easy-to-handle rhombic crystals from a mixture resulting from the condensation reaction of phenol and acetone. The process involves isolating an adduct of bisphenol-A and phenol from the reaction mixture, and treating the adduct using a unique combination of process steps and conditions to cause the selective separation of only the bisphenol-A portion of the adduct in the desired crystalline form.
BACKGROUND OF THE INVENTION
The compound 2,2-bis(4-hydroxyphenyl)propane, also known as bisphenol-A, enjoys major use as a co-reactant for phosgene in the production of aromatic polycarbonate resins suitable for molding applications. It is known that 2,2-bis(4-hydroxyphenyl)propane can be prepared by the acid-catalyzed reaction of acetone with a substantial excess of phenol. Upon completion of the reaction and after the removal of the acid catalyst and by-product water, a mixture comprising bisphenol-A, unreacted phenol and organic by-products of the condensation reaction results.
Various methods for recovering the bisphenol-A from its reaction mixture have been proposed in the art. Dugan et al, U.S. Pat. No. 3,326,986, discloses a procedure wherein "crude" bisphenol-A is separated from its reaction mixture by precipitation or distillation, the "crude" bisphenol-A is melted in the presence of water, and the melt is thereafter crystallized to obtain the bisphenol-A in purer form.
Luten, U.S. Pat. No. 2,791,616, discloses a process for recovering bisphenol-A from a phenol-rich reaction mixture wherein the bisphenol-A and phenol are separated in equimolar proportions in the form of a crystalline adduct, the adduct is thereafter treated to selectively melt only the phenol portion, and the bisphenol-A remaining in solid crystalline form is collected.
Also of interest are Keller et al, U.S. Pat. No. 2,777,183, who uses an alkaline substance to partially neutralize the bisphenol compound during purification; French Pat. No. 1,580,676, which discloses purifying bisphenols by repeated washings with warm water; Boroviska et al, Chem, Abstracts 60:2832(c), which uses even hotter water to purify bisphenols; German Pat. No. 971,013 (1954), which also involves neutralization with base in the purification of bisphenols; Czech Pat. No. 147,105 (1973), which describes countercurrent extraction processes for the purification of bisphenols; Japanese Pat. No. 30269/73, which uses an emulsion of an organic solvent, surfactant and water to purify bisphenol; Japanese Patent Publication No. SHO-45-39251 which discloses distilling an adduct of bisphenol and phenol in the presence of a high melting glycol; Japanese Patent Publication No. SHO-45-22539 which discloses distilling an adduct of bisphenol and phenol in the presence of an aliphatic dicarboxylic acid ester; DeJong, U.S. Pat. No. 3,535,389, who mixes the impure bisphenol with a water-organic solvent mixture and steams out the solvent; Polish Pat. No. 57,925 describes melting bisphenols in water, acid and salt, and then crystallizing; Levkovich et al, Chemical Abstracts Vol. 55:11370h who free bisphenols of impurities by washing with dilute ammonium hydroxide; and Marx et al, U.S. Pat. No. 3,162,690 who form adducts of bisphenols with cresols, then decompose them for purification.
There has now been discovered a new and very simple process for recovering bisphenol-A from a reaction mixture resulting from the condensation of acetone and excess phenol, wherein the bisphenol-A is cleanly separated from a melt of both the phenol and the bisphenol-A in the form of highly desirable, easy-to-handle rhombic crystals, without the need to use high temperatures, liquid-liquid extraction, extraction with water containing surfactants, or sodium chloride, or acid, or alkali or ammonium hydroxide, etc.
DESCRIPTION OF THE INVENTION
This invention, in its broadest aspects, comprises a process for recovering 2,2-bis(4-hydroxyphenyl)propane in the form of rhombic crystals from a non-crystalline mixture, the reaction mixture comprising 2,2-bis(4-hydroxyphenyl)propane, organic by-products resulting from the condensation reaction of phenol and acetone, and phenol, wherein said phenol is present in at least an equimolar amount with respect to said 2,2-bis(4-hydroxyphenyl)propane, the process comprising:
(a) lowering the temperature of the mixture from an elevated temperature at which the 2,2-bis(4-hydroxyphenyl)propane is soluble to a temperature sufficient to cause the separation from the mixture of the 2,2-bis(4-hydroxyphenyl)propane and phenol in equimolar proportions as a crystalline adduct and recovering the adduct;
(b) forming an admixture of the adduct of step (a) with an excess of water at an elevated temperature which is at least sufficient to completely melt the adduct, the water being present in an amount at least sufficient to retain the phenol portion of the adduct upon subsequent separation of the 2,2-bis(4-hydroxyphenyl)propane from the mixture;
(c) lowering the temperature of the mixture of water and melted adduct to a temperature sufficient to cause the selective separation of the 2,2-bis(4-hydroxyphenyl)propane portion of the adduct in the form of rhombic crystals substantially free of said phenol portion; and
(d) recovering the rhombic crystals of 2,2-bis(4-hydroxyphenyl)propane.
In preferred embodiments, the process of this invention also includes the step of (e) contacting the recovered rhombic crystals of 2,2-bis(4-hydroxyphenyl)propane with liquid(s) selected from among water and/or organic hydrocarbons in which the 2,2-bis(4-hydroxyphenyl)propane is insoluble or only slightly soluble, to remove adsorbed water soluble and/or organic solvent soluble impurities from the crystals.
By way of illustration, an essentially non-crystalline reaction mixture resulting from the conventional acid-catalyzed condensation reaction of acetone with an excess of phenol, still at an elevated temperature which is sufficient to maintain the desired product, 2,2-bis(4-hydroxyphenyl)propane, in solution is adjusted to less than about 45° C., preferably from about 38° to about 42° C., whereupon a non-rhombic crystalline adduct of 2,2-bis(4-hydroxyphenyl)propane and phenol, in equimolar proportions, precipitates. The crystalline adduct is then recovered conventionally by means such as filtration, centrifugation, or the like. Centrifugation is preferred as providing a somewhat better separation of the adduct from its mother liquor. Another preferred procedure comprises filtration followed by centrifugation of the filtered adduct.
After recovery, the adduct is preferably washed or rinsed with suitable quantities of phenol to remove any adsorbed phenol-soluble impurities such as color bodies, organic by-products of the condensation reaction, and the like. Preferably, an amount of phenol of about 0.5 part by weight of phenol per part by weight of adduct is employed, but larger or smaller amounts can be used as desired.
The crystalline adduct is then admixed with water to form an aqueous slurry, and mixing is continued at a temperature sufficient to cause the adduct to melt completely. The minimum preferred temperature for this purpose is about 80° C., and preferably from about 80° to about 90° C. In carrying out this procedure, in general, an amount of water sufficient to provide a weight ratio of water to adduct of from about 8:1 to about 10:1, or a weight ratio of water to the phenol portion of the adduct of from about 25:1 to about 31:1, is used. Especially preferably, a weight ratio of water to adduct of 10:1 is employed.
After the adduct is completely melted, the temperature of the mixture of water and melted adduct is gradually lowered, preferably to a temperature in the range of from about 45° to about 50° C., whereupon the 2,2-bis(4-hydroxyphenyl)propane portion of the adduct only selectively crystallizes in the shape of rhomboids, and substantially without co-precipitation of the phenol portion of the adduct. The rhombic crystals are recovered by filtration, centrifugation, or the like.
If desired, the recovered crystals can be washed with water and/or an organic solvent such as a halohydrocarbon, e.g., methylene chloride, or the like, to further purify the crystalline end product. In a preferred procedure, the crystals of 2,2-bis(4-hydroxyphenyl)propane are washed with water in the amount of about 0.5 part by weight of water per part by weight of the crystals, followed by a methylene chloride wash using about 1.5 parts by weight of methylene chloride per part by weight of the crystals.
DESCRIPTION OF THE SPECIFIC EMBODIMENTS
The process of this invention is illustrated in the following examples. These are not intended to be limiting, however.
In each of the examples, the starting mixture comprising bisphenol-A, by-products from the condensation reaction of phenol and acetone, and phenol is obtained upon completion of a conventional acid-catalyzed reaction between acetone and phenol, and removal therefrom by distillation of the acid catalyst and water of reaction. The phenol in the starting mixture in each of the following examples is present in an amount exceeding a molecular equivalent of the bisphenol-A. Adduct formation in each of the examples is accomplished under a nitrogen atmosphere. All analyses are normalized to 100%.
EXAMPLE 1
Four thousand, eight hundred and ninety-five grams of a mixture comprising 60.5% by weight of phenol, 34.1% by weight of bisphenol-A and 5.4% by weight of by-products are cooled to 40° C. to precipitate an equimolar adduct of bisphenol-A and phenol. The adduct and its mother liquor are centrifuged to remove the mother liquor, and the adduct is washed with 1,000 grams of phenol at a temperature of 50° C. Analysis of the adduct indicates a composition as follows:
______________________________________Ingredients Amount, % By Weight______________________________________bisphenol-A 64.7phenol 34.1by-products 1.2______________________________________
Thereafter, a 12-liter flask equipped with a stirrer, condenser and thermometer is charged with 8,200 milliliters (ml) of distilled water. The water is heated to 88° C., and 800 grams of washed adduct is added, whereupon the adduct melts. The mixture of water and adduct is stirred for about 15 minutes, and then allowed to cool to 50° C. over a period of about 13/4 to 2 hours. Crystallization within the mixture begins at about 70° C. Separation of the crystals is accomplished by centrifugation at 50° C., and the crystals are washed with 250 ml of water at 50° C., to yield rhombic crystals of bisphenol-A which are substantially free of phenol.
EXAMPLE 2
Four thousand, five hundred and forty-six grams of a mixture comprising 59.9% by weight of phenol, 34.3% by weight of bisphenol-A and 5.8% by weight of by-products is cooled to 40° C. to precipitate an essentially equimolar adduct of bisphenol-A and phenol. Analysis to the adduct indicates a composition as follows:
______________________________________Ingredients Amount, % By Weight______________________________________bisphenol-A 65.1phenol 33.6by-products 1.2______________________________________
The adduct is separated from its mother liquor by centrifugation and washed with 900 grams of phenol at 50° C.
Thereafter, a 12-liter flask equipped with a stirrer, condenser and thermometer is charged with 7,787 ml of distilled water. The water is heated to 90° C., 800 grams of washed adduct is added, and the temperature is maintained at 85° C. for about 15 minutes, with continuous stirring. The mixture is then allowed to cool to 50° C., with stirring continued, and initial crystal formation is observed to begin at 72° C. The crystals are separated by centrifugation and washed in the centrifuge with 250 ml of water at 50° C., to yield rhombic crystals of bisphenol-A.
In like manner, other mixtures comprising phenol, bisphenol-A and by-products are treated according to this invention. The results are summarized as follows:
ADDUCT CRYSTALLIZATION
Typical compositions of the starting mixtures are shown in Table I. The mixtures are cooled to 40°-45° C. to effect formation of the respective adducts.
TABLE I______________________________________ Mixture Adduct Composition, Composition,Ingredients % By Weight % By Weight______________________________________Bisphenol-A 30-35 63-65Phenol 55-62 30-34By-products 3.5-5.5 0.5-1.5______________________________________
BISPHENOL-A CRYSTALLIZATION
After separation from its mother liquor, the adduct is washed with phenol and then mixed with water at a temperature sufficient to yield a liquor wherein the adduct is melted. Table II shows the average yield and quality of the bisphenol-A and product at various temperatures at which the adduct is melted, using a weight ratio of water to the phenol portion of the adduct of 26:1. As is shown, when the temperature is increased above 80° C. there is no advantage, since the yield of bisphenol-A tends to decrease.
TABLE II______________________________________MeltTemperature Bisphenol-A Yield* % Phenol in Bisphenol-A______________________________________100° C. 83% 0.84 80° C. 84.5% 1.3______________________________________ *Adduct washed with phenol; bisphenolA crystals unwashed
The amount of water employed in melting the adduct should be of a quantity sufficient to retain the phenol portion of the adduct upon subsequent crystallization therefrom of the bisphenol-A portion. Table III compares the average quality of the bisphenol-A end product with various quantities of water employed, reported as a ratio of the weight of water to the weight of the phenol portion of the adduct. As is shown in Table III a ratio of 25:1 is satisfactory, but 18:1 left too much phenol in the product.
TABLE III______________________________________Weight Ratio Bisphenol-A Quality*Water/Phenol % Phenol APHA Value**______________________________________31:1 ND 2725:1 ND 5018:1 1.8 68______________________________________ ND None detected by gas chromatography *Final product quality (adduct washed with phenol; bisphenolA crystals washed with water and methylene chloride) **According to American Public Health Association standards; lower values indicate presence of lesser amounts of color bodies (impurities).
Rhombic crystallization of bisphenol-A from the liquor wherein the adduct is melted is accomplished by cooling this liquor to a temperature which causes crystalline precipitation of the bisphenol-A substantially without co-precipitation of the phenol. The crystals of bisphenol-A are then physically recovered by filtration or centrifugation. Table IV shows average yield and quality of bisphenol-A recovered at various crystallization temperatures. As is shown in Table IV, temperatures in the range of from about 45°-50° C. are preferable. At higher temperatures the yield of bisphenol-A decreases, while at lower temperatures co-precipitation of phenol increases.
TABLE IV______________________________________Effect of Crystallization TemperatureCrystallization Bisphenol-A*Temperature % Phenol in Bisphenol-A Yield______________________________________55° 1.3 84.550° 0.6 93.845° 0.7 89.940° 2.5 91.835° 4.1 89.1______________________________________ *Adduct washed with phenol, bisphenolA-crystals unwashed.
Table V summarizes average final bisphenol-A product quality obtained with processes according to this invention. These are shown as recovered directly upon crystallization, without washing by water or solvent.
TABLE V______________________________________ Bisphenol-A Product*______________________________________Bisphenol-A 98-99.5%Phenol O-1%By-products 2000 ppm.sup.(1)______________________________________ *Adduct washed with phenol; bisphenolA crystals unwashed .sup.(1) Only the o,p'-isomer of bisphenolA
EXAMPLE 3
Five hundred and fifty grams of a mixture comprising 56.8% by weight of phenol, 37.3% by weight of bisphenol-A and 5.9% by weight of by-products is cooled to 40° C. to precipitate an equimolar adduct of bisphenol-A and phenol. The mother liquor is removed from the adduct on a Buchner funnel and the adduct is washed twice with 100 and 62 grams of phenol at a temperature of 42° C. Analysis of the adduct by liquid chromatography indicates a composition as follows:
______________________________________Ingredients Amount, % by Weight______________________________________Bisphenol-A 62.3Phenol 37.2By-products 0.5______________________________________
Thereafter, a five-liter flask equipped with a stirrer, condenser and thermometer is charged with 2500 ml of distilled water. The water is heated to 100° C. and 260 grams of washed adduct is added, whereupon the adduct melts. The mixture of water and adduct is stirred for about 10 minutes and then allowed to cool to 50° C. over a period of about four to five hours with continuous stirring. Initial crystal formation is observed to begin at about 70° C. The crystals are separated from the mother liquor with a Buchner funnel and washed three times with 250 ml, 100 ml and 100 ml of an organic solvent, such as methylene chloride or benzene, to yield rhombic crystals of bisphenol-A.
Obviously, other modifications and variations of the present invention are possible in light of the above teachings. It is, therefore, to be understood that changes may be made in the particular embodiments of the invention described which are within the full intended scope of the invention as defined in the appended claims.
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The compound 2,2-bis(4-hydroxyphenyl)propane is recovered in the form of rhombic crystals from an essentially non-crystalline mixture comprising 2,2-bis(4-hydroxyphenyl)propane, organic by-products of the condensation reaction of phenol and acetone, and phenol by lowering the temperature of the mixture from an elevated state to a temperature which is low enough to cause the separation of the phenol and 2,2-bis(4-hydroxyphenyl)propane in equimolar proportions as a crystalline adduct, recovering the adduct, forming a mixture of the adduct and water at an elevated temperature sufficient to completely melt the adduct, and thereafter lowering the temperature of the mixture of water and melted adduct to cause the separation of the 2,2-bis(4-hydroxyphenyl)propane in the form of rhombic crystals substantially free of the phenol. The crystals are easily handled and recovered by means such as filtration or centrifugation, and they can be formed into high quality polycarbonate molding resins.
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FIELD OF THE INVENTION
[0001] The present invention relates to decontamination systems and methods.
[0002] BACKGROUND
[0003] Class I or Class II (laminar flow) biological safety cabinets are designed to minimize hazards inherent in work with biological agents. BSC's can be used for work with biological agents assigned to biosafety levels 1 through 4, depending on the facility design as described in the CDC/NIH publication Biosafety in Microbiological and Biomedical Laboratories. A BSC is a ventilated device for personnel, product, and environmental protection having an open front with inward airflow for personnel protection, downward HEPA filtered laminar airflow for product protection, and REM filtered exhausted air for environmental protection.
[0004] Class III BSC's or isolators are similar to Class I or II but incorporate glove ports.
[0005] Recommendations and requirements to certify BSC's come from a variety of sources. All manufacturers and NSF International recommend field certification of BSC's. The Center for Disease Control (CDC) and NIH state that it is essential that Class I, II and Ill BSC's be tested and certified.
[0006] Decontamination is a key component of certification and/or maintenance activities.
SUMMARY
[0007] In some embodiments, a system comprises a portable source of gaseous chlorine dioxide (CD) located in an enclosure. An isolated chamber or a flexible tent to form a sealed enclosure for containing a device to be treated with the CD.
[0008] In some embodiments, a system comprises a portable source of gaseous chlorine dioxide (CD) located in an enclosure. The source has first couplings for sealingly connecting a portable scrubber connecting to a scribing flow path comprising at least one gas conduit for removing the CD from the device.
[0009] In some embodiments, a system comprises a portable source of gaseous chlorine dioxide (CD) located in an enclosure. The source has first couplings for sealingly connecting a portable scrubber connecting to a scrubbing flow path comprising at least one gas conduit for removing the CD from the device. The gas conduit has second couplings for connecting the device to the scrubbing flow path to create a closed scrubbing loop.
[0010] In some embodiments, a system comprises a portable source of gaseous chlorine dioxide (CD) located in an enclosure. The source has first couplings for sealingly connecting the building exhaust system or HVAC exhaust system to at least one gas conduit for removing the CD from the device. The source has second couplings connecting to the connection panel, which allows for fresh air to enter and replace the CD gas surrounding the device.
[0011] In some embodiments, a method comprises forming a flexible tent film material or solid isolated enclosure to form a gas-tight enclosure around a device to be treated and joining this to at least one panel having fittings for connecting to gas conduits. The gas conduits are connected to the fittings and to couplings of a portable charcoal scrubber. A source of gaseous chlorine dioxide (CD) is located in the enclosure, so as to form a sealed CD generation chamber wherein the CD generating reaction occurs. Gaseous CD is generated from the source within the chamber to treat the device.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1A is a schematic diagram of one embodiment, during operation in a ClO 2 generation mode.
[0013] FIG. 1B is a schematic diagram of system of FIG. 1A , during operation in a ClO, open scrubbing mode.
[0014] FIG. 1C is a schematic diagram of system of FIG. 1A , during operation in a ClO, closed scrubbing mode.
[0015] FIG. 1D is a schematic diagram of the system if FIG. 1A , during operation in a ClO, building exhaust/HVAC exhaust mode.
[0016] FIG. 2 is a view of the connection panel.
[0017] FIG. 3A is a view of the scrubber assembly of FIG. 1A .
[0018] FIG. 3B is a view of the scrubber assembly of FIG. 1B .
[0019] FIG. 4 is a view of the CD Generation Equipment of FIG. 1A .
[0020] FIG. 5 is a top level flow diagram of a method of using the system of 1 A.
[0021] FIG. 6 is a flow chart of the chamber preparation process of FIG. 5 .
[0022] FIG. 7 is a flow chart of the exhaust/aeration preparation process of FIG. 5 .
[0023] FIG. 8 is a flow chart of intake preparation process solids of FIG. 5 .
[0024] FIG. 9 is a flow chart of determining the amount of CD chemicals required of FIG. 5 .
[0025] FIG. 10 is a flow chart of the CD generation preparation process of FIG. 5 .
[0026] FIG. 11 is a flow chart of the decontamination cycle of FIG. 5 .
[0027] FIG. 12 is a flow chart of the scrubbing cycle of FIG. 5 .
[0028] FIG. 13 is a flow chart of the neutralization process of FIG. 5 .
[0029] FIG. 14 is a flow chart of the post-decontamination procedure of FIG. 5 .
DETAILED DESCRIPTION
[0030] This description of the exemplary embodiments is intended to be read in connection with the accompanying drawings, which are to be considered part of the entire written description. In the description, relative terms such as “lower,” “upper,” “horizontal,” “vertical,”, “above,” “below,” “up,” “down,” “top” and “bottom” as well as derivative thereof (e.g., “horizontally,” “downwardly,” “upwardly,” etc.) should be construed to refer to the orientation as then described or as shown in the drawing under discussion. These relative terms are for convenience of description and do not require that the apparatus be constructed or operated in a particular orientation. Terms concerning attachments, coupling and the like, such as “connected” and “interconnected,” refer to a relationship wherein structures are secured or attached to one another either directly or indirectly through intervening structures, as well as both movable or rigid attachments or relationships, unless expressly described otherwise.
[0031] One embodiment provides an apparatus and method to produce a gas for gaseous decontamination to reduce microorganisms thereon by treating a device (such as a BSC) or item(s) in a temporary enclosed sealed space or chamber. The apparatus includes a gas generating apparatus and a means for removing the gas that is comprised of supply and return ducting with couplings connected to inlet and outlet ports affixed to respective connection panels incorporated onto the device or temporary enclosed sealed space. The apparatus has a closed chamber of gas-tight construction isolated from the ambient space.
[0032] The corresponding embodiment of a method comprises exposing the device or item(s) in a temporary enclosed sealed space or chamber to an atmosphere comprising gaseous chlorine dioxide. It may comprise controlling the concentration and required time cycles of chlorine dioxide generation, dwell and rapid removal. This embodiment of a method also provides the proper humidity to enhance the susceptibility of microorganisms and/or sporicidal action of chlorine dioxide. Neutralizer is added to the residual waste liquid within the apparatus, following which the waste liquid may be discarded by conventional or future developed means. The chlorine dioxide gas is produced from a precursor A and B solid chemical, mixed into an aqueous solution, then transformed to a gaseous state. The method may also be used with larger devices or sealed spaces with additional quantities of Chlorine Dioxide generating chemicals. Additional items may be added to the space under decontamination.
[0033] Embodiments may take physical form in certain parts and arrangement of parts, a preferred embodiment of is described in detail below and illustrated in the drawings.
[0034] FIGS. 1A , 1 B, 1 C and 1 D are schematic views of a Chem CD decontamination system 8833 . The Chem CD 8833 system includes connection panel 200 , a scrubber 300 , and a source 400 . The system is capable of being operated in a chlorine dioxide (CD or ClO 2 ) generation mode or in a scrubbing mode. The CD generation mode flow path is shown in FIG. 1A . The open scrubbing mode flow path is shown in FIG. 1B . The closed scrubbing mode flow path is shown in FIG. 1C . The building exhaust/HVAC exhaust mode flow path is shown in FIG. 1D .
[0035] FIG. 1A shows a device under decontamination 100 . In other embodiments, the device under decontamination 100 is surrounded by a gas tight tent/enclosure 101 , which is in turn connected to the connection panel 200 ( FIG. 2 ).
[0036] An optional biological indicator (not shown) can be placed within the decontamination zone. The device under decontamination 100 is then sealed, incorporating into the connection panel 200 ( FIG. 2 ) a inlet 201 and outlet port 202 for use with the Chem CD 8833 system. In some embodiments, to accomplish the seal, the tent material is taped using a suitable pressure sensitive adhesive tape (such as duct tape) to a connection panel 200 ( FIG. 2 ) having the inlet port 201 and/or outlet port 202 . After an appropriate set up has been achieved, Chlorine Dioxide (ClO 2 ) is produced and released and the decontamination cycle begins. FIG. 1B , 1 C and 1 D show the apparatus with the CD scrubbing flow paths activated. After a suitable exposure time specified by NSF (e.g. 85 minutes), ClO 2 gas is removed from the device under decontamination 100 using one of the scrubbing cycles of the Chem CD 8833 system. After a suitable scrubbing time (e.g., approximately 45 minutes), the Chem CD 8833 system is neutralized and the device under decontamination 100 and the gas tight enclosure 101 may be unsealed.
[0037] FIGS. 1A , 1 B, 1 C and 1 D show a Chem CD decontamination system 8833 using chlorine dioxide (ClO 2 ) gas. The Chem CD 8833 system and the equipment ( FIG. 4 ) is placed within a temporary enclosed sealed space 101 under decontamination. By way of example, and not limited to, a temporary enclosed sealed space 101 may take the form of a Class II type A1, A2, B1, and B2 biological safety cabinet (BSC), Class I BSC, Class III BSC, negative or positive isolators, animal devices, incubators, refrigerators and freezers, room or any other potentially contaminated item(s). The Chem CD 8833 system may be used with devices or temporary enclosed sealed spaces having a volume of typically less than 120 ft 3 (3.4 m 3 ). The Chem CD 8833 system may also be used with larger devices or sealed spaces with additional quantities of ClO 2 generating chemicals. Additional items may be added to the space under decontamination.
[0038] System 8833 includes a “gas tight” system that is comprised of conduit connected between inlet port 201 and outlet port 202 of device 100 or temporary enclosed sealed space 101 . In some embodiments to seal or affix to the device 100 or temporary enclosed sealed space 101 under decontamination, a connection panel 200 is provided. Quick disconnect couplings 304 , 305 (which may include locking levers or other positive sealing mechanisms) connect the lines from the scrubbing loop to the connection panel 200 and to the Chem CD 8833 system. CD Generation Flow Path (represented by the bolded arrows) FIG. 1A : ClO, generation source 400 , is placed within the gas tight enclosure 101 . CD chemical (CD precursor A) 401 is added to the CD generating source 400 and then 250 ml of water 407 is added. Then CD chemical (CD precursor B) 402 is added to CD chemical (CD precursor A) 401 , the CD generating source 400 , and 250 ml of water 407 resulting in the generation of ClO, gas.
[0039] ClO 2 open scrubbing path (represented by bolded arrows) FIG. 1B : The charcoal scrubber 300 is place outside the gas tight enclosure 101 . The blower 303 is located within the open scrubbing loop including the supply ducting 302 , attachment couplings 304 , 305 , 306 , screens 307 a, 307 b, charcoal 301 and Chem CD 8833 system. The ClO 2 scrubbing blower 303 is driven by a motor (not shown). The blower 303 is sized to provide a high airflow volume to quickly scrub the CIO 2 gas from the device under decontamination 100 .
[0040] ClO 2 closed scrubbing path (represented by bolded arrows) FIG. 1C : The charcoal scrubber 300 is place outside the gas tight enclosure 101 . The blower 303 is located within the closed scrubbing loop including the supply ducting 302 , the scrubber 300 , attachment couplings 304 , 305 , 306 , screens 307 a, 307 b, charcoal 301 and Chem CD 8833 system. The ClO 2 scrubbing blower 303 is driven by a motor (not shown). The blower 303 is sized to provide a high airflow volume to quickly scrub the ClO 2 gas from the device under decontamination 100 .
[0041] ClO 2 building exhaust/HVAC exhaust path (represented by bolded arrows) FIG. 1D : The building exhaust./HVAC exhaust system 310 is attached to the connection panel 200 including the supply ducting 302 , attachment couplings 305 , 309 screens and building exhaust/HVAC exhaust system 310 . The ClO 2 scrubbing blower 303 is driven by a motor (not shown). The building exhaust/HVAC exhaust system 310 is sized to provide a high airflow volume to quickly scrub the ClO 2 gas from the device under decontamination 100 .
[0042] A ClO 2 generator within the Chem CD 8833 system includes a CD generating source/reservoir 400 , CD precursor A 401 , CD precursor B 402 , measuring cup 404 , and a porous splash guard 405 . ClO 2 is generated within CD generating source/reservoir 400 and is contained within the temporary enclosed sealed space 101 .
[0043] FIG. 2 shows a connection panel 200 that is incorporated in the scrubbing loop and allows the charcoal scrubber to attach to the gas tight temporary enclosure 101 . Within the connection panel 200 there are inlet 201 and outlet ports 202 allowing the scrubber to remove the ClO 2 from the gas tight temporary enclosure 101 . In some embodiments the connection panel may have a electricity source port 203 with electricity cord 204 to have the option to power an electrical device within the gas tight temporary enclosure during the decontamination cycle.
[0044] FIG. 3A shows a ClO 2 charcoal scrubber 300 including, conduit 302 and fitting 305 and 306 for attaching to the connection panel 200 and the scrubber. ClO 2 charcoal scrubber 300 includes an inlet screen 307 b, outlet screen 307 a with associated conduit 302 , and fittings 305 attaching conduit 302 wherein ClO 2 is removed from the device 100 or temporary enclosed sealed space 101 . The ClO 2 charcoal scrubber 300 includes a blower 303 and coupling 304 to attach to the charcoal scrubber 300 , with associated conduit 302 to draw the ClO 2 gas into the charcoal bed 301 and exhausting out the top creating a open scrubbing path.
[0045] FIG. 3B shows a ClO, charcoal scrubber 300 including, conduit 302 and fitting 305 and 306 for attaching to the connection panel 200 and the scrubber. ClO 2 charcoal scrubber 300 includes an inlet screen 307 b, outlet screen 307 a with associated conduit 302 , and fittings 305 attaching conduit 302 wherein ClO, is removed from the device 100 or temporary enclosed sealed space 101 . The ClO 2 charcoal scrubber 300 includes a blower 303 and coupling 304 to attach to the charcoal scrubber 300 , with associated conduit 302 to draw the ClO 2 gas into the charcoal bed 301 . In some embodiments the blower may include a coupling 308 allowing conduit 302 to attach with coupling 302 to the blower to create a closed scrubbing path or to attach to a building exhaust/HVAC exhaust system.
[0046] FIG. 4 shows the CD Generation and neutralization equipment and chemicals. FIG. 4 includes the CD generating reservoir 400 , CD precursor A 401 , CD precursor B 402 , neutralizing precursor N mixing bottle 403 , measuring cup 404 , porous splash guard 405 and neutralizing precursor N 406 ,
[0047] FIG. 5 is a high level flow chart of a process for performing a decontamination of a Class II Type A1, A2, B1, and B2 Biological Safety Cabinet (BSC) 101 . When the system of FIGS. 1A , 1 B, 1 C and 1 D is applied to other devices, slight modifications on attachment, sealing and circulation are applied, as will be apparent to one of ordinary skill. For example, in other embodiments, the device to be decontaminated is not a BSC, and a tent material is placed around the device, and sealed to appropriate connection panels described herein, using a pressure sensitive adhesive tape (e.g., duct tape). The gas conduit connections to the ports of the connection panels can be made in the same manner as connecting the conduit to the BSC. In addition, a power cord 204 for the running an electrical device can be passed through an opening or fitting 203 in the connection panel 200 and a gas-tight seal formed around the cord.
[0048] Referring again to FIG. 5 , at step 5000 , prior to using the system, the user reviews the manual and safety procedures.
[0049] At step 5001 , the BSC 101 is prepared. Details of this step are discussed below with reference to FIG. 6 .
[0050] At step 5002 , the exhaust/aeration preparations are performed. Details of this step are discussed below with reference to FIG. 7 .
[0051] At step 5003 , the intake preparations are performed. Details of this step are discussed below with reference to FIG. 8 .
[0052] At step 5004 , the overall volume of BSC 101 is determined and annotated.
[0053] At step 5005 , the amount of CD precursor is determined and noted. Details of this step are discussed below with reference to FIG. 9 .
[0054] At step 5006 , the Chem CD 8833 system is prepared. Details of this step are discussed below with reference to FIG. 10 .
[0055] At step 5007 , the decontamination cycle is performed. Details of this step are discussed below with reference to FIG. 11 .
[0056] At step 5008 , the scrubbing cycle is performed. Details of this step are discussed below with reference to FIG. 12 .
[0057] At step 5009 , the neutralization step is performed. Details of this step are discussed below with reference to FIG. 13 .
[0058] At step 5010 , the decontamination is complete, and a post-decontamination procedure is performed. Details of this step are discussed below with reference to FIG. 14 .
[0059] Referring to FIG. 6 , the BSC Preparation is shown.
[0060] At step 6000 , the user verifies that only items to be decontaminated are within the BSC.
[0061] At step 6001 , the user verifies that all items remaining in the BSC are stacked in a way that the humidity and ClO 2 gas can contact all surfaces, and no items lay flat or obstructed. If items require power, they are plugged into the BSC's receptacle and tested for operation ensuring the current draw does not exceed the rated capacity of the BSC's receptacle(s). The BSC may be prepped or moved such that appropriate sealing will be possible (e.g., in animal areas where the BSC units are on casters).
[0062] At step 6002 , the user places the CD generation reservoir into the BSC or temporary gas tight enclosure.
[0063] At step 6003 , the user connects the charcoal scrubber to the BSC or temporary gas tight enclosure.
[0064] At step 6004 , a determination is made whether a biological indicator (BI) was requested.
[0065] At step 6005 , if requested, the user can optionally affix at least one biological indicator (BI) within the BSC(s) at a pre-determined location(s). If using a BI with a Tyvek envelope, the user pushes a hanger (e.g., an opened paperclip or other hanger) through one end of the Tyvek envelope, and then attaches the hanger to an internal surface of the BSC. If the hanger cannot be directly hung, the surface is decontaminated with the appropriate disinfectant or sterilant, ensuring proper contact time prior to affixing the tape.
[0066] FIG. 7 shows the exhaust preparation step. Exhaust preparation of various classifications use different exhaust sealing configurations, as follows:
[0067] At step 7000 , steps 7001 - 7003 are performed for Class I, Class II Type A1, A2 when the air through the BSC is exhausted back into the space.
[0068] At step 7001 , the user removes the exhaust HEPA filter protective screen and places it aside.
[0069] At step 7002 , the user uses isopropyl alcohol (IPA) or other cleaning solvents to clean and remove dust or debris from the top exhaust filter housing.
[0070] At step 7003 , the user seals the exhaust HEPA filter using a return sealing panel (which may be configured with male cam and groove coupling) using duct tape or other sealing material.
[0071] At step 7004 , steps 7005 - 7006 are performed for Class I, Class II Type A2 (when exhausted via thimble or canopy).
[0072] At step 7005 , the user removes the thimble or canopy. Thimble or canopy connections are spelled out in the National Sanitation Foundation (NSF International) Standard No. 49 for Class II (Laminar Flow) Biohazard Cabinetry, for connecting BSC to exhaust systems. This type of connection provides an air gap as to compensate for room pressurization changes.
[0073] Alternatively, at step 7006 , the user closes or seals the sealable type thimbles, canopies, and/or at step 626 , the user closes the exhaust gas tight damper and follows the B1 or B2 procedure dependant on the sealing, and or, damper location relative to the exhaust HEPA filter. The user ensures that this is indeed a gas tight damper with no by-pass leakage. The user temporarily by-passes any low flow alarms.
[0074] At step 7007 , steps 7008 - 7009 are performed for a Class I, Class II Type B1, B2 BSC.
[0075] At step 7008 , the user fully closes the exhaust ductwork gas tight decontamination exhaust damper.
[0076] At step 7009 , the user leaves the back draft, EVAV or other balancing damper(s) in their original position.
[0077] At step 7010 steps 7011 are used for isolators or class III BSC's.
[0078] At step 7011 , the user closes the exhaust ductwork valve.
[0079] FIG. 8 is a flow chart showing intake preparation of classifications. Steps 8000 - 8003 are performed for a Class I, Class II Type A1, A2, or B1 BSC. Steps 8004 - 8005 are performed for Isolators and Class II Type B2 BSC.
[0080] At step 8000 , preparation starts for a Class I, Class II Type A1, A2, or B1 BSC.
[0081] At step 8001 , the user starts to seal the front access opening using the supply connection panel using duct tape or other sealing materials.
[0082] At step 8002 , the user seals the top supply HEPA intake opening.
[0083] At step 8003 , the user clamps the B2 supply recirculation duct line to the connection panel.
[0084] At step 8004 , preparation starts for a isolator or a Class II BSC.
[0085] At step 8005 , the user closes the air supply valve.
[0086] FIG. 9 shows the process by which the user determines and annotates the amount of ClO, generating chemicals need to be used for the decontamination.
[0087] The user multiplies the BSC volume by 0.13 g/ft 3 (4.7, g/ m 3 ) to determine the mass of ClO 2 required to be generated. Then, the user multiplies the ClO 2 mass by the unit mass of the supplied chemical. The following table determines the amount of chemical (e.g., sodium chlorite) required. Need 0.13 g CD/ft 3 of space being decontaminated. For example: a 6 foot BSC is 75 ft 3 .times.0.13=9.75 CD required.
[0000]
TABLE-US-00001
TABLE 1 Chlorine Dioxide Minimum Maximum BSC Size Generating
Table 1
Maximum
BSC Size
Chlorine Dioxide
Volume - ft 3 (m 3 )
Width - ft (m)
Generating Chemical (g)
50
3-4 ft (0.91-1.22)
6.5
75
5-6 ft (1.52-1.83)
9.75
Custom
Custom
(Volume ft 3 ) × (0.13 g/ft 3 )
[0088] FIG. 10 shows the Chem CD System Preparation.
[0089] At step 10 , 000 , the user dons safety glasses, lab coat, gloves and an appropriate respirator.
[0090] At step 10 , 001 , the user places the CD generation reservoir in the center of the enclosure or BSC to be decontaminated.
[0091] At step 10 , 002 , the user obtains Chem CD neutralizer precursor N 406 and adds IL of water to mixing bottle 403 in preparation for neutralization at the end of the decontamination cycle.
[0092] At step 10 , 003 , the user obtains Chem CD precursor A 401 and Chem CD precursor B 402 in preparation for starting the CD generation cycle.
[0093] At step 10 , 004 , the user obtains 250 ml of water 407 using the measuring cup 404 .
[0094] FIG. 11 shows the decontamination Cycle. Before beginning the cycle, the user verifies that a negative pressure secondary containment system is incorporated within the decontamination area‘ 3 or that the BSC is located within an un-recirculated space with a pressure negative relative to all bordering areas, labs and hallways, etc.
[0095] At step 11 , 000 , the user adds the Chem CD precursor A 401 to the CD generation source/reservoir 400 .
[0096] At step 11 , 001 , the user adds 250 ml of water 407 using the measuring cup 404 .
[0097] At step 11 , 002 , the user spreads Chem CD precursor B 402 into Chem CD precursor A 401 and 250 ml of water 407 in the CD generation source/reservoir 400 .
[0098] At step 11 , 003 , the user will quickly seal the BSC or temporary gas tight enclosure 101 to be decontaminated.
[0099] At step 11 , 004 , the user activates the recirculation blower if applicable.
[0100] At step 11 , 005 , the user lets the mixture generate ClO 2 gas and remain in the chamber until the exposure time has elapsed or is complete.
[0101] FIG. 12 is a flow chart of the Scrubbing Cycle
[0102] At step 12 , 000 , the user determines that the ClO 2 gas contact cycle is complete.
[0103] At step 12 , 001 , the user turns on the scrubber 300 or building exhaust/HVAC exhaust system 310 .
[0104] At step 12 , 002 , the user lets the scrubber 300 or building exhaust/HVAC exhaust 310 run until the concentration of ClO 2 gas is reduced to safe levels.
[0105] At step 12 , 003 , the user slowly unseals the BSC 101 or temporary gas tight enclosure 101 in preparation for neutralization.
[0106] FIG. 13 shows the neutralization procedure.
[0107] At step 13 , 000 , the user makes sure to unseal the BSC 101 or temporary gas tight enclosure 101 just enough to add the neutralizing precursor N 406 after it has been mixed in IL of water using the mixing bottle 403 .
[0108] At step 13 , 001 , the user adds the neutralizing precursor N 406 after it has been mixed in 1 L of water using the mixing bottle 403 to the CD generation source/reservoir containing the 250 ml of water 407 , CD precursor A 401 and CD precursor B 402 .
[0109] At step 13 , 002 , once the solution has turned cloudy/white/clear then neutralization is complete (CAUTION: solution may be hot)..
[0110] FIG. 14 shows the final procedure performed when Decontamination is Complete.
[0111] At step 14 , 000 , the user monitors determines that the scrubbing cycle is complete..
[0112] At step 14 , 001 , the user disassembles removes the generation equipment and disposes of the neutralized solution.
[0113] At step 14 , 002 , the user removes all connection materials (ex: tape, connection panel, etc.) and surface decontaminates if necessary.
[0114] At step 14003 , the user returns all air flow systems back to original settings (ex: HVAC system).
[0115] At step 14 , 004 , the user collects the BI(s) if used and sends them out for analysis.
[0116] At step 14 , 005 , the final decontamination report will be filled out completely and the user will make sure the customer gets a copy.
[0117] At step 14006 , the user will turn the BSC 101 or temporary gas tight enclosure 101 over for use.
[0118] Many variations and options are may be included in various embodiments.
[0119] In some embodiments, a gas tight connection panel connector is provided for the return of the scrubbed gas. Gas tight sealing duct ports of various diameters may be used for the return of the scrubbed gas
[0120] In some embodiments, gas tight sealing duct caps of various diameters are provided for the return of the scrubbed gas.
[0121] In some embodiments, the neutralization powder may be a proprietary mixture.
[0122] In some embodiments, the charcoal scrubber box has an inlet incorporating a charcoal retention screen with a gas tight design.
[0123] Preferably, the piping design incorporates the one blower, charcoal scrubber box, and provisions to attach the inlet and outlet lines all incorporated into one system. The blower is for the scrubbing or removal of the ClO 2 gas.
[0124] The Chem CD 8833 allows one to provide complete decontamination services in less than 4 hours, including setup and tear down of Biological Safety Cabinets (BSC) or devices (e.g., Casework, Cabinets, HLF's or VLF's, Containment Devices, CFH's, Centrifuges, Refrigerators, Freezers, Washers, Water Baths, Shakers, Bio-reactors, Tanks, Ctrs, Computers, or any other lab or productions equipment).
[0125] Other Items may be incorporated within the decontamination space, and can be placed within the BSC.
[0126] Examples of BSC's which the Chem CD 8833 is compatible with, are all classes and type classifications.
[0127] Some embodiments include a connection panel with a port to introduce a power cord to energize an electrical device within the device or space under decontamination.
[0128] A gas tight connection panel may be included for “tenting method” or temporary spaces to contain the gas for the introduction of the decontaminating gas. Similarly, a gas tight sealing duct port of various diameters may be included for scrubbing the gas from a BSC (Type B2).
[0129] Although the invention has been described in terms of exemplary embodiments, it is not limited thereto. Rather, the appended claims should be construed broadly, to include other variants and embodiments of the invention, which may be made by those skilled in the art without departing from the scope and range of equivalents of the invention.
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A system includes a portable source of gaseous chlorine dioxide (CD) to be generated within an isolated chamber or tent structure enclosing the device to be treated. A portable scrubber has first sourced couplings for sealingly connecting to a scrubbing flow path comprising at least one gas conduit for removing the CD from the device enclosed within an isolated chamber or tent structure. The gas conduit may have second couplings for connecting the device or isolated chamber or tent structure to the scrubbing flow path by way of a connection panel to complete a closed, filtered gas loop.
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RIGHTS OF THE GOVERNMENT
The invention described herein may be manufactured and used by or for the Government of the United States for all governmental purposes without the payment of any royalty.
CROSS-REFERENCE TO RELATED APPLICATIONS
The present document relates more or less to three earlier filed statutory invention registration documents which originated with the same two inventors and which are assigned to the same assignee as the present application. The three earlier documents titled, "The Polarization Diverse Phase Dispersionless Broadband Antenna", Ser. No. 841,375; "The Mono-Blade Phase Dispersionless Antenna", Ser. No. 841,376; and "The Bi-Blade Century Bandwidth Antenna", Ser. No. 841,381; were filed on Feb. 21, 1986. The disclosure of these three earlier documents is hereby incorporated by reference into the present document.
BACKGROUND OF THE INVENTION
This invention relates to the field of electromagnetic wave antenna apparatus of the large bandwidth, diverse polarization and phase dispersionless type.
The prospect of replacing a plurality of single purpose antennas for a modern military aircraft with a lesser number of antennas that are capable of wideband and multi-functional operation is of significant interest in the aircraft and electronic arts. For reasons which include space availability, maintenance simplification and improved aerodynamic characteristics, the prospect of aircraft and spacecraft antenna count limitation is now carefully considered in the planning of each new aircraft and space vehicle and in each modification of existing equipment. The broadband radiation capability of the presently disclosed antenna together with its desirable polarization and phase characteristics suggest the possibility of its service in such applications. The antenna of the present disclosure can also be arranged for use in other environments such as satellite communications--in both the orbital vehicle and the earthbound receptor functions. In the latter, earthbound satellite receptor use the antenna herein disclosed can be supplemented with a parabolic dish or other reflecting element arrangements.
The prior patent art includes a large number of antenna arrangements, however, the characteristics of these antennas do not include the desirable bandwidth, phase, and polarization characteristics--especially the combination of these characteristics found in the present invention antenna.
The difficulty encountered in simultaneously achieving a combination of no phase dispersion with desirable spatial pattern and bandwidth characteristics in a single antenna is demonstrated by the commonly accepted compromises which lead to use of the log periodic antenna and the cavity backed spiral antenna. Each of these antennas can be arranged to achieve bandwidths exceeding a decade while also providing respectable spatial patterns and relatively desirable radiation efficiency. Along with these desirable properties, however, these antennas are known to have undesirable voltage standing wave ratios, values in the range of 2 to 1 or greater and to also exhibit severe time or phase dispersion of a transmitted or received signal. Such antennas, if fed with a very short pulse of radio frequency energy, a pulse of less than several cycles duration, provide a radiated electromagnetic waveform which contains severe phase and time dispersion effects and thereby cause the radiated waveform to be stretched in time. The combination of non-dispersion and broad frequency band characteristics is particularly unusual in the present state of the antenna art. For use in the spread spectrum signal environment and other broadband applications therefore, an improved antenna such as disclosed herein, is needed--especially in the specialized field of antennas for military use.
SUMMARY OF THE INVENTION
The antenna of the present invention involves a multi-bladed structure wherein active antenna radiating elements are oppositely disposed around a central ground plane member and are electrically coupled to a signal source or signal reception apparatus according to a selected element phasing arrangement. The antenna of the invention provides notably improved phase, bandwidth, and dispersionless operating characteristics.
It is therefore an object of the present invention to provide an antenna that is capable of wideband, multi-octave signal spectrum performance.
It is another object of the invention to provide an antenna that is capable of transmitting and receiving signals of diverse polarization, polarizations which include linear, circular and elliptical polarization patterns.
It is another object of the invention to provide an antenna that is capable of high fidelity, phase dispersionless operation over a wide frequency band.
It is another object of the invention to provide an antenna capable of achieving the aforementioned three objects simultaneously.
It is another object of the invention to provide an antenna which can be adapted to wideband operation in a plurality of different frequency spectrum ranges including, for example, the microwave spectrum, the high frequency spectrum and in the intervening frequency bands.
It is another object of the invention to provide an antenna having a low radar cross-section, an antenna which is therefore suitable for use in military vehicles.
It is another object of the invention to provide an antenna that is capable of replacing a plurality of existing antennas in selected applications.
It is another object of the invention to provide an antenna that is suitable for mounting in the nose cone of an aircraft or missile.
It is another object of the invention to provide an antenna that is capable of use as a radar tracking antenna, as an electronic support measures (ESM) antenna or as an electronic intelligence (ELINT) system antenna.
It is another object of the invention to provide a high precision antenna which may be used in laboratory calibration.
It is another object of the invention to provide an antenna which operates with a low input voltage standing wave ratio, a ratio in the range of 1.1 to 1 or less.
It is another object of the invention to provide an antenna which operates in the non-resonant broad frequency band mode of operation.
It is another object of the invention to provide an antenna which is simple to construct and inexpensive to manufacture.
It is another object of the invention to provide an antenna which is relatively small in comparison with its achieved electrical properties.
Additional objects and features of the invention will be understood from the following description and the accompaning drawings.
These and other objects of the invention are achieved by an antenna apparatus which includes the combination of a tapering-shaped ground plane element disposed around an antenna central axis with an apex portion thereof facing a first axis extremity and a base portion thereof facing the opposite axis extremity, a plurality of plane radiator elements disposed in radial planes that are symmetrically distributed about the axis and orthogonally oriented with respect to the surface of the ground plane element, each of the radiating elements extending along the axis beyond the ground plane apex portion in the direction of the first axis extremity and having a curving cross-sectional shape in its plane of residence including predetermined varying separation between the radiating element axis adjacent edge thereof and the ground plane surface.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an overall perspective view of an antenna embodied according to the present invention.
FIG. 2 is a cutaway partial view of an antenna embodied according to the present invention including structure and dimension details.
FIG. 3 shows a desired surge impedance vs. distance characteristic for an antenna made in accordance with the invention.
FIG. 4 shows one arrangement for electrical coupling with an antenna according to the invention.
FIG. 5 shows another arrangement for electrical coupling with an antenna according to the invention.
FIG. 6 shows another arrangement for electrical coupling with an antenna according to the invention.
FIG. 7 shows the short pulse response of an antenna made in accordance with the invention.
FIG. 8 shows the short pulse response for a prior art antenna.
FIG. 9 shows the response of a typical circularly polarized broadband antenna to a rotating linear polarized source.
FIG. 10 shows the response of an antenna according to the present invention to a rotating linearly polarized source.
FIG. 11 shows a sequence of steps which may be used to fabricate and tune an antenna in accordance with the invention.
FIG. 12 shows a field pattern for the FIG. 1 antenna when coupled in accordance with the arrangement of FIG. 4.
FIG. 13 shows a field pattern for the FIG. 1 antenna when coupled in accordance with the arrangement of FIG. 5.
DETAILED DESCRIPTION
FIG. 1 in the drawings shows an overall perspective view of an antenna 109 that is made in accordance with the present invention. The FIG. 1 antenna 109 includes a truncated cone shaped member 100 which serves as a ground plane element for the antenna. Surrounding this conical ground plane element is an array of antenna radiating elements, which are four in number in the FIG. 1 antenna; the radiating elements are denoted by the identifying numbers 102, 104, 106 and 108.
The conical ground plane element 100 in the FIG. 1 antenna is presumed to be symmetrically disposed about a central axis 101 which passes through the top most or apex portion of the conical ground plane element and extends through the center of the bottom truncation circle of the conical ground plane element. The radiating elements 102, 104, 106 and 108 in the FIG. 1 antenna are disposed radially with respect to the central axis 101. For description convenience, each of the radiating elements 102, 104, 106 and 108 can be considered to reside in a radiating element plane which passes through or incorporates the central axis 101.
Also shown in FIG. 1 is one arrangement of an element supporting structure which may be used to retain the radiating elements 102-108 in fixed predetermined positions with respect to each other and with respect to the conical ground plane element 100. This supporting structure includes a base member 116 and radiating element support arms 110, 112 and 114. Attachment between the radiating elements 102-108 and the support arms 110-114 may be accomplished by way of machine screws or the like, preferably electrically non-conductive machine screws such as are fabricated from nylon or phenolic or other electrical insulation materials. The base member 116 and the support arms 110-114 may also be fabricated of clear acrylic or phenolic or other non-conducting materials which have good electrical properties in the frequency range selected for the FIG. 1 antenna; clear acrylic composition of these elements is presumed in FIG. 1--hence the resulting see through representation of the supporting structure elements in FIG. 1.
The shape shown in FIG. 1 for each of the radiating elements 102-108 may be described as having resemblance to the cross-section of an airfoil member since the illustrated element shape includes a rounded leading edge, a somewhat flattened "lower surface", a humped curving "upper surface", and a tapered trailing edge region, these regions face upward, outward, inward, and downward respectively, in the FIG. 1 antenna 109. This airfoil like shape is desirable in the present invention for the electrical impedance and radiating characteristics achieved by the humped curving element shape in combination with the conical ground plane element 100. The portions of the curving shape indicated at 120, 122, and 124 in FIG. 1 are principally determinative of the radiating element electrical characteristics with each of these portions especially affecting selected portions of the overall electrical characteristics as is described in detail below.
The radiating elements 102, 104, 106 and 108, may also be described as cross-sectional elements of a horn structure. In the FIG. 1 antenna 109, the throat, mouth, and tip regions of the element defined horn are located at the lower mid and upper portions of the FIG. 1 displayed elements.
FIG. 2 in the drawings shows additional details of selected elements from the FIG. 1 antenna. In FIG. 2, several of the identifying numbers used in FIG. 1 are repeated where appropriate for FIG. 1 shown elements with new members in the 200 series being employed for elements first shown in FIG. 2. The FIG. 2 representation of the FIG. 1 antenna is shown in a slightly rotated from head-on condition for drawing convenience and therefore, appears somewhat asymmetric in shape. The repeated elements and numbers in FIG. 2 include the radiating element 108, the conical ground plane 100, the radiating elements support arm 110, the base member 116 and the blade element curvature indications at 120, 122, and 124, that is, the curvature indications at the throat, midpoint, and horn mouth or airfoil leading edge regions of the antenna radiating element 110.
Additional details shown in FIG. 2 of the drawings include three of the four coaxial connector fittings by which electrical signals traveling to or from the antenna elements 102, 104, 106 and 108 are communicated through the electrically conductive surface of the conical ground plane member 100. These coaxial cable fittings are shown at 200, 202 and 204 in the FIG. 2 drawing. As is indicated at 216 and 218 for the fittings 200 and 204, each fitting includes an electrically insulated center conductor by which electrical signal is conveyed through the copper or aluminum or similar conductive sheet 205 of the coaxial ground plane element 100 to the antenna elements. Electrical and physical connections between the center conductor and the antenna elements are made by way of a mating female aperture 218 located in each of the radiating elements 102, 104, 106 and 108. The coaxial cable fittings 200, 202 and 204 therefore, serve as both a portion of the physical structure of the antenna 109 and also serve as terminating fixtures for the coaxial cable transmission line elements used in coupling electrical signals with the radiating elements 102-108. Also shown in FIG. 2 are representative threaded fastener members 206 and 208 by which the conical ground plane element 100 is removably attached to the base member 116. Additionally shown in FIG. 2 are radiating element supporting and bracing elements 212 and 210, the bracing element portion of these structures being located below the base member 116.
The location of the coaxial cable fittings 200, 202, and 204 is indicated at 214 in FIG. 2; the indicated dimension is appropriate for each of the four coaxial fittings of the FIG. 1 and 2 antenna. Significant overall dimensions for the major elements of the FIG. 1 and 2 antenna, dimensions which are applicable to a microwave band embodiment of the antenna--an antenna usable over the band generally extending between frequencies of 0.5 gigahertz and 18 gigahertz are shown at 226, 228, 238 and 240 in FIG. 2. The dimensions in FIGS. 1 and 2 are shown in inches.
The apex portion of the conical ground plane element may be fabricated as a part of the conductive sheet material 205 or alternately may be fabricated as an integral unit 243 which is inserted into the ground plane element during fabrication. At 230, 232 and 234 in FIG. 2, are shown three mounting holes which may be used for maintaining the radiating element 108 in a fixed rigid position by attachment to the radiating element support arm 110, for example--using such attachment arrangements as the threaded screws 242 which are also shown in FIG. 2. Preferably, the threaded screws 242 are made of nylon or some other electrically non-conducting material.
An additional series of radiating element region identifiers are indicated by the letters A through H shown at 236 in FIG. 2. The region identifiers 236 are used herein in connection with the surge impedance characteristics and the curve of FIG. 3 in the drawings and are discussed below.
Additional details of the FIG. 1 and 2 antenna that are identified in FIG. 2 include the radiating element back edge or airfoil underside edge 244, and the series of chord line identifying numbers, numbers between one (1) and twenty-two (22) which are indicated at 246 in FIG. 2. A list of radiating element dimensions along each of the chord lines indicated at 246 in FIG. 2 and applicable to the herein described microwave frequency band embodiment of the antenna invention is presented below as Table 1.
TABLE I______________________________________Radiating Element Chord Line Dimensionsfor Microwave Band Antenna22.94 inch overall lengthFIG. 2 Chord Line Number Chord Length Dimension______________________________________ 1 2.44 2 3.00 3 3.38 4 3.70 5 3.90 6 4.18 7 4.34 8 4.46 9 4.5010 4.4811 4.4212 4.3013 4.1214 3.9015 3.6016 3.3817 3.1018 2.9819 2.1420 2.1021 1.7222 1.34______________________________________
In addition to chord lengths in FIG. 2, Point A is 1/8 inch from Point H.
Since the antenna of the present invention is intended for use with broadband transmission or reception apparatus rather than with the conventional continuous wave single frequency apparatus, many of the theorectical and mathematical concepts used to describe antennas and their electrical characteristics are no longer useful tools in a technical discussion and are more conveniently replaced by concepts which have meaning over wide frequency ranges. Among the concepts includable in this change of descriptive concepts is the familiar characteristic impedance. The concept of characteristic impedance is often used to describe radio frequency hardware such as antennas, transmission lines, and networks but is principally useful at one frequency in the continuous wave or CW operating realm. The characteristic impedance of a transmission line is the driving-point impedance which the line would have if it were of infinite length. However, it is recommended that this term be applied only to lines having approximate electrical uniformity. For wide frequency band antennas and their associated apparatus, the concept of surge impedance is more useful than measurements of characteristic impedance. Surge impedance is therefore used when considering transmission lines and other apparatus designed for broadband applications. The term surge impedance is, therefore, employed herein for describing inter alia the tuning or shaping or refining of the radiating elements 102, 104, 106 and 108 and their spacing 248 from the conical ground plane element 100 and from each other. Values of surge impedance can be measured in a laboratory setting with an apparatus called a time domain reflectometer. One version of a time domain reflectometer, an apparatus which may be used in connection with the present invention antenna is the model HP54120T reflectometer made by Hewlett Packard Corporation.
A procedure for the empirical selection of radiating element size, shape, and spacing parameters using a time domain reflectometer or similar instrument and the concept of surge impedance is shown in FIG. 11 of the drawings. Generally, this fabrication procedure assumes the presence of an initial cut or try at the antenna--an antenna which may be arrived at from the designers previous experience and from conventional continuous wave antenna theory together with a consideration of the aircraft space allocation and shape configuration in the case of airborne antennas. This initial cut antenna may involve, for example, radiating elements formed of wire screening, copper foil or other conveniently workable materials. With this initial cut of the antenna, time domain reflectometer measurements can be made. Preferably, such measurements are made through a length of coaxial transmission line selected to achieve an impedance match with the signal source or receiver.
The feed region of the radiating element 108 in FIG. 2, the region identified with the letter A, is preferably arranged to having a surge impedance of 50 ohms in order that a well matched coupling with common coaxial cable characteristics be possible. The configuration of the feed region of the radiating elements can be approximated theoretically by regarding the spacing 248 between the radiating element 108 and the ground plane element 100 in FIG. 2 as the slot portion of a slot radiator--a radiator which is then analyzed according to the concepts presented in of the text "Antenna Engineering Handbook" by Richard C. Johnson and Henry Jasik, 2nd Edition, 1984, McGraw-Hill Book Company. Both the Chapter 8 Slot Antenna and the Chapter 9 Slot Antenna Arrays Materials from the Johnson and Jasik text are helpful in the initial configuration of radiating element 108 and its spacing 248. The disclosure of the Johnson and Jasik text is hereby incorporated by reference herein.
Theorectical consideration and the initial cut of an antenna according to the invention can also utilize the conceptual dual of a single radiating element antenna. According to the dual concept, when a radiating element is located above a metal ground plane, the dual of this element appears below the ground plane and image theory provides a tool for analyzing the resulting properties. Removal or alternately shrinking of the ground plane cone in the FIG. 2 antenna until only two radiating elements remain is included in an analysis of this type. Transmission line slot theory may then be applied to these remaining two elements and their spacing. The slot width may be presumed to open exponentially from the throat to the mouth regions of the FIG. 1 and 2 elements with the radiating element end opposite the feed point considered as a constant radius arc. A slot radiator of this type has a transverse electromagnetic mode (TEM) of propagation.
As indicated in the second and third blocks of FIG. 11, the block 1 initial cut antenna may be refined through the use of surge impedance measurements achieved with a time domain reflectometer or similar measurement instrument. A desirable configuration of the surge impedance characteristics of the FIG. 1 and FIG. 2 antenna elements is shown in FIG. 3 of the drawings. The above indicated value of 50 ohms for the surge impedance at the element feed point, point A in the region identifiers 236 of FIG. 2, is also identified as point A in FIG. 3. Commencing with this feed point impedance, a smoothly increasing value of surge impedance progressing from feed point through the throat 120, mid region 122, and leading edge region 124, that is, through the points B and C in FIG. 3 is desired.
As indicated above, the radius of the element 108 at the airfoil leading edge or open end of the horn shape in FIG. 2, desirably lies between a too small radius value wherein excessive slope and unwanted energy feedback to the input or point A region of the radiating element horn occurs and a too large radius value wherein the physical size of the antenna becomes excessive. The radiating element backside configuration, that is, the geometry of the element 108 along the points designated as D, E, and F in FIG. 2 is somewhat optional with respect to antenna electrical characteristics and may be disposed in the form of a substantially straight line as indicated in FIG. 2 or otherwise arranged according to structural or other considerations. A long length for the FIG. 2 antenna, together with the relatively slow change of surge impedance as illustrated in the FIG. 3 drawing is desirable in order to realize a low voltage standing wave ratio characteristic for the antenna.
A low voltage standing wave ratio is desirable not only for its usual benefits of minimizing electrical stresses in transmitting apparatus and maximally coupling radio frequency energy into the antenna and to free space, but also in order that a reduced radar cross-section obtain for the antenna. A low radar cross-section is clearly desirable for military uses of antennas made in accordance with the invention as may be surmised from the currently announced interest in stealth aircraft.
The optimum location of the feed point and the aperture 218 with respect to the radiating element 108 in FIG. 2 is one which avoids a "bump" or other irregularities in the surge impedance relationship shown in the FIG. 3 drawing. In addition to location of the feed point according to this criteria, it is desirable for electromagnetic field fringing effects to be avoided in the A, H, and G region of the antenna radiating element 108. A major consideration in achieving desirable electromagnetic field fringing behavior in this region concerns the relative size of the radiating element 108 between the points G and H with respect to the gap spacing 248 in this region. A relationship of at least 10 to 1 and preferably 20 to 1 between the G to H dimension of the radiating element 108 and the ground plane spacing 248 at the feed point is desirable.
The polarization and electromagnetic field patterns achieved with the FIG. 1 and 2 antenna are variable in accordance with the relative electrical phasing of the radiating elements 102, 104, 106 and 108 with respect to each other. Preferably these elements are fed with coaxial cable, the grounded conductor of which is connected with the ground plane element 100 internal of the conical base portion--i.e. at each of the fittings 200, 202, and 204. The center conductors of the element feeding four different coaxial cables are connected to the insulated center conductors of the fittings 200, 202, 204 and the fourth not shown fitting of this type in FIG. 2. The distal end of these coaxial cable transmission lines may be connected to a variety of energy source (or sink) associated phasing apparatus, such as 180 degree hybrid couplers or Magic Tees or the 45 degree and 90 degree phasing apparatus described below herein.
FIG. 4, 5, and 6 in the drawings show three possible arrangements of this type for coupling radio frequency signals to or from the antenna of FIG. 1 and FIG. 2. In the FIG. 4 drawing, a 180 degree hybrid coupler or a broadband magic T network 400 is used to couple between a radio frequency source or sink 406 and the transmission lines feeding two elements of the FIG. 1 and 2 antenna. According to the FIG. 4 coupling arrangement, the radiating elements 412 and 414 are fed in anti-phase, that is 180 degrees out of phase by way of applying signal to the difference port 404 of the coupler 400 and terminating the summation port in a matched load 402 as is indicated at 406. With this coupling arrangement, the instantaneous electric field between radiating elements 412 and 414 extends from one element to the opposite element as shown at 416. The FIG. 4 coupling arrangement, of course, presumes that the non-shown two elements of the FIG. 1 and 2 antenna are connected in a similar fashion. The field pattern resulting from anti-phase connection of antenna elements as shown in FIG. 4 can be expected to be as illustrated in FIG. 12 when measured at 3 gigahertz.
When the radio frequency input signal to the antenna is applied to a sum port of the 180 degree hybrid coupler or broadband magic T as is shown in FIG. 5 of the drawings, the resulting antenna element electric field extends from both radiating elements to the ground plane cone. In the FIG. 5 coupling arrangement, the remaining two sets of coaxial feed cables are connected to the output ports of a different broadband magic T and in exactly the same fashion as the elements shown in FIG. 5 and therefore result in another field pattern of the FIG. 5 type disposed in a plane perpendicular to the FIG. 5 page. With the connection arrangement thereby described for FIG. 5, the field pattern for the antenna as measured at 8 gigahertz is illustrated in FIG. 13. Good monopulse null and low antenna sidelobes were obtained across the microwave band with this arrangement.
In the FIG. 6, coupling arrangement, two anti-phase signals are applied to the difference ports of two antenna element connected or secondary 180 degree hybrid couplers or broadband magic T networks 600 and 602. In the FIG. 6 feed arrangement, one of the networks 602, is fed with a phase adjustable signal from the primary network 604 in order to control the antenna element phase relationships and the resulting antenna radiation. With the use of variable phase shifting elements, signals of any polarization can be radiated from the antenna of FIGS. 1 and 2. Typical values of phase shift and the resulting polarization are listed below in Table II.
TABLE II______________________________________Achieved Polarization -Antenna with Variable Phase ShifterValue of Phase Shift Radiation Polarization______________________________________ 0° +45° Linear Polarized 45° Elliptical CW 90° Circular CW135° Elliptical CW180° -45° Linear Polarized225° Elliptical CCW270° Circular CCW315° Elliptical CCW360° +45° Linear Polarized______________________________________
For achieving good sum or main beam patterns and difference or monopulse patterns as well as desirable circular and elliptical polarization performance and desirable VSWR performance in the microwave frequency range, dimensions as shown in the following Table III are desirable for the FIGS. 1 and 2 antenna.
TABLE III______________________________________Radiating Element Length: 23 inchesMouth Opening: 16 inchesRadiating Element Thickness: 0.1 inchesHeight: 25 inchesCone Half Angle: 12.5 degrees______________________________________
The antenna of FIGS. 1 and 2 when fabricated according to the parameters of the above table provides the following measured performance:
TABLE IV______________________________________Frequency: 4 GHz 6 GHz 8 GHzGain: 20.3 dB 24.1 dB 25.4 dBBeamwidth: 19° 12° 10.5°VSWR: 1.09:1 1.10:1 1.11:1______________________________________
Frequency scaling is applicable to the relationship between dimensions and operating frequency for the antenna of FIGS. 1 and 2. A lower frequency performance fall-off which occurs in the range of 0.5 gigahertz for an antenna according to the above recited Table III dimensions will, for example, be increased to a frequency of 1.0 gigahertz by using an antenna having dimensions that are one-half the values recited in this table. In this manner, desirable antenna performance extending into the very high frequency or high frequency bands may be achieved with proportionately increased dimensions from the disclosed antenna.
The antenna of FIGS. 1 and 2 employs four elements; this number of elements is the minimum number needed to achieve all polarization patterns with feed network arrangements of minimum complexity. A three element antenna, for example, might also achieve all polarization but would require a complex or perhaps unrealizable feed network arrangement. The antenna of the present invention is not, however, limited to this three or four element configuration and, in fact, may be readily extended to six or eight or any larger number of elements which can be physically disposed in the available space. The angular separation between adjacent elements of a larger number of elements array requires that such components as the coaxial cable fittings 200-204 in FIG. 2 being limited in physical size and space for the additional phasing network, transmission lines and support structures, be provided.
FIGS. 7 and 8 of the drawings compare the distortion performance of an antenna made in accordance with the present invention, in FIG. 7, with that of a commercially available broadband antenna, in FIG. 8. Each of the antennas in FIGS. 7 and 8 is impressed with a short duration pulse of radio frequency energy, a pulse of 0.2 nanoseconds duration with equal scales of time along the horizontal axis and amplitude along the vertical axis. Clearly, the ringing and distortion of the commercial antenna in FIG. 8 indicate significantly poorer signal fidelity than does the pattern for the antenna of the present invention as shown in FIG. 7. The response of FIG. 7 is, of course, desirable for use with a high resolution radar apparatus since the large instantaneous bandwidth of the applied short duration pulse is radiated and received without incurring measurable distortion. The dispersive characteristics of the FIG. 8 antenna preclude use of such antennas with large instantaneous bandwidth waveforms.
In a similar manner, FIGS. 9 and 10 of the drawings show the response of a typical circularly polarized broadband antenna to a rotating linearly polarized source in an anechoic test chamber. The response of the typical antenna in FIG. 9 is clearly secondary to the response of the present antenna as shown in FIG. 10. The FIG. 10 response is constant to within limitations of the measuring equipment and indicative of desirable antenna performance.
In addition to the performance indicated by the comparisons of FIGS. 7-10, the antenna of the present invention is found to have desirable collimation between the horizontally and vertically polarized beams over the indicated operating frequency range. Many dual polarized antennas have beam collimation problems, which arise when the horizontally polarized beam points in a different direction than the vertically polarized beam, and may wander about with respect to each other, even over moderate frequency ranges. Examples of this performance have been reported in the literature, especially with respect to military equipment antennas. Measurements made in the antenna disclosed herein show that it has overcome this problem as a result of the described antenna structure and feed arrangement.
The present antenna also provides small monopulse angle tracking error, a characteristic which does not change appreciably with frequency over the entire indicated microwave operating frequency band. This characteristic is used in target detection and tracking. Low angle tracking or pointing direction errors are desirable for present and future radars in which small target tracking capability is needed.
The antenna of the present invention is indicated above to be desirable for laboratory instrument calibration or in-the-field calibration of radar systems in addition to having a number of additional desirable features, advantages, and application.
Among the desirable features and advantages of the invention antenna are the following:
1. The antenna is extremely broadband and is capable of covering, for example, the entire microwave spectrum.
2. The antenna has little or no time (phase) dispersion.
3. The antenna has very low input voltage standing wave ratio (less than 1.1 to 1).
4. The antenna is a nonresonant structure, a contribution to its broadband nature.
5. The antenna is simple to construct and inexpensive to manufacture.
6. The antenna is polarization diverse; it can transmit and receive any polarization including linear, circular, or elliptical.
7. The antenna has desirable phase comparison monopulse response for tracking applications.
8. The antenna is physically small compared to its effective electrical properties.
9. The antenna provides the advantages of items 1 through 8 above all in a single apparatus.
While the apparatus and method herein described constitute a preferred embodiment of the invention, it is to be understood that the invention is not limited to this precise form of apparatus or method, and that changes may be made therein without departing from the scope of the invention, which is defined in the appended claims.
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A broadband multi-element antenna having desirable phase, standing wave and polarization characteristics is disclosed. The antenna is arranged as a plurality of airfoil shaped elements located in radial planes about a central axis with the element peripheries collectively defining a horn shaped surface--centrally disposed of which is a ground plane member of preferably truncated conical shape which includes electrical feeding arrangements having in phase and out of phase element coupling. The antenna is suitable for radar, satellite, and other precision uses including military applications.
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BACKGROUND OF THE INVENTION
The invention relates to a toothed selector clutch in a hydrostatic/mechanical, split-torque power-shift transmission. The transmission includes both a four-shaft epicyclic-gearwheel transmission and an infinitely variable hydrostatic transmission arranged in parallel. The power shift transmission includes a plurality of gearwheel stages each with an associated toothed selector clutch to thereby provide a plurality of gears. The selector clutch is operated to engage a gear within its associated stage. The hydrostatic transmission allows for an infinite variation of the transmission ratio of the overall hydrostatic/mechanical transmission.
German Patent No. 39 03 877 C1 discloses an infinitely variable, hydrostatic/mechanical power-shift transmission with toothed selector clutches, and is hereby incorporated by reference herein.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved selector clutch for effecting gear changes and, in particular, to provide a clutch that is compact in construction and operates reliably. It is another object of the present invention to provide a selector clutch that can effect gear changes at synchronous speeds in a load-free manner and without interruption to the tractive effort of the transmission.
In accomplishing the foregoing objects, there has been provided according to one embodiment of the present invention a toothed selector clutch in a hydrostatic/mechanical, split-torque power shift transmission having a four-shaft epicyclic-gearwheel transmission and an infinitely variable hydrostatic transmission arranged in parallel. The transmission includes downstream gearwheel stages each with associated toothed selector clutches thereby providing a plurality of gears. The hydrostatic transmission provides an infinitely variable transmission ratio for the hydrostatic/mechanical transmission. The toothed selector clutch includes a coaxial double differential clutch comprising: a clutch carrier mounted on a rotatable shaft; a shift bridge operatively connected to the clutch carrier by radial toothing thereby providing for the transmission of torque between the clutch carrier and the shift bridge and for the axial displacement of the shift bridge. The shift bridge is subjected to a pressure medium on axially opposite ends and includes shift toothing on each of the axially opposite ends. The clutch includes a pair of separately controllable pressure spaces internal to the shift bridge for applying pressure to the opposite ends of the shift bridge, each of the pressure spaces being capable of being subjected to pressure simultaneously to place the shift bridge in a neutral, central position. Each of the pressure spaces are capable of being depressurized individually so that the shift toothing at the end of the shift bridge adjacent the pressurized pressure space engages an adjacent gear at a synchronous speed without transferring load from the shaft to the gear being engaged and without interruption to the transmission of torque from the shaft to an engaged gear designated to be disengaged.
Preferably the clutch carrier includes a guide portion projecting between the two pressure spaces and two annular differential pistons which are situated axially opposite one another. Each of the differential pistons projects into one of the pair of pressure spaces and is configured to be supported axially against the clutch carrier only when shift bridge is in the neutral, central position so that when the shift bridge is displaced axially away from the neutral position into a shift position one of the annular differential pistons is displaced by a drive feature of the shift bridge, preferably toothing, into the adjacent pressure space. The clutch carrier may include a hole for guiding lubricating oil to the region of the drive feature.
The clutch is preferably arranged so that when the shift bridge is in the shift position, the displaced one of the annular differential pistons is configured to rest against an interior axial facing surface of the shift bridge. In addition, a pressurized-oil feed passing through the shaft and a rotating joint may be provided for each of the pressure spaces. The pressure of each of the pressure spaces may be controlled by a solenoid valve located upstream of the associated rotating joint. The shift bridge may include a bleed hole, extending between an internal area between the pair of annular differential pistons and an area external to the shift bridge to relieve pressure in the pressure spaces.
According to another embodiment the clutch may comprise a clutch carrier mounted to a casing; a shift bridge including shift toothing mounted on each of its axially opposite ends. The shift bridge is connected to a rotatable shaft by radial toothing thereby allowing torque transmission from the shaft to the shift bridge. The clutch further includes a double piston mounted in the clutch carrier. The shift bridge is also connected kinematically by a ball bearing to the double piston. The clutch further includes a pair of pressure spaces contained in within the clutch carrier. The double piston is capable of being displaced axially between the pressure spaces and the pressure within each of the pressure spaces is capable of being controlled separately so that when the two pressure spaces are simultaneously pressurized the double piston is positioned in a neutral, central position. Each of the pressure spaces is capable of being depressurized individually so that when one of the pressure spaces is depressurized the double piston and the shift bridge move axially into a shift position so that the shift toothing at the end of the shift bridge adjacent the other pressurized pressure space engages an adjacent gear at a synchronous speed without transferring load from the shaft to the gear being engaged and without interruption to the transmission of torque from the shaft to an engaged gear designated to be disengaged.
Preferably, the toothed selector clutch may further include two annular differential pistons situated axially opposite one another, each piston having an axial face adjacent one of the two pressure spaces, the differential pistons being supported axially against the clutch carrier only when the double piston is in the neutral, central position the differential pistons being configured so that when the double piston is displaced into the shift position of the shift bridge, one of the annular differential pistons is displaced by an associated drive feature of the double piston into the adjacent pressure space. The double piston may also be operatively connected to a displacement sensor.
In its generic aspects, the present invention provides a toothed selector clutch in a hydrostatic/mechanical, split-torque power-shift transmission having a four-shaft epicyclic-gearwheel transmission and an infinitely variable hydrostatic transmission arranged in parallel. The transmission includes downstream gearwheel stages with associated toothed selector clutches thereby providing a plurality of gears. The hydrostatic transmission provides an infinitely variable transmission ratio for the hydrostatic/mechanical transmission. The toothed selector clutch includes a coaxial double differential clutch comprising a shift bridge including shift toothing mounted on each of its axially opposite ends. The shift bridge is operatively connected to a rotatable transmission component by radial toothing thereby allowing torque transmission from the rotating component to the shift bridge and axial movement of the shift bridge relative to the rotating component. The clutch includes a pair of separately controllable pressure spaces, the pressure within each of the pressure spaces capable of being controlled separately so that when the two pressure spaces are simultaneously pressurized the shift bridge is positioned in a neutral, central position. Each of the pressure spaces is capable of being depressurized individually so that when one of the pressure spaces is depressurized the shift bridge moves axially into a shift position so that the shift toothing at one end of the shift bridge engages an adjacent gear at a synchronous speed without transferring load from a rotating clutch shaft to the gear being engaged and without interruption to the transmission of torque from the clutch shaft an engaged gear designated to be disengaged. The rotatable transmission component may be the clutch shaft or a clutch carrier mounted to the clutch shaft.
According to a further aspect of the present invention a hydrostatic/mechanical, split-torque power shift transmission is provided.
Further objects, features and advantages the present invention will become apparent from the detailed description of the invention that follows. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention.
In the drawing, FIGS. 1 and 1A show the prior art and FIGS. 2 to 6 show a number of embodiments of the invention serving as examples. In the drawings:
FIG. 1 is a schematic line drawing representing a four-shaft epicyclic transmission;
FIG. 1A is a graph showing the variation in the speed of the output shaft relative to the input shaft;
FIG. 2 is a cross-sectional view through a coaxial double differential clutch of the present invention;
FIG. 3 is a cross-sectional view of the clutch of FIG. 2 with a valve control system for feeding pressurized oil to the clutch;
FIG. 4 is a cross-sectional view of a second embodiment of a selector clutch according to the present invention;
FIG. 5 shows a cross-sectional view of a third embodiment of a selector clutch according to the present invention; and
FIG. 6 shows a cross-sectional view of a fourth embodiment of a selector clutch according to the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The object on which the invention is based is to develop an embodiment which is compact in construction and operates reliably for the toothed selector clutch described at the outset.
Referring to the toothed selector clutch described above, this object is achieved according to the invention by providing a toothed selector clutch designed as a coaxial double differential clutch which has a clutch carrier which is arranged in a rotationally and axially fixed manner on a rotating transmission component, preferably a clutch shaft. A double piston is mounted on the clutch shaft and can be subjected to a pressure medium on both sides. The double piston is designed as a shift bridge and is connected operatively to the clutch carrier by toothing which allows torque transmission and axial displacement. The shift bridge carries shift toothing on each of its axially opposite ends and can be acted upon from two separately controllable pressure spaces which, when subjected to pressure simultaneously, hold the shift bridge in its neutral, central position or displace it into this central position, while the engagement of one of the two gears assigned to the shift toothings is performed by depressurization of the pressure space assigned to the other gear.
At the same time, it is also preferred for the clutch carrier to project a guide portion between the two pressure spaces surrounded by the shift bridge. The guide portion carries two annular differential pistons, which are situated axially opposite one another, each projecting into one of the two pressure spaces. The differential pistons are supported axially against the clutch carrier only in the neutral, central position of the shift bridge, while, when the shift bridge is displaced into a shift position, an annular differential piston is displaced by an associated drive feature of the shift bridge into the associated pressure space.
To avoid power transmission to the clutch shaft via seals, it is preferred if, in the shift position of the shift bridge, the corresponding annular differential piston rests against that piston face of the shift bridge which faces it.
According to the invention, a modified embodiment can be distinguished by the fact that the shift bridge projects an annular, radially inward-projecting double piston of approximately T-shaped cross section into the interior of the clutch carrier surrounding the two pressure spaces and is assigned to two annular differential pistons which are situated axially opposite one another. Each differential piston projects into one of the two pressure spaces and is supported axially against the clutch carrier only in the neutral, central position of the shift bridge. When the shift bridge is displaced into a shift position, an annular differential piston is displaced by an associated drive feature of the shift bridge into the associated pressure space.
In the embodiments described above, it is preferred if a pressurized-oil feed through the clutch shaft in conjunction with a rotating joint is provided for each of the two pressure spaces, control preferably being exercised by means of NO (NORMALLY OPEN) 3/2-way solenoid valves arranged upstream of the rotating joint. When the valve is closed, this allows the pressure space thereby closed off to be emptied toward an oil tank. A corresponding valve circuit can also be found in German Patent No. 40 38 170 A1.
With regard to the the toothed selector clutch described above, the object underlying the invention is also achieved, in an alternative solution according to the invention, by providing a toothed selector clutch that is designed as a coaxial double differential clutch which has a shift bridge which bears respective shift toothing on its axially opposite ends. The shift bridge is connected rotationally by toothing which allows torque transmission and axial displacement to a rotating transmission component, preferably a clutch shaft, and is connected kinematically, by a ball bearing which transmits the required shifting force, to a double piston which is mounted in a clutch carrier. The double piston is arranged in a manner fixed relative to the casing, in such a way that it can be displaced axially between two pressure spaces which are surrounded by the clutch carrier. Each pressure space can be controlled separately from the casing side and, when simultaneously pressurized, hold the double piston in its neutral, central position or displace it into this central position, while the engagement of one of the two gears assigned to the shift toothings is performed by depressurization of the pressure space assigned to the other gear.
In all the embodiments, it is preferred if the angle of the shift toothing points away and is greater than or equal to the self-locking angle; in principle, however, it can also be zero or even less than or equal to the self-locking angle.
FIG. 1 discloses a typical four-shaft epicyclic transmission that includes an epicyclic stage I with a sun gear 1 , an annulus 2 and a planet carrier 3 with planet gears 4 and an epicyclic stage II with a sun gear 1 ′, an annulus 2 ′ and a planet carrier 3 ′ with planet gears 4 ′. The planet carrier 3 ′ and the annulus 2 form an input shaft 5 ; the sun gears 1 , 1 ′ form a shaft 6 for the connection of a constant-volume positive displacement machine 7 ; the planet carrier 3 forms a slow-running coupler shaft 8 ; the annulus 2 ′ forms a fast-running coupler shaft 9 . A variable-volume positive displacement machine 10 is connected by gears 11 , 12 to the input shaft 5 . As shown in FIG. 1A, the coupler shafts 8 , 9 operate so that, at a speed ratio of the positive displacement machines n 7 /n 10 =+1, the coupler shafts 8 , 9 rotate at the same speed. When the hydrostatic transmission is adjusted in the direction n 7 /n 10 −1, the coupler shaft speeds change so that the coupler shaft 9 becomes steadily faster and the coupler shaft 8 becomes steadily slower.
A first double toothed selector clutch Z 1 may connect the first gear K 1 having gearwheels 13 , 14 or the third gear K 3 having gearwheels 15 , 16 to an output shaft 21 , and a second double toothed selector clutch Z 2 may connect the second gear K 2 having gearwheels 17 , 18 or the fourth gear K 4 having gearwheels 19 , 20 to an output shaft 21 .
The coupler shafts 8 , 9 pass the power alternately from the input to the output. The first and the third gear are operatively connected to the coupler shaft 8 and the second and the fourth gear are operatively connected to the coupler shaft 9 .
The speed of the two coupler shafts 8 and 9 may vary relative to the speed of the input shaft 5 as a function of the relative displacement volume of the variable positive displacement machine, as shown in FIG. 1 A.
According to the present invention, a gear change is initiated at synchronous speeds of the new toothed clutch to be closed. The new or engaging clutch is engaged in a load-free condition (i.e. without the transmission of torque) while the old or disengaging toothed clutch remains engaged with its gears and transmitting power. The shift in load from the old clutch to the new clutch is performed by means of a controlled correction or change in volume of the control fluid in the hydrostatic transmission. At the end of this correction, the new clutch carries the load and the old clutch becomes unloaded and may be disengaged in a load-free condition.
A preferred embodiment of the present invention includes a toothed selector clutch Z 1 , Z 2 which may operate as a coaxial double differential clutch. As shown in FIG. 2, the clutch may include a clutch carrier 22 which is positioned in a rotationally and axially fixed manner on a clutch shaft (output shaft 21 in FIG. 1 ). A double piston 23 may be mounted to the clutch carrier 22 . The double piston or shift bridge 23 may be subjected to a pressure source on both sides. The double piston 23 is operatively connected to the clutch carrier 22 by toothing 24 which permits torque transmission between the piston 23 and the clutch carrier 22 . The piston or shift bridge 23 may be displaced in the axial direction and may include shift toothing 25 , 26 , mounted on axially opposite ends so that each tooth points outwardly or toward the adjacent gear. The position of the double piston 23 may be controlled by varying the pressure in two separately controllable pressure spaces 27 , 28 located within the shift bridge 23 . When the pressure spaces 27 , 28 are pressurized simultaneously, the shift bridge 23 is held in its neutral, central position, as shown in FIG. 2 . If the shift bridge 23 is not in the neutral, central position, the pressurized chambers may move the bridge toward the central position. The engagement of one of the two gears (K 1 , K 3 or K 2 , K 4 ) assigned to the shift toothings 25 , 26 may be accomplished by depressurizing the pressure space 27 , 28 assigned to the other one of the two gears.
In all the embodiments of the invention described herein, it is preferred that the angle of the shift toothing points away and is less than or equal to the self-locking angle. However, the angle of the shift toothing may also be zero or even greater than or equal to the self-locking angle.
The clutch carrier 22 may include a guide portion 22 a that projects between the two pressure spaces 27 , 28 to support two annular differential pistons 29 . The pistons 29 are situated axially opposite one another and each project into one of the two pressure spaces 27 , 28 . The annular differential pistons 29 are supported axially by the clutch carrier 22 only while the shift bridge 23 is in the neutral, central position. When the shift bridge 23 is displaced into a shift position away from the central position, an annular differential piston 29 may be displaced by an associated drive feature 30 of the shift bridge 23 into the associated pressure space 27 or 28 . The drive features 30 may include the ends of the internal toothing 24 a of the shift bridge 23 , as shown in FIG. 2 . The size of the shift bridge 23 and of the pressure spaces 27 , 28 is preferably selected so that the corresponding annular differential piston 29 rests against the associated piston face 23 a when the shift piston shifts into a shift position away from the central position. To avoid power transmission to the clutch shaft via seals, it is expedient if, in the shift position of the shift bridge, the corresponding annular differential piston rests against that piston face of the shift bridge which faces it.
The clutch of the present invention may also include a lubricating-oil hole or passage 32 which passes through the clutch carrier 22 and ends in the region of the radially projecting toothing 24 . A bleed hole or passage 33 , which opens between the two annular differential pistons 29 , may pass through the radially outer part of the shift bridge 23 .
Preferably, in all of the embodiments of the invention described herein, each of the two pressure spaces 27 , 28 may be connected to a pressurized-oil feed passage 35 which passes through the clutch shaft 21 . The feed passage 35 may include a rotating joint 36 . Pressure control of the pressure spaces is preferably controlled by the operation of NO (NORMALLY OPEN) 3/2-way solenoid valves 37 arranged upstream of the rotating joints 36 , as shown in FIG. 3 . When the solenoid valve is closed, the corresponding pressure space is thereby closed off to be emptied toward an oil tank. A representative valve circuit can also be found in German Patent DE 40 38 170 A1, which is hereby incorporated by reference herein.
FIG. 4 discloses an alternative emodiment of a clutch according to the present invention. The shift bridge 23 may include an annular, radially inward-projecting double piston 38 having an approximately T-shaped cross section. The piston 38 may project into the interior of the clutch carrier 22 toward the two pressure spaces 27 , 28 . The clutch includes two annular differential pistons 29 , which are situated axially opposite one another and each project into one of the two pressure spaces 27 , 28 . The annular differential pistons may be supported axially by the clutch carrier 22 when the shift bridge 23 is positioned in the neutral, central position, as shown in FIG. 4 . When the shift bridge 23 is displaced axially into one shift position, an annular differential piston 29 is displaced by an associated drive feature 30 of the shift bridge 23 into the associated pressure space 27 or 28 . The drive feature may be a radially projecting tooth.
Another alternative embodiment of the present invention is disclosed in FIG. 5 . The clutch generally corresponds to the clutch disclosed in FIG. 2 . However, the clutch carrier 22 , which is fixed to the shaft 21 , extends radially outward through the shift bridge 23 to form an outer guide portion 22 a . The guide portion 22 a forms a guide for a pair of annular differential pistons 29 positioned on a radially outward annular surface of the shift bridge 23 . As shown in FIG. 5, the pressurized-oil feed 35 passes through the central web of the clutch carrier 22 to the appropriate pressure space 27 , 28 .
FIG. 6 discloses yet another alternative embodiment of a coaxial double differential clutch. The clutch includes a shift bridge 23 having shift toothing 25 , 26 on its axially opposite ends. The shift bridge 23 is operatively connected to the clutch shaft 21 by toothing 39 . The toothing 39 permit torque to be transmitted from the shaft 21 to the shift bridge 23 and for axial displacement of the shift bridge 23 . The shift bridge 23 is also connected kinematically, by a ball bearing 40 which transmits the required shifting force, to a double piston 41 mounted in a clutch carrier 42 fixed to the casing. The double piston 41 is positioned relative to the fixed casing so that it can be displaced axially between two pressure spaces 27 , 28 surrounded by the clutch carrier 42 . The pressure in the pressure spaces 27 , 28 can be controlled separately from the casing side of the double piston. When subjected to simultaneous pressurization, the pressure spaces 27 , 28 hold the double piston 41 in a neutral, central position. Both spaces 27 , 28 may also be pressurized to force the piston 41 into the central position. Engagement of one of the two gears K 1 , K 3 or K 2 , K 4 assigned to the shift toothings 25 , 26 may be accomplished by depressurizing the pressure space assigned to the other of the two gears.
The double piston 41 is operatively connected to two annular differential pistons 29 , which are situated axially opposite one another. Each piston 29 extends toward one of the two pressure spaces 27 , 28 and is supported axially against the clutch carrier 42 only when the double piston 41 is in the neutral, central position (shown in FIG. 6 ). When the double piston 41 is displaced into a shift position of the shift bridge 23 , an annular differential piston 29 is displaced by an associated drive feature 30 of the double piston 41 into the associated pressure space 27 or 28 . As shown in FIG. 6, the drive feature may include a radially projecting tooth. As is also shown in FIG. 6 the double piston 41 may be coupled or operatively connected to a displacement sensor 43 fixed relative to the casing.
Given the disclosure of the present invention, one versed in the art would appreciate that there may be other embodiments and modifications within the scope and spirit of the present invention. Accordingly, all modifications attainable by one versed in the art from the present disclosure within the scope and spirit of the present invention are to be included as further embodiments of the present invention. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
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A toothed selector clutch is provided to operate in a hydrostatic/mechanical, split-torque power-shift transmission comprising a four-shaft epicyclic-gearwheel transmission and an infinitely variable hydrostatic transmission arranged in parallel. The selector clutch is associated with a particular gearwheel stage and is operated to select a particular gear. Gear changes take place at synchronous speeds without loading the engaging gear during the change and without interruption of the transmission of torque from the rotating shaft to the gear being disengaged. The toothed selector clutch is a coaxial double differential clutch with a clutch carrier that is arranged in a rotationally and axially fixed manner on a clutch shaft. A double piston, which can be subjected to a pressure medium on both sides, is provided as a shift bridge and is operatively connected to the clutch carrier by toothing thereby permitting torque transmission and axial displacement. The shift bridge carries shift toothing on each of its axially opposite ends and is acted upon from two separately controllable pressure spaces. When the shift bridge is subjected to pressure from both ends simultaneously, it remains or moves into its neutral, central position. Engagement of one of the two gears associated with the clutch may be accomplished depressurizing the pressure space assigned to the other gear causing the shift bridge to move axially and engage the intended gear.
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STATEMENT OF FEDERALLY SPONSORED RESEARCH
This invention was made with government support under DMR-0605880 awarded by the National Science Foundation. The government has certain rights in the invention.
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a National Stage application under 35 U.S.C. §371 of International Application No. PCT/US2011/028038 having an International Filing Date of Mar. 11, 2011, which claims the benefit of priority of U.S. Provisional Application Ser. No. 61/312,922 having a filing date of Mar. 11, 2010.
TECHNICAL FIELD
This invention relates to polymer membranes and processes for preparing same.
BACKGROUND
Block copolymers are versatile hybrid materials that have been used in the preparation of a wide variety of nano-structured materials. The incompatibility of distinct chemical segments leads to nanometer-scale self-organization, and thus utility as structure directing agents.
SUMMARY
In one general aspect, a process for preparing a polymer composite is described that includes reacting a hydroxyl-terminated, linear polyolefin polymer with a cyclic ester in the presence of a ring opening catalyst to form a block copolymer having at least one polyester block and at least one linear polyolefin block. The block copolymer is in the form of a nano-structured, bicontinuous composite. The composite includes a continuous matrix phase and a second continuous phase, where the continuous matrix phase comprises the linear polyolefin block of the block copolymer, and the second continuous phase comprises the polyester block of the block copolymer.
As used herein, a “nano-structured, bicontinuous composite” refers to a polymer-polymer composite characterized by two continuous polymer phases interspersed throughout each other that exhibits compositional heterogeneity on a nanometer (i.e., 1-500 nanometer) length scale.
In various implementations, the process may include treating the composite to selectively remove the polyester blocks of the block copolymer in the second continuous phase to form a plurality of pores. The composite may be treated by a chemical etchant. The pores may have an average pore diameter of about 1 to about 500 nanometers. The pores may also have an average pore diameter of about 10 to about 50 nanometers. In some embodiments, the resultant composite is in the form of a nano-porous membrane that may be a battery separator or water purification membrane.
Examples of suitable polyolefins include polyethylene and polypropylene. Examples of suitable cyclic esters include D,L-lactide, glycolide, caprolactone, menthide, and dihydrocarvide. When the cyclic ester is D,L-lactide, the resulting triblock copolymer includes polylactide blocks.
In another general aspect, a composition is described that includes a block copolymer that includes at least one polyester block and at least one linear polyolefin block in the form of a nano-structured, bicontinuous composite that includes a continuous matrix phase and a second continuous phase. The continuous matrix phase includes the linear polyolefin block of the block copolymer, and the second continuous phase comprises the polyester block of the block copolymer. Examples of suitable polyolefins include polyethylene and polypropylene. Examples of suitable polyesters include polylactide. The composition exhibits good mechanical properties, including modulus, tensile strength, and elongation at break.
In another general aspect, a composition is described that includes a nano-structured, bicontinuous composite having a continuous matrix phase comprising a linear polyolefin and a second continuous phase comprising a plurality of nano-pores. The pores may have an average pore diameter of about 1 to about 500 nanometers. The pores may also have an average pore diameter of about 10 to about 50 nanometers. In some embodiments, the composition is in the form of a nano-porous membrane that may be a battery separator or water purification membrane. The polyolefin can be polyethylene or propylene.
The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages will be apparent from the description and from the claims.
DESCRIPTION OF DRAWINGS
FIG. 1 shows a reaction scheme for synthesizing a polylactide-linear polyethylene-polylactide (LEL) triblock copolymer.
FIG. 2 is a table reporting the molecular and thermal characteristics for the linear polyethylene (LPE) homopolymer, LEL triblock copolymers, and porous LPE samples prepared according to the Examples described herein.
FIG. 3 is a 1H NMR spectrum of the polycyclooctene (PCOE) precursor used to prepare the LEL triblock copolymers, with the two insets depicting a portion of the spectrum both with acetoxy end-groups (top) and hydrolysis (bottom) to afford hydroxyl end-groups.
FIG. 4 is a 1 H NMR spectrum of hydroxyl telechelic LPE from hydrogenation of the PCOE, giving completely linear chains, with the end methylene proton signal magnified for clarity in the inset. Measured in toluene-d 8 at 100° C.
FIG. 5 is a 1 H NMR spectrum of block polymer LEL [14-28-14] with the inset showing a magnified portion that accentuates the methylene protons at the junction between the two components [H d ; —CH 2 —CH 2 —O—C(O)—CH(CH 3 )—] and the PLA end-group methine protons [H e ; —O—C(O)—CH(CH 3 )—OH]. Measured in toluene-d 8 at 100° C.
FIG. 6 depicts size exclusion chromatograms of the block polymers showing the difference in elution volume between LEL [14-28-14] (—) and LEL [37-28-37] ( - - - ).
FIG. 7( a ) presents DSC measurements for the unsaturated PCOE precursor (HO-PCOE-OH) (M n =27.6 kg mol −1 , PDI=1.76), the saturated HO-LPE-OH (M n =28 kg mol −1 , PDI=2.5) and triblock polymer samples LEL [14-28-14] (M n =55.7 kg mol −1 ; f PLA =0.38) and LEL [37-28-37] (M n =102 kg mol −1 ; f PLA =0.62).
FIG. 7( b ) presents thermograms from cooling the samples to accentuate the relative crystallization exotherm magnitudes and show the crystallization temperatures.
FIG. 7( c ) presents DSC thermograms accentuating the T g of the PLA in block polymer samples. Heating and cooling rates were 10° C. min −1 , and the samples were initially heated to 180° C. and isothermally annealed before analysis to homogenize thermal histories of the samples.
FIGS. 8( a )-( c ) present SAXS analysis for the various samples showing the broad scattering reflections associated with the bicontinuous disordered structure. The primary peak appears in all cases to nestle against the beam stop at ˜0.05 nm −1 . FIG. 8( a ): triblock copolymers in the melt at 160° C. FIG. 8( b ): triblock copolymers after cooling at ˜20° C. min −1 from the melt. FIG. 8( c ): membranes at ambient temperature after PLA removal.
FIGS. 9( a ) and ( b ) present infrared spectra of the film prepared from sample LEL [37-28-37] both (a) before and (b) after removing the PLA. The characteristic signal attributed to the carbonyl functionality of the PLA (ν=1750 cm −1 ) is clearly absent after etching, suggesting complete PLA removal.
FIG. 10 is a scanning electron microscopy (SEM) microphotograph of a freeze-fractured LEL film after PLA etching (the length scale bar represents 300 nm). Surfaces were sputter coated with platinum to prevent charging.
FIG. 11 presents SEM images at a variety of different magnifications for freeze-fractured membrane from sample LEL [37-28-37] showing the disordered bicontinuous nature of the structure where the narrow pore-size distribution and the homogeneity of the pore structure are accentuated at high and low magnification, respectively. (≈2 nm Pt coating).
FIG. 12 presents SEM images from the membrane derived from sample LEL [14-28-24] showing the similarly bicontinuous disordered morphological characteristics despite the significant difference in composition compared with the other sample described. (≈2 nm Pt coating).
FIGS. 13( a )-( b ) represent nitrogen adsorption measurements on membranes measured at T=77K showing the adsorption (filled triangles) and desorption (empty triangles) isotherms with the inset in each plot showing the average pore size distribution calculated using the BJH method from the desorption data. FIG. 13( a ): membrane from LEL [37-28-37]. FIG. 13( b ): membrane from LEL [14-28-14].
FIG. 14 is a graph illustrating the pore size distribution for two different LEL films (LEL [37-38-37] (filled triangles) and LEL [14-28-14] (empty triangles)) after PLA etching calculated from nitrogen desorption isotherms.
FIGS. 15( a )-( b ) are graphs illustrating pore-size distributions from nitrogen adsorption (filled triangles) and desorption (empty triangles) isotherms using the BJH method. FIG. 15( a ) is derived from LEL [37-28-37]. FIG. 15( b ) is derived from LEL [14-28-14].
FIGS. 16( a )-( b ) are SEM images of porous LPE derived from LEL films cast from 10 wt % tetralin solutions at 140° C. FIG. 16( a ) is derived from LEL [14-28-14]. FIG. 16( b ) is derived from LEL [37-28-37]. (˜2 nm Pt coating).
FIGS. 17( a )-( b ) are stress-strain curves representing the results of tensile testing of block copolymer precursors (—) and membranes ( - - - ) from samples LEL [14-28-14] ( FIG. 17( a )) and LEL [37-28-37] ( FIG. 17( b )).
FIGS. 18( a ) and ( b ) are SEM microphotographs corresponding to a freeze-fractured LEL [14-28-14] film after PLA etching (the length scale bars represent 500 nm). FIG. 18( a ) corresponds to the film prior to annealing, and FIG. 18( b ) corresponds to the film after annealing at 150° C. for 5 minutes.
FIGS. 19( a )-( d ) are SEM microphotographs of surfaces exposed to (top, left and right) concentrated sulfuric acid ( FIGS. 19( a ) and ( b )) and concentrated nitric acid for 24 h at RT ( FIGS. 19( c ) and ( d )) for porous sample derived from LEL [37-28-37]. The bicontinuous morphology is well-preserved. (˜2 nm Pt coating)
FIG. 20 is a graph illustrating pore size distributions calculated using the BJH method from desorption isotherms for the membrane from LEL [14-28-14] before (curve (a)) and after (curve (b)) soaking in concentrated hydrochloric acid at 50° C. for 24 h. The overall pore size distribution is minimally affected.
DETAILED DESCRIPTION
Polymer composites are prepared generally according to the reaction scheme shown in FIG. 1 . The nano-structured nature of the composite results in films that exhibit good mechanical properties, including modulus, tensile strength, and ultimate elongation, that make them useful in a variety of applications.
The polyester blocks (e.g., polylactide blocks) are incompatible with the linear polyolefin block (e.g., polyethylene block). The incompatibility results in microphase at some point after the block copolymer synthesis from the initial homogeneous state, and creating a multi-phase composite having a nano-structured, bicontinuous microstructure in which one of the phases includes the polyester blocks.
In some embodiments, the polyester blocks may be selectively removable, e.g., by chemically etching using base or acid. Removal creates a plurality of nano-sized pores. The pores are small (e.g., pore diameters on the order of about 1 to about 500 nanometers, or about 10 to about 50 nanometers). In addition, the pores are characterized by a relatively narrow size distribution, and are substantially homogeneously distributed throughout the film. These features make the nano-porous film particularly useful for applications such as separation membranes (e.g., battery separators). In general, the films are useful in a variety of applications, including separation membranes (e.g., battery separators), membranes for water purification, fuel cell membranes, catalytic reactors, nanotemplates, and the like. The nanoscopic, bicontinuous structure that results from the aforementioned process contains interpenetrating domains that both percolate through the entire material. This co-continuity allows for one mechanically robust phase to support the entire structure and another percolating domain that endows the material with some specific functionality. Generating a nanoporous structure by removal of the functional domain gives a material with a percolating pore structure. Since the pore size distribution is narrow and the pore structure permeates the entire film, such membrane materials are useful as battery separators.
EXAMPLES
Materials
All bulk solvents were purchased from Mallinkrodt and used as received unless otherwise specified. Tetralin was purchased from TCI Chemicals and was vacuum distilled prior to use. The second generation Grubbs catalyst was purchased from Aldrich and used as received. Both cis-cyclooctene from Acros (95%) and cis-1,4-diacetoxy-2-butene from TCI Chemical (95%) were distilled over CaH 2 prior to polymerizations. Tetrahydrofuran (THF) and toluene were passed through alumina columns and thoroughly degassed. Purac provided the D,L -lactide (99%), which was recrystallized twice from toluene prior to being stored in a glove box under N 2 atmosphere. Sn(Oct) 2 from Aldrich was distilled using a Kugelrohr apparatus and stored under N 2 . The catalyst used in hydrogenation reactions was a silica-supported Pt catalyst supplied from Dow Chemical Company.
Characterization
1 H NMR spectra obtained using CDCl 3 as a solvent were measured on a Varian Inova 500 operating at 500 MHz, whereas those in toluene-d 8 solvent were measured on a Varian Inova VI-300 operating at 300 MHz with variable temperature capability up to 100° C. Size-exclusion chromatography (SEC) analysis was performed on two different instruments, depending on the relative solubility of the materials and temperature capabilities of the instruments. Operating at a flow rate of 1.0 mL min −1 and 35° C. is a Hewlett-Packard (Agilent Technologies) 1100 Series liquid chromatograph housing three PlGel 5 μm Mixed-C (Polymer Laboratories) columns with pore sizes of 500 Å, 1×10 3 , and 1×10 4 Å with chloroform as eluent. The refractive index signal was recorded with a Hewlett Packard 1047A refractive index detector. The other instrument, operating at a flow rate of 1.0 mL min −1 and 135° C. with 1,2,4-trichlorobenzene as eluent, is a Polymer Laboratories GPC-220 liquid chromatograph holding three PlGel 10 μm Mixed-B columns and equipped with a refractometer used for samples with saturated polyethylene portions.
Small-angle X-ray scattering experiments were performed at the Advanced Photon Source (APS) at Argonne National Laboratories at Sector 5-ID-D beamline. The beamline is maintained by the Dow-Northwestern-Dupont Collaborative Access Team (DND-CAT). The source produces X-rays with a wavelength of 0.84 Å. The sample to detector distance was 5.65 m and the detector radius is 81 mm. Scattering intensity was monitored by a Mar 165 mm diameter CCD detector with a resolution of 2048×2048. The two-dimensional scattering patterns were azimuthally integrated to afford one-dimensional profiles presented as spatial frequency (q) versus scattered intensity.
Differential scanning calorimetric (DSC) measurements were obtained using a DSC Q-1000 calorimeter from TA Instruments that was calibrated with an indium standard. Samples were loaded into hermetically sealed aluminum pans prior to analysis. The thermal history of the samples were all erased by heating the samples to 180° C. and isothermally annealing for 5 min. The samples were then cooled at 10° C. min −1 to −120° C. followed by a second heating cycle to 180° C. at a rate of 10° C. min −1 , all under a helium purge. Melting enthalpies were evaluated by integration of the melting endotherm using TA Universal Analysis software.
Scanning electron microscopy (SEM) was performed on a Hitachi S-900 FE-SEM operating at 3.0 kV accelerating voltage. Samples were prepared by fracturing small pieces of the films immediately after submerging in liquid N 2 . Before imaging, the samples were coated with platinum using a VCR high-resolution indirect ion-beam sputtering system. The samples were coated for 10 min depositing approximately 2 nm of platinum.
Nitrogen adsorption/desorption was carried out at 77 K using an Autosorb-1 system. The specific surface area of the membranes was calculated using the Brunauer-Emmet-Teller method (Brunauer, S.; Deming, L. S.; Deming, W. E.; Teller, E. J. J. Am. Chem. Soc. 1940, 62, 1723-1732), while the pore-size distributions were determined using the Barret-Joyner-Halenda model (Barrett, E. P.; Joyner, L. G.; Halenda, P. P. J. Am. Chem. Soc. 1951, 73, 373-380).
General Procedure for Synthesis of HO-LPE-OH Macroinitiator
The procedure for preparing hydroxy-telechelic polyolefins by ring-opening metathesis polymerization is generally described in (a) Bielawski, C. W.; Scherman, O. A.; Grubbs, R. H. Polymer 2002, 42, 4939-4045, and (b) Pitet, L. M.; Hillmyer, M. A. Macrmolecules 2009, 42, 3674-3680. Briefly, 0.25 g (0.23 mL; 1.45 mmol) of the chain transfer agent (CTA) cis-1,4-diacetoxy-2-butene was transferred to an air-free flask through a rubber septum along with 180 mL of THF. This mixture was rapidly stirred and the temperature was maintained at 35° C. Using a syringe pump, 40 g (47 mL; 363 mmol) of cis-cyclooctene were added to the mixture over 1.5 h. Shortly (˜5 min) after starting the gradual monomer addition, 15 mg (18 μmol) of Grubbs 2 nd Generation catalyst was added as a solution in 1 mL THF. After 6 h, the reaction contents were slowly poured into 2 L of cold MeOH made slightly acidic with 20 mL of 1M HCl (aq). The precipitated polymer was isolated and dried under reduced pressure at 40° C. for 2 days.
The entire yield was dissolved into 200 mL of THF and stirred at 0° C. for 6 h after adding 10 mL of a 0.7 M solution of NaOMe in MeOH (7 mmol NaOMe). The polymer solution was again precipitated into 2 L of slightly acidic MeOH, isolated, and dried for 2 days, yielding 37.5 g (94%). 1 H NMR (CDCl 3 , 25° C.): δ 5.40 (m, (E)-CH═CHCH 2 CH 2 —, backbone), 5.35 (m, (Z)—CH═CHCH 2 CH 2 —, backbone), 4.20 (t, (Z)—CH═CHCH 2 OH), 4.10 (t, (E)-CH═CHCH 2 OH), 2.05 (Z)—CH═CHCH 2 CH 2 — backbone), 1.95 (m, (E)-CH═CHCH 2 CH 2 backbone), 1.30 (m, (Z)—CH═CHCH 2 CH 2 — backbone).
The hydroxy-telechelic PCOE (HO-PCOE-OH) (10.0 g; 45.4 mmol double bonds) was dissolved in 150 mL cyclohexane and the solution was purged with bubbling argon for 20 minutes. A silica supported Pt/Re catalyst (1.0 g of 10%) was placed in the high-pressure reactor, which was sealed, evacuated of air, and refilled with Ar. The polymer solution was added to the reactor at which point hydrogen was introduced (500 psig) and the temperature increased to 90° C. The reaction mixture was stirred for 24 hours, after which the solvent was removed and replaced with 150 mL toluene. The catalyst was removed by filtering the solution at 110° C. and the solvent was again evaporated to afford 8.2 g of HO-LPE-OH (82% yield). 1 H NMR (toluene-d 8 , 100° C.): δ 3.37 (t, —CH 2 OH), 1.35 (s, —CH 2 —, backbone).
General Procedure for Synthesis of LEL Triblock Polymers
The synthesis of one triblock is described, which is representative of all samples where the D,L -lactide feedstock was adjusted accordingly to target the desired polymer compositions. The concentration of LA was kept constant at 1 M. HO-LPE-OH (2.0 g; 0.14 mmol OH) was placed with a stir-bar in a pressure vessel fitted with a Teflon screw-cap and Viton o-ring seal. This was transferred to a glove box, wherein D,L -lactide (2.5 g; 17 mmol), toluene (17 mL) and Sn(Oct) 2 (7 mg; 17 μmol) were added before sealing and removing from the box. The flask was immersed in an oil-bath at 110° C. for 6 h followed by precipitation into a ten-fold excess by volume of MeOH. The isolated polymer was dried at 60° C. for 24 h to yield 4.2 g (93%). 1 H NMR (toluene-d 8 , 100° C.): δ 5.10 (bm, —C(O)CH(CH 3 )O—backbone), 4.05-4.25 (m, —C(O)CH(CH 3 )OH), 3.70-4.00 (m, —H═CHCH 2 OC(O)CH(CH 3 )O—) 1.40-1.45 (—C(O)CH(CH 3 )O— backbone), 1.30-1.40 (—CH 2 —, backbone).
General Procedure for Preparation of Block Copolymer Films and Nanoporous Membranes.
The block copolymers were cast as films in aluminum pans by first dissolving the polymer as a 10% solution in tetralin at 140° C. The hot solution was transferred to the aluminum pan and the high temperature was maintained while the solvent slowly evaporated over 2 h. This was initially done to attempt to adopt an equilibrium microphase separated structure. The dry polymer film was kept at 140° C. for an additional 4 h. The polymer films stuck to the aluminum. They were separated by dissolving the aluminum in a 4 M solution of HCl (aq). Melt-pressing of the block polymer precursors into cylindrical discs was done in a hot press using molds with 13 mm diameter and 1 mm thickness.
The porous samples were prepared by submerging pieces of the block polymer (either bulk melt-pressed or solvent cast) in a 0.5 M NaOH solution in 40% (aq) MeOH. The solutions were kept at 70° C. for 3 days and the porous pieces were washed with slightly acidic MeOH (aq) and then pure MeOH and further dried for 2 days at 60° C. in vacuo. Subsequent mechanical testing was performed on the solvent-cast films.
Results
The molecular and thermal characteristics for the LPE homopolymer, LEL block copolymers, and porous LPE samples, prepared as described above, are set forth in FIG. 2 . A 1 H NMR spectrum of the polycyclooctene precursor (PCOE) is shown in FIG. 3 . A 1 H NMR spectrum of the hydroxyl telechelic LPE from hydrogenation of the PCOE is shown in FIG. 4 . A 1H NMR spectrum of triblock copolymer LEL [14-28-14] is shown in FIG. 5 . Size exclusion chromatograms of LEL [14-28-14] and LEL [37-28-37] are shown in FIG. 6 .
A sample of LEL [37-28-37] was compression molded at 160° C. SAXS analysis ( FIGS. 8( a )-( c )) at 160° C. showed a broad signal with a maximum at 0.06 nm −1 (d=105 nm) with no discernable higher-order reflections consistent with a microphase separated structure lacking long range order. The high degree of incompatibility between LPE and PLA, combined with low entanglement molecular weight for LPE, hinder the adoption of a well-organized mesophase. Annealing the samples up to 72 h at 160° C. did not appreciably increase the level of organization. Cooling from the melt to ambient temperature results in crystallization of the LPE phase ( FIGS. 7( a )- 7 ( c )). SAXS analysis for either sample at 25° C. ( FIGS. 8( a )-( c )) gave virtually indistinguishable profiles compared to the 160° C. data, which is indicative of confined LPE crystallization and consistent with behavior of other block polymers of polyethylene (i.e., hPB) and a highly incompatible component.
Exposure of molded LEL [37-28-37] samples to a 0.5 M solution of NaOH selectively removed the PLA, as confirmed gravimetrically and by IR spectroscopy ( FIGS. 9( a )-( b )). An interconnected LPE scaffold with a disorganized pore structure was observed by scanning electron microscopy (SEM) ( FIGS. 10-11) . Etched LEL [14-28-14] samples show a similarly disordered bicontinuous morphology ( FIG. 12 ) after PLA removal despite containing significantly less PLA as compared to LEL [37-28-27].
Nitrogen adsorption analysis of nanoporous membranes derived from both samples showed type IV adsorption/desorption isotherms indicative of mesoporosity ( FIGS. 13( a ) and ( b )). Narrow pore-size distributions (BJH method; desorption isotherms) peaked at 24 nm and 38 nm for nanoporous membranes from LEL [14-28-14] and LEL [37-28-37], respectively, with calculated peak widths at half height equal to 3.5 nm and 11.1 nm ( FIGS. 14 and 15) . Specific surface areas calculated for LEL [14-28-14] and LEL [37-28-37] derived membranes were 70 and 96 m 2 g −1 , respectively.
Thin (˜150 μm) films of the LEL samples were cast at 140° C. from tetralin for tensile testing evaluation as described above. These solvent cast films adopted the same disordered bicontinuous morphologies as the molded samples, as determined by SEM ( FIGS. 16( a ) and ( b )). From the stress-strain curves of these samples ( FIGS. 17( a ) and ( b )) the tensile toughness values were determined to be 1.54 and 4.91 MJ m −3 for nanoporous versions of LEL [37-28-37] and LEL [14-28-14], respectively.
Temperature-induced pore collapse is an important attribute in battery separators for preventing thermal runaway and minimizing the potential for ignition upon fortuitous anode/cathode contact. The DSC analysis of the nanoporous LPE membranes ( FIGS. 2 and 7( a )-( c )) gave high melting temperatures (T m,PE ≈130° C.) and levels of crystallinity (˜60%) as compared to typical values for hPB Annealing the nanoporous LPE membranes at 150° C. for 5 min causes pore collapse, as confirmed by SEM analysis ( FIGS. 18( a ) and ( b )).
Chemical resistance to strong acids was evaluated by submerging sections of the LEL [37-28-37] derived nanoporous samples into concentrated sulfuric (@ RT), hydrochloric (@ 50° C.) and nitric (@ RT) acids for 24 h. After rinsing and drying, >95% of the mass was retained in all cases. By SEM, there was little difference in the pore structure at the exposed surface ( FIGS. 19( a )-( d )) in both the sulfuric and nitric acid cases. After the HCl treatment the porosity and pore size distribution were minimally affected according to nitrogen adsorption analysis ( FIG. 20) .
A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.
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A composition comprising a block copolymer that includes at least one polyester block and at least one linear polyolefin block, wherein the composition is in the form of a nano-structured, bicontinuous composite that includes a continuous matrix phase and a second continuous phase. The continuous matrix phase comprises the linear polyolefin block of the block copolymer, and the second continuous phase comprises the polyester block of the block copolymer. The composite may be treated to remove the polyester block, thereby forming a plurality of nano-pores.
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This is a continuation of co-pending application Ser. No. 472,391 filed on Mar. 4, 1983, abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates generally to glassware forming machines of the rotating table type having a plurality of continuously rotating, circumferentially spaced forming units. More particularly, the invention relates to a deflector adjusting means for adjusting the orientation of the deflector of the delivery means of the machine with respect to the blank molds of each forming unit so the deflector may be properly positioned over its corresponding mold in order to accurately deliver a gob of glass thereto.
2. Description of the Prior Art
Glassware forming machines of the rotating table type are well known in the glassware manufacturing industry. One type of such machine is shown in U.S. Pat. No. 1,979,211 and is commonly referred to as the "Emhart H-28 Machine." This type of machine is a single table, continuous rotary motion machine having a plurality of individual forming units mounted for rotation about the axis of the machine. These machines have been available with different numbers of individual forming units, thus constituting, for example, a 6, 12 or 18 section machine. In such H-28 machines each individual forming unit produces one glassware article for each complete revolution or cycle of the machine and will therefore be referred to herein as H-28 single gob machines.
A significant improvement over the H-28 single gob machine is disclosed in U.S. Pat. No. 4,339,264 which describes an H-28 double gob machine where each individual forming unit produces two glassware articles for each complete cycle. This patent is hereby incorporated by reference in this disclosure in its entirety.
One of the unique features of the prior art H-28 double gob machine is its delivery system, that is, the manner in which it guides or delivers gobs to the continuously rotating blank molds of the machine. Each set of inner or outer blank mold has associated with it a gob guiding unit consisting of a scoop, trough and deflector for guiding gobs into the blank. Each gob guiding unit oscillates over a predetermined arcuate path about a delivery system axis parallel to the machine axis so that in one arcuate direction the speed of the deflector of the gob guiding unit will be close to that of the continuously moving blank to facilitate gob delivery.
Because of the continuous rotation of the blank molds and the oscillating motion of the delivery system, it is important in an H-28 machine, whether single or double gob, that the orientation of the deflector be accurate at the delivery position where it is situated over its respective blank mold. In the H-28 single gob machine the deflector is capable of being adjusted in four axes--radial, radial tilt, peripheral and peripheral tilt. These adjustments were effected through the use of a relatively complex array of turnbuckles, pivots, etc. The adjustment of the deflector in each of these four directions is possible because there is only a single blank and corresponding deflector at the delivery position thus making the adjustment components relatively accessible.
However, in a prior art H-28 double gob machine the accessibility of adjustment components is necessarily limited by the increased number of mechanical components required to deliver a pair of gobs to a pair of blanks. Consequently, the prior art H-28 double gob machine shown in U.S. Pat. No. 4,339,264 was provided with only a two axis adjustment means--peripheral and radial tilt--instead of the four axis adjustment means available on the H-28 single gob machine. Because of the critical nature of the delivery it was determined that a two axis adjustment for the deflector of the H-28 double gob machine was insufficient and that a four axis adjustment means was necessary. Because of the complexity of mechanical parts in the delivery system for the H-28 double gob machine, the four axis adjustment means used in the H-28 single gob machine was not suitable and a new four axis adjustment means was necessary. Accordingly, it is an object of this invention to overcome the disadvantages of the deflector adjustment means of prior art H-28 double gob machines.
SUMMARY OF THE INVENTION
These and other objects of the invention are achieved by the preferred embodiment which comprises a deflector orientation adjusting means for a deflector oscillating about a first axis comprising a four axis adjustment system for adjusting the orientation of the deflector in four different directions. The invention comprises a first means for adjusting the deflector within its radial plane relative to its respective deflector axis, a second means for adjusting the deflector tiltably about an axis perpendicular to said radial plane, third means for adjusting the deflector along a peripheral arc within a plane substantially perpendicular to its respective deflector axis and a fourth means for adjusting the deflector tiltably about an axis within said radial plane and perpendicular to its respective deflector axis.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view of the four axis deflector adustment means, partially in cross section;
FIG. 2 is a view of FIG. 1 along the lines 2--2;
FIGS. 3A, 3B and 3C are various views of a portion of FIG. 1;
FIGS. 4A and 4B are various views of another portion of FIG. 1;
FIG. 5 is an end view of FIG. 1 taken along the lines 5--5 partially in cross section with certain portions omitted for clarity;
FIG. 6 is a sectional view of FIG. 5 taken along the lines 6--6;
FIG. 7 is a sectional view of FIG. 5 taken along the lines 7--7;
FIG. 8 is a sectional view of FIG. 5 taken along the lines 8--8;
FIG. 9 is a sectional view of FIG. 6 taken along the lines 9--9.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The invention is a four axis adjustment mechanism 100 shown in FIG. 1 for adjusting the orientation of each deflector of an H-28 double gob machine in four axes--radial, radial tilt, peripheral and peripheral tilt. Each deflector 104 is provided with a separate four axis adjustment mechanism, both being essentially identical except for minor differences necessary to adapt a particular mechanism for either the inner or outer blank mold accordingly.
The four adjustments are essentially made relative to the gob guiding unit axis 110 about which the deflector oscillates, this axis being parallel to the axis of the machine. However, describing the four axes relative to deflector axis 443 will facilitate an understanding of this invention. Each deflector has a generally arcuate shape along the gob path. The gob path lies within a plane which will be defined herein as the radial plane. Generally the radial plane will intersect or substantially intersect deflector axis 443. Movement of the deflector within the radial plane toward or away from axis 443 constitutes a radial adjustment. The radial tilt adjustment tilts the deflector within the radial plane about an axis perpendicular or substantially perpendicular to the radial plane. The peripheral adjustment causes the deflector to generally follow an arcuate path about axis 443, the bottom of the deflector moving along a peripheral arc lying within a horizontal plane perpendicular to axis 443. The peripheral tilt adjustment tilts the deflector about an axis which is both within the radial plane and perpendicular to axis 443.
The invention may best be described by referring to all of the drawings wherein one four axis deflector adjustment mechanism 100 is initially shown in a side elevational view in FIG. 1. For clarity FIG. 1 shows mainly the deflector and trough portions of one gob guiding unit. It will be understood that a similar four axis adjustment mechanism is provided for each gob guiding unit in the machine.
As shown in FIG. 1, gob guiding unit 102 includes a deflector 104, a trough 106 and a scoop (not shown), all mounted to a support frame 108 which arcuately oscillates (by means not shown) about delivery system axis 110. It will be understood that axis 110 is merely diagrammatically located in FIG. 1 to facilitate a description of the invention. An exact location may be determined by one skilled in the art. In one embodiment frame 108 is secured to a pivot shaft (not shown) aligned with axis 110, the frame 108 being pivotable about axis 110 with respect to a main frame which supports the entire delivery system.
The four axis adjustment means 100 is provided with control shafts routed to a common, remote control panel (not shown) where each of the four adjustments radial, radial tilt, peripheral and peripheral tilt may be adjusted by their respective control handles 200, 300, 400 and 500.
Radial adjustments are effected by turning control handle 200 which is connected to stub shaft 202 via a flexible shaft 204 and connector 206. As shown in FIG. 2 shaft 202 is threadably engaged with slide assembly 208 which is slideably engaged within slide keeper 210 which is in turn secured to mounting bracket 211 secured to frame 108. One bracket 211 is secured to each frame 108 and is used to secure trough 106. Trough support adjustment bracket 213 is secured to bracket 211 and has a pair of side plates 215 and 217 (best seen in FIGS. 1, 5 and 7) extending below trough 106. Cross support rod 219 is connected between side plates 215 and 217 to support the bottom of the trough. Adjustment of handle 221 and threaded rod 223 results in vertically adjusting the lower end of the trough.
Slide assembly 208, best seen in FIG. 2, is secured to a shaft 212 having secured near the end thereof a bearing assembly 214 mounted within extension 216 of adjusting bar 220, best seen in FIGS. 3A, 3B and 3C. Referring again to FIG. 1, it will be noted that translational motion of slide assembly 208 within slide keeper 210 causes the upper end of deflector 104 to move parallel to the axis of shaft 202 thus maintaining alignment with the axis of the upper end of the deflector and trough 106. This alignment is reinforced by other means explained below.
Referring to FIGS. 3A, 3B and 3C, adjusting bar 220 is shown to have threaded aperture 224 and through apertures 222 and 226 as well as extension housing 216. Extension 216 is provided with cylindrical recess 228 for receiving bearing assembly 214 (best seen in FIG. 2). Adjusting bar 220 is provided with a raised rib 230 for slideably mating with a complementary groove in a pivot block to be explained below. A threaded stud 232 is welded within aperture 222 as best seen in FIGS. 3B and 3C.
Referring again to FIGS. 1 and 2, adjusting bar 220 is shown attached to lug 242 of deflector 104 with an opposing clamp bar 237. Pin 243 pivotably fit within aperture 226 serves to align adjusting bar 220 with the deflector. Clamp bar 237 is secured to threaded aperture 224 by clamp bolt 233. Lug 240 is slideably pressed between bars 220 and 237 to assist in maintaining lateral alignment of the deflector. (Note that FIGS. 2 and 3A are drawn to different scales.)
As adjusting bar 220 moves translationally with slide assembly 208 the alignment of the upper end of deflector 104 with the lower end of the trough is maintained by the slideable engagement of rib 230 with a corresponding groove in pivot block 250, best seen in FIGS. 4A and 4B. Pivot block 250 is provided with a block portion 252 and a pivot portion 254. Block portion 252 is provided with parallel grooves 256 and 258 symmetrically on each side of the block. Pivot block 250 is suitable for use with both the inner and outer gob guiding units although only one of the grooves 256 or 258 will be used in each assembly. Pivot block 250 is also provided with a through slot 260.
As shown in FIG. 1, adjusting bar 220 is secured to the far side of pivot block 250 with rib 230 mated with groove 258. Stud 232 is secured within slot 260 by a standard hex nut 235 and spring washers, the nut being torqued to predetermined specifications in order to permit slideable motion between the stud and the slot.
It will thus be seen that as shaft 202 is rotated to cause a translational motion of slide assembly 208, adjusting bar 220 will move relative to frame 108 and parallel to the axis of shaft 202, this alignment being maintained by the cooperative action of rib 230 and groove 258. This results in the upper end of deflector 104 being moved radially relative to parallel axes 110 and 443 (i.e. within the radial plane). Motion of the lower end of deflector 104 is limited because of the radial tilt adjustment components described below.
The radial tilt adjustment is effected by rotating control knob 300 to which are connected, in sequence, shaft 302, double universal joint 308 and adjusting rod 310. Shaft 302, as well as corresponding shafts connected to control handles 400 and 500, may be a two piece structure with a universal joint (not shown) in order to accomodate motion of the adjusting mechanisms (mounted near the deflector) relative to the control panel. Rod 302 passes through bearing 309 secured to mounting block 311 which is secured to frame 108. Rod 310 also passes through fixed bearing block 314 having a detent flange 312 pinned to rod 310 on one side of the block and retaining collar 316 pinned to rod 310 on the other side of the block. Block 314 is secured to plate 319. Rod 310 has a threaded end portion 320 in threaded engagement with a cylindrical adjusting post 322 and terminates in a threaded end collar 324 (best seen in FIGS. 6 and 9).
Adjusting post 322 rides within yoke assembly 323 which is connected to a crank lever 330 the other end of which is pinned to shaft 336. Shaft 336, having axis 337, passes through a bearing block 338 mounted on plate 319 and has pinned to its other end another crank lever 340. The other end of crank lever 340 is connected to one end of rod end mounting block 344 via dog link 342. The other end of mounting block 344 is secured to lug 348 of deflector 104.
As best seen in FIG. 9, as rod 310 is rotated crank lever 330 will pivot about axis 337 causing crank lever 340 to tilt the lower end of deflector 104 in a radial plane, about the axes of lug 242 and pin 243 (i.e., about an axis perpendicular to the radial plane). This constitutes a radial tilt adjustment and causes a corresponding motion of all components (pivot block, etc.) attached to the deflector. Detent flange 312 will hold this adjustment during machine operation and during motion of the radial tilt adjusting components caused by other adjustments.
It should be noted that the lower end of deflector 104 not only moves radially but also parallel to axis 110. Furthermore, since link 342 is pivotable about axis 337 which does not move relative to support bracket 211 during radial adjustments, large radial adjustments will cause significant radial tilt. Thus, the radial and radial tilt adjustments are dependent upon each other and adjustment of one may require a compensating adjustment of the other.
The peripheral adjustment is effected by control handle 400 to which is connected a shaft 406. Shaft 406 has pinned to it a detent flange 408 which acts in cooperation with bearing block 410, and retaining collar 412. Block 410 is secured to frame 108 via mounting bracket 311 which is in turn connected via angle bracket 422 to stiffening plate 426, best seen in FIG. 7. The threaded end 430 of shaft 406 is threadably engaged with adjusting post 432 and terminates in a pinned threaded collar 434. Adjusting post 432 is mounted within yoke block 436. One end of lever 438 is connected to yoke block 436 while the other end is provided with an aperture 440 for mateable engagement with shaft 442 having axis 443. As seen in FIGS. 1 and 5 adjusting post 432 is connected to a shaft 435 the upper end of which is rotatably retained within aperture 444 of mounting plate 446 by a pinned retaining collar 448. The function of plate 446 will be explained below with reference to FIG. 8. The other end of shaft 442 is fixedly secured to bell crank and bearing support 450 which is welded to bracket 319, the other end of bracket 319 serves to pivotably secure pivot block 250 (best seen in FIGS. 1 and 5).
In operation, as control handle 400 is rotated, shaft end 430 will rotate within adjusting post 432 causing it to move longitudinally along the shaft. Post 432 is free to rotate within yoke 436 and rotation of the shaft 430 causes yoke 436 and lever 438 to pivot about axis 443. This in turn causes pivot block 250 to move in an arc in a plane perpendicular to axis 443 thus adjusting the peripheral alignment of deflector 104.
The peripheral tilt adjustment is effected by control knob 500 to which is connected a shaft 506 which passes through a fixed bearing block detent arrangement 507 similar to the other control shafts mentioned above. Referring to FIGS. 1, 5 and 8 it will be noted that detent block 507 is welded to plate 446 which is in turn guided by slot 447 in mounting bracket 311. Pin 449 retains plate 446 within the slot. Shaft 506 is provided with a threaded end 510 which is in threaded engagement with adjusting post 512 which is secured to yoke block 514 and operates in a manner similar to that described above with respect to post 432 and yoke block 436. A bell crank assembly 520 is pivotable about shaft 442 and is secured at one end to yoke block 514 and at the other end to follower yoke 526. Follower yoke 526 is attached to an aperture in the end of bell crank 520 by collar 530. Lever 540 has secured at one end thereof a roller 542 for engagement with follower yoke 526, the other end of lever 540 being pinned to pivot portion 254 of pivot block 250.
It will be noted that rotation of control handle 500 causes translational motion of adjusting post 512 along the axis of shaft 506 which in turn causes rotational motion of bell crank 520 about axis 443. The upper end of lever 540 will therefore be caused to rotate about the axis 560 of pivot block 250 cauisng rotation of pivot block 250 thus peripherally tilting deflector 104 (i.e. about an axis within the radial plane and perpendicular to axis 443).
It will be noted that, unlike the mutually dependent radial and radial tilt adjustments, the peripheral and peripheral tilt adjustments are each independent of each other and the other adjustments. As a peripheral adjustment is made, the peripheral tilt adjustment is unaffected because detent block 507 moves with plate 446. The peripheral adjustment causes plate 446 to slide within slot 447, thus affecting the position of detent block 507 on shaft 506, but not the detented position of the shaft.
It will be understood by those skilled in art that numerous modifications and improvements may be made to the preferred embodiment of the invention disclosed herein without departing from the spirit and scope thereof.
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A four axis adjustment mechanism is disclosed for adjusting the orientation of the deflector of the delivery system of a rotating table type of glassware forming machine. The orientation of the deflector is adjustable as it oscillates along a predetermined arcuate path relative to its deflector axis in order to properly position the deflector over a corresponding continuously moving blank mold. These adjustments are termed radial, radial tilt, peripheral and peripheral tilt.
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This is a divisional of copending application Ser. No. 07/928,589 filed on Aug. 13, 1992 now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to novel [4S-(4alpha, 12aalpha)]-4-(dimethylamino)-7-(substituted)-9-[(substituted glycyl)amido]-1,4,4a,5,5a,6,11,12a-octahydro-3,10,12,12a-tetrahydroxy-1,11-dioxo-2-naphthacenecarboxamides herein after called 7-(substituted)-9-[(substituted glycyl)amido]-6-demethyl-6-deoxytetracyclines, which exhibit antibiotic activity againsts a wide spectrum of organisms including organisms which are resistant to tetracyclines and are useful as antibiotic agents.
The invention also relates to novel 9-[(haloacyl)amido]-7-(substituted)-6-demethyl-6-deoxytetracycline intermediates useful for making the novel compounds of the present invention and to novel methods for producing the novel compounds and intermediate compounds.
SUMMARY OF THE INVENTION
This invention is concerned with novel 7-(substituted)-9-[(substituted glycyl)amido]-6-demethyl-6-deoxytetracyclines, represented by formula I and II, which have antibacterial activity; with methods of treating infectious diseases in warm blooded animals employing these new compounds; with pharmaceutical preparations containing these compounds; with novel intermediates compounds and processes for the production of these compounds. More particularly, this invention is concerned with compounds of formula I and II which have enhanced antibacterial activity against tetracycline reisitant strains as well as a high level of activity against strains which are normally susceptible to tetracyclines. ##STR2##
In formula I and II,
R is a halogen selected from bromine, chlorine, fluorine and iodine; or R=--NR 1 R 2 and when R=--NR 1 R 2 and R 1 =hydrogen,
R 2 =methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl; and when R 1 =methyl or ethyl, R 2 =methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl or 2-methylpropyl; and when R 1 =n-propyl, R 2 =n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl or 2-methylpropyl; and when R 1 =1-methylethyl, R 2 =n-butyl, 1-methylpropyl or 2-methylpropyl; and when R 1 =n-butyl, R 2 =n-butyl, 1-methylpropyl or 2-methylpropyl; and when R 1 =1-methylpropyl, R 2 =2-methylpropyl;
R 3 is selected from hydrogen; straight or branched (C 4 -C 8 )alkyl group selected from butyl, isobutyl, pentyl, hexyl, heptyl and octyl; α-mercapto(C 1 -C 4 )alkyl group selected from mercaptomethyl, α-mercaptoethyl, α-mercapto-1-methylethyl and α-mercaptopropyl; α-hydroxy(C 1 -C 4 )alkyl group selected from hydroxymethyl, α-hydroxyethyl, α-hydroxy-1-methylethyl and α-hydroxypropyl; carboxyl(C 1 -C 8 )alkyl group; (C 6 -C 10 )aryl group selected from phenyl, α-naphthyl and β-naphthyl; substituted(C 6 -C 10 )aryl group (substitution selected from hydroxy, halogen, (C 1 -C 4 )alkoxy, trihalo(C 1 -C 3 )alkyl, nitro, amino, cyano, (C 1 -C 4 )alkoxycarbonyl, (C 1 -C 3 )alkylamino and carboxy); (C 7 -C 9 )aralkyl group selected from benzyl, 1-phenylethyl, 2-phenylethyl and phenylpropyl; substituted (C 7 -C 9 )aralkyl group [substitution selected from halo, (C 1 -C 4 )alkyl, nitro, hydroxy, amino, mono-or di-substituted (C 1 -C 4 )alkylamino, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylsulfonyl, cyano and carboxy];
R 4 is selected from hydrogen and (C 1 -C 6 )alkyl selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl and hexyl; when R 3 does not equal R 4 the stereochemistry of the asymmetric carbon (i.e. the carbon bearing the substituent W) maybe be either the racemate (DL) or the individual enantiomers (L or D);
W is selected from hydroxylamino; (C 7 -C 12 ) straight or branched alkyl monosubstituted amino group substitution selected from heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the diastereomers and enantiomers of said branched alkyl monosubstituted amino group; (C 1 -C 4 ) straight or branched fluoroalkylamino group selected from trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 3,3,3,2,2-pentafluoropropyl, 2,2-difluoropropyl, 4,4,4-trifluorobutyl and 3,3-difluorobutyl; (C 3 -C 8 )cycloalkyl monosubstituted amino group substitution selected from cyclopropyl, trans-1,2-dimethylcyclopropyl, cis-1,2-dimethylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]hept-2-yl, bicyclo[2.2.2]oct-2-yl and the diastereomers and enantiomers of said (C 3 -C 8 )cycloalkyl monosubstituted amino group; [(C 4 -C 10 )cycloalkyl]alkyl monosubstituted amino group substitution selected from (cyclopropyl)methyl, (cyclopropyl)ethyl, (cyclobutyl)methyl, (trans-2-methylcyclopropyl)methyl, and (cis-2-methylcyclobutyl)methyl; (C 3 -C 10 )alkenyl and alkynyl monosubstituted amino group substitution selected from allyl, 3-butenyl, 2-butenyl (cis or trans), 2-pentenyl, propynyl, 4-octenyl, 2,3-dimethyl-2-butenyl, 3-methyl-2-butenyl, 2-cyclopentenyl and 2-cyclohexenyl; (C.sub. 6 -C 10 )aryl monosubstituted amino group substitution selected from phenyl and naphthyl; (C 7 -C 1 )aralkylamino group substitution selected from benzyl, 2-phenylethyl, 1-phenylethyl, 2-(naphthyl)methyl, 1-(naphthyl)methyl and phenylpropyl; substituted (C 6 -C 1 )aryl monosubstituted amino group [substitution selected from (C 1 -C 5 )acyl, (C 1 -C 5 )acylamino, (C 1 -C 4 )alkyl, mono or disubstituted (C 1 -C 8 )alkylamino, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkoxycarbonyl, (C 1 -C 4 )alkylsulfonyl, amino, carboxy, cyano, halogen, hydroxy, nitro and trihalo(C 1 -C 3 )alkyl]; straight or branched symmetrical disubstituted (C 6 -C 14 )alkylamino group substitution selected from dibutyl, diisobutyl, di-sec-butyl, dipentyl, diisopentyl, di-sec-pentyl, dihexyl, diisohexyl and di-sec-hexyl; symmetrical disubstituted (C 6 -C 14 )cycloalkylamino group substitution selected from dicyclopropyl, dicyclobutyl, dicyclopentyl, di(dicyclopropyl)methyl, dicyclohexyl and dicycloheptyl; straight or branched unsymmetrical disubstituted (C 3 -C 14 )alkylamino group wherein the total number of carbons in the substitution is nore than 14; unsymmetrical disubstituted (C 4 -C 14 )cycloalkylamino group wherein the total number of carbons in the substitution is no more than 14; (C 2 -C 8 )azacycloalkyl and substituted (C 2 -C 8 )azacycloalkyl group substitution selected from 4-methylpiperidine, 4-hydroxypiperidine, 4-(hydroxymethyl)piperidine, 4-(aminomethyl)piperidine, cis-3,4-dimethylpyrrolidinyl, trans-3,4-dimethylpyrrolidinyl, 2-azabicyclo [2.1.1]hex-2-yl, 5-azabicyclo[2.1.1]hex-5-yl, 2-azabicyclo[2.2.1]hept-2-yl, 7-azabicyclo[2.2.1]-hept-7-yl, 2-azabicyclo[2.2.2]oct-2-yl and the diastereomers and enantiomers of said (C 2 -C 8 )azacycloalkyl and substituted (C 2 -C 8 )azacycloalkyl group; substituted 1-azaoxacycloalkyl group substitution selected from 2-(C 1 -C 3 )alkylmorpholinyl, 3-(C 1 -C 3 )alkylisoxazolidinyl, tetrahydrooxazinyl and 3,4-dihydrooxazinyl; [1,n]-diazacycloalkyl and substituted [1,n]-diazacycloalkyl group selected from piperazinyl, 2-(C 1 -C 3 ) alkylpiperazinyl, 4-(C 1 -C 3 )alkylpiperazinyl, 2,4-dimethylpiperazinyl, 4- (C 1 -C 4 ) alkoxypiperazinyl, 4-(C 6 -C 10 )aryloxypiperazinyl, 4-hydroxypiperazinyl, 2,5-diazabicyclo[2.2.1]hept-2-yl, 2,5-diaza-5-methylbicyclo[2.2.1]hept-2-yl, 2,3-diaza-3-methylbicyclo[2.2.2]oct-2-yl, 2,5-diaza-5,7-dimethylbicyclo[2.2.2]oct-2-yl and the diastereomers or enantiomers of said [1,n]-diazacycloalkyl and substituted [1,n]-diazacycloalkyl group; 1-azathiacycloalkyl and substituted 1-azathiacycloalkyl group selected from thiamorpholinyl, 2-(C 1 -C 3 )alkylthiomorpholinyl and 3-(C 3 -C 6 )cycloalkylthiomorpholinyl; N-azolyl and substituted N-azolyl group selected from 1-imidazolyl, 2-(C 1 -C 3 )alkyl-1-imidazolyl, 3-(C 1 -C 3 )alkyl-1-imidazolyl, 1-pyrrolyl, 2-(C 1 -C 3 )-alkyl-1-pyrrolyl, 3-(C 1 -C 3 )alkyl-1-pyrrolyl, 1-pyrazolyl, 3-(C 1 -C 3 )alkyl-1-pyrazolyl, indolyl, 1-(1,2,3-triazolyl), 4-(C 1 -C 3 )alkyl-1-(1,2,3-triazolyl), 5-(C 1 -C 3 )alkyl-1-(1,2,3-triazolyl), 4-(1,2,4-triazolyl, 1-tetrazolyl, 2-tetrazolyl and benzimidazolyl; (heterocycle)amino group said heterocycle selected from 2- or 3-furanyl, 2- or 3-thienyl, 2-, 3- or 4-pyridyl, 2- or 5-pyridazinyl, 2-pyrazinyl, 2-(imidazolyl), (benzimidazolyl), and (benzothiazolyl) and substituted (heterocycle)amino group (substitution selected from straight or branched (C 1 -C 6 )alkyl); (heterocycle)methylamino group selected from 2- or 3-furylmethylamino, 2- or 3-thienylmethylamino, 2-, 3- or 4-pyridylmethylamino, 2- or 5-pyridazinylmethylamino, 2-pyrazinylmethylamino, 2-(imidazolyl)methylamino, (benzimidazolyl)methylamino, and (benzothiazolyl)methylamino and substituted (heterocycle)methylamino group (substitution selected from straight or branched (C 1 -C 6 )alkyl); carboxy(C 2 -C 4 )-alkylamino group selected from aminoacetic acid, α-aminopropionic acid, β-aminopropionic acid, α-butyric acid, β-aminobutyric acid and the enantiomers of said carboxy(C 2 -C 4 )alkylamino group; 1,1-disubstituted hydrazino group selected from 1,1-dimethylhydrazino, N-aminopiperidinyl, 1,1-diethylhydrazino, and N-aminopyrroli-dinyl; (C 1 -C 4 )alkoxyamino group substitution selected from methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 2-methylpropoxy and 1,1-dimethylethoxy; (C 3 -C 8 )cycloalkoxyamino group selected from cyclopropoxy, trans-1,2-dimethylcyclopropoxy, cis-1,2-dimethylcyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, bicyclo[2.2.1]hept-2-yloxy, bicyclo[2.2.2]oct-2-yloxy and the diastereomers and enantiomers of said (C 3 -C 8 )cycloalkoxyamino group; (C 6 -C 10 )aryloxyamino group selected from phenoxyamino, 1-naphthyloxyamino and 2-naphthyloxyamino; (C 7 -C 1 l)arylalkoxyamino group substitution selected from benzyloxy, 2-phenylethoxy, 1-phenylethoxy, 2-(naphthyl)methoxy, 1-(naphthyl)methoxy and phenylpropoxy; [βor γ-(C 1 -C 3 )acylamido]alkylamino group substitution selected from 2-(formamido)ethyl, 2-(acetamido)ethyl, 2-(propionylamido)ethyl, 2-(acetamido)propyl, 2-(formamido)propyl and the enantiomers of said [β or γ-(C 1 -C 3 )acylamido]alkylamino group; β or γ -(C 1 -C 3 )alkoxyalkylamino group substitution selected from 2-methoxyethyl, 2-ethoxyethyl, 2,2-diethoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3,3-diethoxypropyl and the enantiomers of said β or γ-(C 1 -C 3 )alkoxyalkylamino group; β, γ, or δ (C 2 -C 4 )hydroxyalkylamino group substitution selected from 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl and 4-hydroxybutyl;
or R 3 and W taken together are selected from --(CH 2 ) n (R 5 )N--, n=3-4, and --CH 2 CH(OH)CH 2 (R 5 )N-- wherein R 5 is selected from hydrogen and (C 1 -C 3 )acyl, the acyl selected from formyl, acetyl, propionyl and (C 2 -C 3 )haloacyl selected from chloroacetyl, bromoacetyl, trifluoroacetyl, 3,3,3-trifluoropropionyl and 2,3,3-trifluoropropionyl;
R 6 is selected from hydrogen; straight or branched (C 1 -C 3 )alkyl group selected from methyl, ethyl, n-propyl or 1-methylethyl; (C 6 -C 10 )aryl group selected from phenyl, α-naphthyl or β-naphthyl; (C 7 -C 9 )aralkyl group such as benzyl, 1-phenylethyl, 2-phenylethyl or phenylpropyl; a heterocycle group selected from a five membered aromatic or saturated ring with one N, O, S or Se heteroatom optionally having a benzo or pyrido ring fused thereto: ##STR3## such as pyrrolyl, N-methylindolyl, indolyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 2-pyrrolinyl, tetrahydrofuranyl, furanyl, benzofuranyl, tetrahydrothienyl, thienyl, benzothienyl or selenazolyl, or a five membered aromatic ring with two N, O, S or Se heteroatoms optionally having a benzo or pyrido ring fused thereto: ##STR4## such as imidazolyl, pyrazolyl, benzimidazolyl, oxazolyl, benzoxazolyl, indazolyl, thiazolyl, benzothiazolyl, 3-alkyl-3H-imidazo[4,5-b]pyridyl or pyridylimidazolyl, or a five membered saturated ring with one or two N, O, S or Se heteroatoms and an adjacent appended O heteroatom: ##STR5## (A is selected from hydrogen; straight or branched (C 1 -C 4 )alkyl; C 6 -aryl; substituted C 6 -aryl (substitution selected from halo, (C 1 -C 4 )alkoxy, trihalo(C 1 -C 3 )alkyl, nitro, amino, cyano, (C 1 -C 4 )alkoxycarbonyl, (C 1 -C 3 )alkylamino or carboxy); (C 7 -C 9 )aralkyl group selected from benzyl, 1-phenylethyl, 2-phenylethyl or phenylpropyl) such as γ-butyrolactam, γ-butyrolactone, imidazolidinone or N-aminoimidazolidinone, or a six membered aromatic ring with one to three N heteroatoms such as pyridyl, pyridazinyl, pyrazinyl, sym-triazinyl, unsym-triazinyl, pyrimidinyl or (C 1 -C 3 ) alkylthiopyridazinyl, or a six membered saturated ring with one or two N, O, S or Se heteroatoms and an adjacent appended O heteroatom such as 2,3-dioxo-1piperazinyl, 4-ethyl-2,3-dioxo-1-piperazinyl, 4-methyl-2,3-dioxo-1-piperazinyl, 4-cyclopropyl-2-dioxo-1-piperazinyl, 2-dioxomorpholinyl, 2-dioxothiomorpholinyl; or --(CH 2 ) n COOR 8 where n=0-4 and R 8 is selected from hydrogen; straight or branched (C 1 -C 3 )alkyl group selected from methyl, ethyl, n-propyl or 1-methylethyl; or (C 6 -C 10 )aryl group selected from phenyl, α-naphthyl, or β-naphthyl;
R 7 is selected from hydrogen; straight or branched (C 1 -C 3 )alkyl group selected from methyl, ethyl, n-propyl or 1-methylethyl; (C 6 -C 10 )aryl group selected from phenyl, α-naphthyl or β-naphthyl; (C 7 -C 9 )aralkyl group such as benzyl, 1-phenylethyl, 2-phenylethyl or phenylpropyl; a heterocycle group selected from a five membered aromatic or saturated ring with one N, O, S or Se heteroatom optionally having a benzo or pyrido ring fused thereto: ##STR6## such as pyrrolyl, N-methylindolyl, indolyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 2-pyrrolinyl, tetrahydrofuranyl, furanyl, benzofuranyl, tetrahydrothienyl, thienyl, benzothienyl or selenazolyl, or a five membered aromatic ring with two N, O, S or Se heteroatoms optionally having a benzo or pyrido ring fused thereto: ##STR7## such as imidazolyl, pyrazolyl, benzimidazolyl, oxazolyl, benzoxazolyl, indazolyl, thiazolyl, benzothiazolyl, 3-alkyl-3H-imidazo[4,5-b]pyridyl or pyridylimidazolyl, or a five membered saturated ring with one or two N, O, S or Se heteroatoms and an adjacent appended O heteroatom: ##STR8## (A is selected from hydrogen; straight or branched (C 1 -C 4 )alkyl; C 6 -aryl; substituted C 6 -aryl (substitution selected from halo, (C 1 -C 4 )alkoxy, trihalo(C 1 -C 3 )alkyl, nitro, amino, cyano, (C 1 -C 4 )alkoxycarbonyl, (C 1 -C 3 )alkylamino or carboxy); (C 7 -C 9 )aralkyl group selected from benzyl, 1-phenylethyl, 2-phenylethyl or phenylpropyl) such as γ-butyrolactam, γ-butyrolactone, imidazolidinone or N-aminoimidazolidinone, or a six membered aromatic ring with one to three N heteroatoms such as pyridyl, pyridazinyl, pyrazinyl, sym-triazinyl, unsym-triazinyl, pyrimidinyl or (C 1 -C 3 )alkylthiopyridazinyl, or a six membered saturated ring with one or two N, O, S or Se heteroatoms and an adjacent appended O heteroatom such as 2,3-dioxo-1-piperazinyl, 4-ethyl-2,3-dioxo-1-piperazinyl, 4-methyl-2,3-dioxo-1-piperazinyl, 4-cyclopropyl-2-dioxo-1-piperazinyl, 2-dioxomorpholinyl, 2-dioxothiomorpholinyl; or --(CH 2 ) n COOR 8 where n=0-4 and R 8 is selected from hydrogen; straight or branched (C 1 -C 3 )alkyl selected from methyl, ethyl, n-propyl or 1-methylethyl; or (C 6 -C 10 )aryl selected from phenyl, α-naphthyl or β-naphthyl; with the proviso that R 6 and R 7 cannot both be hydrogen;
or R 6 and R 7 taken together are --(CH 2 ) 2 B(CH 2 ) 2 --, wherein B is selected from (CH 2 ) n and n=0-1, --NH, --N(C 1 -C 3 )alkyl [straight or branched], --N(C 1 -C 4 )alkoxy, oxygen, sulfur or substituted congeners selected from (L or D)proline, ethyl(L or D)prolinate, morpholine, pyrrolidine or piperidine; and the pharmacologically acceptable organic and inorganic salts or metal complexes.
Preferred compounds are compounds according to the above formula I and II wherein:
R is a halogen selected from bromine, chlorine, fluorine and iodine; or R=--NR 1 R 2 and when R=--NR 1 R 2 and R 1 =hydrogen,
R 2 =methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl; and when R 1 =methyl or ethyl, R 2 =methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl or 2-methylpropyl;
R 3 is selected from hydrogen; straight or branched (C 4 -C 8 )alkyl group selected from butyl, isobutyl, pentyl, hexyl, heptyl and octyl; α-hydroxy(C 1 -C 4 )alkyl group selected from hydroxymethyl, α-hydroxyethyl, α-hydroxy-1-methylethyl and α-hydroxypropyl; carboxyl(C 1 -C 8 )alkyl group; (C 6 -C 10 )aryl group selected from phenyl, α-naphthyl and β-naphthyl; substituted (C 6 -C 10 )aryl group (substitution selected from hydroxy, halogen, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkoxycarbonyl and carboxy); (C 7 -C 9 )aralkyl group selected from benzyl, 1-phenylethyl, 2-phenylethyl and phenylpropyl; substituted (C 7 -C 9 )aralkyl group [substitution selected from halo, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylsulfonyl, cyano and carboxy];
R 4 is selected from hydrogen and (C 1 -C 4 )alkyl selected from methyl, ethyl, propyl, isopropyl, butyl and isobutyl; when R 3 does not equal R 4 the stereochemistry of the asymmetric carbon (i.e. the carbon bearing the substituent W) maybe be either the racemate (DL) or the individual enantiomers (L or D);
W is selected from hydroxylamino; (C 7 -C 12 ) straight or branched alkyl monosubstituted amino group substitution selected from heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the diastereomers and enantiomers of said branched alkyl monosubstituted amino group; (C 3 -C 8 )cycloalkyl monosubstituted amino group substitution selected from cyclopropyl, trans-1,2-dimethylcyclopropyl, cis-1,2-dimethylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the diastereomers and enantiomers of said (C 3 -C 8 )cycloalkyl monosubstituted amino group; (C 1 -C 4 ) straight or branched fluoroalkylamino group selected from 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 2,2-difluoropropyl and 3,3-difluorobutyl, [(C 4 -C 10 )cycloalkyl]alkyl monosubstituted amino group substitution selected from (cyclopropyl)methyl, (cyclopropyl)ethyl, (cyclobutyl)methyl, (trans-2-methylcyclopropyl)methyl, and (cis-2-methylcyclobutyl)methyl; (C 3 -C 10 )alkenyl and alkynyl monosubstituted amino group substitution selected from allyl, 3-butenyl, 2-butenyl (cis or trans), 2-pentenyl, propynyl, 4-octenyl, 2,3-dimethyl-2-butenyl and 3-methyl-2-butenyl; (C 6 -C 10 )aryl monosubstituted amino group substitution selected from phenyl and naphthyl; (C 7 -C 10 )aralkylamino group substitution selected from benzyl, 2-phenylethyl, 1-phenylethyl, 2-(naphthyl)methyl, 1-(naphthyl)methyl and phenylpropyl; straight or branched symmetrical disubstituted (C 6 -C 14 )alkylamino group substitution selected from dibutyl, diisobutyl, di-s-butyl, dipentyl, diisopentyl and di-s-pentyl; symmetrical disubstituted (C 6 -C 14 )cycloalkylamino group substitution selected from dicyclopropyl, dicyclobutyl, dicyclopentyl and di(dicyclopropyl)methyl; straight or branched unsymmetrical disubstituted (C 3 -C 14 )alkylamino group wherein the total number of carbons in the substitution is no more than 14; unsymmetrical disubstituted (C 4 -C 14 )cycloalkylamino group wherein the total number of carbons in the substitution is no more than 14; (C 2 -C 8 )azacycloalkyl and substituted (C 2 -C 8 )azacycloalkyl group substitution selected from 4-methylpiperidine, 4-hydroxypiperidine, 4-(hydroxymethyl)piperidine, 4-(aminomethyl)piperidine, cis-3,4-dimethylpyrrolidinyl, trans-3,4-dimethylpyrrolidinyl, 2-azabicyclo [2.2.1]hept-2-yl, 7-azabicyclo[2.2.1]hept-7-yl, 2-azabicyclo[2.2.2]oct-2-yl and the diastereomers and enantiomers of said (C 2 -C 8 )azacycloalkyl and substituted (C 2 -C 8 )azacycloalkyl group; substituted 1-azaoxacycloalkyl group substitution selected from 2-(C 1 -C 3 )alkylmorpholinyl, 3-(C 1 -C 3 )alkylisoxazolidinyl and tetrahydrooxazinyl; [1,n]-diazacycloalkyl and substituted [1,n]-diazacycloalkyl group selected from piperazinyl, 2-(C 1 -C 3 )alkylpiperazinyl, 4-(C 1 -C 3 )-alkylpiperazinyl, 2,4-dimethylpiperazinyl, 4-(C 1 -C 4 )- alkoxypiperazinyl, 4-(C 6 -C 10 )aryloxypiperazinyl, 4-hydroxypiperazinyl, 2,3-diaza-3-methylbicyclo[2.2.2]oct-2-yl, 2,5-diaza-5,7-dimethylbicyclo[2.2.2]oct-2-yl and the diastereomers or enantiomers of said [1,n]-diazacycloalkyl and substituted [1,n]-di-azacycloalkyl group; 1-azathiacycloalkyl and substituted 1-azathiacycloalkyl group selected from thiomorpholinyl, 2-(C 1 -C 3 )alkylthiomorpholinyl and 3-(C 3 -C 6 )cycloalkylthiomorpholinyl; N-azolyl and substituted N-azolyl group selected from 1-imidazolyl, 1-pyrrolyl, 1-pyrazolyl, 3-(C 1 -C 3 )alkylpyrazolyl, indolyl, 1-(1,2,3-triazolyl), 4-(1,2,4-triazolyl), 1-tetrazolyl, 2-tetrazolyl and benzimidazolyl; (heterocycle)methylamino group selected from 2- or 3-furylmethylamino, 2- or 3-thienylmethylamino, 2-, 3- or 4-pyridylmethylamino, 2- or 5-pyridazinylmethylamino, 2-pyrazinylmethylamino, 2-(imidazolyl)methylamino, (benzimidazolyl)methylamino, and (benzothiazolyl)methylamino and substituted (heterocycle)methylamino group (substitution selected from straight or branched (C 1 -C 6 )alkyl); carboxy(C 2 -C 4 )alkylamino group selected from aminoacetic acid, α-aminopropionic acid, β-aminopropionic acid, α-butyric acid, and β-aminobutyric acid and the enantiomers of said carboxy(C 2 -C 4 )alkylamino group; 1,1-disubstituted hydrazino group selected from 1,1-dimethylhydrazino, N-aminopiperidinyl and 1,1-diethylhydrazino; (C 1 -C 4 )alkoxyamino group substitution selected from methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 2-methylpropoxy and 1,1-dimethylethoxy; (C 3 -C 8 )cycloalkoxyamino group selected from cyclopropoxy, trans-1,2-dimethylcyclopropoxy, cis-1,2-dimethylcyclopropoxy, cyclobutoxy, and the diastereomers and enantiomers of said (C 3 -C 8 )cycloalkoxyamino group; (C 6 -C 10 )aryloxyamino group selected from phenoxyamino, 1-naphthyloxyamino and 2-naphthyloxyamino; (C 7 -C 1 )arylalkoxyamino group substitution selected from benzyloxy, 2-phenylethoxy, 1-phenylethoxy, 2-(naphthyl)methoxy, 1-(naphthyl)methoxy and phenylpropoxy; [β or γ-(C 1 -C 3 )acylamido]alkylamino group substitution selected from 2-(formamido)ethyl, 2-(acetamido)ethyl, 2-(propionylamido)ethyl, 2-(acetamido)propyl, 2-(formamido)propyl and the enantiomers of said [β or γ-(C 1 -C 3 )acylamido]alkylamino group; β or γ-(C 1 -C 3 )alkoxyalkylamino group substitution selected from 2-methoxyethyl, 2-ethoxyethyl, 2,2-diethoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3,3-diethoxypropyl and the enantiomers of said β or γ-(C 1 -C 3 )alkoxyalkylamino group; β, γ or δ (C 2 -C 4 ) hydroxyalkylamino group substitution selected from 2-hydroxyethyl, 3-hydroxypropyl, and 4-hydroxybutyl;
or R 3 and W taken together are selected from --(CH 2 ) n (R 5 )N--, n=3-4, and --CH 2 CH(OH)CH 2 (R 5 )N-- wherein R 5 is selected from hydrogen and (C 1 -C 3 )acyl, the acyl selected from formyl, acetyl, propionyl and (C 2 -C 3 )haloacyl selected from chloroacetyl, bromoacetyl, trifluoroacetyl, 3,3,3-trifluoropropionyl and 2,3,3-trifluoropropionyl;
R 6 is selected from hydrogen; straight or branched (C 1 -C 3 )alkyl group selected from methyl, ethyl, n-propyl or 1-methylethyl; (C 6 -C 10 )aryl group selected from phenyl, α-naphthyl or β-naphthyl; (C 7 -C 9 )aralkyl group such as benzyl, 1-phenylethyl, 2-phenylethyl or phenylpropyl; a heterocycle group selected from a five membered aromatic or saturated ring with one N, O, S or Se heteroatom optionally having a benzo or pyrido ring fused thereto: ##STR9## such as pyrrolyl, N-methylindolyl, indolyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 2-pyrrolinyl, tetrahydrofuranyl, furanyl, benzofuranyl, tetrahydrothienyl, thienyl, benzothienyl or selenazolyl, or a five membered aromatic ring with two N, O, S or Se heteroatoms optionally having a benzo or pyrido ring fused thereto: ##STR10## such as imidazolyl, pyrazolyl, benzimidazolyl, oxazolyl, benzoxazolyl, indazolyl, thiazolyl, benzothiazolyl, 3-alkyl-3H-imidazo[4,5-b]pyridyl or pyridylimidazolyl, or a five membered saturated ring with one or two N, O, S or Se heteroatoms and an adjacent appended O heteroatom: ##STR11## (A is selected from hydrogen; straight or branched (C 1 -C 4 )alkyl; C 6 -aryl; (C 7 -C 9 )aralkyl group selected from benzyl, 1-phenylethyl, 2-phenylethyl or phenylpropyl) such as γ-butyrolactam, γ-butyrolactone, imidazolidinone or N-aminoimidazolidinone; or --(CH 2 ) n COOR 8 where n=0-4 and R 8 is selected from hydrogen; straight or branched (C 1 -C 3 )alkyl group selected from methyl, ethyl, n-propyl or 1-methylethyl; or (C 6 -C 10 )aryl group selected from phenyl, α-naphthyl, or β-naphthyl;
R 7 is selected from hydrogen; straight or branched (C 1 -C 3 )alkyl group selected from methyl, ethyl, n-propyl or 1-methylethyl; (C 6 -C 10 )aryl group selected from phenyl, α-naphthyl or β-naphthyl; (C 7 -C 9 )aralkyl group such as benzyl, 1-phenylethyl, 2-phenylethyl or phenylpropyl; a heterocycle group selected from a five membered aromatic or saturated ring with one N, O, S or Se heteroatom optionally having a benzo or pyrido ring fused thereto: ##STR12## such as pyrrolyl, N-methylindolyl, indolyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 2-pyrrolinyl, tetrahydrofuranyl, furanyl, benzofuranyl, tetrahydrothienyl, thienyl, benzothienyl or selenazolyl, or a five membered aromatic ring with two N, O, S or Se heteroatoms optionally having a benzo or pyrido ring fused thereto: ##STR13## such as imidazolyl, pyrazolyl, benzimidazolyl, oxazolyl, benzoxazolyl, indazolyl, thiazolyl, benzothiazolyl, 3-alkyl-3H-imidazo[4,5-b]pyridyl or pyridylimidazolyl, or a five membered saturated ring with one or two N, O, S or Se heteroatoms and an adjacent appended O heteroatom: ##STR14## (A is selected from hydrogen; straight or branched (C 1 -C 4 )alkyl; C 6 -aryl; (C 7 -C 9 )aralkyl group selected from benzyl, 1-phenylethyl, 2-phenylethyl or phenylpropyl) such as γ-butyrolactam, γ-butyrolactone, imidazolidinone or N-aminoimidazolidinone; or --(CH 2 ) n COOR 8 where n=0-4 and R 8 is selected from hydrogen; straight or branched (C 1 -C 3 )alkyl selected from methyl, ethyl, n-propyl or 1-methylethyl; or (C 6 -C 10 )aryl selected from phenyl, α-naphthyl or β-naphthyl; with the proviso that R 6 and R 7 cannot both be hydrogen;
or R 6 and R 7 taken together are --(CH 2 ) 2 B(CH 2 ) 2 --, wherein B is selected from (CH 2 ) n and n=0-1, --NH, --N(C 1 -C 3 )alkyl [straight or branched], --N(C 1 -C 4 )alkoxy, oxygen, sulfur or substituted congeners selected from (L or D)proline, ethyl(L or D)prolinate, morpholine, pyrrolidine or piperidine; and the pharmacologically acceptable organic and inorganic salts or metal complexes.
Particularly preferred compounds are compounds according to formula I and II wherein:
R is a halogen selected from bromine, chlorine, fluorine and iodine; or R=--NR 1 R 2 and when R=--NR 1 R 2 and R 1 =hydrogen,
R 2 =methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl; and when R 1 =methyl or ethyl, R 2 =methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl or 2-methylpropyl;
R 3 is selected from hydrogen; straight or branched (C 4 -C 6 )alkyl group selected from butyl, isobutyl, pentyl and hexyl; (C 6 -C 10 )aryl group selected from phenyl, α-naphthyl and β-naphthyl; (C 7 -C 9 )aralkyl group selected from benzyl, 1-phenylethyl, 2-phenylethyl and phenylpropyl;
R 4 is selected from hydrogen and (C 1 -C 3 )alkyl selected from methyl, ethyl, propyl and isopropyl; when R 3 does not equal R 4 the stereochemistry of the asymmetric carbon (i.e. the carbon bearing the substituent W) maybe be either the racemate (DL) or the individual enantiomers (L or D);
W is selected from (C 7 -C 12 ) straight or branched alkyl monosubstituted amino group substitution selected from heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the diastereomers and enantiomers of said branched alkyl monosubstituted amino group; (C 1 -C 4 ) straight or branched fluoroalkylamino group selected from 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl and 2,2-difluoropropyl; (C 3 -C 8 )cycloalkyl monosubstituted amino group substitution selected from cyclopropyl, trans-1,2-dimethylcyclopropyl, cis-1,2-dimethylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the diastereomers and enantiomers of said (C 3 -C 8 )cycloalkyl monosubstituted amino group; [(C 4 -C 10 )cycloalkyl]alkyl monosubstituted amino group substitution selected from (cyclopropyl)methyl, (cyclopropyl)ethyl and (cyclobutyl)methyl; (C 3 -C 10 )alkenyl and alkynyl monosubstituted amino group substitution selected from allyl, propynyl, 3-butenyl, 2-butenyl (cis or trans) and 2-pentenyl; (C 7 -C 10 )aralkylamino group substitution selected from benzyl, 2-phenylethyl, 1-phenylethyl, 2-(naphthyl)methyl, 1-(naphthyl)methyl and phenylpropyl; straight or branched symmetrical disubstituted (C 6 -C 14 )alkylamino group substitution selected from dibutyl, diisobutyl, di-s-butyl, and dipentyl; symmetrical disubstituted (C 6 -C 14 )cycloalkylamino group substitution selected from dicyclopropyl, dicyclobutyl, dicyclopentyl and dicyclopropylmethyl; straight or branched unsymmetrical disubstituted (C 3 -C 14 )alkylamino group wherein the total number of carbons in the substitution is no more than 14; unsymmetrical disubstituted (C 4 -C 14 )cycloalkylamino group wherein the total number of carbons in the substitution is no more than 14; (C 2 -C 8 )azacycloalkyl and substituted (C 2 -C 8 )azacycloalkyl group substitution selected from 4-methylpiperidine, 4-hydroxypiperidine, 4-(hydroxymethyl)piperidine, 4-(aminomethyl)piperidine, cis-3,4-dimethylpyrrolidinyl, trans-3,4-dimethylpyrrolidinyl, and the diastereomers and enantiomers of said (C 2 -C 8 )azacycloalkyl and substituted (C 2 -C 8 )azacycloalkyl group; substituted 1-azaoxacycloalkyl group substitution selected from 2-(C 1 -C 3 )alkylmorpholinyl and 3 -(C 1 -C 3 )alkylisoxazolidinyl; [1,n]-diazacycloalkyl and substituted [1,n]-diazacycloalkyl group selected from piperazinyl, 2-(C 1 -C 3 )alkylpiperazinyl, 4-(C 1 -C 3 )alkylpiperazinyl, 2,4-dimethylpiperazinyl, 4-hydroxypiperazinyl, and the enantiomers of said [1,n]-diazacycloalkyl and substituted [1,n]-diazacycloalkyl group; 1-azathiacycloalkyl,and substituted 1-azathiacycloalkyl group selected from thiomorpholinyl and 2-(C 1 -C 3 )alkylthiomorpholinyl; (heterocycle)methylamino group selected from 2- or 3-furylmethylamino, 2- or 3-thienylmethylamino, 2-, 3- or 4-pyridylmethylamino, 2- or 5-pyridazinylmethylamino, 2-pyrazinylmethylamino, 2-(imidazolyl)methylamino and the substituted (heterocycle)methylaminno group (substitution selected from straight or branched (C 1 -C 6 )alkyl); 1,1-disubstituted hydrazino group selected from 1,1-dimethylhydrazino, N-aminopiperidinyl and 1,1-diethylhydrazino; (C 1 -C 4 )alkoxyamino group substitution selected from methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 2-methylpropoxy and 1,1-dimethylethoxy; (C 7 -C 11 )arylalkoxyamino group substitution selected from benzyloxy, 2-phenylethoxy, 1-phenylethoxy, 2-(naphthyl)methoxy, 1-(naphthyl)methoxy and phenylpropoxy; [β or γ-(C 1 -C 3 )acylamido]alkylamino group substitution selected from 2-(formamido)ethyl, 2-(acetamido)ethyl, 2-(propionylamido)ethyl, 2-(acetamido)propyl and 2-(formamido)propyl and the enantiomers of said [β or γ-(C 1 -C 3 )acylamido]alkylamino group; β or γ-(C 1 -C 3 )alkoxyalkylamino group substitution selected from 2-methoxyethyl, 2-ethoxyhyl, 2,2-diethoxyethyl, 2-methoxypropyl, 3-methoxyopyl, 3-ethoxypropyl and 3,3-diethoxypropyl and the enantiomers of said β or γ-(C 1 -C 3 )alkoxyalkyl-amino group; β, γ, or δ (C 2 - C 4 ) hydroxyalkylamino group selected from 3-hydroxypropyl and 4-hydroxybutyl;
or R 3 and W taken together are selected from --(CH 2 ) n (R 5 )N--, n=3-4, and --CH 2 CH(OH)CH 2 (R 5 )N-- wherein R 5 is selected from hydrogen and (C 1 -C 3 )acyl, the acyl selected from formyl, acetyl, propionyl and (C 2 -C 3 )haloacyl selected from trifluoroacetyl, 3,3,3-trifluoropropionyl and 2,3,3-trifluoropropionyl; R 6 is selected from hydrogen; straight or branched (C 1 -C 3 )alkyl group selected from methyl, ethyl, n-propyl or 1-methylethyl; (C 6 -C 10 )aryl group selected from phenyl, α-naphthyl or β-naphthyl; (C 7 -C 9 )aralkyl group such as benzyl, 1-phenylethyl, 2-phenylethyl or phenylpropyl; a heterocycle group selected from a five membered aromatic or saturated ring with one N, O, S or Se heteroatom optionally having a benzo or pyrido ring fused thereto: ##STR15## such as pyrrolyl, N-methylindolyl, indolyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 2-pyrrolinyl, tetrahydrofuranyl, furanyl, benzofuranyl, tetrahydrothienyl, thienyl, benzothienyl or selenazolyl, or a five membered aromatic ring with two N, O, S or Se heteroatoms optionally having a benzo or pyrido ring fused thereto: ##STR16## such as imidazolyl, pyrazolyl, benzimidazolyl, oxazolyl, benzoxazolyl, indazolyl, thiazolyl, benzothiazolyl, 3-alkyl-3H-imidazo[4,5-b]pyridyl or pyridylimidazolyl; or --(CH 2 ) n COOR 8 where n=0-4 and R 8 is selected from hydrogen; straight or branched (C 1 -C 3 )alkyl group selected from methyl, ethyl, n-propyl or 1-methylethyl; or (C 6 -C 10 )aryl group selected from phenyl, α-naphthyl, or β-naphthyl;
R 7 is selected from hydrogen; straight or branched (C 1 -C 3 )alkyl group selected from methyl, ethyl, n-propyl or 1-methylethyl; (C 6 -C 10 )aryl group selected from phenyl, α-naphthyl or β-naphthyl; (C 7 -C 9 )aralkyl group such as benzyl, 1-phenylethyl, 2-phenylethyl or phenylpropyl; a heterocycle group selected from a five membered aromatic or saturated ring with one N, O, S or Se heteroatom optionally having a benzo or pyrido ring fused thereto: ##STR17## such as pyrrolyl, N-methylindolyl, indolyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 2-pyrrolinyl, tetrahydrofuranyl, furanyl, benzofuranyl, tetrahydrothienyl, thienyl, benzothienyl or selenazolyl, or a five membered aromatic ring with two N, O, S or Se heteroatoms optionally having a benzo or pyrido ring fused thereto: ##STR18## such as imidazolyl, pyrazolyl, benzimidazolyl, oxazolyl, benzoxazolyl, indazolyl, thiazolyl, benzothiazolyl, 3-alkyl-3H-imidazo[4,5-b]pyridyl or pyridylimidazolyl; or --(CH 2 ) n COOR 8 where n=0-4 and R 8 is selected from hydrogen; straight or branched (C 1 -C 3 )alkyl selected from methyl, ethyl, n-propyl or 1-methylethyl; or (C 6 -C 10 )aryl selected from phenyl, α-naphthyl or β-naphthyl; with the proviso that R 6 and R 7 cannot both be hydrogen;
or R 6 and R 7 taken together are --(CH 2 ) 2 B(CH 2 ) 2 --, wherein B is selected from (CH 2 ) n and n=0-1, --NH, --N(C 1 -C 3 )alkyl [straight or branched], --N(C 1 -C 4 )alkoxy, oxygen, sulfur or substituted congeners selected from (L or D)proline, ethyl(L or D)prolinate, morpholine, pyrrolidine or piperidine; and the pharmacologically acceptable organic and inorganic salts or metal complexes.
Compounds of special interest are compound according to formula I and II wherein:
R is a halogen selected from bromine, chlorine and iodine; or R=--NR 1 R 2 and when R=--NR 1 R 2 and R 1 =methyl or ethyl,
R 2 =methyl or ethyl,
R 3 is selected from hydrogen;
R 4 is selected from hydrogen and (C 1 -C 2 )alkyl selected from methyl and ethyl; when R 3 does not equal R 4 the stereochemistry of the asymmetric carbon (i.e. the carbon bearing the substituent W) maybe be either the racemate (DL) or the individual enantiomers (L or D);
W is selected from (C 7 -C 12 ) straight or branched alkyl monosubstituted amino group substitution selected from heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the diastereomers and enantiomers of said branched alkyl monosubstituted amino group; (C 2 )fluoroalkylamino group selected from 2,2,2-trifluoroethyl and 3,3,3-trifluoropropyl; (C 3 -C 8 )cycloalkyl monosubstituted amino group substitution selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the diastereomers and enantiomers of said (C 3 -C 8 )cycloalkyl monosubstituted amino group; [(C 4 -C 5 )cycloalkyl]alkyl monosubstituted amino group substitution selected from (cyclopropyl)methyl and (cyclopropyl)ethyl; (C 3 -C 4 )alkenyl and alkynyl monosubstituted amino group substitution selected from allyl and propynyl; (C 2 -C 7 )azacycloalkyl and substituted (C 2 -C 7 )azacycloalkyl group substitution selected from 4-methylpiperidine, 4-hydroxypiperidine and 4-(hydroxymethyl)piperidine; substituted 1-azaoxacycloalkyl group substitution selected from 2-(C 1 -C 3 )alkylmorpholinyl; [1,n]-diazacycloalkyl and substituted [1,n]-diazacycloalkyl group selected from piperazinyl and 4-(C 1 -C 3 )alkylpiperazinyl; 1-azathiacycloalkyl and substituted 1-azathiacycloalkyl group selected from thiomorpholinyl and 2-(C 1 -C 3 )alkylthiomorpholinyl; (heterocycle)methylamino group selected from 2- or 3-thienylmethylamino and 2-, 3- or 4-pyridylmethylamino; 1,1-disubstituted hydrazino group selected from 1,1-dimethylhydrazino and N-aminopiperidinyl. [β or γ-(C 1 -C 3 )acylamido]alkylamino group substitution selected from 2-(acetamido)ethyl; β or γ-(C 1 -C 3 )alkoxyalkylamino group substitution selected from 2-methoxyethyl, 2-ethoxyethyl, 2,2-diethoxyethyl, 2-methoxypropyl and 3-methoxypropyl; β, γ or δ (C 2 -C 4 )hydroxyalkylamino selected from 4-hydroxybutyl and 3-hydroxypropyl; or R 3 and W taken together are selected from --(CH 2 ) n (R 5 )N--, n=3, and R 5 is selected from hydrogen and trifluoroacetyl;
R 6 is selected from hydrogen; straight or branched (C 1 -C 3 )alkyl group selected from methyl, ethyl, n-propyl or 1-methylethyl;
R 7 is selected from hydrogen; straight or branched (C 1 -C 3 )alkyl group selected from methyl, ethyl, n-propyl or 1-methylethyl; with the proviso that R 6 and R 7 cannot both be hydrogen; or R 6 and R 7 taken together are --(CH 2 ) 2 B(CH 2 ) 2 --, wherein B is selected from (CH 2 ) n and n=0-1, --NH, --N(C 1 -C 3 )alkyl [straight or branched], --N(C 1 -C 4 )alkoxy, oxygen, sulfur or substituted congeners selected from (L or D)proline, ethyl(L or D)prolinate, morpholine, pyrrolidine or piperidine; and the pharmacologically acceptable organic and inorganic salts or metal complexes.
Also included in the present invention are compounds useful as intermediates for producing the above compounds of formula I and II. Such intermediates include those having the formula III: ##STR19## wherein: Y is selected from (CH 2 ) n X, n=0-5, X is halogen selected from bromine, chlorine, fluorine or iodine;
R is a halogen selected from bromine, chlorine, fluorine and iodine; or R=--NR 1 R 2 and when R=--NR 1 R 2 and R 1 =hydrogen,
R 2 =methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl; and when R 1 =methyl or ethyl, R 2 =methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl or 2-methylpropyl; and when R 1 =n-propyl, R 2 =n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl or 2-methylpropyl; and when R 1 =1-methylethyl, R 2 =n-butyl, 1-methylpropyl or 2-methylpropyl; and when R 1 =n-butyl, R 2 =n-butyl, 1-methylpropyl or 2-methylpropyl; and when R 1 =1-methylpropyl, R 2 =2-methylpropyl;
R 3 is selected from hydrogen; straight or branched (C 4 -C 8 )alkyl group selected from butyl, isobutyl, pentyl, hexyl, heptyl and octyl; α-mercapto(C 1 -C 4 )alkyl group selected from mercaptomethyl, α-mercaptoethyl, α-mercapto-1methylethyl and α-mercaptopropyl; α-hydroxy-(C 1 -C 4 )alkyl group selected from hydroxymethyl, α-hydroxyethyl, α-hydroxy-1-methylethyl and α-hydroxypropyl; carboxyl(C 1 -C 8 )alkyl group; (C 6 -C 10 )aryl group selected from phenyl, α-naphthyl and β-naphthyl; substituted(C 6 -C 10 )aryl group (substitution selected from hydroxy, halogen, (C 1 -C 4 )alkoxy, trihalo(C 1 -C 3 )alkyl, nitro, amino, cyano, (C 1 -C 4 )alkoxycarbonyl, (C 1 -C 3 )alkylamino and carboxy); (C 7 -C 9 )aralkyl group selected from benzyl, 1-phenylethyl, 2-phenylethyl and phenylpropyl; substituted (C 7 -C 9 )aralkyl group [substitution selected from halo, (C 1 -C 4 )alkyl, nitro, hydroxy, amino, mono-or di-substituted (C 1 -C 4 )alkylamino, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylsulfonyl, cyano and carboxy];
R 4 is selected from hydrogen and (C 1 -C 6 )alkyl selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl and hexyl; when R 3 does not equal R 4 the stereochemistry of the asymmetric carbon (i.e. the carbon bearing the substituent W) maybe be either the racemate (DL) or the individual enantiomers (L or D); and the pharmacologically acceptable organic and inorganic salts or metal complexes;
Preferred compounds are compounds according to the above formula III wherein:
Y is selected from (CH 2 ) n X, n=0-5, X is halogen selected from bromine, chlorine, fluorine or iodine;
R is a halogen selected from bromine, chlorine, fluorine and iodine; or R=--NR 1 R 2 and when R=--NR 1 R 2 and R 1 =hydrogen,
R 2 =methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl; and when R 1 =methyl or ethyl, R 2 =methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl or 2-methylpropyl;
R 3 is selected from hydrogen; straight or branched (C 4 -C 8 )alkyl group selected from butyl, isobutyl, pentyl, hexyl, heptyl and octyl; α-hydroxy(C 1 -C 4 )alkyl group selected from hydroxymethyl, α-hydroxyethyl, α-hydroxy-1-methylethyl and α-hydroxypropyl; carboxyl(C 1 -C 8 )alkyl group; (C 6 -C 10 )aryl group selected from phenyl, α-naphthyl and β-naphthyl; substituted(C 6 -C 10 )aryl group (substitution selected from hydroxy, halogen, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkoxycarbonyl and carboxy); (C 7 -C 9 )aralkyl group selected from benzyl, 1-phenylethyl, 2-phenylethyl and phenylpropyl; substituted (C 7 -C 9 )aralkyl group [substitution selected from halo, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylsulfonyl, cyano and carboxy];
R 4 is selected from hydrogen and (C 1 -C 4 )alkyl selected from methyl, ethyl, propyl, isopropyl, butyl and isobutyl; when R 3 does not equal R 4 the stereochemistry of the asymmetric carbon (i.e. the carbon bearing the substituent W) maybe be either the racemate (DL) or the individual enantiomers (L or D); and the pharmacologically acceptable organic and inorganic salts or metal complexes.
Particularly preferred compounds are compounds according to formula III wherein:
Y is selected from (CH 2 ) n X, n=0-5, X is halogen selected from bromine, chlorine, fluorine or iodine;
R is a halogen selected from bromine, chlorine, fluorine and iodine; or R=--NR 1 R 2 and when R=--NR 1 R 2 and R 1 =hydrogen,
R 2 =methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl; and when R 1 =methyl or ethyl, R 2 =methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl or 2-methylpropyl;
R 3 is selected from hydrogen; straight or branched (C 4 -C 6 )alkyl group selected from butyl, isobutyl, pentyl and hexyl; (C 6 -C 10 )aryl group selected from phenyl, α-naphthyl and β-naphthyl; (C 7 -C 9 )aralkyl group selected from benzyl, 1-phenylethyl, 2-phenylethyl and phenylpropyl;
R 4 is selected from hydrogen and (C 1 -C 3 )alkyl selected from methyl, ethyl, propyl and isopropyl; when R 3 does not equal R 4 the stereochemistry of the asymmetric carbon (i.e. the carbon bearing the substituent W) maybe be either the racemate (DL) or the individual enantiomers (L or D); and the pharmacologically acceptable organic and inorganic salts or metal complexes.
Compounds of special interest are compound according to formula III wherein:
Y is selected from (CH 2 ) n X, n=0-5, X is halogen selected from bromine, chlorine, fluorine or iodine;
R is a halogen selected from bromine, chlorine and iodine; or R=--NR 1 R 2 and when R=--NR 1 R 2 and R 1 =methyl or ethyl,
R 2 =methyl or ethyl,
R 3 is selected from hydrogen;
R 4 is selected from hydrogen and (C 1 -C 2 )alkyl selected from methyl and ethyl; when R 3 does not equal R 4 the stereochemistry of the asymmetric carbon (i.e. the carbon bearing the substituent W) maybe be either the racemate (DL) or the individual enantiomers (L or D); and the pharmacologically acceptable organic and inorganic salts or metal complexes.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The novel compounds of the present invention may be readily prepared in accordance with the following schemes.
The preferred method for producing 7-(substituted)-9-[(substituted glycyl)amido]-6-demethyl- 6-deoxytetracyclines or the mineral acid salts, 3, is shown in scheme I. This method uses common intermediates which are easily prepared by reacting commercially available haloacyl halides of the formula: ##STR20## wherein Y, R 3 and R 4 are as defined hereinabove and Q is halogen selected from bromine, chlorine, iodine and fluorine; with 9-amino-7-(substituted)-6-demethyl-6-deoxytetracycline or its mineral acid salt, 1, to give straight or branched 9-[(haloacyl)amido]-7-(substituted)-6-demethyl-6-deoxytetracyclines or mineral acid salts, 2, in almost quantitative yield. The above intermediates, straight or branched 9-[(haloacyl)amido]-7-(substituted)-6-demethyl-6-deoxytetracyclines or mineral acid salts, 2, react with a wide variety of nucleophiles, especially amines, having the formula WH, wherein W is as defined hereinabove, to give a new 7-(substituted)-9-[(substituted glycyl)amido]-7-(substituted)-6-demethyl-6-deoxytetracyclines or the mineral acid salts, 3 of the present invention. ##STR21##
In accordance with scheme I, 9-amino-7-(substituted)-6-demethyl-6-deoxytetracycline or its mineral acid salt, 1, is mixed with
a) a polar-aprotic solvent such as 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)pyrimidone, herein after called DMPU, hexamethylphosphoramide herein after called HMPA, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 1,2-dimethoxyethane or equivalent thereof;
b) an inert solvent such as acetonitrile, methylene chloride, tetrahydrofuran, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethane, diethyl ether, t-butyl methyl ether, isopropyl ether or equivalent thereof;
c) a base such as sodium carbonate, sodium bicarbonate, sodium acetate, potassium carbonate, potassium bicarbonate, triethylamine, cesium carbonate, lithium carbonate or bicarbonate equivalents; and
d) a straight or branched haloacyl halide of the formula: ##STR22## wherein Y, R 3 , R 4 and Q are as hereinabove defined, such as bromoacetyl bromide, chloroacetyl chloride, 2-bromopropionyl bromide or equivalent thereof; the halo, Y, and halide, Q, in the haloacyl halide can be the same or different halogen and is selected from bromine, chlorine, iodine and fluorine; Y is (CH 2 ) n X, n=0-5, X is halogen;
e) for 0.5 to 5 hours at from room temperature to the reflux temperature of the reaction; to form the corresponding 9-[(haloacyl)amido-7-(substituted)-6-demethyl-6-deoxytetracycline, 2, or its mineral acid salt.
The intermediate, 9-[(haloacyl)amido]-7-(substituted)-6-demethyl-6-deoxytetracycline or its mineral acid salt, 2, is treated, under an inert atmosphere of helium, argon or nitrogen, with
a) a nucleophile WH such as an amine, substituted amine or equivalent thereof for example methylamine, dimethylamine, ethylamine, n-butylamine, propylamine or n-hexylamine;
b) a polar-aprotic solvent such as DMPU, HMPA dimethylformamide, dimethylacetamide, N-methylpyrrolidone or 1,2-dimethoxyethane;
c) for from 0.5-2 hours at room temperature or under reflux temperature to produce the desired 7-(substituted)-9-[(substituted glycyl)amido]-6-demethyl-6-deoxytetracycline, 3, or its mineral acid salt. ##STR23##
In accordance with Scheme II, compounds of formula 3 are N-alkylated in the presence of formaldehyde and either a primary amine such as methylamine, ethylamine, benzylamine, methyl glycinate, (L or D)alanine, (L or D)lysine or their substituted congeners; or a secondary amine such as morpholine, pyrrolidine, piperidine or their substituted congeners to give the corresponding Mannich base adduct, 4.
The 7-(substituted)-9-[(substituted glycyl)amido]-6-demethyl-6-deoxytetracyclines may be obtained as metal complexes such as aluminum, calcium, iron, magnesium, manganese and complex salts; inorganic and organic salts and corresponding Mannich base adducts using methods known to those skilled in the art (Richard C. Larock, Comprehensive Organic Transformations, VCH Publishers, 411-415, 1989). It is well known to one skilled in the art that an appropriate salt form is chosen based on physical and chemical stability, flowability, hygroscopicity and solubility. Preferably, the 7-(substituted)-9-[(substituted glycyl)amido]-6-demethyl-6-deoxytetracyclines are obtained as inorganic salt such as hydrochloric, hydrobromic, hydroiodic, phosphoric, nitric or sulfate; or organic salt such as acetate, benzoate, citrate, cysteine or other amino acids, fumarate, glycolate, maleate, succinate, tartrate, alkylsulfonate or arylsulfonate. Depending on the stochiometry of the acids used, the salt formation occurs with the C(4)-dimethylamino group (1 equivalent of acid) or with both the C(4)-dimethylamino group and the W group (2 equivalents of acid). The salts are preferred for oral and parenteral administration.
Some of the compounds of the hereinbefore described Schemes have centers of asymmetry at the carbon bearing the W substituent. The compounds may, therefore, exist in at least two (2) stereoisomeric forms. The present invention encompasses the racemic mixture of stereoisomers as well as all stereoisomers of the compounds whether free from other stereoisomers or admixed with stereoisomers in any proportion of enantiomers. The absolute configuration of any compound may be determined by conventional X-ray crystallography.
The stereochemistry centers on the tetracycline unit (i.e. C-4, C-4a, C-5a and C-12a) remain intact throughout the reaction sequences.
Biological Activity
Methods for in Vitro Antibacterial Evaluation (Table I)
The minimum inhibitory concentration (MIC), the lowest concentration of the antibiotic which inhibits growth of the test organism, is determined by the agar dilution method using 0.1 ml Muller-Hinton II agar (Baltimore Biological Laboratories) per well. An inoculum density of 1-5×10 5 CFU/ml, and an antibiotic concentrations range of 32-0.004 microgram/ml is used. MIC is determined after the plates are incubated for 18 hours at 35° C. in a forced air incubator. The test organisms comprise strains that are sensitive to tetracycline and genetically defined strains that are resistant to tetracycline, due to inability to bind bacterial ribosomes (tetM).
E. coli in Vitro Protein Translation System (Table II)
An in vitro, cell free, protein translation system using extracts from E. coli strain MRE600 (tetracycline sensitive) and a derivative of MRE600 containing the tetM determinant has been developed based on literature methods [J. M. Pratt, Coupled Transcription-translation in Prokaryotic Cell-free Systems, Transcription and Translation, a Practical Approach, (B. D. Hames and S. J. Higgins, eds) p. 179-209, IRL Press, Oxford-Washington, 1984].
Using the system described above, the tetracycline compounds of the present invention are tested for their ability to inhibit protein synthesis in vitro. Briefly, each 10 microliter reaction contains S30 extract (a whole extract) made from either tetracycline sensitive cells or an isogenic tetracycline resistant (tetM) strain, low molecular weight components necessary for transcription and translation (i.e. ATP and GTP), a mix of 19 amino acids (no methionine), 35 S labeled methionine, DNA template (either pBR322 or pUC119), and either DMSO (control) or the novel tetracycline compound to be tested ("novel TC") dissolved in DMSO.
The reactions are incubated for 30 minutes at 37° C. Timing is initiated with the addition of the S30 extract, the last component to be added. After 30 minutes, 2.5 μl of the reaction is removed and mixed with 0.5 ml of 1N NaOH to destroy RNA and tRNA. Two ml of 25% trichloroacetic acid is added and the mixture incubated at room temperature for 15 minutes. The trichloroacetic acid precipitated material is collected on Whatman GF/C filters and washed with a solution of 10% trichloroacetic acid. The filters are dried and the retained radioactivity, representing incorporation of 35 S-methionine into polypeptides, is counted using standard liquid scintillation methods.
The percent inhibition (P.I.) of protein synthesis is determined to be: ##EQU1##
In Vivo Antibacterial Evaluation
The therapeutic effects of tetracyclines are determined against an acute lethal infection with Staphylococcus aureus strain Smith (tetracycline sensitive). Female, mice, strain CD-1(Charles River Laboratories), 20±2 grams, are challenged by an intraperitoneal injection of sufficient bacteria (suspended in hog mucin) to kill non-treated controls within 24-48 hours. Antibacterial agents, contained in 0.5 ml of 0.2% aqueous agar, are administered subcutaneously or orally 30 minutes after infection. When an oral dosing schedule is used, animals are deprived of food for 5 hours before and 2 hours after infection. Five mice are treated at each dose level. The 7 day survival ratios from 3 separate tests are pooled for calculation of median effective dose (ED 50 ).
Testing Results
The claimed compounds exhibit antibacterial activity against a spectrum of tetracycline sensitive and resistant Gram-positive and Gram-negative bacteria, especially, strains of E. coli, S. aureus and E. faecalis, containing tetM and tetD resistance determinants; and E. coli containing the tetB and tetD resistance determinants. Notable are compounds D, G, and K, as shown in Table I, which demonstrated excellent in vitro activity against tetracycline resistant strains containing the tetM resistance determinant (such as S. aureus UBMS 88-5, S. aureus UBMDS 90-1 and 90-2, E. coli UBMS 89-1 and 90-4) and tetracycline resistant strains containing tetB resistance determinants (such as E. coli UBMS 88-1 and E. coli TN10C tetB). These compounds also have good activity against E. coli tetA, E. coli tetC and E. coli tetD and are equally as effective as minocycline against susceptible strains and are superior to that of minocycline against a number of recently isolated bacteria from clinical sources (Table I).
Minocycline and compounds B, C, D, G and H are assayed in vitro for their ability to inhibit protein synthesis taking place on either wild type or tetM protected ribosomes using a coupled transcription and translation system. All compounds are found to effectively inhibit protein synthesis occuring on wild type ribosomes, having equivalent levels of activity. Minocycline is unable to inhibit protein synthesis occurring on tetM protected ribosomes. In contrast, compounds B, C, D, G and H are effective at inhibiting protein synthesis occurring on tetM protected ribosomes (Table II).
Compounds B, C, D, G and H bind reversibly to its target (the ribosome) since bacterial growth resumes when the compound is removed from the cultures by washing of the organism. Therefore, the ability of these compounds to inhibit bacterial growth appears to be a direct consequence of its ability to inhibit protein synthesis at the ribosome level.
The activity of compound G against tetracycline susceptible organisms is also demonstrated in vivo in animals infected with S. aureus Smith with ED 50 's between 1-2 mg/kg when administered intravenously, and ED 50 's of 4-8 mg/kg when given orally.
The improved efficacy of compounds D, G and K is demonstrated by the in vitro activity against isogenic strains into which the resistance determinants, such as tetM and tetB, were cloned (Table I); and the inhibition of protein synthesis by tetM ribosomes (Table II).
As can be seen from Table I and II, compounds of the invention may also be used to prevent or control important veterinary diseases such as diarrhea, urinary tract infections, infections of skin and skin structure, ear, nose and troat infections, wound infections, mastitis and the like.
______________________________________COMPOUND LEGEND FOR TABLES______________________________________A [7S-(7alpha,10aalpha)]-N-[9-(Aminocarbonyl)- 4,7-bis(dimethylamino)-5,5a,6,6a,7,10,10a, 12-octahydro-1,8,10a,11-tetrahydroxy-10,12- dioxo-2-naphthacenyl]-1-(trifluoroacetyl)-2- pyrrolidinecarboxamide dihydrochlorideB [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- amino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10, 12,12a-tetrahydroxy-9-[[[(2-(methoxyethyl)- amino)acetyl]amino]-1,11-dioxo-2-naphthacene- carboxamide dihydrochlorideC [4S-(4alpha,12aalpha)]-9-[[[(2,2-Diethoxy- ethyl)amino)acetyl]amino]-4,7-bis(dimethyl- amino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10, 12,12a-tetrahydroxy-1,11-dioxo-2-naphthacene- carboxamide dihydrochlorideD [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- amino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10, 12,12a-tetrahydroxy-1,11-dioxo-9-[[(2-pro- penylamino)acetyl]amino]-2-naphthacenecarbox- amide dihydrochlorideE (4S-(4alpha,12aalpha)]-4,7-bis(dimethyl- amino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10, 12,12a-tetrahydroxy-1,11-dioxo-9-[[[(2- pyridinylmethyl)amino]acetyl]amino-2-naphtha- cenecarboxamide dihydrochlorideF [7S-(7alpha,10aalpha)]-N-(9-(Aminocarbonyl)- 4,7-bis(dimethylamino)-5,5a,6,6a,7,10,10a,12- octahydro-1,8,10a,11-tetrahydroxy-10,12- dioxo-2-naphthacenyl)-4-thiomorpholineacet- amide dihydrochlorideG [7S-(7alpha,10aalpha)]-N-[9-(Aminocarbonyl)- 4,7-bis(dimethylamino)-5,5a,6,6a,7,10,10a,12- octahydro-1,8,10a,11-tetrahydroxy-10,12- dioxo-2-naphthacenyl]-4-methyl-l-piperidine- acetamide dihydrochlorideH [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- amino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10, 12,12a-tetrahydroxy-9-[[[(3-methoxypropyl)- amino]acetyl]amino)-1,11-dioxo-2-naphthacene- carboxamide dihydrochlorideI 7[7S-(7alpha,10aalpha)]-N-[9-(Aminocarbonyl)- 4,7-bis(dimethylamino)-5,5a,6,6a,7,10,10a,12- octahydro-1,8,10a,11-tetrahydroxy-10,12- dioxo-2-naphthacenyl]-4-methyl-1-piperazine- acetamide dihydrochlorideJ [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- amino)-9-[[(heptylamino)acetyl]amino]-1,4,4a, 5,5a,6,11,12a-octahydro-3,10,12,12a-tetra- hydroxy-1,11-dioxo-2-naphthacenecarboxamide dihydrochlorideK [4S-(4alpha,12aalpha)]-9-[[(Cyclopropyl- methyl)amino]acetyl]amino]-4,7-bis(dimethyl- amino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10, 12,12a-tetrahydroxy-1,11-dioxo-2-naphthacene- carboxamide dihydrochlorideL [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- amino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10, 12,12a-tetrahydroxy-1,11-dioxo-9-[[(undecyl- amino)acetyl]amino]-2-naphthacenecarboxamide dihydrochlorideM [4S-(4alpha,12aalpha)]-9-[(Bromoacetyl)- amino]-4,7-bis(dimethylamino)-1,4,4a,5,5a,6, 11,12a-octahydro-3,10,12,12a-tetrahydroxy-1, 11-dioxo-2-naphthacenecarboxamide dihydro- chlorideN TetracyclineO MinocyclineP [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- amino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,- 12,12a-tetrahydroxy-9-[[[(2-hydroxyethyl)- amino]acetyl]amino]-1,11-dioxo-2-naphthacene- carboxamide monohydrochlorideQ [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- amino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,- 12,12a-tetrahydroxy-9-[[[(2-hydroxyethyl)- methylamino]acetyl]amino-1,11-dioxo-2- naphthacenecarboxamideR [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl-4- amino-1-amino)-1,4,4a,5,5a,6,11,12a-octa- hydro-3,10,12,12a-tetrahydroxy-9-[[[(4- (hydroxybutyl)amino]acetyl]amino]-1,11-dioxo- 2-naphthacenecarboxamideS [4S-(4alpha,12aalpha))-4,7-Bis(dimethyl- amino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,- 12,12a-tetrahydroxy-1,11-dioxo-9-[[[2,2,2- trifluoroethyl)amino]acetyl]amino-2-naphtha- cenecarboxamideT [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- amino)-9-[[[(2-fluoroethyl)amino]acetyl]- amino]-1,4,4a,5,5a,6,11,12a-octahydro- 3,10,12,12a-tetrahydroxy-1,11-dioxo-2- naphthacenecarboxamideU [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- amino)-1,4,4a,5,5a,6,11,12a-octahydro- 3,10,12,12a-tetrahydroxy-1,11-dioxo-9- [[[[2-(1-piperidinyl)ethyl]amino]acetyl]- amino]-2-naphthacenecarboxamideV [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- amino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,- 12,12a-tetrahydroxy-9-[[[methyl-2-propynyl- amino]acetyl]amino]-1,11-dioxo-2-naphtha- cenecarboxamideW [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- amino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,- 12,12a-tetrahydroxy-hydroxy-1,11-dioxo-9- [[(1-piperidinylamino)acetyl]amino]-2- naphthacenecarboxamideX [4S-(4-alpha,12aalpha)]-4,7-Bis(dimethyl- amino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,- 12,12a-tetrahydroxy-1,11-dioxo-9-[[[(phenyl- methoxy)amino]acetyl]amino]-2-naphthacene- carboxamide______________________________________
TABLE I ANTIBACTERIAL ACTIVITY OF 9-[(SUBSTITUTED GLYCYL)AMIDO]-6-DEMETHYL-6-DEO XYTETRACYCLINES MIC (μg/ml) Compound Organism A B C D E F G H I J K L M N O E. coli UBMS 88-1 Tet B 8 2 16 1 16 >32 2 2 8 2 0.5 32 >32 >32 16 E. coli J3272 Tet sens. 8 2 8 0.5 NT >32 1 1 NT NT NT NT 16 0.5 0.5 E. coli M C 4100 Tet sens. NT NT NT NT 2 NT NT NT 1 1 0.12 2 NT NT NT E. coli PRP1 Tet A >32 8 >32 8 32 >32 2 4 16 2 4 32 >32 32 4 E. coli MC 4100 TNIOC Tet B 8 2 8 1 NT >32 2 2 NT NT NT NT >32 >32 8 E. coli J3272 Tet C 8 4 16 1 16 >32 1 1 8 2 0.5 32 >32 >32 2 E. coli UBMS 89-1 Tet M 8 2 4 0.5 8 >32 0.5 2 8 0.5 0.5 16 4 8 8 E. coli UBMS 89-2 Tet sens. 8 2 8 0.5 16 >32 2 1 8 2 0.5 16 32 1 0.5 E. coli J2175 8 2 8 0.5 16 >32 1 1 8 2 0.5 16 32 1 0.5 E. coli BAJ9003 IMP MUT 1 0.25 0.5 0.12 1 0.5 0.12 0.12 0.5 0.25 0.12 1 0.25 0.25 0.03 E. coli UBMS 90-4 Tet M NT 2 4 0.5 8 >32 1 1 8 2 0.5 32 NT 16 >32 E. coli UBMS 90-5 4 2 8 0.5 16 >32 2 1 8 2 0.5 16 16 1 0.5 E. coli #311 (MP) 8 2 8 0.5 8 >32 1 1 8 2 0.5 8 8 1 0.25 E. coli ATCC 25922 8 2 8 0.5 8 32 1 1 8 2 0.5 8 16 0.5 0.5 E. coli J3272 Tet D 2 1 4 0.25 8 16 0.25 0.5 4 2 0.25 32 32 >32 8 S. mariescens FPOR 8733 >32 >32 >32 8 >32 >32 16 16 >32 16 8 >32 >32 32 2 X. maltophilia NEMC 87210 Ps. acruginosa ATCC 278583 >32 >32 >32 16 >32 >32 32 32 >32 >32 16 >32 >32 8 8 S. aureus NEMC 8769 1 0.5 0.25 0.12 8 0.25 0.12 0.25 0.5 no 1 0.5 0.12 0.03 <0.015 growth S. aureus UBMS 88-4 4 0.5 1 0.25 8 1 0.5 1 2 0.5 0.5 0.5 0.5 0.06 0.03 S. aureus UBMS 88-5 Tet M 4 1 1 0.25 8 1 0.5 0.5 4 0.5 1 16 1 >32 4 S. aureus UBMS 88-7 Tet K 16 16 8 8 32 4 0.5 8 16 1 4 2 2 >32 0.12 S. aureus UBMS 90-1 Tet M 8 2 1 0.5 8 1 0.5 2 8 1 1 16 1 32 4 S. aureus UBMS 90-3 1 0.5 0.5 0.25 4 1 0.5 0.5 2 0.5 0.5 0.5 0.5 0.06 0.03 S. aureus UBMS 90-2 Tet M 2 0.5 1 0.25 8 1 0.5 0.5 2 0.5 0.5 4 0.5 32 2 S. aureus IVES 2943 16 32 8 8 >32 4 0.5 16 >32 0.5 8 16 4 >32 2 S. aureus ROSE (MP) 32 32 16 8 >32 8 1 16 >32 2 8 16 8 >32 0.5 S. aureus SMITH (MP) 2 0.5 0.5 0.12 4 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.06 0.03 S. aureus IVES 1 983 16 32 16 8 >32 4 0.5 16 >32 1 8 16 4 >32 2 S. aureus ATCC 29213 4 1 1 0.25 8 1 0.5 1 2 0.5 1 1 0.5 0.06 0.03 S. hemolyticus AVHAH 88-3 8 2 2 0.5 16 4 1 2 16 2 2 8 2 0.5 0.12 Enterococcus 12201 0.5 0.51 0.25 4 1 0.25 0.5 2 0.5 0.25 4 1 32 8 E. faecalis ATCC 29212 2 0.25 0.5 0.12 2 0.25 0.12 0.25 1 0.25 0.25 2 0.5 8 1 Compound Organism P Q R S T U V W X E. coli UBMS 88-1 Tet B >32 32 >32 32 16 >32 >32 >32 >32 E. coli J3272 Tet sens. NT NT NT NT NT NT NT NT NT E. coli MC 4100 Tet sens. 4 4 8 16 2 4 32 32 4 E. coli PRP1 Tet A >32 >32 >32 >32 >32 > 32 >32 >32 >32 E. coli MC 4100 TNIOC Tet B >32 >32 >32 >32 16 32 >32 >32 >32 E. coli J3272 Tet C >32 >32 >32 >32 >32 16 >32 >32 >32 E. coli UBMS 89-1 Tet M >32 32 32 32 8 16 >32 >32 16 E. coli UBMS 89-2 Tet sens. >32 32 32 >32 16 32 >32 >32 >32 E. coli J2175 32 32 32 >32 16 32 >32 >32 >32 E. coli BAJ9003 IMP MUT 2 2 4 1 1 2 4 16 1 E. coli UBMS 90-4 Tet M 32 16 32 >32 8 16 >32 >32 >32 E. coli UBMS 90-5 32 32 32 >32 16 16 >32 >32 >32 E. coli #311 (MP) 16 32 32 >32 16 16 >32 >32 16 E. coli ATCC 25922 16 32 32 >32 8 16 >32 >32 16 E. coli J3272 Tet D 16 32 8 >32 8 8 >32 >32 16 S. mariescens FPOR 8733 >32 16 8 >32 >32 >32 >32 >32 >32 S. maltophilia NEMC 87210 >32 8 8 16 16 16 32 >32 16 Ps. acruginosa ATCC 27853 >32 >32 >32 >32 >32 >32 >32 >32 >32 S. aureus NEMC 8769 4 8 8 4 4 8 4 >32 1 S. aureus UBMS 88-4 8 8 8 4 4 8 4 >32 1 S. aureus UBMS 88-5 Tet M 32 16 32 8 4 16 8 >32 2 S. aureus UBMS 88-7 Tet K 32 32 32 32 >32 16 32 >32 4 S. aureus UBMS 90-1 Tet M 32 32 32 16 4 32 16 >32 2 S. aureus UBMS 90-3 8 8 8 4 2 8 4 16 1 S. aureus UBMS 90-2 Tet M 16 16 16 4 4 8 8 >32 2 S. aureus IVES 2943 >32 >32 >32 >32 >32 >32 >32 >32 8 S. aureus ROSE (MP) >32 >32 >32 >32 >32 >32 >32 >32 16 S. aureus SMITH (MP) 4 8 8 1 1 8 4 16 0.5 S. aureus IVES 1 983 >32 >32 >32 >32 >32 >32 >32 >32 8 S. aureus ATCC 29313 8 16 16 4 4 8 4 32 1 S. hemolyticus AVHAH 88-3 32 16 32 16 8 32 32 >32 4 Enterococcus 12201 8 4 8 4 2 8 8 >32 4 E. faecalis ATCC 29212 4 4 8 2 1 8 4 >32 N = Not tested
TABLE II______________________________________In Vitro Transcription and TranslationSensitivity to Tetracycline Compounds % InhibitionCompound Conc. Wild Type S30 TetM S30______________________________________B 1.0 mg/ml 98 97 0.25 mg/ml 96 95 0.06 mg/ml 92 91C 1.0 mg/ml 98 96 0.25 mg/ml 95 84 0.06 mg/ml 88 65D 1.0 mg/ml 99 98 0.25 mg/ml 98 96 0.06 mg/ml 93 83G 1.0 mg/ml 99 99 0.25 mg/ml 97 92 0.06 mg/ml 90 83H 1.0 mg/ml 99 98 0.25 mg/ml 96 94 0.06 mg/ml 88 85O 1.0 mg/ml 98 68 0.25 mg/ml 89 43 0.06 mg/ml 78 0______________________________________
When the compounds are employed as antibacteriais, they can be combined with one or more pharmaceutically acceptable carriers, for example, solvents, diluents and the like, and may be administered orally in such forms as tablets, capsules, dispersible powders, granules, or suspensions containing, for example, from about 0.05 to 5% of suspending agent, syrups containing, for example, from about 10 to 50% of sugar, and elixirs containing for example, from about 20 to 50% ethanol and the like, or parenterally in the form of sterile injectable solutions or suspensions containing from about 0.05 to 5% suspending agent in an isotonic medium. Such pharmaceutical preparations may contain, for example, from about 25 to about 90% of the active ingredient in combination with the carrier, more usually between about 5% and 60% by weight.
An effective amount of compound from 2.0 mg/kg of body weight to 100.0 mg/kg of body weight should be administered one to five times per day via any typical route of administration including but not limited to oral, parenteral (including subcutaneous, intravenous, intramuscular, intrasternal injection or infusion techniques), topical or rectal, in dosage unit formulations containing conventional non-toxic pharmaceutically acceptable carriers, adjuvants and vehicles. It will be understood, however, that the specific dose level and frequency of dosage for any particular patient may be varied and will depend upon a variety of factors including the activity of the specific compound employed, the metabolic stability and length of action of that compound, the age, body weight, general health, sex, diet, mode and time of administration, rate of excretion, drug combination, the severity of the particular condition, and the host undergoing therapy.
These active compounds may be administered orally as well as by intravenous, intramuscular, or subcutaneous routes. Solid carriers include starch, lactose, dicalcium phosphate, microcrystalline cellulose, sucrose and kaolin, while liquid carriers include sterile water, polyethylene glycols, non-ionic surfactants and edible oils such as corn, peanut and sesame oils, as are appropriate to the nature of the active ingredient and the particular form of administration desired. Adjuvants customarily employed in the preparation of pharmaceutical compositions may be advantageously included, such as flavoring agents, coloring agents, preserving agents, and antioxidants, for example, vitamin E, ascorbic acid, BHT and BHA.
The preferred pharmaceutical compositions from the standpoint of ease of preparation and administration are solid compositions, particularly tablets and hard-filled or liquid-filled capsules. Oral administration of the compounds is preferred.
These active compounds may also be administered parenterally or intraperitoneally. Solutions or suspensions of these active compounds as a free base or pharmacologically acceptable salt can be prepared in glycerol, liquid, polyethylene glycols and mixtures thereof in oils. Under ordinary conditions of storage and use, these preparations contain a preservative to prevent the growth of microorganisms.
The pharmaceutical forms suitable for injectable use include sterile aqueous solutions or dispersions and sterile powders for the extemporaneous preparation of sterile injectable solutions or dispersions. In all cases, the form must be sterile and must be fluid to the extent that easy syringability exists. It must be stable under the conditions of manufacture and storage and must be preserve against the contaminating action of micoorganisms such as bacterial and fungi. The carrier can be a solvent or dispersion medium containing, for example, water, ethanol, polyol (e.g., glycerol, propylene glycol and liquid polyethylene glycol), suitable mixtures thereof, and vegetable oil.
The invention will be more fully described in conjunction with the following specific examples which are not be construed as limiting the scope of the invention.
EXAMPLE 1
[4S-(4alpha,12aalpha)]-9-[(Chloroacetyl)amino]-4,7-bis(dimethylamino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,12,12a-tetrahydroxy-1,11-dioxo-2-naphthacenecarboxamide dihydrochloride
To a room temperature solution of 0.334 g of 9-amino-4,7-bis(dimethyamino)-6-demethyl-6-deoxytetracycline disulfate, 6 ml of 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone, hereinafter called DMPU, and 2 ml of acetonitrile is added 0.318 g of sodium carbonate. The mixture is stirred for 5 minutes followed by the addition of 0.068 g of chloroacetyl chloride. The reaction is stirred for 30 minutes, filtered, and the filtrate added dropwise to 100 ml of diethyl ether, containing 1 ml of 1M hydrochloric acid in diethyl ether. The resulting solid is collected and dried to give 0.340 g of the desired intermediate. MS (FAB): m/z 549 (M+H) .
EXAMPLE 2
[4S-(4alpha,12aalpha)]-9-[(Bromoacetyl)amino]-4,7-bis(dimethylamino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,12,12a-tetrahydroxy-1,11-dioxo-2-naphthacenecarboxamide monohydrobromide
The title compound is prepared by the procedure of Example 1, using 6.68 g of 9-amino-4,7-bis(dimethylamino)-6-demethyl-6-deoxytetracycline disulfate, 50 ml of DMPU, 30 ml of acetonitrile, 6.68 g of sodium carbonate and 0.215 g of bromoacetyl bromide. 5.72 g of the desired intermediate is obtained. MS (FAB): m/z 593 (M+H).
EXAMPLE 3
[4S-(4alpha,12aalpha)]-9-[(2-Bromo-1-oxopropyl)amino]-4,7-bis(dimethylamino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,12,12a-tetrahydroxy-1,11-dioxo-2-naphthacenecarboxamide sulfate
The title compound is prepared by the procedure of Example 1, using 1.00 g of 9-amino-4,7-bis(dimethylamino)-6-demethyl-6-deoxytetracycline disulfate, 1.0 g of sodium carbonate and 0.648 g of 2-bromopropionyl bromide to give 0.981 g of the desired product. MS(FAB): m/z 607 (M+H).
EXAMPLE 4
[4S-(4alpha,12aalpha)]-9-[(4-Bromo-1-oxobutyl)amino]-4,7-bis(dimethylamino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,12,12a-tetrahydroxy-1,11-dioxo-2-naphthacenecarboxamide dihydrochloride
The title compound is prepared by the procedure of Example 1, using 1.34 g of 9-amino-4,7-bis(dimethylamino)-6-demethyl-6-deoxytetracycline disulfate, 1.3 of sodium carbonate, 24 ml of DMPU, 8 ml of acetonitrile and 0.389 g of 4-bromobutyryl chloride to give 1.45 g of the desired product.
EXAMPLE 5
[7S-(7alpha,10aalpha)]-N-[9-(Aminocarbonyl)-4,7-bis(dimethylamino)-5,5a,6,7,10,10a,12-octahydro-1,8,10a,11-tetrahydroxy-10,12-dioxo-2-naphthacenyl]-1-trifluoroacetyl)-2-pyrrolidinecarboxamide dihydrochloride
The title compound is prepared by the procedure of Example 1, using 0.334 g of 9-amino-4,7-bis(dimethylamino)-6-demethyl-6-deoxytetracycline disulfate, 10 ml of DMPU, 2 ml of acetonitrile, 0.34 g of sodium carbonate and 7.5 ml of 0.1M (S)-(-)-N-(trifluoroacetyl)prolyl chloride to give 0.292 g of the desired product. MS(FAB): m/z 666 (M+H).
EXAMPLE 6
[4S-(4alpha,12aalpha)]-9-[[[(Cyclopropylmethyl)amino]acetyl]amino]-4,7-bis(dimethylamino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,12,12a-tetrahydroxy-1,11-dioxo-2-naphthacenecarboxamide dihydrochloride
A mixture of 0.20 g of product from Example 2, 0.50 g of (aminomethyl)cyclopropane and 5 ml of DMPU, under Argon, is stirred at room temperature for 1 hour. The excess amine is removed in vacuo and the residue diluted with a small volume of methyl alcohol. The diluted reaction solution is added dropwise to a misture of diethyl ether and 5 ml of 2-propanol. 1M Hydrochloric acid in diethyl ether is added until a solid is formed. The resulting solid is collected and dried to give 0.175 g of the desired product. MS (FAB): m/z 584 (M+H) .
Substantially following the methods described in detail herein above in Example 6, the compounds of this invention listed below in Examples 7-16 are prepared.
__________________________________________________________________________Example Starting Material MS (FAB):# Name Prod. of Exp. Reactant Rx Time m/z__________________________________________________________________________ 7 [4S-(4alpha,12aalpha)]-9-[[[(2,2- 2 or 1 2,2-Diethoxy- 3 hrs. 646 (M + H)Diethoxyethyl)amino]acetyl]amino]-4,7- ethylaminebis(dimethylamino)-1,4,4a,5,5a,6,11,-12a-octahydro-3,10,12,12a-tetrahydroxy-1,11-dioxo-2-naphthacenecarboxamidedihydrochloride 8 [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- 2 or 1 2-Methoxy- 2 hr. 588 (M + H)amino)-1,4,4a,5,5a,6,11,12a-octahydro- ethylamine3,10,12,12a-tetrahydroxy-9-[[[2-(methoxy-ethyl)amino]acetyl]amino]-1,11-dioxo-2-naphthacenecarboxamide dihydrochloride 9 [4S-(4alpha,12aalpha)]-4,7-Bis(di- 2 or 1 Allylamine 2 hr. 570 (M + H)methylamino)-1,4,4a,5,5a,6,11,12a-octa-hydro-3,10,12,12a-tetrahydroxy-1,11-dioxo-9-[[(2-propenylamino)acetyl]amino]-2-naphthacenecarboxamide dihydrochloride10 [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- 2 or 1 3-Methoxy- 2 hr. 602 (M + H)amino)-1,4,4a,5,5a,6,11,12a-octahydro- propylamine3,10,12,12a-tetrahydroxy-9-[[[(3-methoxy-propyl)amino]acetyl]amino]-1,11-dioxo-2-naphthacenecarboxamide dihydrochloride11 [7S-(7alpha,10aalpha)]-N-[9-(Aminocar- 2 Thiomorpholine 3 hr. 616 (M + H)bonyl)-4,7-bis(dimethylamino)-5,5a,6,6a,7,10,10a,12-octahydro-1,8,10a,11-tetra-hydroxy-10,12-dioxo-2-naphthacenyl]-4-thiomorpholineacetamide dihydrochloride12 [7S-(7alpha,10aalpha)]-N-[9-(Amino- 2 4-Methylpiperi- 2 hrs. 612 (M + H)carbonyl)-4,7-bis(dimethylamino)-5,5a,- dine6,6a,7,10,10a,12-octahydro-1,8,10a,11-tetrahydroxy-10,12-dioxo-2-naphthacenyl]-4-methyl-1-piperidineacetamidedihydrochloride13 [7S-(7alpha,10aalpha)]-N-[9-(Aminocar- 2 4-Methyl-1- 0.75 hr. 613 (M + H)bonyl)-4,7-bis(dimethylamino)-5,5a,6,- piperazine6a,7,10,10a,12-octahydro-1,8,10a,11-tetrahydroxy-10,12-dioxo-2-naphtha-cenyl]-4-methyl-1-piperazineacetamidedihydrochloride14 [4S-(4alpha,12aalpha)]-4,7-Bis(di- 2 N-Heptylamine 2 hr. 628 (M + H)methylamino)-9-[[(heptylamino)acetyl]amino]-1,4,4a,5,5a,6,11,12a-octahydro-3,10,12,12a-tetrahydroxy-1,11-dioxo-2-naphthacenecarboxamide dihydrochloride15 [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- 2 Undecylamine 3.5 hr. 684 (M + H)amino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,12,12a-tetrahydroxy-1,11-dioxo-9-[[(undecylamino)acetyl]amino]-2-naphthacenecarboxamide dihydrochloride16 [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- 2 2-(Aminomethyl) 1.5 hr. 621 (M + H)amino)-1,4,4a,5,5a,6,11,12a-octahydro- pyridine3,10,12,12a-tetrahydroxy-1,11-dioxo-9-[[[(2-pyridinylmethyl)amino]acetyl]amido]-2-naphthacenecarboxamide dihydrochloride__________________________________________________________________________
EXAMPLE 17
[4S-(4alpha,12aalpha)]-4,7-Bis(dimethylamino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,12,12a-tetrahydroxy-9-[[[(2-hydroxyethyl)amino]acetyl]amino]-1,11-dioxo-2-naphthacenecarboxamide monohydrochloride
To a solution of 0.10 g of product from Example 7A in 2 ml of 1,3-dimethyl-2-imidazolidinone is added 0.70 ml of 2-amino-1-ethanol. The solution is stirred at room temperature for 20 minutes, added to 100 ml of diethyl ether and the resulting precipitate collected to give 0.055 g of the desired product. MS (FAB): m/z 574 (M+H).
Substantially following the method described in detail hereinabove in Example 17, the compounds of this invention listed below in Examples 18-24 are prepared.
__________________________________________________________________________Example Starting Material MS (FAB):# Name Prod. of Exp. Reactant Rx Time m/z__________________________________________________________________________18 [4S-(4alpha,12aalpha)]-4,7-Bis(di- 7A 4-methylamino- 0.5 hrs. 588 (M + H)methylamino)-1,4,4a,5,5a,6,11,12a-octa- 1-butanolhydro-3,10,12,12a-tetrahydroxy-9-[[[(2-hydroxyethyl)methylamino]acetyl)amino-1,11-dioxo-2-naphthacenecarboxamide19 [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- 7A 4-amino-1- 0.5 hr. 602 (M + H)amino)-1,4,4a,5,5a,6,11,12a-octahydro- butanol3,10,12,12a-tetrahydroxy-9-[[[(4-(hydroxy-butyl)amino]acetyl]amino]-1,11-dioxo-2-naphthacenecarboxamide20 [4S-(4alpha,12aalpha)]-4,7-Bis(di- 7A 2,2,2-tri- 2 hr. 612 (M + H)methylamino)-1,4,4a,5,5a,6,11,12a-octa- fluoromethyl-hydro-3,10,12,12a-tetrahydroxy-1,11- aminedioxo-9-[[[2,2,2-trifluoroethyl)amino]-acetyl]-2-naphthacenecarboxamide21 [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- 7A 2-fluoro- 2 hr. 576 (M + H)amino)-9-[[[(2-fluoroethyl)amino]acetyl)- ethylamineamino]-1,4,4a,5,5a,6,11,12a-octahydro-3,10,12,12a-tetrahydroxy-1,11-dioxo-2-naphthacenecarboxamide22 [4S-(4alpha,12aalpha)]-4,7-Bis(dimethyl- 7A 1-(2-amino- 2 hr. 627 (M + H)amino)-1,4,4a,5,5a,6,11,12a-octahydro- ethyl)pyrro-3,10,12,12a-tetrahydroxy-1,11-dioxo-9- lidine[[[[2-(1-piperidinyl)ethyl]amino]acetyl]-amino]-2-naphthacenecarboxamide23 [4S-(4alpha,12aalpha))-4,7-Bis(di- 7A N-methylpro- 2 hrs. 581 (M + H)methylamino)-1,4,4a,5,5a,6,11,12a-octa- pargylaminehydro-3,10,12,12a-tetrahydroxy-9-[ [[methyl-2-propynylamino]acetyl]amino]-1,11-dioxo-2-naphthacenecarboxamide24 [4S-(4alpha,12aalpha)]-4,7-Bis(di- 7A 1-amino- 2 hrs. 613 (M + H)methylamino)-1,4,4a,5,5a,6,11,12a-octa- piperidinehydro-3,10,12,12a-tetrahydroxy-1,11-dioxo-9-[[(1-piperidinylamino)acetyl]-amino]-2-naphthacenecarboxamide__________________________________________________________________________
EXAMPLE 25
[4S-(4-alpha,12aalpha)]-4,7-Bis(dimethylamino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,12,12a-tetrahydroxy-1,11-dioxo-9-[[[(phenylmethoxy)amino]acetyl]amino]-2-naphthacenecarboxamide
To 0.50 g of O-benzylhydroxylamine and 2.5 ml of 1,3-dimethyl-2-imidazolidinone is added 0.80 g of sodium bicarbonate. The mixture is stirred at room temperature for 2 hours, filtered and the filtrate added to 0.10 g of product from 7A. The reaction solution is stirred at room temperature for 2 hours and then added to 100 ml of diethyl ether. The resulting precipitate is collected and dried to give 0.90 g of the desired product. MS(FAB): m/z 636 (M+H).
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The invention provides compounds of the formula: ##STR1## wherein R, R 3 , R 4 and W are defined in the specification. These compounds are useful as antibiotic agents.
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BACKGROUND OF THE INVENTION
1. Field of the Invention:
The present invention relates to a cap opening and closing mechanism which is attached to a discharge port portion of a container.
2. Description of the Related Art
As a cap which is fitted to a discharge port of a container in which a seasoning such as salt or pepper is filled, there is a type which has a structure for opening and closing a lid by a so-called push-and-push mechanism in view of the ease of use.
As shown in FIGS. 14 to 18, in a cap 300 of this type, a button 304 which is adapted to be pushed is provided on a side surface of a hollow cylindrical cap body 303 attached to a container 302.
A slide lever 308 is connected to a reverse surface of the button 304 by means of a thin-walled hinge 306 in such a manner as to be swingable with respect to the button 304. This slide lever 308 is passed through a housing 310 disposed in such a manner as to traverse the discharge port of the container 302, and reaches a rotatably supporting portion of a lid 314 which is rotatably attached to the cap body 303 by means of a rotating shaft 312.
An elongated hole 316 is formed in the slide lever 308 along a longitudinal direction thereof. A pin 313 provided at one end of a link lever 318 is swingably inserted in the elongated hole 316, so that the link lever 318 is movable while swinging. Further, the link lever 318 is urged toward the rotatably supporting portion of the lid 314 by means of a spring 320 which is held by the slide lever 308.
Meanwhile, an engaging recessed portion 322 is provided at the other end of the link lever 318. In a state in which the lid 314 is closed, the engaging recessed portion 322 is slidably engaged with a receiving portion 324 which is provided on the rotatably supporting portion of the lid 314 and projects from a lower side of the rotating shaft 312 toward the button 304. In addition, pressing surfaces 326, 328, and 330 against which a distal end of the slide lever 308 abuts in steps are formed on the reverse surface of the lid 314.
In such a structure of the cap 300, as shown in FIG. 15, in the state in which the lid 314 is closed, the distal end of the slide lever 308 is opposed to the pressing surface 326. At this time, the link lever 318 presses the receiving portion 324 by the urging force of the spring 320. Accordingly, counterclockwise angular moment is produced about the rotating shaft 312. Consequently, the lid 314 is maintained in the closed state, so that the lid 314 canny be opened inadvertently.
Next, if the button 304 is pushed, as shown in FIG. 16, the slide lever 308 first presses the pressing surface 328 and then presses the pressing surface 326 of the lid 314, thereby inclining the lid 314. Consequently, the receiving portion 324 rotates clockwise about the rotating shaft 312 such that a tip of the receiving portion 324 comes to be located at a position higher than that of the rotating shaft 312.
At this time, the link lever 318 moves along the elongated hole 316 against the urging force of the spring 320, and the engaging recessed portion 322 moves to a position higher than that of the distal end of the slide lever 308 while being guided by the receiving portion 324, thereby producing clockwise angular moment about the rotating shaft 312. As a result, even if the lid 314 is not completely opened by pushing the slide lever 308, the lid 314 is automatically opened to its completely open state.
Here, if the operator releases his or her finger from the button 304, as shown in FIG. 17, the slide lever 308 together with the button 304 moves in the direction of arrow A by the urging force of the spring 320, and the distal end of the slide lever 308 moves from the pressing surface 326 to the pressing surface 330 located below the rotating shaft 312. In addition, at this time, the link lever 318 presses the receiving portion 324, which has been moved to the position higher than the that of the rotating shaft 312, by the urging force of the spring 320, so that the lid 314 is maintained in the open state without rattling.
Next, if the button 304 is pushed, the slide lever 308 presses the pressing surface 330 located below the rotating shaft 312, so that counterclockwise angular moment is produced in the rotatably supporting portion of the lid 314, thereby closing the lid 314. A shown in FIG. 18, when the receiving portion 324 moves to the position below the rotating shaft 312 by the rotation of the lid 314, the link lever 318 pushes down the receiving portion 324 by the urging force of the spring 320, so that the lid 314 is automatically closed.
That is, in the structure of this cap, the closed or open state of the lid 314 can be maintained as the tip of the receiving portion 324 of the lid 314 which has been rotated about the rotating shaft 312 is pressed by the action of the link lever 318 supported rotatably and slidably by the slide lever 308. In addition, even if the lid 314 is not completely opened or closed by the slide lever 308, the lid 314 is automatically opened or closed from a predetermined position by the link lever 318 urged by the spring 320. However, in commodities which are premised on mass production as in the case of caps of containers, it is required that the number of component parts be small and the structure be simple in the light of assembly and production cost.
In addition, since the slide lever 308 for imparting the pressing force from the button 304 to the rotatably supporting portion of the lid 314 traverses the discharge port of the container 302, a fixed limitation is imposed on a discharge rate at the discharge port.
Further, with the conventional cap 300, since the ability of the lid to hermetically seal the container 302 is low, if the container 302 containing a liquid topples over, there are cases where the liquid leaks from the gap.
SUMMARY OF THE INVENTION
In view of the above-described facts, it is an object of the present invention to provide a cap opening and closing mechanism in which the number of component parts used is small, and whose lid can be opened and closed by the so-called push-and-push mechanism without adopting a structure in which the discharge port is traversed.
Another object of the present invention is to provide a cap opening and closing mechanism in which even if the container is toppled over with the lid closed, the liquid does not leak from the discharge port.
In accordance with the present invention, there is provided a cap opening and closing mechanism including a cap body attached to a discharge port portion of a container and having a pouring port through which a content of the container can be discharged, and a lid pivotally supported by the cap body and capable of opening and closing the pouring port, the cap comprising: a pushing member whose intermediate portion is pivotally supported by a pivotally supporting portion on a side surface of the cap body, the pushing member being swingable about the pivotally supporting portion; and connecting means for connecting an end portion of the pushing member and a rotatably supporting portion of the lid, the connecting means being adapted to convert swinging motion of the pushing member into motion for opening or closing the lid.
In the present invention, the cap body having an opening is attached to the discharge port portion of a container, and the opening can be opened or closed as the lid pivotally supported by the cap body is opened or closed.
The intermediate portion of the pushing member is pivotally supported at the pivotally supporting portion on a side surface of the cap body, and the pushing member is swingable about the pivotally supporting portion as an either end portion of the pushing member is pushed. One end of the pushing member is connected to an axially supporting portion of the lid by means of the connecting means.
Here, if one end portion of the pressing member is pushed, the pushing member swings about the axially supporting portion, and the connecting means, in turn, presses the axially supporting portion of the lid toward the inner side of the cap body. As a result, angular moment acting in the direction in which the lid is opened is produced about the axially supporting portion of the lid, thereby opening the lid.
Then, if the other end portion of the pressing member is pushed, the pushing member swings about the axially supporting portion, and the connecting means, in turn, pulls the axially supporting portion of the lid toward the outer side of the cap body. As a result, angular moment acting in the direction in which the lid is closed is produced about the axially supporting portion of the lid, thereby closing the lid.
Thus, as the connecting means for converting the swinging motion of the pushing member into motion for opening or closing the lid is provided on the axially supporting portion of the lid, it is possible to construct a lid opening/closing mechanism of a push-and-push type having a simple structure.
In addition, in the present invention, a slit is formed in a connecting portion between the coupling means and the pushing member so as to provide a spring hinge structure. Consequently, if the pushing member is swung, and even if the lid is not completely opened or closed, the lid is automatically opened or closed by the urging force of the spring hinge after the lid is opened or closed by a predetermined angle.
Further, in the present invention, locking means is provided at one end of the pushing member, and is capable of engaging in or disengaging from grooves formed in the cap body.
Accordingly, even if the pushing member is not continued to be pushed, the pushing member can be locked, so that the closed state of the cap can be maintained. Even if the spring hinge is not provided, the lid does not rattle.
The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description of the invention when read in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view illustrating a cap in accordance with a first embodiment;
FIG. 2 is an exploded perspective view illustrating the cap in accordance with the first embodiment;
FIG. 3 is a perspective view illustrating a locked state of a pushing member of the cap in accordance with the first embodiment;
FIG. 4 is a cross-sectional view illustrating the opening/closing operation of a lid of the cap in accordance with the first embodiment;
FIG. 5 is a cross-sectional view illustrating the opening/closing operation of the lid of the cap in accordance with the first embodiment;
FIG. 6 is a cross-sectional view illustrating the opening/closing operation of the lid of the cap in accordance with the first embodiment;
FIG. 7 is an exploded perspective view illustrating the cap in accordance with a second embodiment;
FIG. 8 is a cross-sectional view of the cap in accordance with the second embodiment when the lid is closed;
FIG. 9 is a cross-sectional view of the cap in accordance with the second embodiment when the lid is open;
FIG. 10 is an exploded perspective view of a cap in accordance with a third embodiment;
FIG. 11 is a cross-sectional view of the cap in accordance with the third embodiment when the lid is closed;
FIG. 12 is a cross-sectional view of the cap in accordance with the third embodiment when abutment between a third wall portion and a third projection is canceled;
FIG. 13 is a cross-sectional view of the cap in accordance with the third embodiment when the lid is open;
FIG. 14 is a perspective view illustrating a conventional cap;
FIG. 15 is a cross-sectional view illustrating the opening/closing operation of the conventional cap;
FIG. 16 is a cross-sectional view illustrating the opening/closing operation of the conventional cap;
FIG. 17 is a cross-sectional view illustrating the opening/closing operation of the conventional cap; and
FIG. 18 is a cross-sectional view illustrating the opening/closing operation of the conventional cap.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As shown in FIGS. 1 to 4, a cap 10 in accordance with a first embodiment has a hollow cylindrical cap body 16 which is attached to a discharge port portion of a container 12.
The discharge port portion of the container 12 is inserted in the cap body 16, and the content of the container 12 is discharged through a hollow cylindrical portion 20 which passes through and projects from the top surface 18 of the cap body 16. Incidentally, a hollow cylindrical insert 23 formed on a reverse surface of a lid 22, which will be described later, is inserted in the hollow cylindrical portion 20 when the lid 22 is closed.
Meanwhile, a part of the side surface portion i.e., a side wall, of the cap body 16 is recessed in a vertical direction to form an accommodating portion 24. Each of a pair of shafts 26 projects from the upper portion of a side wall 24A of this accommodating portion 24. Each of a pair of shaft holes 28, which is formed in a shaft body 30 protruding orthogonally from an outer peripheral portion of the circular lid 22, rotatably receives to the respective shaft 26. A recessed portion 30A is formed on an outer surface of the shaft body 30, and an upper end of a pushing member 34 is connected to a lower end thereof (on the lower side of the shaft holes 28) by means of a thin-walled hinge 32.
As shown in FIG. 1, two slits 60 are formed at an upper end of the pushing member 34 in such a manner that the thin-walled hinge 32 is provided between the slits 60. A remaining portion which is not cut out by the slits 60 is formed as a leaf spring 62, and is capable of exerting a deflecting urging force toward the inner side (see FIG. 5).
The pushing member 34 has the shape of a box with a hollow interior, and the top surface 37 is inclined from longitudinally opposite ends of the pushing member 34 toward its center in such a manner as to reduce the height of side walls 39. A pair of shafts 36 is respectively provided projectingly on central portions of both side walls 39. These shafts 36 are respectively inserted from below into a pair of elongated grooves 38 formed vertically in the side walls 24A of the accommodating portion 24. Consequently, the pushing member 34 is swingable about the shafts 36 which are pivotally supported in the respective elongated grooves 38.
In addition, a pair of projections 40, which are provided projectingly on lower end portions of the side walls 39 of the pushing member 34, is engaged in the elongated grooves 38 while inwardly deflecting the side walls 39, and can be disengaged from the elongated grooves 38. Consequently, when the lower side of the pushing member 34 is pushed, the projections 40 engage in the elongated grooves 38, thereby locking the pushing member 34.
Further, a rib 66 is formed inside the pushing member 34 at its longitudinal center, and abuts against a retaining piece 68 which juts diagonally upward from a lower end of the accommodating portion 24, so that the rotating shafts 36 are held so as to not be removed from the elongated grooves 38. In addition, a stopper 70 is provided projectingly on a lower end portion of the pushing member 34, and abuts against a bottom surface 24B of the accommodating portion 24, thereby restricting the swinging motion of the pushing member 34 within a fixed range.
Next, a description will be given of the operation of the cap in accordance with the above-described embodiment.
As shown in FIG. 4, in the state in which the lid 22 is closed, the lower end of the pushing member 34 is pushed toward the bottom surface 24B side, and the projections 40 are engaged in the elongated grooves 38, thereby locking the pushing member 34. In this state, since a force for pulling the lower end (the lower side of the shaft holes 28) of the shaft body 30 toward the outer side of the cap body 16 acts on the thin-walled hinge 32, angular moment in the direction in which the lid 22 is closed is produced about the rotating shafts 28 of the lid 22. For this reason, the lid 22 is maintained in its closed state.
Here, if the upper end of the pushing member 34 is pushed as shown in FIG. 5, the projections 40 are disengaged from the elongated grooves 38, thereby allowing the pushing member 34 to swing about the rotating shafts 36. Consequently, a force for pushing the lower end of the shaft body 30 toward the bottom surface 24B side acts on the thin-walled hinge 32, so that the lid 22 is opened gradually. At this time, the leaf spring 62 is deflected inwardly, and the thin-walled hinge 32 is pressed further toward the bottom surface 24B side by the spring force. For this reason, as shown in FIG. 6, angular moment in the direction of opening the lid 22 is produced about the shafts 28, and when the lid 22 is opened by a predetermined angle, the lid 22 is automatically opened. Here, as shown in FIG. 3, since the projections 40 abut against the outer edges of the accommodating portion 24, the swinging motion of the pushing member 34 is stopped in this state, and the lid 22 is locked in its open state.
Next, if the lower end of the pushing member 34 is pushed, the pushing member 34 swings about the shafts 36, and the projections 40 engage in the elongated grooves 38, thereby locking the pushing member 34. Through this operation, a force for pulling the lower end (the lower side of the shaft holes 28) of the shaft body 30 toward the outer side of the cap body 16 acts on the thin-walled hinge 32, thereby closing the lid 22. At this time, the amount of the pushing member 34 pushed in is restricted as the stopper 70 abuts against the side surface of the cap body 16.
Although, in this embodiment, the slits 60 are formed at the upper end of the pushing member 34 to constitute the leaf spring 62, the lid 22 can be opened and closed by the thin-walled hinge 32 alone.
Thus, in the present invention, the number of component parts is small, and the lid can be opened and closed by the so-called push-and-push mechanism without adopting the structure in which the discharge port is traversed.
FIGS. 7 to 9 show a cap 100 in accordance with a second embodiment of the present invention.
This cap 100 has a hollow cylindrical cap body 102 which is attached to a discharge port portion of an unillustrated container.
A pouring port 106 is formed, on a top surface 104 of the cap body 102, by an opening 108 and a hollow cylindrical body 110 projecting uprightly from the periphery of the opening 108. The content of the container is discharged from this pouring port 106.
A thin-walled flexible piece 112 having the shape of an inverted hollow truncated cone and narrowed down toward the interior of the cap body 102 from at an upper end of the hollow cylindrical body 110 is formed as a sealing means. As will be described later, when a hollow cylindrical insert 116 formed on a reverse surface of a lid 114 is inserted into the pouring port 106, an outer periphery of the insert 116 is sealed by the thin-walled flexible piece 112.
A portion of the side surface of the cap body 102 is recessed to form an accommodating portion 118. A pair of shafts 122 is provided projectingly on a pair of side walls 120 of the accommodating portion 118 at upper portions thereof, respectively.
A shaft body 124 protrudes downward from an outer peripheral portion of the lid 114. The shafts 122 are rotatably fitted in a pair of shaft holes 126 provided in the shaft body 124.
A wall portion 132 projects from the outside of the shaft holes 126 of the lid 114 toward shafts 130 of a pushing member 128 which will be described later. A corner of a distal end of the wall portion 132 is cut to form a taper 134. A wall portion 136 projects from the inside of the shaft holes 126 of the lid 114 in parallel with the wall portion 132. Two projecting walls 138 are formed in a vertical direction on an outer surface of the wall portion 136.
The pushing member 128 has the shape of a box with a hollow interior, and the top surface 128A is inclined from longitudinally opposite ends of the pushing member 128 toward its center in such a manner as to reduce the height of side walls 140. A pair of shafts 130 is respectively provided projectingly on central portions of both side walls 140. These shafts 130 are respectively inserted from below into a pair of elongated grooves 142 formed vertically in lower portions of the side walls 120 of the accommodating portion 118. Consequently, the pushing member 128 is swingable about the shafts 130 which are pivotally supported at the upper ends of the respective elongated grooves 142.
In addition, a pair of projections 144, which are provided projectingly on lower portions of the side walls 140 of the pushing member 128, are engaged in the elongated grooves 142 while inwardly deflecting the side walls 140, and can be disengaged from the elongated grooves 142. Consequently, when the lower portion of the pushing member 128 is pushed, the projections 144 engage in the elongated grooves 142, thereby locking the pushing member 128.
In addition, when the upper portion of the pushing member 128 is pushed and the pushing member 128 is set in the state shown in FIG. 9, the projections 144 are retained at the edges of the side walls 140, thereby locking the pushing member 128.
Further, a rib 146 is formed at the center of the interior of the pushing member 128, and is retained by a retaining piece 148 which juts diagonally upward from the lower end of the accommodating portion 118, so that the shafts 130 are held so as to not be removed from the elongated grooves 142. In addition, a stopper 150 reinforced by being provided with a cross section of a cruciform plate is provided projectingly above the rib 146. When the upper portion of the pushing member 128 is pushed, the stopper 150 abuts against the bottom surface 152 of the accommodating portion 118, thereby restricting the swinging motion of the pushing member 128 within a fixed range (see FIG. 9).
Meanwhile, when the lower portion of the pushing member 128 is pushed, the edge portion 158 of the cap body 102 side of the lower end of the pushing member 128 abuts against the lower end of the accommodating portion 118, thereby restricting the swinging motion of the pushing member 128 within a fixed range (see FIG. 8).
An elongated plate-like projection 154 projects upward from the upper end of the pushing member 128. In the state in which the lower portion of the pushing member 128 is pushed in, and the lid 114 is closed, the tip of the projection 154 abuts against the distal end of the wall portion 132.
In addition, a pair of projections 156 projects from vicinities of opposite ends of the projection 154 toward a side surface of the wall portion 136. In the state in which the lower portion of the pushing member 128 is pushed in, and the lid 114 is closed, the interval between the wall portion 136 and each projection 156 is set to be narrower than the interval between the projection 154 and each projecting wall 138. If the upper portion of the pushing member 128 is pushed to swing the pushing member 128, the abutment of the projection 154 against the wall portion 132 first canceled, and the projections 156 are brought into contact with the side surface of the wall portion 136.
Next, a description will be given of the operation of the cap 100 in accordance with this embodiment.
As shown in FIG. 8, in the state in which the lid 114 is closed, the projections 144 are engaged in the elongated grooves 142 and are locked.
At this time, the insert 116 formed on the reverse surface of the lid 114 is inserted in the pouring port 106. The insert 116 is inserted by expanding the diameter of the thin-walled flexible piece 112, and the thin-walled flexible piece 112 is brought into close contact with the periphery of the insert 116 and seals the same, so even if the container is toppled over, the liquid in the container does not leak from the pouring port 106.
If a force for the lid 114 in the opening direction acts on the lid 114, the wall portion 132 also tends to rotate correspondingly. Here, the distal end of the wall portion 132 abuts against the projection 154, and the force imparted to the pushing member 128 through the wall portion 132 is transmitted to the rib 146. Here, the rib 146 is retained by the retaining piece 148, and angular moment is not produced, so that the pushing member 128 does not swing. Accordingly, the wall portion 132 is locked by the projection 154 of the pushing member 128 which does not swing, with the result that the lid 114 naturally remains closed.
Here, if the upper portion of the pushing member 128 is pushed as shown in FIG. 9, the projections 144 are disengaged from the elongated grooves 142, and the pushing member 128 swings about the shafts 130. As a result of this swinging, the abutment of the projection 154 against the distal end of the wall portion 132 is canceled, and the projections 156 are brought into contact with the side surface of the wall portion 136.
If the upper portion of the pushing member 128 is further pushed, the projections 156 press the side surface of the wall portion 136, and produces angular moment centering around the shaft holes 126 in the lid 114 in the opening direction, thereby opening the lid 114. When the lid 114 is opened to a certain degree, the projections 156 are disengaged from the side surface of the wall portion 136, and the projection 154 presses the projecting walls 138 of the wall portion 136, thereby completely opening the lid 114.
It should be noted that the projecting walls 138 may not necessarily be provided, and are formed, as required, depending on the content filled in the container (in a case where it is sufficient for the lid 114 to be half-opened as in the case of a liquid).
In addition, as shown in FIG. 8, the projections 156 are more distant from the shaft holes 126 than the projection 154, so that the projections 156 produce large angular moment for opening the lid 114, and the operating force during an early period of lid opening is small. However, if the aspect of the operating force is not taken into consideration, the lid 114 may be opened by the projection 154 alone.
Here, when the lid 114 is fully opened, the stopper 150 abuts against the bottom surface 152, restricting the swinging range of the pushing member 128. In this state, the projections 144 are retained at the outer edges of the accommodating portion 118, thereby locking the pushing member 128. In addition, since the projecting walls 138 abut against the projection 154 at this time, the lid 114 is also locked in its open state.
Next, if the lower portion of the pushing member 128 is pushed, the pushing member 128 is swung about the shafts 130, and the projection 154 slides on the projecting walls 138 and is disengaged from the projecting walls 138, allowing the lid 114 to be rotated in the closing direction. Then, a corner of the projection 154 presses the taper 134 of the wall portion 132, and causes the lid 114 to produce angular moment in the closing direction, thereby closing the lid 114. Here, the projections 144 are engaged in the elongated grooves 142, thereby locking the pushing member 128.
Next, FIGS. 10 to 13 show a cap 200 in accordance with a third embodiment of the present invention.
In the same way as the cap 100 of the first embodiment, this cap 200 also has a cap body 202 which is attached to a discharge port portion of an unillustrated container. A pouring port 206, which is constituted by an opening 208 and a hollow cylindrical body 210, is formed on the top surface 204 of the cap body 202. In addition, a thin-walled flexible piece 212 is formed on the hollow cylindrical body 210 as a sealing means.
A pair of elongated grooves 242 is respectively formed in lower portions of a pair of opposing side walls 220 of an accommodating portion 218 recessed in a portion of a side surface of the cap body 202. A pair of shafts 230 projecting from both sides of a pushing member 228 is respectively inserted from below into the elongated grooves 242, thereby axially supporting the pushing member 228 swingably.
A rib 246 is formed at the center of the inside of the pushing member 228, and is retained by a retaining piece 248 located at a lower end of the accommodating portion 218, so as to hold the shafts 230 such that the shafts 230 do not come out from the elongated grooves 242.
The width of an upper portion of the accommodating portion 218 is narrow, and a pair of shafts 222 projects from side walls of this narrow-width portion in mutually opposing directions. A pair of shaft holes 226 is formed in a shaft body 224 which is provided on an inner peripheral portion of a circular lid 214. The shafts 222 are respectively fitted to the shaft holes 226 so as to pivotally support the lid 214. A wall portion 258 is formed on an outer surface of the shaft body 224 in such a manner as to extend toward the shafts 230 of the pushing member 228. An upper end of a pushing member 228 is connected to a lower end of the wall portion 258 (on the outer side of the shaft holes 226) by means of a thin-walled hinge 260. In addition, distal ends on both sides of a lower end portion of the wall portion 258 respectively abut against upper ends of a pair of projections 262 which will be described later.
As shown in FIG. 10, two slits 264 are formed in an upper end surface of the pushing member 228 in such a manner that the thin-walled hinge 260 is provided between the slits 264. A remaining portion which is not cut out by the slits 264 is formed as a leaf spring 266, and is capable of exerting a deflecting urging force. Instead of the slits 264, if these portions are formed as thin-walled portions, the portion formed between the thin-walled portions is capable of serving as a leaf spring. The pair of projections 262 is respectively formed on the outer sides of the slits 264 in such a manner as to project upward. In the state in which the lower portion of the pushing member 228 is pushed in and the lid 214 is closed, the tips of the projections 262 abut against the wall portion 258 (see FIG. 11).
Next, a description will be given of the operation of the cap 200 in accordance with the third embodiment.
As shown in FIG. 11, in the state in which the lid 214 is closed, an insert 216 on the reverse surface of the lid 214 is inserted in the pouring port 206 in the same way as in the first embodiment. Since the thin-walled flexible piece 212 is brought into close contact with the periphery of the insert 216 and seals the same, even if the container is toppled over, the liquid in the container does not leak from the pouring port 206.
If a force for the lid 214 in the opening direction acts on the lid 214, the wall portion 258 also tends to rotate correspondingly. Here, the distal end of the wall portion 258 abuts against the projections 262, and the force imparted to the pushing member 228 through the wall portion 258 is transmitted to the rib 246. Here, the rib 246 is retained by the retaining piece 248, and angular moment is not produced, so that the pushing member 228 does not swing. Accordingly, the wall portion 258 is locked by the projections 262 of the pushing member 228 which does not swing, with the result that the lid 214 naturally remains closed.
Here, if the upper portion of the pushing member 228 is pushed as shown in FIG. 12, the pushing member 228 is swung about the shafts 230, and the state of abutment between the distal end of the wall portion 258 and the tips of the projections 262 is canceled, thereby rendering the lid 214 rotatable. If the upper portion of the pushing member 228 is further pushed, as shown in FIG. 13, the thin-walled hinge 260 pulls the lower end of the shaft body 224 toward the bottom surface 252 side of the accommodating portion 218, thereby allowing the lid 214 to be opened gradually. At this time, the leaf spring 266 is deflected toward the outer side, and angular moment in the direction of opening the lid 214 is produced about the shafts 222 due to the urging force of the leaf spring 266. Consequently, when the lid 214 is opened by a predetermined angle, the lid 214 is opened automatically.
Next, if the lower portion of the pushing member 228 is pushed, the pushing member 228 is swung about the shafts 230, and corners of the projections 262 press the wall portion 258 and cause angular moment to be produced in the lid 214 in the closing direction, thereby closing the lid 214.
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A cap includes a cap body attached to a discharge port portion of a container and having a pouring port through which a content of the container can be discharged, and a lid pivotally supported by the cap body and capable of opening and closing the pouring port. The cap is provided with: a pushing member whose intermediate portion is pivotally supported by a pivotally supporting portion on a side surface of the cap body, the pushing member being swingable about the pivotally supporting portion; and a thin-walled hinge for connecting an end portion of the pushing member and a rotatably supporting portion of the lid, the thin-walled hinge being adapted to convert swinging motion of the pushing member into motion for opening or closing the lid as an upper portion or a lower portion of the pushing member is operated by being pushed.
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CROSS REFERENCE TO RELATED APPLICATIONS
The present application is a national stage application under 35 U.S.C. 371 of International Application No. PCT/CA2008/000522 filed Mar. 19, 2008, the contents of which are hereby incorporated by reference into the present disclosure.
FIELD OF THE INVENTION
The present invention relates to micromanipulation, automation, computer vision, and microrobotics, and more specifically to a system and method for micromanipulating samples, such as microorganisms and cells.
BACKGROUND OF THE INVENTION
The micromanipulation of microorganisms, including unicellular and multicellular microorganisms and cells permits the insertion of foreign materials into individual cells for genetic manipulation, cellular response quantification, or intracellular structure imaging. Possessing many advantages, mechanical cell injection is highly effective for delivering macromolecules and is free from concerns about phenotype alteration.
As cell injection is a labor intensive task, efforts for automating cell injection have been continuous. The vast majority of these systems were developed to facilitate the handling of mouse/Drosophila/zebrafish embryos/oocytes for genetics and reproduction applications (See Y. Sun and B. J. Nelson, “Biological cell injection using an autonomous microrobotic system,” Int. J. Robot. Res., Vol. 21, No. 10-11, pp. 861-868, 2002; L. Mattos, E. Grant, R. Thresher, and K. Kluckman, “New developments towards automated blastocyst microinjections,” in Proc. IEEE International Conference on Robotics and Automation (ICRA'2007), 2007; R. Kumar, A. Kapoor, and R. H. Taylor, “Preliminary experiments in robot/human cooperative microinjection,” Proc. IEEE International Conf on Intelligent Robots and Systems, pp. 3186-3191, Las Vegas, 2003; and H. Matsuoka, T. Komazaki, Y. Mukai, M. Shibusawa, H. Akane, A. Chaki, N. Uetake, and M. Saito, “High throughput easy microinjection with a single-cell manipulation supporting robot,” J. of Biotechnology , Vol. 116, pp. 185-194, 2005; W. H. Wang, X. Y. Liu, D. Gelinas, B. Ciruna, and Y. Sun, “A fully automated robotic system for microinjection of zebrafish embryos,” PLoS ONE, vol. 2, no. 9, p. e862, September 2007; and S. Zappe, M. Fish, M. P. Scott, and O. Solgaard, “Automated MEMS-based drosophila embryo injection system for high-throughput RNAi screens,” Lap Chip, Vol. 6, pp. 1012-1019, 2006).
In microrobotic injection of suspended cells (e.g., embryos/oocytes), cells must be immobilized, preferably into a regular pattern to minimize cell searching and switching tasks and increase injection speed. Differently, most mammalian cells (e.g., HeLa cells, fibroblasts, and endothelial cells) adhere to the bottom surface of a culture dish/plate during in vitro culture into an irregular pattern. Although adherent cells do not require immobilization efforts, they are highly irregular in morphology, which makes robust pattern recognition difficult and full automation challenging. Additionally, they are only a few micrometers thick, posing more stringent requirements in microrobotic positioning. The small thickness and large variations require precise determination of relative vertical positions between the micromanipulating device and the cell.
A microinjection system for microinjecting adherent cells is disclosed in Lukkari et al (Proc. 2005 IEEE International Symposium on Computational Intelligence in Robotics and Automation). The micromanipulator of the system, however, is a joystick-controlled semi-automatic device that necessitates an operator to control movement of an injecting device and the microinjection of the cells. Hence, the semi-automatic system of this disclosure is immune to operator proficiency variations and from human fatigue.
Currently, no automated, high-throughput adherent cell micromanipulation systems are known. Such automated systems can serve as an important tool in the biotech industry and will have significant implications in molecule testing and the creation of stem cell lines for individualized stem cell-based therapy.
In view of the foregoing, what is needed is a system and method for cellular micromanipulation that overcomes the limitations of the prior art, such that the system and method is capable of automation, provides robustness, high-throughput (including sample positioning), high success rates, and high reproducibility.
SUMMARY OF THE INVENTION
Briefly described, one aspect of the present invention is a method for micromanipulation of a plurality of samples, said method comprising: providing a system for micromanipulating samples, the system including: a microscopic means, a micromanipulating means having a tip, a positioning device to control motion of the tip and means for determining a shortest path along the plurality of samples, determining a home point for the tip, establishing a shortest path along the plurality of samples, and moving the tip by means of the positioning device from the home point to the samples and micromanipulating the samples in sequence along the shortest path.
In another aspect, the method of the present invention further comprises selecting destination targets in the plurality of samples and micromanipulating the plurality of samples in sequence along the shortest path at the destination targets.
One aspect of the present invention is a system for the micromanipulation of samples in a container, the system comprising: a positioning device operable to control motion of a tip of a micromanipulating means, a microscopic means and a means for generating the shortest path along the samples, wherein the system is operable to micromanipulate the samples in sequence along the shortest path.
In one aspect of the present invention, the system further comprising a pattern recognition means to select a destination target within the samples, wherein the system is operable to micromanipulate the samples at the destination target in sequence along the shortest path.
The present invention overcomes the problems of poor reproducibility, human fatigue, and low throughput inherent with traditional manual adherent cell micromanipulation techniques. Advantages of the present invention also include automating sample micromanipulation high reproducibility, and genuine high-throughput biological research.
BRIEF DESCRIPTION OF THE DRAWINGS
A detailed description of the preferred embodiments is provided herein below by way of example only and with reference to the following drawings, in which:
FIG. 1 illustrates a schematic diagram of components of the automated adherent cell injection system.
FIG. 2 illustrates an example system setup.
FIG. 3 illustrates coordinate frames in the present invention.
FIG. 4 illustrates an image projection model relating camera/image frames.
FIG. 5 illustrates micropipette motion pattern for injecting each adherent cell.
FIG. 6 illustrates 3-D profile of endothelial cells. Reconstructed from a stack of confocal fluorescence images.
FIG. 7 illustrates an example showing the shortest injection path for the system to inject a number of cells. Each deposition destination represents a node.
FIG. 8 illustrates automatic injection control flow.
FIG. 9 illustrates a micropipette moving in the image plane.
FIG. 10 illustrates contact between micropipette tip and bottom surface of a cell dish.
FIG. 11 illustrates alternative injection control flow with an on-line pixel size calibration step.
FIG. 12 illustrates an example showing nucleoli cell recognition.
FIG. 13 illustrates an example showing cells microinjected with fluorescent dyes.
In the drawings, one embodiment of the invention is illustrated by way of example. It is to be expressly understood that the description and drawings are only for the purpose of illustration and as an aid to understanding, and are not intended as a definition of the limits of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The system and methods of the present invention are designed for the micromanipulation of samples.
The term “samples” as used herein refers to any object suited for micromanipulation. Without limitation, samples include unicellular and multicellular microorganisms, cells (animal and plant cells), and bacteria.
The term “micromanipulation” as used herein includes, without limitation, microinjection of a substance or material into a sample, aspiration or withdrawal of substances or materials from a sample, sample isolation and electrophysiological (electrical) measurements.
With reference to FIG. 1 , a system in accordance with one aspect of the present invention includes a microscopic means 3 , micromanipulating means 8 having a tip, a positioning device 2 to control motion of the tip and means for determining a shortest path along the plurality of samples.
In one aspect of the present invention, a positioning control device 14 is included to physically provide control signals to the positioning device 2 .
The micromanipulating means 8 can be embodied as an injection micropipette 8 (glass capillary or microfabricated needle) attached to the positioning device 2 . For microinjecting embodiments, the tip of the micropipette 8 is within 1 μm in outer diameter.
The microscopic means 3 can be embodied as an inverted optical microscope 3 .
In another aspect, the system of the invention may further comprise:
a) Utilities running on a computer 12 for motion control and image processing. The utilities include, without limitation, an interactive control program interface. Motion control may be provided by a control utility, provided in a manner that is known, to enable the control functions described herein. Image processing may be provided by means of an image processing means or utility, also provided in a mariner that is known, to enable image processing in support of the control functions as described herein. The image processing utility, in one implementation, is linked to the camera described below and is thereby operable to capture an image corresponding to the field of view of the microscope means, and enables a user by operation of the computer to interact with one or more resulting images for the purpose of optionally manually selecting target(s); reviewing the results of automatic target selection as described; and optionally manually adjusting the target(s) selected. The image processing utility is linked to or includes the pattern recognition means so as to enable automatic target selection as described.
In addition, the control utility and the image processing utility are linked so as to enable the control utility to utilize images captured by operation of the image processing utility for example for the purpose of determining the shortest path between selected targets or between the samples (for example), and then displaying an image that includes the results of the determination of the shortest path, as shown in FIG. 7 .
b) A positioning means 1 , such as a multi-DOF motorized positioning stage or microrobots that control the motion of a sample container.
c) A sample container 7 placed on positioning means 1 . Sample container 7 can be embodied as a Petri dish, glass slide, PDMS device, or containers made of other transparent, biocompatible materials with a uniform and flat bottom surface. Sample container 7 may contain one or a plurality of samples.
d) A computer-controlled pressure unit 11 .
e) A vibration isolation table 15 to minimize vibration.
f) A CCD/CMOS camera 4 mounted on the microscopic means 3 .
FIG. 2 shows an example system setup. Although this particular configuration of the system relates to the microinjection of material into endothelial cells, it should be expressly understood that this is an illustrative example only and the present invention is directly applicable for the automated micromanipulation of samples as would be recognized and understood by a person of skill in the art.
The coordinate frames of the system used in FIG. 3 and FIG. 4 are summarized in Table 1.
TABLE 1
Coordinate frames (FIG. 3 and FIG. 4) of the system.
Symbol
Coordinate frame
e
End-effector coordinate frame X e -Y e -Z e attached to
positioner 2 (micromanipulating means 8 as the end-
effector)
t
Target coordinate frame X t -Y t -Z t attached to
positioner 1 that controls the motion of cells
c
Camera coordinate frame X c -Y c -Z c
i
Coordinate frame x i -y i (or x-y) for the image plane
A point P=(x, y, z) in the camera frame X c -Y c -Z c is mapped to a point p=(u,v) in the image plane x-y via
[ s x 0 0 s y ] [ u v ] = [ x y ]
where s x and s y are fixed scale factors or pixel size in x-axis (s x ) and y-axis (s y ) respectively that can be either calibrated off-line manually or on-line automatically as discussed later. They will be referred to as s thereafter.
Overall Micromanipulation Method
A method for the micromanipulation of a plurality of samples according to the present invention includes:
(a) providing a microscopic means 3 , a micromanipulating means 8 having a tip, a positioning device 2 to control motion of the tip and means for determining a shortest path along the plurality of samples; (b) determining a home point for the tip; (c) establishing a shortest path along the plurality of samples; and
moving the tip by means of the positioning device 2 from the home point to the samples and micromanipulating the samples in sequence along the shortest path.
Although the aspect of the method described in this section relates to the microinjection of material into endothelial cells, it should be expressly understood that the present invention is directly applicable for the micromanipulation of samples as would be recognized and understood by a person of skill in the art.
A large number of endothelial cells are seeded on the surface of cell container 7 . The cells in the container 7 are brought into focus, for example using a known auto-focusing algorithm, and viewed with the microscopic means. The vertical position of the micropipette 8 tip is viewed, for example with a vision-based contact detection algorithm. Destination targets within the cells under the field of view (“cell segment”) are recognized through pattern or cell recognition means and selected. A shortest injection path is generated based on the destination targets. Along the shortest path, the micropipette tip penetrates the membrane of each target cell and deposits a pre-specified amount of any material of interest into all the target cells sequentially at approximately the destination target. Upon the completion of injecting all the cells within the cell segment, the next cell segment is then brought into the field of view. The cells are recognized, the shortest path is generated, and injection process is repeated for all segments on the cell container.
Micropipette Motion Control Sequence for Infecting Each Cell
As shown in FIG. 5 , the micropipette 8 tip moves along its diagonal direction. The motion sequence of the micropipette 8 for injecting a cell is as follows:
1. Move micropipette 8 to home point A simultaneously in X e -Y e plane with positioner 2 . 2. Penetrate the cell membrane and move to the destination target B in nucleus along its diagonal direction. Upon reaching destination target B, a pre-specified amount of genetic materials is deposited by the computer-controlled pressure unit 11 . 3. Retreat from destination target B along its diagonal direction back to home point A.
The deposition destination or destination target can be, without limitation, inside the cell, such as in the nucleus or cytoplasm or on the cell membrane. The present invention allows for precise, highly reproducible micromanipulation of cells at either nucleus or cytoplasm or other cytoplasmic organelles.
For a given cell type, its height can be measured by measuring means such as by confocal imaging. Referring to FIG. 6 , the endothelial cells used in this embodiment range from 3.8 to 5.5 μm in height. Thus, in this example the home point A may be defined as 8 μm above the container surface, while destination target B is defined as 2 μm above the container surface. Points A and B are collinear with the micropipette diagonal axis and have a distance of octan(α)μm along the X e axis, where α is the tilting angle of the micropipette with respect to the container surface. X e -coordinate of home point A=[X e -coordinate of destination target B+octan(α)]μm, Y e -coordinate of home point A=Y e -coordinate of destination target B.
Shortest Injection Path
The cell recognition results provide destination targets B for each cell, producing an array of destination points with x- and y-coordinates in the image plane. Coordinates in the image plane are on-line transformed to X e - and Y e -coordinates according to the defined coordinate frames. Including the initial position of the micropipette, a shortest injection path is generated, such as using the classical traveling salesman algorithm (See D. L. Applegate, R. E. Bixby, V. Chvtal, and W. J. Cook, “The traveling salesman problem: A computational study.” Princeton University Press, 2006). As shown in FIG. 7 , the injection sequence can either be clockwise or counter-clockwise.
If desired, the destination points can be alternatively specified manually by an operator through interactive input (e.g., through computer mouse clicking).
Injection Control Flow
The control flow of automated adherent cell injection is described in FIG. 8 .
Cell Auto-Focusing 701 :
Prior to injection, the cells need to be brought into focus. Movement of cells in the container are controlled by positioner 1 upwards (or downwards) through a certain distance (e.g., 20 μm) to cross the focal plane. An autofocusing algorithm (e.g., Tenenbaum gradient) is used to locate the focal plane by constantly calculating the focus measure for each frame of image. The cells are moved to the focal plane that corresponds to the maximum (or minimum) focus measure. Depending on the unevenness of the container surface (commercial Petri dishes commonly used in a biology laboratory is found to often vary by 1-2 μm even within a small neighbourhood), this auto-focusing step 701 may need to be repeated for each cell segment.
Identification of Micropipette Tip ROI (Region of Interest) 702 .
This step is to locate the tip of the micropipette 8 for use in contact detection 703 . The micropipette 8 controlled by positioner 2 moves only along the Y e direction. The moving micropipette that stands out in the image subtracted from the background is recognized (i.e., a region of interest 81 around the tip of the micropipette, shown in FIG. 9 is identified). Upon identification, the coordinates of the tip both in the image plane x-y and in the end-effector frame X e -Y e -Z e are determined. The x-coordinate and y-coordinate in the image plane x-y, X e -coordinate and Y e -coordinate in the end-effector frame X e -Y e -Z e are taken as the lateral components of the home position of the micropipette tip.
Contact Detection 703 Using Computer Vision Feedback:
This step is to automatically align the tip of the micropipette 8 with the destination target B in the vertical direction. In this procedure, the top surface of the cell holding device 7 where the cells are seeded serves as the reference plane. The micropipette 8 moves only along the Z e direction. Upon the establishment of the contact between the micropipette tip and the top surface, further vertical motion of the micropipette tip along the Z e direction results in lateral movement along the X e direction. As shown in FIG. 10 , the micropipette tip is located at point a (initial contact) and b (after contact) in the surface plane. Before and after contact, the micropipette tip changes its x coordinate in the image plane x-y vs. time (i.e., image frame number), resulting in a V-shaped curve. The peak of the V-shaped curve represents the contact position along the vertical direction between the micropipette tip and the top surface of device 7 .
The Z e -coordinate of the home position of the micropipette 8 tip is determined by moving upwards with respect to the contact position by more than the cell height, i.e., 8 μm for endothelial cells.
Upon the completion of 702 and 703 , the home position of the micropipette tip both in the x-y image plane and the X e -Y e -Z e frame has been automatically determined and will be fixed for use in the following procedures of injecting all cells within the segment.
Moving to the Home Position 704 .
After 702 and 703 , positioner 2 following a position control law (e.g., PID) moves the micropipette 8 tip upwards to its home position determined in 702 and 703 from the vertical contact position in order to prevent the micropipette 8 from crashing with cells in between injections.
Cell Recognition 705 :
The task of this step is to identify cell structures or targets (i.e., nucleus 41 and cytoplasm 42 ). The cell recognition steps are summarized in Table 2. The identification of targets within the cells may be done manually or automatically.
TABLE 2
Cell recognition 705.
Step #
Processing
1
Nucleolus 40 recognition
2
Nucleus 41 recognition
3
Cytoplasm 42 recognition
An example recognition process can be as follows:
(1) Nucleolus 40 recognition. A gray-level template containing a single nucleus is used to locate all nucleoli in the image of the current cell segment, using a template matching method.
(2) Nucleus 41 recognition. All recognized nuclei are clustered with each cluster containing a single nucleus or two nuclei. Circumscribing a cluster, a circle is virtually specified as the initial points for ‘snakes’, which form a closed curve representing the contour of nucleus envelope. The centroid of the contour is recognized as the nucleus center B.
(3) Cytoplasm 42 recognition. In between nucleus contours is cytoplasm, from which deposition destinations beyond nucleus can be selected.
Another example recognition process can be as follows:
Nucleoli 40 recognition. With reference to FIG. 12 , an original image is normalized to make all pixels in the image have an intensity between 0 and 255 in order to increase image contrast. Based on the normalized image, for the fixed configuration, two thresholds, T 1 and T 2 , are specified to distinguish the light surface and dark shadow regions of nucleoli. Pixels with an intensity>T 1 are classified as the light surface regions, and neighbouring pixels with intensity<T 2 in one particular direction of the light surface regions are classified as the dark shadow regions.
The pairs of light and dark regions are then considered to be candidate nucleoli, which are checked against a set of criteria before being identified as nucleoli, as outlined in FIG. 9 b . These criteria include:
The area is large enough but not too large (i.e., 80<Area<500, measured in pixels).
The smallest distance in the x or y direction is no smaller than one tenth of the largest distance in the opposite direction.
The dark shadow is in the right direction with respect to the light region within a tolerance.
The dark and light regions are about the same size within a factor of 2.
The dark region is not simply a vertical or horizontal line (which would indicate a ridge).
The candidate nucleolus does not have more than 5 neighboring candidate nucleoli.
Based on the recognized nucleoli, Delaunay triangulation (Mark de Berg, Marc van Kreveld, Mark Overmars, and Otfried Schwarzkopf, Computational Geometry, 2nd edition, Springer-Verlag. 2000) is used to find close nucleoli which stays inside one nucleus. A virtual circle centered at the centroid of the nucleoli with radius of 100 pixels is constructed as the initial curve for ‘snakes’, which will form a closed curve that represents the contour of nucleus.
For selecting a destination target inside the nucleus: For the nuclei containing more than one nucleolus, the centroid of the nucleoli can be selected as the destination target in nucleus to minimize diffusion paths. For nuclei containing only one nucleolus, the centroid of the nucleus can be selected as the deposition destination. The ‘+’s in FIG. 12 represent a set of selected destinations.
For selecting a destination target outside nucleus, in cytoplasm: A point 10-20 pixels away from the nucleus contour can be selected as the deposition destination.
Generating Shortest Injection Path 706 :
x- and y-coordinates of the micropipette 8 tip and all the nuclear centers of the recognized cells in the cell segment are input to the traveling salesman problem algorithm to generate a shortest injection path, along which sequential injection is conducted. Each cell is injected according to the procedures 7071 - 7074 .
Moving the Micropipette Tip to Ready Point 7071 :
From its resting position, the micropipette 8 is moved by positioner 2 to the home point A by a position control law (e.g., PID).
Entry into the Cell 7072 :
The micropipette tip is controlled to start from the home point A to reach the destination point B by a position control law at an appropriate speed without causing cell lysis.
Material Deposition 7073 :
Based on a desired deposition volume, the micropipette tip size (inner diameter) and specified injection pressure level determine the positive pressure pulse length (i.e., pressure ‘on’ time). Injection pressure is maintained high for the determined time period through the computer-controlled pressure unit 11 , precisely depositing a desired volume of materials at the destination point B.
Exiting from the Cell 7074 :
Controlled by positioner 2 , the micropipette 8 is retracted out of the cell by a position control law at an appropriate speed that does not cause cell lysis.
Repeating 7071 - 7072 - 7073 - 7074 to inject each cell in the whole cell segment in sequence along the shortest path.
After injecting one cell segment, the next segment is brought into the field of view. The system repeats injection according to 705 - 706 - 7071 - 7072 - 7073 - 7074 .
Moving the Next Cell Segment into the Field of View 708 :
This step brings the next cell segment into the field of view (the image plane x-y). Positioner 1 moves the cell container by traveling fixed relative displacements along x t and Y t .
An Alternative Injection Control Flow
The control flow described in FIG. 8 requires a prior knowledge of pixel size s that is obtained through off-line pixel size calibration. The pixel size s varies with different microscopy magnifications that are typically determined by microscope objectives, couplers, and the camera. In order to eliminate the magnification/hardware dependence, on-line calibration can be conducted with a visual tracking means to automatically determine the pixel size. The visual tracking means is best understood an aspect of the image processing utility described above that enables the visual markers indicating targets for micromanipulation and/or shortest path information to be visible to a user regardless of different microscopy magnifications by adjusting the pixel size of the markers. Accordingly, the control flow is modified as shown in FIG. 11 .
On-Line Calibration of Pixel Size 710 :
After identification of the tip, the x- and y-coordinates of the tip in the image plane are determined. Before contact detection, positioning device 2 moves micropipette tip in X e -Y e plane by a known distance, e.g., 50 μm on both axes. During the course of motion, the tip is selected as the image feature for tracking and a visual tracking method (e.g., sum-squared-difference) is applied. Based on the visual tracking results (i.e., pixel displacement in the image plane x-y) and the travelling distance in the plane X e -Y e , the pixel size s is calibrated on line. The micropipette 8 tip is moved back to its initial position by the known distance on both axes.
It will be appreciated by those skilled in the art that other variations of the aspects of this invention may also be practised without departing from the scope of the invention.
The following non-limiting example is illustrative of the present invention:
EXAMPLE 1
A. Materials
The cells: porcine aortic endothelial cells, isolated from porcine aorta and cultured in cell medium (M199 medium, 5% calf serum, and 5% fetal bovine serum with a pH value of 7.4). Microrobotic injection was performed after 2 or 3 days of cell passage.
During system testing, fluorescent dyes (dextran, Texas Red, 70,000 MW, neutral, Invitrogen) mixed with PBS buffer.
The system, used in this example is the system shown in FIG. 2 , which employs a three-degrees-of-freedom microrobot (MP-285, Sutter) with a travel of 25 mm and a 0.04 μm positioning resolution along each axis. One motion control card (NI PCI-6289) is mounted on a host computer (3.0 GHz CPU, 1 GB memory) where control algorithms operate. Visual feedback is obtained through a CMOS camera (A601f, Basler) mounted on an inverted microscope (IX81, Olympus). A Polystyrene Petri dish (55 mm, Falcon) where the endothelial cells are seeded is placed on a motorized precision XYstage (ProScanII, Prior). A glass micropipette, heated and pulled using a micropipette puller (P-97, Sutter), is connected to the microrobot via a micropipette holder. The micropipette is tilted 45° C. with respect to the XY stage. A computer-controlled pico-injector (PLI-100, Harvard Apparatus) with a femto-liter resolution provides positive pressure for material deposition. All units except the host computer and pressure unit are placed on a vibration isolation table.
B. Results
The system injected a total of 1012 endothelial cells, demonstrating an operation speed of 25 cells/minute. Cytoplasm instead of nucleus was selected as injection destination target for each cell. The injected cells were inspected under a fluorescence microscope (IX81, Olympus), excited by 540 nm laser light and observed through a TRITC filter set. Visual inspection was conducted right after injection. FIG. 13 shows microrobotically injected endothelial cells under both bright-field ( FIG. 13( a )) and fluorescence microscopy ( FIG. 13( b )). The deposited fluorescent dyes (high-brightness) can be clearly observed in the cells. Normal cell morphology is maintained after injection.
To quantitatively evaluate the performance of the microrobotic adherent cell microinjection system, two measures were defined. (1) Survival rate: This measure is defined as the ratio between the number of live cells after injection and the total number of cells injected, essentially representing the severity and frequency of cell damage from injection. Based on the 1012 injected endothelial cells, the microrobotic injection system produced a survival rate of 96%, which was determined through Trypan blue exclusion testing of cell viability. (2) Success rate: This measure is defined as the ratio between the number of cells with materials successfully deposited inside the cell and the total number of injected cells. Essentially, this measure represents the reliability and the reproducibility of the system. Visual inspection revealed that the success rate of the 1012 injected endothelial cells was 82%.
The system is immune from large variations in performance since efforts from operator intervention are trivial (computer mouse clicking) without causing human fatigue as in manual injection. Additionally, the system has a high degree of performance consistency, independent of proficiency differences across operators.
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A system and method for micromanipulating samples are described to perform automatic, reliable, and high-throughput sample microinjection of foreign genetic materials, proteins, and other molecules, as well as drawing genetic materials, proteins, and other molecules from the sample. The system and method overcome the problems inherent in traditional manual micromanipulation that is characterized by poor reproducibility, human fatigue, and low throughput. The present invention is particularly suited for adherent cell microinjection but can be readily extended to aspiration, isolation, and electrophysiological measurements of microorganisms, unicellular organisms, or cells.
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FIELD OF THE INVENTION
[0001] This invention generally relates to a wooden casing, such as a door frame or window frame, that prevents wood rot when installed on a horizontal base, such as a concrete slab, where the base may be comprised of a porous material or subjected to moisture accumulation. The invention prevents the communication of moisture from the base to the casing because the casing is spaced above the base a distance exceeding the meniscus of water. The invention specifically relates to a design for a rot resistant wooden window or door frame. The invention also relates to a method of making a rot resistant casing.
BACKGROUND OF THE INVENTION
[0002] Many wooden door and window frames provide no protection for the wooden surfaces that abut a floor or base. Consequently moisture may be “wicked up” from (or through) the floor or similar horizontal surface and into the associated wooden structure. Doorjamb end grains have proven to be particularly problematic because of their affinity for absorbing moisture. Should the moisture in the wood achieve a sufficiently high level, then the wood may eventually rot. Wood rot typically cannot be repaired in situ, thus necessitating the replacement of the door or window frame.
[0003] Several techniques and systems have been used address the problem associated with wood rot in door frames and other similar structures. One such system involves splicing a rot resistant material, such as plastic or plastic composite, with a wooden frame member to create a wooden door frame having a finger-joint connecting the wood and plastic components together. This method is relatively expensive and the spliced portion of the door frame may not accept paint or finish in the same manner as a wooden door frame, and consequently the finished door frame does not have a uniform finish and appearance.
[0004] The prior art also includes the use of an insulating strip across the door frame end grain, as shown in U.S. Pat. No. 6,161,343 to Young, entitled Wood Rot Preventing Wood Casing End Grain Moisture Barrier Assembly and Method, the inventor of which is also the inventor hereof. While this method is effective, it requires relatively precise placement of the insulating strip. Additionally, the applicant has found that most wood rot can be prevented by securing the frame to a sill in order to space the door frame or exposed end grain wood surface a distance from the floor or base that is greater than the meniscus of water. Precisely spacing a door frame relative to a sill in a large-scale production process is difficult and cost prohibitive.
[0005] The need exists for an effective and efficient assembly that is inexpensive to manufacture and effectively prevents wood rot. The disclosed invention provides an end grain assembly that incorporates at least two button-type components to precisely space a wooden casing such as door frame, window frame, brick mold or the like, above a horizontal surface and thereby prevent moisture from “wicking up” into the associated wooden casing. The “buttons” require less material and a less sophisticated manufacturing process than the prior art rot prevention methods, while still effectively preventing wood rot.
SUMMARY OF THE INVENTION
[0006] The present invention is an assembly comprising a vertical wooden member with at least two buttons attached to the lower exposed end grain of the vertical member. The vertical member is attached to a sill assembly, which extends perpendicular to the vertical member. The sill assembly has a lower planar surface that defines a horizontal plane. The buttons elevate the vertical member above the horizontal plane defined by the planar lower surface of the sill assembly.
[0007] The present invention also comprises a door frame assembly that includes a vertically extending wooden door frame that is spaced above an essentially horizontal floor by two cylindrical buttons. The top of each button is attached to a doorjamb exposed end grain, and the bottom of each button abuts the floor. A doorsill assembly is secured to the doorjamb and extends normal to the doorjamb. The buttons elevate the doorjamb end grain above the floor and thereby prevent wood rot in the doorjamb.
[0008] The present invention also comprises a method of making a rot resistant assembly. The method comprises providing a vertical wooden member that has an end grain face. At least two buttons are attached to the end grain face. A frame assembly is created by connecting a sill assembly to the vertical member so that the bottom of the sill assembly is disposed in the same horizontal plane as the bottom of the buttons. The frame assembly is then installed on a horizontal surface so that the vertical member is elevated above the horizontal surface to a height greater than the meniscus of water, thereby preventing water from being drawn up from the horizontal surface and rotting the vertical member.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 is a fragmentary perspective view of a present invention.
[0010] FIG. 2 is a fragmentary cross-sectional view of the present invention taken along the line 2 - 2 in FIG. 1 .
[0011] FIG. 3 is an elevational view of a doorjamb button.
[0012] FIG. 4 is an elevational view of a door and door frame in accordance with the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0013] The present invention comprises a rot resistant casing 10 , primarily designed for door and window frames. Specifically, the invention comprises a casing 10 that prevents communication of moisture from a floor or horizontal base upwardly into a wooden window or doorjamb 12 . Although the rot-resistant casing shown in the drawings and described in the specification is generally applicable to a door frame, the invention also has application in other types of structures, and the scope of the invention is not limited to doors or windows.
[0014] As best shown in FIG. 1 , the rot-resistant casing 10 is comprised of a vertically extending wooden doorjamb 12 with at least two doorjamb “buttons” 14 attached to the exposed end grain 16 of the doorjamb 12 . The doorjamb buttons 14 elevate the doorjamb 12 above a floor or horizontal surface to a height greater than the meniscus of water so that water is not “wicked-up” from the floor into the doorjamb 12 . At least two buttons 14 should be used in order to prevent the doorjamb 12 from canting and thereby causing a portion of the doorjamb 12 to contact the floor or horizontal base. A doorsill 18 extends horizontally from the doorjamb 12 . The exposed doorjamb end grain 16 may be coated with wax or finish to further seal the door frame and protect the exposed surfaces from moisture.
[0015] As best shown in FIG. 2 , a tack 20 may be used to attach the top surface 17 of button 14 to the doorjamb end grain 16 . Alternatively, the button 14 may be attached by a screw, nail, staple, adhesive, a different attachment component, or by any method known in the art consistent with the function of the button 14 . The tack 20 may also be an integral part of the button 14 , so that the tack 20 and button 14 comprise a single component. Button 14 are sometimes in the industry referred to as tack glides.
[0016] As best shown in FIG. 3 , button 14 may have a cylindrical shape. Other shapes such as domes, squares, rectangles, diamonds, triangles, etc. should also be considered within the scope of the invention. In the preferred embodiment, the buttons 14 have a diameter that is less than the width of the end grain 16 of the doorjamb 12 , so that the buttons 14 do not engage the doorsill 18 . In an alternate embodiment, the buttons 14 may also have a diameter that is equal to the width of the end grain 16 and may abut the doorsill 18 , as best shown in FIG. 2 .
[0017] Although three buttons 14 are shown in FIG. 1 , any number of buttons 14 should also be considered within the scope of the invention. Similarly, although the buttons 14 are shown as uniformly spaced along the end grain 16 , the buttons 14 need not be evenly spaced and may be positioned as required for a specific application. Although the buttons 14 preferably are identical, the shape and properties of individual buttons 14 may be altered as required for a particular application.
[0018] The hole 22 shown in the button 14 in FIG. 3 is intended to accommodate a connector such as a tack 20 , however the button 14 may be solid if another connecting method is used. The button 14 may also be hollow or perforated as required for a specific application. The preferred material of construction for the buttons 14 is plastic. Buttons 14 may be comprised of metal, fiberglass, or a composite material. The buttons 14 should be made from a material which does not wick water, so that the buttons 14 thereby do not inadvertently serve as a mechanism for communicating water to the exposed end grain 16 .
[0019] A method of making a rot-resistant assembly is also within the scope of the invention. The casing 10 is constructed by attaching at least two buttons 14 to the end grain portion 16 of a doorjamb 12 . The casing 10 is connected to a doorsill 18 so that the bottom faces 23 of the buttons 14 are disposed on the same horizontal plane as the planar lower surface 19 of the doorsill 18 , thereby creating a door frame assembly. The door frame assembly is installed on a horizontal surface so that the doorjamb 12 is elevated above the horizontal surface 19 to a height exceeding the meniscus of water, thereby preventing water from being drawn up from the horizontal surface and subsequently rotting the doorjamb 12 . As best shown in FIG. 4 , the assembled door frame includes casings 10 , each providing one of the opposing door jambs 12 , a header 13 , and the doorsill 18 . Door D may be conveniently attached to one of the jambs 12 by means known in the art.
[0020] For the foregoing reasons, it is clear that the present invention provides a rot-resistant assembly that addresses the problem of moisture migration from a horizontal base to an adjacent wooden member. The method and apparatus described above is effective as well as relatively inexpensive to construct.
[0021] The invention may be modified in multiple ways and applied in various technological applications. For example, the invention may be used with a garage door frame or in applications that do not include a doorsill 18 . Although the materials of construction are described, they may include a variety of alternative compositions consistent with the function of the invention. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.
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An wood rot resistant assembly comprises a vertical wooden member having an exposed end grain. At least two buttons extend from the end grain. A sill assembly defines a horizontal base plane. The sill assembly extends perpendicular to the vertical member. The buttons elevate the vertical member end grain above the horizontal base plane.
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BACKGROUND OF THE INVENTION
The present invention pertains to a portable motorized chain saw and more particularly to a portable motorized chain saw having a clutch which is arranged between the motor drive shaft and the chain sprocket and wherein a brake band acts on a drum which is adjacent to the chain sprocket.
In the case of motorized chain saws of this type, the chain runs over a guide bar, which is in the same plane as the chain sprocket and, in order to keep friction and wear as small as possible, the chain is constantly lubricated, often by applying drops of oil. This lubrication of the chain necessarily contributes to better adhesion of sawn particles, i.e., saw dust, chips and the like on the chain. Therefore, when considering the small constructional proportions in relation to justifiable expenses, it is practially unavoidable that dirt and oil are thrown out, especially in the area of the sharp change in direction of the chain which occurs at the chain sprocket. In this manner, oil particles, in particular, but also dirt particles reach the area of the contact surface of the brake band on the drum of the clutch, as a result of which the braking effect and thus also the safety of the saw is deleteriously influenced in emergency situations.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide an improved portable motorized chain saw.
Another object of the invention is to provide such a portable motirzed chain saw which is designed in such a manner that the above-mentioned dangers are reduced or avoided.
Still another object is to provide a portable motorized chain saw wherein lubrication and dirtying of the contact surface of the brake band on the drum of the clutch are correspondingly reduced.
Another object of the invention resides in providing an improved brake band design for a portable motorized chain saw.
In accomplishing the foregoing objects, there has been provided in accordance with the present invention a portable motorized chain saw, comprising: a chain sprocket; clutch means positioned between the chain sprocket and the drive shaft of the motor for selectively coupling the chain sprocket with the drive shaft, the clutch means including a drum member; and a brake band positioned in contiguous relationship with the outer circumferential surface of the drum member and including at least one oil stripping opening therein. Preferably, the brake band includes a plurality of said oil stripping openings and each of the openings comprises a sharpened stripping edge located at the forward edge of the opening in the direction of movement of the drum member and at the surface of the brake band which faces the drum member. In accordance with another preferred aspect of the invention, the forward most edge of the opening slants forwardly toward the side of the brake band which is adjacent the chain sprocket.
There has also been provided according to the present invention an improved brake band design as set forth above.
Other objects, features and advantages of the invention will become readily apparent from the detailed description of preferred embodiments which follows, when read in light of the attached figures of drawing.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a brake band according to the invention;
FIGS. 2a to 2d are segmented frontal views illustrating various possibilities of the configuration and shape of cross-sections for oil stripping openings in brake bands for chain brakes of portable motorized chain saws according to the invention, especially of the type illustrated in FIG. 1; and
FIG. 3 is a schematic plan view of a portion of a chain saw including a brake band according to the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In accordance with the present invention, a portable motorized chain saw of the type described in the introductory part above is modified so that the brake band is provided with oil stripping openings. By means of these oil stripping openings, in accordance with this invention, the oil, and obviously also the dirt particles, reaching the contact surface between the brake band and the drum of the clutch are removed, whereby the edges of the oil stripping opening act at least in part as stripping edges.
In this case, it proves to be advantageous if at least one oil stripping opening is provided with a sharp stripping edge positioned on its opening side which faces the drum of the clutch and at least on its front edge, in relation to the direction of rotation of the drum of the clutch. This stripping edge can be configured, in particular, so that the edge is disposed at an acute angle with the corresponding tangent on the drum of the clutch.
This edge configuration can be attained in a simple manner by forming the oil stripping opening so that it opens radially conically toward the outside, at least over a portion of its periphery.
While this can be attained in a simple manner in the case of a round cross-section of the oil stripping opening, the formation of the oil stripping opening with a configuration which is not round, e.g., in particular a square opening, affords an additional possibility. Thus, it is possible, with a stripping edge extending essentially over the width of the contact surface and slanted in the direction of rotation obliquely forward toward the chain sprocket which is provided adjacent to the drum of the clutch, to deflect the stripped oil particles in the direction of the chain sprocket and reuse them for chain lubrication.
In the following section, the invention is described in greater detail with reference to exemplary embodiments which illustrate brake bands for configurations for chain brakes of motorized chain saws.
In FIGS. 1 and 3, brake band 1 of a chain brake of a portable motorized chain saw 20 is associated with the drum 22 of the clutch mechanism (not illustrated in detail) which is arranged in the drive train of the motor 24 which includes drive shaft 26 to act as a brake drum. The brake drum is normally adjacent to the chain sprocket 28, which is in the same plane as the plane of the guide bar 30 and over which the saw chain 32 moves. As a result of lubrication of the chain, the drum is exposed to fouling by oil and dirt particles along its circumference, which forms the contact surface for the brake band. The particles lie between the brake band and the drum when brake band 1 is tightened and thus more or less considerably reduce the effect of the brake. Therefore, the particular braking effect which is attained with the tightening of brake band 1, which is provided at its ends with eyes 2 and 3 for connection to a customary linkage which is not illustrated here, cannot be predicted even approximately exactly, if this dirt is not removed. For this purpose, brake band 1 in accordance with this invention is now provided with a number of oil stripping openings 4 over its circumference. These openings have a round cross-section in the embodiment illustrated in accordance with FIG. 1. With a view to improvement of the stripping action, it has proven advantageous in this case to outwardly open or flair the oil stripping openings, so that a sharp edge of the opening results adjacent to the front edge of the drum, in the direction of rotation. The sharp edge removes dirt from the contact surface formed by the drum circumference with a knife-like action. Additional configurations of these oil stripping openings are illustrated in FIGS. 2a through 2d, whereby a section of a corresponding brake band 1a, 1b, 1c, 1d is shown in a view taken radially from the outside.
In the embodiment in accordance with FIG. 2a, the brake band is designated as 1a, and oil stripping openings 4a with a triangular configuration are associated with the brake band. The point of the triangle opposes the direction of rotation of the clutch drum, which direction is symbolized by arrow 5. With an essentially equilateral configuration of the triangular oil stripping opening, the base of the triangle is positioned transverse to the direction of rotation 5 and extends over a significant portion of the width of brake band 1a, so that the contact surface between the brake band 1a and the clutch drum, which serves as brake drum but is not illustrated here, is essentially covered. As a modification of the illustrated embodiment, it would of course also be possible, within the scope of the invention to stagger in the lateral direction the oil stripping openings which are sequentially located with respect to the direction of rotation 5. In order to improve the stripping action, in the configuration in accordance with FIG. 2a, the edge forming the base 6 of the triangle is sharpened as a knife, resulting in a cutting edge 7, of which the sharp edge is disposed next to the clutch drum, which is here not illustrated but which should be imagined as lying underneath the brake band in the drawing.
In the embodiment in accordance with FIG. 2b, the brake band as a whole is designated as 1b and is provided with oil stripping openings 4b. While these openings also comprise a triangular shape, they are configured as non-equilateral triangles in such a manner that the base 8 slants forwardly with respect to the direction of rotation 5, i.e., toward the edge of the brake band 1b which is on the right hand side of the illustration. If the chain sprocket is arranged on the right hand side of the brake band, the stripped oil is directed in the direction of this chain sprocket. In this configuration also, the edge which forms the base 8 is again configured as a knife edge 9, in order to obtain an improved stripping action. In this case, the two legs of the triangle are of unequal length and intersect approximately in the middle of the band.
In the embodiment in accordance with FIG. 2c, a brake band 1c is illustrated in which the oil stripping openings 4c are formed by extended, parallelogram-shaped rectangles. The long sides 10 of the rectangles, with respect to the direction of rotation 5, are forwardly slanted toward the right hand side, to achieve a configuration such as described in connection with FIG. 2b. In order to also obtain an improved stripping action in this case, the edge 10 forming the front, long side with respect to the direction of rotation 5 is configured as a cutting edge 11.
While in the embodiments in accordance with FIGS. 2a through 2c the oil stripping openings are always completely opened, the oil stripping opening 4d in the embodiment in accordance with FIGS. 2d is formed by a rasp-shaped pocket, which is however, open in this case, e.g., like a food grater. For this purpose, as shown in the illustration, brake band 1d is cut open only along the edge 13 of the stripping opening 4d, which is configured as a cutting edge 12, and the opening adjacent to edge 13 results due to the fact that the band is pressed radially outwardly, for example by stamping, so that an open pocket results extending toward the inside of the band. Thus, the pocket extends in the direction of the clutch drum, which is located behind the band, and the pocket is covered by the cap-shaped portion of the band 14, as shown in the illustrated view which is taken from the outside. In this embodiment the cutting edge 12 is slanted obliquely toward the outside, i.e., away from the saw and toward the chain sprocket so that here also a movement of the stripped particles results in the direction of the chain sprocket, which is here imagined as being located on the right hand side adjacent to the band.
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Disclosed is a portable motorized chain saw, comprising: a chain sprocket; clutch means positioned between the chain sprocket and the drive shaft of the motor for selectively coupling the chain sprocket with the drive shaft, the clutch means including a drum member; and a brake band positioned in contiguous relationship with the outer circumferential surface of the drum member and including one or more oil stripping openings therein.
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FIELD
[0001] The present disclosure relates to a method and a computer system for processing redeemable instruments, such as virtual scratch cards or virtual coupons.
BACKGROUND
[0002] Conventional scratch cards are physical entities comprising one or more areas on which information is printed. The information is concealed by an opaque panel which can be scratched off to reveal the information.
[0003] In some instances, the information may relate to a win or lose outcome in gambling, thus indicating a loss or a payout. In the latter case, the information may effect the disbursement of a gain when it is presented for the first time to a provider of the gambling service. In other examples, similar to information printed on a coupon, the information may serve as a one-time password (such as a code number) which, when being entered into some device for the first time, releases some service, credit or access right such as a phone service or other prepaid service.
[0004] A recipient of such a conventional scratch card or coupon may, for example, copy the information and input it into some electronic device, or he or she may present it to another person. Alternatively, the recipient may pass on the scratch card or coupon to another person who may use the information accordingly. Once the information is thus used, it is voided. Often, the mere fact that the opaque panel of a scratch card has been scratched off indicates that the scratch card has been devaluated. On the other hand, the information being covered by the panel assures a holder or recipient of the scratch card that the information has not been used so far and thus is still valid.
[0005] Due to the specified applicability of the revealed information on the scratch cards, the concept of distributing scratch cards provides for a controlled allocation of rights or other advantages.
[0006] However, the concept of such conventional scratch cards relies solely on physical distribution channels, such as inserts in magazines, newspapers or periodicals, or inclusions with delivery notes, direct mail-outs, indirect mail-outs, physical handouts from an individual to a potential customer, or physical attachment to a product. These delivery methods are expensive, require long planning cycles, have very long lead times and are impossible to adjust or to alter once a campaign is up and running.
[0007] There is, therefore, a need for a technique supporting a more diversified and flexible allocation of benefits.
SUMMARY
[0008] This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This summary is not intended to identify key features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
[0009] According to the present disclosure, one or more of the above issues may be solved by a method of processing redeemable instruments, by one or more computer readable media, and by a computer system for processing redeemable instruments.
[0010] According to a first aspect of the present disclosure, a method of processing redeemable instruments is disclosed, wherein the method comprises delivering a redeemable instrument to a first electronic device, wherein the redeemable instrument includes a user interface configured to react to a redemption activity of a user, the redemption activity causing redeemable instrument information of the redeemable instrument to be first provided to the user, determining that the redeemable instrument has been redeemed using a second electronic device different from the first electronic device, and recording in a memory that the redeemable instrument has been redeemed.
[0011] According to a second aspect of the present disclosure, at least one computer readable medium stores instructions which, when executed by a computer device connected to a communications network connected to a first and a second electronic device, enable the computer device to process redeemable instruments in accordance with the method of the first aspect of the present disclosure.
[0012] According to a third aspect of the present disclosure, a computer system for processing redeemable instruments comprises at least one server device configured to communicate with a first and second electronic device via a communications network, wherein the server device is configured to deliver a redeemable instrument to the first electronic device, wherein the redeemable instrument includes a user interface configured to react to a redemption activity of a user, the redemption activity causing redeemable instrument information of the redeemable instrument to be first provided to the user, observe whether the redeemable instrument has been redeemed using the second electronic device, and if so, record in a memory that the redeemable instrument has been redeemed.
[0013] According to an embodiment, the redeemable instrument can be a virtual redeemable instrument. Preferably, the redeemable instrument is a virtual scratch card or a virtual coupon. In the following description, embodiments and examples of the present disclosure may refer to a scratch card or a virtual scratch card. However, it is to be understood that the respective embodiments and examples may also be used with a redeemable instrument of any type, such as a coupon.
[0014] In response to the redemption activity, according to embodiments, the scratch card information is first (i.e., for the first time) provided to the user. Accordingly, the scratch card information is kept unrecognizable (in particular, invisible and inaudible) until completion of the redemption activity.
[0015] The redemption activity may include, for example, a swiping movement made with a moveable input device (such as a computer mouse), or with a finger or stylus on a touch pad or touch screen. In such examples, when the scratch card information is devised for visual provision, the redemption activity may virtually reveal the scratch card information gradually in accordance with the swiping movement.
[0016] Additionally or alternatively, the redemption activity may comprise a click on a button, or another interaction with an input device.
[0017] The scratch card information may indicate that the virtual scratch card has been a blank or loss not providing any benefit. Alternatively, the scratch card information may indicate that the virtual scratch card provides a benefit such as a discount in some transaction, or it may indicate some PIN, discount code or phone number that may provide for some advantage when it is entered in some device or presented to another person. The scratch card information may be provided in codified form (such as a barcode or a QR code) that can be presented to a scanning device to provide some advantage.
[0018] Data encoding the scratch card information may be included in the virtual scratch card, or it may be delivered separately, e.g., upon determining that the virtual scratch card has been redeemed using the second electronic device. The virtual scratch card may be delivered through one or more social networking sites or platforms.
[0019] Accordingly, the various aspects provide a technique for processing redeemable instruments, such as virtual scratch cards, which overcomes the above drawbacks of conventional scratch cards. The virtual scratch cards allow for a flexible allocation of benefits. In particular, they allow for an improved control and tracking of a course that a passed-on scratch card is taking, and for a modification of one or more associated privileges subsequent to issuing the virtual scratch card.
[0020] Preferably, the virtual scratch card is identified by a unique identification code. The identification code may be included in the delivered scratch card. Alternatively, the unique identification code may be generated in response to the redemption activity.
[0021] Such unique identification allows for a precise recording, tracking and devaluating of the scratch card. The unique identification code may be associated with the scratch card information.
[0022] According to an embodiment, the method according to the first aspect comprises updating the virtual scratch card before determining that the virtual scratch card has been redeemed, by replacing previous scratch card information with the updated scratch card information. Analogously, the at least one computer readable medium preferably comprises respective instructions, and the server device included in the computer system according to the third aspect is preferably adapted to update the virtual scratch card accordingly.
[0023] The updating may be carried out, for example, responsive to some event, such as a time-out, a determination that a current holder of the scratch card is among a predetermined set of users or has one or more particular properties, or responsive to a notification received, e.g., from a publisher of the virtual scratch card.
[0024] This embodiment allows for an advantageous adjustment of a given campaign according to particular trends, needs, etc. For instance, the scratch card information may be associated with a unique identification code of the virtual scratch card, and the association may be registered in a memory. The updating may thus comprise updating a record, in the register, related to the unique identification code accordingly.
[0025] The updated virtual scratch card may be delivered to the second electronic device.
[0026] According to an embodiment, the virtual scratch card is associated with at least one privilege.
[0027] Such a privilege may relate, for instance, to an action, such as an electronic transaction. In such a case, the privilege may, for example, provide for some safety improvement in the electronic transaction. In a case where the action comprises a billable transaction, the privilege may effect a price reduction for the user of the second electronic device redeeming the virtual scratch card.
[0028] As further examples, a privilege may relate to access rights to one or more data sources, to an interactive session (such as a session within a social networking service that a user redeeming the virtual scratch card may wish to participate in), or to a video game (in which case the privilege may effect an improved game level for the user redeeming the virtual scratch card).
[0029] The virtual scratch card may further include data enabling the second electronic device to implement the at least one privilege.
[0030] Additionally or alternatively, the method may comprise conferring the at least one privilege to a user of the second device who has redeemed the virtual scratch card. Analogously, the at least one computer readable medium may include respective instructions, and the server device may be adapted to confer the at least one privilege accordingly.
[0031] This embodiment provides the advantage that the server device may control the conferment of the privilege(s), and the delivered virtual scratch card may be a small data entity which can be easily dispatched and passed on, as it may be disburdened from a main data package that can instead be queried when the virtual scratch card is indeed redeemed.
[0032] Conferring the at least one privilege to a user of the second device may include delivering data required for the second electronic device implementing the at least one privilege.
[0033] For instance, when the privilege is related to consuming a video, the conferring may include delivering streamed video data to the second electronic device.
[0034] When the privilege relates to an interactive session as mentioned above, conferring the privilege may comprise establishing a connection of the second electronic device to the interactive session. When the privilege relates to access rights to one or more data sources (such as a data source stored in a memory of the server device), conferring the privilege may comprise providing the user of the second electronic device with such an access right.
[0035] In a case where the privilege relates to an action initiated by the user of the second electronic device as mentioned above, conferring the at least one privilege to the second electronic device may comprise modifying one or more parameters related to said activity; therein, the one or more parameters may be recorded in a database stored in a memory of the server device. For instance, the one or more parameters may refer to a price in an electronic transaction initiated by the user of the second electronic device.
[0036] An allocation associating the scratch card information or the unique identification code, or both, with the at least one privilege may be stored in a memory (e.g., of the server device or accessible by the server device), and accordingly, the method may include storing such allocation. This embodiment allows for a centralized control of the allocation of privileges by means of the virtual scratch cards, thus permitting proactive and dynamical adjustments.
[0037] According to an embodiment, recording that the virtual scratch card has been redeemed comprises recording an identification of a user of the second electronic device or of the second electronic device.
[0038] Preferably, the method further comprises keeping a record of at least one current holder of the virtual scratch card in a memory. The method may comprise storing and matching user data of the user of the first electronic device, or of the user of the second electronic device, or of both. In particular, it may comprise collecting, recording and computing data about interactions of said users, about their friends registered in some data base and about redemptions made.
[0039] For instance, the method according to the first aspect may comprise keeping and updating a register with respect to one or more of: a current holder of the virtual scratch card, a user of the second electronic device redeeming the virtual scratch card, a user of a third electronic device trying to redeem the virtual scratch card, users that the user of the first electronic device is interacting with, and users that the user of the second electronic device is interacting with. Analogously, the at least one computer readable medium according to the second aspect may comprise respective instructions, and the server device of the computer system according to the second aspect may be adapted to keep and update a register accordingly. The register may be stored in a memory, e.g., in a memory included in or accessible by the server device, such as by way of a communications network.
[0040] Thereby, targeted campaigns are made possible. In particular, the at least one privilege associated with the virtual scratch card may be updated based on the current holder or based on collected, recorded or computed data, or a further virtual scratch card may be created and delivered based on such data.
[0041] The virtual scratch card may be configured so as to cause a notification to be sent to a (or the) server device when a user of the first electronic device passes on or has passed on the virtual scratch card. For example, the virtual scratch card may be configured so as to interact with a messaging environment (such as an email program or a social networking service), and to thereby cause the messaging environment to send the notification when the virtual scratch card is up to be passed on, is being passed on, is being received or has been received by means of the messaging environment.
[0042] According to an exemplary embodiment, the method comprises receiving, from the first electronic device, a message indicating that the first electronic device has passed on the virtual scratch card to the second electronic device, or indicating that the first electronic device has passed on the virtual scratch card to a third electronic device.
[0043] Additionally or alternatively, the method may comprise receiving, from the second or from a (or the) third electronic device, a notification indicating that the second or the third electronic device, respectively, has received the virtual scratch card from the first electronic device.
[0044] These embodiments allow for tracking the virtual scratch card and, therewith, for accurate in-campaign and post-campaign monitoring and analysis.
[0045] Preferably, as long as the virtual scratch card has not been redeemed, a recipient of the virtual scratch card, e.g., a user of the first electronic device, can freely pass on the virtual scratch card to his or her friends or to the general public. Thus, the virtual scratch card may be passed on an arbitrary number of times. In particular, the method may include recording in a memory, prior to determining that the virtual scratch card is redeemed using the second electronic device, that the virtual scratch card is being held by both a user of the second electronic device and a user of a third electronic device. Thus, the virtual scratch card may be passed on concurrently to various users.
[0046] According to an embodiment, the method comprises determining that the user of the first electronic device has signed up (also referred to herein as registered) for receiving the virtual scratch card. Analogously, the at least one computer readable medium may include respective instructions, and the server device according to the third aspect may be adapted to determine such signing up. The determining may comprise querying a database recording users who have registered themselves accordingly. As a consequence, the virtual scratch card can be delivered in a target-oriented way to appropriate users.
[0047] The signing up may comprise a conventional registering procedure, such as the user of the first electronic device entering a name, an email address or an identifying number into a database. Additionally or alternatively, the signing up may comprise scanning some code (such as a barcode or a QR code) with an optical device such as a camera of a mobile phone, a smart phone or a tablet computer; preferably, the signing up can be realized solely by such scanning.
[0048] According to an embodiment, the communications network and the computer system may be running a social networking service. In such an embodiment, the virtual scratch card is preferably delivered or passed on using the social networking service. Additionally or alternatively, at least one privilege that may be associated with the virtual scratch card may relate to features of the social networking service. For instance, it may provide a recipient thereof with additional or improved tools to be used within the social networking service, such as an enhanced data connection or some merit in a real or virtual event operated by means of the social networking service.
[0049] Preferably, the method further comprises delivering, to the first electronic device, a notification including information related to the fact that the virtual scratch card has been redeemed. Analogously, the server device is preferably configured to deliver such notification. The information may, for instance, include an indication of the second electronic device, or of a user of the second electronic device who has redeemed the virtual scratch card. For instance, the notification may be delivered using a social networking service.
[0050] According to an embodiment, recording in a memory that the virtual scratch card has been redeemed comprises devaluating the virtual scratch card.
[0051] Accordingly, recording that the virtual scratch card has been redeemed may comprise updating the virtual scratch card by replacing a privilege associated with the virtual scratch card by at least one other privilege, e.g., by a void privilege.
[0052] Additionally or alternatively, said recording may comprise causing that the virtual scratch card is deleted on the second electronic device. Preferably, the recording even comprises causing that the virtual scratch card is deleted on any electronic device registered in a memory as a current holder of the virtual scratch card. Thereby, a devaluation is made possible also in cases where the virtual scratch card has been passed on concurrently to various electronic devices.
[0053] As a further example, the method according to the first aspect may include receiving a notification indicating that redemption of the virtual scratch card is attempted using a third electronic device, querying the memory to determine that the virtual scratch card has been redeemed already and refusing a conferment of at least one privilege associated with the virtual scratch card to the third electronic device. The refusal may include sending a notification to the third electronic device, the notification indicating that the virtual scratch card is invalid, for it has been redeemed already. As is to be understood, the at least one computer readable medium may analogously include instructions which cause the computer device to carry out such steps, and the server device of the computer system according to the third aspect may be adapted to do so.
[0054] Additionally or alternatively, recording that the virtual scratch card has been redeemed may include inhibiting that the virtual scratch card is further passed on. For instance, the recording may include inhibiting that the second electronic device further forwards the virtual scratch card.
[0055] The various embodiments provide several advantages. In particular, allowing the passing on of redeemable instruments, such as virtual scratch cards or virtual coupons, creates value and awareness of a product, service or brand of a business or company and of social networking sites or platforms. The technique provided by the present embodiment is highly efficient and inexpensive to implement and run.
[0056] As is to be understood, some or several of the features described herein may be combined with each other. In particular, the server device of the system of the third aspect may be adapted to carry out one or more of the particular embodiments of the method according to the first aspect of the present disclosure. Analogously, the one or more computer readable media may include instructions which, when executed by a computer, carry out any of the embodiments of the method according to the first aspect.
DESCRIPTION OF THE DRAWINGS
[0057] The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:
[0058] FIG. 1 depicts an exemplary method in accordance with one embodiment of the present disclosure;
[0059] FIG. 2 shows an exemplary record scheme and a data structure representing a virtual scratch card;
[0060] FIG. 3 depicts a system including a server device in accordance with an embodiment of the present disclosure.
DETAILED DESCRIPTION
[0061] While illustrative embodiments have been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention.
[0062] As schematically illustrated in FIG. 1 , a method according to the present disclosure includes a step 100 of delivering a virtual scratch card to a first electronic device. As detailed above and further illustrated in FIG. 2 , the virtual scratch card includes a user interface receptive for a redemption activity of a user, the redemption activity causing scratch card information to be first provided to the user. The virtual scratch card may be associated with a unique identification code that identifies the virtual scratch card, or with at least one privilege or with both. The virtual scratch card may have been created based on a request received from a scratch card publisher.
[0063] The virtual scratch card including the user interface may be visually represented on a display of the first electronic device. The representation may include the user interface which may comprise a button, wherein the redemption activity may be realized by or include clicking on the button. Additionally or alternatively, the user interface may comprise a field receptive for a swiping movement of a user with a movable device or with a finger, wherein the redemption activity may be realized by or include the swiping movement.
[0064] In step 110 , it is determined that the virtual scratch card has been redeemed using a second electronic device; this may be a result of the first electronic device passing on the virtual scratch card.
[0065] In step 120 it is recorded in a memory that the virtual scratch card has been redeemed. The recording allows for devaluating the virtual scratch card; indeed, when an attempt of redeeming the virtual scratch card is determined later on, the memory may be queried, and it may be determined that the virtual scratch card has been redeemed already. As a consequence, a conferment of the at least one privilege associated with the virtual scratch card may be refused. Further steps possibly included in the method are detailed herein.
[0066] FIG. 2 schematically shows a record scheme that may be stored in a memory of an electronic device, e.g., of a server device of a computer system in accordance with an aspect of the present disclosure. As depicted in FIG. 2 , a table 200 relates to various virtual scratch cards that may be delivered to appropriate users. The users may have registered themselves in a database as being interested in receiving scratch cards; the registering may include specifying a particular publisher or a particular type of scratch card the user is interested in. As detailed above, the registering may, in particular, be realized by scanning a particular information (such as a number, a barcode or a QR code) with a digital camera, e.g., with a camera of a smart phone or other electronic device.
[0067] As depicted in FIG. 2 , each scratch card is identified by a respective unique identification code. In the exemplary table shown, the identification codes are registered in column 202 .
[0068] Moreover, the table specifies various privileges associated with each scratch card, wherein a respective privilege may be granted to a user carrying out the redemption activity; in the exemplary table shown, the privileges are recorded in column 201 . The exemplary privileges indicated relate to a 5% discount that may be granted to a user in a billable transaction, and to a data access privilege, e.g., to a right of accessing a video database.
[0069] Further stored in the table 200 are parameters related to a current state and history of the virtual scratch cards identified by the respective unique identification codes. For instance, as can be recognized from column 203 , the virtual scratch card having the identification code ID 1 has been redeemed already, whereas the virtual scratch cards having identification codes ID 2 and ID 3 , respectively, are still unredeemed.
[0070] As the redemption of the virtual scratch card having the identification code ID 1 has caused a devaluation of the virtual scratch card, there is no current holder of this virtual scratch card recorded in column 204 . Previous holders of this virtual scratch card have been users “u 1 ” and “u 2 ,” as recorded in column 205 . Indeed, it has been user u 2 who has redeemed the virtual scratch card having ID 1 , as is further registered in column 203 .
[0071] The path of the virtual scratch card 300 identified by the unique identification code ID 2 is exemplarily depicted in the bottom of FIG. 2 . As indicated by the dotted arrow, the virtual scratch card 300 has been delivered to a first electronic device 10 which may be used by previous holder a 1 . The previous holder a 1 , however, has passed on the virtual scratch card 300 to user A 1 of a second electronic device 20 , which user in the situation depicted is a current holder of the virtual scratch card.
[0072] As indicated in field 302 of the virtual scratch card 300 , the virtual scratch card includes the identification code ID 2 . Additionally, in field 301 the virtual scratch card 300 includes a user interface 303 which is receptive of a redemption activity of a user.
[0073] As can be seen in table 200 , the scratch card identified by ID 2 relates to a privilege which in the present case confers a 5% discount in a billable transaction. Accordingly, the scratch card information to be presented to a redeeming user may indicate that such discount is granted to a redeeming user. Alternatively or additionally, the scratch card information may include a code a user may present within a transaction in order to enjoy the privilege.
[0074] The scratch card information is provided to a user for the first time when the user has redeemed the virtual scratch card. Accordingly, as indicated in FIG. 2 , when the virtual scratch card is delivered to the first electronic device 10 and passed on therefrom, the scratch card information is still unrecognizable. However, when the virtual scratch card has been redeemed using electronic device 20 , the scratch card information (schematically indicated by “−5%” in the figure) is provided to the user of the second electronic device.
[0075] When the virtual scratch card is passed on using the first electronic device 10 , a respective notification is sent to a server device storing the table 200 , as indicated by the discontinuous arrow starting from first electronic device 10 . According to an alternative embodiment, a respective notification may be sent from the second electronic device upon receiving the virtual scratch card 300 . Due to the notification, the server device can update the table 200 .
[0076] Moreover, in cases where the privilege associated with the virtual scratch card has been modified (not shown), e.g., by a scratch card publisher adapting a related campaign to recent developments, the server device may update table 200 so as to include the association of the virtual scratch card with the modified privilege. The server device may deliver an updated virtual scratch card to the current holder Al using the second electronic device. For example, when the virtual scratch card is updated such that the unique identification is associated to a 7% discount, updated scratch card information referring to the modified discount may be provided to the user Al of the second electronic device once he or she has redeemed the virtual scratch card.
[0077] FIG. 3 shows an exemplary system and a set of communications among the included entities in accordance with the present disclosure. Some or all of the communications may be operated by employing a social networking service.
[0078] The system includes a scratch card publisher 1 activating a server device 2 . Accordingly, by an operation 30 , the scratch card publisher 1 may cause the server device 2 to create a set of virtual scratch cards and to deliver the virtual scratch cards to certain users; as mentioned above, the users may have registered themselves as being interested in receiving scratch cards from the scratch card publisher 1 . The operation 30 may identify the respective devices of the users, or it may specify the users by certain characteristics, in particular by a reference to a database recording registered users.
[0079] As a consequence, the server device 2 may create the virtual scratch cards and deliver them, within a communication 31 , to the various first electronic devices 10 . Each of the virtual scratch cards may include a unique identification code identifying the respective virtual scratch card.
[0080] The server device 2 may keep a table such as table 200 depicted in FIG. 2 , the table referring to various virtual scratch cards, unique identification codes and privileges respectively associated therewith, a respective redemption status and previous and current holders of the virtual scratch card.
[0081] A user of a first electronic device 10 may not be interested in a privilege offered by means of the virtual scratch card, and within a communication 32 , he or she may thus pass on the virtual scratch card to a second electronic device 20 . A user of the second electronic device 20 may indeed redeem the virtual scratch card, and in a transmission 33 , the server device 2 may be informed about the redemption. As a consequence, the server device records the redemption. Preferably, the server device further records data identifying the second electronic device or of a user thereof or of both. The server device 2 may send a further transmission (not shown) to the first electronic device, the transmission including a notification that the virtual scratch card has been redeemed using the second electronic device. Moreover, as indicated by arrow 34 , the server device may provide (e.g., display) information to the scratch card publisher, informing the scratch card publisher about the redemption of the virtual scratch card by using the second electronic device. Additionally or alternatively, the server device may provide information related to a path the virtual scratch card has taken (e.g., represented by previous holders of the scratch card) or to user characteristics of previous or current users (such as registered friends or recent or frequent activities of the users).
[0082] As a consequence, the scratch card publisher is kept informed about the course of the virtual scratch cards, and can adjust a present or future campaign accordingly.
[0083] While some embodiments have been described in detail, it is to be understood that the aspects of the present disclosure can take many forms. In particular, the claimed subject matter may be practiced or implemented differently from the examples described and the described features and characteristics may be practiced or implemented in any combination. The embodiments shown herein are intended to illustrate rather than to limit the invention as defined by the claims.
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A method of processing redeemable instruments, such as virtual scratch cards or virtual coupons, is described. A redeemable instrument is delivered to a first electronic device. The redeemable instrument includes a user interface configured to react to a redemption activity of a user, the redemption activity causing redeemable instrument information of the redeemable instrument to be first provided to the user. Furthermore, it is determined that the redeemable instrument has been redeemed using a second electronic device different from the first electronic device, and recorded that the redeemable instrument has been redeemed. Furthermore, a computer system for processing redeemable instruments is described.
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BACKGROUND OF THE INVENTION
The invention relates to timing apparatus, and in particular to timing devices for coin-operated, elapsed time apparatus such as classified in class 194, subclasses 9,16 and 18.
Counting circuits for adding and subtracting digital pulses, such as described in U.S. Pat. No. 2,735,005 to Steele, are well known.
Coin receiving circuits, such as described in U.S. Pat. No. 3,279,480 to Jarvis and U.S. Pat. No. 4,124,110 to Hovorka are likewise well known.
Elapsed time timing devices are well known, and the use of such timers for counting down a purchased period of time, such as taught in U.S. Pat. No. 4,176,739 to Corcoran, are well known.
SUMMARY OF THE INVENTION
The invention comprises electronic logic circuitry which is combined in a manner to function with mechanical coin receiving apparatus so as to provide the consumer of the rented or purchased service or use of apparatus means for increasing and displaying the additional time being rented in predetermined increments at lower costs while said paid for service or apparatus use is being utilized without waiting for the timer to run out before depositing additional coins.
It is an object of applicant's invention to provide the consumer of rented or purchased services or apparatus use with the means of increasing the period of time and having the additional elapsed time being rented displayed while utilizing said service or apparatus.
It is a further object of applicant's invention to provide the consumer of rented or purchased services or apparatus use with more economical and efficient services or use of apparatus.
It is yet a further object of applicant's invention to provide the consumer of rented or purchased service or apparatus use with simple means for monitoring said services or use.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric projection of the apparatus comprising applicant's invention.
FIGS. 2a and 2b comprise the block diagram of the circuit components comprising applicant's invention.
FIGS. 3(a), 3(b), and 3(c) comprise the schematic drawing of the detailed circuit components for applicant's invention shown in FIGS. 1,2a and 2b.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows applicant's inventive apparatus 10 comprising frame 12, panel cover 14, LCD display readout 16, alarm 18, system on light 20, and last minute light 22.
The operation of the apparatus 10, which is compatible with most mechanical coin acceptors (not shown) is initiated by inserting the required coins into the coin acceptor, the alarm 18 will momentarily beep and the LCD readout 16 will display the amount of time paid for in minutes and seconds, the service or apparatus being paid for will function, the system on light 20 will be lit and the timer will count down displaying the time as it elapses. When only one minute of service or use time remains, the LCD readout 16 will indicate 59 seconds and counting down, the last minute light 22 will flash, and the alarm 18 will sound. The consumer of the rented service or apparatus use will have the option of allowing his time to run out or purchase additional time at a cost less than it would cost to start the service or use of apparatus over again if the time was allowed to run out. This option is easily exercised by inserting the coin or coins for the additional time to be purchased. The additional time paid for plus the time remaining will appear in the LCD readout 16, and the service or apparatus use will continue until the time displayed has run out. The last minute light 22 will go out and the alarm 18 will cease until the LCD readout 16 again indicates 59 seconds.
FIGS. 2a and 2b comprises the block diagram of the circuit components and their primary interconnections for the apparatus shown in FIG. 1. A primary 24 volt ac power line supplies a power supply 24, relay 28 associated with coin switch 26, count down oscillator 30, LCD display readout 16, and the system relay coil 34.
The power supply 24 provides the required voltage for the alarm and 5 volts dc to divider 36, count down oscillator 30, dip switches 38 for setting the time period per coin, dip switches 40 for setting the time period before system relay coil 34 is energized, BCD Up/Down Counters 42,44,46, & 48, grounded emitter, switching transistors 50, trigger circuits 52, grounded emitter, transistor 54 and BCD to 7 Segment Decoder/Drivers 56,58,60 & 62.
Relay 28 is energized by the closing of coin switch 26, and under this condition provides a ground to the one shot circuitry comprising trigger circuits 52, which results in grounded emitter transistor 54 resetting Divider 36 to zero. The output of Divider 36 actually goes to its high setting and enables the 1,000 pulses per second count up oscillator 66 to feed pulses as through a window into BCD Up/Down Counter 42 as well as Divider 36. Divider 36 allows a predetermined quantity of pulses at 1,000 pps selected by setting dip switches 38; at which time the output of Divider 36 goes to its low setting and inhibits any further delivery of the 1,000 pps from the count up oscillator 66. This low setting of Divider 36 will remain until reset by grounded emitter transistor 54 by the insertion of coins into coin switch 26. The time period per coin is the predetermined quantity described above as selected by the setting of dip switches 38. The primary reason for introducing pulses at a high rate is to enable the display to instantly show the up count pulses without showing a count up to the eye which would be the case if the additional pulses were introduced at low rates.
The BCD Up/Down Counters 42,44, count seconds and tens of seconds and the output of BCD Up/Down Counter 44 is decoded by NAND gate 78' to produce an output whenever it reaches a count of six. The cross-coupled NAND gates 78" and 78'" produce a one shot momentary pulse to reset BCD Up/Down Counters 42 and 44 and a count up pulse to the up input of BCD Up/Down Counter 46. BCD Up/Down Counters 46 and 48 count minutes and tens of minutes. When the total count of BCD Up/Down Counters 42 and 44 reaches a count of sixty, a carry pulse is generated to BCD Up/Down Counter 46 and BCD Up/Down Counters 42 and 44 are reset to zero. The LCD Display 16 actually receive a sixty display, but it happens so fast that the eye can't detect it even though the display may be capable of instantaneously displaying it. The BCD UP/Down Counter 42 receives the count up pulses and the count down pulses for transmission to LCD display readout 16 via BCD to 7 Segment Decoder/Drivers 56,58,60 and 62. It is noted that the binary information at the outputs of BCD Up/Down Counter 42, 44, 46 and 48 is static unless the count is physically changing. There are no pulses visible at the outputs of zero seconds Detector 88 which produces a low output when all of the inputs from the BCD Up/Down Counters 42 & 44 are low, while detector 90 produces a low output when all of the inputs from BCD Up/Down Counters 46 & 48 are low. Dip switches 40 are set to predetermine the time period before the system relay coil 34 is energized. Logic circuit components employing NAND Gates 78, inverters 80, grounded emitter transistor 50 and System On Flip-Flop logic chip 82 are employed to control the bidirectional transfer of pulses between BCD Up/Down Counters 42, 44 and BCD Up/Down Counters 46, 48 as well as the energizing of the system relay coil 34, the system on light 20, last minute light 22 and alarm 18.
After the BCD Up/Down Counters have been loaded with a time and the system goes on, the down input of BCD Up/Down Counter 42 receives a pulse every second from the down count oscillator 30. When BCD Up/Down Counter 42 reaches a count of zero, the borrow output of BCD Up/Down Counter 42 generates a pulse into the down input of BCD Up/Down Counter 44. When BCD Up/Down Counter 44 reaches a count of zero its borrow output pulses the down input of BCD Up/Down Counter 46 through NAND gate 78""' and 78 """ which generates a one shot narrow pulse to the load inputs of BCD Up/Down Counters 42 and 44 to effect a display of the unit nine seconds and tens of seconds of five for a total of 59 seconds.
Counting down continues in this fashion of borrowing and preset load conditions until all counters contain zero counts; causing each of the outputs of detectors 88 and 90 to go low. The low outputs of detectors 88 and 90 causes the output of NAND gates 80 to go high. The high outputs of NAND gates 80 are inputs to NAND gates 78 whose output at the next down count pulse from down count oscillator 30 is a low to inverter 80, which in turn resets System On Flip-Flop logic chip 82, and this in turn switches off the system relay coil 34 through grounded emitter transistor 50 which deenergizes the triac associated therewith. Detector 90 keeps the above operation from occurring as long as there is a positive count in either or both BCD Up/Down Counters 46 and 48.
As previously stated, zero seconds detector 88 is connected to output lines of BCD Up/Down Counters 42 and 44. NAND gate 78 is connected to the first and third output lines which are weighted in binary coding as 1 and 4. This connection, among other functions, determines the length of time the alarm sounds during the last minute of operation. This is easily seen because at this time detector 90 is low and the output of detector 88 is high since there are no minute counts in BCD Up/Down Counters 46 and 48 and there are second counts remaining in BCD Up/Down Counters 42 and 44, therefore NAND gate 78 will result in the alarm 18 sounding as long as the output of BCD Up/Down Counter 44 reads a count five or greater. This alarm will sound until the input to NAND gate 78 that is connected to the primary 1 line goes low thereby resulting in an alarm sounding for 9 seconds. Removing the primary 1 input to NAND gate 78 will increase the alarm time an additional ten seconds since the alarm will then sound until the primary 4 line goes low.
Detector 40 dip switches which are positioned between the outputs of BCD Up/Down Counters 46 and 48 and a source of voltage select the minimum quantity of minutes before the System On Flip-Flop logic chip 82 is reset, resulting in the energizing of the triac associated with grounded emitter 50, and the energizing of system relay coil 34. The output of System On Flip-Flop logic chip 82 inhibits the one pps down count from reaching the down input of the BCD Up/Down Counter 42 until the system relay coil 34 is energized. The output of the System On Flip-Flop logic chip 82 inhibits the NAND gate 80 associated with down count oscillator 30.
Referring to FIG. 3a, the operation of applicant's inventive apparatus is initiated by the insertion of coins in the coin receptor which closes coin switch 26 and thereby grounds relay coil 28 thereby energizing it, so as to close its relay contact and grounding the input circuitry to trigger circuit 52, whose function is to generate a step voltage approximately 250 milliseconds long that is transmitted to the alarm circuitry, resulting in a momentary beep, as well as to Divider 36 via grounded emitter switching transistor 50. Prior to the receipt of the step voltage by Divider 36, dip switches 38 were set so that the time period per coin would be determined and the step voltage in conjunction with these predetermined dip switch voltages would enable Divider 36 to act as a window to allow the passage of count up pulses, generated at 1,000 pulses per second in the count up oscillator 66, to produce quantities of pulses per coin to the BCD Up/Down Counter 42. A count down oscillator 30 which produces pulses at the rate of one pulse per second sends these pulses only to the BCD Up/Down Counter 42 when the system coil 34 is energized because at this time a non-inhibiting signal arrives at the inverter 80 associated with the count down oscillator 30.
Referring to Circuit 3b, the count up and count down pulses received in the BCD Up/Down Counter 42, and transmitted to BCD Up/Down Counters 44,46 and 48 are transmitted to the LCD display readout 16 via BCD to 7 Segment Decoder/Drivers 56,58,60, and 62, shown in FIG. 3(c). The up count pulses, being generated at a higher pulse rate, are counted first in units of seconds, and when BCD Up/Down Counter 42 is filled, carrys over to tens of units of seconds, and when BCD Up/Down Counter 44 is filled, carrys over via logic circuits to units of minutes, and when BCD Up/Down Counter 46 is filled, carrys over to tens of units of minutes, but for all practical purpose never completely fills BCD Up/Down Counter 48. The count down pulses which results in the diminishing of the number of pulses are counted so that when the pulses in the unit of seconds BCD Up/Down Counter 42 are depleted it borrows pulses from the tens of units of seconds BCD Up/Down Counter 44, which in turn borrows from the unit of minutes BCD Up/Down Counter 46 through logic circuits, which in turn borrows from the tens of units of minutes BCD Up/Down Counter 48 until it is emptied, and the process of borrowing then continues until BCD Up/Down Counter 46 is emptied, and the process then continues until BCD Up/Down Counter 44 is emptied, and then the process continues until BCD Up/Down Counter 42 is emptied, after which the system relay coil 34 is de-energized by a signal generated by the zero seconds detector 88, and the system shut down. It is noted that insertion of a coin anytime before the generation of the zero second signal will produce up count pulses, which because they are at a greater pulse rate than the pulse rate of the down count pulses, in effect are able to increase the period of time in the device. The dip switches 40 determining the time period before the system relay coil 34 is energized effectively determine the minimum time required to be purchased before the service or use is rented. At this time a signal is sent through System On Flip-Flop logic chip 82 and grounded emitter transistor 50 associated with said System On Flip-Flop logic chip. System On Flip-Flop logic chip 82 produces at this time a count down control signal which is sent to inverter 80 associated with the count down oscillator 30 and therefore allows the count down pulses to be sent to the BCD Up/Down Counters 42,44,46, & 48 for transmission to the LCD display readout to start the counting down of the elapsed time as stated in the foregoing paragraphs. At the same time the system relay coil 34 is energized, and the system on light 20 is lit.
As the counting down of the time being purchased continues to the point when the outputs of BCD Up/Down Counters 46 & 48 are at zero that is to say both BCD Up/Down Counters are depleted a logic high will be generated and transmitted at this time via inverter 80 associated with the zero minute detector 90 to NAND gate 78 in the last minute light circuit, thereby producing no signal to the input of its associated inverter 80 therefore producing a signal to the input of the grounded emitter, switching transistor 50, energizing last minute lamp 22.
As the count down continues, providing no additional coin has been inserted in the coin receptacle, there will come a time when BCD Up/Down Counters 42 & 44 will become depleted At this time a logic high will be generated and transmitted through the inverter 80 associated with the zero second detector 88 to NAND gate 78. At NAND gate 78, there are four inputs; which are as follows: two logic lows from the zero minute detector 90; a logic low from inverter 80 associated with the signal from the System on Flip-Flop logic chip 82 and a logic low from inverter 80 associated with the zero second detector 88. This condition at the input of NAND gate 78 will produce an logic high to associated inverter 80 thereby producing a logic low at the input of System On Flip-Flop logic chip 82 turning its output off and therefore effecting the deenergizing of associated grounded emitter switching transistor 50 and de-energizing system relay coil 34 and the system on light 20. However, as stated in the foregoing paragraphs, if an additional coin is inserted in the coin receptacle at any time before the signal from the zero second detector 88 is sent out, the count up pulses generated as a result of this coin being at a greater rate than the one pulse per second down count will refill the BCD Up/Down Counters and therefore increase the time elapsed with the additional time purchased.
The logic circuitry between the BCD Up/Down Counters 42,44 and BCD Up/Down Counters 46,48 employs NAND logic circuits in the carry and borrow circuits between the seconds and minutes BCD Up/Down Counters 44 and 46. The NAND logic circuit in the carry circuit between BCD Up/Down Counters 44 and 46 comprises a NAND gate 78' at the output of the second and third lines corresponding to binary weights of 2 and 4, which produces an output whenever the output of BCD Up/Down Counter 44 reaches a count of six. NAND gates 78" and 78'" are a configuration of cross coupled devices which produce a one shot momentary pulse to the up input of BCD Up/Down Counter 46 as well as a momentary pulse through NAND gate 78 to the reset inputs of BCD Up/Down Counters 42 and 44.
After the BCD Up/Down Counters have been loaded and the system relay coil 34 energized, as stated previously, the down input of BCD Up/Down Counter 42 receives a pulse every second. When BCD Up/Down Counter 42 reaches a count of zero, it borrow output generates a pulse and delivers it into the down input of BCD Up/Down Counter; reloading BCD Up/Down Countrer 42 at the same time. When BCD Up/Down Counter 44 reaches a count of zero, its borrow output pulses the input of cross coupled NAND gates 78""' and 78""" to deliver a pulse into the down input of BCD Up/Down Counter 46; reloading the BCD Up/Down Counters 42 and 44 at the same time by a load pulse resulting in the resetting of said counters to a predetermined count of 59 because each of the BCD Up/Down Counters 42 and 44 has been hard wired for said predetermined binary code.
As previously stated, counting down continues in this fashion of borrowing and preset load conditions until all BCD Up/Down Counters 42,44,46 and 48 reach the count of zero, at which time each of the outputs of the detectors 88 and 90 are in their logic lows resetting System On Flip-Flop logic chips 82 and resulting in the system relay coil being deenergized.
Referring to FIG. 3(c), the outputs from BCD Up/Down Counters 42,44,46, & 48 are the inputs to BCD to 7 Segment Decoder/Drivers 58,60, & 62 respectively where the binary logic is decoder for utilization in the LCD display readout 16.
Although applicant's inventive apparatus has been described in only one apparatus and circuit embodiment, it is expected that applicant's invention will not be so limited or restricted but shall be limited only by the scope and breadth of the claims annexed hereto.
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A coin operated elapsed time apparatus capable of receiving coins at any time, even while counting down, in order to increase the time remaining and therefore avoid the additional costs required to activate the system again if the service or use of apparatus required that more time be rented or purchased. The apparatus continuously displays the time remaining and gives a warning a predetermined period of time before the time runs out, thereby enabling the purchase of additional time and displaying the sum of the elapsed time remaining and the additional time purchased immediately after the insertion of an additional coin.
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BACKGROUND OF THE INVENTION
This invention relates generally to the field of minimally invasive surgery, such as intervertebral disc and cataract surgery and more particularly to a handpiece for practicing the liquefraction technique.
The human eye in its simplest terms functions to provide vision by transmitting light through a clear outer portion called the cornea, and focusing the image by way of the lens onto the retina. The quality of the focused image depends on many factors including the size and shape of the eye, and the transparency of the cornea and lens.
When age or disease causes the lens to become less transparent, vision deteriorates because of the diminished light which can be transmitted to the retina. This deficiency in the lens of the eye is medically known as a cataract. An accepted treatment for this condition is surgical removal of the lens and replacement of the lens function by an artificial intraocular lens (IOL).
In the United States, the majority of cataractous lenses are removed by a surgical technique called phacoemulsification. During this procedure, a thin phacoemulsification cutting tip is inserted into the diseased lens and vibrated ultrasonically. The vibrating cutting tip liquifies or emulsifies the lens so that the lens may be aspirated out of the eye. The diseased lens, once removed, is replaced by an artificial lens.
Recently, a new tissue removal technique has been developed that involves the injection of hot (approximately 45° C. to 105° C.) water or saline to liquefy or gellate tissue, such as the hard lens nucleus, thereby making it possible to aspirate the liquefied tissue. Aspiration is conducted with the injection of the heated solution and the injection of a relatively cool solution, thereby quickly cooling and removing the heated solution. One application of this technique is more fully described in U.S. Pat. No. 5,616,120 (Andrew, et al.), the entire contents of which is incorporated herein by reference. The apparatus disclosed in the publication, however, heats the solution separately from the surgical handpiece. Temperature control of the heated solution can be difficult because the fluid tubings feeding the handpiece typically are up to two meters long, and the heated solution can cool considerably as it travels down the length of the tubing.
The use of electrosurgical handpieces to remove tissue is known. For example, U.S. Pat. No. 5,009,656 (Reimels), the entire contents of which is incorporated herein by reference, describes an electrosurgical handpiece having an inner and an outer tube separated by an insulator. Current is passed between the inner and the outer tube to cause a spark that is used to cut tissue. This device intentionally creates an air gap between the electrodes to facilitate sparking, and does not use heated fluid as the cutting medium.
Therefore, a need continues to exist for a surgical handpiece that can heat internally the solution and create high pressure, high rise rate waves or pulses used to perform the liquefraction technique.
BRIEF SUMMARY OF THE INVENTION
The present invention improves upon the prior art by providing a surgical handpiece having a tip with at least two coaxially spaced electrically conductive tubes. The tubes are separated by an electrical insulator. The interior of the inner tube is used for aspiration of liquefied tissue. The distal portion of the interior tube terminates just inside of the outer tube so as to form a boiling region. Electrical current is passed between the inner and outer tube to rapidly boil any surgical fluid in the boiling region. The boiling fluid rapidly expands out of the ring between the tube ends and forces hot fluid to contact the targeted tissue, thereby liquefying the tissue and allowing the tissue to be aspirated.
Accordingly, one objective of the present invention is to provide a surgical handpiece having a tip with at least two tubes.
Another objective of the present invention is to provide a handpiece for practicing the liquefraction method of tissue removal.
Another objective of the present invention is to provide a handpiece for practicing intervertebral disc surgery.
These and other advantages and objectives of the present invention will become apparent from the detailed description and claims that follow.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic, cross-sectional view of a first embodiment of a tip that can be used with the handpiece of the present invention.
FIG. 2 is a block diagram of a first control system that can be used with the surgical handpiece of the present invention.
FIG. 3 is a schematic, cross-sectional view of a second embodiment a tip that can be used with the handpiece of the present invention.
FIG. 4 is a perspective view of a handpiece and control console that may be used with the present invention.
FIG. 5 is a block diagram of a second control system that can be used with the surgical handpiece of the present invention which is similar to the control system illustrated in FIG. 2 except for the addition of a control valve in the aspiration line.
DETAILED DESCRIPTION OF THE INVENTION
As best seen in FIGS. 1 and 4, in the first embodiment of the present invention tip 10 to be used with handpiece 9 generally includes inner tube 12 and outer tube 14 separated by insulator 16. Inner tube 12 has an inside diameter D 1 of between 0.010 inches and 0.050 inches, with 0.030 being preferred, and an outside diameter of between 0.015 inches and 0.060 inches, with 0.036 inches being preferred. Outer tube 14 has an outside diameter D 2 of between 0.025 inches and 0.075 inches, with 0.045 inches being preferred. Inner tube 12 and outer tube 14 may be made of any electrically conductive material, such as stainless steel or titanium tubing. Insulator 16 may be made of any electrically nonconductive material resistant to high temperatures, such as polyimide, silicone or ceramic. Insulator 16 may be any suitable thickness, but between 0.001 inches and 0.003 inches is preferred, with 0.002 inches being most preferred.
Outer tube 14 extends distally past inner tube 12 a distance L 1 of between 0.010 inches and 0.030 inches, with 0.020 inches being preferred. Insulator 16 may be flush with inner tube 12 or may extend distally past inner tube 12 a distance L 2 of between 0.00 inches and 0.020 inches. The space between outer tube 14 and inner tube 12 forms boiling region 18. While only two embodiments of the tip of the present invention are disclosed herein, any tip producing adequate pressure pulse force, rise time and frequency may also be used. For example, any suitable tip producing a pressure pulse force of between 0.03 grams and 20.0 grams, with a rise time of between 1 gram/sec and 20,000 grams/sec, with between 3000 grams/sec and 20,000 grams/sec being more preferred and a frequency of between 1 Hz and 400 Hz may be used, with between 25 Hz and 200 Hz being most preferred.
In use, surgical fluid (e.g. saline irrigating solution) enters boiling region 18. Electrical current (preferably Radio Frequency Alternating Current "RFAC") is delivered to and across inner tube 12 and outer tube 14 through the surgical fluid in boiling region 18 because of the conductive nature of the surgical fluid. As the current flows through boiling region 18, the surgical fluid boils. As the surgical fluid boils, it expands rapidly out of tip 10. Subsequent pulses of electrical current form sequential gas bubbles. The size and pressure of the fluid pulse obtained by boiling region 18 can be varied by varying the length, timing and/or power of the electrical pulse sent to tubes 12 and 14 and by varying the dimensions of boiling region 18.
As seen in FIGS. 2, 4 and 5, control system 300 or 300' for use in operating handpiece 9, 311 or 311' containing tip 10, 110, 310 or 310' includes control module 347 or 347', RF amplifier 312 or 312' and function generator 314 or 314'. Power is supplied to RF amplifier 312 or 312' by DC power supply 316 or 316', which preferably is an isolated DC power supply operating at ±200 volts. Control module 347 or 347' may be any suitable microprocessor, and may receive input from operator input device 318 or 318'. Function generator 314 or 314' provides the electric wave form to amplifier 312 or 312' and preferably operates at 200 KHz to 10 MHz, and more preferably between 450 KHz and 1 MHZ, to help minimize corrosion.
In use, control module 347 or 347' receives input from surgical console 320 or 320'. Console 320 or 320' may be any commercially available surgical control console such as the LEGACY® SERIES TWENTY THOUSAND® surgical system available from Alcon Laboratories, Inc., Fort Worth, Tex. Console 320 or 320' is connected to handpiece 9, 311 or 311' through irrigation line 322 or 322' and aspiration line 324 or 324', and the flow through lines 322 or 322' and 324 or 324' is controlled by the user via footswitch 326 or 326'. Irrigation and aspiration flow rate information in handpiece 9, 311 or 311' is provided to control module 347 or 347' by console 320 or 320' via interface 328 or 328', which may be connected to the ultrasound handpiece control port on console 320 or 320' or to any other output port. Control module 347 or 347' uses footswitch 326 or 326' information provided by console 320 or 320' and operator input from input device 318 or 318' to generate two control signals 330 or 330' and 332 or 332'. Signal 330 or 330' is used to control function generator 314 or 314'. Based on signal 330 or 330', function generator 314 or 314' provides a wave form at the operator selected frequency and amplitude determined by the position of footswitch 326 or 326' to RF amplifier 312 or 312' which is amplified to advance the powered wave form to tip 10, 110, 310 or 310' to create heated, pressurized pulses of surgical fluid.
As best seen in FIG. 5, control system 300' may also use valve 350 placed in aspiration line 324'. Valve 350 is controlled by control module 347' to alternate between an open and a closed position, thereby creating pulsed aspiration flow.
As best seen in FIG. 3, in a second embodiment of the present invention, tip 110 which may be used with handpiece 9 or 311 generally includes inner tube 112 and outer tube 114 separated by insulator 116. Inner tube 112 has a generally conical distal end 113. Conical end 113 creates a boiling region 118 between inner tube 112 and outer tube 114 that generally increases in size from region 118 to region 118' and 118". As current flows between outer tube 114 and inner tube 112, boiling begins at region 118 where the electrode gap is the smallest. As the fluid in area 118 boils, the resistance to current flow is increased as the fluid turns to steam or vapor. In this manner, the boiling of the fluid moves sequentially from region 118 to region 118' and then to region 118" where the steam escapes out port 115 in outer tube 114 where the steam and/or heated fluid liquefies the targeted tissue at region 117 adjacent to port 115.
The present invention may also be used for intervertebral disc surgery, such as intradisc thermal annuloplasty. During this surgery, the ligaments encasing a spinal disc are heated to destroy invading veins and nerves and to shrink the ligaments to seal any tears or ruptures. This surgical procedure is more completely described in U.S. Pat. Nos. 5,201,729 and 5,433,739 and in U.S. patent application Ser. Nos. 08/881,525, 08/881,527, 08/881,692, 08/881,693 and 08/881,694 which correspond to WIPO Publication No. WO 98/17190, the entire contents of which are incorporated herein by reference.
This description is given for purposes of illustration and explanation. It will be apparent to those skilled in the relevant art that changes and modifications may be made to the invention described above without departing from its scope or spirit. For example, it will be recognized by those skilled in the art that the present invention may be combined with ultrasonic and/or rotating cutting tips to enhance performance.
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A surgical handpiece tip with at least two coaxially spaced electrically conductive tubes. The tubes are separated by an electrical insulator. The interior of the inner tube is used for aspiration of liquefied tissue. The distal portion of the interior tube terminates just inside of the outer tube so as to form a boiling region. Electrical current is passed between the inner and outer tube to rapidly boil any surgical fluid in the boiling region. The boiling fluid rapidly expands out of the ring between the tubes and contacts the targeted tissue, thereby liquefying the tissue and allowing the tissue to be aspirated.
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FIELD OF THE INVENTION
[0001] The present invention relates to an oxygen separation module and apparatus that incorporates a plurality of tubular membrane elements, each configured to separate oxygen from an oxygen containing feed stream when an electric potential difference is applied to produce oxygen ion transport through an electrolyte of the tubular membrane elements. More particularly, the present invention relates to such an oxygen separation module and apparatus in which manifolds to collect the separated oxygen are positioned at opposite ends of the tubular membrane elements and are connected to the tubular membrane elements such that a portion of the tubular membrane elements are connected to one of the manifolds and another portion of the tubular membrane elements are connected to the other of the manifolds.
BACKGROUND OF THE INVENTION
[0002] Electrically driven oxygen separators are used to separate oxygen from oxygen containing feed, for example, air. Additionally, such devices are also used in purification application where it is desired to purify an oxygen containing feed by separating oxygen from the feed. The device can also be configured to separate H2O into H2 and O2 or CO2 into CO and O2. Electrically driven oxygen separators can utilize tubular membrane elements having a layered structure containing an electrolyte layer capable of transporting oxygen ions when subjected to an elevated temperature, cathode and anode electrode layers located at opposite surfaces of the electrolyte layer and current collector layers to supply an electrical current to the cathode and anode electrode layers.
[0003] When the tubular membrane elements are subjected to the elevated temperature, the oxygen contained in a feed will ionize on one surface of the electrolyte layer, adjacent the cathode electrode layer by gaining electrons from an applied electrical potential. Under the impetus of the applied electrical potential, the resulting oxygen ions will be transported through the electrolyte layer to the opposite side, adjacent the anode layer and recombine into elemental oxygen.
[0004] The tubular membrane elements are housed in an electrically heated containment to heat the tubular membrane elements to an operational temperature at which oxygen ions will be transported. Additionally, such tubular membrane elements can be manifolded together such that the oxygen containing feed is passed into the heated containment and the separated oxygen is withdrawn from the tubular membrane elements through a manifold. In certain purification applications, the oxygen containing feed can be passed through the interior of the tubular membrane elements and the separated oxygen can be withdrawn from the containment.
[0005] Typical materials that are used to form the electrolyte layer are yttrium or scandium stabilized zirconia and gadolinium doped ceria. The electrode layers can be made of mixtures of the electrolyte material and a conductive metal, a metal alloy or an electrically conductive perovskite. Current collectors in the art have been formed of conductive metals and metal alloys, such as silver as well as mixtures of such metals and metallic oxides.
[0006] The tubular membrane elements can be contained in one or more modules in which in each module, the tubular membrane elements are arranged in bundles and are held in place by end insulation members adjacent to the opposite ends of the tubular membrane elements. These modules can be positioned within insulated, heated enclosures to heat the tubular membrane elements to an operational temperature at which oxygen ion transport can occur. The insulated enclosure also has inlets and outlets within end walls of the enclosure to allow an oxygen containing feed stream to be passed into the enclosure and thereby to contact the tubular membrane elements. As a result of the oxygen separation, a retentate stream is formed that is discharged from the enclosure through the outlet. This type of electrically driven oxygen separation device is shown in U.S. Patent Appln. Ser. No. 2010/076280 A1.
[0007] As can be appreciated, it is important that electrically driven oxygen separation devices reliably deliver the oxygen and at the lowest cost possible. With respect to reliability, a major problem with electrically driven oxygen separation devices, is that failure of the tubular membrane elements can occur. As a result, the oxygen containing feed stream will pass through the point of failure in a particular tubular membrane and little if any oxygen will be separated by the membrane that has the defect. Since, a major advantage of supplying oxygen from an electrically driven oxygen separation device is that the oxygen can be produced at ultra-high purity, the defective tubular membrane element will result in an unacceptable decrease in purity of the oxygen product. Therefore, as a result of such failure, the electrically driven oxygen separation device will have to be removed from service. Furthermore, such a device is most useful if the outlet of oxygen separation modules are connected to a storage tank and the oxygen is stored at pressure. In the case of a tube failure, the stored oxygen in the tank will discharge through the fractured ceramic tube. In order to reduce costs, the electrically driven oxygen separator has to be assembled in a cost efficient manner. In the patent application discussed above, the use of modules of such elements coupled with polymeric end seals go a long way toward reducing assembly costs. However, such ends seals represent another possible point of failure because they have only a limited ability to withstand the high temperatures that are necessary to induce the oxygen ion transport in the tubular membrane elements.
[0008] As will be discussed, the present invention provides a module and an electrically driven oxygen separation device that, among other advantages is capable of operating upon failure of one or more tubular membrane elements and that is specifically designed to cool the end seals.
SUMMARY OF THE INVENTION
[0009] The present invention provides, in one aspect, a module for an electrically driven oxygen separator that incorporates a plurality of tubular membrane elements. Each of the tubular membrane elements is configured to separate oxygen from an oxygen containing feed stream when an electric potential difference is applied to induce oxygen ion transport in an electrolyte thereof A first manifold and a second manifold, configured to collect the oxygen, are spaced apart from one another with the tubular membrane elements situated between the first manifold and the second manifold. The first and second manifold are connected to the tubular membrane elements such that oxygen is received by the first manifold from a first portion of the tubular membrane elements and by the second manifold from a second portion of the tubular membrane elements.
[0010] Therefore, upon failure of at least one of the tubular membrane elements in either the first portion or the second portion of the tubular membrane elements, oxygen is able to be collected from either the first portion or the second portion of the tubular membrane elements that do not include the at least one of the tubular membrane elements that has failed. Check valves can be provided to pneumatically isolate the failed tube and associated first or second tubular membrane elements. While the oxygen will of course be delivered at a lower rate after such a failure, unlike electrically driven oxygen separators of the prior art, the failure of one or more elements will not necessarily result in the electrically driven oxygen separator being withdrawn from service.
[0011] End seals can be located at opposite ends of the tubular membrane elements. Each of the first manifold and the second manifold have a collection element to collect the oxygen produced by the tubular elements and first and second elongated elements connected at one end to the collection element and at the other end penetrating the end seals at the opposite ends of the tubular membrane elements. The first of the elongated elements are of tubular configuration to conduct the oxygen and the second of the elongated elements are configured to prevent flow of the oxygen to the collection element of each of the first manifold and the second manifold. The first of the elongated elements alternating with the second of the elongated elements such that as between two adjacent tubular membrane elements, the oxygen flows from one of the two adjacent tubular membrane elements to the collection element of the first manifold and from the other of the two adjacent tubular membrane elements to the collection element of the second manifold. The second of the elongated elements can be of solid configuration.
[0012] The end seals can comprise plug-like members located within the tubular membrane element and formed by an elastomer to produce hermetic seals at the opposite ends of the tubular membrane elements and deposits of a ceramic adhesive located within the tubular membrane elements adjacent to the plug-like members and positioned to prevent outward movement of the plug-like members. The tubular membrane elements can be arranged in a bundle and are held in place by two opposed end insulation members located adjacent to the opposed ends of the tubular membrane elements. In such case, each of the first manifold and the second manifold has a spider-like configuration with the first and the second elongated elements radiating from the collection element of each of the first manifold and the second manifold. Further, each of the two opposed end insulation members has an inlet opening for passage of the oxygen containing feed stream.
[0013] Each of the tubular membrane elements has an inner anode layer, an outer cathode layer and an electrolyte layer located between the anode layer and the cathode layer to form the electrolyte. Two current collector layers are located adjacent to and in contact with the anode layer and the cathode layer and situated on the inside and outside of the tubular membrane element to allow the electrical potential to be applied by a power source. The tubular membrane elements can be connected in series and contain current distributors of helical configuration in contact with one of the two current collector layers on the inside of the tubular membrane elements to conduct an electrical current applied by electrical conductors passing through the feed throughs.
[0014] In another aspect, the present invention provides an electrically driven oxygen separation apparatus. Such apparatus is provided with an enclosure having two inlet regions, a heated interior region located between the inlet regions and having opposed end walls positioned adjacent to the inlet regions, opposed openings defined in the end walls, a sidewall connecting the end walls and heating elements positioned to heat the heated interior region. An outlet extends from the heated interior region and through the sidewall. A plurality of tubular membrane elements are provided that are each configured to separate oxygen from an oxygen containing feed stream when an electric potential difference is applied to induce oxygen ion transport in an electrolyte thereof. End seals are located at opposite ends of the tubular membrane elements.
[0015] The tubular membrane elements are arranged in a bundle and held in place by two opposed end insulation members located adjacent to the opposed ends of the tubular membrane elements. The bundle is positioned within the enclosure and with the end insulation members situated within the openings of the end walls and the opposed ends of the tubular membrane elements and the end seals thereof projecting outwardly from the end insulation members and into the two inlet regions. At least one manifold is connected to the tubular membrane elements and configured to collect the oxygen produced by the tubular membrane elements. Inlets are located within the two end insulation members for passage of two oxygen containing feed streams from the inlet regions to the heated interior region and two blowers connected to the two inlet regions to circulate the oxygen containing feed stream into the inlet region and past the end seals to cool the end seals and then, through the inlets, thereby to contact the membrane elements inside the heated enclosure and to discharge a heated retentate from the heated enclosure that is formed by separation of the oxygen from the oxygen containing feed stream. The cooling of the end seals help to prevent failure of the electrically driven oxygen separator in the first instance.
[0016] As set forth above, the at least one manifold can be a first manifold and a second manifold spaced apart from one another with the tubular membrane elements situated between the first manifold and the second manifold. The first manifold and the second manifold are connected to the tubular membrane elements such that oxygen is received by the first manifold from a first portion of the tubular membrane elements and by the second manifold from a second portion of the tubular membrane elements. Upon failure of at least one of the tubular membrane elements in either the first portion or the second portion of the tubular membrane elements, oxygen is able to be collected from either the first portion or the second portion of the tubular membrane elements that do not include the at least one of the tubular membrane elements that has failed.
[0017] Each of the first manifold and the second manifold can be provided with a collection element to collect the oxygen produced by the tubular elements and first and second elongated elements connected at one end to the collection element and at the other end penetrating the end seals at the opposite ends of the tubular membrane elements. The first of the elongated elements are of tubular configuration to conduct the oxygen and the second of the elongated elements are configured to prevent flow of the oxygen to the collection element of each of the first manifold and the second manifold. The first of the elongated elements alternate with the second of the elongated elements such that as between two adjacent tubular membrane elements, the oxygen flows from one of the two adjacent tubular membrane elements to the collection element of the first manifold and from the other of the two adjacent tubular membrane elements to the collection element of the second manifold.
[0018] The end seals can comprise plug-like members located within the tubular membrane element and formed by an elastomer to produce hermetic seals at the opposite ends of the tubular membrane elements and deposits of a ceramic adhesive located within the tubular membrane elements adjacent to the plug-like members and positioned to prevent outward movement of the plug-like members. As indicated above, the cooling of such end seals has proven to be critical for preventing failure of the electrically driven oxygen separation device. The second of the elongated elements can be of solid configuration. Each of the first manifold and the second manifold has a spider-like configuration with the first and the second elongated elements radiating from the collection element of each of the first manifold and the second manifold.
[0019] Each of the membrane elements has an inner anode layer, an outer cathode layer and an electrolyte layer located between the anode layer and the cathode layer to form the electrolyte. Two current collector layers are located adjacent to and in contact with the anode layer and the cathode layer and situated on the inside and outside of the tubular membrane element to allow the electrical potential to be applied by a power source. The tubular membrane elements can be connected in series and the tubular membrane elements can contain current distributors of helical configuration in contact with one of the two current collector layers on the inside of the tubular membrane elements to conduct an electrical current applied by electrical conductors passing through the feed throughs.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] While the specification concludes with claims that distinctly point out the subject matter that Applicants regard as their invention, it is believed that the invention will be understood when taken in connection with the accompanying drawings in which:
[0021] FIG. 1 is a schematic sectional view of an electrically driven oxygen separation apparatus of the present invention;
[0022] FIG. 2 is an elevational view of a module of the present invention;
[0023] FIG. 3 is an enlarged, fragmentary perspective view of the module shown in FIG. 2 ;
[0024] FIG. 4 is a schematic, transverse cross-sectional view of a tubular membrane element used in a module of the present invention; and
[0025] FIG. 5 is a schematic, sectional view of a tubular membrane element used in a module of the present invention.
DETAILED DESCRIPTION
[0026] With reference to FIG. 1 , an electrically driven oxygen separator 1 of the present invention is illustrated that has two modules 10 housed within an enclosure 12 . It is understood that there could be more or fewer modules 10 depending upon the application of an oxygen separation in accordance with the present invention.
[0027] With reference to FIG. 2 , each of the module 10 are formed by a bundle of tubular membrane elements that are divided into a first portion of the tubular membrane elements 14 and a second portion of the tubular membrane elements 16 . The first and second portions of the tubular membrane elements are held in position by end insulation members 18 and 20 that are fabricated from high purity alumina fiber. The tubular membrane elements for exemplary purposes can have an outer diameter of about 6.35 mm., a total wall thickness of about 0.5 mm. and a length of about 55 cm. The oxygen that is separated by such first and second portions of the tubular membrane elements 14 and 16 are collected by first and second manifolds 22 and 24 that as illustrated are spaced apart from one another with the first and second portions of the tubular membrane elements 14 and 16 located between the first and second manifolds 22 and 24 .
[0028] The first and second manifolds 22 and 24 are connected to the first and second portions of the tubular membrane elements 14 and 16 such that oxygen is received by the first manifold 22 from the first portion of the tubular membrane elements 14 and by the second manifold 24 from the second portion of the tubular membrane elements 16 . With additional reference to FIG. 3 , the connection of the first manifold 22 is illustrated. Each of the first and second manifolds 22 and 24 are provided with first elongated elements 26 and second elongated elements 28 that radiate in a spider-like arrangement from a collection element 30 that actually collects the oxygen that is separated by the first and second portions of the tubular membrane elements 14 and 16 . As illustrated, the first portion of the tubular membrane elements 14 alternate with the second portion of the tubular membrane elements 16 and the elongated elements 26 alternate with the elongated elements 28 . The elongated elements penetrate the end seals 70 and 72 provided in opposite ends of both of the first and second portions of the tubular elements 14 and 16 . The first elongated elements 26 are hollow tubes and the second elongated elements 28 are of solid configuration, although such elongated elements 28 could be hollow tubes that are plugged. In any case, since the first elongated elements 26 are hollow tubes, the oxygen will flow from the first portion of the tubular membrane elements 14 to the collection element 30 while the oxygen will not flow from the second portion of the tubular membrane elements 16 to the collection elements 30 . At the opposite end of the module 10 , however, the second manifold 24 , that is identical to the first manifold 22 , is slightly rotated such that the first elongated elements 26 penetrate the end seals 72 of the second portion of the tubular membrane elements 16 and the second elongated elements 28 penetrate the end seals 70 of the first portion of the tubular membrane elements 16 . As a result, the oxygen produced by the second portion of the tubular membrane elements 16 is collected by the collection element of the second manifold 24 . Consequently, if one or more of the first portion of the tubular membrane elements 14 fail, oxygen will still able to be produced, albeit at a lower flow rate, from the second portion of the tubular membrane elements 16 that have not failed and vice-versa.
[0029] As can be appreciated, it is possible to construct an embodiment of the present invention in which there is no such alternation of tubular membrane elements and elongated elements. For example the first portion of the tubular membrane elements 14 could be located on one side and the second portion of the tubular membrane elements 16 could be located on the other side of the module. In such case, the first elongated elements 14 would be located one side of the module 10 and the second elongated elements 16 would be located on the opposite side. Furthermore, embodiments of the present invention are also possible in which the tubular membrane elements are located in the same plane. As can be appreciated, the manifold in such case would have an elongated collection element with elongated elements extending therefrom at right angles to penetrate the end seals of the tubular membrane elements. In any embodiment, the tubular membrane elements are divided into portions such that one manifold will conduct the oxygen from one portion and the other manifold will conduct oxygen from the other portion.
[0030] With additional reference to FIG. 4 , each of the tubular membrane elements 14 is provided with a cathode layer 34 , an anode layer 36 and an electrolyte layer 38 . Two current collector layers 40 and 42 are located adjacent the anode layer 36 and the cathode layer 34 , respectively, to conduct an electrical current to the anode layer and the cathode layer. Tubular membrane elements 16 are identical to tubular membrane elements 14 . Although the present invention has application to any composite structure making up a tubular membrane element 14 , for exemplary purposes, the cathode layer 36 and the anode layer 34 can be between about 10 and about 50 microns thick and the electrolyte layer 38 can be between about 10 microns and about 1 mm. thick, with a preferred thickness of about 500 microns. The electrolyte layer 38 is gas impermeable and can be greater than about 95 percent dense and preferably greater than 99 percent dense. Each of the cathode layer 36 and the anode layer 34 can have a porosity of between about 30 percent and about 50 percent and can be formed from (La 0.8 Sr 0.2 ) 0.98 MnO 3-δ . The electrolyte layer 38 can be 6 mol % scandium oxide, 1 mol % cerium oxide doped zirconium oxide. The current collector layers 40 and 42 can each be between about 50 and about 150 microns thick, have a porosity of between about 30 percent and about 50 percent and can be formed from a powder of silver particles having surface deposits of zirconium oxide. Such a powder can be produced by methods well known in the art, for example by wash-coating or mechanical alloying. For exemplary purposes, a silver powder, designated as FERRO S7000-02 powder, can be obtained from Ferro Corporation, Electronic Material Systems, 3900 South Clinton Avenue, South Plainfield, N.J. 07080 USA. The size of particles contained in such powder is between about 3 and about 10 microns in diameter and the particles have a low specific surface are of about 0.2 m 2 /gram. Zirconia surface deposits can be formed on such powder such that the zirconia accounts for about 0.25 percent of the weight of the coated particle.
[0031] During operation of the oxygen separator 1 , the oxygen contained in oxygen containing feed stream 44 contacts the current collector layer 40 and permeates through pores thereof to the cathode layer 36 which as indicated above is also porous. The oxygen ionizes as a result of an electrical potential applied to the cathode and anode layers 34 and 36 at current collector layers 40 and 42 . The resulting oxygen ions are transported through the electrolyte layer 38 under the driving force of applied potential and emerge at the side of the electrolyte layer 38 adjacent the anode layer 34 where electrons are gained to form elemental oxygen. The oxygen permeates through the pores of the anode layer 36 and the adjacent current collector 42 where the oxygen passes into the interior of the tubular membrane elements 14 . The same function, in the same manner would be obtained for tubular membrane elements 16 .
[0032] It is to be noted, that although the cathode layer is located on the outside of the tubular membrane elements 14 and 16 , it is possible to reverse the layers so that the anode layer were located on the outside of the tubular membrane elements 14 and 16 and the cathode layer were located on the inside. Such an embodiment would be used where the device were used as a purifier. In such case the oxygen containing feed would flow on the inside of the tubular membrane elements 14 .
[0033] With continued reference to FIG. 5 , it can be seen that the outer, opposite end sections of each of the tubular membrane elements 14 are located within end insulation members 18 and 20 . It is to be noted that the following discussion would have equal applicability to tubular membrane elements 16 . As a result, there is essentially no oxygen transport taking place at such locations. As illustrated, the ends of each of the tubular membrane elements 14 are devoid of both the cathode layer 36 and its associated current collector 40 and the anode layer 34 and its associated current collector 42 so that current does not flow within the tubular membrane elements 14 at such locations. It has been found that where the tubular membrane elements are designed with electrical current flow within such insulated end section, the ceramic will tend to undergo a chemical reduction reaction at such end sections with a consequent potential of a failure of the elements. It is to be noted that embodiments of the present invention are possible in which the anode and cathode layers and their associated current collector layers extend to the physical ends of the tubular membrane elements 14 even when covered with an end insulation members.
[0034] Tubular membrane elements 14 and 16 incorporate end seals 70 and 72 formed at the opposite ends thereof. Each of the end seals 70 and 72 are formed by plug-like members 74 and 76 that are each fabricated from an elastomer to effect a hermetic seal at the ends of the tubular membrane elements 14 and 16 . A suitable elastomer is a VITON® fluoroelastomer obtained through Dupont Performance Elastomers of Willmington, Del., United States of America.
[0035] During operation of tubular membrane elements 14 and 16 oxygen will accumulate and will tend to force the plug-like members 74 and 76 in an outward direction and from the ends of tubular membrane elements 14 and 16 . In order to retain the plug-like members 74 and 76 within the end of tubular membrane elements 14 and 16 , deposits of a ceramic adhesive 78 and 80 are introduced into the ends of tubular membrane elements 14 and 16 at a location adjacent to plug-like member 74 and plug-like member 76 , respectively. A suitable ceramic adhesive can be a RESBOND™ 940 fast setting adhesive manufactured by Cotronics Corporation of Brooklyn, N.Y., United States of America. It is to be noted that other suitable means to retain plug-like member 74 and 76 could be employed such as mechanical keys located adjacent to plug-like member 74 that penetrate opposed transverse bores defined at the ends of tubular membrane elements 14 and 16 or sleeves cemented in place within the ends of tubular membrane elements 14 and 16 .
[0036] As illustrated, an elongated element 28 penetrates the deposit 78 and the plug-like member 74 along with an electrical feed through 82 and an elongated elements 26 penetrates deposit 80 and plug-like member 76 . In this regard an axial bore 84 and 86 are defined within plug-like member 74 for penetration of electrical feed through 82 and the second elongated element 28 . An axial bore 88 is provided within plug-like member 76 for penetration of the elongated element 26 .
[0037] In order to install plug-like members 74 and 76 within the end of tubular membrane elements 14 and 16 , the same is fabricated with a larger outer diameter than the inner diameter of tubular membrane elements 14 and 16 and then cooled with liquid nitrogen. The percentage difference in diameters can be about 10 percent. Thereafter, plug-like members 74 and 76 are installed in the ends of tubular membrane elements 14 and 16 and as such members warm to ambient temperature, the same expands to produce a hermetic seal within the ends of tubular membrane element 14 and 16 . Additionally, each of the bores 84 , 86 and 88 are all sized smaller than the associated electrical feed through 82 and the elongated elements 28 and 26 . After installation and warming of the plug-like members 74 and 76 , the electrical feed through 84 and the elongated elements 28 and 26 are forced through the smaller bores to create hermetic seals. Thereafter, the ends are filled with the deposits of ceramic adhesive 78 and 80 to complete the end seals. As could be appreciated, other types of end seals are known in the art such as ceramic end caps and ceramic deposits within the tubes.
[0038] The potential is applied to each of the tubular membrane elements 14 and 16 by means of a connection to the current collector layer 42 adjacent of the cathode layer 34 by means of a conductor 90 that is looped around the current collector layer 42 by a loop 92 that is held in place by silver paste 94 . Connection is established to current collector layer 40 adjacent the anode layer 36 by means of a conductor 90 that is attached to a current distributor 98 of helical configuration. Conductor 90 passes through the electrical feed through 82 .
[0039] Although the tubular membrane elements 14 and 16 could be connected in parallel, preferably a series connection is established in which the current collector 40 of each of the tubular membrane elements 14 and 16 is connected to the current collector 42 of the next in series of the tubular membrane elements 14 and 16 . Therefore, the current collector 40 of each particular first tubular membrane element 14 is connected to the current collector 42 of the second tubular membrane element 16 located directly adjacent thereto and the current collector 42 of the second tubular membrane element 16 is connected to the current collector elements 40 of the next, adjacent first tubular membrane element. Thus, as can best be seen in FIG. 3 , the conductor 90 of each of the first tubular membrane elements 14 is connected to the end of the electrical feed through 82 of each of the adjacent second tubular membrane elements 16 and the conductor 90 passes through the second insulating member 20 for connection to such adjacent first tubular element 14 at loop 92 thereof Since the first tubular membrane elements 16 and the second tubular membrane element 14 are reversed, at the first insulating member 18 , the conductor 90 connects to the electrical feed through 82 of each of the first tubular membrane elements 14 , passes through the first insulating member 18 and then is connected to the second tubular membrane elements 16 via the loop 92 thereof This being said in case of two adjacent first and second tubular membrane elements 14 and 16 , such connection between the elements as aforesaid is not established and instead, power cords 100 and 102 are connected to the electrical feed through 82 of the second tubular membrane element 16 and the current collector layer 42 of the first tubular membrane element 14 so that the electrical potential can be applied to the first and second tubular membrane elements 14 and 16 .
[0040] With reference again to FIG. 1 , the enclosure 12 has two opposite end walls 104 and 106 provided within opposite openings 108 and 110 within which the insulating members 18 and 20 are lodged with the ends of the first and second tubular membrane elements 14 and 16 exposed. The opposite end walls 104 and 106 are connected by a sidewall 112 thereby define a heated enclosure 114 that is heated by heating elements 116 embedded within the sidewall 112 . Attached to the end walls 104 and 106 are inlet regions 120 and 122 defined by the interior of cowlings 124 and 126 , respectively. Attached to the cowlings 124 and 126 are blowers 128 and 130 , respectively, that direct feed air streams 44 and 44 to the inlet regions 120 and 122 . With brief reference to FIG. 3 , the insulating member 20 is provided with an opening in the form of an axial bore 136 that allows part of the feed air stream 44 to flow past the ends of the tubular membrane elements 14 , 16 and thereby cool the ends and the deposits of elastomer that form the end seals before passing into the heated enclosure 114 and contact the first and second tubular membrane elements 14 and 16 . Although not illustrated, insulating member 18 is provided with a like opening to allow at least a portion of the feed air stream 44 to flow past the exposed ends of the first and second tubular membrane elements 14 and 16 and into the heated enclosure 114 for the same purpose. The separation of the oxygen from the feed air streams 44 and 44 form a retentate that is discharged from the heated enclosure 114 , through an exhaust 136 as a retentate stream 138 .
[0041] As can be appreciated, embodiments of the present invention are possible in which in place of the axial bores or other openings within insulating members 18 and 20 , openings could be situated within the end walls 104 and 106 . The ends of the first and second tubular membrane elements 14 and 16 would not be cooled to the same extent as in the illustrated embodiment. Also, the openings in the insulating members, such as the illustrated insulating members 18 and 20 could be used in connection with an embodiment that did not have the first and second manifolds 22 and 24 of the present invention; or in other words, a single manifold collecting oxygen from all tubular membrane elements used in such embodiment.
[0042] With reference again to FIG. 2 , oxygen product streams 140 and 142 are withdrawn from the first tubular elements 14 and the second tubular elements 16 by lines 144 and 146 connected to the collection elements 30 of second and first manifolds 24 and 22 , respectively. Although not illustrated, the lines would pass through the cowlings 124 and 126 and then to a collection tank that would collect the oxygen product at pressure. As mentioned above, a central advantage of having the separate portions of the tubular membrane elements 14 and 16 is to prevent failure of the oxygen separation device 1 upon failure of a tubular membrane element. Moreover, where oxygen separation device 1 is used to supply oxygen to a tank under pressure, if a tubular membrane element failed, then product would be lost from the tank. In order to prevent this, check valves 148 and 150 are provided to isolate the first tubular membrane elements 14 from the second tubular membrane elements 16 , respectively, and thereby to prevent the loss of pressurized product oxygen upon failure of a tubular membrane element of either of the two portions.
[0043] Although the present invention has been described with reference to a preferred embodiment, as will occur to those skilled in the art, numerous changes, additions and omission may be made without departing from the spirit and scope of the present invention as set forth in the appended claims.
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A module and an apparatus incorporating such module utilizing a plurality of tubular membrane elements, each configured to separate oxygen from an oxygen containing feed stream when an electric potential difference is applied to induce oxygen ion transport in an electrolyte thereof. The tubular membrane elements can be arranged in a bundle that is held in place by end insulating members. The insulating members can be positioned within opposed openings of end walls of a heated enclosure and can incorporate bores to allow an oxygen containing feed stream to flow past exposed ends of the tubular membrane elements for cooling the end seals of such elements. Further, first and second manifolds can be provided in a module in accordance with the present invention to collect separated oxygen from two separate portions of the tubular membrane elements.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is related to, and claims priority from, U.S. Provisional Patent application No. 60/464,406 on April, 18th, 2003 , by Thomas H. Watkins III and Linardo Thorne titled “Method and apparatus for digitally integrating sales, confirmation and billing of published advertising”, the contents of which are hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to methods, apparatus and systems for digitally integrating the sales, confirmation and billing functions of published advertising, and particularly to web-based methods and systems that incorporate convincing digital proof of publication.
BACKGROUND OF THE INVENTION
[0003] Publishers of periodicals and daily newspapers derive significant revenue from selling print advertisements in their publications. Traditionally, selling the advertising in such publications has been done by third party agencies know as “reps”. Agencies that provide advertising rep services typically take a significant fraction of the advertising revenue.
[0004] Once the advertising has been printed, the publisher needs to generate both a bill and a confirmation of that printing. This confirmation needs to satisfactorily prove to the purchaser details such as that the advertisement was printed in the publication on the correct date, in the required position and was produced to an agreed or acceptable standard or quality. Traditionally this is done by sending a tearsheet along with the bill. A tearsheet is an actual, physical copy of the page on which the advertising appeared, taken from a copy of the publication. It is usual to supply a tearsheet for each billing line item. Such a system requires physically mailing the tearsheet, which is both costly and time consuming.
[0005] Prior art attempts to digitize and integrate some of the actions related to publishing printed advertisements include U.S. Pat. No. 6,505,173 to Weibel, et al. entitled “Method for electronically merging digitized data system of generating billing statement for published advertising”, the contents of which are hereby incorporated by reference. The system described by Weibel et al. is limited to the integration of a bill with a reference to a digital tearsheet substitution. In the Weibel system, the tearsheet substitution may be generated either from the digital publishing system used to produce the advertising or by scanning the publication. A problem with sending the image generated from the publishing system is that there is no indication whether the advertisement was actually printed. A problem with scanning the publication is that, if there are defects of quality, it is not clear from the scanned image if these defects occurred in the printing process or in the subsequent scanning. Neither of these methods fully satisfies an advertiser's need to know that the advertisement was actually printed in the publication, was the right size and was produced to the desired level of quality.
[0006] What is needed is an integrated system that allows advertisers to negotiate and purchase advertising, and also allows publishers to simply, promptly and digitally produce bills that contain acceptable proofs of publication. A further requirement of such an integrated system is provision of a system that allows the advertiser to simply and promptly pay the bill, once they receive satisfactory proof of publication.
SUMMARY OF THE INVENTION
[0007] The present invention relates to a web-site based, integrated electronic transaction system that allows the full range of activities associated with buying and selling advertising in printed publications to be accomplished electronically, online and preferably at a single website.
[0008] The invention allows a purchaser of advertising to use a website to submit a bid or an offer for having advertising published in one or more of a group of publications represented on that website. As part of that offer the purchaser may also upload a digital version of the advertisement they want published. Using the same website, the publishers can accept or decline the offer. When the publisher accepts the offer, the website automatically generates a run schedule, i.e., list of dates and details that remind the publisher of when and how to print the advertising. One the advertisement has been printed, the website also allows the publisher to upload a digital proof of publication and generate a bill for the purchaser. The purchaser may then use the website to review the bill and associated proof of publication. If satisfied, the purchaser may then pay the bill electronically using the website. In paying the bill, any commissions due to advertising agencies and rep firms are calculated and also automatically paid.
[0009] In a preferred embodiment, the integrated system of the present invention includes provision for the purchaser of advertising to select publications either directly by name or website code word, or by entering requirements such as, but not limited to, publication frequency, readership demographic, advertising types and classifications available. On entering their requirements, the purchaser may be presented with a list of suitable publications which match those requirements. Once the user selects their list of publications, an insertion request form may display the costs associated with selection, including totals, based on standard rates charged for the advertising schedule proposed. The purchaser may then amend their list or insertion requirements, including entering offered rates different from the standard rates. The offer from the purchaser, and any attached digital version of the advertisement, is then made available to the publisher who may accept, reject or negotiate further by making a counter-offer.
[0010] In the preferred embodiment, the digital proof of publication is in the form of a digital image of a traditional tearsheet, photographed on a fiducial underlay, which may include markings that allow the user to ascertain if the advertisement was produced to the required quality, which may include size, placing, resolution and color reproduction.
[0011] This and further advantages are explained in more detail blow with reference to the attached drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] [0012]FIG. 1 is a schematic overview showing an embodiment of the inventive concepts of the present invention.
[0013] [0013]FIG. 2 is a schematic flow chart showing one embodiment of the methods of the present invention as applicable to an advertiser.
[0014] [0014]FIG. 3 is a schematic flow chart showing one embodiment of the methods of the present invention as applicable to a publisher.
[0015] [0015]FIG. 4. is a plan view of an electronic proof of publication as generated in accordance with the inventive concepts of the present invention.
[0016] [0016]FIG. 5 is a schematic view of the generation and transmission of a proof of publication in accordance with the inventive concepts of the present invention.
[0017] [0017]FIG. 6 is a schematic view of a further method of generation and transmission of a proof of publication in accordance with the inventive concepts of the present invention
DETAILED DESCRIPTION
[0018] The invention of this application relates to an integrated system that satisfies the needs of both publisher and advertiser. In particular, the preferred embodiment of the invention includes web-based methods and apparatus designed to eliminate the need for costly transfer fees by providing a direct, effective and streamlined process for purchasing advertising space in newspapers. In addition, the invention of this application provides apparatus and method for simply and efficiently producing a digitized proof of publication that fully satisfies the advertiser's need to know that the advertisement was published on the right day at the right size and was produced to the necessary level of quality.
[0019] In a preferred embodiment, the invention simplifies the extensive, often time-consuming, paperwork traditionally associated with ad placement without compromising the efficient and accurate communication that advertisers and newspapers rely on.
[0020] In a preferred embodiment, the functions integrated into a single website based, electronic business system include, but are not limited to, publication selection, advertising placement offer submission, provision for negotiation of offers, proof of publication, payment and reporting. All of these functions may be made available at a website via an Internet connection such as, but not limited to, a dial up line, a high speed cable connection, a high speed land line or a suitable wireless connection.
[0021] In a preferred embodiment, publication selection may be facilitated by means of an extensive query page on the web site. This query page allows the advertiser to define the type of publications the advertiser wishes to use by specifying search criteria including but not limited to, readership demographics, publication frequency, types of advertising accepted and space availability on required dates. The site may return a list of the publications that match the search criteria and displays them along with relevant related material including, but not limited to, the column inch rate of the publication and a link to the each publication's online press kit by clicking on an individual publication. Each online press kit includes information such as, but not limited to, demographic, geographic and rate sheet information plus a link to the publications web site for optional more detailed investigation.
[0022] In a preferred embodiment advertising placement is further facilitated by a web page that produces an offer from the potential advertiser to the publication that the advertiser wishes to advertise in. Once a publication has been selected, the advertiser may use the offer function to do the following:
[0023] 1. Negotiate price. In the preferred embodiment this is facilitated by changing the column inch rate, which is shown along with the selected publication identifier. This allows the advertiser to submit bids with prices different from those on record as the standard price. The offer facility of the preferred embodiment helps the advertiser place a comprehensive bid that will meet their budget by keeping a running total of the cost of the buy based on the offered column inch rate.
[0024] 2. Select run-dates using an automated calendar. By simply clicking on the dates the advertisement is required to appear in the selected publications, the dates selected will automatically be attached or associated to the appropriate insertion order.
[0025] 3. Up-load digital advertisements. This may be done using the browser buttons to select previously stored advertising files for uploading. The stored digital advertisement will be automatically attached to the appropriate insertion order.
[0026] Once the necessary information has been entered and reviewed a single create offer button click will send each offer to each selected publication in the form of an insertion order. Each insertion order contains all information needed for placement, tracking and billing of the advertisement.
[0027] In a preferred embodiment the system also produces an automatic notification of offer by sending each publication an offer is made to, an appropriate e-mail notification. In the preferred embodiment, this e-mail informs them that an offer has been submitted and includes a reminder to sign-on to their account on the system in order to process the offer, including the opportunity to accept or reject your offer. In one embodiment of the system they also have the option to enter into negotiations regarding offers. In the event that the publication accepts the offer, a run-sheet is created for the paper to prevent the ad from being missed. The publication can also download the attached advertisement at this time.
[0028] In a preferred embodiment, the system also facilitates proof of publication. After the advertisement runs, i.e. the advertisement has been published, and the publisher up-loads the digital proof, in compliance with guides lines supplied by the web-site provider, the advertiser is notified via e-mail to go on-line and approve or reject the digital proof of publication. In a preferred embodiment, the publisher produces the digital proof of publication by placing a tearsheet on a graphic background board and taking a high quality digital photograph of the tearsheet on the background board. The resultant digital proof of publication shows everything a paper proof would in terms of the advertisement, as published, including its size, quality and position on page. The digital proof is provided on the website, appropriately linked to the original insertion order.
[0029] In a further embodiment of the system, payment from the advertiser to the publisher is facilitated by incorporating an electronic payment scheme such as, but not limited to, the well known PayPal system. This allows the advertiser, after all appropriate digital proofs of publication have been approved, to send or authorize payment simply and efficiently from the same website. In a preferred embodiment this payment is facilitated by a single click of an update button.
[0030] In a further embodiment, the system of this invention further facilitates advertising by generation of appropriate reports. These reports, which may be customized by the user making appropriate choices, allow the user to for instance, but not limited to, view the advertisements that ran and which periodicals they were published in along with the rates charged. Additional reports can be created. The system also generates reports for the publisher, including reports which allow the publisher to view which ads are scheduled to run in which of their publications.
[0031] In a preferred embodiment of the invention, all reports are available to be downloaded in standard formats such as, but not limited to Excel, PDF, Word or Text Files.
[0032] Advantages of the system of this invention for the advertiser include the fact that they are not forced to use a pre-packaged group of publications. The advertiser may research, and select the areas where they want the advertisement to run. They have the option to set the exact advertisement size and price they are prepared to pay for the advertisement.
[0033] Advantages of the system of this invention include the fact that once the approval process is completed, the system handles the rest of the publication details. A further advantage is that all proofs of publication (also known as digital tear sheets) are online. Once the advertiser is satisfied that the publication has completed their obligation, they may approve the invoice online. As soon as the invoice is approved, the check may be sent to the publication on the next business day. The advertiser needs to send only one check, or make one electronic payment, for the total cost of the advertising. The system handles payments to all parties involved in the transaction, including but not limited to publisher, agencies and reps, once the advertiser has verified the proof of publication.
[0034] Advantages for the publisher include the ability for them to securely enter their own publication data, circulation data and rates into the system. A further advantage to the advertiser is that the Advertisement Requests are sent through the system. The publisher has the option to accept, reject or negotiate the rate. The system helps facilitate actual publication by showing the publisher what advertisements are suppose to run on what dates. The publishers provide and load the proof that the ad ran themselves. The publisher only needs to view the invoice, the check is sent as soon as the advertiser approves the invoice.
[0035] The present invention will now be described by reference to the drawings in which like numbers represent like elements.
[0036] [0036]FIG. 1 is a schematic overview showing an embodiment of the inventive concepts of the present invention, including a website 10 , a web server 12 , a server 14 , a network 16 , a first user computer 18 , a second user computer 20 and a third user computer 22 . The website 10 is comprises well known electronically executable computer code, typically residing in a well known memory device on a server 14 , which may be any suitable well known digital computer. A web-server 12 is a computer program residing on the server 14 and capable of communicating over a network 16 . The web-server 12 mediates with the web-site 10 , allowing interaction of elements and databases of the web-site with remote computers 18 , 20 and 22 in forms such as, but not limited to, well known an active server page (ASP) pages, HTML pages, CGI scripts and other suitable network and computer constructs. Network 16 may be any suitable network such as, but not limited to the Internet or World Wide Web. Computers 18 , 20 and 22 may be any suitable well known digital computers. Computer 18 represents a adverting user computer accessing the web-site 10 via an submission page 24 . The submission page 24 is a graphical representation of HTML page code and may have functionality restricted to an advertising user of the system such as, but not limited to submitting an offer. Computer 20 represents a publisher accessing the web-site 10 via a processing page 26 . Processing page 26 may be an HTML page having functionality restricted to publishing members such as, but not limited to, processing an offer. Computer 22 represents a provider of the service accessing the web-site either directly or via the network, using an administration page 28 . Administration page 28 may be a well known HTML page allowing the provider to administer the website 10 .
[0037] [0037]FIG. 2 is a schematic flow chart showing one embodiment of the methods of the present invention as applicable to an advertiser. In a preferred embodiment the system is implemented as a software package on a centrally located server. In a first step 32 , an advertising user accesses the system via a web-browser over the Internet or other suitable information exchange network. At the next step 34 in the user/system interaction, the system queries the user as to whether they are previously registered users or not. If the user is not previously registered, they are invited to register in step 36 by filling in a form, which may be presented as, but not limited to, an active server page (ASP).
[0038] In a preferred embodiment, registration 36 includes, but is not limited to providing a 4 - 12 character ID, an e-mail address, a password and auxiliary identification information such as, but not limited to, a birth date. Important information such as, but not limited to, the password is typically asked for more than once to ensure accurate entry. The registration information may be e-mailed to a system administrator, where the information is processed, an appropriate account set up and the user informed of the outcome of their application and the steps necessary to access the required functions on the system.
[0039] Once the user is registered, they are able to proceed to Logon in step 38 . In the log on procedure 38 , of the preferred embodiment, the user is asked for their user ID, their password and a media code. The user ID and password authenticate the user while the media code ensures access to the appropriate functions. Media codes include, but are not limited to newspaper publishers, advertisers and system managers. As an advertiser, the user would need an appropriate advertiser media code.
[0040] In a preferred embodiment, an advertiser user is then presented with a web page having links that will allow them to perform a number of functions including, but not limited to, submitting an offer, check on the status of an offer or an insertion, or pay for services rendered.
[0041] If the user chooses to submit an offer in step 40 , they will be presented with one or more submission pages. These submission pages will enable them to proceed to step 42 , in which they will select one or more printed publications in which to place their print advertisements. The publication selection step 42 may include one or more publication selection pages with questions designed to find suitable printed publications from the systems database of publications. In a preferred embodiment, the information requested includes criteria such as, but is not limited to, advertising type, i.e., whether the advertising is black and white, 1 color, 2 color, 3 color or 4 color; a classification, out of a list such as but not limited to, Arts & Entertainment, Automotive, Business, Consumer, Display, Education, General Classified, Healthcare, Magazine, Media, Real Estate, Recruitment, Retail, Technology, Travel; what the publication format is, out of a list such as but not limited to, Broadsheet, Magazine, or Tabloid; the publication frequency, from a list such as but not limited to, Bi-weekly, daily, monthly, semi-weekly, weekly; the column width of the advertisement, the total column inches for the ad, the required run dates. The user may also be prompted for their requirements of the publication including, but not limited to, publication readership demographics, including but not limited to state or zip code of residence, median head of house income, age, education and work experience. The magazines may also be chosen by specialized interest requirement, chosen from a list such as, but not limited to circulation, minority ownership, readership gender or publication type including, but not limited to, college, ethnic, general, military, senior, agriculture, antiques, automobiles, aviation/aerospace, boats & yachting, business, cattle/livestock, Clubs, College/Alumni, Communications, Community, Court, Electronics, entertainment, farming, fishing & hunting, florist, gay & lesbian or sports, or some combination thereof.
[0042] Once the information is entered, the publication selection page may show a list of suitable publications and may include details of costs and other appropriate data such as any of the selection criteria. The advertising user may then select publications from this list of suitable publications.
[0043] The user may also select publications by name or system ID number and they may also use a view a publication option to show them the publications available of the system along with the appropriate details of the publications, including but not limited to, any of the categories listed above. The system may also have links to the web pages of the magazines themselves.
[0044] Once the advertiser has selected appropriate publications, they may proceed to step 44 of creating an offer. In this step they will be presented with one or more offer creation pages that may allow them create, generate or complete an insertion request form, thereby generating or creating an offer. The appropriate information gathered in the publication selection step 42 is now displayed along with costs, including standard rates charged by the publications. In step 44 of creating an offer, the advertiser may also negotiate by submitting bids (also known as “an offered amount”) in which an offered rate is proposed for the column inch rate, or other method of pricing the insertion, the offered rate being different from the standard rate presented in the publications media kit or by the system of this invention. In a preferred embodiment, the offer creation step will generate a page that shows total amounts based on the offered rate (also known as “bid rate) so that the advertiser is aware of the actual costs that will be incurred if the bid is successful. In the preferred embodiment, the advertiser will also include a digital form of each of the advertisements along with the bid. This may be done by uploading the appropriate advertisement file to the offer form or submission page. Once the advertiser has put together a satisfactory offer to the various publications, the advertiser may submit the offer in step 46 by pressing an appropriate button on the offer form page.
[0045] In the preferred embodiment, the step 46 of submitting the offer results in the offer details, including pricing bids (also known as “the offer amount”), run dates, advertising copy in digital form and other data necessary for the publication both to decide whether to accept the offer or not and to run in the insertion if they choose to accept, being placed in a file or position accessible by authorized entities of the selected publications. In the preferred embodiment, step 46 of submitting the offer also generates a notification of offer, in the form of an e-mail, instant message or other electronic communication, to the appropriate contact person or authorized entity at each of the selected publications informing them of the offer and prompting them to access the appropriate section of the system in order to further process the insertion request.
[0046] The advertising user may wish to check the status of an insertion request in step 48 by proceeding to the web page provided by the view insertion status link. In the step 50 of viewing insertion status, the advertising user may be presented with one or more status pages which are web page displaying all their past bids for a selected time period and the status of those bids. On these pages they are be able to see which bids where accepted or rejected, and of the accepted bids what their status is with respect to being run. Once the advertisements have been run, advertising user may also be able to access a digital proof of publication from these pages. In the preferred embodiment, this proof of publication may consist of a digital image of an actual printed page that contains the advertisement, taken from the publication on the required date and placed in position on a standard background containing fiduciary markings such as, but not limited to, a sized grid, company logos, numbers, letters or a combination thereof. This digital image may be taken with a digital camera of sufficient resolution such as but not limited to, a 2-3 Megapixel camera such as but not limited to the Fuji FinePix 3800 , the Kodak EasyShare DX4330 or the Fuji Finepix F601Z models.
[0047] If the advertiser is satisfied that the advertisement has been satisfactorily run, then in step 52 the advertiser may approve the insertion on the web page. Approving the insertion may cause the system to record the approval in step 54 and also automatically generate an invoice for payment.
[0048] In one embodiment of the invention, if the advertiser is ready to pay, they may choose the pay invoice option in step 56 that may lead them to a suitably secure web page linked to a suitable electronic payment system. Such suitable electronic payment systems are well known and include, but are not limited to, the well-known PayPal system operated by eBay. In step 58 , the advertising user isbe able to view the invoice. In step 60 , the advertising user may approve payment. In step 61 , the advertising user may to send the payment.
[0049] In the preferred embodiment, step 60 of the electronic payment system is used in such a way that all parties involved are automatically paid correctly. For instance, in many advertising transactions, it is customary for the advertising agency that produced the artwork used in the advertisement to receive a percentage of the revenue when an advertisement is run. Similarly, in many advertising transactions, it is customary for the rep firm that sold the advertising space to the advertiser to receive a percentage of the revenue when an advertisement is run. An advertising agency typically receives a payment of 15% of the revenue, although this may vary. A rep firm typically receives a payment of 6%, although this may vary. In the integrated system of this invention, the percentages due to each of such parties is reflected in the bill sent to the advertiser. When the advertiser makes the single payment of the invoice presented to them, the electronic payment system of this invention automatically generates appropriate payments to all parties involved in the particular transaction, including if appropriate, but not limited to, the publisher, the advertising agency and the rep firm.
[0050] Once the advertising user has completed using the system in step 62 , they may log off in step 64 .
[0051] Providing a proof of publication is an important part of advertising practice. Traditionally, in non-electronic systems, this is done by sending a tearsheet along with the bill. This tearsheet is a physical page containing the advertiser's insertion taken from the actual publication on the day it is printed. Seeing the actual page asures the advertiser that the advertisement was placed on an appropriate page at the required size and produced with appropriate quality. In order to provide a comprehensive and completely electronic solution covering all the process required in advertising transactions in a printed publication, it is necessary to provide an electronic equivalent of the tearsheet. Solutions such as simply sending an electronic copy of the file or of scanning in a page fail to provide such an electronic equivalent, primarily because digital images are so easy to manipulate.
[0052] [0052]FIG. 3 is a schematic flow chart showing one embodiment of the methods of the present invention as applicable to a publisher. The publishing user accesses the website in step 32 and proceeds to steps 34 , 36 and 38 as described above. However, in step 38 , the publishing user has an appropriate media code allowing them access to the functions appropriate to a newspaper publisher including, but not limited to the ability to review insertion offers in step 66 , check runsheets in step 68 , view invoices in step 70 , view reports in step 72 and update publication details in step 74 .
[0053] If the publishing user selects to review insertion offers in step 66 , they may be presented with one or more processing pages which allow them to process any offered amounts. In step 76 they may view the offers and elect to approve them or not. In one embodiment of the invention, step 76 allows them to not approve the offer by submitting counter bides (also known as counter offer rates) different from both the offered rates of the advertising user and the standard rates of the publisher. If the publishing user approves the offer, accepting the offered amount for publishing one or more print advertisements in their print publication, they may proceed to step 78 in which a run sheet is generated. The run sheet may be a schedule comprising a list of dates on which to publish the print advertisements of the offer in the publisher's print publication. The run sheet may also include other relevant data such as, but not limited to, details of the advertisement.
[0054] If the publisher selects to check runsheets in step 68 , they may proceed to step 80 in which they may review the daily runsheets. If the advertisements have run, i.e., the print advertisement has been run in the appropriate printed publications, the publisher may select to verify the run in step 82 . In a preferred embodiment the step 82 of verifying the run may include being presented with one or more proof of publication pages which allow the publisher to upload digital proof of publications. In a preferred embodiment, this digital proof of publication may be in the form of a digital tearsheet, i.e. a digital image of a paper tearsheet placed on a fiducial underlay. Details of how to supply such digital tearsheet is described below in greater detail.
[0055] On reviewing the runsheet in step 80 , the publishing user may also wish to correct a proof in step 84 . If a publishing user either corrects a proof in step 84 or verifies a run in step 82 , they may proceed to step 86 in which these actions or changes are recorded.
[0056] In step 70 the publishing user may to view an invoice by proceeding to step 88 in which one or more web pages are presented with appropriate invoice data.
[0057] In step 72 , the publishing user may proceed to step 90 and view activity reports. This reports may include, but are not limited to, reports of daily, weekly, monthly activity related to an account, an advertiser, a publication or some portion or combination thereof. These reports, which may be customized by the user making appropriate choices, allow the user to for instance, but not limited to, view the advertisements that ran and which periodicals they were published in along with the rates charged. Additional reports can be created. The system also generates reports for the publisher, including reports which allow the publisher to view which ads are scheduled to run in which of their publications. In a preferred embodiment of the invention, all reports are available to be downloaded in standard formats such as, but not limited to Excel, PDF, Word or Text Files.
[0058] In step 74 , the publishing user may select to update the publication details by proceeding to step 92 . The details up loaded may include, but are not limited to, publication data, circulation data and rates. In a preferred embodiment these are accomplished via a secure web page.
[0059] [0059]FIG. 4 shows a simple proof of publication that can be digitized and still function satisfactorily as a proof of publication. In the proof of publication shown in FIG. 3, a tearsheet 94 is digitized along with a fiduciary underlay 96 . By digitizing a page containing the advertiser's insertion taken from the actual publication on the day it is printed along with a fiducial underlay, the advertiser is able to judge size and quality even from a digitized image. The fiducial underlay may include a board marked with appropriate fiducial markings including, but not limited to, a grid pattern 98 , alpha numeric characters 100 , including lettering and numbering, and logos 102 , or some combination thereof. The alpha numeric characters may be chosen to be representative of advertising text in their choice or range of font size and/or font type. By including known or fiducial markings along with the tearsheet, the advertiser can, by comparison, judge the size and quality of the advertisement in the tearsheet. In one embodiment of the invention, the fiducial markings include specific colored markings to provide a color reference or fiducial. In one embodiment a color fiducial may be a color marking or indicia representative of a printed advertisement. For instance, the color fiducial may be a color image that appears as part of an advertisement that has been printed to the accepted color requirement on the fiducial underlay. A digital color image of the tearsheet with the color advertisement as printed in the print publication alongside a copy of the same of similar color image, pre-printed to the required acceptable quality standards, easily shows any differences, even if the digital image has color distortions. This is because the distortions will be the same in both images and therefore all the advertiser has to look for is differences between the images. If there are no differences, the advertiser can be assured that the of that the absolute color of the printed advertisement is acceptable.
[0060] [0060]FIG. 5 shows a schematic view of one method of producing and distributing an electronic proof of publication. A suitable digital camera 104 is held in place by a suitable support structure 106 so as to be able to photograph a tearsheet 94 placed on top of a fiducial underlay 98 An optional transparent overlay 108 may be used to hold the tearsheet in place while the photograph is being taken. The digitized image or digital proof of publication is transmitted from the camera to a local server 110 . In one embodiment of the invention this transmission may be wireless. From the local server 110 , the digital proof of publication may for instance, be linked to a bill and transmitted over a suitable network 16 to a remote computer with an attached viewing monitor 18 where the advertiser may view a copy 112 .
[0061] [0061]FIG. 6 shows a schematic view of the generation and transmission of a proof of publication by the preferred embodiment of the integrated system of this invention. In this the fiducial underlay 98 is attached to a vertical surface 114 such as, but not limited to a wall, door or window. The tearsheet 94 is placed over the underlay 98 and held in place by holding means 116 which may for instance be, but is not limited to, adhesive tape, thumb-tacks or magnetic material. A digital image is then taken of the tearsheet 94 appropriately aligned over the fiducial underlay 98 by an operator 118 using an appropriate digital camera 104 . The image in the digital camera 104 may then be transferred to the server. This transfer may be via a physical medium such as but not limited to, a memory card, a floppy disc or a removable drive. The transfer may alternatively be made by a wired connection or by a suitable wireless transmission including, but not limited to, well-known wi-fi or blue-tooth wireless transmission devices and protocols. Digital camera 104 may also be a cell phone having an appropriate imaging system, in which case the digital proof of publication may be transmitted by cellular network to the electronic transaction website.
[0062] Although the proof of publication is shown as being digitized by photography, one skilled in the art will readily appreciate that other methods of digitizing the tearsheet in place on the fiducial underlay may be substituted. The digitizing may be done by for instance, but not limited to, placing the tearsheet on a fiducial underlay and scanning the combination. In an alternate embodiment of the invention, the fiducial underlay may for instance be integrated into the cover of a flatbed scanner.
[0063] Although that present invention has been described with reference to discrete embodiments, one of skill in the art will recognize certain insubstantial modifications, minor substitutions, and slight alterations of the apparatus and method described herein, that nonetheless embody the spirit and essence of the described invention.
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An integrated electronic system enabling the transaction of advertising business related to printed publications over an electronic network, using standard web interfaces, including well known browsers. Advertisers my use the system to negotiate and purchase advertising space from a variety of printed publications and to upload digitized advertising copy. Publishers may securely accept and process the bids for advertising space, including keeping track of agreed upon run schedules, also using standard web interfaces and browsers. The system and apparatus also allows publishers to simply, securely, promptly and digitally produce bills that contain, or are linked to, acceptable proofs-of-publication. The acceptable proofs-of-publication may be digitized images of tearsheets placed on fiducial under-lays. The integrated system and apparatus also allows the advertiser to simply and promptly pay acceptable bills by using electronic payment systems incorporated into the web pages.
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BACKGROUND OF INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to power consumption during digital image processing in video compression. More specifically, a device and method that reduce power consumption by reducing the number of memory accesses when calculating absolute difference values for image correlation is disclosed.
[0003] 2. Description of the Prior Art
[0004] Video compression standards have long been available to lower the required bandwidth and alternatively to increase the amount of video data that can be stored in any given sized storage media. In line with these goals, motion estimation is widely used for video compression standards such as MPEG-1, MPEG-2, and MPEG-4 among others.
[0005] The conventional methods for motion estimation are well known to those skilled in the art. In general, each frame goes through a process where a current video frame is read into memory. A small reference block is located within a larger search window of the current frame and a motion vector is generated estimating the direction of motion of the reference block within the search window. This motion vector is used in conjunction with information from the previous frame to generate an estimated image frame in respect to the current frame. The estimated image frame is then subtracted from the current frame, which effectively removes duplicated imagery and results in much less data necessary to be saved in the output file.
[0006] Because the estimated image frame is subtracted from the current frame and only the difference is saved, it is obvious that the more accurate the estimation is, the smaller the output file is. The accuracy of the estimated image frame to a large degree depends on the accuracy of the motion vector. The accuracy of the motion vector in turn depends on the accuracy of locating the reference block within the search window.
[0007] It is generally accepted that the reference block can be located within the search window most accurately using a full search. A full search consists of comparing the reference block sequentially with every possible location within the search window. For each location, the comparison is done by adding the absolute values of the difference between the brightness of each pixel in the reference block and the brightness of the corresponding pixel in the current search location. The location with the lowest total of absolute values is considered the best match and is selected to be used to calculate the motion vector.
[0008] Obviously, methods other than a full search that compare the reference block with a more limited number of search locations are frequently employed with satisfying results. However, nearly every method used today selects the best match based on the absolute differences in brightness between the pixels in the reference block and the pixels in the search locations. Therefore, the calculation and summing of the needed absolute differences is the common core of video image correlation.
[0009] Please refer to FIG. 1 that is an absolute difference accumulator circuit (ADAC) according to a prior art. The ADAC comprises a plurality of absolute difference calculation circuits, a multiple input adder, a full adder, and an accumulator. A full description of this particular ADAC can be found in U.S. Pat. No. 5,610,850 incorporated herein by reference. Basically, pixel values from the reference block are inputted to the X 1 -Xn inputs and pixel values from the current search location are inputted into the Y 1 -Yn inputs of the absolute difference calculation circuits. The results of the absolute difference calculation circuits are added by the multiple input adder and output to the full adder. The full adder sums the output from the multiple input adder and the current value in the accumulator and places the sum back into the accumulator. When all of the pixel values for one search location have been processed, the value in the accumulator represents the match value for that particular search location. This match value is then stored elsewhere in memory, the value in the accumulator is reset to zero, and the process repeats for each search location.
[0010] Nearly all image correlation methods used today select search locations that at least in part overlap one another. Because the match value for each search location is independently calculated, the pixel values in the overlapping portions of the search locations need to be loaded into memory multiple times. Each memory access uses power. Often motion estimation is used in devices, such as a PDA or cellular phone, which obtain power from a limited power source such as a battery. Power consumed by unneeded memory accesses prevents that same limited power from being used for other purposes and generates unnecessary heat within the device.
SUMMARY OF INVENTION
[0011] It is therefore a primary objective of the claimed invention to reduce power consumption and system load for digital signal processing by reducing the number of memory accesses when calculating absolute difference values in image correlation by calculating match values for multiple search locations simultaneously.
[0012] Briefly summarized, the preferred embodiment of the claimed invention discloses a circular reference block buffer, a circular search window buffer, a plurality of absolute difference calculation circuits, a multiple input adder, a full adder, a plurality of accumulators, and a control circuit. The degree of plurality of the absolute difference calculation circuits is normally equal to the degree of plurality of accumulators and equal to the number of match values being simultaneously calculated. The control circuit includes a storage unit having four pointers, or indices, to control accessing of data in the two circular buffers. The buffers are normally registers.
[0013] A preferred example of the present invention has the plurality of absolute difference calculation circuits and the plurality of accumulators equal to four. At least one word-sized chunk of pixel data is loaded from the search window in memory into the circular search window buffer and a word of pixel data from the reference block is loaded into the circular reference block buffer. The first four bytes of pixel data from the circular reference block buffer are sent to a first input of the four absolute difference calculation circuits respectively. The first four bytes of pixel data from the circular search window buffer are sent to a second input of the four absolute difference calculation circuits respectively. The results of the absolute difference calculations are summed by the multiple input adder and output to the full adder.
[0014] Because each accumulator represents a different search location, the control circuit determines which of the accumulators requires incrementing the value already in that accumulator by the current output of the multiple input adder. The value in the accumulator indicated by the control circuit is then sent to the full adder, added by the full adder to the output from the multiple input adder, and the result placed back into that accumulator. A new set of bytes from the circular search window buffer, offset from the previously sent set of bytes, is then sent to the second input of the absolute difference calculation circuits respectively, a new sum is calculated, and a second accumulator is incremented by the new sum. The cycle repeats using a new set of search window data and incrementing a corresponding accumulator until all accumulators have been updated. The next four bytes of data from the circular reference block buffer and the next set of bytes from the circular search window buffer are then sent to the absolute difference calculation circuits respectively. The process is repeated until the accumulators hold the total match values for their respective search locations. Data for the circular reference block buffer and the circular search window buffer are loaded from memory as needed.
[0015] It is an advantage of the claimed invention that pixel value data is loaded into memory only one time when calculating the match values for a plurality of search locations, reducing system load and power consumption.
[0016] These and other objectives of the claimed invention will no doubt become obvious to those of ordinary skill in the art after reading the following detailed description of the preferred embodiment, which is illustrated in the various figures and drawings.
BRIEF DESCRIPTION OF DRAWINGS
[0017] [0017]FIG. 1 is a block diagram of a circuit used for calculating match values according to the prior art.
[0018] [0018]FIG. 2 is a block diagram of a circuit used for calculating match values according to the present invention.
[0019] [0019]FIG. 3 illustrates a circular data buffer according to the present invention.
[0020] [0020]FIG. 4 is a block diagram of a control circuit according to the present invention.
[0021] [0021]FIG. 5 is a flow chart of calculating match values according to the present invention.
DETAILED DESCRIPTION
[0022] Please refer to FIG. 2 through FIG. 4. FIG. 2 is a block diagram of an accumulation circuit 100 for calculating match values according to the present invention. FIG. 3 illustrates a circular data buffer 200 used in the present invention. FIG. 4 is a block diagram of a control circuit 300 for the present invention.
[0023] The accumulation circuit 100 comprises a plurality of absolute difference calculation circuits (ADCC) 110 , a multiple input adder 150 , a full adder 160 , a multiplexer 180 , a demultiplexer 170 , and a plurality of accumulators 192 , 194 , 196 , and 198 . Each accumulator may be a register or in memory and of a size sufficient to insure an accurate total of the absolute differences between a reference block and a search location, which in turn depends upon the size of a reference block being used.
[0024] In a preferred embodiment of the present invention shown in FIG. 2, each ADCC 110 comprises a subtractor 115 , a multiplexer 130 , and diode inverter 120 . The subtractor 115 has a first input and a second input for receiving data, a first output, a second output, and a third output for transmitting the result of the subtraction. The first output transmits a one's complement result, the second output transmits the normal output of subtractor, and the third output transmits a carry signal Cn according the result of the subtraction. The multiplexer 130 selects for output to the multiple input adder. If the Cn is equal to 0, i.e., the result of subtractor is a positive number, the normal output of subtractor is transmitted to the multiple adder. If the Cn is equal to 1, i.e., the result of subtractor is a negative number, the ones complement result is transmitted to the multiple input adder 150 . All the Cn will be decoded by decode circuit 140 . The decode circuit 140 is used to count the number of Cn is equal to one. The output of decode circuit 140 is transmitted to the multiple adder.
[0025] Regardless if the ADCC disclosed by the preferred embodiment is used or an ADCC of another type is used, the control circuit 300 then causes the multiplexer 180 to sequentially select one accumulator 192 , 194 , 196 , 198 . The value stored in the selected accumulator 192 , 194 , 196 , 198 is added in the full adder 160 to the value output by the multiple input adder 150 . The control circuit 300 then causes the demultiplexer 170 to route the output of the full adder 160 to the same selected accumulator 192 , 194 , 196 , 198 so that the value in that same accumulator 192 , 194 , 196 , 198 is incremented by the amount being output by the multiple input adder 150 . The multiplexer 180 and the demultiplexer 170 are both controlled by signals from the control circuit 300 . The signals comprise the least significant bits of the number of the first byte being currently transmitted from the circular SW buffer. In this example, bytes 0 - 3 are transmitted first, followed sequentially by bytes 1 - 4 , bytes 2 - 5 , and bytes 3 - 6 . Thus a 2-bit signal can indicate which accumulator 192 , 194 , 196 , 198 is to be active. The control circuit selects each accumulator 192 , 194 , 196 , 198 in a round-robin fashion, with the accumulator 192 , 194 , 196 , 198 selected rotating with each transfer of new data to the accumulation circuit 100 , allowing four different search locations to be calculated in one pass of a reference block.
[0026] Data destined for the accumulation circuit 100 comprises pixel data included in the reference block (RB) and a search window (SW), the search window including at least one search location. The pixel data for both the reference block and the search window is usually stored in memory. Because accessing memory consumes more power than accessing a local buffer, the present invention comprises two circular buffers 200 : a circular SW buffer 200 S and a circular RB buffer 200 R. Obviously, the term “circular” refers to the method of accessing the circular buffers 200 S, 200 R rather than to a physical arrangement. Methods of providing circular access to a buffer are know in the art. The circular buffers 200 S, 200 R shown in FIG. 3 each comprise 4 words with each word 4 bytes in length, but another size for either or both of the buffers 200 S, 200 R can easily be employed in another example of the present invention. The point is that using the buffers as disclosed in the present invention minimizes the number of memory accesses, and therefore reduces power consumption.
[0027] To control access to each circular buffer 200 S, 200 R, the control circuit 300 comprises a storage unit 310 for storing addresses of current locations within the circular buffers 200 S, 200 R. For this purpose, the storage unit 310 of the control circuit 300 comprises indices VWP 0 320 , VWP 1 330 , VRP 0 340 , and VRP 1 350 . The VWP 0 320 is a word index and comprises the address of where in the circular buffer 200 S a next word of SW data is to be loaded. The VWP 1 330 is also a word index and comprises the address of where in the circular buffer 200 R a next word of RB data is to be loaded. The VRP 0 340 is a byte index and indicates the next byte of data in the circular buffer 200 S to be sent to the accumulation circuit 100 . The VRP 1 350 is also a byte index and indicates the next byte of data in the circular buffer 200 R to be sent to the accumulation circuit 100 .
[0028] The present invention can best be described by example. Please refer to FIG. 5. To simplify the explanation, each of the circular buffers 200 S, 200 R in this example comprises 4 words of address space with each word 4 bytes in length. The first byte in each of the circular buffers 200 S, 200 R has an address of 0, although obviously in reality a different address may be used. The indices VWP 0 , VWP 1 increment by word and the indices VRP 0 , VRP 1 increment by byte. When incremented beyond the address space of the applicable circular buffer 200 S, 200 R, all indices VWP 0 , VWP 1 , VRP 0 , and VRP 1 wrap around so that the first byte in the circular buffer 200 S, 200 R sequentially follows the last byte in the circular buffer 200 S, 200 R. The present invention comprises the following steps in this example to calculate match values for four search locations. A 16 pixel by 16 pixel reference block and a 16 pixel by 19 pixel search window are used. In this example, it is assumed that the start addresses of the reference block and the search window are in word alignment. If the start addresses of reference block and search window are not in word alignment, the following steps can be modified with a suitable VRPn and VWPn.
[0029] Step 400 : Initialization. All accumulators=0. VWP 0 =0. VRP 0 =0. VWP 1 =0. VRP 1 =0.
[0030] Step 405 : Load 1 word of SW pixel data into the circular SW buffer at VWP 0 . Increment VWP 0 .
[0031] Step 410 : Load 1 word of SW pixel data into the circular SW buffer at VWP 0 . Increment VWP 0 .
[0032] Step 415 : Load 1 word of reference data into the circular RB buffer at VWP 1 . Increment VWP 1 .
[0033] Step 420 : Send bytes VRP 0 through VRP 0 +3 from the circular SW buffer and bytes VRP 1 through VRP 1 +3 from the circular RB buffer to the absolute difference calculation circuits.
[0034] Step 425 : Increment the value in a first selected accumulator by the value in the full adder. Increment VRP 0 .
[0035] Step 430 : Send bytes VRP 0 through VRP 0 +3 from the circular SW buffer and bytes VRP 1 through VRP 1 +3 from the circular RB buffer to the absolute difference calculation circuits.
[0036] Step 435 : Increment the value in a second accumulator by the value in the full adder. Increment VRP 0 .
[0037] Step 440 : Send bytes VRP 0 through VRP 0 +3 from the circular SW buffer and bytes VRP 1 through VRP 1 +3 from the circular RB buffer to the absolute difference calculation circuits.
[0038] Step 445 : Increment the value in a third accumulator by the value in the full adder. Increment VRP 0 .
[0039] Step 450 : Send bytes VRP 0 through VRP 0 +3 from the circular SW buffer and bytes VRP 1 through VRP 1 +3 from the circular RB buffer to the absolute difference calculation circuits.
[0040] Step 455 : Increment the value in a fourth accumulator by the value in the full adder. Increment VRP 0 .
[0041] Step 460 : Finished with reference block? Yes→end.
[0042] Step 465 : VRP 1 =VPR 1 +4. Go to step 410 .
[0043] The search locations in the above example are offset from one another by one pixel and overlap to a great degree. Another example of the present invention is extended to function using different offsets or locations by having the control circuit 300 select different accumulators 192 , 194 , 196 , 198 , not in a round-robin sequence, but according to a look-up table (or a programmable decoder circuit). The look-up table indicates which comparisons of bytes from the reference block and bytes from the search window belong to a specific search location and the accumulator 192 , 194 , 196 , 198 representing that specific location is then selected by the control circuit 300 for updating. Additionally, the number of absolute difference calculation circuits 110 and corresponding number of accumulators 192 , 194 , 196 , 198 may be altered to suit design purposes. For example, another embodiment of the present invention uses 8 absolute difference calculation circuits 110 and 8 accumulators 192 , 194 , 196 , 198 and merely adjusts the indices 320 , 330 , 340 , 350 accordingly. However, the embodiment disclosed in FIG. 5 comprising 4 absolute difference calculation circuits 110 and 4 accumulators 192 , 194 , 196 , 198 works well with little overhead for small screened devices such as a PDA or a cellular phone.
[0044] By comparing the same group of reference block bytes sequentially with the corresponding data from each search location before loading new reference data, the match values from four search locations can be calculated at the same time. Each byte of data, whether from the reference block or the search window, needs to be fetched from memory and stored in the corresponding buffer only one time for each four search locations. This present invention feature is in stark contrast with the prior art where the reference block must be reloaded into memory once for each search location and pixels in overlapping search locations may be loaded several times. Therefore, by reducing the number of memory accesses, the present invention reduces the power consumed and system load when calculating absolute difference values during image correlation.
[0045] Those skilled in the art will readily observe that numerous modifications and alterations of the device and method may be made while retaining the teachings of the invention. Accordingly, the above disclosure should be construed as limited only by the metes and bounds of the appended claims.
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A method and apparatus to reduce the system load of motion estimation for DSP discloses circular buffers, a plurality of absolute difference calculation circuits, a multiple input adder, a full adder, a plurality of accumulators, and a control circuit. The first four bytes from the reference block buffer and the first four bytes from the search window buffer are sent to the four absolute difference calculation circuits. The control circuit determines which of the accumulators requires incrementing the value already in that accumulator by the current output of the multiple input adder. A new set of bytes from the search window buffer is then sent to the absolute difference calculation circuits, a new sum is calculated, and a second accumulator is incremented by the new sum. When all accumulators have been updated, new reference block data used. Each byte of data is loaded from memory only once.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an apparatus for receiving and delivering sheets between one sheet dealing apparatus and another sheet dealing apparatus. In particular, the invention relates to terminal units of a bank such as an automatic transaction apparatus and a movable bill receiving apparatus, and an automatic transaction system in a bank.
2. Description of the Prior Art
In a conventional sheet receiving apparatus, as shown in, for example, Japanese Patent Unexamined Publication No. 59-33590, sheets are gripped by a gripper of an arm portion in a feeding portion, and the gripped sheets are received in a receiving portion by a transport means, thus automatically receiving the sheet in a batch manner. Also, as shown in Japanese Patent Unexamined Publication No. 59-208685, there is an automatic transaction apparatus in which a manipulator is used for delivering medium to be processed such as cash.
The above-described conventional sheet receiving apparatuses is of the batch receiving type using a kind of a manipulator. However, the conventional technique suffers from the following problems. Namely, first, since the manipulator is used for a simple operation such as delivering the sheets and receiving the sheets, the apparatus becomes large. Second, in the case where valuable sheets such as bills should be dealt with, it is necessary to confirm the number of the bills and the values thereof for every operation. Accordingly, in this case, a feeding system for delivering the sheets one by one is more effective than the batch system for feeding the sheets in a batch manner.
The above-described automatic transaction apparatus also suffers from exactly the same problems. Also, it should be noted that a manipulator fails to deliver a lot of sheets at once.
SUMMARY OF THE INVENTION
An object of the invention is to provide a movable sheet receiving apparatus that may feed and receive sheets with a simple structure and with a high reliability.
Another object of the invention is to provide an automatic transaction apparatus which is highly reliable in operation.
Still another object of the invention is to provide a sheet delivery apparatus that may change a length of its delivery path as desired.
The sheet receiving apparatuses according to the invention are classified by a portion of delivery path for feeding and receiving the sheets in cooperation with another sheet dealing apparatus, into one type in which the delivery portion has an extensible/retractable delivery path and the other type in which a delivery module automatically detachable from a body of the sheet receiving apparatus is used as the delivery portion. Also, in the case where the valuable sheets such as bills should be dealt with, since the system needs a high reliability, a discriminating portion is added to the sheet receiving apparatus.
Further, an automatic transaction apparatus of the invention comprises a bill transfer apparatus which includes the above-described extensible/retractable delivery path or the automatic detachable delivery module and a discriminating portion.
Also, according to the invention, in order to attain the foregoing and other objects of the invention, there is provided a sheet transfer apparatus comprising delivery belts extended between rotatable pulleys, a plurality of driven rollers disposed in contact with and in confronted relation with the delivery belts and rotated by the movement of the delivery belts, and guide members provided between the driven rollers for guiding sheets transfered by the delivery belts at a delivery portion, wherein a sheet delivery path is formed by the delivery belts, the driven rollers, and the guide members, delivery belt length adjusting means for adjusting a length of a horizontal portion of the delivery belts by drawing and returning the delivery belts, and the guide members include a collapsible structure that is extensible and retractable in cooperation with the delivery belt length adjusting means.
The sheet receiving apparatus according to the invention is of the movable type for example and may be used to deliver the sheets such as bills from one sheet dealing apparatus within a safe, to another sheet dealing apparatus such as a cash automatic dealing unit. In the case where the sheets received in the sheet dealing apparatus are fed out to the movable sheet receiving apparatus or where the sheets are received from the sheet dealing apparatus to the movable sheet receiving apparatus, the extensible sheet delivery portion is extended to be inserted into a delivery port of the sheet dealing apparatus when the movable sheet receiving apparatus is positioned at a predetermined position. Thus, the sheet dealing apparatus and the movable sheet receiving apparatus are connected together, to thereby form a single sheet dealing system. Therefore, the sheets within the sheet dealing apparatus may be delivered to the movable sheet receiving apparatus without using any manipulator or the like. Also, the reverse operation may be similarly attained. The delivery path of the delivery portion may be a delivery path module which is automatic detachable to the apparatus. In this case, when the movable sheet receiving apparatus reaches a predetermined position, the delivery path module is inserted into a delivery port of the sheet dealing apparatus.
Furthermore, in order to enhance the reliability of the sheet receiving apparatus, a discriminating portion is provided in the movable sheet receiving apparatus. With such an arrangement, when the bills are fed or received between the movable sheet receiving apparatus and another bill dealing apparatus, it is possible to confirm whether the exact feeding/receiving of the bills is performed. In addition, it is possible to facilitate to know the total amount of the bills received in the movable bill receiving apparatus.
Furthermore, if the above-described bill receiving apparatus is used, it is possible to provide an automatic transaction system with high reliability.
Further, if the delivery belts are drawn or returned by delivery belt length adjusting means, it is possible to vary the length of a horizontal portion of the delivery belts. In this case, the guide members having collapsible structure are opened or closed in cooperation with the delivery belt length adjusting means. As a result, when the driven rollers at both ends of the guide member are moved along the delivery belts and the length of the horizontal portion of the delivery belts is changed, the sheet may be delivered while being clamped by the driven rollers and the delivery belts without fail.
Also, if the guide member is structured by an extensible material, it is possible to ensure the foregoing effect without making the guide member collapsible.
Furthermore, without using the guide member or the driven rollers, the same effect as described above may be insured by providing a pair of delivery belts whose horizontal portions are confronted in contact with each other and drawing or returning the pair of delivery belts by the delivery belt length adjusting means.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a structural view showing a sheet receiving apparatus according to an embodiment of the invention;
FIG. 2 is a perspective view showing in more detail a delivery portion of the sheet receiving apparatus shown in FIG. 1:
FIGS. 3, 4 and 5 are flowcharts showing a primary operation of the apparatus according to the invention;
FIG. 6 is a structural view showing a sheet receiving apparatus according to another embodiment of the invention;
FIG. 7 is a view showing an embodiment of the invention in which automatically detachable delivery path modules are used;
FIG. 8 is a schematic view showing an automatic transation apparatus provided with the sheet receiving apparatus according to the invention; and
FIG. 9 is a schematic view showing a cash automatic transaction apparatus having a sheet delivering apparatus of the invention to which a driver in a car is accessible.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will now be described with reference to FIGS. 1 to 4.
FIG. 1 shows a movable sheet receiving apparatus according to an embodiment of the invention. Within a box 100 of the sheet receiving apparatus, there are arranged delivery belts 1, 1a for delivering sheets, a plurality of pulleys 2, 2a for engagement with the delivery belts 1, 1a, a plurality of driven rollers 3, 3a disposed in contact with and in confronted relation with the delivery belts 1, 1a, and guides 4, 4a disposed in confronted relation with the delivery belts 1, 1a for insuring the stable delivery of the sheets. These components are arranged to define a first delivery path 101, a second delivery path 102, a third delivery path 103, a fourth delivery path 104, a fifth delivery path 105 and a sixth delivery path 106. Sheet receiving boxes (three boxes 51, 52 and 53 in the case of this embodiment) which may be slidingly drawn are arranged in the box 100. For these receiving boxes 51, 52 and 53, there are provided receiving mechanism 6 such as rollers for receiving the sheets into the respective boxes 51, 52 and 53, separating mechanism 7 for separating the sheets one by one, and feeding out mechanism 8 for feeding out the sheets for separation. Further, a first gate mechanism 61, a second gate mechanism 62, a third gate mechanism 63, a fourth gate mechanism 64 and a fifth gate mechanism 65 for switching the delivery direction of the sheets are provided. An extensible member 10 such as a bellows is mounted on the box 100. A delivery port 11 at which sheets are received and delivered is formed in the extensible member 10. Also, the above-described delivery path 106 is provided in connection with the delivery port 11. The above-described receiving mechanisms 6 are used for receiving new sheets one by one on the sheets stacked within the receiving boxes. In accordance with the receiving operation, bottom plates 51a, 52a and 53a of the receiving boxes 51, 52 and 53 are moved downwardly to keep the stacking position of the sheets, namely, the position of the top sheet.
The above-described feeding out mechanism 8 includes pressing means (not shown) for applying a pressing force necessary for separation of the sheets and a feeding out roller 8 for feeding out the stacked sheets, and the separating mechanism 7 includes separating rollers 7, 7a for separating the top sheet and the second sheet thereunder. On account of these mechanisms 7 and 8, the sheets are fed out and in accordance with the sheet feeding out operation, the bottom plates 51a, 52a, 53a of the receiving boxes 51, 52, 53 are moved upwardly.
The gate mechanisms 61, 62, 63, 64 and 65 are operated as follows. When the sheets are received in the first receiving box 51, the sheets are fed along the sixth delivery path 106 and the first delivery path 101 and to the first receiving box 51 by the first gate mechanism 61. When the sheets are fed out from the first receiving box 51, the sheets are fed along the sixth delivery path 106 to the delivery port 11 by the fifth gate mechanism 65. When the sheets are received in the second receiving box 52, the sheets are fed along the sixth delivery path 106, the first delivery path 101 and the second delivery path 102 to the second receiving box 52 by the second gate mechanism 62. When the sheets are fed from the second receiving box 52, the sheets are fed along the fifth delivery path 105 to the sixth delivery path 106 and the delivery port 11 by the fifth gate mechanism 65. Further, when the sheets are received in the third receiving box 53, the sheets are fed along the sixth delivery path 106, the first delivery path 101, the second delivery path 102 and the third delivery path 103. Also, when the sheets are fed out from the third receiving box 53, the sheets are fed from the third receiving box 53 along the fourth delivery path 104, the fifth delivery path 105 and the sixth delivery path 106.
In this embodiment, a moving mechanism 12 is provided for moving a whole of the apparatus.
This moving mechanism 12 for moving the whole apparatus is driven by a drive mechanism 9. Also, the above-described mechanisms are drivingly controlled by a controller 25. This movable sheet receiving apparatus is used to receive the sheets from one sheet dealing apparatus, temporarily receiving in the receiving boxes within the box 100 and moving to another sheet dealing apparatus to feeding the sheets. In this delivering operation, the pulleys 2a and 2b engaged with the delivery belt 1a at a delivery portion is moved from the original positions indicated in dotted lines and to the positions indicated in solid lines in FIG. 1. In accordance with this movement, the guides 4a and the extensible member 10 are extended so that the delivery port 11 is inserted into a delivery port of another associated sheet dealing apparatus.
An example of the delivery portion mechanism is shown in FIG. 2. The delivery portion mechanism includes delivery belts 1a, pulleys 2a, driven rollers 3a, guides 4a, shafts 15 for supporting the driven rollers 3a, a connecting linkage rod 17 for connecting these shafts 15, connecting members 18 mounted so that a shaft 13a for carrying the pulleys 2a and the shaft 15 for carrying the driven rollers 3a may be cooperatively moved, an actuator 19 for driving the shafts 13a and 15 to change a length of the path, and a telescopic arm 20 for connecting the connecting member 18 and the actuator 19. These components are drivingly controlled by drive means and controller (not shown in FIG. 2). In this embodiment, the two shafts 13a and 13b are movable whereas the other two shafts 13c are held in a stationary manner. With respect to the shafts for carrying the driven rollers 3a and the drive guides 4a, only the shaft 15a is held in a stationary manner, whereas the other shafts 15 are movable. When the length of the delivery path is determined and a command signal is issued from the controller to the actuator 19, the actuator 19 moves the telescopic arm 20 in a direction indicated by an arrow A corresponding to the assigned length. At this time, the shafts 13a, 15 and the bellows 10 (shown in FIG. 1) carried on the connecting members 18 mounted at a distal end of the arm 20 are moved together. Since the shafts 15 are connected to each other through the connecting linkage rods 17, the drive rollers 3a and the guides 4a are drawn as necessary, thus defining a suitable delivery path. On the other hand, due to the fact that the shaft 13a for carrying the pulleys 2a is moved, it is necessary to keep the length of the delivery belts 1a at the initial constant length. Accordingly, in this embodiment, the shaft 13b is moved in a direction indicated by an arrow B so that the effective length of the delivery belts 1a may be kept at a constant.
By a signal from the outside, such as another sheet dealing apparatus that deals the sheets with the present apparatus, it is determined which receiving box should be used to receive the sheets received from its delivery port or which receiving box should be used to feed out the sheets. For this reason, the respective gates are to be mainly controlled on the basis of the signals from the outside. However, in the case where the receiving boxes are filled with the sheets, it is possible to perform the above-described judgement and control in accordance with a signal from a sensor provided within the present apparatus. FIGS. 3, 4 and 5 are flowcharts showing the main operation of the present apparatus. In particular, FIG. 3 is a flowchart showing the overall operation of movement, sheet dealing and receiving the sheets in the present apparatus. FIG. 4 shows the receiving operation and FIG. 5 shows the feeding out operation. In the present apparatus, when the sheets are received therein, the sheets are stacked one by one on the sheets stacked in the receiving box, whereas, when the sheets are fed out, the sheets are fed out by the frictional force of the feeding rollers 8 and are separated one by one by the separators 7a, 7b.
According to the foregoing embodiment, it is unnecessary to deliver a block or stack of sheets for the feeding and receiving operation of the sheets, and it is possible to perform the sheet receiving and feeding operation smoothly with ease.
FIG. 6 shows another embodiment of the sheet receiving apparatus which is applied to a bill receiving apparatus. The bill receiving apparatus includes delivery belts 31 for feeding the bills, pulleys 32 for engagement with the delivery belts 31, a plurality of driven rollers 33 disposed in contact with and in confronted relation with the delivery belts 31, and guides 34 mounted for stable delivery of the bills when the bills are delivered. A plurality of delivery paths are defined by the delivery belts, driven rollers and guides. Also, the apparatus includes a plurality (three in this case) of receiving boxes 35a, 35b and 35c for receiving bills, receiving mechanisms 36 such as rollers for receiving the bills, separating mechanism 37 for separating the received bills one by one, feeding out mechanisms 38 for feeding out the bills for separation, gate mechanisms (not shown) for switching the delivery direction of the bills, a drive mechanism 39 for driving a bill transport mechanism or the entire apparatus, an extensible bellows 40, a delivery port 41 for receiving and feeding out the bills, a moving mechanism 42 for moving the overall apparatus, a discriminating portion 43 for discriminating the bills, and a controller (not shown) for controlling the apparatus.
This movable bill receiving apparatus is used for receiving bills from one bill dealing apparatus, temporarily receiving the bills, and moving to another bill receiving apparatus and feeding out the received bill to another apparatus. According to this embodiment, when the bills are received or fed out, the apparatus is operated in the same manner as shown in FIGS. 1 and 2. However, in the case where a valuable sheets such as bills are dealt with, it is absolutely necessary to confirm the value of the bill. Therefore, in the movable bill receiving apparatus according to this embodiment, the discriminating portion 43 is provided in the interior of the apparatus. Also, the receiving boxes are separated into a 10,000 yen bill receiving box 35a, a 1,000 yen bill receiving box 35b, and a temporarily receiving box 35c. First of all, when the bills are received, the bills that have passed through the delivery port 41 are received through the discriminating portion 43 via the respective delivery paths to the temporarily receiving box 35c. Then, the value of the bills is compared with the value of the bills of the associated bill dealing apparatus. If the value is correct, the bill is delivered from the temporarily receiving box 35c through the delivery paths to the discriminating portion 43, so that the 10,000 yen bills are received in the 10,000 yen receiving box 35a and the 1,000 yen bills are received in the 1,000 yen bill box 35b. If the value is not correct, the bills are returned from the temporarily receiving box 35c through the delivery paths, the discriminating portion 43 and a bill payout route 44 back to the associated bill dealing apparatus.
In the case where the bills are fed out, the 10,000 yen bills and 1,000 yen bills are separately fed out from the 10,000 yen bill receiving box 35a and the 1,000 yen bill receiving box 35b, respectively. After the passage of the discriminating portion 43, the bills are paid out through the payout route 44 and delivery port 41. According to this embodiment, the bills are received one by one into the receiving boxes. Also, the separation of the bills may be attained by a frictional type separator whose detailed explanation will be omitted herein. The feeding out rollers 38 feeds out the bills due to the friction and the separating rollers 37a, 37b separate the sheets one by one. After the payment, the value of bills is confirmed. If the value is correct, the dealing operation is finished, whereas if the value is not correct, the bills fed out are again returned to the movable bill receiving apparatus in the same manner as in the case of the bill receiving operation., and the value is again checked.
According to this embodiment, it is possible to provide a movable bill receiving apparatus that may readily perform the bill dealing without fail and with high reliability. Although the extensible delivery path shown in FIG. 2 is used at the delivery portion in both the sheet receiving apparatus shown in FIG. 1 and the bill receiving apparatus shown in FIG. 6, it is possible to use another delivery path module, that is automatically detachable, at the delivery portion.
FIG. 7 shows one embodiment of a movable bill receiving apparatus in which an automatically detachable delivery path module is used. The bills are delivered from a bill dealing apparatus 46 within a safe 45 to a movable bill receiving apparatus by the above-described delivery path module 47a. The movable bill receiving apparatus 48 is moved to a position below another bill dealing apparatus 49. The bills are fed out to the bill dealing apparatus 49 by a delivery path module 47b. The delivery path modules 47a, 47b are also movable to necessary positions. These modules are automatically mounted on the movable bill receiving apparatus 48 during the feeding/receiving operation. These modules are automatically removed from the apparatus. In this embodiment, although the movable bill receiving apparatus and the delivery path modules 47 are made discrete from each other, the delivery path modules 47 may be mounted on the movable bill receiving apparatus 48 or the bill dealing apparatuses 46, 49.
FIG. 8 shows one embodiment of an automatic dealing system in which the above-described movable bill receiving apparatus is used. The automatic dealing system includes a safe 71, a plurality of automatic transaction machines 72 through which customers or bank clerks may access medium to be processed such as cash, bankbooks, cash cards and the like for trading, a programmed controller (not shown), a plurality of processors 74 for processing the cash, bankbooks, cash cards and the like respectively under the control of the programmed controller, and a movable bill receiving apparatus 73 for transporting the medium to be processed such as cash, bankbooks, cash cards or the like between the automatic transaction machines 72 and the processors 74. In this embodiment, the movable bill receiving apparatus shown in FIG. 6 is used as a movable sheet receiving apparatus. The delivery of bills is performed through a delivery window 75 from the processors 74 disposed within the safe 71 to the movable bill receiving apparatus 73. The movable bill receiving apparatus 73 is moved to the automatic transaction machines 72 along a predetermined route 76. When the bill receiving apparatus 73 reaches a predetermined position, the bills are delivered to the automatic transaction machines. In the case where the bills are received from the automatic transaction machines 72 to the safe 71, the operation is reversely performed. The delivery window 75 is closed by a shutter except for the operative time. Also, in case of bill delivery accident or burglar, a sensor incorporated in the movable apparatus may detect the accident and issue a warning signal to a guarding room or the like. According to this embodiment, it is possible to provide an automatic dealing or trading system that has a high reliability.
FIG. 9 shows a drive-through type cash dealing apparatus to which applied is the sheet receiving apparatus according to the present invention. In this automatic cash dealing apparatus 80, a box 100 is fixed on a base 200. The apparatus includes, in addition to the components shown in FIG. 1 or FIG. 6, an operation panel 81 to which the customers may access for trading, at least one distance measuring sensor 87 for measuring a distance between the apparatus 80 and the vehicle 90 when the customer's vehicle 90 accesses, a controller 88 for outputting a signal for driving the apparatus 80, and a proximity sensor 89 for preventing the cash delivery window 41 from colliding with the customers or the vehicle.
In such an automatic cash dealing apparatus, when the vehicle 90 approaches the apparatus, the distance measuring sensor 87 measures a distance between the vehicle 90 and the apparatus and issues a signal to the controller 88. When the controller 88 judges that the distance between the cash dealing apparatus 80 and the vehicle 90 is too long for the customers to safely deal with the apparatus, the cash delivery window 41 is moved, as indicated by dotted lines in FIG. 9, to a position where the dealing may safely be performed. In this case, for instance, the sheet delivery apparatus shown in FIG. 2 is incorporated within the arm 82 surrounded by the bellows. The arm 82 may extend by a length assigned by the controller 88. The proximity sensor 89 is provided for safety when the arm 82 is extended. If this sensor is turned on, the controller 88 issues a signal for stopping the movement of the arm 82.
According to the above-described cash dealing apparatus, since it is possible to automatically extend the cash delivery window 41 in correspondence with the distance between the vehicle 90 and the apparatus, it is possible to perform the safety cash delivery with ease even if the vehicle is stopped at a position somewhat far from the cash dealing apparatus 80.
As described above, according to the present invention, when the sheets are delivered, a large amount of sheets may be delivered without fail. Also, since the high reliable, automatic dealing system may be constructed by the application of the invention, it is possible to provide a new automatic trading system which does not need a lot of manual work of bank clerks.
Furthermore, it is possible to facilitate the positioning between the movable sheet receiving apparatus and the sheet dealing apparatus that performs the delivery of the sheets.
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A sheet dealing apparatus feeds sheets, received within the apparatus, to a user through a sheet delivery portion by an operation of the user or receives the sheets into the sheet dealing apparatus from the user. Also, this operation may be similarly applied to the sheet delivery mode between the sheet dealing apparatus and another sheet dealing apparatus. The sheet delivery portion is contructed so as to be retractable or extensible with respect to a body of the apparatus. A sheet delivery window formed at the delivery portion is variable in position as necessary.
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This is a continuation of application Ser. No. 07/907,055, filed Jul. 1, 1992 now abandoned.
BRIEF SUMMARY OF THE INVENTION
This invention relates to rearview mirrors for automotive vehicles and, more particularly, to an improved outside automatic rearview mirror for automotive vehicles.
Heretofore, various automatic rearview mirrors for automotive vehicles have been devised which automatically transfer from the full reflective mode (day) to the partial reflectance mode (night) for glare protection purposes from light emanating from the headlights of vehicles approaching from the rear. The electrochromic mirrors disclosed in U.S. Pat. No. 4,902,108, issued Feb. 20, 1990, for single-compartment, self-erasing, solution-phase electrochromic devices, solutions for use therein, and uses thereof, and U.S. Pat. No. 4,917,477, issued Apr. 17, 1990, for automatic rearview mirror system for automotive vehicles, each of which patents is assigned to the assignee of the present invention, are typical of modem day automatic rearview mirrors for automotive vehicles. Such electrochromic mirrors may be utilized in a fully integrated inside/outside rearview mirror system or as an inside or an outside rearview mirror system. In general, in automatic rearview mirrors of the type disclosed in U.S. Pat. Nos. 4,902,108 and 4,917,477, both the inside and the outside rearview mirrors are comprised of a thin chemical solution sandwiched and sealed between two glass elements. When the chemical solution is electrically energized, it darkens and begins to absorb light. The higher the voltage, the darker the mirror becomes. When the electrical voltage is removed, the mirror returns to its clear state. Also, in general, the chemical solution sandwiched and sealed between the two glass elements is comprised of solutions of electrochromic compounds which function as the media of variable transmittance in the mirrors. Such automatic rearview mirrors incorporate light sensing electronic circuitry which is effective to switch the mirrors to the night time mode when glare is detected, the sandwiched chemical layer being activated when glare is detected thereby darkening the mirror automatically. As glare subsides, the mirror glass returns to its normal clear state without any action being required on the part of the driver of the vehicle. The electrochromic compounds are disposed in a sealed chamber defined by a clear front glass, an edge seal, and a rear mirror element having a reflective layer, the electrochromic compound filling the chamber. Transparent conductive layers are provided on the inside of the glass elements, the transparent conductive layers being connected to the electronic circuitry which is effective to electrically energize the electrochromic compounds to switch the mirror to the night time mode when glare is detected.
While mirrors of the indicated character have operated satisfactorily, particularly as inside rearview mirrors in automotive vehicles, the useful life of such mirrors may be diminished when such mirrors are used as outside mirrors on automotive vehicles. For example, outside rearview mirrors must survive extreme environmental conditions such as extreme heat and/or cold, increased ultraviolet light exposure, alternate wetting and freezing followed by thawing conditions, exposure to salt spray and other corrosive sprays, and high liquid pressure sprays such as are encountered in car wash facilities. Heretofore, when outside automatic rearview mirrors have been exposed to extreme environmental conditions, difficulties have been encountered in maintaining suitable seals for the electrochromic compounds as well as the electrical connections thereto over a relatively long useful life. For example, heretofore efforts were made to seal the exterior automotive glass assemblies utilizing materials which were not ultraviolet stable with the result that it was necessary to paint exposed surfaces thereof in order to meet conventional outdoor ultraviolet light motor vehicle specifications. The problems encountered in masking areas that must not be painted, such as the mirror surfaces, are not trivial, and the cost of masking such areas during manufacture of the mirror resulted in a substantial increase in the manufacturing cost. Moreover, because of glass manufacturing tolerances, the glass mirror elements vary in thickness under mass production conditions. Because of such variations in thickness, it is difficult to obtain a long lasting, satisfactory seal to the front glass surface during manufacturing operations. This can result in excessive trimming operations to remove excess sealing material. Moreover, excessive clamping pressure during curing of the sealing material can tend to rupture the seal elements thereby causing premature seal element failure, and since the seal itself is normally not readily visible, such a defect is not readily apparent. In addition, since it is necessary for the electrochromic elements to have at least two wires for a connection to a power source, it is extremely difficult to seal the wire ports or connector assembly and at the same time prevent excessive molding material flash requiring subsequent removal during manufacturing operations.
An object of the present invention is to provide an improved automatic rearview mirror for automotive vehicles, which mirror incorporates improved means enabling the mirror to survive extreme environmental conditions, such as extreme heat and/or cold, ultraviolet light exposure, alternate wetting, freezing and thawing conditions, exposure to salt spray and other corrosive conditions, and high liquid pressure sprays such as may be encountered in car wash facilities.
Another object of the present invention is to provide an improved automatic rearview mirror incorporating improved means for sealing components of the mirror against air leaks, liquid leaks and other fluid leaks which could cause malfunctions in the operation of the mirror.
Another object of the present invention is to provide an improved automatic rearview mirror structure which enables the use of ultraviolet stable materials in the manufacture thereof thereby reducing or eliminating the necessity of painting exposed surfaces thereof in order to meet outdoor ultraviolet light motor vehicle specifications.
Another object of the present invention is to provide an improved automatic rearview mirror which eliminates the necessity of masking areas thereof during the manufacturing process thereby reducing the manufacturing costs.
Another object of the present invention is to provide an improved automatic rearview mirror which may be manufactured and assembled with a minimum of breakage of components thereof during the manufacturing and assembly operations.
Another object of the present invention is to provide an improved automatic rearview mirror incorporating improved sealing means providing multiple seals that have surprising resistance to high liquid pressure sprays such as are encountered in car wash facilities, and surprising resistance to freezing water, salt sprays and other extreme environmental conditions including ultraviolet light exposure.
Another object of the present invention is to provide an improved automatic rearview mirror assembly that may be directly substituted for plain mirror glass into many conventional outside rearview mirror housings and motorized mechanisms.
Another object of the present invention is to provide an improved automatic rearview mirror incorporating improved means of increasing the efficiency of heating elements which may be incorporated therein for defrosting purposes.
Another object of the present invention is to provide an improved automatic rearview mirror incorporating improved means for effecting improved sealing of the components thereof with a minimum reduction in the effective reflective area of the minor.
Another object of the present invention is to provide improved means for sealing structures incorporating glass components whereby such components may be assembled into a rugged unitary device capable of indoor and outdoor applications.
The above as well as other objects and advantages of the present invention will become apparent from the following description, the appended claims and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front elevational view of an automatic rearview mirror embodying the present invention, the mirror being particularly adapted for use as an outside rearview mirror on automotive vehicles.
FIG. 2 is an elevational view of the reverse side of the bezel of the mirror illustrated in FIG. 1.
FIG. 3 is an elevational view of the electrochromic assembly incorporated in the rearview mirror illustrated in FIG. 1; and
FIG. 4 is an enlarged cross-sectional view, with portions broken away for clarity of illustration, of the automatic rearview mirror illustrated in FIG. 1.
DETAILED DESCRIPTION
In general, in automatic rearview mirrors embodying the present invention, the rearview mirror is comprised of a thin layer of a chemical solution sandwiched between two substantially fiat glass elements. As the chemical layer is electrically energized, it darkens and begins to absorb light. The higher the voltage, the darker the mirror becomes. When the electrical voltage is removed, the outside mirror returns to its clear state. Automatic rearview mirrors embodying the present invention may incorporate light sensing electronic circuitry of the type illustrated and described in U.S. Pat. No. 4,917,477, issued Apr. 17, 1990, for Automatic Rearview System for Automotive Vehicles, and assigned to the assignee of the present invention. Also, the electrochromic components of mirrors embodying the present invention may be of the type disclosed in U.S. Pat. No. 4,902,108, issued Feb. 20, 1990, for Single-Compartment, Self-Erasing, Solution-Phase Electrochromic Devices, Solutions for Use Therein, and Uses Thereof, and assigned to the assignee of the present invention. The entire disclosures of U.S. Pat. Nos. 4,917,477 and 4,902,108 are incorporated herein by reference.
An electrochromic mirror, generally designated 10, embodying the present invention is depicted in simplified cross-section in FIG. 4. Since some of the layers of the mirror are very thin, the scale has been distorted for pictorial clarity. As shown in FIG. 4, the electrochromic assembly 11 includes a sealed chamber 12 defined by a clear front glass 14, an edge seal 16, and a clear rear glass 18 having a reflective layer 20. A chemical solution 22 having the desired electrochromic properties fills the chamber 12, and transparent conductive layers 24 and 26 are connected to an electrical circuit as will be described hereinafter in greater detail. Light rays enter through the front glass 14, the transparent conductive layer 24, the electrochromic layer 22, the transparent conductive layer 26, and the mirror glass layer 18 before being reflected from the reflective layer 20 provided on the mirror glass layer 18. Light in the reflected rays exit by the same general path traversed in the reverse direction. Both the entering rays and the reflected rays are attenuated in proportion to the degree to which the electrochromic layer 22 is light absorbing. When the electrochromic layer 22 is highly light absorbing, the intensity of the exiting rays is diminished, the dim image remaining being from light rays which are reflected off of the front and back surfaces of the front glass 14. Thus, the basic structural elements of the electrochromic assembly include two planar electrode-bearing sides or walls, a spacing and sealing layer 16, which spaces apart and holds the walls in substantially parallel relationship in an assembled device, and which surrounds a volume which in an assembled device is comprised of electrode layers on the electrode-bearing walls as well as the circumferential inside walls 28 of the spacing and sealing layer 16. The volume of the chamber 12 is preferably filled with any of the solutions disclosed in U.S. Pat. No. 4,902,108 which have reversibly variable transmittance in the operation of the device, the solution in the chamber 12 being in contact with both electrode layers 24 and 26 during operation of the mirror.
With reference to FIGS. 3 and 4, a preferred arrangement for connecting the electronic conductive layers 24 and 26 to a power source is illustrated. In this arrangement, the two electrode-bearing front and rear glass plates 14 and 18 are displaced is opposite directions, laterally from, but parallel to the chamber 12 in order to provide exposed areas 30 and 32. Electrically conductive spring clips 34 are provided which are placed on the coated glass sheets to make electrical contact to the exposed areas 30 and 32 of the transparent conductors 24 and 26, respectively. Suitable electrical conductors (not shown) may be soldered or otherwise connected to the spring clips so that desired voltage may be applied to the device from a suitable power source.
As illustrated in the drawings, automatic rearview mirrors 10 embodying the present invention include a bezel 36, the electrochromic assembly 11 previously described, a heater 38, and a mirror back 40 which is adapted to snap into an outside mirror housing (not shown) that may be of any desired configuration, the outside mirror housing being supported on the outside of the automotive vehicle in any desired or conventional manner whereby the field of view of the minor may be adjusted by the driver of the vehicle in a conventional manner, as for example through manual adjustment or by mechanical or electrical means of the type conventionally provided on modem day automobiles.
As shown in FIGS. 1 and 4, the bezel 36 surrounds the electrochromic assembly 11 in a circumferential manner, the bezel 36 overlying the electrochromic assembly 11 so as to conceal the edge portions thereof including the electrically conductive spring clips 34. The bezel includes an exposed, curvilinear main body portion 42 which extends around the entire circumference of the electrochromic mirror assembly 11. The main body portion 42 includes a flat surface 44 which is sealed to the exposed surface 46 of the glass element 14 through the agency of a glass sealant 48 which is preferably comprised, 60% by weight of a rubber based sealant such as HM-1081A dissolved in a VM+P naphtha solvent. The rubber based sealant 48 may be obtained from H. B. Fuller Company, 1200 Wolters Blvd. in Vaonais Heights, Minn., while the naphtha solvent may be obtained from Haviland Products Co., 421 Ann Street N.W., Grand Rapids, Mich. It has been found that if during the manufacturing operation the sealant 48 is only applied to approximately 25% of the area of the flat surface of the bezel, that the sealant will not weep out onto the exposed face of the glass but rather flows towards the periphery of the bezel with the result that an effective seal is obtained without weepage onto the exposed face of the glass that would require clean up operations during manufacture of the mirror. The bezel 36 also includes a skin portion 50 which extends around the entire periphery of the side edges of the electrochromic assembly 11 and also overlies the outside wall of the mirror back 40. The bezel itself is preferably injected molded from a plastic suitable for exterior automotive use such as Cadon 127 available from Monsanto Chemical Company, 800 N. Lindbergh Blvd., St. Louis, Mo. The electrical spring clips 34 may be formed from a tin plated strip of spring material such as half hard brass, phosphor bronze or beryllium copper, and the underside 52 of the clips 34 which contact the conductive layers on the glass elements are overcoated with a rubber based material such as Hyseal 5000 available from J. Dedos Inc., 400 Ann Street N.W., Grand Rapids, Mich., such rubber based material constituting approximately 33% of the overcoat which is dissolved in the VM+P naphtha solvent previously described. The clip contact overcoating may be approximately 0.005 to 0.010 inches thick. In the alternative, the Hyseal 5000 may be applied as 100% solids with a hot melt application.
If desired, outside mirrors embodying the present invention may also include the electrical heater 38 which functions to defrost the mirror, the heater 38 being a full surface heater such as those that are available from RayChem Corp. of Menlo Park, Calif. or from ITW Chronomatic of Chicago, Ill.
The mirror back 40 is preferably formed of the same material as the bezel, the mirror back 40 including a centrally disposed support plate portion 54 surrounded by an upstanding flange wall portion 56 integrally joined to the support plate portion by a bight portion 58. The heater 38 is preferably adhered to the adjacent surface of the reflective layer 20 on the glass plate 18 through the agency of a non-corrosive pressure sensitive adhesive or film such as AS-98 available from Adhesives Research Inc. in Glen Rock, Pa., or 3M-447 available from 3M Industrial Tape Division in Southfield, Mich. The centrally disposed support plate portion 54 of the mirror back 40 is preferably adhered to the heater through the agency of a non-corrosive elastomeric adhesive 60, such as Dow Coming 739 RTV available from Dow Coring Corporation in Midland, Mich., the mirror back adhesive 60 being in the form of spaced pad portions such as 62 and 64 disposed between the heater 38 and the support plate portion 54 of the mirror back 40, it having been found that it is preferable for the mirror back adhesive to cover only spaced areas rather than the entire support plate portion of the mirror back. It will be understood that it would be possible to print or deposit the electrical heater circuitry directly on the back of the glass plate rather than adhere a separate heater to the back of the glass plate. It has also been found that the defrost heater is surprisingly effective considering that the electrochromic assembly includes two layers of glass separated by an electrochromic solution and functions to defrost the exposed surface of the mirror encompassed by the bezel in a minimum of time.
As shown in FIGS. 2 and 4, the reverse side 66 of the bezel 36 is provided with circumferentially spaced support ribs 68 each terminating in a knife-like edge 70 which engages, with substantially line contact, the flat surface 72 defining the ends of the upstanding wall 56 of the mirror back 40. The spaces 74 between the support ribs 68 are filled with a semi-flexible, water resistant potting compound 76 such as 50% by weight of Shell 828 epoxy resin, 20% by weight Shell 871 epoxy resin and 30% by weight of Ancamine 1768, which potting material functions as a secondary seal for the electrochromic assembly 11. With such a construction, the bezel and the associated electrochromic assembly constitutes an encapsulation vessel for the potting material during curing of the potting material which, when cured, forms a secondary sea/for the electrochromic assembly. In addition, the mirror is provided with a bezel to glass seal and the electrochromic solution itself is sealed between the two glass plates as previously described. It has been found that the clip contact overcoating prevents the potting material from seeping between the clip contacts and the conductive coating material so that the potting material does not interfere with the electrical contact between the clips and the electrically conductive coating provided on the glass plates. The Shell 828 and 871 epoxy resins may be obtained from the Shell Chemical Company in Houston, Tex., while the Ancamine 1768 may be obtained from Pacific Anchor Chemical Corporation, 1224 Mendon Road in Cumberland, R.I.
During the manufacture of the outside rearview mirrors embodying the present invention, the potting material 76 does not adhere to the knife-like edges 70 of the support ribs 68, and the potting material is only present in the spaces 74 between the support ribs 68. Accordingly, the assembly comprising the bezel 36 and the electrochromic assembly 11 tends to float on the knife-like edge supports thereby substantially preventing cracking of the glass elements due to tension or compression forces exerted on the glass elements during manufacturing operations. It has been found that if the mirror back is fastened around the entire periphery of the bezel, that tension and compression stresses may be encountered in the glass plates which will cause breaking of the glass elements during the manufacturing operations. With such a construction, the bezel overlies a minimum of the reflective surface area of the mirror elements, and at the same time conceals the electrical clips and the potting material thereby providing a maximum reflective viewing area for mirrors embodying the present invention. In practice it has been found, for example, that the entire assembly may be held together through the agency of elastic bands while the various adhesives and the potting material are in the curing stages.
From the foregoing it will be appreciated that the present invention enables the provision of a multiple sealed electrochromic mirror that has surprising resistance to car washes, freezing water, salt sprays and other adverse conditions that may be encountered when the mirror is utilized as an outside rearview mirror on an automotive vehicle. There is a minimum of moisture permeation and a minimum of oxygen permeation through the sealants thereby preventing adverse penetration of moisture and oxygen to the electrochromic assembly including the electrical contacts with the result that the useful life of the mirror is substantially increased.
While a preferred embodiment of the invention has been illustrated and described, it will be understood that various changes and modifications may be made without departing from the spirit of the invention.
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An automatic electrochromic rearview mirror for automotive vehicles, the mirror being particularly adapted for use as an outside rearview mirror and incorporating improved means enabling the mirror to survive, over a relatively long useful life, extreme environmental conditions, such as extreme heat and/or cold, ultraviolet light exposure, alternate wetting, freezing and thawing conditions, exposure to salt spray and other corrosive conditions as well as high pressure sprays such as may be encountered in car wash facilities. Mirrors embodying the present invention may be manufactured and assembled with a minimum of breakage of glass components and/or rupture of sealing components during the manufacturing and assembly operations, and also incorporate improved means for increasing the efficiency of heating elements which may be utilized for defrosting purposes.
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BACKGROUND OF INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a method for generating a write clock of a constant angular velocity optical storage device, and more particularly, to a method that uses a wobble signal to generate a write clock of a constant angular velocity mode optical disk recorder.
[0003] 2. Description of the Prior Art
[0004] For companies or the end users, the management and storage of documents is regarded as an important task. In the past, documents were printed or written on paper. Therefore, when a user deals with a huge amount of documents, it is not convenient for the user to manage those documents because of a great size or a heavy weight. With the development of computer technology, digital data and digital documents are widely stored in a plurality of data storage media. Many kinds of data storage media are developed to help users with those digital data conveniently. An optical disk recorder such as a CD-RW drive takes advantage of recordable compact disks to record data. The compact disk has a low production cost, a small size, and a great storage capacity.
[0005] Generally speaking, the optical storage device has two operation modes according to the mode of the motor control. One is a constant linear velocity (CLV) mode, and the other is a constant angular velocity (CAV) mode. With improvements in access speed, constant linear velocity mode is not suitable for a high efficiency or a high resolution application. The reasons are as follows. Under the constant linear velocity mode, the rotational speed of a spindle varies constantly in order to make the associated linear velocity at each position of a disk constant. The rotational speed of the spindle is increased and decreased alternately so that associated power dissipation is raised. The optical storage device, therefore, will suffer a high temperature, a great deal of vibration, and a slow access speed while operating. Therefore, is hard to improve the access speed under the constant linear velocity mode. On the contrary, the rotational speed of the spindle is fixed under the constant angular velocity mode. In other words, the rotation speed of the spindle is fixed, and the associated linear velocity at each position of the disk varies when the optical storage device accesses data from the disk. In addition, when an optical disk recorder under a constant linear velocity mode wants to burn data into the disk, the optical disk recorder cannot record data with a high recording speed because the limitation of keeping a constant linear velocity will prevent the spindle from having a high rotational speed. However, if the constant angular velocity mode is adopted, the spindle operates with a fixed angular velocity so that the outer circle of the disk has a greater linear velocity to improve the corresponding recording speed.
[0006] Please refer to FIG. 1, which is a diagram of recording frames according to a prior art disk. The data are first transferred into corresponding eight-to-fourteen modulation (EFM) data when being recorded on a disk. The EFM data are recorded on the disk according to EFM frame format. As shown in FIG. 1A, every 98 EFM frames are combined together to form an absolute time in pre-groove (ATIP) frame. As shown in FIG. 1B, each EFM frame has 588 bits, and the EFM frame comprises synchronization data, subcode data, main data, p-parity data, and q-parity data. The main data, p-parity data, and q-parity data within the 98 EFM frames (ATIP frame) are combined to form a main channel of the corresponding ATIP frame so as to store actual written data. But, the subcode data within every 98 EFM frames are used for storing associated information about the written data such as track numbers. In addition, the subcode data S 0 of a first EFM frame F 1 and the subcode data S 1 of a second EFM frame F 2 are used for generating a subcode synchronization signal. The subcode synchronization signal is used for determining synchronization between the EFM data that is prepared to be written and the ATIP data that is pre-recorded on the disk. In addition, when the optical disk recorder transfers the written data into EFM data, the optical disk recorder will simultaneously generate an encoder EFM frame synchronization (EEFS) signal corresponding to each ATIP frame, and an encoded subcode frame synchronization (ESFS) signal corresponding to each EFM frame. The EEFS signal and the ESFS signal are used for determining synchronization status of the written data when the written data are burned into the disk.
[0007] Please refer to FIG. 2, which is a diagram of prior art ATIP data 30 . When a recordable disk is manufactured, a wobbling track is formed on the surface of the recordable disk. After a pick-up head of the optical disk recorder senses the wobbling track, a wobble signal comprising waveforms with different frequencies is generated. The wobble signal is then decoded according to a frequency modulation (FM) for generating the ATIP data 30 that are related to the recording frames on the recordable disk. The ATIP data 30 are established by blocks. The bit length of each block is equal to 42. The ATIP data 30 has a synchronization mark 31 whose bit length is 4, a data code 32 whose bit length is 24, and a cyclic redundancy check (CRC) code whose bit length is 14. The data code 32 further has minute 34 , second 35 , and frame 36 information of the recording frame on the recordable disk.
[0008] Please refer to FIG. 3, which is a diagram of the prior art ESFS synchronization signal and a prior art ATIP synchronization signal. The synchronization mark 31 of the ATIP data 30 corresponds to an ATIP synchronization signal. According to specification of the optical disk recorder, an error 39 between the ATIP synchronization signal and the ESFS synchronization signal must be controlled within an interval, that is, 2 recording frames of the disk. If the error 39 is greater than 2 recording frames, the recording process fails.
[0009] Please refer to FIG. 4, which is a block diagram of a write clock generator 40 according to the prior art CAV optical disk recorder. As mentioned above, the ATIP synchronization signal 41 and the ESFS signal 42 are used to determine whether the recordable disk is ready to record data. Under the CAV mode, the rotational speed of spindle is fixed so that the linear velocity at each position of the disk varies. In other words, the frequency of the wobble signal is unstable due to the frequency variation so that the frequency of the ATIP synchronization signal 41 is affected. In order to make the error between the ATIP synchronization signal 41 and the ESFS signal conform to the limitation defined by the specification, the write clock generator 40 is used for generating a write clock 43 so as to synchronize the ATIP synchronization signal 41 and the ESFS signal 42 . A phase detector 44 will generate an output voltage according to a phase difference between the ESFS signal 42 and the ATIP synchronization signal 41 . The output voltage is passed through a low-pass filter 46 , and is transmitted to a voltage controlled oscillator (VCO) 48 . The voltage controlled oscillator 48 then generates a reference clock 50 with a specific frequency according to the output voltage. The reference clock 50 is passed through a frequency divider 52 , and a write clock 43 is outputted from the frequency divider 52 . Furthermore, the write clock 43 is passed through another frequency divider 54 to alter the frequency of the ESFS signal 42 . The above-mentioned process is repeated until the error between the ATIP synchronization signal 41 and the ESFS signal 42 complies with the required specification. That is, when the error between the ATIP synchronization signal 41 and the ESFS signal 42 meets the desired requirement according to the specification, the optical disk recorder can start burning data onto the disk. The write clock 43 is inputted to an EFM encoder 58 so that the EFM encoder 58 can transfer data 56 into a corresponding EFM data signal with the help of the write clock 43 . The EFM data signals, which are synchronized with the write clock 43 , are then transmitted to a pick-up head 60 . Finally, the pick-up head 60 writes data 56 on the disk according to the received EFM data signal.
[0010] Based on the ATIP synchronization signal 41 , the prior art write clock generator 40 of a CAV compact disk recorder uses a phase-lock loop (PLL) to lock the ESFS signal 42 and the related write clock 43 . However, the ATIP synchronization signal 41 has a low frequency. For example, the ATIP synchronization signal 41 has a frequency equal to 75 hertz under “1×” recording speed. Therefore, the phase-lock process requires a long time to compare the phase difference and to adjust the corresponding frequency. That is, the write clock 43 will become stable only after a long period of time, meaning that the recording efficiency and stability of the optical disk recorder are greatly deteriorated.
SUMMARY OF INVENTION
[0011] It is therefore a primary objective of the claimed invention to provide a method that uses a wobble signal to generate a write clock of a constant angular velocity optical disk recorder so that the write clock achieves a stable state quickly to improve the recording quality and efficiency.
[0012] Briefly, the claimed invention provides a method for generating a write clock of an optical storage device. The optical storage device has a counter for generating a count number by using a reference clock to count a first signal, and a phase detector for generating an adjustment value by detecting a phase shift between a second signal and a frame synchronization signal. The method includes generating a rectification value according to the count number and the adjustment value, generating a reference write clock according to the rectification value and the reference clock, modifying the frame synchronization signal according to the reference write clock, and comparing the second signal with the frame synchronization signal. If the phase shift between the second signal and the frame synchronization signal is less than a predetermined value, the reference write clock is the write clock of the optical storage device.
[0013] It is an advantage of the claimed invention that the write clock generator uses a reference clock with a higher frequency to count the wobble signal for generating a count number, and generates a first reference synchronization signal based on the count number and the wobble signal. Because the frequency of the first reference synchronization signal is greater than the frequency of the ATIP synchronization signal, a lock time required by the corresponding phase-lock loop is greatly reduced, and a process time required for the write clock to be stable is reduced as well.
[0014] These and other objectives of the claimed invention will no doubt become obvious to those of ordinary skill in the art after reading the following detailed description of the preferred embodiment which is illustrated in the various figures and drawings.
BRIEF DESCRIPTION OF DRAWINGS
[0015] [0015]FIG. 1 is a diagram of recording frames according to a prior art disk.
[0016] [0016]FIG. 2 is a diagram of prior art ATIP data.
[0017] [0017]FIG. 3 is a diagram of the prior art ESFS synchronization signal and a prior art ATIP synchronization signal.
[0018] [0018]FIG. 4 is a block diagram of a write clock generator according to a prior art CAV optical disk recorder.
[0019] [0019]FIG. 5 is a block diagram showing a write clock generator of a CAV optical disk recorder according to the present invention.
[0020] [0020]FIG. 6 is a diagram of a relation between the reference clock and the wobble signal.
DETAILED DESCRIPTION
[0021] Please refer to FIG. 5, which is a block diagram showing a write clock generator 80 of a CAV optical disk recorder according to the present invention. The present invention uses the wobble signal 82 to generate the write clock 84 . The write clock generator 80 has a plurality of function blocks including a reference clock generator 88 for generating a reference clock 86 , a digital average processor 92 for outputting an average number 120 , a plurality of frequency dividers 94 , 96 , 98 , 100 for changing frequencies of inputted signals, a plurality of phase detectors 102 , 104 for comparing phases of different signals, a low-pass filter 106 for smoothing signals outputted from the phase detector 104 , a voltage controlled oscillator 108 for generating a signal with a specific frequency according to an input voltage, and a controller 110 for controlling operation of the frequency divider 94 .
[0022] The operation of the write clock generator 80 according to the present invention is described as follows. The reference clock generator 88 will output the reference clock 86 that has a fixed frequency. For example, the reference clock 86 could be a system clock of the optical disk recorder. Basically, the frequency of the reference clock 86 is fixed and is much higher than the frequency of the wobble signal 82 . After the wobble signal 82 is retrieved from the recordable disk, the reference clock 86 and the wobble signal 82 are both passed to a counter 90 . The counter 90 calculates a total number of reference periods (period of the reference clock 86 ) during one period of the wobble signal 82 .
[0023] Please refer to FIG. 6, which is a diagram of a relation between the reference clock 86 and the wobble signal 82 . In FIG. 6, the horizontal axis represents time. Two waveforms shown in FIG. 6 represent the wobble signal 82 and a count number 118 outputted from the counter 90 at node A. As described above, the wobble signal 82 is established by two different waveforms, and each waveform has a specific frequency. As shown in FIG. 6, the wobble signal 82 has sectors TP 2 , TP 4 with one frequency 1/T1 (period T1), and sectors TP1, TP3 with another frequency 1/T2 (period T2). When the counter 90 operates, the counter 90 uses reference period of the reference clock 86 as a unit to calculate the total number of reference periods during one period of the wobble signal 82 . Please refer to FIG. 6A, which is detailed diagram of a period T2 associated with the wobble signal 82 . Because the frequency of the reference clock 86 is greater than 1/T1 and 1/T2, the reference period T3 of the reference clock 86 is certainly shorter than the periods T1, T2 of the wobble signal 82 . Therefore, the period T2 corresponds to a plurality of reference periods T3. Generally, the period T2 corresponds to hundreds of reference periods T3, but the actual number is determined by the frequency of the reference clock 86 . Similarly, the period T1 of the wobble signal 82 , as shown in FIG. 6B, corresponds to a plurality of reference periods T3 of the reference clock 86 . After counting the number of reference periods in one period of the wobble signal 82 , the counter 90 will output the count number 118 to the digital average processor 92 . As the timing sequence of the count number 118 shows in FIG. 6, the number of reference periods T3 within one period T2 is less because the period T2 is shorter (high frequency). Therefore, the count number 118 corresponding to the sectors TP1, TP3 having the period T2 is less, too. On the contrary, the number of reference periods T3 within one period T1 is greater because the period T1 is longer (low frequency). Therefore, the count number 118 corresponding to the sectors TP 2 , TP 4 having the period T1 is greater, too. Considering the count number 118 , the sectors with regard to different frequencies correspond to different signal levels. In addition, the count number 118 generated from the counter 90 is then transmitted to the digital average processor 74 to calculate a long-term average of the count number 118 , that is, to generate an average number 120 . The related signal level of the average number 120 is also shown in FIG. 6 for clarity.
[0024] The frequency of the reference clock 86 is equal to the frequency of the wobble signal 82 times the average number 120 . The controller 110 , therefore, can adjust a dividing ratio of the frequency divider 94 according to the average number 120 . In the preferred embodiment, the controller 110 adopts half the average number 120 as a fundamental dividing ratio of the frequency divider 94 . In other words, without considering an additional factor, that is, an adjustment value 129 generated from the phase detector 102 to the controller 110 , a first reference synchronization signal 124 that has a frequency doubling the frequency of the wobble signal 82 is generated when the reference clock 86 passed to the frequency divider 94 . Moreover, the phase detector 102 will also generate the adjustment value 129 according to the phase difference between the ATIP synchronization signal 122 and the ESFS signal 124 . The adjustment value 129 is used for further tuning the dividing ratio of the frequency divider 94 . The controller 110 , therefore, has to modify the dividing ratio of the frequency divider 94 according to a rectification value generated from both the average number 120 and the adjustment value 129 . In addition, the phase detector 104 will output an output voltage according to a phase difference between the first reference synchronization signal 126 and a second reference synchronization signal 128 . The output voltage is first passed through the low-pass filter 106 , and then is transmitted to the voltage-controlled oscillator 108 . The voltage-controlled oscillator 108 is used for generating a signal with a specific frequency according to the output voltage generated by the phase detector 104 . The signal generated by the voltage-controlled oscillator 108 is further passed to a frequency divider 96 for generating a write clock 84 . The write clock 84 is passed to a frequency divider 98 for generating the second reference synchronization signal 128 , and the second reference synchronization signal 128 will further alter frequency of the ESFS signal 124 . The above-mentioned process is repeated until the error between the ATIP synchronization signal 122 and the ESFS signal 124 conforms to an associated requirement defined in the specification of the optical disk recorder. That is, when the error between the ATIP synchronization signal 122 and the ESFS signal 124 meets the desired requirement according to the specification, the optical disk recorder can start burning data 114 onto the disk. The write clock 84 is inputted to an EFM encoder 112 so that the EFM encoder 112 can transfer data 114 into corresponding the EFM data signal with the help of the write clock 84 . The EFM data signals, which are synchronized with the write clock 84 , are then transmitted to a pick-up head 116 . Finally, the pick-up head 116 writes data 114 into the disk according to the received EFM data signal.
[0025] In contrast to the prior art write clock generator, the claimed write clock generator uses a reference clock with a higher frequency to count the wobble signal for generating a count number, and generates a first reference synchronization signal based on the count number and the wobble signal. The first reference synchronization signal is used for locking a write clock and the ESFS signal. Because the frequency of the reference synchronization signal is greater than the frequency of the ATIP synchronization signal, a lock time required by the corresponding phase-lock loop is greatly reduced according to the claimed write clock generator, and a process time required for the write clock to be stable is reduced as well. Eventually, the efficiency and stability of the optical disk recorder is improved.
[0026] In other words, the present invention is a circuit for generating a write clock for controlling a writing sequence according to a reference clock, a wobble signal read from an optical disc, an ATIP synchronization signal and an ESFS signal in an optical storage device, the circuit comprise a counter, a first phase detector, a controller, a PLL circuit and a first frequency divider; wherein the counter for counting the wobble signal according to the reference clock to obtain an average count number; the first phase detector for generating an adjustment value by comparing a phase difference between the ATIP synchronization signal and the ESFS signal; the controller for generating a rectification value according to the adjustment value and the count number; the PLL circuit for synchronizing the ATIP synchronization signal and the ESFS signal; the first frequency divider connected to the controller and the PLL circuit for generating a write clock according to the rectification value from the controller and the reference clock if the phase difference between the ATIP synchronization signal and the ESFS signal is less than a predetermined value.
[0027] The reference signal can be a system clock of the optical storage device. The optical storage device can be a CD-RW drive. The optical storage device further comprises a digital average processor electrically connected to the counter for averaging count numbers outputted from the counter. The PLL circuit further comprises a second phase detector for comparing a phase difference between a first reference synchronization signal from the first divider and a second reference synchronization signal from the PLL circuit.
[0028] Those skilled in the art will readily observe that numerous modifications and alterations of the device may be made while retaining the teaching of the invention. Accordingly, the above disclosure should be construed as limited only by the metes and bounds of the appended claims.
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A method for generating a write clock of a constant angular velocity compact storage device and the device thereof. The compact storage device has a counter for generating a count number by a reference clock counting a wobble signal, and a phase detector for generating an adjustment value by comparing a phase shift between an ATIP synchronization signal and an encoded subcode frame synchronization signal. According to the count number and the adjustment value, a rectification value is found, and the rectification value and the reference clock is used for generating a reference write clock to modify the encoded subcode frame synchronization signal. If the phase shift between an ATIP synchronization signal and an encoded subcode frame synchronization signal is smaller than a predetermined value, the reference write clock is the write clock used by the compact storage device.
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This application is a continuation of application Ser. No. 414,921, filed on Sept. 3, 1982, now abandoned.
BACKGROUND OF THE INVENTION
The present invention generally relates to a word information storage and retrieval device, and more particularly to an electronic translator for providing efficient and rapid retrieval of any desired words or sentences stored therein.
Recently, electronic devices called electronic translators have become available on the market. The electronic translators require efficient and rapid retrieval of word information stored in a memory.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide an improved electronic translator for enabling rapid input of word information into the translator.
It is another object of the present invention to provide an improved electronic translator for inputting word information to be retrieved from a memory with few operations of input key means.
It is a further object of the present invention to provide an improved electronic translator for retrieving word information from a memory with a letter-inputting key switch and a search key.
Briefly described, in accordance with the present invention, an electronic translator comprises a specifying device for specifying letters, an input device for controlling input of the specified letters into the electronic translator, a memory for memorizing a plurality of words containing the letters, an access circuit for addressing the memory to retrieve such words, and a display responsive to the access circuit for displaying the retrieved words and translated words.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be more fully understood from the detailed description of selected embodiments given hereinbelow and accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention and wherein:
FIG. 1 shows a plan view of an electronic translator according to the present invention;
FIG. 2 shows a table representing the relation between key switches actuated and displays, in a specific form of the present invention;
FIG. 3 shows a block diagram of a circuit implemented within the translator of FIG. 1;
FIG. 4 shows exemplary contents of a memory connected in the circuit of FIG. 3;
FIGS. 5 and 6 show flow charts of the operations of a microprocessor provided in the circuit of FIG. 3 to enable the operation shown in FIG. 2;
FIG. 7 shows a table representing the relation between key switches actuated and displays, in another specific form of the present invention; and
FIGS. 8 and 9 show flow charts of the operations of the microprocessor provided in the circuit of FIG. 3 to enable the operation shown in FIG. 7.
DESCRIPTION OF THE INVENTION
First of all, any kind of language can be translated by an electronic translator according to the present invention. Words are input in a specific language to obtain equivalent words, or translated words in a different language corresponding thereto. The kind of language can be freely selected. According to an example of the present invention, it is assumed that the input language is English and the translated language is Japanese. The electronic translator can operate as a conventional electronic calculator.
FIG. 1 shows the electronic translator according to the present invention. The translator comprises a power on/clear key 1, a power off key 2, a backward search key 3, a forward search key 4, a letter inputting key 5, a translation key 6, a display 7, A-Z indices 8, a dot display 9, a first-inputted letter display 10 and a cursor 11. The A-Z indices 8 are printed above the display 7. The dot display 9 is displayed to indicate a presently selected letter from A-Z by specifying one from the A-Z indices 8.
Other key switches are actuated to enable the conventional electronic calculator.
FIG. 2 shows a table representing the relation between key switches actuated and displays, in which an English word "BOAT" is inputted to develop its translated Japanese word.
FIG. 2-(1):
The forward search key 4 is actuated to place the dot display 9 under "A" of the A-Z indices 8, indicating that the presently selected letter is "A". At the same time, "A" is displayed at the first digit position of the display 7.
FIG. 2-(2):
The forward search key 4 is further actuated to place the dot display 9 under "B" of the A-Z indices 8 and to display "B" as the first digit of the display 7.
FIG. 2-(3):
Under the circumstances, the letter inputting key 5 is actuated to input "B", so that the cursor 11 is positioned at the second digit of the display 7.
FIG. 2-(4):
The backward search key 3 is actuated to back up the dot display 9 in "A" of the A-Z indices 8 and to display "A" as the second digit of the display 7.
FIG. 2-(5):
The backward search key 3 is further actuated to shift the dot display 9 under "Z" of the A-Z indices 8 and to display "Z" in the second digit.
FIG. 2-(6):
The above operations are repeated until the dot display 9 is displayed under "O" of the A-Z indices 8 and "O" is displayed in the second digit of the display 7.
FIG. 2-(7):
The letter inputting key 5 is actuated to input "O", so that words starting with "BO" are retrieved from a memory to output a leading word of a group of words starting with "BO". "BOARD" is the leading word in this case.
FIG. 2-(8):
The forward search key 4 is actuated to retrieve and display a word, "BOAT", subsequent to "BOARD" in an alphabetical order.
FIG. 2-(9):
The translation key 6 is actuated to translate the word "BOAT" into Japanese and display the Japanese word or words.
FIG. 3 shows a circuit implemented within the translator of FIG. 1. The circuit comprises a microprocessor 12, a keyboard 13, a memory 14 for storing a great number of words, a driver 15, and the display 7.
The microprocessor 12 develops key strobe signals KS toward the keyboard 13 and receives key inputted signals KI therefrom to determine whether any key switch is operated. The microprocessor 12 selects an address of the memory 14 to read-in the contents of the memory 14. The driver 15 enables character patterns to be displayed in the display 7 in response to the introduction of display pattern information developed from the microprocessor 12. An address bus 16 and a data bus 17 are provided.
FIG. 4 shows part of the contents of the memory 14. A great number of pairs of English words and their translated Japanese words are stored in the alphabetical order of the English words.
FIG. 5 shows a flow chart showing the operational steps of the microprocessor 12.
The microprocessor 12 comprises flags F 1 , F 2 and F 3 and buffers SC and B.
The flag F 1 indicates that the forward search key 4 () or the backward search key 3 () has been operated. The flag F 2 indicates that the letter inputting key 5 has been once operated. The flag F 3 indicates that the second letter is inputted and the first letter has been already retrieved. The buffer SC stores a serial number of a letter.
The 26 letters are related to their serial numbers as follows:
______________________________________ A:1 B:2 C:3 . . . X:24 Y:25 Z:26______________________________________
In the flowchart of FIG. 5, [SC] indicates a letter defined by the serial number stored in the buffer SC.
The operation of the microprocessor 12 is described with reference to the case where the word "BOAT" is translated to display its translated word.
Upon the power on, the flags F 1 , F 2 and F 3 are reset. When the forward search key 4 is actuated, "1" is entered into the buffer SC and the flag F 1 is set. Upon the introduction of "1" into the buffer SC, the display of FIG. 2-(1) is enabled.
When the forward search key 4 is operated, the buffer SC is counted up because of the set condition of the flag F 1 . Therefore, the display of FIG. 2-(2) is enabled.
When the letter inputting key 5 is operated, the flag F 2 is set to thereby enter letter "B", corresponding to the contents of the buffer SC, into the buffer B, as indicated in the display of FIG. 2-(B).
When the backward search key 3 is operated, the buffer SC is counted down so that the contents of the buffer SC become "1". The display of FIG. 2-(4) is enabled.
When the backward search key 3 is further operated, the buffer SC is counted down so that the contents of the buffer SC become "0". Therefore, "26" is inputted into the buffer SC. The display of FIG. 2-(5) is indicated.
Each time the backward search key 3 is operated, the buffer SC is counted down. When the contents of the buffer SC become "15", the display of FIG. 2-(6) is provided.
When the letter inputting key 5 is operated, alphabet "0" corresponding to the contents of the buffer SC is entered into the buffer B. A leading word of the group of words starting with input letters "BO" is retrieved to read out the word "BOARD". The flag F 3 is set. The display of FIG. 2-(7) is provided.
When the forward search key 7 is operated, the next word "BOAT" is outputted because of the set condition of the flag F 3 . The display of FIG. 2-(8) is enabled.
Since the desired word "BOAT" is developed, the translation key 6 is operated to read out its translated word which is stored corresponding with the English word. After the flags F 1 , F 2 and F 3 are reset, the display of FIG. 2-(9) is provided.
It may be possible that the backward search key 3 can be operated to retrieve any word preceding the presently retrieved word.
Thus, the forward/backward key is operated to retrieve any word belonging to a selected group of words.
The above retrieval operation may be enabled within the knowledge of the ordinary skilled person as shown in Kehoe et al, U.S. Pat. No. 4,159,536, issued June 26, 1979, entitled "Portable Electronic Language Translation Device". Kehoe et al patent is incorporated herein by reference.
FIG. 6 shows a flow chart showing the operational steps of the microprocessor 12.
This flow chart is characterized as follows:
It is detected whether the actuation of the forward search key 4 or the backward search key 3 is continued for at least a predetermined time interval. The dot display 9 is continuously forwarded or backed up one letter at a time after each such predetermined interval so long as the search key 4 or 3 is operated.
For this purpose, the microprocessor 12 comprises a flag F 4 for indicating that the search key 4 or 3 is to be continuously operated for the predetermined time, and a counter C for counting the predetermined time. In the flow chart of FIG. 6, Cm indicates the predetermined time.
Attention is directed to another preferred embodiment of the present invention as shown in FIGS. 1, 3 and 7 to 9.
FIG. 7 shows a table representing the relation between key switches actuated and displays. The table of FIG. 7 is identical with that of FIG. 2 except that, in the step of FIG. 7-(8), the letter inputting key 5 is actuated to retrieve and display the word "BOAT" after the leading word "BOARD".
FIG. 8 shows a flow chart showing the operational steps of the microprocessor 12 to enable the operation shown in FIG. 7. Also in this example, the microprocessor 12 comprises those elements as required for enabling the steps of FIG. 5.
The operation of the microprocessor 12 as shown in FIG. 8 is characterized in that the letter inputting key 5 is operated to read out the word "BOAT" after the leading word "BOARD" because of the set condition of the flag F 3 . Thus, display of FIG. 7-(8) is provided.
FIG. 9 shows a flow chart of the microprocessor 12 having the same purpose as that of the flow chart of FIG. 6. In FIG. 9, the letter inputting key 5 is also operated to read out the word "BOAT" after the leading word "BOARD".
It may be possible in FIG. 7 that the letter inputting key 5 can be operated to read out a word preceding another word.
Thus, the letter inputting key 5 is operated to retrieve any word belonging to a selected group of words.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications are intended to be included within the scope of the following claims.
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An electronic translator comprises a specifying device for specifying letters to be input. An input device cooperates with the specifying device to input the specified letters into the electronic translator. The translator also includes a memory for memorizing a plurality of words containing the input letters, an access circuit for addressing the memory to retrieve such words and a display responsive to the access circuit for displaying the retrieved words and translated equivalent words. The specifying device is operated with only a few keys to enable input of any letter of the alphabet.
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BACKGROUND
This application is a continuation-in-part of U.S. application Ser. No. 08/106,216, filed Aug. 13, 1993, now abandoned.
There are many examples in which relatively dilute solutions of polymers under poor solvent conditions form thermally reversible gels. Although this phenomenon can be understood in general to arise from chain interactions which intercept microscopic phase separation it is often far from clear how the phase behavior relates to the gelation and also what exact structural mechanism exists to anchor the reversible crosslink points which are essential to the gel formation. See, e.g., P. J. Flory Faraday Discussions of the Chemical Society, 1974, 57(7); P. S. Russo in "Reversible Polymeric Gels and Related Systems" edited by P. S. Russo, ACS Symposium Series 350, 1987, Ch. 1; S. B. Ross-Murphy in "Polymer Gels, Fundamentals and Biomedical Applications" edited by D. DeRossi, K. Kajiwara, Y. Osada, A. Yamaguchi, Plenum Press, NY 1989, pp 21 ff; J. S. Tsau, J. P. Heller, G. Pratap, Thermally Reversible Organogels Of 12-Hydroxystearic Acid; Polymer Preprints, V. 35, No. 1, March 1994, pp 737-738. In fact, one noted review of this field has gone so far to point out that to date, no general theories have emerged to explain thermally reversible gel formation. See, e.g., "Thermoreversible Gelation of Polymers and Biopolymers", by Jean-Michel Guenet, Academic Press (1992).
Driven by its commercial importance the earliest well studied thermally reversible gel was gelatin in water where it was shown that profound optical activity changes signal the transition to the gel state. See, e.g., H. Morawetz "Macromolecules in Solution" Wiley-Interscience, 1975, pp 78-81 and C. R. Smith, J. Am. Chem Soc. 1919, 41, 135. This optical activity work was followed by many structural studies which finally revealed the precise chain-chain interactions leading to the reversible gel state.
Some earlier work by one of the inventors herein concerning poly(alkyl isocyanates) have led to the conclusion that such polymers, known to adopt a stiff helical conformation in solution, afford a highly temperature and solvent dependent optical activity. Such activity was shown by circular dichroism measurements to involve a surprising influence of tiny proportions of chiral monomer on the overall chain conformation. See, Green and Reidy, "Macromolecular Stereochemistry: The Out-of Proportion Influence of Optically Active Comonomers on the Conformational Characteristics of Polyisocyanates-The Sergeants and Soldiers Experiment", J. Am. Chem. Soc. 1989, 111, 6452-6454. This same disclosure also revealed, as a footnote, that a very particular optically active copolyisocyanate, apparently gave rise to a thermally reversible gel in n-hexane when present in an amount of greater than 5 mg/ml. This single copolymer was also reported to be a high molecular weight copolyisocyanate (Mv=670,000) of poly-n-hexyl isocyanate and (S)-(-)-2,2-dimethyl-1, 3-dioxolane-4-methylene isocyanate as the comonomer unit. Accordingly, this disclosure hinted at the possibility of thermally reversible gels in the single solvent of n-hexane, but was unclear as to the criticality of copolymer structure as well as optical activity towards obtaining thermally reversible gel formation, and in fact, called attention to polar types of copolyisocyanates (i.e., polyisocyanates with polar ring type branched structures) as the principal candidate to achieve thermally reversible gel formation in a non-polar medium.
Gels have also been observed from poly-n-butyl isocyanate in two aromatic solvents, benzene and toluene (see e.g., R. Olayo and W. G. Miller, J. Polym. Sci., Physics, 1991, 29 (1473)and reference therein).
One of the inventors herein also recently reported in an approximately 60 word abstract focused on dilute solution aggregates, which might be related to gelation at higher concentrations, that higher concentrations of unspecified molecular weight solutions of poly(n-hexyl isocyante) show thermally reversible gels at unspecified temperatures in hydrocarbon solvents of unspecified structure. See, "Thermally Reversible Gelatin of Poly(n-hexyl isocyante) in Hydrocarbon Solvents and the Bad Neighbor Theory", Green et al., Bulletin of the American Physical Society, March 1992, Vol. 37, No. 1, p. 415.
However, to date, none of the above disclosed, studied or recognized how to optimize the formation of thermally reversible gel formation by a consideration of, as now described, the combined effects of polymer side-chain structure, molecular weight, and concentration. Nor, and most importantly, have the above recognized the enormous utility of such a method for various commercial applications, such as, e.g., the control of flame spread in fires driven by hydrocarbon fuels or the control of hydrocarbon spills with environmental consequences.
Since general theories regarding thermally reversible gel formation have been elusive, to date, it is not surprising that there have been no systematic findings regarding, e.g., what type of polymer side-chain structures on a rigid polymer chain tend to produce thermally reversible gels in a given solvent, or how to change the rheological properties of the gel with and without changing polymer concentration, or how to alter the onset of gel temperature, in a given solvent, for a given polymer. Accordingly, the instant invention represents a consideration of such variables in poly(alkyl isocyanates) which are rigid polymers in which such variables can be uniquely controlled and provides therefore for the first time a rational technique for identifying and developing thermally reversible gels in a wide variety of organic solvent media.
Accordingly, it is a general object of this invention to monitor and establish the thermally reversible gel forming capability of rigid polymers in liquid media and to ascertain the variables that promote thermally reversible gel formation. Such polymers come in a wide variety of structures but all are characterized by the ability to form liquid crystals. For this invention these polymers must form dilute solutions in liquid solvents where the relatively poor solvent conditions allow temperature to cause the phase conditions necessary for the gel formation. One good example is the polypeptides such as alkyl substituted poly (δ-glutamic acids). Although alkyl substituted polypeptides are known structurally and form thermotropic liquid crystals they have not been studied as a class for their lyotropic characteristics. One example of the latter is the octadecyl ester of poly(δ-glutamic acid) and its copolymers. It is encouraging in this regard that poly (-benzylglutamic acid) forms thermally reversible gels in dimethylformamide and certain other solvents which dissolve it but which are not excellent solvents. These solvents though are not hydrocarbons. In accordance with the present invention, we find that long-chain hydrocarbon substituted esters of poly(δ-glutamic acid) are soluble in n-hexane and octane. The methods disclosed for identifying and developing thermally reversible gels now apply to such polymers.
It is a more specific object of this invention to establish the gel forming capability of the rigid polymers, e.g., polyisocyanates with a wide variety of hydrocarbon side chains which allow homo, co- or higher order polymerizations so as to mix side chain structure when necessary so as to promote gelation in a controlled range of hydrocarbon solvents, and to ascertain the variables that control reversible gel formation.
It is also an object of this invention to prepare thermally reversible gels from polyisocyanate polymers, containing aliphatic, branched aliphatic, and cycloaliphatic side chains, as polymers and as copolymers, terpolymers and higher orders, and to determine, e.g., the effect of side chain structure, molecular weight and polymer concentration that will give rise to gel formation in various hydrocarbon media.
It is also an object of this invention to utilize the reversibility of the gelation with temperature to control hydrocarbon flow and to utilize the thermal instability of the polyisocyanates to irreversibly convert the gel to the flowing solution state. On heating to greater than about 100° C. to 200° C. depending on structure, these polymers are converted to small molecules.
Finally, it is also an object of the present invention to describe a process for preparing the thermally reversible gels by the combination of polyisocyanate homopolymers with various hydrocarbon media under controlled conditions which favor thermally reversible gel formation.
SUMMARY OF THE INVENTION
This invention comprises thermally reversible gels comprising liquid solvents wherein the solvent is converted into a thermally reversible gel upon the addition of a rigid polymer, preferably, a liquid crystal forming polymer. Structural modifications of the rigid polymer, and in particular modifications of the side-chain, adapt the rigid polymer to form thermally reversible gels in any given solvent media.
In process form the invention comprises methods for identifying and developing a thermally reversible gel in liquid media comprising the steps of supplying a solvent, followed by the addition of a sufficient amount of a rigid or wormlike polymer to said solvent, as is exemplified by the polyisocyanate polymer, wherein the side-chain structure of the polymer, the molecular weight of the polymer, and the concentration of the polymer are controlled not only to provide thermally reversible gel formation but also to control the sol-gel temperature of the transition. By the term rigid polymer, it is meant to include polymers that will form liquid crystals in solution (the so-called lyotropic liquid crystalline polymers), as well as polymers that form liquid crystals upon heating (the so-called thermotropic liquid crystalline polymers). In either case, and in accordance with the present invention, it has been found that as long as this basic rigidity, or liquid crystal forming capability is maintained, structural modifications can now be installed in such polymers which lead to thermally-reversible gel formation in various liquid media.
In the case of thermotropic liquid crystals, it should be made clear that although such polymers are generally insoluble, such polymers can now be adapted to not only promote liquid solubility, but to promote, as noted, thermally-reversible gel formation. This is uniquely achieved by modifying the structure of such polymers to promote both solubility, and gel-forming capability, without destructions of the basic mesogenic character of the polymer chain.
More particularly, this invention comprises methods for developing thermally reversible gels comprising polyisocyanate polymers in combination with aliphatic hydrocarbon solvents. The polyisocyanate polymers are substituted with linear aliphatic, branched aliphatic, or cycloaliphatic side chains or mixtures of all these types.
The molecular weight and concentration of the polyisocyanate polymer, as well as the type of substitution on the polyisocyanate polymer chain, all combine to control the onset, i.e. temperature of gel formation in a given aliphatic hydrocarbon solvent, in addition to the rheological properties of gel formed (e.g., the relative viscosity of the gel, or the stability of the gel viscosity upon application of increased shear). The side chain structure in particular will control the solubility of the polyisocyanate in various hydrocarbons and this is a prerequisite to gel formation. In addition, lowering of molecular weight, for example, below a certain critical value, removes the onset of gel formation, while an increase in molecular weight results in a stronger gel (again, a higher viscosity gel). At constant but high enough molecular weight, low concentrations of polymer, i.e., concentrations below a critical level, restrict gel formation, but do reveal polymer aggregation in solution ultimately responsible for gelation. The precise concentration for gel formation, and the precise temperature for gel formation, varies amongst different hydrocarbon solvents. Finally, the molecular weight of the polyisocyanate, in addition to having some effect on the critical concentration required for gelation, may also affect the temperature at which gel formation occurs.
In accordance with the above, poly(n-hexyl isocyante) (PHIC), a typical worm-like polymer with locally rigid features and therefore an example of the class of polymers of this invention, of about 200,000-300,000 viscosity average molecular weight, at a concentration of about 5 mg/ml, has been found to form a thermally reversible gel in the following hydrocarbon solvents: n-hexane, n-heptane, n-octane, 2-methylpentane, 2,2-dimethyl butane, 2,3,4-trimethylpentane, 2,2-dimethylhexane and 2,5-dimethylhexane, 2,3 dimethylbutane, 3-methylpentane, and 2-methylkeptane. Copolymers of n-hexyl isocyanate with branched hydrocarbon side chains such as 2,6-dimethylheptyl and 3,7 dimethyloctyl isocyanate as well as homopolymers of these latter two branched isocyanates also form gels in non-polar solvents such as n-hexane. This demonstrates the variability of the side chain structure which has never been disclosed. Such variability is one important aspect of this invention as discussed above.
The above noted variability can be seen, for example, when using "Pacoa" triple distilled kerosene as a hydrocarbon solvent. Whereas poly(n-hexyl isocyanate) of weight average molecular weight 283,000 at a concentration of 5 mg/ml will only gel the kerosene at about -20° C., poly (nonyl isocyanate) of near to the same degree of polymerization, at 5 mg/ml, forms a thermally reversible gel at 0° C. within 30 minutes. Moreover, whereas the poly(hexyl isocyanate) solution described above will not gel at any temperatures higher than about -20° C., the poly (nonyl isocyanate) solution described above will form a gel at 42° C. in 24 hours, or at room temperature in 2 hours. These gels return to the sol state very quickly at near to 70° C. We have also discovered that varying the concentration of the poly(nonyl isocyanate) solution in kerosene affects the gelation. For example, 1.5 mg/ml will not gel above 0° C. When one considers that the kerosene described above is closely related to jet fuel one can see the practical nature of this result for forming a safe fuel in a gel form which can be reversibly returned to the sol state.
Finally, a further aspect of the present invention comprises a thermally reversible gel comprising a hydrocarbon solvent wherein the hydrocarbon solvent is converted into a gel upon the addition of a rigid polymer whose side chain structure, molecular weight and concentration are adjusted to provide thermally reversible gel formation, and wherein the gel is converted back to the solution state and said rigid polymer contained in said gel is converted to a low molecular weight compound, upon appropriate selection of temperature.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the extinction coefficient against temperature for the UV band for PHIC copolymer.
FIG. 2 shows optical rotation v. temperature for a copolymer of 99.5% n-hexyl isocyante and 0.5% (R)-2,6-dimethyl heptyl isocyante.
FIG. 3 shows intrinsic viscosity v. temperature for a poly-n-hexyl and branched hydrocarbon isocyante copolymer.
DETAILED DESCRIPTION OF THE INVENTION
Following Ferry's definition of a gel as quoted by Russo, P. S. Russo ("Reversible Polymeric Gels and Related Systems" edited by P. S. Russo, ACS Symposium Series 350, 1987, Ch. 1) we have found that a 5 mg/ml clear apparently true solution of a sample of PHIC (300,000 M v ) in the following hydrocarbons in a sealed tube formed a gel when stored for several days in a freezer at -20° C. In this state, no flow was observed although in some cases clear solvent was apparently excluded as temperature increased but still below the sol state. A 520 mg magnetic stirring bar could not be moved by gravity or by the movement of a similar magnet outside the sealed tube. The gel forming hydrocarbons are: n-hexane; n-heptane; n-octane; 2-methylpentane; 2,2-dimethylbutane; 2,3,4-trimethyl pentane; 2,2-dimethylhexane; 2,5-dimethylhexane; 2,3 dimethylbutane; 3-methylpentane; and 2-methyl heptane. Cis and trans decalin and 1 and 2-chlorobutane gave no evidence of gel formation or cloudiness while inconsistent observations of "gelatinous cloudy properties" were seen in: 1-chlorohexane; 1-chloroheptane. Significantly we see gel formation for the branched side chain homopolymer of 3,7-dimethyloctyl isocyanate at lower concentrations in n-hexane than for poly(n-hexyl isocyanate). The molecular weight of the polymer also plays a role here.
On warming, the various gels returned to the clear solution state at various temperatures with only n-octane; n-heptane; 2-methylpentane; 2,2-dimethylhexane and 2,5-dimethylhexane maintaining gel properties (with considerable sol) on longstanding at room temperature. On further warming the true sol state is obtained in these solvents and this sol state is prerequisite for return to the cohesive gel on re-cooling.
Although, as noted above, a general theory for gel formation has not yet been established, and in no way effects the findings disclosed herein, it is believed that certain experiments can assist in understanding reversible gel formation in the polyisocyanate-hydrocarbon solvent system and therefore in other rigid or worm-like appropriately soluble polymer such as the alkyl substituted polypeptides, for one example, as discussed above in this disclosure. As seen below, the connection of the polyisocyanates, in particular here, to a specific phase diagram first described by P. Flory (see below) makes it certain that many polymers described by this phase diagram, i.e. rigid or stiff polymers, will also cause thermally reversible gelation in hydrocarbon solvents when their side chain structure, if allowed, is appropriately adjusted by alkyl substitution.
Experiments discussed below on spectroscopic changes may be insightful concerning the chain-chain and chain-solvent interactions in these gels. Such experiments though may not be helpful in understanding the many other thermally reversible gels which have been reported which are not of the stiff polymer type (J. M. Guenet, "Thermally Reversible Gelation of the Polymers and Biopolymers." Academic Press, N.Y. 1992).
The temperature dependent UV spectra in very dilute solutions for the same PHIC sample used for the gel work in all the solvents listed above revealed a sudden reproducible shift in the long wavelength backbone conjugation band at temperatures which do not match but do parallel the temperature necessary to form the gel., i.e., gels stable at higher temperatures exhibit a UV shift at higher temperatures. Representative data for this UV effect are seen in FIG. 1 for n-hexane for PHIC of an appropriate molecular weight. Although the direction of the λ max shift is from dissolved PHIC to the film, in these dilute solutions there is no evidence above or below the critical temperature for any phase separation by eye or by a reduction in the light intensity as measured by the spectrometer.
A further clue comes from study of the optical activity of a random copolymer prepared from 1% (R)-2,6-dimethylheptyl isocyanate and 99% of n-hexyl isocyanate. An identical result arises from a copolymer with 0.1% and 99.9% of these comonomers. These copolymers at 5 mg/ml in n-hexane or in n-octane show the same gel formation characteristics as PHIC discussed above but a study of their optical activities either by polarimetry or by circular dichroism spectrometry show a strong increase to large negative values at the identical temperature of the UV shift. FIG. 2 exhibits this effect for the 99/1 copolymer in both n-hexane and n-octane. Moreover, the optical rotation at which the effect levels off (FIG. 2) is near to the maximum rotation possible for a single helical sense of PHIC.
The UV and optical activity temperature dependence (FIGS. 1 and 2) can be shown theoretically by connections to "Flory's phase diagram and to the Khokhlov-Semenov theory" to suggest a sudden aggregation driven by crossing a phase boundary into the broad biophasic LC-isotropic region of the Flory phase diagram at low temperature. Such an effect is not unreasonable for a stiff polymer even at very low concentrations and is supported by the intrinsic viscosity temperature data shown in FIG. 3 for the 98/2 copolymer. A. R. Khokhlov in Ch.3 and A. Abe and M. Ballauft in Ch.4 of "Liquid Crystallinity in Polymers, Principles and Fundamental Properties, " A Ciferri, editor, VCH Publ. 1991; A. R. Khokhlov and A. N. Semenov, Macromolecules., 1984, 17, 2678). These arguments (see below) are made in detail in: M. M. Green, C. A. Khatri, M. P. Reidy, K. Levon, Macromolecules, 1993, 26, 4723.
If the aggregate structure involves a nematic-like side by side arrangement of the worms one could understand the optical activity properties since this property is intensity limited by helix reversals. Such angular "defects" can be easily seen as bad neighbors to a side by side aggregation, and their easy movement along the chain would allow their exclusion and therefore an extension of the favored helical sense. Moreover the λ max of PHIC is known to be sensitive to even slight changes in solvent polarity and it would therefore not be surprising that exclusion of solvent would shift this UV parameter.
The discussion above shows that this invention is not limited to the poly(alkyl isocyanates) and is applicable in any rigid polymer described by this phase diagram (see above). Therefore, this invention allows the adoption by structural change of any rigid or stiff polymer, as long as the change does not remove the stiffness, to cause appropriate solubility in liquid solvents. On changing the conditions such as by temperature, so as to cause the solvent to be a poorer solvent, we can expect the formation of a thermally reversible gels, as we find in the polyisocyanates discussed here which are a typical example of such a stiff polymer. In support of this poly(octadecyl-1-glutamate), which is a stiff backbone polymer, at molecular weight of 96,000, forms thermally reversible gels at 0° C. for 5 mg/ml solutions in n-hexane or n-octane or Pecora Kerosene.
EXAMPLE I
Syntheses and characterizations of the optically active co-polyisocyanates are described in M. M. Green, M. P. Reidy, R. D. Johnson, G. Darling, D. O'Leary, G. Willson, J. Am. Chem. Soc. 1989, 111, 6452. Poly(n-hexyl isocyanate) is also described in this communication although it was first described earlier (V. E. Shashoua, W. E. Sweeney, R. F. Tietz, The Homopolymerization of Monoisocyanates, J. Amer. Chem. Soc., 82, 866-873 (1960). All solvents were purchased from Alrich Chemical Co. and were checked for purity and structure by using gas chromatography and 13 C NMR spectroscopy (on JEOL FX90Q FTNMR). Cis and trans decalin, which had some absorption in the UV region were further purified as mentioned in "Purification of Laboratory Chemicals" by D. D. Perrin, W. L. F. Armargeo 3rd Ed. Pergamon Press. 1988. The following standard procedure was used to prepare solutions for all the gel experiments: 10 mg of polymer was transferred into a heavy wall glass tubing containing an oval shaped stirrbar which weighed 520 mg. 2 cc of solvent was transferred and then the tube was sealed under vacuum after removing dissolved gas by freeze drying with liquid nitrogen several time. To facilitate the dissolution of polymer, tubes were heated on a water bath at 50° to 55° C. and stirred vigorously on a vortex shaker. After the solution became transparent, the tube was allowed to shake for a further 3 to 4 hrs or overnight in some cases. All tubes were then kept in a refrigerator which could attain a temperature of -20° C. Observations were made visually by looking at the movement of the magnet and the clarity of the solution as discussed above.
UV and circular dichroism spectra and optical rotatory dispersion measurements were carried out on the dilute solutions on a Varian Cary 2300, AVIV 60DS or 62DS spectrophotometer and on a Perkin-Elmer 141 spectropolarimeter respectively.
UTILITY
As disclosed herein, thermally reversible gel formation can now be optimized for rigid rod polymeric structures formed by polymerization of. e.g., alkyl isocyanates, and more generally, any rigid or stiff polymer chain. The rigidity of the polymers used will allow the formation of these thermally reversible gels at low concentrations of the polymers so as to decrease expense (cost of polymers used) and not interfere with the primary function of the hydrocarbon. In addition, the rigidity of the polymer which is directly connected to the low concentration necessary for thermally reversible gel formation distinguishes this invention from thermally reversible gels formed from flexible polymers, e.g., polystyrene. These gels form in hydrocarbon solvents, and it is possible to promote gel formation, e.g., at different concentrations, and at different temperatures. The variables of molecular weight and polymer side-chain structure are seen to control thermally reversible gel formation in this system and these variables are readily controlled in these polymers.
The ability to create thermally reversible gels in hydrocarbon solvents, or in particular, liquid hydrocarbon fuels, provides an extremely effective method for controlling the physical character of hydrocarbon fuels along with extraordinary implications with respect to their ability to restrict the damaging effects of such fuels in a given crisis situation. For example, hydrocarbons can now be converted into a much less dangerous form, a gel, which would minimize their ability to spread if, upon accident, they were to escape from a containment vehicle. However, upon appropriate selection of temperature, as disclosed herein, (i.e. by thermally reversing the gel in general by temperature change or by depolymerization, e.g., of the polyisocyanate to trimer structure) these gels can be reconverted back to a free-flowing fluid, and be delivered in the manner made necessary by a particular combustion mechanism.
Furthermore, when large quantities of hydrocarbons are shipped, the risk of environmental contamination can now be minimized, as gels can now be rationally developed for such hydrocarbons on a predictable basis, and accordingly, such gels would not release as quickly into the environment in the event of leakage or the complete rupture of a storage tank when in transport. The implication of minimizing, or even eliminating the risks involved in petroleum shipment transport, for example, is extraordinary.
Those skilled in the art will recognize or be able to recognize, by no more than routine experimentation, many equivalents of the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.
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Thermally reversible gels comprising liquid solvents wherein the solvent is converted into a thermally reversible gel upon the addition of a rigid polymer, preferably, a liquid crystal forming polymer. Structural modifications of the rigid polymer, and in particular modifications of the side-chain, adapt the rigid polymer to form thermally reversible gels in any given solvent media.
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This application is a continuation-in-part of my co-pending U.S. patent application Ser. No. 954,726 filed Oct. 25, 1978, which is itself a continuation-in-part of my U.S. application Ser. No. 851,966 filed Nov. 16, 1977, which was issued on Mar. 20, 1979 as U.S. Pat. No. 4,144,923.
The present improvements are concerned with a machine for cutting the tread of tires, as by circumferential grooving and/or siping.
OBJECTS OF THE INVENTION
A first object of the present invention is to provide an improved groove cutter for cutting a circumferential groove in a tire by relative rotary movement between the tire and a groove cutter.
A second object of the invention is to provide an improved means for driving a wheel mounted and inflated tire by means of a feed screw, during siping.
A third object of the invention is to provide an improvement in axial shifting of a siping cutter assembly relative to the tire, whereby there is obtained electric motor driven traversing of the siping cutter, with adjustable automatic stop.
SUMMARY OF THE INVENTION
According to a first aspect of these improvements, a machine, for cutting circumferential grooves in a tire tread, comprises:
(i) a support including
(a) means for carrying a tire rotatable about an axis, and
(b) a member positioned radially beyond the tire
(ii) a mounting carried by said support member and adjustable on said support member in the axial direction relative to the tire axis
(iii) a grooving cutter carried by said mounting and adjustable thereon radially with respect to the tire axis, and
(iv) drive means to act between said support and the tire for rotating the tire relative to the grooving cutter.
The support member may include an elongated slotted opening extending parallel to the tire axis, said mounting being secured to said support member by a fastener engaged through said slotted opening, and in a preferred form said grooving cutter is mounted on a stem which is slidable in said mounting radially of the tire axis, a portion of said stem being screw-threaded and having engaged thereon an internally threaded knob for manual adjustment of the grooving cutter radially of the tire axis.
According to a second aspect, a machine, for cutting sipes in a tire tread, comprises:
(i) a support including means for carrying a tire rotatable about an axis,
(ii) bearing means on said support for a shaft rotatable about an axis substantially tangential to said tire axis, said bearing means being adjustable radially with respect to the tire axis,
(iii) a helical siping cutter and a helical lead screw on said shaft, and
(iv) driving means to act between said support and said shaft for rotating said cutter and feed screw.
The bearing means may be movable on said support parallel to said tire axis, and in a preferred form said support includes slide means extending parallel to said tire axis, a lead screw extending parallel to said slide means, a slider slidable on said slide means and engaged as a follower with said lead screw, said slider carrying said bearing means, an electric motor drive on said support coupled to said lead screw for rotating it, a switch on said slider in a current feed circuit for said motor drive, and stop means adjustable along said slide means and securable thereon in any selected position of adjustment to coact with said switch means to break the current feed circuit.
The machine may serve for cutting both circumferential grooves and sipes in a tire tread, and may comprise:
(i) a support including means for carrying a tire rotatable about an axis and a member positioned radially beyond the tire,
(ii) a mounting carried by said support member and adjustable on said support member in the axial direction relative to the tire axis,
(iii) a grooving cutter carried by said mounting and adjustable thereon radially with respect to the tire axis,
(iv) bearing means on said support for a shaft rotatable about an axis substantially tangential to said tire axis, said bearing means being adjustable radially with respect to the tire axis,
(v) a helical siping cutter and a helical lead screw on said shaft, and
(vi) driving means to act between said support and said shaft for rotating said cutter and feed screw.
Further objects of the invention will be partly pointed out in and partly obvious from the following detailed description with respect to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
FIG. 1 is a perspective view of a machine adapted for siping only;
FIG. 2 is a central longitudinal section, with parts shown broken away to reveal internal details;
FIG. 3 is a horizontal section taken at the line III--III of FIG. 2;
FIG. 4 is a scrap vertical section taken on the line IV--IV of FIG. 3;
FIG. 5 is a perspective view, with the elements shown in axially separated condition, of a cutter head assembly, with lead screw omitted;
FIG. 6 is a partial perspective elevation to show details of means for direct drive engagement of the tire when the circumferential groove cutter is to be used on the tire;
FIG. 7 is a partial perspective elevation of a groove cutter, on a larger scale;
FIG. 8 is a perspective of traversing means.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The machine comprises a stationary support 1 having opposed spaced parallel side walls 2, 3, and a front wall 4, the rear end being open. Carried by the side walls 2, 3, adjacent the open end and at the upper part of the support there is provided a transverse shaft 5 which sits on blocks 6 so as to be readily removable and replaceable. The shaft 5 carries a frusto-conical sleeve 7 which serves to receive and center a mandrel 8 bolted to the hub 9 of a vehicle wheel 10 having a tire 11. The mandrel is adjustable along the shaft 5 so that the wheel 10 may be positioned with its axial plane of symmetry X--X' substantially centrally in the support. For siping purposes only, the wheel and tire are freely rotatable. On the side walls 2, 3, there are provided flanges 12, 13, which are inclined so as to act as guide for facilitating insertion of the wheel into the support.
On the support, adjacent the upper end of the front wall 4, there is provided on each side wall 2, 3, a pivot 14 carrying a mounting indicated generally by reference numeral 15. A spring 16 is connected at one end to the side wall 2 and at the other end to the mounting 15 to urge the mounting in the direction of the arrow "A" in FIG. 2. The mounting may be releasably latched in a non-operative position, seen in FIG. 2, by means of a latching lever 17, pivoted on the side wall 2 at 18 and protruding through an opening 19 in the mounting 15, the lever 17 having a notch 20 in which the wall of the mounting 15 can be retained. When the lever 17 is raised manually, the wall of the mounting is disengaged from the notch 20 and the mounting 15 is then moved by the spring 16 in the direction of the arrow "A."
On the mounting 15 there is carried a guide frame assembly denoted generally by reference numeral 21. The guide frame assembly comprises a pair of side plates 22, 23, which are rigidly connected in spaced parallel relationship by an upper slide tube 24 and a lower slide tube 25 which are secured to the side plates by bolts 26. The frame assembly as a whole is mounted on the mounting 15 by a respective pivot 27 at each side engaged through the side plate and a side wall portion of the mounting 15, and can be moved with the aid of a handle 15a.
On the upper and lower slide tubes 24, 25, there is carried an assembly of a rotary lead screw 28, a rotary siping cutter 29, and an electrical driving motor 30 for the cutter coupled by dog clutch elements 31, 32. Referring to FIG. 4, this assembly includes a bracket 33 on which are welded sleeves 34, 35 which respectively slide on the upper and lower slide tubes 24, and 25. For shifting the assembly along the slide tubes there is provided a block 36 which is secured to the bracket 33 and which is internally threaded and is engaged on a threaded lead screw 37 journalled in the side plates 22, 23, of the mounting 15. The lead screw 37 is rotated manually by means of a reduced-speed electric motor 38 mounted at one end of the lead screw and coupled thereto by a ratchet drive device (not shown).
The electric motor 38 is under the control of a snap switch 38a which is adapted to be put into "off" position when it contacts an adjustable end-stop 38b which can be slid along the upper slide tube 24 and then locked in a selected position of adjustment.
On the upper part of the bracket 33 there is welded a sleeve 39 having ball races 40, 41, for a cutter shaft 42 carrying the cutter 29 which will be described hereinbelow in greater detail with reference to FIG. 5. The lower part of the bracket 33 has secured thereon the electric motor 30 coupled through the dog clutch 31, 32, to a shaft 46 secured in the cutter shaft 42.
Referring now to FIG. 5, the rotatable cutter has the cutter shaft 42, a lower clamping block 59 to seat on the shaft 42, the helical cutter blade 29, an upper clamping block 61, a washer 62, a centering sleeve 63 to seat within the two blocks and the blade, and the helical feed screw 28, the whole being held in assembly by a screw (not shown) engaged into a threaded bore 65 in the shaft 42. The blade is helical and accordingly one end 29a is axially offset from the other end 29b, the two blocks 59 and 61 being appropriately cut away to conform to the shaping of the blade.
The operation of the machine when used for tire siping is as follows:
A vehicle wheel with its tire is mounted on the shaft 5 and is adjusted so that its center line X--X' is substantially central in the support 1. With the mounting 15 in the non-operative position of FIG. 2, the cutter assembly is adjusted laterally until the axis of the cutter blade 29 is aligned with a first one of the usual several sections of tread which occur taken across the tire in order.
Then the latching lever 17 is released to permit the lead screw 28 and cutter 29 to rest stationarily against the tire tread. The handwheel 43 is then rotated to rotate threaded shaft 44 in nut 45 (see FIG. 2) to adjust the position of the guide frame assembly 21 so as to place the axis of rotation of the cutter blade 29 at a true tangential position in relation to the circumference of the tire thread section. The motor 30 is then switched on to cause the cutter blade to rotate and cut the tread section. Due to the helical nature of the lead screw 28 and of the cutter blade, at each time of rotation the tire is pulled around by a circumferential increment of movement corresponding to the degree of axial offset of the two edges of the cutter blade. Accordingly, as cutting proceeds, the tire rotates until the entire tread section has been cut. The motor is then switched off, and the cutter assembly is adjusted laterally until the cutter is aligned with the next tread section, again with adjustment of the tangential position. The motor 30 is again energised to rotate the cutter and cut the section of tread. These operations are repeated until all the sections of tread have been cut. When the last section of tread has been cut, the motor is switched off, and the mounting 15 is pulled manually back to the non-operative position and is latched therein by the lever 17. The wheel and tire are removed, and a fresh wheel and tire can be inserted.
A pipe 68 is mounted on the bracket 33 and has a jet nozzle 69 adjacent the cutter blade for supplying a lubricating liquid to the cutter. An inlet conduit union 70 for the liquid supply is provided on the support.
Referring now to FIG. 6, there are shown details of a means for direct drive of the tire when the grooving cutter is to be used.
At an end of the support 1, on each of the side walls 2, 3, there is mounted a slide block 85 in which is vertically slidable a rod 86, the two rods carrying at their upper end an inverted U-shaped frame 87. In the frame 87 there is journalled a transverse drive shaft 88 which has an integral roller portion 89 with radial spikes 90 adapted to bite into the tread of the tire 11 and give position drive engagement. The shaft 88 is connected through a speed reduction gear box 91 to an electrical drive motor 92. On each side wall 2, 3, there is mounted a bracket 93 on which is coupled a cylinder 94 of a hydraulic or pneumatic ram, the piston rod 95 of the ram being connected to a lug 96 on the frame 87. The cylinders 94 of the rams at each side of the machine are coupled by common piping (not shown) to a conventional hand-operable pump, with release valving. Coiled springs 97 are provided on the rod 86, above and below the block 85 to reduce shock when the rams reach the ends of their stroke. When the machine is being used for siping, the rams are actuated to maintain the frame 87 at an increased height such that the spikes 90 are clear of the tire tread. When the machine is to be used for cutting of circumferential grooves, using the U-shaped cutter described below, the rams are actuated to permit lowering of the frame 87 to give positive drive between the spiked roller 89 and the tread of the tire.
Referring now to FIGS. 6 and 7, there is shown a U-shaped or V-shaped groove cutter 98 carried on a stem 99 which can be adjusted vertically, i.e. radially with respect to the tire, by means of a knurled knob 100 threaded onto a threaded portion of the stem 99, the latter being slidable in a mounting 101 which is secured to the cross-piece of the frame 87 by a bolt 102 passed through an elongated slot 103 in the frame 87. By releasing the bolt 102, the entire assembly 98, 99, 100, 101, can be adjusted axially of the tire, and then the bolt is tightened again. The depth of cut of a groove in the tire is controlled by adjustment of the knob 100.
The term "siping" as used herein is to indicate the formation of a shallow cut or slash laterally of the tread and a satisfactory siping of a tire is accomplished by forming about eight shallow slashes to the running inch, for example, in a tread section completely across the tread, but at a depth in the tread so that the cuts are almost invisible unless said tread is flexed.
When siped tires are used on a vehicle running on a dry road, the narrow rubber ribs of the tread between the siper slashes therein easily buckle and flex over sharp bumps and pits with less strain on the tire sidewalls so that the tire carcass life is extended. When the siped tires are used on ice or rain-slick roads, the tread bends at each tiny slash formed by the siping, forming a saw-toothed surface or squeegee-edged rubber ribs, which gives enhanced traction.
Also a siped tire resists skidding and jack-knifing on fast stops of the vehicle as each rubber rib of the cross-cut tread bends back and its squeegee-shaped edge grabs the road.
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A tire cutting machine can rotatably support a wheel mounted and inflated tire with the tread thereof facing one or the other, or both, of a groove cutter, and a rotatable siping blade assembled with a lead screw. The tire can be driven by a spiked roller for cutting circumferential grooves, or can be driven by the siping cutter and a lead screw when siping. The siping cutter can be shifted axially of the tire by a motor-driven feed screw with adjustable automatic shut-off.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method of making a magnetic recording material, more particularly, to a method of making a magnetic recording material having a ferromagnetic metal thin layer, such as a magnetic tape, by a plating method.
2. Description of the Prior Art
It is known that ferromagnetic metal thin layers can be used for a magnetic recording materials. Firstly, because a thin magnetic recording layer provides a high saturated magnetic flux density, and, secondly, while a ferromagnetic metal thin layer can be used for magnetic recording in general, it is especially useful for high density magnetic recording due to its capability of exhibiting a very low to a very high coercive force.
As uses of ferromagnetic metal thin layers, it is known that a ferromagnetic metal thin layer having a low coercive force; i.e., a soft ferromagnetic metal thin layer, can be used as a core matrix memory element and an alternating current memory element, while a ferromagnetic metal thin layer having a high coercive force, i.e., a hard ferromagnetic metal thin layer, can be used as to a medium for magnetic recording as disclosed in, for example Soshin Chikazumi "Kyojiseitai no Butsuri" (Physics of Ferromagnetism) pages 327 to 330, published by Shyokabo Co., Ltd. Ferromagnetic metal thin layers are also useful for photomagnetic recording using a photomagnetic effect e.g., the Kerr magnetic effect, Faraday rotation, etc.
Further, it is known in the use of ferromagnetic metal thin layers that more effects appear when the ferromagnetic metal thin layer exhibits magnetic anisotropy. With respect to the orientation of such magnetic recording materials, this has been studied and is disclosed in U.S. Pat. Nos. 1,949,840; 2,418,479, Japanese Patent Publications 3427/1957; 21,158/1964, etc.
In order to obtain a ferromagnetic metal thin layer exhibiting magnetic anisotropy, many methods in which a web support is plated in a magnetic field have been proposed. The inventors of the present invention have also studied methods of making a ferromagnetic metal thin layer which is suitable for magnetic recording materials having a high coercive force, especially with respect to methods of applying uniaxial anisotropy to the ferromagnetic metal thin layer, and they made it clear in Japanese Patent Application (OPI) 15999/1974 that in order to obtain a ferromagnetic metal thin layer exhibiting uniaxial anisotropy, a magnetic field of a definite direction need not be applied during the total plating time, but need only be applied for a certain period after the beginning of plating.
The degree of orientation R is expressed as R = (SQ// - SQ⊥)/(SQ// + SQ⊥). SQ is the ratio of the maximum magnetic flux density Bm to the residual magnetic flux density Br: Br/Bm, where the squareness ratio SQ// is measured along the axis of the easy magnetization direction and the squareness ratio SQ⊥ is measured at right angles to the axis of the easy magnetization direction. When a magnetic field as shown in FIG. 1 is applied during a plating process, R has the relationship as shown in FIG. 2.
In more detail, assuming that the time of finishing of magnetic field application t 2 is the time of finishing plating, the relationship of R to the time of beginning the magnetic field application t 1 is shown as a t 1 -R curve. The more t 1 increases, the more the period of magnetic field application and the R value decreases. On the other hand, assuming that t 1 is the time of beginning plating, the relationship of R to t 2 is shown as a t 2 -R curve. The more t 2 decreases, the more the period of magnetic field application and the R value decreases. It can be understood by comparing these two curves that the saturated R values of both curves are naturally equal to each other, and the time t 0 which indicates the half saturated R value of both curves are almost equal each other, too.
Expanding somewhat upon the above, assume that t 1 is the time between the time of beginning plating and the time of beginning magnetic field application and t 2 is the time between completing magnetic field application and completing plating. First, assume the time of completing plating is fixed at t 2 ; the case of changing t 1 will be discussed. In this case, the t 1 -R curve shows the changes in R. When t 1 is small, R is large since the period of orientation will be increased. On the other hand, when t 1 is large, R will be small since the period of orientation is decreased (when t 1 = t 2 , R = 0). Second, assume the time of beginning plating is fixed at t 1 ; the case of changing t 2 will be discussed. In this case, the t 2 -R curve shows changes in R. If magnetic field orientation is halted a long period of time before the termination of plating, R will be small since the period of orientation is decreased. On the other hand, if t 2 approaches the time of completing plating, R will be large since the period of orientation is increased. When t 1 is small (magnetic orientation begins very shortly after plating) and t 2 is large (magnetic orientation ends very close to the end of plating), then the orientation time will be long, and, accordingly, R approaches the saturation value.
As one skilled in the art will appreciate, the squareness ratio of a magnetic recording material shows the difference between the orientation direction and a direction perpendicular to the direction of orientation. The greater the orientation value, the greater the difference between SQ // and SQ⊥, and the more R is increased. With reference to the t 1 -R curve, one can select an appropriate time on the t 1 -R curve which brings the R value to 90% of its saturated value, i.e., the time of beginning magnetic field application t a can be obtained. In a similar manner, with reference to the t 2 -R curve, the time of completing magnetic field application t b can be obtained.
Based on the above, one skilled in the art can easily select a R value under the conditions t 1 = t a , t 2 = t b .
In FIG. 2, assuming that t 2 is the time of finishing plating, t a corresponds to the value of t 1 indicating the time when the R value becomes 90% of the saturated R value, t 1 is the time of beginning plating, and t b corresponds to the value of t 2 indicating the time when the R value becomes the 90% of the saturated R value, a ferromagnetic metal thin layer having an almost saturated uniaxial anisotropy can be obtained with good efficiency by a plating in a magnetic field if t a and t b are selected as the time of beginning magnetic field application and the time of finishing magnetic field application, respectively, i.e., t 1 = t a and t 2 = t b . Even if the period of magnetic field application is greatly reduced, the degree of orientation R which is 90% of the saturated value can be still obtained.
In this point, the degree of orientation R value of 90% of the saturated value is selected for t a and t b . As one skilled in the art will appreciate, an extremely long orientation time is required to increase R to its saturation value, i.e., large scale magnetic field apparatus is required in a continuous process as is contemplated in the present invention. Accordingly, orientation is finished at a level lower than the saturation value. If this level was too low as compared with the saturation value, product quality problems sometimes occur. However, no problems are encountered on a commercial scale when R is about 90% or more, and, considering the orientation period, from a process viewpoint a value of about 90% of saturation is quite economical. This value is not, however, to be construed as limitative upon the present invention since the exact product quality required will vary from user to user, and in certain instances R values higher than 90% of the saturated value may be required by an user without any particular reference to process economics.
Since magnetic recording materials are used in many different applications as described before, orientation must be conducted in any direction. For instance, a magnetic tape for magnetic video recording must be oriented diagonally to the long direction.
Prior art processes where a magnetic field is applied while plating cannot provide a magnetic axis of easy magnetization in any desired direction. Further, it is not preferred that abrasion and/or a scratches occur on a web during conveying a web with a roller. Furthermore, if a process in which a web is conveyed without any contact was used in order to remove the defects produced by conveying with a roller, it was impossible to uniformly provide an orientation effect on the surface of the web since the conveying without contact was unstable due to flapping and the like.
SUMMARY OF THE INVENTION
One object of the present invention is to remove the defects of the prior art and to provide a process for the production of a magnetic recording material having a ferromagnetic metal thin layer which has superior magnetic properties in order to satisfy the demands for magnetic recording materials useful in different arts.
Another object of the present invention is to provide a process for the production of a magnetic recording material having a ferromagnetic metal thin layer to which can be applied an uniform uniaxial anisotropy in any arbitrary desired direction while in web form without forming any defects therein which lower quality, such as a scratch and the like.
These objects of the present invention are attained by plating while applying a magnetic field to a web which is kept away from the surface of a conveying pipe by the spouting force of plating solution spouted out through holes in the surface of the conveying pipe which is set in a plating bath, and conveying the web in a helical path along the conveying pipe without contacting the conveying pipe.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 and 2 are theoretical figures to explain the process of applying a magnetic field with regard to the present invention.
FIG. 3 is a general view of a ferromagnetic metal thin layer production apparatus showing an embodiment of the present invention.
FIG. 4 is a summary plane figure of FIG. 3.
FIG. 5 shows the orientating effect in the case of continuously plating while applying a magnetic field according to the present invention.
FIG. 6 is a general view of ferromagnetic metal thin layer production apparatus showing another embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
FIGS. 3 and 4 are general views of a ferromagnetic metal thin layer production apparatus showing one embodiment of the present invention, wherein 1 is a plating solution tank filled with a conventional electroless magnetic plating bath 2 containing cobalt ions and hypophosphite ions, and 3 is a web. Web 3 can be, for example, a polyethylene terephthalate film, and is supplied into the plating solution tank in the direction indicated by the arrow A, and web 3 is taken out from the plating solution tank 1 in the direction indicated by arrow B. Web 3 is generally subjected to a conventional pre-treating process; for example, the web 3 is immersed in an aqueous sodium hydroxide solution (5 mol/l heated at 80° C) for 2 to 4 minutes in order to degrease, swell and roughen the web and then washed with water, immersed in or sprayed with an activating treating solution and lastly washed with water before supplying it into the plating solution tank 1. (none of the above conventional processings are shown in the figures).
Any well known processes can be used for the above described pre-treatment; for example, the processes disclosed in U.S. Pat. Nos. 2,702,253; 3,011,920; 3,142,582; 3,150,939; 3,245,826 and 3,532,518 can be used.
As one skilled in the art will appreciate, the mandatory step of electroless plating is, of course, to pass the material through the plating solution, or to contact the material with the plating solution, and, then, typically, to wash the plated material with water and dry the same. While degreasing, sensitization and activation are often practiced, they are not mandatory.
Typical electroless plating baths as may be utilized in accordance with the present invention are disclosed in the following U.S. Pat. Nos. 3,116,159; 3,219,471; 3,353,986; 3,370,979; 3,379,539; 3,416,932; 3,523,823; 3,549,417; 3,138,479; 3,238,061; 3,360,397; 3,372,037; 3,385,725; 3,446,657; 3,483,029; 3,702,263, etc.
Typical reducing agents used for electroless plating as can be utilized in the present invention are disclosed in U.S. Pat. Nos. 2,532,283; 2,583,284; and 2,658,842.
Typical electroplating baths as may be utilized in accordance with the present invention are disclosed in, for instance, U.S. Pat. Nos. 3,227,635; 3,578,571; 3,672,968; 3,489,661; 3,637,471; and 3,634,209, in British Pat. No. 1,322,365 and the like.
From the basis of the present invention, one skilled in the art will appreciate that the present invention is not limited to the above electroless plating bath, reducing agents or electrolytic plating baths.
The web 3 supplied into the plating solution tank 1 is conveyed in a helical path along the surface of a cylindrical conveying pipe 4 in the plating bath 2, and then the web 3 is taken out of the plating solution tank 1 via conveying roller 5. Conveying pipe 4 comprises a sintered metal pipe having many small holes of an average diameter of about 10 microns.
The plating bath 2 is generally continuously removed from the tank 1 via a circulation path which includes a filter for continuous operation. For example, a system for controlling the concentration, pH and temperature of the plating bath 2 can be provided in the circulation filter system in order to insure uniform plating conditions by controlling changes of the above factors with time. By such a removal and the circulation of plating solution, effects such as uniform continuous plating and an improvement in the surface properties of the magnetic thin film can be obtained since the re-introduction of the thus treated plating bath provides a fine movement and a convection current at the contact between the support being plated and the plating bath. As one skilled in the art will appreciate, the most important effect of the circulation-filter system is to remove foreign substances and/or dust from which might be introduced into the plating bath so as to maintain the composition thereof, with make-up, substantially identical to that of the original starting composition (constant process conditions).
The circulation and treatment of the plating bath 2 can be effected as follows; the plating solution is removed via outlet 6 and then the plating solution composition, etc., adjusted as required, and filtered, is introduced into the conveying pipe 4 via inlet 7 and spouted out onto the web 3 via the small holes (not shown in the figures) on the surface of the conveying pipe 4. The web 3 is thus slightly floated away from the surface of conveying pipe 4 by the spouting plating solution from the small holes of the conveying pipe 4 and is conveyed in a stable fashion without contacting the conveying pipe 4.
This conveying procedure is a modification of the technique disclosed in Japanese Patent Publication 20438/68, and an extremely stable conveying can be obtained using this conveying technique, that is, abrasion and scratching of the surface of web 3 due to contact between the web 3 and the conveying pipe 4 are prevented during conveying, and, further, flapping does not occur to any substantial extent. Accordingly, this "non-contact" conveying system is extremely useful in the present invention to obtain an uniform magnetic orientation effect. This Japanese patent publication (which corresponds to U.S. Pat. No. 3,481,046), of course, merely teaches web drying; it does not in any manner suggest the liquid plating/orientation of the present invention.
It should be clearly understood by one skilled in the art that the use of a circulation-filter system and a circulation path as above described is not mandatory in the present invention. No theoretical mechanism of the plating of the present invention requires the same. However, for economic reasons, such will generally be practiced since it permits long process runs with the plating bath. As will be apparent, usually the circulation rate is substantially equal to the ejection rate x the cross-sectional area of the conveying pipe.
A magnetic field from a solenoid 8 is applied to web 3 while the web 3 is conveyed along the surface of the conveying pipe 4. The time distribution of the magnetic field applied to any point of web 3 from the solenoid 8 is as shown as FIG. 5.
The magnetic field applied to a point on the web 3 is Ho = H(t c ) when the point is located at the center of the solenoid 8 and is H = (t c ± l/2ν) when the point is located on both sides of the solenoid 8. Hence the direction of magnetic field is parallel with the axis of conveying pipe 4.
The web 3 starts to be plated as it enters the plating bath 2 (this point corresponds to "time-distance t=0) and the magnetic field is applied in the direction parallel to the axis of the conveying pipe 4 as the web 3 passes between the solenoid 8 as shown in FIG. 3 while the web 3 is moved along the surface of conveying pipe 4. Further, web 3 continues to be plated to complete the ferromagnetic metal thin film thickness required by passing the conveying roller 5 and is taken out from the plating tank 1. At this point, the web 3 has been subjected to an uniform magnetic field application since the web 3 is helically conveyed with excellent stability without contacting conveying pipe 4.
The manner of magnetic field application in the plating bath 2 disclosed in Japanese Patent Application (OPI) 15999/74 is used in the present invention. Namely, as is clear from the distribution of the magnetic field as shown in FIG. 5, in the case that a magnetic field is formed by solenoid 8 which is designed to make l/ν equal (t b -t a ) and the web is plated when the t c of FIG. 5 almost equals the t 0 of FIG. 2, R indicates the maximum saturation value, and, this time, an R value which is almost saturated can be obtained when H 0 is large enough. This fact was also experimentally confirmed. In more detail, from FIG. 2 it can be seen that when t = t 0 , the inclination of the t 1 -R curve and the t 2 -R curve are largest, i.e., the orientation effect is most effective at t = t 0 . Accordingly, to obtain the most effective orientation, the magnetic field should be applied in such a manner that the largest power is applied at t = t 0 , considering the orientation effect R is maximized when the magnetic field is applied at t c = t 0 .
Since the web 3 is in helical form along the surface of the conveying pipe 4, it can be understood that each arrival time at the time t c of each point which is on a straight line and perpendicular to a center line of the web 3 will differ from each other. However, the magnetic field is applied, as discussed above, in an amount sufficient to effect saturation, based on the time, that is, the magnetic field required to orientate each point of the web is applied. Accordingly, it was confirmed that the orientation effect was sufficient, although the arrival time of each point was different.
Discussing the above in somewhat greater detail, as will be apparent from the above discussion the magnetic field orientation must begin at a certain time and must finish at a certain time during the plating. On the other hand, as one skilled in the art will appreciate, since the web is conveyed in helical form around the conveying pipe, different points along a line transverse the center line of the web are not immersed at exactly same time into the plating bath, i.e., if it is assumed that the web enters the plating bath with the center line of the web making some angle with respect to the plating bath (vertical orientation of the flat plane of the web), the lowermost portion of the web will enter the plating bath prior to the uppermost portion of the web. Keeping in mind that orientation must begin at a certain time and finish at a certain time in the plating period, this demand cannot be satisfied unless each point on a line transverse the center line of the web undergoes an identical magnetic field orientation. Assuming that the line of solenoid magnetic field application is vertical, it will be seen that the point which last enters the plating bath in the above illustration arrives first at the vertical solenoid magnetic field application line, i.e., despite the fact that this point undergoes the minimum plating period it receives the first magnetic field orientation. Each point on the line transverse the center line of the web thus has different period of arrival at the magnetic field orientation center line. This problem is effectively overcome, however, by the process of the present invention.
Assuming that the outside diameter of the conveying pipe 4 is "D", the width of the web 3 is "a" and an angle between the long direction of the web 3 and the direction of the axis of easy magnetization; i.e., an angle between the long direction and a direction of the magnetic field is "θ", the web 3 can be conveyed without overlapping, i.e., without alternate coils of the helices, when the relationship of "a", "D" and "θ" is a/cosθ<πD. Accordingly, a ferromagnetic metal thin layer having a preferred axis of easy magnetization can be obtained by properly selecting the outside diameter D of the conveying pipe 4 for a width a of the web 3.
The web 3 thus plated while having a magnetic field applied therto is then ordinarily subjected to a coarse washing with a spray of recycled water, running water and boiled water followed by drying in a hot air stream duct or in an infrared furnance. (typically, the conditions utilized in the earlier cited patents teaching electroless or electroplating can be used).
The plating bath used for the present invention can be selected from any plating bath which can deposit a ferromagnetic metal thin layer from a liquid phase, e.g., an electroplating bath, an electroless deposition bath and the like.
The aforesaid embodiment illustrates the case of an electroless plating. On the other hand, it can be easily understood that the system as shown in FIG. 6 can be used in the case of an electroplating. In FIG. 6, 9 is an electromagnetic plating bath and 10 and 11 are anode plates. Other numerals have the same meaning as in FIG. 3.
The web used in the present invention can be selected from any materials which are flexible and capable of being plated; e.g., thin materials of plastics, rubbers, metals, alloys and ceramics, or laminates thereof, for example, a plastic/metal laminate e.g., plastics such as polyethylene terephthalate, polypropylene, triacetyl cellulose, diacetyl cellulose, polyvinyl chloride, polycarbonate, etc., alloys such as stainless steel, etc., metals such as foils or leafs of copper, aluminum, etc.
The conveying pipe used in the present invention can be selected from any materials which generally have the external form of a cylindrical tube and are corrosion resistant and durable in the plating bath, e.g., metals, alloys, ceramics, rubbers and plastics, for example, stainless steel and brass are often profitably used. Especially, a sintered pipe of metal is conveniently used convey the web with uniform floating. The diameter of the holes on the conveying pipe is about 1 to about 1000 microns, preferably about 5 to 100 microns. The hole density which is expressed by the ratio of the area occupied by the holes to the surface area of conveying pipe is about 1 to about 50%, preferably 5 to 20%. Further, the distribution of holes is substantially uniform.
The velocity of the plating solution spouted from the holes of conveying pipe is sufficient to slightly float the web away from the surface of the conveying pipe by keeping a balance with the tensile force of the web.
The magnetic field generator useful in the present invention is not limited only to a solenoid as described but any material which is well known such as an electromagnet, a magnet and the like can be used. For instance, the magnet can be prepared in the same shape as the solenoid earlier described with a hole therethrough, and such is used in the same manner as the solenoid. As another example, a magnetic field in the direction of the circumference of the conveying pipe can be generated by setting materials of good electrical conductive, such as a super-conductive material, in the conveying pipe and charging a high electrical current therethrough.
According to the present invention the novel effects disclosed below are obtained.
(1) It is possible to obtain a magnetic recording material having an axis of easy magnetization in any directions by properly selecting the angle of the web with respect to the conveying pipe. The exact angle selected is, of course, dependent upon the type of product desired; generally, it is on the order of about 10° to about 75°, with typically 50° or less being used for video tape and 20° less being used for audio tape, with reference to the center-line of the conveying pipe. These ranges are merely recited as illustrative, and are not to be construed as limitative.
(11) It is possible to obtain a magnetic recording material having an uniform magnetic field orientation effect since the magnetic field for orientation is applied to the web while conveying the web in a plating bath in a "non-contacting" helical manner, as disclosed in Japanese Patent Publication 20438/1968.
(111) It is possible to produce a magnetic recording material having superior magnetic properties without the occurence of surface faults which lower quality such as scratches and the like.
It is believed that the heretofore offered disclosure makes clear the broad nature of the present invention. As should be clear to one skilled in the art considering the foregoing disclosure, so long as the essential spirit of the invention as heretofore described is followed, the process parameters of the present invention can be widely and substantially varied. However, as with any processing invention, certain preferred and highly preferred conditions do exist for general operation on a commercial scale, and these are discussed in more detail below. The following disclosure should not be taken as limitative on the present invention, merely illustrative of currently preferred modes of practicing the invention.
The plating of the present invention is typically performed at a temperature of 0° to 100° C; temperatures lower than 0° C are obviously not used due to the possibility of freezing, and temperatures above 100° C are not used at atmospheric pressure due to the possibility of system boiling. Higher temperatures could be used, of course, if one would wish to go to higher pressures, but little is to be gained by such a procedure. A most preferred range of operation is from 20° to 90° C.
The plating of the present invention is conveniently performed in a time as little as 2 to 3 seconds, or may be performed over a time of several hours. As one skilled in the art will appreciate, the plating rate and the thickness of the resulting plated layer can be varied depending upon the type of product desired. Accordingly, it is impossible to give an unequivocal range for the plating time.
As generally alluded to above, plating is most conveniently performed at atmospheric pressure, though nothing would, in theory, prevent one from plating at sub- or super-atmospheric pressure. The extra apparatus required in such cases, however, renders such commercially undesirable.
The thickness of the plated layer is not unduly restricted, but considering currently desired commercial products, usually plated layers having a thickness of from about 0.05 to about 1 μ are obtained, even more preferably from 0.05 to 0.5 μ.
The support can, in a similar fashion, have various thickness, depending upon user requirements. Again, for most important commercial products as are currently desired in the art, supports typically have a thickness on the order of about 1 μ to about 100 μ.
The magnetic field intensity applied during the plating of the present invention can be widely varied, depending on the requirements of the user of the product. Typically, for a soft magnetic thin layer a magnetic field intensity on the order of about 1 to about 100 Oe is utilized, while, on the other hand, for a hard magnetic thin layer an intensity of about 10 Oe or greater is used. Applying conventional techniques in the art (utilizing conventional magnetic orientation fields), usually the maximum magnetic field intensity used is about 3,000 Oe.
As one skilled in the art will appreciate from the heretofore offered discussion, a certain liquid flow rate or impact force against the "floating" support is necessary to maintain the same away from the conveying pipe. The general rule in this regard is that the exact value determined for any particular process run is best empirically determined. Such can, generally, be determined in an easy fashion; for example, without the application of the magnetic field a process run is conducted at a certain liquid flow rate; if a proper "floating" effect is achieved, thereafter actual plating is conducted. However, if, for example, the support contacts the conveying pipe, the liquid flow rate is increased, while, on the other hand, if turbulence or the like is noted, i.e., the liquid flow rate is so high that the support begins to waver in the plating bath, the liquid flow rate is decreased. Generally, flow rates in the order of 0.05 to about 1000 cc/cm 2 . min., even more preferably 1 to 100 cc/cm 2 . min., (per cm 2 of the cross-sectional area of the conveying pipe) are utilized in combination with supports as earlier defined.
The present invention will be illustrated in greater detail by reference to the following examples. Unless otherwise indicated, all parts, percents, ratios and the like are by weight. In the example, the apparatus shown in FIG. 3 was utilized.
EXAMPLE
After a polyethylene terephthalate film having a width of 520 mm and a thickness of 25 microns was immersed for 3 min. in a sodium hydroxide aqueous solution (5 mole/liter) heated to 80° C to conduct a degreasing, swelling and surface roughening, the polyethylene terephthalate film was washed in flowing water for 2 min. at room temperature and then immersed in the solution disclosed in Table 1 for 2 min. at room temperature and then washed in flowing water for 2 min. at room temperature. The film was again immersed in 5% dilute sulfuric acid for 2 min. at room temperature and washed in flowing water for 2 min. at room temperature. The polyethylene terephthalate film was thus activated in the manner as above described.
The polyethylene terephthalate film thus prepared was passed in an electroless plating bath having the composition described in Table 2 which was heated to 80° C and had a pH of 7.3 ± 0.1 by adding a sodium hydroxide aqueous solution. The immersion time in the plating bath was 4 min.
A sintered metal pipe having an outer radius of 100 mm (pipe wall thickness was minimal, and can be ignored; the average diameter of holes thereon was 10 microns, and the ratio of the area occupied by the holes to the surface area of the pipe was 10%) was employed as the conveying pipe. In this example, the plating fluid was ejected through the holes at a total flow rate of 50 cc/cm 2 . min. the surface area of the pipe. The film was taken on the conveying pipe to make the winding angle of 30° and conveyed at a linear velocity of 10 m/min. In this example, t 0 was 30 sec., t a was 15 sec., t b was 45 sec. (t a and T b were selected from the values of t which make R=90% of the saturation value) and the value of the magnetic field required to obtain the saturated value of R was 1300 Oe; a solenoid having a cylindrical, inner hollow area 300 mm in diameter and a length of 4.33 m was employed.
In this example, a circulation -- filter system was not utilized. However, if one had been utilized, a filter would be provided to remove particulate materials found in the plating bath and, for long -- term process runs, make-up components would be added at a point in the circulation -- filter system so as to maintain the original composition of the plating bath. If such a circulation -- filter system was utilized, the circulation rate in this example would be 50 cc/cm 2 . min. × the cross-sectional area of the circulation pipe.
TABLE 1______________________________________ PdCl.sub.2 1 g SnCl.sub.2 10 g HCl (35%) 10 ml______________________________________
These components were dissolved in ion exchanged water to make 1 liter.
TABLE 2______________________________________CoCl.sub.2 . 6H.sub.2 O 0.04 moleCitric acid 0.09 moleNH.sub.4 Cl 0.20 moleBoric acid 0.50 moleNaH.sub.2 PO.sub.2 . H.sub.2 O 0.06 mole______________________________________
These components were dissolved in ion exchanged water to make 1 liter.
The polyethylene terephthalate film plated and orientated by magnetic field in this manner was subjected to a coarse washing, running water, boiling water washing and dried in an infrared furnace.
The magnetic properties of the magnetic material obtained in the Example are shown in Table 3. In this example, the plated layer was 0.1 μ thick. Further, it was confirmed that the orientation effect due to the magnetic field were uniform.
TABLE 3______________________________________ φm 0.10 Mx/cm Hc// 830 Oe Hc⊥ 820 Oe SQ// 0.84 SQ⊥ 0.64 R 0.135______________________________________
φm is the magnetic flux per unit length; Hc// is the coercive force in the same direction as the axis easy magnetization and Hc is the coercive force in the direction vertical to the axis of easy magnetization.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modification can be made therein without departing from the spirit and scope thereof.
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An improved method of making a magnetic recording material comprises providing a ferromagnetic metal thin layer which has uniaxial anisotropy in any direction on a web by means of plating.
A plating solution is jetted onto the web through holes in a conveying pipe set in a plating bath. The web is then moved from the vicinity of the conveying pipe by the spouting force of the plating solution, and then conveyed along a helical path about the conveying pipe without contacting the surface of conveying pipe. Plating occurs while applying a magnetic field to the web.
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BACKGROUND OF THE INVENTION
This invention generally relates to optical receivers, and more specifically, to transimpedance circuits used in optical receivers.
Optical receivers are used in a variety of devices such as photodetectors, optical detectors and optical sensors, to convert light to an electric current or voltage. An optical communication receiver starts with a photodiode, the device that converts input light intensity into a proportional electrical current. Typical values of the current are in the range of tens of microamperes, but can be smaller or larger, depending on the application. In order to be useful for the digital processing on the receiving side, this current has to be converted into the voltage domain and amplified. This function is typically performed by a transimpedance amplifier (TIA), followed by a limiting amplifier (LA). After the LA, the signal can be sampled (sliced) in a clocked decision circuit (latch). This completes the optical receiver function at the physical level.
The TIAs must provide sufficient bandwidth, sensitivity, dynamic range, high gain and low noise to achieve good system performance. In a conventional TIA receiver though, the requirements for high gain and low noise are in direct conflict with the requirement of high bandwidth.
One standard approach to increase the bandwidth of the receiver is to place a peaking amplifier immediately after the TIA. While overall bandwidth of the receiver can be increased in this manner, the main drawback of the peaking amplifier is that it will amplify high frequency noise, significantly degrading the input referred current noise and, as a result, dramatically reducing the sensitivity of the receiver.
BRIEF SUMMARY
Embodiments of the invention provide an optical receiver, a method of operating an optical receiver, a correction based transimpedance amplifier, and a method of adjusting an output of a transimpedance amplifier. In one embodiment, the optical receiver comprises an optical-to-electrical converter, a transimpedance amplifier, and a correction circuit. The optical-to-electrical converter is provided for receiving an optical signal and converting the optical signal to an electrical signal. The transimpedance amplifier is provided for receiving the electrical signal from the optical-to-electrical converter and for generating from said electrical signal an amplified electrical signal. The amplified electrical signal has inter symbol interference resulting from a reduced bandwidth of the transimpedance amplifier. The correction circuit is provided for receiving the amplified electrical signal from the transimpedance amplifier and for generating, from the amplified electrical signal, an output signal including corrections for the inter symbol interference in the amplified electrical signal effectively increasing a bandwidth of the optical receiver.
In one embodiment, the correction circuit includes a decision-feedback equalizer (DFE) including a series of time delay feedback loops. In an embodiment, the DFE effectively increases the bandwidth of the optical receiver without adding any noise to said amplified elect.
In an embodiment, the electrical signal from the optical-to-electrical converter has no significant inter symbol interference (ISI), and substantially all of the ISI in the amplified electrical signal is caused by the transimpedance amplifier as the transimpedance amplifier amplifies the electric signal from the optical-to-electrical converter.
In one embodiment, the amplified electric signal from the transimpedance amplifier is not further amplified between the transimpedance amplifier and the correction circuit. In an embodiment, the output signal of the correction circuit is a digital signal, and the correction circuit converts the amplified electrical signal from the transimpedance amplifier to said digital signal using an adjustable voltage threshold level. In an embodiment, the correction circuit adjusts said voltage threshold level to compensate for the inter symbol interference in said amplified electrical signal.
In one embodiment, the correction circuit samples the voltage of the amplified electrical signal, and updates said voltage threshold level on a basis of said samples. For example, each update of said threshold voltage level may be based on a plurality of samples of the voltage of the amplified electrical signal prior to said each update.
In an embodiment, the transimpedance amplifier has a resistance above a defined level to maintain a sensitivity and a gain of the transimpedance amplifier above defined levels, and to facilitate operation of the transimpedance amplifier with an output signal from the optical-to-electrical converter having no inter symbol interference.
Although the tradeoff between TIA gain, noise and bandwidth appears to be fundamental, embodiments of the invention resolve this tradeoff. First, it may be pointed out that the main application of the TIA based optical receiver is digital communication. The receiving system needs to only be able to differentiate a high level (“1”) from a low level (“0”) at a given data rate. So the high bandwidth is only needed as far as the receiving latch (clocked comparator) can make a correct decision. Second, it may be noted that the thermal noise nature of the input referred noise makes it truly random, while the bandwidth reduction due to RC time of the TIA has a deterministic, predictable effect on the data. The inter-symbol interference (ISI) in digital data resulting from bandwidth limitations in the system is a very well known effect.
Since ISI is a purely deterministic phenomenon, it is possible to correct for it, using wireline communication techniques like decision-feedback equalizer (DFE). The function of the DFE is to essentially move the decision threshold dynamically, based on the previous data history.
The DFEs have been shown to operate at high data rates and they are very effective in correcting for the bandwidth limitations in the system. The net result of the correctly operating DFE is an “open” eye diagram at the output, even though the input data eye diagram is completely “closed”, due to severe ISI.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
FIG. 1 shows a typical optical receiver block diagram.
FIG. 2 illustrates a transimpedance converter comprised of a resistor.
FIG. 3 shows a transimpedance amplifier comprised of an amplifier and a resistor in parallel.
FIG. 4 schematically illustrates inter symbol interference in a digital data stream.
FIG. 5 is a block diagram showing a decision-feedback equalizer.
FIG. 6 shows closed and open eye diagrams that are, respectively, inputs to and outputs from the decision-feedback equalizer of FIG. 5 .
FIG. 7 is a block diagram of an embodiment of the invention.
FIG. 8 shows an embodiment of a decision-feedback equalizer that may be used in an embodiment of the invention.
DETAILED DESCRIPTION
A typical optical receiver block diagram is shown in FIG. 1 . The optical receiver 10 starts with a photodiode 12 , which converts input light intensity into a proportional electric current. Typically the current is in the range of tens of microamperes; and in order to be useful for digital processing, this current is converted into the voltage domain and amplified. This function is performed by a transimpedance amplifier (TIA) 14 , followed by a limiting amplifier (LA) 16 . After the LA, the signal can be sampled in a clocked decision circuit 18 .
Receiver 10 is capable of receiving an optical signal from an optical transmission medium such as an optical fiber or the like, and may comprise an optical-to-electrical (OLE) converter 12 which may comprise, for example, a photodetector or the like, a transimpedance amplifier (TIA) 14 , a limiting amplifier (LA) 16 , and a clock data recovery module 18 . Clock data recovery module 18 may include a clock data and recovery (CDR) circuit coupled to a decoder to provide an electrical output representative of the optical signal received at OLE converter 12 .
The electrical signals generated by the photodetector of OLE converter 12 may be relatively weak so they may be converted to a voltage equivalent, as well as being squared-off as digital pulses, regenerating clock signals, and/or noise filtering induced by transmission and dark noise generated by the photodetector of O/E converter 12 . The current signal generated by photodetector of O/E converter 12 may be converted into a corresponding voltage for further processing. This conversion may accomplished by TIA 14 which typically may be characterized by a higher transimpedance on the front end and a lower impedance on the back end. TIA 14 provides higher transimpedance with lower noise amplification.
The current signal received by TIA 14 from the photodetector of O/E converter 12 may be relatively small, and TIA 14 may also function as a preamplifier to provide an output signal having an amplitude ranging from about a few millivolts to a about a few hundred millivolts. In optical communications systems, the average power of the received optical signals may vary by orders of magnitude depending on span losses, fiber nonlinearities, and so on. Thus, TIA 14 may be arranged to operate over a wide dynamic range of input currents received from the photodetector of O/E 12 .
Limiting amplifier (LA) 16 may function to produce a consistent waveform in response to an input received from TIA 14 . Because the input signal received by LA 16 from TIA 14 may still be relatively small, LA 16 may provide a relatively higher gain factor to generate higher output signal levels. Such gain typically may be provided via multiple amplification stages in order to achieve higher stability at higher bandwidths than would otherwise be achieved with a single higher gain amplification stage. LA 16 is capable of increasing the voltage gain of the signals received from TIA 14 to a signal level suitable for CDR circuit 18 . CDR circuit 18 is capable of recovering both the data and/or the clock signal embedded in the input data stream received by the photodetector of O/E converter 12 .
The design of the TIA/LA chain involves a number of classical tradeoffs between gain, bandwidth and noise. To illustrate these tradeoffs, we first consider the example of the simplest transimpedance converter—a resistor, as shown in FIG. 2 .
The transimpedance gain of the resistor 22 is given by the following equation:
V
OUT
I
IN
=
R
L
Clearly, higher values of R L will result in higher gain.
The bandwidth of the resistor based receiver shown in FIG. 2 is determined by the RC filter, formed by the resistor R L and photodiode (or, more generally, photo detector) capacitance C PD 24 .
BW
=
1
2
π
R
L
C
PD
In order to achieve the highest possible data rate, the bandwidth has to be as high as possible.
One way to increase the bandwidth is to reduce the photodiode capacitance C PD . This is often limited by the size available photo detector, electrical connections to the detector (wirebond pad, etc.), the input capacitance of the TIA, and other parasitic capacitances.
In the silicon photonics scenario, C PD is greatly reduced, due to 1) very small size of the integrated detector and 2) absence of the wirebond pad. There still would remain a small finite value of the order of several fF, due to on-chip parasitics.
When C PD is considered to be fixed, the only way to increase the bandwidth then is to reduce R L . Note, however, that, as described above, reducing R L will result in reduced gain.
Another key parameter of TIA performance is the total integrated input referred current noise, given by the following equation:
I
n
,
in
2
=
kT
R
L
2
C
PD
At a given temperature and C PD , the only way to improve the input referred noise is to increase R L .
A more realistic practical TIA design is shown in FIG. 3 .
The introduction of a gain element 32 helps to somewhat resolve the optimization problem outlined above, although only partially. Gain of the TIA shown in FIG. 3 is given by
V
OUT
I
IN
=
R
F
The bandwidth of the design is
BW
=
A
2
π
R
F
C
PD
The introduction of gain can help correct for BW reduction resulting from increase in R F 34 . But note that the input referred noise is now given by
V
OUT
I
IN
=
R
F
The bandwidth of the design is
BW
=
A
2
π
R
F
C
PD
The introduction of gain can help correct for BW reduction resulting from increase in R F 34 . But note that the input referred noise is now given by
I
n
,
in
2
=
kT
R
F
2
C
PD
+
V
n
,
A
2
R
F
2
The additional term here is the noise of the amplifier.
Thus, in a conventional TIA receiver, the requirements for high gain and low noise are in direct conflict with the requirement of high bandwidth. The present invention addresses this conflict.
First, it may be noted that the main application of the TIA based optical receiver is digital communication. The receiving system needs to only be able to differentiate a high level (“1”) from a low level (“0”) at a given data rate. So the high bandwidth is only needed as far as the receiving latch (clocked comparator, see FIG. 1 ) can make a correct decision. Second, it may also be pointed out that the thermal noise nature of the input referred noise makes it truly random, while the bandwidth reduction due to RC time of the TIA has a deterministic, predictable effect on the data. The inter-symbol interference (ISI) in digital data resulting from bandwidth limitations in the system is a very well known effect. it is schematically illustrated in FIG. 4 .
FIG. 4 illustrates at 42 an input digital data stream. This data stream, with inter-symbol interference, is illustrated at 44 . As can be seen, the inter-symbol interference in the digital data stream can result in errors when the decision threshold 46 is constant (independent of data history).
Since ISI is a purely deterministic phenomenon, it is possible to correct for it, using wireline communication techniques like decision-feedback equalizer (DFE). The function of the DFE is to essentially move the decision threshold dynamically, based on the previous data history. A typical DFE block diagram is shown in FIG. 5 .
The DFE is comprised of a summer 52 and a series of delay circuits 54 , 56 and 58 . A portion of the output of each of the delay circuits is fed back to summer 52 , which adds these feedback signals to the input signal.
The DFEs have been shown to operate at high data rates and they are very effective in correcting for the bandwidth limitations in the system. The net result of the correctly operating DFE is an “open” eye diagram at the output, even though the input data eye diagram is completely “closed”, due to severe ISI. This point is illustrated in FIG. 6 . The DFE with a built-in 1:2 demultiplexer processes an 11 Gbps input data with server ISI (shown at 62 ) and outputs two clean error-free 5.5 Gbps data streams (shown at 64 ; only one half-rate 5.5 Gbps output is shown).
Embodiments of the invention address the conflict in the design and operation of the TIA between high gain and low noise, on the one hand, and high bandwidth, on the other hand. This is done by reducing or minimizing the input-referred noise by increasing the value of R f . This increases the TIA sensitivity and gain. The resulting degradation of the TIA bandwidth is corrected with a DFE.
An important difference between this approach and a well-known TIA plus peaking amplifier combination is that, unlike the continuous time equalizer, the DFE does not amplify high-frequency components of the signal, so there is no additional degradation in the value of the input referred noise.
The overall block diagram of the proposed TIA+DFE receiver is shown in FIG. 7 . the input optical data stream has no ISI and it is converted into electrical current in the photodiode (PD) 72 . The TIA 14 amplifies this signal and converts it into voltage without attempting to keep the bandwidth adequate for the data rate. The TIA bandwidth can be much smaller (a factor of 10 or more) than what is required to prevent the ISI in the input data stream. The TIA output voltage waveform will have a significant amount of ISI. This signal is applied to the DFE 14 which samples the TIA output voltage, makes digital decisions and continuously updates the decision threshold based on the previous data bits (one or several). Note that, unlike the block diagram shown in FIG. 1 , the system of FIG. 7 has no LA's.
With the embodiment of FIG. 7 , if LAs were placed after the TIA with severe ISI input, the “0010100” signal shown in FIG. 4 would be driven to “0011110” by the LA, resulting in irreversible loss of information.
Also, the LA's are simply not needed: the gain of the TIA is high and the limiting action happens inside the DFE.
Note that in a standard TIA+LA receiver, most of the power dissipation occurs in the LA's, due to the small gain of the TIA and due to high bandwidth and over system gain requirements. Embodiments of the invention can achieve significant power savings due to the absence of LA's.
FIG. 8 illustrates, as one example, a decision-feedback equalizer (DFE) 80 that may used in an implementation. As with the DFE of FIG. 5 , the DFE of FIG. 8 also includes a summer and a series of delay circuits. FIG. 8 also shows an adaption circuit 82 for adjusting the DFE taps to an optimum point.
As shown in FIG. 8 , DEG 80 includes three taps 84 , 86 and 88 (although the DEF may include more). Each tap receives the amplified electrical signal from the transimpedance amplifier. Each of the time delay feedback loops 54 , 46 , 58 receives the amplified electrical signal from a respective one of the taps and introduces a respective one time delay into the amplified electrical signal. With the embodiment of FIG. 8 , each of these time delays is one unit interval (UI). Unit Interval is the same as bit period, or the inverse of data rate. For example, at 10 Gbls, the Unit Interval equals 100 ps.
Embodiments of this invention have a wide range of applications in all optical communication systems. Embodiments of the invention are particularly suited for applications in highly integrated silicon photonics designs, where system clock is already available and digital output is expected (as opposed to continuous time output in standalone optical receivers). Additionally, the extremely high sensitivity of the receiver of embodiments of the invention, combined with low capacitance of the integrated photodiode, can result in a very low power, compact, mostly digital solution that can operate at extremely high data rates. The resulting savings in the system optical budget is also very important since the optical power from a single continuous laser source can be split between a larger number of channels.
While it is apparent that the invention herein disclosed is well calculated to achieve the features discussed above, it will be appreciated that numerous modifications and embodiments may be devised by those skilled in the art, and it is intended that the appended claims cover all such modifications and embodiments as fall within the true spirit and scope of the present invention.
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An optical receiver, a method of operating an optical receiver, a correction based transimpedance amplifier circuit, and a method of adjusting an output of a transimpedance amplifier. In one embodiment, the optical receiver comprises an optical-to-electrical converter, a transimpedance amplifier, and a correction circuit. The optical-to-electrical converter is provided for receiving an optical signal and converting the optical signal to an electrical signal. The transimpedance amplifier is provided for receiving the electrical signal from the optical-to-electrical converter and for generating from the electrical signal an amplified electrical signal. The amplified electrical signal has inter symbol interference resulting from a reduced bandwidth of the transimpedance amplifier. The correction circuit is provided for receiving the amplified electrical signal from the transimpedance amplifier and for generating, from the amplified electrical signal, an output signal including corrections for the inter symbol interference in the amplified electrical signal effectively increasing a bandwidth of the optical receiver.
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This is a divisional of application Ser. No.: 799,404, filed Nov. 19, 1985, now U.S. Pat. No. 4,678,818, issued July 7, 1987.
FIELD OF THE INVENTION
This invention relates to a friction material used for making brake linings for applying braking forces to automobile wheels and the like. More particularly an improved friction material is disclosed for preventing creaking noises which are otherwise produced during the braking action of a disk brake.
DESCRIPTION OF THE PRIOR ART
When a brake disk rotor is braked at low temperatures below 100° C., creaking noises with a low frequency of about 50-500 HZ are often produced immediately before the wheels come to a stop or when a car with an automatic transmission is started or when the brake is released. These creaking noises are produced in organic type friction materials and are noticeable particularly in semimetallic friction materials using steel fiber material.
It has been found that the reason for these creaking noises produced by friction materials including steel, is that the steel and graphite ingredients in a steel type friction material cause so-called "stick slip" at very low speeds. It has also been found that such creaking noises tend to be produced even in organic type friction materials which do not use steel fibers, but have a high graphite content.
To reduce said creaking noises, therefore, it would appear to be effective to reduce the steel fiber content or the graphite content. However, the smaller the amount of steel, the lower the friction coefficient. If the steel content is less than 5% by volume, it is no longer possible to maintain the practical function of friction materials. Further, the smaller the amount of graphite, the lower the wear resistance. If the graphite content is less than 5% by volume, the amount of wear of the friction materials increases substantially. In friction materials not using steel fibers, the addition of graphite is an effective means for increasing wear resistance. Therefore, it is not preferable to reduce the amount of graphite or do away with it.
Japanese Patent Publication No. 22984/1984 discloses that the aforesaid creaking noises may be prevented, if the steel fibers are combined with nickel, zinc, tin, lead or an alloy thereof by melting. This method, however, is expensive.
SUMMARY OF THE INVENTION
Accordingly, an object of the invention is to provide a friction material which reduces creaking noises, contains an amount of graphite required to prevent a degradation of the wear resistance and is also cost-effective.
This invention provides a friction material which is a mixture containing fibers, graphite and one or more metals or alloys which are softer than steel embedded in a binder or matrix material, wherein all or part of said graphite is first mixed with said metal or alloy before further mixing with the fibers and binder.
These objects and other objects, features, aspects, and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic sectional view of an example of a friction material according to this invention; and
FIG. 2 is a schematic sectional view of an example of a conventional friction material.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
We have found that the above mentioned creaking noises of brake linings can be effectively prevented by first physically mixing all or part of the graphite with one or more metals or alloys, which are softer than steel to prepare a first metal graphite mixture in which the softer metal or alloy is bonded to the graphite. This first softer than steel metal graphite bonded mixture is then further mixed with the fibers and a binder to form a friction material. FIG. 1 shows an example of a friction material according to this invention comprising said bonded mixture 4 of graphite and metal or alloy, and steel fibers 1 in a matrix material. On the other hand, a conventional friction material shown in FIG. 2 contains graphite 2 separate from the steel fibers 1. That is, this invention is characterized in that all or part of the graphite has been first physically mixed and bonded with one or more metals or alloys.
As for metals or alloys which are softer than steel, lead, tin, zinc and copper are effective and brass and bronze, which are alloys thereof, are effective.
There are various methods of physically combining e.g. by mixing and bonding graphite with metal or alloy to form a first bonded mixture which is then further combined with fibers in a matrix to form a second mixture. For example, graphite and metal or alloy may be physically mixed and bonded together by a first binder which intimately bonds the graphite and the metal or metal alloy to each other. Among first binders to be used are rubber, epoxy resin, phenol resin and other organic matter, water glass and other inorganic matter. Further, graphite and metal or alloy may be physically combined together by mixing, pressing and sintering. It is also possible to physically combine graphite and metal or alloy together by plating the graphite with the metal or alloy. Further, graphite and metal or alloy may be physically combined together by melting.
The components which are effective as a frictant or friction causing agent in the friction material of this invention are inorganic fibers of asbestos, glass, rock wool, glass wool and the like, metal fibers such as steel fibers, and organic fibers such as carbon fibers, acrylic fibers treated for flame resistance, and aramid fibers. Further, to ensure a satisfactory friction coefficient and wear resistance, preferably, the friction material contains, on a volume basis, 5-35% of steel fibers or steel powder as a frictant, 10-35% of a further binder or matrix material, and 0.5-15% of metal other than steel, the balance being graphite, and organic and/or inorganic filler.
Functional tests were conducted using friction materials A-E formulated according to Table 1 shown below. In the table 1, samples A-D are examples of the invention and sample E is a control sample.
TABLE 1______________________________________Formulation (volume percent) Example of Invention ControlSample A B C D E______________________________________Steel fiber 30 30 32 32 30Phenol resin 25 25 27 27 25Barium sulfate 12 12 13 13 12Silica 3 3 3 3 3Combination ○a 30Combination ○b 30Combination ○c 12Combination ○d 25Graphite 13 21Epoxy resin 6Zinc powder 3______________________________________
Sample A (example of the invention)
On a volume basis, 5% zinc powder with a grain size of less than 200 mesh, 25% epoxy resin as a first binder, and 70% graphite with a grain size of less than 200 mesh were mixed, and the mixture was maintained in a hot air furnace in a 200° C. atmosphere for 4 hours and cured to provide the softer metal graphite bonding. Thereafter, it was crushed to provide a first bonded mixture or combination ○a . This first bonded combination or mixture ○a was further combined with a second mixture of steel fiber, phenol resin as a second binder or matrix material, barium sulfate and silica prepared according to Table 1. The result of combining the first and second mixtures was press-molded and after-cured to thereby prepare a friction material having a porosity of about 5%.
Sample B (example of the invention)
On a volume basis, 5% lead-tin alloy powder with a grain size of less than 200 mesh, 25% epoxy resin as a first binder, and 70% graphite with a grain size of less than 200 mesh were mixed, and the mixture was maintained in a hot air furnace in a 200° C. atmosphere for 4 hours and cured to provide the softer metal graphite bonding. It was crushed to provide a first combination or mixture ○b , which is then further combined with a second mixture including steel fiber, phenol resin as a second binder or matrix material, barium sulfate and silica prepared according to Table 1. The result of combining the first and second mixtures was press-molded and after-cured to thereby prepare a friction material having a porosity of about 5%.
Sample C (example of the invention)
On a volume basis, 70% graphite and 30% zinc powder were mixed together with a caking agent. The mixture was pressed and sintered to provide the softer metal graphite bonding and then crushed to provide a first bonded combination or mixture ○c which is then further combined with a second mixture of steel fiber, phenol resin as a matrix material, barium sulfate, silica and graphite prepared according to Table 1. The result of combining the first and second mixtures was press-molded and after-cured to thereby prepare a friction material having a porosity of about 5%. The term "caking agent" means a molding auxiliary, such as an organic substance, e.g. paraffin or camphor.
Sample D (example of the invention)
Porous graphite was impregnated with molten zinc to provide the softer metal graphite bonding and then crushed to form a first bonded combination or mixture ○d of 70% graphite and 30% zinc, on a volume basis. This first bonded combination or mixture ○d was then further combined with a second mixture of steel fiber, phenol resin as a matrix material, barium sulfate and silica prepared according to Table 1. The result of combining the first and second mixtures was press-molded and after-cured to thereby prepare a friction material having a porosity of about 5%.
Sample E (control)
Steel fibers, phenol resin, barium sulfate, silica, graphite, epoxy resin and zinc powder were mixed according to the formulation shown in Table 1. Under the following condition, it was press-molded and after-cured to thereby prepare a friction material having a porosity of about 5%.
Press condition: Putting the mixture in a mold heated to 150° C. and pressing it therein for 10 minutes.
In addition, the mold was a force-cut type mold designed for a constant volume, and the mixture was charged into the mold with sufficient accuracy to ensure that the porosity of the friction material was 5%. The mixture was maintained in a hot air furnace in a 250° C. atmosphere for 10 hours and then after-cured.
Results of Functional Tests
Functional tests in creaking noises were conducted using said friction material A-E in ordinary automobiles.
The magnitude of the creaking noises produced was evaluated as shown in Table 2 below.
TABLE 2______________________________________Friction RotorMaterial Tempera- Deceleration (g)Class ture (°C.) 0.05 0.10 0.15 0.20 0.25 0.30______________________________________Example A 30 2 2 0 1 1 0of the 50 2 1 1 0 0 0Invention 70 1 0 0 0 0 0 100 0 0 0 0 0 0 B 30 2 2 2 1 1 0 50 2 1 2 1 1 0 70 0 0 1 0 0 1 100 0 0 1 0 0 0 C 30 2 1 1 1 1 0 50 1 1 1 1 0 0 70 1 1 1 0 0 0 100 0 1 0 0 0 0 D 30 1 1 1 1 0 0 50 1 1 1 0 0 0 70 1 1 1 0 0 0 100 0 0 0 0 0 0Control E 30 3 2 2 2 1 0 50 3 3 3 3 2 1 70 2 2 2 0 2 2 100 2 2 1 0 0 0______________________________________
The initial velocity of the automobile was 20 Km/hr., and the rotor temperature Ti (°C.) was changed in 4 steps as shown in Table 2. Further, the deceleration β (g) was changed in 6 steps for each temperature step, as shown in Table 2. Thus, brake tests were conducted once for each combination of values, and the magnitude of the creaking sound was evaluated. Cracking noises were evaluated by conducting a functional test in which the driver evaluated it with his ears, rating the noises at 3, 2 or 1 in the decreasing order of magnitude, using 0 to indicate the absence of any cracking noises.
It can be seen from Table 2 that the friction materials according to the invention are effective in preventing creaking noises. Further, fade tests were conducted for the friction materials using a dynamometer.
When the initial velocity of the automobile was 100 Km/hr. and the deceleration was 0.45 g, the brake was applied 10 times at intervals of 35 seconds to determine the friction coefficient (μ). Each friction material showed its minimum value at the 6th braking, the respective values being as follows.
Sample A (example of the invention): 0.23
Sample B (example of the invention): 0.24
Sample C (example of the invention): 0.26
Sample D (example of the invention): 0.28
Sample E (control): 0.19
The above results prove that the fade resistance and creaking noise reduction of the examples of the invention are superior to the fade resistance and creaking noise reduction of the control example. In addition, concerning the samples C and D it is to be noted that the improvement of the fade resistance is particularly remarkable since substantially no organic matter was used in producing the friction brake material.
As described above, friction materials according to the invention are effective in preventing creaking noises and are superior in fade resistance.
Although the present invention has been described and illustrated in detail, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, the spirit and scope of the present invention being limited only by the terms of the appended claims.
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A friction brake material contains fibers, graphite and a binder. All or part of the graphite is physically combined with one or more metals or alloys which are softer than steel to form a first combination or mixture. A separate combination or mixture is formed to include friction increasing fibers in a binder. Both mixtures are then combined to form the friction brake material which has an ability to cause substantially less creaking noise upon brake application as compared to differently prepared friction brake material.
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BACKGROUND
The present invention relates to microfabrication of semiconductor devices, and, more specifically, to methods for taking into account signal integrity in the automatic generation of test patterns for semiconductor devices and/or semiconductor device manufacture.
Semiconductor devices and components thereof continue to decrease in size, resulting in increasing circuit density. As a result, the effect of crosstalk defects has emerged as a factor to consider during manufacturing testing of a chip. Crosstalk faults can arise when two lines in a circuit are so close that their parasitic capacitances influence their signal states. A decrease in feature size can increase parasitic capacitance so that the effect of a crosstalk fault can become more prominent. When this coupling capacitance exceeds a certain threshold value, the state of one signal will influence the other if there are transitions on either or both lines. If there is a transition on only one line, a crosstalk glitch is produced; on the other hand, transitions on both lines result in a crosstalk delay. It should be noted that crosstalk faults are different from bridging faults, which can also arise when two lines are in close proximity. However, the cause of bridging faults is a resistive connection between the two lines and not capacitive. Also, the effects of the two faults are different: bridging faults result in wired-AND and wired-OR logic functions, thus incurring a stuck-at defect on a signal, whereas crosstalk faults result in glitch or delay.
SUMMARY
According to one embodiment of the present invention, a method of automatically generating test patterns for a semiconductor device design to detect crosstalk induced faults can include generating a list of aggressor-victim (AV) pairs of nets of a design that exceed a threshold value of a crosstalk effect criterion, each AV pair including an aggressor net and a victim net. Each AV pair can be translated into a respective AV crosstalk fault model, and an automated test pattern (ATP) can be generated based on the design and including at least one constraint configured to switch at least one AV crosstalk fault model. At least one care bit configured to propagate at least one AV crosstalk fault to an observation node can be generated, and each AV crosstalk fault model and a respective path to the observation node can be sensitized. It can be determined whether any crosstalk fault is observed and a number of crosstalk faults observed, and the generating of the ATP, the generating of the at least one care bit, the sensitizing, and the determining can be repeated until at least one of a desired number of faults is observed or a maximum number of repetitions has been completed, each repetition of the generating of the ATP producing a different pattern.
Another embodiment of the invention disclosed herein can include a computer program product for detecting crosstalk related transition faults in a semiconductor design, the computer program product being stored on a non-transitory computer readable storage medium and including instructions in the form of computer readable code. When executed by a computing device, the computer program product can configure the computing device to extract a respective parasitic capacitance for every net in the design, generate a list of aggressor-victim (AV) pairs of nets each exhibiting a high degree of signal cross talk based on a first criteria set, and translate each AV pair into a respective AV fault model configured to model at least one of a crosstalk setup fault, a hold violation fault, and a value change fault. Any intermediate circuit node to be switched to observe crosstalk faults can be identified, and an automated test pattern can be generated accounting for circuit constraints to sensitize aggressor/victim pairs selected for switching. Care bits to propagate the crosstalk faults to an observation node can be generated, and each one of the plurality of aggressor/victim pairs and a corresponding victim to observation path can be sensitized iteratively to detect the crosstalk fault. A set of patterns generated for each one of the plurality of aggressor/victim pairs can be selected with an optimized algorithm to detect a maximum number of crosstalk faults.
An additional embodiment of the invention disclosed herein can take the form of a system for detecting crosstalk related transition faults in a semiconductor design, the system including at least one computing device connected to a non-transitory computer readable storage medium on which instructions in the form of computer readable code reside. When the instructions and/or computer readable code is executed by a computing device, the system can be configured to extract a respective parasitic capacitance for every net in the design, generate a list of aggressor-victim (AV) pairs of nets each exhibiting a high degree of signal cross talk based on a first criteria set, and translate each AV pair into a respective AV fault model configured to model at least one of a crosstalk setup fault, a crosstalk hold violation fault, and a crosstalk value change fault. Any intermediate circuit node that switched to observe crosstalk faults can be identified, and an automated test pattern can be generated accounting for circuit constraints to sensitize aggressor/victim pairs selected for switching. Care bits can be generated to propagate the crosstalk faults to an observation node, and each one of the plurality of aggressor/victim pairs and a corresponding victim to observation path can be sensitized iteratively to detect the crosstalk fault. A set of patterns generated for each one of the plurality of aggressor/victim pairs can be selected with an optimized algorithm to detect a maximum number of crosstalk faults.
Additional features and advantages are realized through the techniques of the present invention. Other embodiments and aspects of the invention are described in detail herein and are considered a part of the claimed invention. For a better understanding of the invention with the advantages and the features, refer to the description and to the drawings.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
The subject matter which is regarded as the invention is particularly pointed out and distinctly claimed in the claims at the conclusion of the specification. The foregoing and other features, and advantages of the invention are apparent from the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic block diagram illustrating a crosstalk setup fault that can be addressed according to embodiments of the invention disclosed herein.
FIG. 2 is a schematic block diagram illustrating a crosstalk hold fault that can be addressed according to embodiments of the invention disclosed herein.
FIG. 3 is a schematic block diagram illustrating a crosstalk hold fault model according to embodiments of the invention disclosed herein.
FIG. 4 is a schematic block diagram illustrating a crosstalk setup fault model according to embodiments of the invention disclosed herein.
FIG. 5 is a schematic block diagram illustrating a crosstalk value change fault model according to embodiments of the invention disclosed herein.
FIG. 6 is a schematic flow diagram of a method that can be implemented according to embodiments of the invention disclosed herein.
FIG. 7 is a schematic block diagram of a general purpose computer system which may be used to practice aspects of embodiments of the invention disclosed herein.
DETAILED DESCRIPTION
Existing transition fault testing techniques include lumped delay defect testing countered by transition testing, distributed delay defect testing countered by path test, and small delay defects. However, none of these techniques address and/or take into account crosstalk faults.
Crosstalk faults are typically studied using aggressor-victim models. An affected line or net is typically designated as a victim, while any influencing line or net is typically designated as an aggressor. Together, the aggressor(s) and the victim can be called an AV pair. In many situations, there can be multiple aggressors for a single victim and/or multiple victims for a single aggressor. In the case of crosstalk delay, a negative delay can be caused when both an aggressor signal and a victim signal are transiting in the same direction; a negative delay results when the transition direction is opposite. These delays can result in setup and/or hold violation if the victim falls in a path between two flops. For example, FIG. 1 shows two flops A and B, here aggressors, and a victim between the flops. If three aggressors affect the line, then if all the aggressor signals undergo a 1 to 0 transition and the victim signal is transiting from 0 to 1, there will be a setup violation at B. The actual delay effect is shown in FIG. 2 , where it can be seen that the victim transits at a Δt after the actual scheduled transition time, which results in a setup violation.
Embodiments of the invention disclosed herein can provide an efficient automatic test pattern generation (ATPG) method that can activate transitions on the aggressor(s) and the victim of an AV pair while also considering delay testing. Current techniques for multi-aggressor/victim focus on activation of the various aggressors so that the cross-talk fault is activated and typically do not deal with fault propagation, that is, observation of the cross-talk effect. A delay defect, like any timing error, should be propagated to a flip-flop for detection.
Broadly, embodiments of the invention disclosed herein can be implemented as a method of automatically generating test patterns for a semiconductor device designed to detect crosstalk induced faults, as will be additionally explained below using a particular example shown in FIG. 6 . A list of aggressor-victim (AV) pairs of nets of a design can be generated based on a crosstalk effect criterion. Any pair of nets that exceeds a threshold value of the crosstalk effect criterion can be designated an AV pair and added to the list, each AV pair including an aggressor net and a victim net. Each crosstalk effect criterion can include, for example, parasitic capacitance, and the generating of the list of AV pairs can include obtaining a respective parasitic capacitance for each net of a design, the design including at least two nets. A respective degree of a crosstalk effect between each pair of nets can be determined based on the parasitic capacitance, and any net pair exceeding a threshold value of parasitic capacitance can be added to the list as an AV pair. While parasitic capacitance is used as a crosstalk effect criterion by way of example, it should be understood that any suitable criterion can be used, such as relative coupling capacitance between nets, 3D coupling between dies, relative physical distance between nets, trace length along which lines of nets run together, timing, and/or driver strength threshold.
Each AV pair can be translated into a respective AV crosstalk fault model, which can be configured to model, for example, an AV crosstalk hold fault, an AV crosstalk setup violation, and/or an AV crosstalk value change fault. For an AV crosstalk hold fault, as illustrated in FIG. 3 , an AV crosstalk fault model can be configured to produce with each aggressor net and each victim net of the respective AV pair a respective signal transitioning in a first direction. For example, where each aggressor is modeled with a signal transitioning from zero to one, each victim is also modeled with a signal transitioning from zero to one, and where each aggressor is modeled with a signal transitioning from one to zero, each victim is also modeled with a signal transitioning from one to zero. By contrast, for an AV crosstalk setup violation, as seen in FIG. 4 , if each aggressor is modeled with a signal transitioning from zero to one, each victim is modeled with a signal transitioning from one to zero, and where each aggressor is modeled with a signal transitioning from one to zero, each victim is modeled with a signal transitioning from zero to one. For a crosstalk value change fault, as shown in FIG. 5 , the aggressor(s) can be modeled with a signal either steady state or transitioning, and the victim(s) can be modeled with a signal the other of steady or transitioning.
An automated test pattern (ATP) can be generated based on the design and including at least one constraint configured to switch at least one AV crosstalk fault model. A path between each AV crosstalk fault model and an observation node can be identified, and any intermediate circuit node on a path that should be switched to observe a crosstalk fault can be identified. At least one care bit can be generated, each care bit being configured to propagate at least one AV crosstalk fault to an observation node, such as an output or a flop at an end of a path. Each AV crosstalk fault model and its respective path to the observation node can be sensitized, and if any crosstalk fault is observed at the output node, a number of observed crosstalk faults can be determined. The generating of the ATP, the generating of the at least one care bit, the sensitizing, and the determining can be repeated until a desired number of faults has been observed or a maximum number of repetitions has been completed, each repetition of the generating of the ATP producing a different pattern. In embodiments, the repetition can include applying an optimization algorithm to obtain a set of patterns that can detect as many crosstalk faults as possible within any constraints imposed, including time.
As illustrated in FIG. 6 , an example of embodiments of the invention disclosed herein can be implemented as a method 600 of automatically generating test patterns for a semiconductor device designed to detect crosstalk induced faults. A list of aggressor-victim (AV) pairs of nets of a design can be generated based on a crosstalk effect criterion, such as by determining circuit and layout parasites (block 602 ) and performing a parasitic analysis (block 604 ), which can take into account mutual coupling threshold(s), a number of aggressors (A) and/or victims (V), and/or drive strength threshold. Top AV pairs can be extracted (block 606 ) using one or more crosstalk effect criteria, such as parasitic capacitance, relative coupling capacitance between nets, 3D coupling between dies, relative physical distance between nets, trace length along which lines of nets run together, timing, and/or driver strength threshold. An optimization routine can be implemented using the list of AV pairs (block 608 ), which can begin by translating each AV pair into a respective AV crosstalk fault model (block 610 ), which can be configured to model, for example, an AV crosstalk hold fault, an AV crosstalk setup violation, and/or an AV crosstalk value change fault. Translation can also include identifying intermediate nodes to be excited and/or switched to enable propagation and/or observation of a particular crosstalk fault, though this can also be regarded as a separate step in embodiments. Translation can additionally take into account feedback from functional bench, automatic test equipment (ATE), and/or other testing, as well as field reports and/or other reporting of relevant information (block 611 ).
A check can then be made to determine whether all AV lines have been marked off (block 612 ), and if not, the aggressor(s) and/or victim(s) can be sensitized (block 614 ), such as to enable a transition in preparation for a launch pulse. In addition, any victim(s) observation path(s) can be sensitized (block 616 ), such as to enable capture and/or observation of a given crosstalk fault. For example, each potential endpoint flop can be tried a threshold number of times, and a threshold number of such flops can be tried, each threshold being one of a minimum or a maximum number of tries, such as by using level-sensitive scan design (LSSD). Sensitizing of aggressors, victims, and/or observation paths can take into account various factors, such as test models, design of the particular circuit and/or device(s) being considered, circuit constraints, and/or other factors as may be desired and/or appropriate. Once the threshold values for sensitation have been reached, a test pattern can be created (block 618 ), such as by ATPG, and the check of AV line mark-off can be repeated (block 612 ). When all AV lines have been marked off, vector patterns, coverage details, and other information about each crosstalk fault model can be stored (block 620 ), such as in a memory or in/on another computer readable storage medium, particularly a non-transitory computer readable storage medium.
As will be appreciated by one skilled in the art, aspects of the present invention may be embodied as a system, method or computer program product. Accordingly, aspects of the present invention may take the form of an entirely hardware embodiment, an entirely software embodiment (including firmware, resident software, micro-code, etc.) or an embodiment combining software and hardware aspects that may all generally be referred to herein as a “circuit,” “module” or “system.” Furthermore, aspects of the present invention may take the form of a computer program product embodied in one or more computer readable medium(s) having computer readable program code embodied thereon.
Any combination of one or more computer readable medium(s) may be utilized. The computer readable medium may be a computer readable signal medium or a computer readable storage medium. A computer readable storage medium may be, for example, but not limited to, an electronic, magnetic, optical, electromagnetic, infrared, or semiconductor system, apparatus, or device, or any suitable combination of the foregoing. More specific examples (a non-exhaustive list) of the computer readable storage medium would include the following: an electrical connection having one or more wires, a portable computer diskette, a hard disk, a random access memory (RAM), a read-only memory (ROM), an erasable programmable read-only memory (EPROM or Flash memory), an optical fiber, a portable compact disc read-only memory (CD-ROM), an optical storage device, a magnetic storage device, or any suitable combination of the foregoing. In the context of this document, a computer readable storage medium may be any tangible medium that can contain, or store a program for use by or in connection with an instruction execution system, apparatus, or device.
A computer readable signal medium may include a propagated data signal with computer readable program code embodied therein, for example, in baseband or as part of a carrier wave. Such a propagated signal may take any of a variety of forms, including, but not limited to, electro-magnetic, optical, or any suitable combination thereof. A computer readable signal medium may be any computer readable medium that is not a computer readable storage medium and that can communicate, propagate, or transport a program for use by or in connection with an instruction execution system, apparatus, or device.
Program code embodied on a computer readable medium may be transmitted using any appropriate medium, including but not limited to wireless, wireline, optical fiber cable, RF, etc., or any suitable combination of the foregoing. Computer program code for carrying out operations for aspects of the present invention may be written in any combination of one or more programming languages, including an object oriented programming language such as Java, Smalltalk, C++ or the like and conventional procedural programming languages, such as the “C” programming language or similar programming languages. The program code may execute entirely on the user's computer, partly on the user's computer, as a stand-alone software package, partly on the user's computer and partly on a remote computer or entirely on the remote computer or server. In the latter scenario, the remote computer may be connected to the user's computer through any type of network, including a local area network (LAN) or a wide area network (WAN), or the connection may be made to an external computer (for example, through the Internet using an Internet Service Provider).
Aspects of the present invention are described above with reference to flowchart illustrations and/or block diagrams of methods, apparatus (systems) and/or computer program products according to embodiments of the invention. It will be understood that each block of the flowchart illustrations and/or block diagrams, and combinations of blocks in the flowchart illustrations and/or block diagrams, can be implemented by computer program instructions. These computer program instructions may be provided to a processor of a general purpose computer, special purpose computer, or other programmable data processing apparatus to produce a machine, such that the instructions, which execute via the processor of the computer or other programmable data processing apparatus, create means for implementing the functions/acts specified in the flowchart and/or block diagram block or blocks.
These computer program instructions may also be stored in a computer readable medium that can direct a computer, other programmable data processing apparatus, or other devices to function in a particular manner, such that the instructions stored in the computer readable medium produce an article of manufacture including instructions which implement the function/act specified in the flowchart and/or block diagram block or blocks. The computer program instructions may also be loaded onto a computer, other programmable data processing apparatus, or other devices to cause a series of operational steps to be performed on the computer, other programmable apparatus or other devices to produce a computer implemented process such that the instructions which execute on the computer or other programmable apparatus provide processes for implementing the functions/acts specified in the flowchart and/or block diagram block or blocks.
The flowchart and block diagrams in the Figures illustrate the architecture, functionality, and operation of possible implementations of systems, methods and computer program products according to various embodiments of the present invention. In this regard, each block in the flowchart or block diagrams may represent a module, segment, or portion of code, which comprises one or more executable instructions for implementing the specified logical function(s). It should also be noted that, in some alternative implementations, the functions noted in the block may occur out of the order noted in the figures. For example, two blocks shown in succession may, in fact, be executed substantially concurrently, or the blocks may sometimes be executed in the reverse order, depending upon the functionality involved. It will also be noted that each block of the block diagrams and/or flowchart illustration, and combinations of blocks in the block diagrams and/or flowchart illustration, can be implemented by special purpose hardware-based systems that perform the specified functions or acts, or combinations of special purpose hardware and computer instructions.
FIG. 7 shows a schematic block diagram of a general-purpose computer/system/computing device 700 that can be used to implement and/or practice the method(s) and/or system(s) described herein, which can be coded as a set of instructions on removable or hard media for use computer 700 as suggested above. Computer 700 can include at least one microprocessor or central processing unit (CPU) 705 , which can also be construed as a computing device and can be interconnected via a system bus 720 to machine readable media 775 . Machine readable media 775 can include, for example, a random access memory (RAM) 710 , a read-only memory (ROM) 715 , a removable and/or program storage device 755 and a mass data and/or program storage device 750 . An input/output (I/O) adapter 730 can connect mass storage device 750 and removable storage device 755 to system bus 720 . A user interface 735 can connect a keyboard 765 and a mouse 760 to system bus 720 , and a port adapter 725 connects a data port 745 to system bus 720 and a display adapter 740 can connect a display device 770 . ROM 715 can contain the basic operating system for computer system 700 . Examples of removable data and/or program storage device 755 include magnetic media such as floppy drives, tape drives, portable flash drives, zip drives, and optical media such as CD ROM or DVD drives. Examples of mass data and/or program storage device 750 include hard disk drives and non-volatile memory such as flash memory. In addition to keyboard 765 and mouse 760 , other user input devices such as trackballs, writing tablets, pressure pads, microphones, light pens and position-sensing screen displays may be connected to user interface 735 . Examples of display device 770 include cathode-ray tubes (CRT) and liquid crystal displays (LCD).
A machine readable computer program may be created by one of skill in the art and stored in and/or executed by computer system 700 or a data and/or any one or more of machine readable medium 775 to simplify the practicing of this invention. In operation, information for the computer program created to run the present invention can be loaded on the appropriate removable data and/or program storage device 755 , fed through data port 745 or entered using keyboard 765 . A user can control the program by manipulating functions performed by the computer program and providing other data inputs via any of the above mentioned data input means. Display device 770 can provide a means for the user to accurately control the computer program and perform the desired tasks described herein.
The descriptions of the various embodiments of the present invention have been presented for purposes of illustration, but are not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein was chosen to best explain the principles of the embodiments, the practical application or technical improvement over technologies found in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
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Crosstalk effects can be taken into account in automatic test pattern generation (ATPG) by providing crosstalk fault models, determining paths and/or nodes to be sensitized to activate each crosstalk fault, and optimizing to enable as many crosstalk faults as possible with a given pattern, subject to constraints. Constraints can include threshold numbers of endpoints/observation points and/or attempts to sensitize. Intermediate nodes in a crosstalk fault model path to an observation point can also be determined and/or sensitized.
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CROSS-REFERENCE TO RELATED PATENT APPLICATION
This application claims priority to and the benefit of U.S. Patent Application Ser. No. 61/050,992, filed on May 6, 2008, in the United States Patent and Trademark Office, the entire content of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
The present invention relates to a modular rack assembly. While there are a variety of modular rack assemblies that have been designed to store various items, they are not easily configurable for shipping. Further, conventional modular racks are not formed of a simple construction and may be expensive to manufacture and difficult to assemble and adjust.
SUMMARY OF THE INVENTION
An embodiment of the present invention provides an end support unit for supporting the ends of at least one front and one rear cross beam including: a generally vertical front support post having at least one column of slots along its length for receiving at least one slot engaging member of the front cross beam; a generally vertical rear support post having at least one column of slots along its length for receiving at least one slot engaging member of the rear cross beam; a generally horizontal upper brace fixedly attached to and extending from the upper end of the front support post to the upper end of the rear support post; a generally horizontal lower brace fixedly attached to and extending from the lower end of the front support post to the lower end of the rear support post; and at least one diagonal brace fixedly attached to and extending diagonally between the front support post and the rear support post.
The upper brace may have at least one hole for receiving the shaft of a connector for securely mounting a secondary component to the end support unit.
The lower brace may have at least one hole for receiving the shaft of an anchor for securely anchoring the end support unit to a floor location or a connector for securely mounting a secondary component to the end support unit.
The slots may be key-hole shaped. The slot engaging members may be rivets. The slots may be wedge-shaped. The slot engaging members may be lances.
The end support units may be about 3, inches wide, about 17, inches deep, and about 36 inches high.
The support posts may be c-shaped. The braces may be c-shaped.
Another embodiment of the present invention provides an end support unit assembly including an upper end support unit stacked on top of a lower end support unit for supporting the ends of at least one front and one rear cross beam. Each end support unit includes: a generally vertical front support post having at least one column of slots along its length for receiving at least one slot engaging member of the front cross beam; a generally vertical rear support post having at least one column of slots along its length for receiving at least one slot engaging member of the rear cross beam; a generally horizontal upper brace fixedly attached to and extending from the upper end of the front support post to the upper end of the rear support post; a generally horizontal lower brace fixedly attached to and extending from the lower end of the front support post to the lower end of the rear support post; at least one diagonal brace fixedly attached to and extending diagonally between the front support post and the rear support post; and a pair of connectors extending through holes in the lower brace of the upper end support unit and the upper brace of the lower end support unit to secure the upper end support unit to the lower end support unit.
Each connector may include a bolt, a lock washer, and a nut.
Another embodiment of the present invention provides a storage rack including: at least one left end support unit and at least one right end support unit for supporting the ends of at least one front and one rear cross beam. Each end support unit includes: a generally vertical front support post having at least one column of slots along its length for receiving at least one slot engaging member of the front cross beam; a generally vertical rear support post having at least one column of slots along its length for receiving at least one slot engaging member of the rear cross beams; a generally horizontal upper brace fixedly attached to and extending from the upper end of the front support post to the upper end of the rear support post; a generally horizontal lower brace fixedly attached to and extending from the lower end of the front support post to the lower end of the rear support post; and at least one diagonal brace fixedly attached to and extending diagonally between the front support post and the rear support post; at least one front cross beam, wherein the at least one front cross beam is mounted on and extending between the left and right front support posts of the left and right end support units; at least one rear cross beam, wherein the at least one rear cross beam is mounted on and extending between the rear support posts of the right and left end support units at about the same elevation as the front cross beam; and at least one shelf panel, wherein the at least one shelf panel is supported at its front and rear edges by at least one front and rear cross beam.
The storage rack may include four pairs of front and rear cross beams, four shelves, and four end support units, and wherein the disassembled storage rack is packaged in a space that is about 39, inches by about 17, inches by about 16, inches.
The front and rear cross beams may include at each end an L-shaped flange with a pair of slot engaging members extending inwardly from the flange to engage the slots.
The front and rear cross beams may include a ledge for receiving the shelf panel.
Another embodiment of the present invention provides a work bench assembly including: right and left end support units for supporting the ends of at least one front and one rear cross beam. Each end support unit includes: a generally vertical front support post having at least one column of slots along its length for receiving at least one slot engaging member of the front cross beam; a generally vertical rear support post having at least one column of slots along its length for receiving at least one slot engaging member of the rear cross beam; a generally horizontal upper brace fixedly attached to and extending from the upper end of the front support post to the upper end of the rear support post; a generally horizontal lower brace fixedly attached to and extending from the lower end of the front support post to the lower end of the rear support post; at least one diagonal brace fixedly attached to and extending diagonally between the front support post and the rear support post; an upper front cross beam extending between the upper ends of the front support posts of the right and left end support units; an upper rear cross beam extending between the upper ends of the rear support posts of the right and left end support units; a lower rear cross beam extending between a lower portion of the rear support posts of the right and left end support units; a top panel having front and rear edge portions supported at its front and rear edge portions by the upper front cross beam and upper rear cross beam; right and left upright supports mounted to and extending upwardly from a rear portion of the right and left end support units; a cross beam mounted to and extending between the upper ends of the right and left upright supports; and a generally vertical panel extending between at least a portion of the right and left upright supports and below the cross-beam that extends between the upper ends of the upright supports.
The generally vertical panel may include pegboard.
The generally vertical panel may include upper and lower pegboard panels connected by an elongated strip connector having a generally H-shaped cross-sectional configuration that forms a pair of grooves for receiving the lower end of the upper pegboard panel and the upper edge of the lower pegboard panel.
The workbench assembly may further include a cover mounted over the upper braces.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, together with the specification, illustrate exemplary embodiments of the present invention, and, together with the description, serve to explain the principles of the present invention.
FIG. 1 is a front perspective view of a storage rack according to an embodiment of the present invention.
FIG. 1 a , is a cross-sectional view of a portion of the storage rack of FIG. 1 .
FIG. 2 is a front perspective view of a storage rack according to another embodiment of the present invention.
FIG. 3 is an exploded view of the storage rack shown in FIG. 2 .
FIG. 4 is a front perspective view of a storage rack according to another embodiment of the present invention.
FIG. 5 is perspective view of the components of the storage rack shown in FIGS. 2-4 arranged for shipping.
FIG. 6 is an end-view of the exemplary storage racks shown in FIGS. 2-4 assembled for shipping.
FIG. 7 is a perspective view of a storage rack according to another embodiment of the present invention.
FIG. 8 is a perspective view of a storage rack according to another embodiment of the present invention.
FIG. 9 is a perspective view of a storage rack according to another embodiment of the present invention.
FIG. 10 is a perspective view of a storage rack according to another embodiment of the present invention.
FIG. 11 is a perspective view of a storage rack according to another embodiment of the present invention.
FIG. 12 is a perspective view of a storage rack according to another embodiment of the present invention.
DETAILED DESCRIPTION
In the following detailed description, only certain exemplary embodiments of the present invention have been shown and described, simply by way of illustration. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature and not restrictive. Like reference numerals designate like elements throughout the specification.
With reference to FIG. 1 there is shown a boltless storage rack assembly 10 according to an embodiment of the present invention. The rack assembly 10 comprises right and left end support units 12 , each end support unit 12 comprising a front support post 13 , a rear support post 14 , an upper brace 18 , a lower brace 20 , and a diagonal brace 22 . The upper, lower and diagonal braces 18 , 20 , 22 are fixedly attached at their ends, preferably by welding, to the front and rear support posts 13 and 14 . The front and rear support posts 13 and 14 include at least one column of aligned slots 16 for receiving slot engaging members of cross beams 26 , 28 . The front and rear support posts 13 and 14 of the end support units 12 may include right and left columns of slots 16 . Front cross beams 26 are boltlessly mounted at their ends to the front posts 13 of right and left end support units 12 . Rear cross beams 28 are likewise boltlessly mounted at their ends to the rear support posts 14 of the right and left end support units 12 at the same elevations as the front cross beams 26 .
It is understood that the cross-sectional configuration of the support posts and braces may vary as desired. In the embodiment shown in FIG. 1 , the cross-sectional configuration of the posts and braces are generally C-shaped.
Likewise the cross-sectional configuration of the cross beams may vary as desired. In the embodiment of FIG. 1 , the cross beams 26 , 28 have cross-sectional configurations as shown in FIG. 1 a . Here, the cross beams have a ledge for receiving a shelf panel 32 . The cross beams 26 and 28 have an L-shaped flange 29 at each end. A pair of slot engaging members (in this case lances) 30 extend inwardly from the flange 29 to engage wedge-shaped slots 16 in the support posts 13 and 14 .
The slots 16 and slot engaging members 30 may also vary as desired. For example, in another exemplary embodiment, the slots have a key-hole shape and the slot engaging members are rivets that extend inwardly from the ends of the cross beams.
The dimensions of the end support units 12 and cross beams 26 and 28 may also vary. In one embodiment, the end support units 12 are about 3, inches high and about 17, inches deep. In one embodiment, the length of the cross beams is about 39, inches so that the overall width of the rack is about 41, inches.
With reference to FIGS. 2 and 3 , there is shown a stacked rack assembly 38 according to an embodiment of the present invention. The stacked rack assembly 38 comprises right and left end support assemblies 40 , each end support assembly 40 including a pair of end support units 12 a , 12 b , stacked one on top of the other. The upper end support unit 12 a , is securely mounted to the lower end support unit 12 b , with connectors 42 , e.g., bolts which extend through holes 24 in the lower brace 20 of the upper end support unit 12 a , and aligned holes 24 in the upper brace 18 of the lower end support unit 12 b . The bolts 42 are secured with appropriate lock washers and nuts. It is to be understood that any suitable connector may be used.
A plurality of front and rear cross beams 26 and 28 are boltlessly mounted to the front and rear support posts 13 and 14 of the end support units 12 that make up the end support assemblies 40 . Shelf panels 32 are positioned between and supported at their front and rear edge portions by the front and rear cross beams 26 and 28 . As shown, the stacked rack assembly 38 can be anchored at a particular floor location by means of anchors 28 or the like which extend through holes 24 in the lower brace 20 of the lower end support unit 12 b , and into the floor. The type of anchor will vary depending on the material of the floor. For example, expandable wedge anchors, sleeve anchors, etc., as are well-known in the art may be used with concrete floors, whereas leg bolts or the like may be used for wood floors.
Another modular rack assembly 44 according to an embodiment of the present invention is shown in FIG. 4 . As shown in this embodiment, the upper and lower end support units 12 a , and 12 b , may be secured together by means of front and rear cross beams 26 and 28 wherein the upper slot engaging members 30 at each end of the cross beams engage the lowest slot 16 in the front and rear posts 13 and 14 of the upper end support unit 12 a , and the lower slot-engaging members 30 of the cross beams engage the uppermost slot 16 of the front and rear post 13 and 14 of the lower end support unit 12 b . In this way, seating of the slot-engaging members 30 into the slots 16 secures the upper and lower end-support units 12 a , and 12 b , together. Optionally, the upper and lower end support units 12 a , and 12 b , may be further secured together by bolts 42 or the like, as described with respect to FIGS. 2 and 3 .
One of the benefits of the present invention is that a 72-inch high by 17, inch deep by 41 inch wide rack assembly having four pairs of front and rear cross-beams and four shelves may be packaged in a space having the dimensions 39, inches by 17, inches by less than 16, inches. This allows the rack assembly to be packaged in a container that is 40, inches by 18, inches by 16, inches. Such a packaged arrangement provides significant cost savings as compared to racks having 72-inch long side support units. For example, this set of dimensions enables three packages to fit on a standard forty inch by forty-eight inch pallet. An exemplary arrangement of the components for packaging is shown in FIGS. 5 and 6 .
The end support units 12 may also be used as intermediate support units in larger shelf and/or bench assemblies. For example, FIG. 7 shows another exemplary assembly comprising four end-support units 12 used to form an elongated workbench with three shelf panels 32 .
FIG. 8 shows another exemplary assembly including left and middle support assemblies 40 a, , 40 b, , which each include three stacked end support units 12 . The right support assembly 40 c includes two stacked end support units 12 . Cross-beams 26 and 28 are mounted between the left and middle end-support assemblies 40 a , and 40 b , to provide support for four shelf panels 32 . Cross-beams 26 and 28 are mounted on and extended between the middle and right support unit assemblies 40 b , and 40 c , to provide three shelf panels 32 , as shown. FIGS. 9 and 10 show other exemplary assemblies using end support units 12 .
The present invention also provides work benches that utilize the benefits of the end support units 12 described above. With the reference to FIG. 11 , there is provided a work bench 50 with a pair of opposing right and left end support units 12 , and front and rear cross-beams 26 and 28 are mounted on and extend between the left and right front and rear support posts 13 and 14 of the right and left end support units 12 at the top of the support posts 13 and 14 . For stabilization, a lower rear cross-beam 28 extends between the rear posts 13 of the right and left end support units 12 at a lower portion of those support posts. A panel 32 is supported at its front and rear edge portions by the upper front and rear cross beams 26 and 28 .
A cover 52 is mounted over the upper braces 18 of the right and left end support units 12 to create a generally flat surface at about the same level as the top surfaces of shelf panel 32 . In an embodiment of the present invention, the cover 52 has the same cross-sectional configuration as the support posts 13 , 14 of the end-support units 12 , but without the slots.
A pair of upright supports 54 extend upwardly from the rearward portion of the end support units 12 . In an embodiment of the present invention, the uprights supports 54 are made of the same material and have the same cross-sectional configuration of the support posts 13 , 14 of the end-support units 12 . The upright supports 54 have a generally horizontal flange 56 at their lower ends. The flange 56 extends forwardly and has a hole that aligns with holes in the cover 52 and upper brace 18 of the end support units 12 . The upright supports 54 may be secured to the end support units 12 by connectors, such as bolts as previously described. A cross-beam 58 is mounted at its ends to and extends between top ends of the left and right upright supports 54 . In the embodiment shown, there is provided a pegboard assembly 60 which extends between the left and right upright supports 54 and between the top of the workbench 50 and the cross-beam 58 at the upper end of the upright supports 54 . The pegboard assembly 60 preferably comprises two pegboard panels 62 a , and 62 b , connected together by a plastic strip connector 64 having an H-shaped cross-sectional configuration. Such a connector 64 comprises a pair of grooves or recesses for receiving the lower edge of the upper pegboard panel 62 a , and the upper edge of a lower pegboard panel 62 b.
In the exemplary embodiment shown in FIG. 11 , the workbench 50 comprises a drawer assembly. Any suitable drawer assembly may be used. Likewise, the workbench 50 could be provided with a lower shelf for storage purposes, if desired.
With reference to FIG. 12 , there is shown another exemplary workbench constructed according to another embodiment of the present invention. As can be seen, the workbench comprises two workbench assemblies as generally as described in FIG. 11 , except that the middle end support unit 12 and upright support 54 provide common support for both workbench units.
While the present invention has been described in connection with certain exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements thereof.
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An end support unit for supporting the ends of at least one front and one rear cross beam including: a front support post having a column of slots along its length for receiving at least one slot engaging member of the front cross beam; a rear support post having a column of slots along its length for receiving at least one slot engaging member of the rear cross beam; an upper brace fixedly extending from the upper end of the front support post to the upper end of the rear support post; a lower brace fixedly extending from the lower end of the front support post to the lower end of the rear support post; and a diagonal brace extending diagonally between the front support post and the rear support post.
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This is a division of application Ser. No. 07/432,927, filed Nov. 7, 1989 now U.S. Pat. No. 5,034,170, issued Jul. 23, 1991.
BACKGROUND OF THE INVENTION
This invention relates to connectors and, more particularly, to high-precision molding of connectors for single-mode optical fibers.
Optical fibers are being increasingly used for a wide variety of purposes in the communication field. As the use of optical fibers increases, a significant need has arisen for low-cost connectors suitable for joining fiber ends together in a way that results in low transmission loss of the optical signal at the joint.
Several types of losses typically occur when the ends of optical fibers are connected together. Among these are losses which stem from angular misalignment between the fiber ends, from gaps between the fiber ends, and from axial misalignment (lack of concentricity) between the fibers.
A number of types of connectors are known for joining fiber ends together. One such type, commonly called a biconic connector, includes two substantially identical apertured plugs designed to respectively engage, in a mirror-image fashion, the two fiber ends to be joined. In the molding operation described herein, the axis of each plug aperture is intended to be positioned with a prescribed high precision with respect to the axis of the plug profile. When the fiber-containing plugs are brought into contact, the cores of the fibers are intended to be substantially concentric.
The cores of multi-mode optical fibers are large relative to those of single-mode fibers. Thus, establishing axial alignment between the cores of multi-mode fiber ends is far less difficult than it is with single-mode fibers. In practice, low-cost connectors for multi-mode optical fibers have been realized by high-volume forming of plastic parts in a conventional injection molding operation.
For single-mode fibers having, for example, a core diameter (mode field diameter) of only about 8.7-to-10 micrometers (μm), axial alignment of the fiber ends must typically be maintained below one μm to ensure that losses are kept at an acceptable level. The machining of suitable mold details to consistently achieve sufficient precision in a molded single-mode connector to ensure that such high-precision axial alignment is realized is a formidable task. This obstacle has priorly stood in the way of economically fabricating suitable single-mode connectors by conventional injection molding techniques.
Accordingly, considerable efforts have been made by workers skilled in the art aimed at trying to devise improved techniques for molding low-cost connectors suitable for joining single-mode fiber ends together in a low-loss way. It was recognized that these efforts, if successful, would contribute importantly to enhancing the quality and lowering the cost of communication systems that utilize single-mode optical fibers.
SUMMARY OF THE INVENTION
In accordance with the principles of the present invention, a mold for forming single-mode fiber optic connector parts includes an adjustment feature. In particular, a mold for forming an apertured connector plug includes an adjustment by means of which any measured eccentricity existing between the longitudinal axis of the plug aperture and the longitudinal axis of the plug profile can be reduced to and maintained within an acceptable tolerance. Adjustment of the eccentricity is carried out as part of the molding process and can be performed with the molding equipment idling at operating temperatures.
More specifically, a mold made in accordance with this invention includes two circular cams. An inner cam comprising a conically shaped front portion is mounted in a through opening formed in an outer cam. The front inner wall of the outer cam is conically shaped to be in contacting relationship with the front portion of the inner cam when the two cams are spring biased together.
The front face of the inner cam includes a hole. This front face comprises one wall of the mold cavity in which a hollowed-out apertured plug is formed in an injection molding operation. During molding, a mold core pin fits into the hole in the inner cam, which thereby determines the location of the pin as molding material flows around the pin to form the aperture in the plug. Rotation of either or both of the cams is effective to move the inner cam hole relative to the main longitudinal axis of the mold cavity. In that way, the position of the mold core pin is precisely determined.
In accordance with the invention, the axis of rotation of the outer cam is offset by a first distance from the main longitudinal axis of the mold cavity. Also, the axis of rotation of the inner cam is offset by a second distance from the axis of rotation of the outer cam. Further, the longitudinal axis of the hole in the front face of the inner cam is offset by a third distance from the axis of rotation of the inner cam. To be able to rotate the cams to concentrically position the hole in the inner cam with respect to the longitudinal axis of the mold cavity, the sum of the second and third distances must be equal to or greater than the first distance.
BRIEF DESCRIPTION OF THE DRAWING
A complete understanding of the present invention and of the above and other features and advantages thereof may be gained from a consideration of the following detailed description presented hereinbelow in connection with the accompanying drawing, in which:
FIG. 1 is a side view, partially broken away, of a portion of a conventional biconic connector for optical fibers;
FIG. 2 is a simplified cross-sectional representation of a portion of an adjustable mold cavity made in accordance with the principles of the present invention;
FIG. 3 is an isometric view showing more details of the mold cavity of FIG. 2;
FIG. 4 is an isometric view of the two cams included in the adjustable mold cavity of FIG. 2; and
FIG. 5 is a schematic depiction of the offsets included in the dual-cam arrangement of the adjustable mold cavity.
DETAILED DESCRIPTION
FIG. 1 shows a portion of a priorly known biconic connector designed to join together two optical fiber ends. The depicted connector includes two identical parts each including a cylindrical body portion and a hollowed-out conically shaped plug portion made, for example, of a suitable plastic material. Thus, one part of the connector includes body portion 10 and a plug 12 typically formed as a single integral unit. The other part includes body portion 14 and a plug 16 also formed as a single integral unit.
The plugs 12 and 16 depicted in FIG. 1 each include an apertured pedestal. The pedestals in the plugs 12 and 16 are respectively designated by reference numerals 18 and 20. The apertures in the pedestals 18 and 20 each have a diameter slightly larger than the outside diameter of an optical fiber end to be inserted therethrough. By way of example, the diameter of each of the apertures in the pedestals 18 and 20 is approximately 126-to-128 μm.
In FIG. 1, optical fibers 22 and 24 are shown butted together at the interface formed by the contacting pedestals 18 and 20. In practice, before butting the pedestals together as shown, the inserted fiber ends are glued into their respective apertures. After the glue has cured, excess fiber is scribed and removed. Then, the fiber end faces, any remaining glue and the pedestal end faces are simultaneously ground to provide the final correct geometry (not only flat end faces but also desired pedestal projection). This ensures that substantially no gap will exist between the fiber ends when the pedestals are butted together.
A standard sleeve 26 is shown in FIG. 1 surrounding the plugs 12 and 16 of the depicted connector. Additionally, as is well known, the connector includes other conventional parts (for example, springs, washers, housing) which are not shown in FIG. 1.
Heretofore, various expedients have been tried to ensure that the axis of the aperture in each of the pedestals 18 and 20 (FIG. 1) is approximately colinear with the axis of its respective plug profile. In one such typical expedient, each apertured plug was machined after being molded to form a plug profile whose cross-section was approximately concentric with that of the aperture in the plug pedestal. Although tedious and expensive, such machining of the plugs after molding can serve to achieve a connector characterized by acceptably small axial misalignment of the fiber ends to be joined together.
In accordance with the principles of the present invention, the location of the longitudinal (horizontal) axis of the aperture in each of the pedestals 18 and 20 in FIG. 1 is controlled by an adjustment mechanism built into the molding apparatus itself. In that way, the longitudinal axis of the aperture is adjusted to be colinear with the main longitudinal axis of the plug profile with a high degree of precision. No secondary finishing operations on the molded plugs are necessary to achieve the desired degree of colinearity. As molded, plugs made in accordance with this invention are suitable for inclusion in the connector represented in FIG. 1 to achieve low-cost joining together of fiber ends in a low-loss manner. In particular, such plugs have been found to enable the cores of fiber ends to be consistently joined with a maximum eccentricity of less than one μm.
FIG. 2 depicts a portion of a conventional injection molding apparatus as modified in accordance with the principles of the present invention. The molding apparatus includes one or more cavities in which plugs of the type shown in FIG. 1 are formed. Subsequently, each molded plug is attached in any standard way to its respective body portion. By way of example, the plugs are advantageously molded of a conventional thermoplastic material.
As indicated in FIG. 2, standard so-called A and B sides 28 and 30, respectively, of a conventional injection molding apparatus partially define a cavity within which a plug 32 is to be molded. The molding apparatus includes a standard ejector sleeve 34. Positioned within the ejector sleeve 34 is a core pin 36 having a conical front portion which extends into the cavity in which the plug 32 is to be formed. As a result of the core pin 36 extending into and along the full extent of the plug cavity, the molded plug formed therein has a conically shaped hollowed-out interior portion.
Fitted into the right-hand end of the core pin 36 is a multi-diameter stepped pin 38 whose smallest size determines the diameter of the hole to be formed in the pedestal of the molded plug. Illustratively, the pin 38 has a smallest diameter of 126-to-128 μm.
In a conventional molding apparatus as heretofore constructed, the right-hand wall of the mold cavity that defines the shape of the plug 32 shown in FIG. 2 would comprise a stationary plate. In turn, this plate would include a hole designed to receive the pin 38. In practice, however, such a fixed or non-adjustable mold cavity has been found to be incapable of consistently forming high-precision plugs suitable for use in connectors designed to join together the ends of single-mode fibers.
As a practical matter, machining of an economically feasible mold cavity of the type shown in FIG. 2 produces a cavity whose features are, for example, accurate only to about 0.0005 inches (0.5 mil) ±0.1 mil. With such a mold cavity, it is virtually impossible to ensure that the pedestal aperture of a plug formed therein will be concentric with the plug profile to a tolerance of less than one μm (0.000039 inches).
In accordance with the principles of the present invention, the right-hand wall of the mold cavity shown in FIG. 2 comprises the front (or left-hand) face of a rotatable cam 40 which is mounted within a well 41 formed in a rotatable outer cam 42. In turn, the outer cam 42 is mounted within a well 44 formed in the A side 28 of the molding apparatus.
The inner cam 40 (FIG. 2) comprises a front (left-hand) portion 46 that is conically shaped. The outer surface of the portion 46 is designed to intimately contact the inner surface of the front portion of the well 41 in the outer cam 42. This front portion of the well 41 is also therefore correspondingly conically shaped.
Similarly, the outer cam 42 comprises a front portion 48 whose outer surface is conically shaped. In turn, this front portion 48 is designed to intimately contact the surface of the well 44 which is conically shaped in a corresponding manner (and is an integral detail of the A-side cavity 28).
The cams 40 and 42 of FIG. 2 each include cylindrical flange portions 50 and 52, respectively. Further, each of the flange portions 50 and 52 includes a number of regularly spaced indentations formed in the peripheral surface thereof. Access to the indentations is obtained via window 54 formed in housing 56. As indicated in FIG. 2, two indentations 58 and 60 are accessible via the window 54.
By means of a simple tool (not shown) inserted through the window 54 into the indentations of FIG. 2, the cams 40 and 42 can be rotated to any desired angular position. To aid in the rotational adjustment, standard scale markings in appropriate increments such as one-half of a degree may be included on the apparatus.
In one specific illustrative embodiment of the invention, each of the flange portions 50 and 52 had a diameter of about 2.5 inches and each included 24 regularly spaced-apart circumferentially located adjustment indentations such as the ones designated 58 and 60 in FIG. 2. In practice, it is feasible to control the rotation of each of the inner and outer cams of such an embodiment to within about 0.25 degrees ±0.1 degrees.
A conventional illustrative mechanism is schematically shown in FIG. 2 for locking the cams 40 and 42 in place to prevent inadvertent rotation thereof. The depicted mechanism includes a movable arm 62 with an end finish containing an angled face 63, a multi-diameter pin 64 having a head with an angled face 65 which has the same relative angle as angled face 63 of the movable arm 62 but counter positioned so as to allow the two angled faces to be in intimate contact over their mating surfaces, and which also includes a smaller-diameter cylindrical extension 67 which is positioned in a cylindrical well 69 within the cylindrical flange portion 50 to maintain a coaxial relationship between the pin 64 and the inner cam 40, and a spring member 66 that comprises, for example, a cupped washer made of spring steel.
FIG. 3 shows two parts 68 and 70 that when assembled together constitute the A side 28 of the mold cavity prepresented in FIG. 2. Longitudinal axis 69 defines the true central axis of the mold cavity. The parts 68 and 70 are secured together by, for example, screws (not shown) that pass through holes (only holes 71, 72 are shown) in the part 70 and into tapped receiving holes (not shown) in the part 68.
The part 68 of FIG. 3 constitutes the mold cavity block in which the plug 32 shown in FIG. 2 is formed. In particular, the conical outer surface of the molded plug 32 is defined by the walls of cavity 73 in the part 68.
The part 70 depicted in FIG. 3 includes the conically shaped well 44 shown in FIG. 2. As specified earlier above, the well 44 is designed to have the front conically shaped portion 48 of the outer cam 42 seated therein. Significantly, in accordance with the principles of the present invention, the longitudinal axis of the circularly symmetrical well 44 is purposely offset by a prescribed distance from the longitudinal axis 69 of the mold cavity. This feature of the apparatus will be specified in more detail later below in connection with the description of FIG. 5.
FIG. 4 is an isometric view of the two cams 40 and 42 included in the adjustable mold cavity of FIG. 2. When the portion 46 of the inner cam 40 of FIG. 4 is seated in the well 41 formed in the outer cam 42, the front or left-hand face 43 of the inner cam 40 forms, in combination with the cavity 73 (FIG. 3), a partial enclosure into which plastic material can be injected to mold plugs for the herein-described connectors.
The front face 43 of the inner cam 40 includes an indentation into which plastic material flows to form the pedestal portion of the molded plug. This indentation is shown in FIG. 2 wherein it is designated by reference numeral 39. Centrally disposed within the indentation 39 is a hole formed in the front face 43 of the inner cam 40. As previously mentioned, this hole is designed to receive the smallest diameter of the pin 38 that constitutes an extension of the core pin 36 shown in FIG. 2. The location of this hole relative to the longitudinal axis of the mold cavity is adjustable, as specified in detail below.
As indicated earlier, the axis of rotation or center of the circular outer cam 42 is purposely offset from, but is in a fixed relationship as far as distance and direction to, the true center of the mold cavity. This relationship is schematically depicted in FIG. 5 wherein the distance d1 indicates the noted offset. Further, in accordance with this invention, the center of the well 41 formed in the outer cam 42 is purposely offset from the center of the outer cam. Thus, the axis of rotation or center of the circular inner cam 40 will also be offset from the center of the outer cam. In FIG. 5, this last-mentioned offset is indicated by the distance d2.
Additionally, the previously described hole formed in the front face of the inner cam 40 is purposely offset from the center of the inner cam. This offset is indicated in FIG. 5 by the distance d3. As a basis for always being able to move the hole (by selective rotation of the cams 40 and 42) to a position concentric with the center of the mold cavity, the sum of the distances d2 and d3 must be equal to or greater than the distance d1. Additionally, d1 must be greater than zero (i.e. the axis of rotation of the outer cam must be offset from the center of the mold cavity) to allow for manufacturing tolerances on d2 and d3.
In practice, molded plugs fabricated in an adjustable mold cavity made in accordance with the principles of this invention are measured by conventional techniques to ascertain the amount and direction of any eccentricity between the axis of the pedestal hole and the axis of the plug profile. If the measured eccentricity exceeds, for example, one μm, the mold cavity can be adjusted on-line, at operating temperatures, to move the hole in the inner cam to a location with respect to the center of the mold cavity that falls within the submicron range. Straightforward calculations determine the exact amount of rotation of each of the cams to achieve the desired new hole location. Once so located, the hole in the inner cam forces the core pin to assume a corresponding location.
One specific illustrative procedure to follow to move the hole in the inner cam 40 towards the center of the mold cavity will now be described by reference to FIG. 5. Dash-line circular path 76 in FIG. 5 constitutes a reference circle whose radius is the distance d1. Counter-clockwise rotation of the inner cam 40 is effective to move the hole in the inner cam along a circular path 77 to intersect the circle 76. Then clockwise rotation of the entire dual-cam assembly as an integral unit causes the hole in the inner cam to follow the path 76 to the point at which the center of the hole and the center of the mold cavity are coincident.
In practice, the aforedescribed adjustment procedure can, for example, be carried out as follows. First, the dual-cam assembly is enabled for rotation by releasing the locking mechanism that includes the movable arm 62 (FIG. 2). With tools inserted in the adjustment indentations in the inner and outer cams, the inner cam only is then rotated while holding the outer cam stationary. Subsequently, both cams are moved together jointly to rotate the hole in the inner cam to its desired location. (Alternatively, equivalent results can be obtained by rotating each cam independently from its existing to its final desired position). Within at the most several such successive adjustment cycles, an acceptable eccentricity dimension in the submicron range is consistently realized. And once realized, the adjustment can be locked in place and then maintained during molding, and even from day to day, over an extended period of time.
In one specific illustrative embodiment of the present invention, each of the offsets d1, d2 and d3 was established to be approximately 0.5 mil ±0.1 mil. Machining of molding apparatus with dimensions of this magnitude and precision is economically feasible. With such offsets and with cam structures of the type specified earlier above, submicron adjustability of an aperture or other feature is practicable. Such a specific embodiment is characterized by an asymmetrical polar adjustment range of from 0.5-to-1.5 mil.
In practice, the magnitude of the aforedescribed offsets is designed to be as small as economically achievable. This is so because as the magnitude of the offsets decreases, the smaller the change in distance between the feature being adjusted (for example, the receiving hole for the core pin) and the target (the axis of the cavity) per degree of rotation of the cams, thus yielding an appropriate increment for sub-micron adjustability. With offsets of the specific magnitude noted above, adequate fineness of movement of the hole in the inner cam be realized without necessitating excessive precision in the adjustment of the rotation angles of the movable cams.
An important feature of the dual-cam adjustment structure described herein is that the conically shaped portions of the inner and outer cams fit together in an intimate contacting relationship with no play therebetween when the cams are spring-biased in their locked or non-rotatable position. Moreover, due to the circularly symmetrical nature of the assembly, the components expand and shrink together during temperature cycling without ever seizing. Adjustment of the mold cavity by means of the cams is thus possible at any time, even at elevated operating temperatures, once the locking mechanism is released.
Finally, it is to be understood that the above-described arrangements and techniques are only illustrative of the principles of the present invention. In accordance with these principles, numerous modifications and alternatives may be devised by those skilled in the art without departing from the spirit and scope of the invention. Thus, for example, while emphasis herein has been directed to the inner cam 40 including a hole that is intended to receive the pin 38 connected to the end of the core pin 36, it is apparent that variations of this arrangement are feasible. Illustratively, the structural feature included on the front face of the inner cam can be a protruding pin instead of a hole. In that case, the pin 38 is omitted and the core pin 36 is designed to include a hole at its end to receive the pin on the inner cam.
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A injection-molded connector for single-mode optical fibers includes two mating plugs having aligned fiber-receiving holes. To keep transmission losses in the connector at an acceptable level, the eccentricity of each hole relative to its plug profile must be maintained within a fraction of a micron. The mold utilized to form the plugs includes a dual-eccentric-cam adjustment mechanism that comprises nested conically shaped cams. In a method for fabricating such plugs, rotation of the cams serves to move a part of the mold that positions a hole-forming pin. By rotating this mechanism, the eccentricity of the fiber hole relative to the profile of the molded plug can be established and maintained within the required precision.
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BACKGROUND OF THE INVENTION
Most of the bronchodilators used at present for the therapy of diseases showing tracheal abnormality such as asthma are β-adrenoceptor stimulants as typically represented by isoproterenol, terbutaline, salbutamol, trimetoquinol and the like and their pharmacological action is based on that they stimulate β-adrenoceptors in tracheal smooth muscles to dilate the muscles. It is, however, well known clinically that these pharmaceutical agents also act on β-adrenoceptors present in other sites than tracheal smooth muscles and cause serious side effects such as tachycardia, vasodilatation, tremor and the like. These known bronchodilators, therefore, have a serious defect that they have to be used, upon administration, with a sufficient care for the above side effect and depending on the patient's pathological conditions. It is therefore considered at present that the essential condition for desired bronchodilators are that they selectively act only to the tracheal smooth muscles.
The inventors of the present application have made various studies for developing new pharmaceutical agents free from the foregoing defects and, as the result, discovered that the compounds represented by the above general formula (I) are very useful as new type bronchodilators in view of their mechanism of action and chemical structure, different from conventional β-adrenoceptor stimulants, in that they selectively act on the tracheal smooth muscles to thereby provide relaxation therein while causing only very weak cardiovascular effects. The present invention has been accomplished based on the above findings.
It is known that the compounds represented by the following general formula: ##STR2## where R' represents n-propyl, n-butyl, cyclohexyl, phenyl, benzyl and phenetyl, R" represents lower dialkylamino, X represents oxygen or sulfur atom and A represents an organic or inorganic acid has a local anesthetic action as disclosed in Japanese Pat. No. 426,718 (Japanese Patent Publication No. 1671/1964), Folia Pharmacol Japan [vol. 58, p 67-77 (1962)] and the like.
The local anesthetic action of the compound having the following general formula: ##STR3## where R', R" and A have the same meaning as above, is also disclosed in Japanese Pat. No. 426,717.
Further, Japanese Pat. No. 277,099 (Japanese Patent Publication No. 18278/1960) also describes that the compound represented by the following general formula: ##STR4## where R is alkyl, R 1 and R 2 individually represent methyl or form a heterocyclic ring together with nitrogen atom, has an antibiotic effect against influenza virus.
None of these known literatures, however, contain descriptions which suggest the bronchodilatation action of the compounds according to the present invention.
SUMMARY OF THE INVENTION
The object of the present invention is, as apparent from the foregoings, to provide quite new bronchodilators capable of selectively acting on tracheal smooth muscles to dilate them while causing only very weak cardiovascular effects.
The present invention concerns new α-methyl-β-aminopropiophenone derivatives having bronchodilatation effect, their non-toxic salts, process for the production thereof, as well as human and animal bronchodilatation by using them.
The novel α-methyl-β-aminopropiophenone derivatives according to the present invention are represented by the following general formula: ##STR5## where R is alkyl having 1-6 carbon atom, benzyl, or phenyl; R 1 and R 2 individually represent alkyl having 1-6 carbon atom or they form, joining to each other together with the adjacent nitrogen atom with or without intervening an atom other than carbon atoms, a saturated heterocyclic ring which may be substituted with lower alkyl; and n is an integer of 0, 1 or 2 providing that R is methyl or ethyl if n is 0, and their non-toxic salts include those of various organic and inorganic acids such as hydrochloric acid, sulfuric acid, hydrobromic acid, acetic acid, oxalic acid, citric acid, malic acid, tartaric acid, fumaric acid, maleic acid and succinic acid and the like.
The alkyl group having 1-6 carbon atom number includes, for example, methyl, ethyl, propyl, butyl, pentyl and hexyl.
The saturated heterocyclic ring includes 5- or 6-membered rings such as pyrrolidino, piperidino, morpholino, 4-methylpiperazino and the like.
The atom other than carbon atom through which R 1 and R 2 are joined includes oxygen, nitrogen, sulfur atoms and the likes.
The compounds represented by the general formula (I) can be prepared by reacting a propiophenone derivative represented by the following general formula: ##STR6## where R represents alkyl having 1-6 carbon atoms, benzyl or phenyl, with formaldehyde or para-formaldehyde and a secondary amine represented by the following general formula: ##STR7## where R 1 and R 2 have the same meaning as above and performing oxidation if required. Their non-toxic salts can be produced by reacting the compound represented by the general formula (I) with a physiologically non-toxic organic or inorganic acid in an adequate solvent. When para-formaldehyde is used, the above reaction is proceeded preferably in the presence of hydrochloric acid.
Bronchodilatation according to the present invention can be achieved by applying to men or animals an effective dose of the compound represented by the general formula (I) or their non-toxic salt.
The bronchodilating composition according to the present invention comprises an effective amount of the compound of the general formula (I) or their non-toxic salts and medicinal adjuvant and the composition is applied to men or animals through oral dosage or injection.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph showing the relation between the dose-response curve for the compound No. 51 of the present invention and that for the compound 51 in the presence of propranolol,
FIG. 2 shows the relation between dose-response curve for the compound No. 29 of the present invention and that for the compound 29 in the presence of propranolol,
FIG. 3 shows the relation between the dose-response curve of the compound No. 16 of the present invention and that for the compound 16 in the presence of propranolol, and
FIG. 4 shows the relation between the dose-response curve of the isoproterenol and that for the isoproterenol in the presence of propranolol.
DETAILED DESCRIPTION OF THE INVENTION
In the general formula (I) of the compounds according to this invention, R is preferably alkyl having 1-4 carbon atoms or phenyl and, most preferably, methyl, ethyl, n-butyl and phenyl. Preferably, R 1 and R 2 individually represent methyl and/or ethyl or join with or without intervening an oxygen or nitrogen atom so that ##STR8## represents a 5- or 6-membered saturated heterocyclic ring which may be substituted with a lower alkyl having 1-6 carbon atoms, preferably, with methyl. The 5- or 6-membered saturated heterocyclic ring includes, for example, pyrrolidino, morpholino, 4-methylpiperazino or piperidino, preferably, pyrrolidino, 4-methylpiperazino or piperidino and, most preferably, piperidino.
Accordingly preferred compounds of the present invention are those of the general formula (I) where R is alkyl having 1-4 carbon atoms or phenyl; R 1 and R 2 individually represent methyl and/or ethyl or form a saturated heterocyclic ring so that ##STR9## represents pyrrolidino, 4-methyl piperazino or piperidino, and a more preferably, those of the formula (I) where R is alkyl having 1-4 carbon atoms or phenyl; R 1 and R 2 individually represent methyl or form a saturated heterocyclic ring so that ##STR10## represents piperidino and n is 0 or 2 (provided that R is methyl if R 1 and R 2 are methyl). Further preferred are the compounds where R, R 1 and R 2 are methyl and n is 0 or the compounds where R is methyl, ethyl, n-butyl or phenyl and ##STR11## is peperidino and n is 0 or 2. The most preferred are the compounds where R is methyl or ethyl, ##STR12## is piperidino and n is 0.
TABLE 1__________________________________________________________________________Compound No.poundCom-R ##STR13## n Salt °C.M.P.__________________________________________________________________________1 CH.sub.3 ##STR14## 1 fuma- rate 139-1412 CH.sub.3 ##STR15## 1 fuma- rate 100-1013 CH.sub.3 ##STR16## 1 fuma- rate 118-1194 CH.sub.3 ##STR17## 1 fuma- rate 127-1285 CH.sub.3 ##STR18## 1 fuma- rate 119-1206 CH.sub.3 ##STR19## 1 fuma- rate 150-1527 C.sub.2 H.sub.5 ##STR20## 1 fuma- rate 143-1458 C.sub.2 H.sub.5 ##STR21## 1 fuma- rate 145-1469 C.sub.2 H.sub.5 ##STR22## 1 fuma- rate 103-10510 C.sub.2 H.sub.5 ##STR23## 1 fuma- rate 100-10211 C.sub.2 H.sub.5 ##STR24## 1 fuma- rate 108-11112 C.sub.2 H.sub.5 ##STR25## 1 fuma- rate 152-15313 CH.sub.3 ##STR26## 2 hydro- chlo- ride 170-17214 CH.sub.3 ##STR27## 2 fuma- rate 99-10015 CH.sub.3 ##STR28## 2 hydro- chlo- ride 142-14316 CH.sub.3 ##STR29## 2 hydro- chlo- ride 144-14717 CH.sub.3 ##STR30## 2 hydro- chlo- ride 159-16118 CH.sub.3 ##STR31## 2 hydro- chlo- ride 198-20019 C.sub.2 H.sub.5 ##STR32## 2 hydro- chlo- ride 158-15920 C.sub.2 H.sub.5 ##STR33## 2 fuma- rate 101-10221 C.sub.2 H.sub.5 ##STR34## 2 hydro- chlo- ride 149-15022 C.sub.2 H.sub.5 ##STR35## 2 hydro- chlo- ride 148-14923 C.sub.2 H.sub.5 ##STR36## 2 hydro- chlo- ride 156-15724 C.sub.2 H.sub.5 ##STR37## 2 hydro- chlo- ride 217-21825 C.sub.2 H.sub.5 ##STR38## 0 hydro- chlo- ride 160-16126 C.sub.2 H.sub.5 ##STR39## 0 hydro- chlo- ride 188-18927 n-C.sub.4 H.sub.9 ##STR40## 1 fuma- rate 141-14428 n-C.sub.4 H.sub.9 ##STR41## 1 fuma- rate 145-14629 C.sub.2 H.sub.5 ##STR42## 0 hydro- chlo- ride 158-16030##STR43## ##STR44## 1 free base 128-13131##STR45## ##STR46## 1 fuma- rate 150-15232##STR47## ##STR48## 1 fuma- rate 161-16233 n-C.sub.3 H.sub.7 ##STR49## 2 hydro- chlo- ride 209-21034 n-C.sub.3 H.sub.7 ##STR50## 2 fuma- rate 148-14935 n-C.sub.4 H.sub.9 ##STR51## 2 fuma- rate 114-11536 n-C.sub.4 H.sub.9 ##STR52## 2 hydro- chlo- ride 143-14437 C.sub.2 H.sub.5 ##STR53## 0 hydro- chlo- ride 97-9838##STR54## ##STR55## 2 maleate 143-14439##STR56## ##STR57## 2 hydro- chlo- ride 115-11640##STR58## ##STR59## 2 hydro- chlo- ride 172-17441##STR60## ##STR61## 2 hydro- chlo- ride 151-15242##STR62## ##STR63## 2 hydro- chlo- ride 172-17443 n-C.sub.3 H.sub.7 ##STR64## 1 fuma- rate 118-11944 n-C.sub.3 H.sub.7 ##STR65## 1 fuma- rate 149-15045##STR66## ##STR67## 1 free base 115-11646 n-C.sub.4 H.sub.9 ##STR68## 2 hydro- chlo- ride 179-18047##STR69## ##STR70## 2 maleate 103-10448 CH.sub.3 ##STR71## 0 hydro- chlo- ride 160-16149 CH.sub.3 ##STR72## 0 fuma- rate 101-10250 CH.sub.3 ##STR73## 0 hydro- chlo- ride 138-13951 CH.sub.3 ##STR74## 0 hydro- chlo- ride 146-14952 CH.sub.3 ##STR75## 0 hydro- chlo- ride 159-16053 CH.sub.3 ##STR76## 0 hydro- chlo- ride 164-16554 C.sub.2 H.sub.5 ##STR77## 0 hydro- chlo- ride 125-12855 C.sub.2 H.sub.5 ##STR78## 0 fuma- rate 91-93__________________________________________________________________________
In the compounds listed in Table 1, the followings show excellent effects:
1-(4-methylthiophenyl)-3-dimethylamino-2-methylpropanone-1,
1-(4-methylsulfonylphenyl)-3-piperidino-2-methylpropanone-1,
1-(4-ethylsulfonylphenyl)-3-piperidino-2-methylpropanone-1,
1-(4-butylsulfinylphenyl)-3-piperidino-2-methylpropanone-1,
1-(4-butylsulfonylphenyl)-3-piperidino-2-methylpropanone-1,
1-(4-phenylsulfonylphenyl)-3-piperidino-2-methylpropanone-1,
1-(4-methylthiophenyl)-3-piperidino-2-methylpropanone-1 or
1-(4-ethylthiophenyl)-3-piperidino-2-methylpropanone-1 and the like.
1-(4-methylthiophenyl)-3-piperidino-2-methylpropanone-1 and
1-(4-ethylthiophenyl)-3-piperidino-2-methylpropanone-1 show particularly excellent effect.
Since the new compounds according to the present invention, theoretically, comprise two types of optical isomers because at least one asymmetric carbon atom is present in the molecule thereof, this invention includes racemates and their optical isomers to be isolated therefrom.
The reaction of the compound represented by the general formula (I) with formaldehyde or paraformaldehyde and the compound represented by the general formula (III) is preferably effected according to Mannich reaction in a conventional solvent, in particular, a lower alcohol having, preferably, 1-6 carbon atoms and, most preferably, those alcohols having 2-4 carbon atoms such as ethanol, butanol and the like.
The amine represented by the general formula (III) is usually used in the form of a salt, preferably, of hydrochloride.
Although the starting compounds have no particular restriction for their ratio, 0.2 or more, preferably, 1-4 and, more preferably, 1.5-2.0 in chemical equivalent of formaldehyde or paraformaldehyde and 0.2-5, preferably, 0.5-2 and, more preferably, 1.0-1.1 in chemical equivalent of the compound of the general formula (III) are preferably used per chemical equivalent of the compound of the general formula (II).
There is also no particular restriction for reaction temperature but the reaction can be effected at a temperature between 20°-200° C. and, preferably, 60°-160° C. Usually, the reaction is carried out under reflux of the solvent employed.
While the reaction time varies depending on the starting materials, reaction conditions employed and the like, the reaction is preferably conducted for about 3-12 hours where it is effect in a lower alcohol such as ethanol, butanol and the like under reflux of the solvent.
The desired compound can be isolated from the reaction mixture by distilling off the solvent at first, adding water to the residue thus obtained to dissolve out the contents, thereafter, neutralyzing with a base such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, ammonia and the like to precipitate crystals or oily products, extracting them with a non-hydrophilic organic solvent such as ether, benzene, chloroform and the like, washing the extracts with water and drying by usual method and then distilling off the solvent.
When the compound thus prepared is a thio-compound or sulfinyl compound, the compound is oxidized by an oxidizing agent, if required, into the desired compound represented by the general formula (I) of which n is 1 or 2, respectively.
The oxidation for the thio-compund or the sulfinyl compound in the present invention can be conducted in a conventional manner comprising the steps of converting the thio- or sulfinyl compound prepared into the salt of an organic or inorganic acid, wholly or partially dissolving the salt in water, methanol, ethanol, or a mixed solvent of water and methanol or water and ethanol and adding 1 or 2 equivalent hydrogen peroxide or sodium periodate at a temperature from 0° C. to room temperature thereby reacting them from several hours to overnight.
The desired compound obtained after the oxidation can be isolated from the reaction mixture by the steps of removing alcohol from the reaction mixture obtained, neutralizing the residue with a base such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, extracting the precipitated substance in a solvent, drying the extract with a usual drying agent and then removing the solvent by distillation.
The compound of the general formula (I) prepared by the process according to the present invention can be purified by re-crystallization of it from a suitable solvent such as cyclohexane and hexan or its non-toxic crystarizable salt from suitable solvent such as methanol, ethanol, propanol, acetone and ethyl acetate. Said salt is for example, an additional salt of an organic or inorganic acid such as hydrochloride, sulfate, hydrobromide, acetate, oxalate, citrate, malate, tartarate, fumarate, malate or succinate.
Typical compounds represented by the above general formula (II), for example, include:
1-(4-methylthiophenyl)propanone-1,
1-(4-ethylthiophenyl)propanone-1,
1-(4-n-propylthiophenyl)propanone-1,
1-(4-i-propylthiophenyl)propanone-1,
1-(4-n-butylthiophenyl)propanone-1,
1-(4-i-butylthiophenyl)propanone-1,
1-(4-phenylthiophenyl)propanone-1,
1-(4-benzylthiophenyl)propanone-1,
1-(4-methylsulfinylphenyl)propanone-1,
1-(4-ethylsulfinylphenyl)propanone-1,
1-(4-propylsulfinylphenyl)propanone-1,
1-(4-i-propylsulfinylphenyl)propanone-1,
1-(4-n-butylsulfinylphenyl)propanone-1,
1-(4-i-butylsulfinylphenyl)propanone-1,
1-(4-phenylsulfinylphenyl)propanone-1,
1-(4-benzylsulfinylphenyl)propanone-1,
1-(4-methylsulfonylphenyl)propanone-1,
1-(4-ethylsulfonylphenyl)propanone-1,
1-(4-n-propylsulfonylphenyl)propanone-1,
1-(4-i-propylsulfonylphenyl)propanone-1,
1-(4-butylsulfonylphenyl)propanone-1,
1-(4-i-butylsulfonylphenyl)propanone-1,
1-(4-phenylsulfonylphenyl)propanone-1,
1-(4-benzylsulfonylphenyl)propanone-1.
These compounds can be synthesized through condensation between the compound represented by the formula: ##STR79## where R and n have the same meanings as above, and a propionyl halide utilizing Friedel-Crafts reaction. Where the compound represented by the general formula(II) is a sulfinyl or sulfonyl compound, it can be prepared by oxidizing the corresponding thio-compound with an oxidizing agent. Where the compounds of the general formula (II) are thio-compounds, most of them are known by Folia Pharmacol Japan vol. 58, p 67-77 (1962) and J. Proc. Pay. Soc., vol. 82, p 262-4 (1948), or J. Org. Chem. vol. 18, p 1209-1211 (1953). Where the compounds of the general formula (II) are sulfinyl or sulfonyl compounds, most of them are novel although they are partially known by Chemical Abstract vol. 47, 2740c. Examples of the process for the production of these sulfinyl and sulfonyl compounds are shown as follows. Synthesis of 1-(4-n-propylsulfinylphenyl)propanone-1
1-(4-n-Propylthiophenyl)propanone-1 (20.83 gr) was dissolved in 600 ml of methanol, to which was added dropwise an aqueous solution containing 22.46 g of sodium metaperiodate. The reaction mixture were stirred overnight at room temperature and, then, methanol was distilled off. The residue was extracted with chloroform and the chloroform layer was washed with water and dried over anhydrous magnesium sulfate. Usual work-up gave the crystalline product, which was recrystallized from benzene-hexane to obtain 20.8 g (yield 94.5%) of 1-(4-n-propylsulfinylphenyl)propanone-1. M.P.: 53°-56° C.
Elemental analysis (C 12 H 16 O 2 S): Calculated; C: 64.25%, H: 7.19%; Found; C: 64.38%, H: 7.39%
IR (KBr) (cm -1 ): 1674 (C=O), 1020 (SO).
In the same manner, the following compounds were also synthesized:
______________________________________Compound Yield M.P.______________________________________1-(4-benzylsulfinylphenyl)propanone-1 59.7% 155-156° C.1-(4-phenylsulfinylphenyl)propanone-1 48.4% 98-100° C.______________________________________
Synthesis of 1-(4-methylsulfonylphenyl)propanone-1
Mixture of 108.2 g of 1-(4-methylthiophenyl)propanone-1 and 122.5 ml of 30% aqueous solution of hydrogen peroxide was heated under reflux for 15 hours. Then, the reaction mixture was poured into ice-water and the precipitated crystal was filtered, washed with water, and dried. The crystal recrystallized from ethanol to give 71.1 g (yield 56.3%) of the products. M.P. 106°-108° C.
Elemental analysis (C 10 H 12 O 3 S): Calculated; C: 56.58%, H: 5.70%; Found; C: 56.71%, H: 5.73%
In the same manner, the following compounds were synthesized:
______________________________________Compound Yield M.P.______________________________________1-(4-ethylsulfonylphenyl)propanone-1 81.3% 80-82° C.1-(4-n-propylsulfonylphenyl)propanone-1 83.3% 64-65° C.1-(4-n-butylsulfonylphenyl)propanone-1 65.3% 63-64° C.1-(4-benzylsulfonylphenyl)propanone-1 68.2% 157-158° C.1-(4-phenylsulfonylphenyl)propanone-1 66.1% 104-105° C.______________________________________
The compounds represented by the general formula (III) include hydrochloride of dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylpiperazine and the like.
The compounds represented by the general formula (I) can also be produced in the following process ##STR80## where R, R 1 , R 2 and n have the same meanings as foregoings, and Y represents ##STR81## in which X is halogen atom.
As foregoings, the compounds of the general formula (I) can be prepared by reacting propiophenones represented by the general formula (V) and secondary amines represented by the general formula (III) in the inert solvent such as ethanol, chloroform, benzene and the like at temperature between 0° and 200° C., preferably, at room temperature or, as the case may be, at the boiling point of the solvent for a time between one hour and overnight, and then by treating the reaction product in the same way as in the foregoing reaction scheme (A) if Y represents ##STR82## or by removing the solvent through distillation where Y represents ##STR83##
The compounds thus prepared and represented by the general formula (I) can be purified either by recrystallization from a proper solvent or by conversion to the non-toxic salts of an organic or inorganic acid and recrystallization. The compounds represented by the general formula (V), for example, include: ##STR84##
The compounds represented by the general formula (V) can be prepared by condensation of the compound represented by the general formula: ##STR85## where R and n have the same meanings as above, and methacryoyl halide or α-halogenomethylpropionyl halide in the presence of anhydrous aluminium chloride.
The production process according to the present invention is to be described specifically referring to examples.
EXAMPLE 1
Synthesis of 1-(4-n-propylsulfinylphenyl)-3-diethylamino-2-methylpropanone-1 (compound No. 43) and its fumarate
1-(4-n-Propylsulfinylphenyl)propanone-1 (6.73 g), diethylamine hydrochloride (6.57 gr) and paraformaldehyde (2.0 gr) were mixed with 20 ml of ethanol and 0.2 ml concentrated hydrochloric acid was added. The reaction mixture was refluxed for 24 hours. Ethanol was removed under reduced pressure. The residue was dissolved in a mixture of water and chloroform, the chloroform layer was removed and the aqueous layer was neutralized with sodium carbonate under ice-cooling. The oily product separated was extracted with ether and the ethereal layer was washed with water followed by drying over anhydrous magnesium sulfate. Ether was distilled off to give 1.43 g (yield 15.3%) of 1-(4-propylsulfinylphenyl)-3-diethylamino-2-methylpropanone-1. The oily 1-(4-n-propylsulfinylphenyl)-3-diethylamino-2-methylpropanone-1 was reacted with an equimolar amount of fumaric acid dissolved in acetone, and the solution was stirred to give crystals. The crystals were filtered and then dried. M.P. 118°-119° C.
Elemental analysis (C 21 H 31 NO 6 S): Calculated; C: 59.27% H: 7.34% N: 3.29%; Found; C: 59.53% H: 7.30% N: 3.50%
In the same manner, compounds No. 27, 30, 31, 32, 44 and 45, as well as their corresponding salts listed in the Table 1 were synthesized.
EXAMPLE 2
Synthesis of 1-(4-methylsulfonylphenyl)-3-piperidino-2-methylpropanone-1 (compound No. 16) and its hydrochloride
1-(4-Methylsulfonylphenyl)propanone-1 (10.61 g), piperidine hydrochloride (6.07 g) and paraformaldehyde (2.25 g) were mixed with 15 ml ethanol and 0.2 ml of concentrated hydrochloric acid was added. The reaction mixture was refluxed for 15 hours. The reaction mixture was treated as described in the example 1, but chloroform for extraction was used instead of ether. The crystals obtained were crystallized from ether to obtain 10.23 g (yield 66.2%) of 1-(4-methylsulfonylphenyl)-3-piperidino-2-methylpropanone-1. M.P. 81.5°-82° C.
IR (KBr) (cm -1 ); 1674 (C=O), 1310, 1290, 1150 (SO 2 )
NMR (CDCl 3 ) (ppm); 1.17 (3H, d, J=7.5 Hz, CH 3 -C), 1.38 (6H, m, CH 2 ), 2.2-3.0 (6H, m, CH 2 -N), 3.08 (3H, s, CH 3 S), 3.67 (1H, m, CH), ##STR86##
Mass: (M + /e) 279
Elemental Analysis (C 16 H 23 NO 3 S): Calculated; C: 62.11% H: 7.49% N: 4.53%; Found; C: 61.95% H: 7.39% N: 4.45%.
The above crystal was dissolved in dry ether and gaseous hydrogen chloride was introduced thereinto to give hydrochloride. M.P. 144°-147° C.
Elemental Analysis (C 16 H 24 ClNO 3 S): Calculated; C: 55.56% H: 6.69% N: 4.05%; Found; C: 55.38% H: 7.21% N: 4.23%
In the same manner, Compounds No. 13, 14, 15, 17, 18, 19, 20, 21, 22, 23, 24, 33, 34, 35, 36, 38, 39, 41, 42, 46 and 47, as well as their corresponding salts listed in the Table 1 were synthesized.
EXAMPLE 3
Synthesis of 1-(4-methylsulfinylphenyl)-piperidino-2-methylpropanone-1 (compound No. 4) and its fumarate
1-(4-Methylthiophenyl)-3-piperidino-2-methylpropanone-1 hydrochloride (13.0 g) was dissolved in 120 ml of water, and to this solution was added dropwise 7.15 ml of 30% aqueous hydrogen peroxide at 5° C. The reaction mixture was stirred at room temperature overnight and once extracted with chloroform to remove by-products. Then, the remaining aqueous layer was neutralized with sodium hydrogen carbonate and extracted again with chloroform. The chloroform layer was treated as usual work to give 9.74 g (yield 82.3%) of 1-(4-methylsulfinylphenyl)-3-piperidino-2-methylpropanone-1. M.P. 79°-81° C.
IR (KBr) (cm -1 ): 1680 (C=O), 1050 (SO)
NMR (CDCl 3 ) (ppm): 1.18 (3H, d, J=7.5, CH 3 -C), 1.40 (6H, m, CH 2 -C), 2.78 (3H, s, CH 3 -S), 2.2-3.0 (6H, m, CH 2 -N), 3.70 (1H, m, CH), ##STR87##
Mass (M + /e): 293
The above base (5.89 g) was dissolved 500 ml of acetone solution containing 3.48 g of fumaric acid. The solution was stirred at room temperature for 4 hours to give 7.27 g (yield 77.6%) of fumarate. M.P. 127°-128° C.
Elemental Analysis (C 20 H 27 NO 6 S): Calculated; C: 58.66% H: 6.65% N: 3.42%; Found; C: 58.87% H: 6.72% N: 3.53%
In the same manner, the compounds No. 1, 2, 3, 5, 6, 7, 8, 9, 10, 11, 12 and 28, L as well as their corresponding salts listed in the Table 1 were synthesized.
EXAMPLE 4:
Synthesis of 1-(4-methylthiophenyl)-3-piperidino-2-methylpropanone-1 (compound No. 51) and its hydrochloride
1-(4-Methylthiophenyl)propanone-1 (264.6 g), paraformaldehyde (110.4 g) and piperidine hydrochloride (196.6 g) were added to 350 ml of sec.-butanol containing 5.9 ml concentrated hydrochloride acid. The reaction mixture was refluxed for 4 hrs. Butanol was distilled off under reduced pressure, and the residue was dissolved in water. The aqueous solution was washed with ether, and was neutralized with sodium carbonate. The isolated oily product was extracted with ether. The ethereal solution was treated as usual work to give 369.3 g (yield 95.0%) of 1-(4-methylthiophenyl)-3-piperidino-2-methylpropanone-1.
IR (neat) (cm -1 ): 1670 (C=O)
NMR (CDCl 3 ) (ppm): 1.15 (3H, d, J=7.3 Hz, CH 3 -C) 1.40 (6H, m, -CH 2 -) 2.47 (3H, s, -SCH 3 ) 2.1-3.0 (6H, m, N-CH 2 ) 3.60 (1H, m, CH) ##STR88##
The above oily product was dissolved in ether and gaseous hydrogen chloride was introduced to the solution to obtain 1-(4-methylthiophenyl)-3-piperidino-2-methylpropanone-1 hydrochloride. M.P. 146°-149° C.
Elemental Analysis (C 16 H 24 ClNOS): Calculated; C: 61.22% H: 7.71% N: 4.46%; Found; C: 61.24% H: 7.76% N: 4.36%
The reaction was conducted in the same manner as in this example, while replacing the reaction solvent from butanol to ethanol and extraction solvent for the reaction products from ether to benzene to synthesize the compounds No. 48, 49, 50, 52, 53, 55, 37, 29 and 26, as well as their corresponding salts listed in the Table 1.
EXAMPLE 5
Synthesis of 1-(4-ethylthiophenyl)-3-piperidino-2-methylpropanone-1 (compound No. 29) and its hydrochloride
In the same procedures as described in Example 4 while replacing 1-(4-methylthiophenyl)propanone-1 with 1-(4-ethylthiophenyl)propanone-1, 1-(4-ethylthiophenyl)-3-piperidino-2-methylpropanone-1 was prepared.
Yield: 85.8%
Hydrochloride M.P.: 158°-160° C.
Elemental Analysis (C 17 H 26 ClNOS): Calculated; C: 62.27% H: 7.99% N: 4.27%; Found; C: 62.38% H: 8.00% N: 4.15%
EXAMPLE 6
Synthesis of 1-(4-ethylthiophenyl)-3-morpholino-2-methylpropanone-1 (compound No. 25) and its hydrochloride
1-(4-Ethylthiophenyl)propanone-1 (40.7 g), morpholine hydrochloride (25.9 g) and paraformaldehyde (9.46 g) were added to 80 ml of ethanol containing 1 ml of concentrated hydrochloric acid. The reaction mixture was refluxed for 12 hrs. After removal of ethanol, the resulting solid was recrystallized from acetone to give 58.93 g (yield 95.6%) of 1-(4-ethylthiophenyl)-3-morpholino-2-methylpropanone-1 hydrochloride. M.P. 160°-161° C.
Elemental Analysis (C 16 H 24 ClNO 2 S); Calculated; C: 58.25% H: 7.33% N: 4.25%; Found; C: 58.27% H: 7.31% N: 4.17%
Compound No. 54 was also synthesized in the same manner as in this Example.
The compounds of the general formula (I) according to the present invention are used together with conventional medicinal adjuvants as a bronchodilator composition in the form of final products such as tablet, granule, dry syrup, powder, capsule, aerosol and the like. The above composition usually comprises 1.0-99%, preferably, 5-50% by weight of the compound of the general formula (I) and 1-99%, preferably, 50-95% by weight of the adjuvant.
The adjuvants used herein include the followings. For tablets, excipients an disintegrants such as lactose mannitol, calcium hydrogen phosphate and corn starch, binders such as hydroxypropylcellulose, hydroxypropylmethylcellulose and polyvinylpyrrolidone and lubricants such as magnesium stearate and calcium talc. For granules, the above composition except for the lubricant. For dry syrups, excipients such as powder sugar, mannitol, lactose and maltose, binders such as hydroxypropylcellulose, hydroxypropylmethylcellulose and polyvinylpyrrolidone and flavoring and odoring agents such as saccharin and perfumes. For powder composition, excipient and the like described with respect to the tablets and granules can be used.
Descriptions are to be made for specific examples of the compositions according to the present invention.
EXAMPLE 7
______________________________________Preparation of TabletsIngredient parts______________________________________Compound No. 29 50Lactose 30Corn starch 17Hydroxypropylmethylcellulose 2Magnesium stearate 1______________________________________
The above composition except for magnesium stearate was added to 13 parts of isopropyl alcohol-acetone (2:8) solvent for the composition, well compounded, dried and pelletized, to which magnesium stearate was mixed. Then, they were compression-molded into tablets using a tablet machine.
EXAMPLE 8
______________________________________Compound No. 51 98 partsPolyvinylpyrrolidone 2 parts______________________________________
The above ingredients were well compounded together, further mixed with 15 parts chloroform, then pelletized using an extruding pelletizer of 0.8 mm in diameter, dried, and then shaped into granules.
The compounds of the general formula (I) according to the present invention can be applied through oral administration or injection in an effective amount, preferably, 0.1 mg/kg--3 mg/kg and, more preferably, 0.5 mg/kg--2 mg/kg at a time to thereby dilate human and animal tracheas. Accordingly, the above compounds are very useful for the therapy of diseases showing tracheal abnormality such as asthma.
Reference will now be made to pharmacological effects of the compounds according to the present invention. For the experimental evaluation of bronchodilatation and side effect of the compounds in clinical use, the guinea-pig isolated tracheal chain preparation in vitro and the canine blood-perfused tracheal preparation in situ were used for the former effect, and the canine femoral arterial preparation, the canine blood-perfused tracheal preparation and the canine isolated and cross-circulated right atrial preparation were used for the latter side effect respectively, in which the selectivity of the above compounds to trachea was expressed by the ratio between the former and the latter in comparison with that of isoproterenol which is one of the most common bronchodilators at present.
Another experiment was also conducted using mice as an index for the acute toxicity to the whole body.
PHARMACOLOGICAL EVALUATION
(1) Relaxant action on the guinea-pig isolated tracheal smooth muscles and the vasodilating action on the canine anesthetized femoral arterial preparation were employed to compare the pharmacological effects of each of the compounds. The relaxant action on the tracheal smooth muscles was expressed by a molar concentration (A) of a compound required for attaining 50% relaxation in the isolated tracheal smooth muscles which had been contracted by 10 -4 M histamine and the vasodilator action was expressed by an administered amount (B), μg, of the compound upon close arterial injection required for increasing the blood flow by 30 ml/min. Ratio B/A was used as an index indicative of the selectivity of each of the compounds to the tracheal smooth muscles and B/A values were calculated for each compound based on the reference B/A value for isoproterenol specified as 1. Greater B/A value shows higher selectivity to the tracheal smooth muscles. The results for the main compounds of the present invention are shown in Table 2.
(2) In order to confirm the pharmacological effect of the above compounds under the conditions closer to those in the living body, experiments were conducted for the canine blood-perfused tracheal preparation in situ and effects of decrease in the tracheal intraluminal pressure (bronchodilatation) and the effect of increase in the perfused-blood flow (vasodilator action) were compared with those of current bronchodilators in clinical use. The bronchodilator action was represented by a dose (C), μg, of a compound required for decreasing the intraluminal pressure by 20 cm H 2 O and the vasodilator action was represented by a dose (D), μg, of the compound required for increasing the perfused-blood flow by 5 ml/min. D/C was employed as an index indicative of the selectivity and determined based on the reference D/C value for isoproterenol specified as 1. The results are also shown in Table 2.
(3) The effect of the above compounds on the heart was studied using the canine isolated and cross-circulated right atrial preparation. The compound was administrated through arterial injection and the above effect was expressed by changes (E) in sinus rate (sinus rate/min). The results are shown in Table 2.
(4) Acute Toxicity
Approx. LD 50 value on intraperitoneal injection for mice was determined. The results are shown in Table 2.
TABLE 2__________________________________________________________________________ Pharmacological eva- luation method (3) Pharmacological eva- Pharmacological eva- E luation method (1) luation method (2) Changes of Acute toxicity A B C D D/C Dose sinus rate FCompound M( × 10.sup.-6) (μg) B/A (μg) (μg) × 10 (μg) (min) mg/kg__________________________________________________________________________Control isoproterenol 0.005 0.0053 1 0.1 0.01 1 0.001 +18Com- salbutamol 2 0.4 2pound terbutaline 0.5 0.2 4 trimetoquinol 0.2 0.05 2.5Compound 4 300 800 3 300 1,000ut.of the 10 200 700 4 300invention 16 60 750 12 300 1,000ut. 22 60 580 9 100 300bout. 28 60 460 8 100 300bout. 36 20 360 18 333 100 3 100 -2 100 300bout. 42 20 175 9 100 300bout. 48 6 100 17 100 300bout. 50 6 43 7 100 ˜ 51 6 240 40 62.5 50 8 100 -2 100 300bout. 53 200 430 2 100 300bout. 54 60 350 6 200 55 60 270 5 200 37 30 175 6 200 29 2 180 90 109 77 7 100 -6 100 300bout. 25 100 100 1 200__________________________________________________________________________ A: 50% effective amount for the guineapig isolated tracheal smooth muscles. B: Dose required for 30 ml/min. increase in the perfusedblood flow in the canine femoral arterial preparation. C: Dose required for 20 cm H.sub.2 O decrease in the tracheal intralumina pressure in the canine bloodperfused tracheal preparation. D: Dose required for 5 ml/min. increase in the perfusedblood flow in the canine bloodperfused tracheal preparation. E: Changes in sinus rate in the canine isolated and bloodperfused right atrial preparation. F: Approx. LD.sub.50 value (intraperitoneal injection to mice) B/A: B/A for each compound determined based on the reference B/A value 1 for isoproterenol. D/C: D/C for each compound determined based on the reference D/C value 1 for isoproterenol.
Based on the foregoing results, it was found that the compounds of the present invention showed higher selective effects to the tracheal smooth muscles when compared with those of conventional bronchodilators.
(5) The relaxant action of the compounds according to the present invention was also studied using the same preparations as in the Pharmacological Evaluation (1) at the presence of propranolol (10 -7 g/ml) as a β-adrenoceptor blocking agent in order to demonstrate that the bronchodilator action of the compounds of the present invention is not due to the stimulation of β-adrenoceptors.
The results are shown in FIGS. 1, 2, 3 and 4, in which FIG. 1 shows the effect of the compound No. 51, FIG. 2 shows the effect of the compound No. 29 and FIG. 3 shows the effect of the compound No. 16 respectively. Histamine (10 -4 M in the bath medium) was applied to the guinea-pig isolated tracheal preparation to contract the muscles, and the effect of the above compounds to inhibit the contraction (%) was plotted along the ordinate on each of the points for concentration which were connected by a solid line into a curve. Then, the dose-response curve for the compound in the presence of propranolol (2.5×10 -5 M) was obtained and plotted in a dotted line. In the figures, there is no substantial difference between the solid line curve and dotted line curve. This shows that the compounds of the present invention scarcely has a stimulating action on β-adrenoceptor.
While on the hand, in FIG. 4 showing the effect of isoproterenol which is considered to have a typical β-adrenoceptor stimulating action, there is a significant difference between the solid line where the isoproterenol is used alone and the dotted line where the isoproterenol is used together with propranolol. This shows that isoproterenol has a marked stimulating action on β-adrenoceptor.
From the foregoing experimental results, it has been found that the bronchodilator action of the compounds according to the present invention is developed, different from isoproterenol, not due to stimulating action on β-adrenoceptor but based on other mechanism of action.
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Novel α-methyl-β-aminopropiophenone derivatives having bronchodilator activity represented by the following general formula: ##STR1## where R represents alkyl having 1-6 carbon atom benzyl or phenyl; R 1 and R 2 individually represent alkyl having 1-6 carbon atom or they form, joining to each other together with the adjacent nitrogen atom with or without intervening an atom other than carbon atom, a saturated heterocyclic ring which may be substituted with lower alkyl; n is an integer of 0, 1 or 2 on the proviso that R represents methyl or ethyl if n is 0, as well as their non-toxic salts are presented. Method of producing the new derivatives and the bronchodilatation method using them are disclosed as well.
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This is a division of application Ser. No. 264,543, filed Oct. 31, 1988 now U.S. Pat. No. 4,916,250.
BACKGROUND OF THE INVENTION
The present invention relates to novel phosphonates which can be employed as precursors to a variety of biologically-active materials; including 13-cis retinoic acid (accutane), retin-A and beta carotene. The phosphonates of the present invention can be synthesized by the reaction of a cyclohexenyl-group-containing C-14 through C-16 aldehyde, such as 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, with a phosphonic acid ester, such as methylenebisphosphonic acid, tetraethyl ester.
A procedure for producing vitamin A acetate from beta-ionone has been described by Reif and Grassner [Chemie-Ing. Techn., 45, 646-652 (1973)]: ##STR2##
Similarly, Pommer and Kuhn [Angew.Chem., 72, 911 (1960)] have described a procedure for preparing beta-carotene from the same beta-ionone-derived triphenylphosphonium salt: ##STR3## formed in the course of the Reif et al., synthesis. The disadvantages of these procedures include the fact that the triphenylphosphine reactant required for the syntheses is relatively expensive and that the byproduct of the reactions, pH 3 PO, is not water soluble, thus making it difficult to isolate the desired product.
Surmatis and Thommen have described a process for preparing beta-carotene utilizing a phosphonate in a Wittig-type reaction [J. Org. Chem., 34, 559 (1969)]. As essential step of this procedure involves the reaction of a C-20 dibromo compound with a trialkyl phosphite: ##STR4##
Although the C-20 dibromo compound of Surmatis et al. can be reacted with trialkyl phosphites, the literature does not report similar reactions for structurally related C-15 halides. Indeed, the literature shows that the compound 1-bromo-3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadiene ##STR5## is not stable at room temperature. (Bull. Soc. Chim. Fr., Part II, 746-750 (1973)].
Other procedures for preparing retinoid intermediates and beta-carotene are shown in the prior art, e.g., Babler U.S. Pat. No. 4,175,204; F. Frickel, "The Retinoids", edited by M. B. Sporn, A. B. Roberts and D. S. Goodman, Academic Press (Orlando, Fla., 1984), pp. 77-145; and R. S. H. Liu and A. E. Asato, Tetrahedron, 40, 1931-1969 (1984).
SUMMARY OF THE INVENTION
The novel phosphonate compounds of the present invention have the structural formula: ##STR6## in which R is an alkyl group having up to four carbon atoms, and R 1 is a 3-alkyl pentadienyl group wherein the alkyl group at the 3 position is methyl, ethyl or propyl. The two double bonds in the 3-alkyl pentadientyl group, R 1 , can be in the 1,3 or 2,4 positions (conjugated) or in the 1,4 positions (non-conjugated).
The compounds of the present invention are systematically named as esters of an alkenylphosphonic acid. Thus, for example, when R 1 is: ##STR7## and R is ethyl, the compound is named 3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienylphosphonic acid, diethyl ester. When R 1 is: ##STR8## and R is isopropyl, the compound is named 3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,4-pentadienylphosphonic acid, diisopropyl ester.
Other compounds within the scope of the present invention include:
3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3-pentadienylphosphonic acid, diethyl ester;
3-ethyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienylphosphonic acid, diethyl ester;
3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienylphosphonic acid, dimethyl ester;
3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienylphosphonic acid, dipropyl ester;
3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienylphosphonic acid, dibutyl ester;
3-propyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3-pentadienylphosphonic acid, diethyl ester; and
3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienylphosphonic acid, diisopropyl ester.
Because of their ability to form known biologically-active compounds, dialkyl esters of 3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienylphosphonic acid, are especially preferred.
The compounds of the present invention can be formed by the base-promoted reaction of a C-14 through C-16 aldehyde having the structure ##STR9## wherein R 2 is ##STR10## and R 3 is methyl, ethyl or propyl, with a methylenebisphosphonic acid ester having the structure: ##STR11## wherein each R, which can be the same or different, is selected from the class consisting of alkyl groups having up to four carbon atoms. The preferred aldehydes are C-14 materials which are derived from beta-ionone. At room temperature, reaction of the aldehyde and bisphosphonate ester proceeds rapidly (<30 minutes) in an organic solvent containing one equivalent of a base (e.g., a Group I metal alkoxide or sodium hydride): ##STR12## wherein R 1 is a 3-methyl pentadienyl group, as defined above, and R is a C-1 to C-4 alkyl group. The phosphonate ester product is soluble in a variety of organic solvents and can be isolated from the reaction mixture by conventional techniques. Yields are typically in excess of 90%.
A variety of organic solvents, both polar and nonpolar, can be employed in the foregoing reaction, including hydrocarbons such as benzene, hexane, cyclohexane, and toluene; ethers such as tetrahydrofuran and diethyl ether; ethyl alcohol; polar solvents such as dimethylformamide and dimethyl sulfoxide; or mixtures of such organic solvents. Suitable bases include sodium hydride, Group I metal alkoxides, and alkali metal carbonates.
As noted previously, the double bonds in the pentadienyl moiety can be in the 1,3-; 1,4- or 2,4-positions. The 1,3- and 1,4-compounds can be isomerized to the preferred 2,4-pentadienyl phosphonates by employing a base catalyst such as an alkoxide of a Group I metal, i.e., KOC(CH 3 ) 3 , NaOCH 3 , or NaOCH 2 CH 3 with an organic solvent such as dimethyl sulfoxide (DMSO). ##STR13##
In general, any organic solvent in which the reactants are soluble may be employed in the practice of the above two steps (i.e., preparation of the phosphonate ester and its subsequent isomerization). Any base whose conjugate acid has a pK 2 of approximately 8 or above can be utilized to promote these reactions.
The aldehyde reactant [e.g., 2-methyl-4-(2', 6'6'-trimethyl-1'-cyclohexen-1'-yl)-3-butenal] used to synthesize the phosphonate esters can be prepared in accordance with known procedures. Processes for synthesizing such aldehyde from beta-ionone are shown, for example, in O. Isler, et al., Helv. Chim. Acta., 30, 1911 (1947); V. Ramamurthy, et al., Tetrahedron, 31, 193 (1975); or M. Rosenberger, et al., Helv. Chim. Acta, 63, 1665 (1980).
The methylenebisphosphonic acid ester reactant can be prepared by reacting methylene bromide with a trialkyl phosphite [P(OR) 3 ] in accordance with the procedure shown in B. Costisella, J. fur prakt. Chemie, 324, 537 (1982), e.g., ##STR14## methylenebisphosphonic acid, tetraisopropyl ester, 73% yield.
The compounds of the present invention can be used in the synthesis of retinoids or beta-carotene. Illustrative examples of three such syntheses employing the novel phosphonate compounds are as follows: ##STR15##
DETAILED DESCRIPTION OF THE INVENTION
The following examples illustrate in greater detail the practice of the present invention, specifically: (i) the preparation of intermediates which can be utilized to form the phosphonate compounds of the present invention (Examples I-V); (ii) the preparation of representative novel phosphonate compounds (Examples VI-XI); (iii) the preparation of intermediates which can be reacted with the compounds of the present invention to form biologically-active materials (Examples XII-XIV); and, (iv) the preparation of biologically-active compounds utilizing the novel phosphonate compounds of the invention (Examples XV-XVII).
EXAMPLE I
Preparation of Methylenebisphosphonic Acid, Tetraethyl Ester
In accordance with a procedure suggested by H. Gross, et al., Journal fur prakt. Chemie, 324, 537 (1982), a mixture of 4.00 ml (57.0 mmoles) of dibromomethane and 30 mL (175 mmoles) of triethyl phosphite was gradually warmed to 90° C. over a period of 15 minutes. After maintaining the temperature at 90° C. for an additional 10 minutes, the solution was warmed to 140° C. and kept at that temperature for 2 hours. At that point, the mixture was warmed to 160° C. (external bath temperature) and heated at that temperature for an additional 15 hours, during which time ethyl bromide was slowly distilled out of the reaction mixture. Next, excess triethyl phosphite was distilled from the reaction flask, followed by distillative removal of minor amounts of ethylphosphonic acid, diethyl ester. The desired product was then obtained by distillation under reduced pressure, affording 9.03 g (55% yield) of bisphosphonate; bp 145°-160° C. (bath temperature, 0.25 mm). H. Gross, et al., reported a 70% yield of the same compound, prepared on a larger scale (150 mmoles of dibromomethane).
EXAMPLE II
Preparation of Methylenebisphosphonic Acid, Tetraisopropyl Ester
A mixture of 1.00 ml (14.25 mmoles) of dibromomethane and 11.0 mL (44.5 mmoles) of triisopropyl phosphite was heated in the same manner as described in the procedure of Example I. Removal of excess triisopropyl phosphite, followed by a minor amount of isopropylphosphonic acid, diisopropyl ester, by distillation at reduced pressure, and subsequent evaporative distillation [bath temperature: 138°-152° C. (0.25 mm)] afforded 3,57 g (73% yield) of the desired bisphosphonate.
EXAMPLE III
Preparation of 2-Methyl-2-[2-(2,6,6-trimethyl-1-cyclohexen-1-yl)ethenyl]oxirane
A mixture of 762 mg (19.1 mmoles) of sodium hydride (60% dispersion in mineral oil, which are removed by washing with hexane prior to the addition of DMSO) and 6.0 mL of anhydrous dimethyl sulfoxide (DMSO) was heated, protected from atmospheric moisture, at a bath temperature of 65° C. for approximately 45 minutes--until evolution of hydrogen had ceased. After cooling this mixture to room temperature, it was added dropwise over a period of 10 minutes to a stirred slurry of 3.95 g (19.38 mmoles) of trimethylsulfonium iodide in 12.0 mL of 1:1 (v/v) anhydrous DMSO: tetrahydrofuran, protected from atmospheric moisture and kept cold in an ice-brine bath at approximately -5° C. The resulting gray suspension was stirred for an additional 5 minutes, after which a solution of 1.42 g (7.38 mmoles) of betaionone in 3.00 mL of anhydrous tetrahydrofuran was added dropwise rapidly. This mixture was subsequently stirred at approximately 0° C. for 2 hours, after which it was allowed to warm to room temperature. The product was isolated, after addition of 1 mL of water to quench the reaction, by dilution of the mixture with 50 mL of pentane and 100 mL of 10% aqueous sodium chloride. Separation of the layers was followed by washing the organic layer with 10% aqueous sodium chloride (2×100 mL), water (1×100 mL), and saturated brine (1×100 mL) in successive order. The organic extracts were then dried over anhydrous sodium sulfate and subsequently filtered. Removal of the pentane and tetrahydrofuran by evaporation at reduced pressure afforded 1.52 g (100% yield) of the desired epoxide.
EXAMPLE IV
Preparation of 2-Methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-butenal
A solution of 1.502 g (7.28 mmoles) of the epoxide, prepared as described in Example III, in 6.00 mL of anhydrous ether was added dropwise over 5 minutes to a stirred suspension of magnesium bromide [prepared in situ from 355 mg (1.88 mmoles) of 1,2-dibromoethane and 48 mg (1.98 milli-g-atoms) of magnesium turnings] in 3.00 mL of anhydrous ether, protected from atmospheric moisture, at -10° C. The resulting mixture was stirred at -10° C. for an addition 5 minutes, after which it was diluted with 20 mL of solvent ether. The organic layer was washed in successive order with 15 mL portions of water and saturated brine, after which it was dried over anhydrous sodium sulfate and subsequently filtered. Removal of the ether by evaporation at reduced pressure afforded 1.40 g (93% yield) of the desired aldehyde, whose structure was verified by NMR analysis [δ 9.69, doublet, J=1.8 Hz, CHO; δ 1.25, doublet, J=7 Hz, CHCH 3 ]. The procedure used in Examples III and IV was developed by M. Rosenberger, et al. [Helv. Chim. Acta, 63, 1665 (1980)]. An alternate route to this same aldehyde can be found in O. Isler, et al., Helv. Chim. Acta. 30, 1911 (1947), subsequently modified by R. S. H. Liu, et al., Tetrahedron, 31, 193 (1975).
EXAMPLE V
Preparation of 2-Methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal
A mixture of 920 mg (4.46 mmoles) of the aldehyde prepared as described in Example IV and 45 mg of potassium hydroxide pellets in 3.0 mL of methyl alcohol containing 0.05 mL of water was stirred, protected from atmospheric moisture, at 20° C. for 35 minutes. The product was isolated after dilution of the mixture with 30 mL of 1:1 (v/v) pentane: ether and subsequent washing of the organic layer with 25 mL portions of 10% aqueous sodium chloride and saturated brine. Drying of the organic extracts over anhydrous magnesium sulfate, followed by filtration and removal of the pentane and ether at reduced pressure, afforded 916 mg (99.6% yield) of the isomerized aldehyde, whose structural identity was confirmed by NMR analysis (δ 9.45, singlet, CHO).
EXAMPLE VI
Preparation of 3-Methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3-pentadienylphosphonic acid, Diethyl Ester
A solution of 508 mg (1.76 mmoles) of methylenebisphosphonic acid, tetraethyl ester, prepared as described in Example I, in 2.5 mL of benzene and 1.5 mL of anhydrous tetrahydrofuran (THF) was added dropwise slowly over 5 minutes to a stirred mixture of 69 mg (1.7 mmoles) of sodium hydride (60% dispersion in mineral oil, which was removed prior to the reaction by washing with hexane) and 1.0 mL of benzene, protected from atomspheric moisture and maintained at a temperature of 15°-20° C. by use of an external cold water bath. This mixture was stirred for an additional 15 minutes, after which a solution of 208 mg (1.01 mmole) of aldehyde (prepared as described in Example V) in 2.5 mL of benzene was added dropwise rapidly. After stirring this mixture at room temperature for 25 minutes, it was diluted with 20 mL of 1:1 (v/v) pentane:ether and washed in successive order with 7:3 (v/v) 1M aqueous sodium hydroxide:methyl alcohol (2×40 mL) to remove excess bisphosphonate and then with saturated brine (20 mL). The organic layer was then dried over anhydrous magnesium sulfate and subsequently filtered. Removal of the pentane, ether, and benzene by evaporation at reduced pressure afforded 320 mg (93% yield) of the desired vinyl phosphonate.
EXAMPLE VII
Preparation of 1,3-Methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-pentadienylphosphonic Acid, Diisopropyl Ester
The ylide was prepared in the manner described in the procedure of Example VI by reaction of 605 mg (1.76 mmoles) of methylenebisphosphonic acid, tetraisopropyl ester (produced in accordance with Example II), with 69 mg (1.7 mmoles) of 60% sodium hydride. Subsequent addition of 195 mg (0.95 mmole) of the unsaturated aldehyde produced in accordance with Example V and stirring of the mixture at 20° C. for 25 minutes completed the reaction. The product was isolated after dilution of the mixture with 20 mL of 1:1 (v/v) pentane:ether and washing in successive order with 1:1 (v/v) 1M aqueous sodium hydroxide:methyl alcohol (2×40 mL) to remove excess bisphphosphonate and then with saturated brine (20 mL). The organic layer was then dried over anhydrous magnesium sulfate and subsequently filtered. Removal of the pentane, ether, and benzene by evaporation at reduced pressure afforded 313 mg (90% yield) of the desired vinyl phosphonate.
EXAMPLE VIII
Preparation of 3-Methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,4-pentadienylphosphonic Acid, Diethyl Ester
The reaction was conducted in the manner described in the procedure of Example VI using the following reagents: 2.96 g (10.25 mmoles) of methylenebisphosphonic acid, tetraethyl ester (produced in accordance with Example I), in 20 mL of 3:2 (v/v) benzene:anhydrous tetrahydrofuran; 413 mg (10.3 mmoles) of 60% sodium hydride in 8.0 mL of benzene; and 1.204 g (5.85 mmoles) of unsaturated aldehyde (produced in accordance with Example IV) in 12.0 mL of benzene. Isolation of the product as described in the procedure of Example VI afforded 1.901 g (95.5% yield) of the desired vinyl phosphonate.
EXAMPLE IX
Preparation of 3-Methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,4-pentadienylphosphonic Acid, Diisopropyl Ester
The reaction was conducted in the manner described in the procedure of Example VII using the following reagents: 303 mg (0.88 mmole) of methylenebisphosphonic acid, tetraisopropyl ester (produced in accordance with Example II), in 2.5 mL of 3:2 (v/v) benzene:anhydrous tetrahydrofuran; 36 mg (0.9 mmoles) of 60% sodium hydride in 1.0 mL of benzene; and 98 mg (0.47 mmole) of unsaturated aldehyde (produced in accordance with Example IV) in 1.5 mL of benzene. Isolation of the product as described in the procedure of Example VII afforded 104 mg (60% yield) of the desired vinyl phosphonate.
EXAMPLE X
Preparation of 3-Methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienylphosphonic Acid, Diethyl Ester
A mixture of the vinyl phosphonate produced in accordance with Example VIII (943 mg, 2.77 mmoles) and 99 mg (0.88 mmoles) of potassium tert-butoxide in 12 mL of anhydrous dimethyl sulfoxide (DMSO) was stirred, protected from atmospheric moisture, at 20° C. for 80 minutes. The product was isolated by dilution of the reaction mixture with 100 mL of ether and subsequent washing with 120 mL portions of 10% aqueous sodium chloride (4×120 mL). The organic layer was then dried over anhydrous magnesium sulfate and filtered. Removal of the ether by evaporation at reduced pressure afforded 718 mg (76% yield) of the desired allylic phosphonate, whose structural integrity was confirmed by NMR analysis [δ 2.75, doublet of doublets, J=8 Hz and 22 Hz, CH 2 P]. In a similar manner, this allylic phosphonate could be prepared by isomerization of 3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,3-pentadienylphosphonic acid, diethyl ester, produced in accordance with Example VI.
EXAMPLE XI
Preparation of 3-Methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienylphosphonic Acid, Diisopropyl Ester
A mixture of vinyl phosphonate produced in accordance with Example VII (308 mg, 0.84 mmole) and 88 mg. (0.78 mmole) of potassium tert-butoxide in 4 mL of anhydrous dimethyl sulfoxide was stirred, protected from atmospheric moisture, at 20° C. for 30 minutes. Isolation of the product in the manner described in the procedure of Example X afforded 238 mg (77% yield) of the desired allylic phosphonate. This latter compound could also be prepared by isomerization of 3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,4-pentadienylphosphonic acid, diisopropyl ester, produced in accordance with Example IX.
EXAMPLE XII
Preparation of 2-Butenyl-1,4-bisphosphonic Acid, Tetraethyl Ester
A solution of 2.00 mL (18.9 mmoles) of trans-1,4-dichloro-2-butene in 3.00 mL (17.5 mmoles) of triethyl phosphite was added dropwise slowly over 25 minutes to a flask containing 5.00 mL (29.2 mmoles) of triethyl phosphite, maintained at a temperature of approximately 140° C. (external oil bath temperature). This mixture was subsequently heated at 140° C. for an additional 12 hours, during which time ethyl chloride was continously distilled out of the reaction flask. At that point, the external oil bath temperature was raised to 180° C. to distill over as much of the remaining triethyl phosphite as possible. The desired product was then obtained by fractional distillation under reduced pressure, affording 5.40 g (87.5% yield) of bisphosphonate: bp 161°-184° C. (bath temperature, 0.25 mm).
EXAMPLE XIII
Preparation of 1,1,8,8-Tetramethoxy-2,7-dimethyl-2,4,6-octatriene
To a solution of 312 mg (0.95 mmole) of 2-butenyl-1,4-bisphosphonic acid, tetraethyl ester (produced in accordance with Example XII), and 0.25 mL (2.07 mmoles) of pyruvic aldehyde dimethyl acetal (available from Aldrich Chemical Co.) in 3.25 mL of 12:1 (v/v) anhydrous tetrahydrofuran:dimethyl sulfoxide, protected from atmospheric moisture and maintained at a temperature of approximately 5° C. by use of an external ice water bath, was added 211 mg (1.88 mmoles) of potassium tert-butoxide. This mixture was subsequently stirred in the cold for 15 minutes and then at room temperature for 7 hours. The product was isolated by dilution of the mixture with 30 mL of 1:1 (v/v) ether:pentane and subsequent washing of the organic layer with 10% aqueous sodium chloride (3×30 ml). The organic layer was then dried over anhydrous sodium sulfate and filtered. Removal of the volatile organic solvents by evaporation at reduced pressure afforded 151 mg (62% yield) of bisacetal.
EXAMPLE XIV
Preparation of 2,7-Dimethyl-2,4,6-octatrienedial
A solution of 150 mg (0.585 mmole) of 1,1,8,8-tetramethoxy-2,7-dimethyl-2,4,6-octatriene, produced in accordance with Example XIII, in 3.5 mL of 4:2:1 (v/v/v) glacial acetic acid:tetrahydrofuran:water was heated at 45° C. (external oil bath temperature) for 3 hours. After cooling the solution to room temperature, the product was isolated by dilution of the mixture with 25 mL of 4:1 (v/v) ether:dichloromethane and washing the organic layer in successive order with saturated brine (2×25 mL), 4:1 (v/v) saturated brine: 1M aqueous sodium hydroxide (2×25 mL), and saturated brine (25 mL). The organic layer was then dried over anhydrous magnesium sulfate and filtered. Removal of the volatile organic solvents by evaporation at reduced pressure afforded 86 mg (90% yield) of the desired bisaldehyde, previously prepared in a similar manner by H. Pommer, et al., Angew. Chem., 72, 911 (1960).
EXAMPLE XV
Preparation of Beta-Carotene
To a solution of 192 mg (0.564 mmole) of 3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienylphosphonic acid, diethyl ester (produced in accordance with Example X) and 41 mg (0.25 mmole) of 2,7-dimethyl-2,4,6-octatrienedial (produced in accordance with Example XIV) in 2.25 mL of 8:1 (v/v) anhydrous tetrahydrofuran:dimethyl sulfoxide, protected from atmospheric moisture and maintained at a temperature of approximately 5° C. by use of an external ice water bath, was added 59 mg (0.526 mmole) of potassium tert-butoxide. This mixture was subsequently stirred in the cold for 15 minutes and then at room temperature for 3.5 hours. The product was isolated by dilution of the mixture with 25 mL of 4:1 (v/v) ether:dichloromethane and subsequent washing of the organic layer with 25 mL portion of 10% aqueous sodium chloride (3×25 mL). The organic layer was then dried over anhydrous magnesium sulfate and filtered. Removal of the volatile organic solvents by evaporation at reduced pressure, followed by filtration through a small column of silica gel (10 mL, 60-200 mesh, elution with 40 mL of 3:1 (v/v) hexane:benzene) to remove any unreacted starting materials afforded 82 mg (61% yield) of deep-purple crystals, identified by NMR analysis as beta-carotene: mp 183°-185° C.
EXAMPLE XVI
Preparation of all-trans Retinoic Acid, Ethyl Ester
To a solution of 57 mg (0.40 mmole) of ethyl 3-methyl-4-oxobutenoate [prepared according to a procedure described by R. W. Curley, Jr., et al., J. Org. Chem., 51, 256 (1986); an alternate synthesis has been described by A. Guingant, et al., J. Org. Chem., 52, 4788 (1987); the compound is commercially available from Fluka Chemical Corp., Ron Kon Koma, N.Y. 11779.] and 132 mg (0.388 mmole) of 3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienylphosphonic acid diethyl ester (produced in accordance with Example X) in 3.5 mL of 6:1 (v/v) anhydrous tetrahydrofuran:dimethyl sulfoxide, protected from atmospheric moisture and maintained at a temperature of approximately 5° C. by use of an ice water bath, was added 43 mg (0.38 mmole) of potassium tert-butoxide. This mixture was subsequently stirred in the cold for 10 minutes and then at room temperature for 6 hours. The product was isolated by dilution of the mixture with 30 mL of 1:1 (v/v) pentane:ether and subsequent washing of the organic layer with 30 mL portions of 10% aqueous sodium chloride (3×30 mL). The organic layer was then dried over anhydrous magnesium sulfate and filtered. Removal of the volatile organic solvents by evaporation at reduced pressure, followed by filtration through a small column of silica gel (15 mL, 60-200 mesh, elution with 75 mL of hexane--4% ether) to remove any unreacted starting materials, afforded 76 mg (61% yield) of ethyl retinoate shown by high-field (300 MHz) NMR analysis to be predominantly the all trans stereoisomer. The product was characterized by three broad singlets of equal intensity at δ 2.37, 2.02, and 1.73 (3 vinyl methyls). For tables listing spectroscopic properties of retinoids, see: R. S. H. Liu, et al. Tetrahedron, 40, 1931-1969 (1984). Ethyl retinoate was also prepared in a similar manner from ethyl 3-methyl-4-oxobutenoate and 3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienylphosphonic acid diisopropyl ester (produced in accordance with Example XI).
EXAMPLE XVII
Preparation of 13-cis-Retinoic Acid
To a solution of 88 mg (0.258 mmole) of 3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienylphosphonic acid diethyl ester (produced in accordance with Example X) and 37 mg (0.324 mmole) of 5-hydroxy-4-methyl-2-(5H) furanone [prepared according to a procedure described by G. Pattenden, et al., J. Chem. Soc.(C), 1984 (1968). An alternate synthesis has been described by C. G. Wermuth, et al., J. Org. Chem., 46, 4889 (1981).] in 2.25 mL of 8:1 (v/v) anhydrous tetrahydrofuran:dimethyl sulfoxide, protected from atmospheric moisture and maintained at a temperature of approximately 5° C. by use of an ice water bath, was added 64 mg (0.57 mmole) of potassium tert-butoxide. This mixture was subsequently stirred in the cold for 15 minutes and then at room temperature for 3.5 hours. After acidifying the mixture by addition of 0.50 mL of 2M aqueous hydrochloric acid, it was diluted with 25 mL of 4:1 (v/v) ether:dichloromethane. The organic layer was washed in successive order with 10% aqueous sodium chloride (2×25 mL), water (1×25 mL), and saturated brine (1×25 mL), dried over anhydrous magnesium sulfate, and filtered. Removal of the volatile organic solvents by evaporation at reduced pressure, followed by filtration through a small column of silica gel (6 mL, 40-140 mesh, elution with 25 mL of pentane--20% ether) to remove any unreacted phosphonate afforded 44 mg (57% yield) of orange crystals, shown by NMR analysis (in CDCl 3 solution) to be a mixture of stereoisomers. The predominate stereoisomer (comprising approximately 75-80% of the mixture) was characterized by a doublet (J=15 Hz) at δ 7.81 (vinyl hydrogen bonded to C-12), a broad singlet at δ 5.68 (vinyl hydrogen bonded to C-14), and a broad singlet at δ 2.11 (CH 3 bonded to C-13). By comparison with the NMR data reported (in "tau values", where "tau"=10-δ) for various stereoisomers of retinoic acid by Pattenden, et al., [J. Chem. Soc., C., 1984-1997 (1968)], this major component was shown to be 13-cis-retinoic acid. The other (minor) component in the product exhibited broad singlets at δ 5.82 (vinyl hydrogen bonded to C-14) and δ 2.37 (CH 3 bonded to C-13), absorptions characteristic of all-trans retinoic acid.
Although the foregoing invention has been described in some detail by way of example, various changes and modifications to the specific procedures which have been illustrated may be practiced within the scope of the appended claims.
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Processes for synthesizing novel phosphonate diester compounds of the general formula ##STR1## are disclosed and claimed. The claimed process includes forming a reaction mixture of a C-14 aldehyde and a methylene-bis-phosphonic acid ester, separating a pentadienyl phosphonic acid dialkyl ester intermediate from the reaction mixture, optionally isomerizing the intermediate in the presence of a basic catalyst, and isolating the desired pentadienylphosphonic acid dialkyl ester compound. The isolated phosphonate compounds made according to the processes of the present invention may be employed in synthesizing retinoids such as retinoic acid or carotenoids such as beta-carotene.
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FIELD OF THE INVENTION
[0001] This invention relates to a drive coupling for the connection of a load device to a rotating shaft while allowing for the ready disconnection of the load device.
DESCRIPTION OF THE PRIOR ART
[0002] Throughout this description and the claims which follow, unless the context requires otherwise, the word “comprise’, or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated integer or step or group of integers or steps.
[0003] The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement or any form of suggestion that that prior art forms part of the common general knowledge in Australia.
[0004] The requirement to connect a driven device to a shaft providing motive power is a situation arising in many appliances and industrial applications. The shaft providing motive power will generally be the output shaft of an electric motor, but may be another intermediate driven shaft as will be the case in many industrial applications. The nature of the driven device can vary widely. The device may be a fan or pump to be connected to a motor shaft. Another familiar application is the connection of a wheel to a hub shaft as in automotive applications. In industrial applications, the coupling device may be required as an intermediate part in a complex drive train and may simply connect a driven shaft to a driving shaft.
[0005] Many devices have been developed over time to fulfil this function. U.S. Pat. No. 4,338,036 describes a tapered bushing and hub assembly, in which a tapered, split bush is inserted in a tapered bore. Threaded fasteners force the bushing inwardly to the tapered bore.
[0006] U.S. Pat. No. 4,944,562 describes an adapter for a wire wheel hub as used on an automobile. In this instance, the wheel is secured to the adapter by a separate spinning nut to the threaded hub, with torque transmitted through splines formed on the hub.
SUMMARY OF THE INVENTION
[0007] In accordance with one aspect, the present invention provides a single piece coupling device for connecting a load component to a rotatable shaft, said device comprising a sleeve having a bore for containing a rotatable shaft, an externally threaded portion and a tapered engagement face on the outer surface of the sleeve, radial compression relief means associated with the tapered engagement face, such that when the device is fitted on a shaft and as the threaded portion engages with a corresponding threaded region on the load component the tapered engagement face engages the load component and the compression relief means enables the sleeve to be radially compressed to grip the shaft.
[0008] In a preferred form the coupling device comprises an engagement projection within the bore of the sleeve adapted to mate with a complementary recess on a shaft to be gripped by the device. The projection functions to restrain relative longitudinal displacement between the device and a shaft when mounted on the shaft.
[0009] In a further preferred form the bore of the sleeve of the coupling device is shaped to transmit torque when fitted on a shaft.
[0010] Preferably, the compression relief means is formed by at least one longitudinal slotted region in the sleeve wall adjacent the tapered engagement face.
[0011] It has been discovered that when a device in accordance with the broadest aspect of this invention is used in applications in which one or both of the components of the sleeve or the load component are thermally cycled, that it is possible for the action of the engaged threaded portions with the tapered engagement face to become progressively tighter with each complete cycle of heating and cooling of a component. Each cycle of temperature thereby results in an increase in load on the components, and an increase in stress in the parts of the components subjected to this load. If this thermal and operational cycling is allowed to continue, then eventually one of the components of the thread engagement between the sleeve and load components will fail due to excessive stress, these components being subjected to the highest stress during operation.
[0012] The eventual failure of the threaded portions of the sleeve or load component can be prevented if the progressive movement of the threaded portions is limited to a degree whereby the stresses in the material of either component does not exceed the maximum allowable working stress recommended by the material manufacturer.
[0013] If the component parts of the sleeve and load component are normally manufactured using an injection moulding process from polymer material, the geometric relationships between the respective components when in threaded engagement will always be the same. These geometric relationships are determined by the geometry of the injection moulding tools used in their manufacture, and hence each individual part manufactured will be identical. The repeatability of manufacture of components presents an opportunity to fix the allowable extent of movement of the threaded engagement of the respective components by arranging for a physical constraint to prevent movement beyond which maximum allowable stresses in the material would be exceeded.
[0014] This further aspect provides a mechanism whereby the progressive movement of the threaded portions is limited to the extent that maximum allowable stresses are not exceeded.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The present invention will now be described by way of example with reference to the accompanying drawings, in which:
[0016] [0016]FIG. 1 is a series of plan and sectioned views of a shaft drive coupling in accordance with an embodiment of the present invention;
[0017] [0017]FIG. 2 is a longitudinal section view of an embodiment of an engagement part of a load device to be fitted by the coupling of FIG. 1;
[0018] [0018]FIG. 3 is the view of FIG. 2 showing engagement of the load device on the shaft drive coupling of FIG. 1;
[0019] [0019]FIG. 4 an isometric perspective of another embodiment of a sleeve of the coupling device in accordance with the first aspect of the present invention;
[0020] [0020]FIG. 5 is an isometric view of a modified form of the embodiment of FIG. 4 incorporating projections that have been added to provide engagement of the modified flange portions of the sleeve of the coupling device of FIG. 4; and
[0021] [0021]FIG. 6 is a perspective view of a load component, in the form of a fan, incorporating additional projections that have been added to provide for engagement with the modified flange portions of the sleeve of the coupling device of FIG. 5.
DESCRIPTION OF EMBODIMENTS
[0022] [0022]FIG. 1 shows a shaft drive coupling device 30 which is adapted to be fitted over a driving shaft 40 (partly shown in section A-A). The shaft drive coupling of this embodiment comprises a single component which has the features of a coarse, fast lead male thread 10 , a tapered engagement 11 , slotted relief 12 , a “D” shaped bore 14 and an engagement projection 13 . The male thread 10 may be left or right handed according to the direction of rotation of the driving and driven devices.
[0023] [0023]FIG. 2 shows a part section of driven device 20 . The features on the driven device required for operation of the shaft drive coupling are a formed female thread 15 within the bore 17 , and an engagement face 16 .
[0024] [0024]FIG. 3 shows the shaft drive coupling 30 with the driven device 20 in the normal operating position. In this position, the female thread 15 of the driven device is engaged fully with the male thread 10 of the shaft drive coupling 30 , while simultaneously the engagement face 16 of the driven load device 20 is frictionally engaged with the tapered engagement face 11 of the shaft drive coupling 30 .
[0025] The shaft drive coupling 30 is preferably manufactured as a single component, such as by plastic injection moulding, although other manufacturing techniques such as machining from solid, or metal casting could be used. The shaft drive coupling 30 is preferably fitted to a driving shaft 40 which has had a flat machined on the surface, making a section of the shaft appear as a “D” shape, shown as 14 in Section B-B of FIG. 1. The interference of the “D” shaped shaft on the bore of the drive shaft coupling provides the necessary torque resistance to drive the driven load device. It will be appreciated by those skilled in the art that the outside diameter of the shaft and corresponding bore of the shaft drive coupling could have many shapes which provide the necessary torque resistance without detracting from the operation of embodiments of the invention. One such shape could, for example, be longitudinal splines on both the shaft and coupling.
[0026] In operation, the shaft drive coupling 30 is slid along a driving shaft 40 , after correct alignment of the “D” shape interference in the preferred embodiment. The coupling is engaged on the shaft 40 until the projection 13 on the bore of the drive shaft coupling shown in Section A-A of FIG. 1 engages with a corresponding depression (not shown) in the driving shaft 40 . The slots 12 in the drive shaft coupling enable that end of the coupling to readily flex open while the coupling is slipped along the shaft, thereby allowing the projection 13 to be deflected away from the shaft until the projection 13 is adjacent to the corresponding shaft depression.
[0027] The load device 20 is then slipped over the shaft drive coupling until the female thread form 15 of the load device engages on the male thread form 10 of the shaft drive coupling. The load device 20 is then rotated in a direction in which the engaging threads drive the driven device to a position where the engagement taper 11 of the drive shaft coupling engages the engagement face 16 of the load device. Further relative rotation of the load device 20 on the shaft coupling causes additional loading on the tapered engagement of face 11 with face 16 , with consequent squeezing of the shaft coupling bore towards the driving shaft. The slots 12 in the shaft drive coupling in the vicinity of tapered face 11 allow the bore of the shaft coupling to be readily crushed towards the driving shaft, thereby firmly engaging the “D” shape and ensuring drive torque resistance. Furthermore, thc crush of the drive shaft coupling onto the driving shaft ensures that the projection 13 engaged in a corresponding depression on the shaft cannot disengage, thus resisting any possible longitudinal movement of the drive shaft coupling along the shaft.
[0028] In the preferred embodiment, the female thread 15 formed within the load device is formed with less than 360 degrees of thread, such as to allow the thread to be formed as part of an injection moulding which can be removed from the moulding tool without the need to unscrew the thread.
[0029] When the drive is started, the rotational inertia of the driven device results in further tightening of the threaded engagement, and hence further locking of the coupling to the driving shaft. Since starting torque for most driven loads is generally much larger than the torque in the opposite direction when the drive is turned off, the overall tendency of the shaft coupling and load combination is to keep the engaged threads 10 , 15 tight. By careful selection of the pitch of the engaging threads and the angle of the tapered face 11 , the mechanism will lock light on the first starting of the drive and have no tendency to disengage while slowing down.
[0030] A practical example of the application of an embodiment of the invention is in the fitting of an axial flow fan to the shaft of an electric motor in this application, the shaft of the motor is machined with a flat along the shaft, and a depression or dimple located at a suitable position on the shaft. The drive shaft coupling is slipped over the driving shaft until the projection 13 engaged in the depression on the shaft. The fan, corresponding to load device 20 in FIGS. 2 and 3, is then slipped over the shaft coupling, and rotated until the tapered face of the shaft coupling engaged on the engaging face, corresponding to face 16 in FIGS. 2 and 3, of the fan. In operation, the motor only turns in one direction, such direction keeping the threaded engagement of the fan on the coupling constantly tight. The shaft coupling keeps the drive tight without any free clearance, accurately centres the fan hub, transmits all the required torque and power, and can be readily disassembled for maintenance and repair. For removal of the driven device from the shaft coupling, a hexagon shape 18 is provided on the end of the drive shaft coupling as shown in Section C-C of FIG. 1. To remove the load, a conventional spanner is applied to the hexagon end 18 of the shaft coupling while restraining the load device or the driven shaft. The threaded engagement is then readily released, and the entire mechanism removed from the shaft.
[0031] [0031]FIG. 5 shows a shaft drive coupling device with a modified flange detail. The flange 15 has been modified from the form as shown in the embodiment of FIGS. 1 - 3 and 4 by the addition of radial projections 19 which extend beyond the original boundary of the flange, and which are of such a shape as to provide for ready engagement onto a corresponding projection on the load device.
[0032] [0032]FIG. 6 shows a typical load device 40 . In the case of this illustration the load device is an injection moulded polymer fan. The internal detail of the load device moulding has raised projections 41 , shown enlarged at inset FIG. 6 a . The positions of raised projections 41 are such that when the projections 19 on the shaft drive coupling device engage on projections 41 , any further thread engagement movement between the thread 10 of the device 30 and the threaded portion of load device 40 is prevented. By analysis and experiment, the actual positions of projections 41 and projections 19 are arranged such that the restrained engagement position illustrated in FIG. 6 does not allow for stresses in either of the components of the shaft drive coupling device 30 or the load device 40 to exceed the maximum allowable stresses.
[0033] The shape of the projections on the shaft drive coupling device 30 and the load device 40 are arranged such that further movement of the thread engagement between the devices is restrained, without resulting in excessive stresses generated at or as a result of the engagement of the projections.
[0034] The embodiment of FIGS. 5 and 6 provides an inexpensive and effective means of restraining the threaded engagement of a shaft coupling device and a load component in such a way as to prevent stressing of components beyond maximum allowable stresses.
[0035] The present invention provides an inexpensive and effective means of coupling a driving shaft to a driven load in a single component, which is self locking once installed, yet can be readily removed using simple tools.
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A single piece coupling device for connecting a load component to a rotatable shaft. The device comprises a sleeve having a bore for containing a rotatable shaft, an externally threaded portion and a tapered engagement face on the outer surface of the sleeve. Radial compression relief associated with the tapered engagement face is provided such that when the device is fitted on a shaft, and as the threaded portion engages with a corresponding threaded region on the load component, the tapered engagement face engages the load component and the compression relief enables the sleeve to be radially compressed to grip the shaft.
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BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a new and useful protective envelope for storing a flexible disk cartridge for information processing systems.
Flexible disk cartridges are well known in the art and used extensively in computers and other information processing systems for storage of information signals. The disk itself on which information signals are stored is a circular device which has a magnetic coating on at least one side thereof. The disk is enclosed in a plastic jacket which includes an outer cover and a non-abrasive liner. Accordingly, a disk cartridge is an assembly of the jacket and the disk.
Because of the extensive use of flexible disk cartridges by the computer industry it was necessary that the general, physical and magnetic characteristics of the disk cartridge be standardized to allow interchangeability. Such standardization is evidenced by the regulations promulgated by the American National Standards Institute, Inc. (ANSI), such as those set forth in an ANSI X3.82-1980 report which relates to a 5.25 inch flexible disk cartridge.
It is very important that the flexible disk cartridges be treated with care to prevent inadvertent damage to the disk or non-reproducibility of the information stored thereon. These flexible disks are susceptible to extreme temperature conditions, exposure to magnetic fields or static electricity, dust and dirt and are sensitive to pressure caused by, for example, a writing instrument. Exposure to such conditions may adversely affect the operation of the disk cartridge and the reproducibility of the stored information. For these reasons, the industry found it advantageous to store such disk cartridges in protective envelopes.
The protective envelopes currently on the market comprise basically a rear wall and a front wall joined together at the bottom and two opposite sides to form an open pocket, which is dimensioned to receive the disk cartridge. The height of the rear wall may be greater than that of the front wall so that it extends beyond the opening of the pocket. Such a design allows the cartridge to be easily inserted into and removed from the protective envelope. The depth of the pocket formed by joining the rear and front walls of the protective envelope is usually about 2/3 to 3/4 the diameter of the disk.
There are many inherent problems with this open pocket protective envelope design. The protective envelope described above allows a portion of the disk jacket to be exposed, including the important "write-enable" notch formed on a side edge of the jacket. The disk jacket has several openings formed thereon. A circular opening centrally located exposes the index opening formed in the disk. Another opening formed in the jacket is elongated and extends radially from the center of the jacket. This opening exposes a portion of the disk so that the information stored on the disk may be read by computer peripheral equipment without removing the disk from the jacket. It is possible to inadvertently insert the disk cartridge upside down into the protective envelope thus leaving the elongated opening of the jacket extending beyond the confines of the envelope pocket and exposing a portion of the disk itself to dirt, dust or other adverse conditions. This may result in either damage to the disk or loss of information stored thereon. Even if the cartridge is correctly inserted, the current design of protective envelopes does not prevent potential magnetic film damaging particles from entering the jacket through the exposed write-enable notch or entering the protective envelope pocket.
Furthermore, the jacket itself may be damaged. Because the depth of the pocket is usually less than the height of the jacket, the cartridge projects from the pocket and leaves two corners of the jacket and the write-enable notch exposed. The exposed corners can be easily bent or crinkled causing the disk reader to malfunction or reject the cartridge. In addition, it is a common practice to cover the write-enable notch with a tab to prevent inadvertent erasure or writing over of the information stored on the disk. The write-enable tab may come loose or be pulled off thus voiding the intended purpose of write protecting the data stored on such flexible disk cartridge.
Another inherent problem with the protective envelopes currently known in the art is that the disk may be damaged when the protective envelope is labeled by writing with a sharp instrument, such as a pen or pencil, when the cartridge is in the envelope. Usually the extension of the rear wall does not provide sufficient space for properly labeling the envelope. In such cases it is necessary to write on portions of the front and rear walls which form the pocket. The contact pressure of the writing instrument may be sufficient to cause an impression to be left on the surface of the disk thus damaging the disk or causing the disk to be non-operative when read by a disk reader. In order to protect the disk from being damaged, it would be necessary to remove the cartridge before labeling the envelope. Furthermore, unlike a disk which can be erased and reused many times, protective envelopes cannot be recycled as they are often marked in ink or heavy pencil. The many labeling systems available today compound this problem by offering non-standard and often messy labeling alternatives. In addition, current designs have sacrificed a detailed disk table of contents or index area for necessary promotional or corporate image considerations, leaving only a relatively small area for labeling the envelope.
Furthermore, most of the protective envelopes currently on the market are constructed from very thin and flimsy material. As such they do little to support the disk cartridge and to prevent the cartridge from being inadvertently bent or creased.
OBJECTS AND SUMMARY OF THE INVENTION
An object of the present invention is to provide a new and useful protective envelope for a flexible disk cartridge which provides the cartridge with maximum protection against damage.
A further object of the present invention is to provide a protective envelope for a flexible disk cartridge which supports the disk cartridge over its entire surface and leaves no portion of the disk or jacket exposed.
A still further object of the present invention is to provide a protective envelope for standard sized flexible disk cartridges which meets or exceeds the requirements established by the ANSI.
Yet another object of the present invention is to describe a protective envelope for disk cartridges which provides maximum writing area for labeling the envelope and which allows the disk cartridge to remain in the envelope fully protected while the envelope is being labeled.
The flexible disk cartridge envelope of the present invention basically comprises a single sheet of paper material or the like which is shaped and folded to form a front wall, a rear wall and a protective cover or flap. The front and rear walls are joined on three sides at corresponding peripheral edges thereof by either side flaps or folds to form an open pocket dimensioned to receive at least a portion of the disk cartridge. The height of the rear wall may be greater than that of the front wall so that a portion of the rear wall extends above the opening of the pocket. The protective cover is pivotally joined to the outermost edge of the rear wall extension and should have a length at least equal to the distance the rear wall projects above the pocket opening. In this manner, the cover can be pivoted away from the pocket opening so that a disk cartridge contained in the pocket can be removed or pivoted downward to meet the front wall so that the disk cartridge is entirely enclosed within the protective envelope.
The envelope may further include a locking device to insure that the envelope remains closed. This locking device may comprise recontact adhesive applied to the cover so that the cover adheres to the front wall of the envelope when in the closed position.
The above and other objects, features and advantages of this invention will be apparent in the following detailed description of illustrative embodiments thereof, which are to read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a two-dimensional view of a first embodiment of the disk cartridge envelope before assembly.
FIG. 2 is a perspective view of the embodiment shown in FIG. 1 after assembly.
FIG. 3 is a sectional view of the disk cartridge envelope taken along lines 3--3 of FIG. 2.
FIG. 4 is a sectional view of the disk cartridge envelope taken along lines 4--4 of FIG. 2.
FIG. 5 is a perspective view of the embodiment shown in FIG. 2 with the protective cover opened to show a flexible disk cartridge inside the envelope.
FIG. 6 is a perspective view of a second embodiment of the disk cartridge envelope.
FIG. 7 is a sectional view of the disk cartridge envelope taken along lines 7--7 of FIG. 6.
FIG. 8 is a perspective view of a third embodiment of the disk cartridge envelope.
FIG. 9 is a sectional view of the disk cartridge envelope taken along lines 9--9 of FIG. 8.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings in detail and to FIGS. 1-5 thereof, it will be seen that a flexible disk cartridge protective envelope, constructed in accordance with the present invention, has a front wall 2, a rear wall 4 and a protective cover or flap 6. The walls 2, 4 and protective cover 6 may be individual sections joined together but are preferably constructed from a single sheet of paper material which is shaped and folded to form the assembled envelope shown in FIG. 2. If constructed from a single sheet of paper, the unassembled envelope has its rear wall 4 joined to and interposed between the front wall 2 and the protective cover 6. The points at which the rear wall 4 joins the cover 6 and front wall 2, shown in FIG. 1 by broken lines A and B respectively, are scored to allow the front wall and cover to be easily folded to meet the rear wall.
The front wall 2 may also include side flaps 8. The side flaps 8 are used to join the front wall 2 to the rear wall 4 and are preferred over other means of joining the two because they provide the envelope with additional strength and rigidity. The side flaps 8 project outwardly from opposite sides of the front wall 2 of the unassembled envelope. They may have an angled edge 10 which facilitates assembly by allowing a cleaner fold with no trimming of the bottom edge of the envelope necessary after assembly. A center strip 12 of permanent adhesive is provided on one surface of each side flap 8 to permanently join the side flap to the rear wall 4. The front wall/side flap junctures are scored along broken lines C, as shown in FIG. 1, to facilitate folding.
Assembly of the protective envelope according to the present invention, as shown in FIG. 1, is as follows:
The front wall 2 is folded along broken line B so that it meets the rear wall 4. The side flaps 8 are then folded along broken lines C around the side edges 14 of the rear wall 4 and are joined to the rear wall by the adhesive center strips 12. Thus, a pocket 16 is formed having an opening 18 on one side into which a disk cartridge 20 may be inserted. The width of the rear wall 4 and front wall 2 should be slightly larger than that of the cartridge 20. This will compensate for the slightly smaller pocket width due to folding along lines C and will allow the disk cartridge 20 to be easily inserted and removed from the pocket 16. The protective cover 6 is folded along broken line A so that in the assembled envelope the front wall 2 lies partially between the rear wall 4 and the protective cover 6.
The assembled envelope according to the present invention is shown in FIG. 2. The top, bottom and side edges 22, 24, 26 of the assembled envelope correspond to the folds along lines A, B and C respectively of FIG. 1.
The height of the rear wall 4 should be slightly greater than that of the disk cartridge 20 to compensate for folding and to allow the assembled envelope to fully support and enclose the cartridge. The height of the rear wall 4 of the envelope may equal that of the front wall 2. More preferably, the height of the rear wall 4 is greater than the height of the front wall 2 so that when the envelope is assembled, a portion of the rear wall extends above the top edge 28 of the front wall 2 which defines the opening 18 of the pocket. As such the pocket 16 will provide a partial housing for the disk cartridge 20, leaving a portion of the cartridge extending from the pocket as shown in FIG. 5. In this way, it is easily discernible whether the envelope contains a disk cartridge by merely lifting the protective cover. If desired, the cover 6 may have an opening (not shown) which may be covered with a transparent material. This opening can act as a "viewing window" to conveniently determine whether the envelope contains a cartridge without lifting the cover.
The length of the protective cover 6, which is preferably rectangularly shaped with rounded corners, is such that, when folded toward the front wall 2 in a closed position, it extends below the top edge 28 of the front wall and, therefore, covers any portion of the disk cartridge 20 protruding from the pocket. This will protect the entire disk, including that portion exposed by the elongated opening 30 formed in the jacket, as well as the corners 32 of the jacket and the write-enable notch 33 not contained within the pocket. The lower edge 7 of the cover can extend to the bottom edge 24 of the envelope but more preferably extends to just above the bottom edge. In this design, in which the lower edge 7 of the cover 6 extends substantially to the bottom edge 24 of the envelope, the distance between the lower edge 7 of the cover and the bottom edge 24 of the envelope is preferably not more than one inch or the width of a thumb. Such a design provides the envelope with greater rigidity and support, making it more difficult to bend or crease the disk cartridge 20 through three layers of material, i.e., the rear and front walls 4, 2 and the protective cover 6. This provides the disk cartridge with maximum protection. Such a design also provides the bottom of the envelope with a single leading edge in which the lower edge 7 and the bottom edge 24 may be grasped between the thumb and forefinger in order to facilitate insertion of the envelope between adjacent envelopes of, for example, a closely packed disk cartridge tray.
To keep the protective cover 6 closed, the protective cover/rear wall juncture may be double scored in the area of broken line A with a spacing of about 1/8 inch. The natural tendency of the paper to retain its folded shape will keep the lowermost edge 34 of the protective cover in close contact with the front wall 2 of the envelope.
To further insure that the protective cover remains closed, the envelope may be provided with a locking device. Although interlocking tab and slot means is contemplated, a more preferred locking means is recontact cement applied to the front wall or the inner surface 36 of the cover either as a single patch 38 centrally located between opposite sides of the cover near the lowermost edge 34 thereof, as shown in FIG. 1, or as a pair of circular adhesive patches 40, each of which is positioned near a corresponding corner of the cover, as shown in FIG. 5. The latter is preferred because it tends to keep the corners of the cover fixed to the front wall, even if the corners should become bent or creased over time by careless use.
An alternative embodiment to that previously described is shown in FIGS. 6 and 7. The structure of this embodiment is very similar in construction and layout to that shown in FIGS. 1-5 and includes a front wall 42, rear wall 44, side flaps 46 with permanent adhesive and a protective cover 48. The joined front and rear walls 42, 44 form a pocket 50 with the top edge 52 of the front wall defining a pocket opening 54. As is seen from FIGS. 6 and 7, the protective cover 48 extends only slightly below the top edge 52 of the front wall. Rather than provide the inner surface of the cover 48 with recontact adhesive, the cover can be easily "tucked" into the pocket 50 to keep the cover closed. The corners 56 of the cover are preferably rounded so that they are not bent when the cover is inserted into the pocket. As with the previously described embodiment, the entire disk cartridge is enclosed and locked within the protective envelope.
A third embodiment of the present invention is shown in FIGS. 8 and 9. A rear wall 58 and front wall 60 with side flaps 62 are provided which are similar in construction and design to that of the embodiment shown in FIGS. 1-5. However, a protective cover 64 which is also provided extends below the bottom edge 66 of the envelope and is either single or double scored and folded around the bottom edge 66 to extend slightly upward adjacent the outer surface of the rear wall 58. The cover will retain its folded shape and, acting in conjunction with the bottom edge 66 of the envelope about which it is folded, will remain in a closed position. As with the other embodiments described previously, a single leading bottom edge is provided for easy insertion into a pack of disk cartridge envelopes.
The embodiments described above provide maximum protection for the disk cartridge. In addition, sufficient writing space is provided for labeling the envelopes without it being necessary to remove the disk cartridge from the envelope before labeling. Both sides of the protective cover are suitable for this purpose. Preferably, the inner side of the cover is used to provide space for an index of the contents of the enclosed disk in order to maintain the privacy of this information when the envelope is closed. Of course, the exposed surfaces of the front and rear walls which form the pocket may be provided with a design or pattern or coating to prevent inadvertent writing on these surfaces which may damage a disk contained in the envelope. If still additional space if required, the disk cartridge can be removed, as should be done when using the currently known disk cartridge envelopes, and the exposed surfaces of the rear and front walls may be used.
The paperlike material used to construct the protective envelope in accordance with the present invention should be 0.003 to 0.015 inches in thickness to provide the protective envelope with sufficient rigidity. The material may be uncoated, coated or coated one side paper, or a spunbonded olefin commonly referred to by the trade name Tyvek. Alternatively, the envelope may be entirely or partially formed of a vinyl material. A portion of the surfaces of the envelope which are exposed when the cover is in the closed position may be covered with a protective coating. Actual choice of construction material may be based on strength, rigidity, smoothness, anti-static, anti-lint or any other desired properties.
With slight modification, the protective envelope according to the present invention may be adapted to store a non-flexible or rigid disk cartridge.
While there are several flexible disk cartridge sizes and several rigid cartridge designs available today, with reference to FIG. 1, the following are the preferred dimensions of an unassembled envelope designed to accept a standard 5.25 inch flexible disk cartridge:
The front wall is 37/8" H×55/8" W (measured between lines C); the rear wall is 51/2" H (line A to line B) ×5 9/16" W; and the cover is 5 5/16" L (measured from line A to the outermost edge) ×5 9/16" W. Each side flap is 3/4" width with a 1/4" center strip of adhesive.
The following preferred dimensions are for the "tucked cover" embodiment shown in FIGS. 6 and 7, which is designed to accept a standard 8 inch disk cartridge:
The front wall is 53/4" H×83/8" W; the rear wall is 83/8" H×8 5/16" W; and the cover is 23/4" L ×8 5/16" W. The side flaps are 1" in width with a 1/4" center strip of adhesive.
The flexible disk cartridge envelope according to the present invention meets all the requirements set forth by the ANSI. The envelope is designed to further enhance the usable life of the disk cartridge by providing the cartridge with maximum protection against damage through normal use.
The envelope according to the present invention also provides a much greater area for labeling the envelope thus enhancing the life of the envelope itself. For example, envelopes currently on the market designed to accept 5.25 inch disk cartridges provide a usable writing space of approximately 50 square inches and, for maximum protection of the disk, would require the removal of the disk cartridge before labeling. In comparison, an envelope constructed in accordance with the present invention to accept 5.25 inch disk cartridges can provide nearly 120 square inches of usable writing space, approximately half of which does not include surfaces of walls which form the pocket for the disk cartridge.
Although illustrative embodiments of the invention have been described herein with reference to the accompanying drawings, it is to be understood that the invention is not limited to those precise embodiments, and that various other changes and modifications may be effected therein by one skilled in the art without departing from the scope or spirit of this invention.
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A protective envelope for a disk cartridge assembly including a disk for storage of information signals thereon and a jacket for housing said disk has a rear wall, a front wall and a cover. Each of the rear and front walls has corresponding bottom and opposite side edges joined together and unjoined top edges which form a pocket having an opening on one side thereof and dimensioned to receive at least a portion of the disk cartridge. The cover is pivotally joined to the top edge of the rear wall and is capable of pivoting between an open position to allow removal of the disk cartridge from the pocket and a closed position to enclose the entire disk cartridge within the envelope. The rear wall may be extended above the top edge of the front wall to facilitate removal of the disk cartridge from the pocket, in which case the cover, when in a closed position, extends below the top edge of the front wall. Recontact adhesive may be affixed to a surface of the cover to cause the cover to separably adhere to the front wall in a closed position.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a national stage filing under 35 U.S.C. §371 of PCT/NL96/00163.
BACKGROUND
1. Field of Invention
The invention relates to a method for carrying out endothermic and exothermic chemical reactions.
2. Description
A great many chemical reactions are characterized by a positive heat effect (exothermic reaction) or a negative heat effect (endothermic reaction). To enable chemical reactions to proceed in the desired manner, an efficient supply or removal of the reaction heat is indispensable. In some exothermic reactions, the thermodynamic equilibrium shifts in an undesired direction if the temperature rises. Examples are the synthesis of ammonia and methanol, the oxidation of sulfur dioxide to sulfur trioxide in the production of sulfuric acid, the reaction of sulfur dioxide with hydrogen sulfide in the Claus process, the selective oxidation of H 2 S to elementary sulfur and the reaction of carbon monoxide with hydrogen to methane. Since in the course of these reactions thermal energy is released, the temperature of the reaction mixture will rise and the thermodynamic equilibrium will shift in an unfavorable direction, unless the reaction heat released is removed fast and efficiently from the reactor.
In endothermic reactions too, a shift of the thermodynamic equilibrium in an undesired direction can occur, now by the consumption of thermal energy. Examples are methane-steam reforming and the dehydrogenation of ethylbenzene to styrene. A problem may also arise in that as a result of the consumption of energy by the reaction, the temperature of the reaction mixture decreases unduly, so that the desired reaction no longer proceeds.
Not only can a temperature change cause a shift of the thermodynamic equilibrium in an unfavorable direction, it can also adversely affect the selectivity of catalytic reactions.
Examples of reactions where the temperature affects the selectivity are the production of ethylene oxide from ethylene (the undesired reaction is the formation of water and carbon dioxide), the selective oxidation of hydrogen sulfide to elementary sulfur (the undesired reaction is the formation of SO 2 ) and the Fischer Tropsch synthesis. In all cases, a temperature rise occurs as a result of the release of the reaction heat. If this temperature rise is not prevented through a rapid removal of the reaction heat, the selectivity decreases greatly.
In most conventional catalytic reactors, use is made of a fixed bed of catalyst particles. In such a catalyst bed, porous bodies of catalyst particles have been poured or piled.
In order to avoid an undesirably high pressure drop across such a catalyst bed, it is preferred to use bodies or particles of dimensions of at least 0.3 mm. These minimum dimensions of the catalyst bodies are necessary to keep the pressure drop that occurs upon the passage of a stream of reactants through the catalyst bed, within technically acceptable limits. While the dimensions are limited at the lower end of the range by the permissible pressure drop, the necessary activity of the catalyst imposes an upper limit on the dimensions of the catalytically active particles. The high activity required for a number of types of technical catalysts can mostly be achieved only with a surface of the active phase of 25 to 500 m 2 per ml catalyst volume. Surfaces of such an order of magnitude are possible only with very small particles, for instance with particles of 0.05 μm. Since particles with such dimensions no longer allow a liquid or gas mixture to flow through them, the primary, extremely small particles have to be formed into high-porous bodies with dimensions of at least about 0.3 mm, which can possess a large catalytic surface. An important task in the production of technical catalysts is to combine the required high porosity with a sufficiently high mechanical strength. The catalyst bodies cannot be allowed to disintegrate upon filling of the reactor and upon exposure to sudden temperature differences (thermal shock).
Under the conditions of the thermal pretreatment and/or catalytic reaction to be carried out, nearly all catalytically active materials soon sinter to form large conglomerates with a negligibly small active surface. Therefore, the active component (finely divided) is generally applied to a so-called support. This support exhibits the necessary thermal stability and hardly sinters, if at all, at high temperatures. Often used as supports are silicon dioxide, aluminum oxide or activated carbon.
As appears from the above examples, there is a very great need for a fast supply or removal of thermal energy in catalytic reactors, but the total heat transfer coefficient is mostly very low in a fixed catalyst bed. According to the present state of the art, it is virtually impossible to supply thermal energy to or remove it from a fixed catalyst bed in an efficient manner. This is indeed evident from the manner in which chemical reactions are carried out in fixed catalyst beds.
It is possible that of an exothermic reaction only the thermodynamic equilibrium shifts in adverse direction upon a temperature rise, without the selectivity decreasing unallowably. In that case, the reaction in a fixed catalyst bed can be made to proceed adiabatically. After passage through the reactor, the stream of reactants is cooled off in a separate heat exchanger. Because the conversion of the reactants is now thermodynamically limited by the temperature rise in the reactor, the unconverted reactants have to be reacted again upon cooling. The reaction product can be separated and the reactants can be recycled through the fixed catalyst bed. This occurs, for instance, in the ammonia and methanol synthesis. If the reaction product cannot be easily separated, downstream of the heat exchanger a second fixed bed reactor with a heat exchanger must be linked up. This is for instance the case in the oxidation of sulfur dioxide to sulfur trioxide. Sometimes, to prevent emission of harmful compounds, even a third reactor with heat exchanger is necessary. If connecting a number of reactors and heat exchangers in series is not properly possible and the separation of the reaction product is not either, the reaction product is sometimes recirculated through the catalyst bed. Per passage through the reactor, so little of the reactants is added to the circulating reaction product that it is converted completely. Because the rise of the temperature must then be properly controlled, per passage through the reactor only very little can be converted. In cases where the reaction must be carried out at a greatly increased pressure, the problems with the supply or removal of the reaction heat are extra large.
In the ammonia synthesis and the methanol synthesis, a catalyst bed is employed in which reactants are injected at different points at a relatively low temperature.
Such an implementation of the method, whereby gas streams must be passed through high pressure reactors in a complicated manner, obviously also requires high investments.
In a number of technically important cases, it is desired in catalytic reactions to work with a high to very high spatial throughput rate, with a great pressure drop across the reactor being considered a less serious drawback. In the conventional fixed bed reactors, a high pressure drop with the corresponding high spatial throughput rate is not properly possible. If the pressure at the reactor inlet is increased, the catalyst may be blown (gaseous reactants) or washed (liquid reactants) out of the reactor. It is also possible that at a particular critical value of the pressure at the reactor inlet “channeling” occurs. In that case, the catalyst particles in a particular part of the reactor are going to move. In that case, the reactants are found to flow virtually exclusively through the part of the catalyst bed that is in motion.
With the fixed bed reactors current at present, the catalyst bed clogs up. Therefore the reactor must be regularly opened and the cumulated layer of dust removed. It would be favorable if a pulse of gas of high pressure could be sent through the reactor in a direction opposite to that of the stream of reactants. This pressure pulse would blow the dust off the catalyst bed; thus, clogging could be prevented without opening the reactor, which is technically very attractive. With the fixed bed catalysts according to the present state of the art, however, this is not possible; along with the dust, the catalyst bodies would be blown out of the catalyst bed.
It will be clear that a number of disadvantages can be associated with the use of fixed bed reactors. In general, it requires costly facilities, while recirculation and separation of reaction products present in low concentration require a great deal of energy. For that reason, in a number of cases a whirling bed is employed. In a whirling bed the transport of thermal energy is much easier, while the problems with pressure drop and clogging do not occur. In a whirling bed, however, the catalyst to be used must meet very high standards regarding mechanical strength and wear resistance, which is not at all possible with every catalyst. Finally, the catalyst consumption in a whirling bed is relatively high due to the unavoidable wear. Accordingly, in many cases it will not be possible to use a whirling bed.
There are cases where it is not possible to work either with a whirling bed or with an adiabatic reactor. This applies in particular to highly endothermic reactions and reactions where the selectivity decreases unallowably upon increase of the temperature. Examples are methane-steam reforming and the selective oxidation of ethylene to ethylene oxide. In a selective oxidation of ethylene, a very large heat exchanging surface is employed by utilizing a reactor with no less than 20,000 long tubes. In methane-steam reforming it is attempted to optimize the heat supply and to limit the pressure drop by adjusting the dimensions and the shape of the catalyst bodies. In this last reaction too, a large number of costly tubes have to be used in the reactor.
It has also been proposed to apply the catalyst exclusively to the wall of the reactor. An example of such a system is described in the abstract of JP-A 6/111838. According to this publication, a reform catalyst has been provided in grooves of a plate, while in grooves of a second plate a combustion catalyst has been provided. These plates have been arranged against each other, so that through the heat generated with the combustion the reforming can take place.
Also in carrying out the Fischer Tropsch reaction, in which from a mixture of hydrogen and carbon monoxide higher hydrocarbons are produced, a system has been employed, in which a catalyst is provided on the wall of the reactor. This catalyst provided on the wall ensures a good heat transfer from the catalyst to the outside of the reactor. For providing the catalyst on the wall, inter alia the following method has been proposed. The catalyst is applied as a Raney metal, an alloy of the active metal and aluminum. After being applied, the catalyst is activated by dissolving the aluminum with lye. The greater part of the reactor volume is empty, as a result of which the contact between the reactants and the catalytically active surface is slight and the conversion per passage through the reactor is greatly limited. The reactants must therefore be frequently recirculated through the reactor.
In a number of technically important cases, the pressure drop upon passage of the reactants through the catalyst bed must remain very low. This applies, for instance, to reactors in which flue gas of large plants is to be purified, as with the catalytic removal of nitrogen oxides from flue gas. Because a flue gas stream is generally very large, a substantial pressure drop requires a very great deal of mechanical energy. The same applies to the purification of exhaust gases of automobiles. In this case too, a high pressure drop is unallowable.
Currently, the use of catalysts provided on a honeycomb is one of the few possibilities of achieving an acceptable pressure drop without unallowably reducing the contact with the catalyst. To that end, often ceramic honeycombs (honeycombs, monoliths) are used, in which the catalytically active material has been provided.
A variant of the method in which the catalyst is provided exclusively on the wall, is the use of monoliths made up of thin metal sheets. Such a reactor is manufactured, for instance, by rolling up a combination of corrugated and flat thin metal sheets and subsequently welding them together. It is also possible to stack the flat sheets in a manner leading to a system with a large number of channels. On the wall of the thus-obtained channels the catalyst is then provided.
As has been noted, the thermal conduction in a fixed catalyst bed is poor. This has been ascribed to the low thermal conductivity of the high-porous supports on which the catalytically active material has been provided. Therefore Kovalanko, O. N. et al., Chemical Abstracts 97 (18) 151409u have proposed to improve the thermal conduction by increasing the conductivity of the catalyst bodies. They did this by using porous metal bodies as catalyst support. Now, it has already been described by Satterfield that the thermal conductivity of a pile of porous bodies is determined not so much by the conductivity of the material of the bodies, as by the contacts between the bodies among themselves (C. N. Satterfield, “Mass Transfer in Heterogeneous Catalysis”, MIT Press, Cambridge, Mass., USA (1969), page 173). The inventors' own measurements have shown that the thermal conductivity of catalyst bodies indeed does not greatly affect the heat transport in a catalyst bed.
In WO-A 86/02016 a reactor is described, comprising a reaction bed provided with a catalyst, which bed consists of sintered metal particles which are in good heat conducting communication with the reactor wall, which wall is externally provided with sintered metal particles for removing reaction heat. Further, on the outside of the reactor a phase transition occurs. Such a reactor system is found to be able to realize a large heat dissipation, but has the disadvantage that a good setting and/or control of the reaction is not possible, or very difficult. This is evident inter alia from the example in which the catalytic combustion of a combustible gas with a heat of combustion of 35.530 kJ/m 3 is described. This would have to occur at a temperature of 350° C. However, by the cooling of the reactor with evaporating water (steam production) at 110° C., the entire reactor is cooled to 110° C., so that the reaction will not occur.
In U.S. Pat. No. 4,101,287 a combined heat exchanger reactor is described, consisting of a monolith, through a part of the channels of which flow the reactants and through a part of which flows the cooling agent. Here the same disadvantage as in the system of WO-A 8602016 presents itself.
In EP-A 416710 a method is described, based on the use of a catalytic reactor in which the reactor bed consists of elementary particles of metal sintered to each other and to one side of the reactor wall, while no sintered metal particles are present on the other side of the reactor wall. When in such a reactor the diameter of the reactor bed is chosen in relation to the heat effects, which vary from one reaction to another, but are known and, depending on the reaction conditions, can be calculated, reactions of the type referred to can be carried out optimally.
In carrying out chemical reactions, especially if they are reactions which are carried out on a large scale, if a strong heat effect is involved, or if high pressures are required, problems accruing from the heat economy of the reaction are encountered. It appears that in a number of cases it is not easy to efficiently supply the necessary heat or remove the heat produced. For instance in steam-reforming natural gas or other hydrocarbons, the necessary amount of heat is so large that complex systems with burners and heating tubes are needed to supply the necessary heat. This kind of problems also occurs with other reactions with great thermal effects, such as the production of ammonia, the preparation of ethylene oxide, the selective oxidation of H 2 S, and the like. Even in reactors according to the above-mentioned EP-A 416710 or U.S. Pat. No. 4,101,287, it is found this can give rise to problems.
Presently, mixtures of hydrogen and carbon monoxide (synthesis gas) are produced through reaction of methane with steam, the so-called methane-steam reforming process. If only hydrogen is desired, the carbon monoxide is allowed to react with steam to form carbon dioxide and hydrogen. The carbon dioxide formed is removed through dissolution under pressure in aqueous solutions or regenerable solid sorbents.
For this process, it is possible to use, besides methane, other gaseous hydrocarbons or naphtha or other hydrocarbons that can be readily brought into the gas phase.
To enable the highly endothermic reaction between methane and steam to proceed, the necessary reaction heat must be supplied to the reaction mixture at a high temperature, for instance 850° C. (allothermic process). In general, the necessary heat is generated outside the reaction mixture by combustion of, for instance, methane. In order to transfer the thus generated thermal energy to the reaction mixture, a partition with a sufficiently high thermal conductivity must be used.
Through radiation the reaction heat generated in the combustion reaction is transferred to the reaction mixture. The reaction mixture is passed through tubes of a high-grade alloy in which a suitable catalyst has been provided. The tubes are exposed to the radiation of the burners.
To prevent oxidation of the tubes at the necessary high temperatures, costly (nickel-containing) alloys must be used for the reactor wall. To save energy, the methane-steam reforming process is often carried out at elevated pressure, for instance at 30 bar, which imposes even more stringent requirements of oxidation resistance.
For the steam-reforming mentioned, it has previously been proposed to carry out a partial oxidation of the hydrocarbon prior to the reaction. The heat thereby produced is then stored in the gas and carried to the steam reforming. Such a method, however, cannot be employed in all cases.
BRIEF SUMMARY OF THE INVENTION
The object of the invention is to provide a suitable method for carrying out chemical reactions and in particular chemical reactions with a great thermal effect, whereby in a simple manner the transport of the necessary or redundant heat is provided for.
The invention is based on the surprising insight that it is possible to optimally adjust the heat conduct of combined endothermic and exothermic reactions to each other if use is made of a specific reactor system in which at least two reactor beds based on porous structures are in heat exchanging relation with each other.
The invention accordingly relates to a method for carrying out two chemical reactions in a reactor system comprising at least two mutually separate reactor beds, of which the surfaces exposed to the reactants are catalytically active for the chemical reactions concerned, and at least one partition, wherein
at least one first reactor bed is present, which is bounded by at least one partition, which bed is based on a continuous porous structure and which bed is fixedly connected to said partition,
at least one second bed is present, which is based on a continuous porous structure, and which bed is fixedly connected to said partition, and
said second bed, with respect to the first bed, is disposed on the other side of said partition, so that a heat exchanging contact between said beds is present and the reaction heat of a first chemical reaction which is carried out in said first reactor bed is supplied or absorbed by carrying out a second chemical reaction in said second bed.
Over the above-described known systems, the invention has the advantage that during the process a greater stability is obtained, inter alia because of the self-regulating character of the system.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a flow diagram of an endothermic reaction and an exothermic reaction occurring in a two-reaction system; and
FIG. 2 schematically represents a reaction system based on a plate reaction.
DETAILED DESCRIPTION OF THE INVENTION
According to an embodiment of the method according to the invention, a reactor is used in which two or more first reactor beds and/or two or more second reactor beds are used which, through a corresponding number of partitions, are in heat exchanging relation with each other.
According to the invention, it is possible in a simple manner to efficiently transport the necessary heat to the desired place. According to a first variant of the method according to the invention, in the first reactor bed an endothermic reaction is carried out and in the second reactor bed an exothermic reaction is carried out.
According to another variant of the invention, in the first reactor bed an exothermic reaction is carried out and in the second reactor bed an endothermic reaction is carried out.
According to yet another embodiment of the method according to the invention, a multi-stage reaction is carried out, wherein at least one stage of this reaction has a positive and at least one stage has a negative heat effect, and wherein said stages are carried out in said first and second reactor bed.
An example of this last variant is formed by the above-mentioned steam reforming, preceded by partial oxidation. The heat necessary for the steam reforming is then supplied by the partial catalytic combustion of the hydrocarbon in the first reactor bed, while the heat produced is supplied to the steam reforming via the common partition. The gases are thereupon supplied to the second reactor bed, where they are further converted.
Other suitable reactions that can be carried out according to the invention are, for instance, the preparation of ethylene oxide, the selective oxidation of H 2 S. hydrogenation reactions, dehydrogenation reactions, such as the formation of styrene from ethylbenzene, the oxidation of methanol to formaldehyde, the conversion of methanol into synthesis gas, and the like. It is noted in this connection that the catalytic combustion of hydrocarbons to form CO 2 , water and heat, can also be regarded as a chemical reaction within the scope of this invention.
A suitable possibility for carrying out the method according to the invention, with the desired chemical reaction being an endothermic reaction, is therefore the catalytic combustion of hydrocarbons, in particular natural gas, in the first reactor bed, while the endothermic reaction is carried out in the second reactor bed.
The catalytic combustion occurs in the presence of a suitable combustion catalyst, for instance copper oxide or manganese oxide on a thermostable support. A very suitable catalyst is described, for instance, in EP-A 327,177. However, the art has a large number of other suitable combustion catalysts.
The chemical reactions that are carried out according to the invention take place under the most suitable conditions for the reactions chosen. With a view to a good heat exchange between the reactor beds, the temperatures in the two reactor beds will not differ greatly. In general, the temperature difference will not be more than about 100° C., more particularly this difference will be less than 50° C. As a result, also the stability and the self-regulating character are improved.
Through a suitable choice of load and degree of conversion in the two reactors, the temperatures in the two beds can be optimally adjusted to each other. In doing so, it is obviously possible to use all conventional variants in the manner of supplying reactants, recirculating a part of the reaction mixture, supplying or discharging reactants and/or reaction products at different points in the reactor, and the like.
The temperature employed in the reactors is dependent on the nature of the reactions. In general, an elevated temperature is employed, because then the advantages of the system are most pronounced. In general, the temperature will be above 100° C., an upper limit being formed by the maximum temperature at which the material is still stable, or the temperature that can be achieved with a chemical reaction. However, temperatures in excess of 1250° C. are generally not preferred because of the difficulties in achieving them and the requirements that such temperatures impose on the materials of the reactors and the supply and discharge systems.
The pressures at which the various reactions are carried out, can be varied within wide limits, it being noted that it is also possible to carry out the reactions at different pressures. Although this imposes more stringent requirements on the equipment, there is no fundamental problem.
In the present description, the term “partition” is understood to refer to the physical separation between the space where the first reaction occurs, that is, the first reactor bed, and the space where the second reaction occurs, the second reactor bed. This can obviously be the outer wall of the catalyst bed, but it also encompasses, for instance, a wall of channels of a monolith or the metal sheets of a rolled-up assembly.
The wall can consist of the conventional materials that are known for these purposes. These walls can consist of a single layer, but it is also possible to use more than one layer, and it can specifically provide advantages if the surface to which the elementary bodies are to be fixedly connected, improves the bond with the elementary bodies. In this connection one can think, for instance, of the use of enamel coating in ceramic elementary bodies.
The continuous porous structure which is used in the reactor in accordance with the invention can be constructed in various ways, as will also appear from the further explanation and the examples of suitable structures. In general, the continuous porous structure should meet the requirement that there is a heat exchanging contact between the partition and the structure, while further the porous structure extends through the entire reactor bed.
This means that the porous structure is fixedly connected to at least one reactor wall, while the reactor bed consists of a structure which fills the entire reactor bed, at least, extends through the entire reactor bed, for instance in the form of fixedly interconnected elementary particles, such as particles sintered together, or channels, arranged parallel, of a suitable sheet construction or of a monolith.
Accordingly, this does not encompass the system as described in JP-A 6/111838, since no continuous porous structure is thereby obtained. In fact, the walls of each channel constitute a reaction wall, whereas according to the invention a porous structure is required.
With the invention, the degree of porosity of the reactor bed can be varied within wide limits. This porosity, that is, the portion of the bed that allows gas or liquid to flow through, is generally between 20 and 95% by volume. The most suitable value depends on the nature of the reactor, the desired surface, the desired pressure drop and the extent of heat transport in the bed.
The porosity can be distributed uniformly in the reactor bed, but it is also possible to provide a gradient in the porosity, for instance in the longitudinal direction viewed in the direction of flow of the reactants, or in the transverse direction. It is also possible for this porosity not to be uniformly distributed through the reactor bed, for instance as is the case when a monolith is used.
The extent of heat transport is a relatively important factor in the reactor system according to the invention. Obviously, the heat conductivity of the total system, that is, from the partition as far as into the beds, is partly determined by the heat conductivity of the material of the catalyst support used and of the construction material of the reactor.
Preferably, the heat conductivity is not less than 10% of the heat conductivity of the material used in massive condition; preferably, this value is between 10 and 75%. In absolute terms, the heat conductivity is preferably between 0.2 and 300 W/m·K.
The heat conductivity is highly dependent on the heat conductivity of the elementary materials used. Al 2 O 3 extrudate, for instance, has a conductivity of 0.32 W/m.K, while a sintered body of 316L has a value of 3-12 W/m·K. Powder of 316L, by contrast, has a value of 0.55, while massive material possesses 20 W/m·K. Massive copper has a heat conductivity of 398 W/m·K. All of these values relate to the condition at room temperature. At other temperatures, the absolute value of the numbers changes, but the relative ratio remains approximately the same.
The heat conductivity of the system as a whole is also important for the operation thereof. As has been indicated, there should be a heat exchanging contact between the two reactor beds. More particularly, it is of importance that there is a fixed connection, under reaction conditions, between the partition and each reactor bed. More particularly when using sintered metals as support of the catalyst bed, this can be obtained by sintering the elementary metal particles fixedly onto the wall, but it is also possible for the materials to be applied in such a manner as to have a heat transfer comparable to that of the sintered-on metals. When using a catalyst provided on the partition, optionally with a support material interposed between them, obviously one also has a good heat exchanging contact between the beds. Such systems can, for instance, consist of an assembly of (rolled-up) sheets or a monolith, in which on the walls a catalyst (optionally supported) has been provided, by means of a wash coat. In such a variant, a part of the rolled-up sheets or the monoliths, for instance an inner core, constitutes the first reactor bed, while another part, for instance a ring around the core, constitutes the second reactor bed. Obviously, there may be more than two reactor beds. It is possible, for instance, to make a kind of shell structure with different ‘rings’.
The reactor system according to the invention is applicable to each heterogeneously catalyzed gas phase reaction, but is more particularly suitable for those reactions that have a strong thermal effect, that is, highly endothermic or exothermic reactions, or reactions whose selectivity is highly temperature-dependent.
In the embodiment according to the invention based on sintered metal beds, it is possible to work with a high to very high spatial throughput rate without the catalyst being blown (gaseous reactants) or washed (liquid reactants) from the reactor. Nor does “channeling” occur. Because in the reactor according to the invention the catalyst particles are much better fixed, such a reactor allows working at a much higher velocity of the reactants (and consequently a much higher pressure drop across the reactor). Another important advantage of fixing the catalyst bodies in the reactor according to this embodiment, is evident when dust is deposited on the catalyst bed. In reactors according to the present invention, a pulse of gas of high pressure can be sent through the reactor in a direction opposite to that of the stream of reactants. This pressure pulse blows the dust off the catalyst bed; as a result, clogging can be prevented without opening the reactor, which is technically very attractive.
With non-sintered material, the reactor bed has a high porosity adjacent the wall, owing to the fact that the shape of the material particles and the wall do not conform to each other. As a result, there is little catalyst present at this location and relatively much less feed will be converted. This effect is enhanced in that the high porosity has low pressure losses and the feed will flow preferentially along the wall. By sintering, on the other hand, conformity with the wall is improved and the porosity adjacent the wall is of the order of magnitude of the bed material not located adjacent the wall. Moreover, by applying the catalyst after filling and sintering of the reactor, catalyst is also deposited on the wall. These two effects have as a result that leakage along the wall is much less and the reactor as a whole can be made of shorter construction. Thus the pressure drop remains limited.
When using a reactor system based on plates or a honeycomb, the advantage that no leakage occurs is gained to a lesser extent, but on the other hand these reactors are simpler to construct and have a lower pressure drop and are less prone to clogging.
The invention is particularly suitable for carrying out highly exothermic or endothermic catalytic reactions. As an example of such a reaction, the oxidation of methane is described. As an example of a reaction whose selectivity is to a large extent determined by the temperature, the selective oxidation of hydrogen sulfide is taken. In this case the removal of thermal energy is of great significance since above a temperature of about 300° C. the oxidation of sulfur vapor to the undesired sulfur dioxide starts to proceed. Use of a reactor system according to the invention makes it possible to purify gas streams of a hydrogen sulfide content of, for instance, 10% by volume highly efficiently. The hydrogen sulfide is selectively oxidized to elementary sulfur which is extremely easy to separate through condensation. Because such gas mixtures cannot be properly processed in a Claus process, the invention is of particularly great importance for this purpose.
As has already been indicated, the reactor system that is used according to the invention can be made up in a number of ways.
When using reactor beds based on sintered metal particles, in a first variant the reactor beds are arranged concentrically around each other. According to another variant, the reactor beds are plate-shaped, one or more first interconnected reactor beds being alternated in layers with one or more interconnected second reactor beds.
The reactor beds based on sintered particles are most preferably made up of more or less isotropic particles, more particularly with a fairly narrow particle size distribution. When using such elementary particles, a catalyst system with very good properties is obtained.
The material of which the elementary particles consist is preferably metal, but can also be alumina, silica, silica-alumina, zeolite, titanium dioxide, zinc oxide or zirconium oxide, or oxides of a combination of elements, such as spinel (MgAl 2 O 4 ), mullite (3Al 2 O 3 .2SiO 2 ) or cordierite (2MgO.2Al 2 O 3 .5SiO 2 ), as well as carbides, nitrides and borides of elements such as silicon, tungsten, titanium and vanadium. The preference is for metal or metal alloys, because elementary particles consisting of these materials can be fixedly connected to each other and to the partition wall relatively easily by sintering. The metal or the metal alloy can then be catalytically active itself or be rendered catalytically active, but it is also possible to provide a catalytically active material thereon. One of the advantages of a catalyst on such metal particles resides in the better heat distribution by the use of the metal. On a microscale it is observed that the heat conduct in the catalyst is better, so that a more efficient use can be made of the catalyst. This has an influence inter alia on the activity, but can also be of importance for the selectivity, for instance in case the selectivity is highly dependent on the temperature, since according to the invention a much more homogeneous temperature distribution is obtained in the catalyst.
Suitable metals for use in elementary particles are inter alia nickel, iron, chromium, manganese, vanadium, cobalt, copper, titanium, zirconium, hafnium, tin, antimony, silver, gold, platinum, palladium, tungsten, tantalum, as well as the lanthanides and actinides. The elementary particles can consist of substantially pure metal or of an alloy of two or more metals, which alloy can also contain non-metallic components, such as carbon, nitrogen, oxygen, sulfur, silicon, and the like.
According to another embodiment of the invention, the elementary particles consist of fibers or threads, preferably of a diameter of 0.5 mm at most, preferably of 1-250 μm. The materials of which these particles are manufactured preferably comprise carbon and metal or metal alloys.
According to another embodiment of the invention, a plate reactor is used, for instance made up of a more or less flat plate, which is provided with a corrugated plate, welded onto the flat plate along the tops of the corrugated plate. This assembly is then (for instance rolled up and) welded together again, so that a reactor is obtained, consisting of a large number of channels which extend parallel to each other, on opposite sides of the plates. This reactor can be provided with a coat with catalyst in a manner similar to that described hereinabove. The ends of the reactor are provided with appropriate constructions to ensure that the various reactants and reaction products are distributed over the proper channels. The metals of which such a reactor can be manufactured are generally the same metals as described hereinabove in relation to the sintered metals. There is a particular preference for an alloy of inter alia iron and chromium, known under the name of FeCralloy R . The invention also relates to such a plate reactor.
According to yet another variant of the invention, as reactor system a honeycomb or monolith is used. Such systems are known and are generally characterized on the basis of the materials of which they are made and the number of channels per unit area. Monoliths can be manufactured from ceramic materials, such as mullite (Al 6 Si 2 O 13 ), titanium dioxide, and α-alumina, or of metals, the above-mentioned metals being specifically eligible. Typical cell densities of monoliths are between 100 and 400 cells per (inch) 2 . The cell walls are thin and vary between 50 and 200 μm. At a cell density of 400 cpi, about 3500 m 2 surface per m 3 monolith is available.
In a next variant of the invention, as a reactor system a foam or other porous structure is used.
The reactor system according to the invention, as has already been indicated, can already be catalytically active of itself or be activated by treatment. However, it is also very well possible to provide a catalytically active material on the fixedly connected elementary bodies. More particularly, it is possible first to provide a (highly) porous support on the metal surface or alloy surface and thereafter to provide the catalytically active component on the support. This last can be of significance if the catalytically active component may not come into direct contact with the material of the bodies sintered together, so as to prevent undesired interactions between the material of the bodies and the catalytically active component.
When applying the catalyst, first a dispersion of a support and/or the catalytically active material (or a precursor thereof) in a liquid is prepared and thereafter this liquid is suitably applied to the fixedly connected elementary bodies. This can be done, for instance, by vacuumizing the bed to which the support and/or the catalytically active material are to be applied and thereafter sucking the dispersion into the bed, so that the bed is impregnated. If a support is provided first, the operation can be repeated with the catalytically active component or precursor thereof.
The composition of the dispersion and the conditions for manufacturing the system are preferably chosen such that the viscosity of the impregnation liquid is raised upon impregnation, since in that way it is possible to remove the liquid phase from the dispersion without the distribution of the catalytically active material being substantially disturbed. Moreover, in this way a better distribution of the catalytically active material over the fixedly connected elementary bodies is obtained. A number of methods are conceivable for increasing the viscosity of the liquid. A first method is to cool to below the solidification point thereof, so that the entire mass solidifies. By using vacuum, the system can then be freeze-dried. Another possibility, and this one is preferred, is to incorporate a small amount of agar or another substance with comparable activity into the dispersion, which affords the possibility of introducing the dispersion into the system at increased temperature and thereafter fixing the system by simply cooling off. Thereupon the liquid can be removed under vacuum or otherwise, and the agar can be removed at increased temperature through pyrolysis. The suitable amount of agar is substantially determined by the desire that it must be possible for the liquid to become sufficiently viscous or even solid. Suitable concentrations are between 0.05 and 1.0% by weight.
It is also possible to apply the catalyst as a so-called wash coat.
In the drawing, the invention is further explained. FIG. 1 shows a flow diagram of a reaction in which in a first stage an exothermic reaction is carried out, while in a second stage an endothermic reaction occurs.
FIG. 2 schematically represents a reactor system based on a plate reactor.
FIG. 1 shows two reactors 1 , 2 which via a wall 3 are in heat exchanging contact with each other. Via line 4 , reactants are supplied to reactor 1 , while the reaction mixture is discharged via line 5 and is passed to the inlet of reactor 2 . Via line 6 the reaction mixture egressing from reactor 2 is thereupon discharged.
In FIG. 2 a schematic arrangement of a plate reactor is given. The compartments of the first reactor ( 1 a , 1 b , 1 c , 1 d , 1 e ) are separated from the compartments of the second reactor ( 2 a , 2 b , 2 c , 2 d ) by the intervening partitions.
The invention will now be elucidated in and by a few examples, which are not intended as a limitation of the invention.
EXAMPLE 1
A reactor consisting of a continuous porous metal structure is fixedly connected through the partition to a second reactor, likewise consisting of a continuous porous metal structure, so that a heat exchanging contact is present. The porous metal structures are made up of metal particles fixedly sintered to each other and to the partition.
In the first reactor, the surface exposed to the gas phase is catalytically active for the oxidation of methane. To that end, a thermostable alumina support provided with copper has been applied to the surface of the metal in the first reactor.
In the second reactor, the surface exposed to the gas phase is catalytically active for the steam reforming of methane. To that end, an alumina support with nickel thereon has been applied to the metal surface of the second reactor.
Through the first reactor, a methane/air mixture is passed continuously, with a methane/air ratio (based on volume) at the reactor inlet of 0.03, and with a temperature of 550° C. In the first reactor the methane reacts completely with the oxygen through the contact with the catalyst, so that the temperature in the reactor rises. The maximum value the temperature achieves is about 900° C.
Through the second reactor, cocurrently and continuously, a methane/steam mixture is passed with a methane/steam ratio (molar) at the reactor inlet of 0.33.
In the presence of the catalyst, methane reacts completely with steam to form CO and H 2 . The temperature at the inlet is 600° C., which achieves a maximum value of about 800° C.
The heat generated in the first reactor is sufficient for the endothermic reaction in the second reactor. This heat is passed to the second reactor through the conducting partition. For transferring a sufficient amount of heat to the second reactor, the amount of methane that is converted in the first reactor is approximately half of the amount of methane that reacts in the second reactor.
EXAMPLE 2
A reactor consisting of a continuous porous metal structure is fixedly connected via the partition to a second reactor, likewise consisting of a continuous porous metal structure, so that a heat exchanging contact is present. The porous metal structures are made up of metal particles sintered fixedly to each other and to the partition.
In the first reactor, the surface exposed to the gas phase is catalytically active for the oxidation of methane. To that end, a thermostable alumina support provided with copper has been applied to the surface of the metal in the first reactor.
In the second reactor, the surface exposed to the gas phase is catalytically active for the conversion of ethylbenzene into styrene. To that end, an iron/chromium oxide catalyst on an alumina support has been applied to the metal surface of the second reactor.
Through the first reactor, a methane/air mixture is passed continuously, with a methane/air ratio (based on volume) at the reactor inlet of 0.03, and with a temperature of 550° C. In the first reactor the methane reacts completely with the oxygen through the contact with the catalyst, so that the temperature in the reactor rises. The maximum value the temperature achieves is about 900° C.
Through the second reactor, cocurrently and continuously, an ethylbenzene/steam mixture is passed with an ethylbenzene/steam mass ratio at the reactor inlet of 1.
In the presence of the catalyst, ethylbenzene reacts with steam to form styrene at a pressure of 0.4 bar. The temperature at the inlet is 550° C., which rises with the passage through the reactor and achieves a maximum value of about 650° C. The conversion of ethylbenzene is 50%.
The unreacted ethylbenzene is separated from the reaction mixture and returned to the reactor inlet. Styrene is also separated and recovered.
The heat generated in the first reactor is sufficient for the endothermic reaction in the second reactor. This heat is passed to the second reactor through the conducting partition. For transferring a sufficient amount of heat to the second reactor, the amount of methane that is converted in the first reactor is 15 mol. % of the amount of ethylbenzene supplied to the second reactor.
EXAMPLE 3
A reactor consisting of a continuous porous metal structure is fixedly connected via the partition with a second reactor, likewise consisting of a continuous porous metal structure, so that a heat exchanging contact is present. The porous metal structures are made up of metal particles fixedly sintered to each other and to the partition.
In the first reactor, the surface exposed to the gas phase is catalytically active for the oxidation of methanol. To that end, an iron/molybdenum oxide catalyst on alumina has been applied to the surface of the metal in the first reactor.
In the second reactor, the surface exposed to the gas phase is catalytically active for the conversion of methanol into synthesis gas. To that end, a copper/zinc catalyst on alumina has been applied to the metal surface of the second reactor.
Through the first reactor, a methanol/air mixture is passed continuously, with a methanol/air ratio (based on volume) at the reactor inlet of 0.06 and a temperature of about 300° C. In the first reactor the methanol reacts in the presence of the catalyst with oxygen. As a result, the temperature rises and achieves a maximum value of about 400° C. The conversion of methanol into formaldehyde is 95%.
Through the second reactor, cocurrently and continuously, a methanol/steam mixture is passed with a methanol/steam ratio (molar) at the reactor inlet of 0.8.
In the presence of the catalyst, methanol reacts with steam to form CO and H 2 . The temperature at the inlet is 200° C. With the passage through the reactor, it rises and achieves a maximum value of about 250° C. The conversion of methanol is 100%.
The heat generated in the first reactor is sufficient for the endothermic reaction in the second reactor. This heat is passed to the second reactor through the conducting partition. For transferring a sufficient amount of heat to the second reactor, the amount of methanol that is supplied to the first reactor is about 60% of the amount of methanol that reacts in the second reactor.
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The invention relates to a method for carrying out two chemical reactions in a reactor system comprising at least two mutually separate reactor beds, of which the surfaces exposed to the reactants are catalytically active for the chemical reactions concerned, and at least one partition; wherein at least one first reactor bed is present, which is bounded by at least one partition, which bed is based on a continuous porous structure extending throughout the reactor, and which bed is fixedly connected to said partition; wherein at least one second bed is preset, which is based on a continuous porous structure extending throughout the reactor, and which bed is fixedly connected to said partition, and said second bed, with respect to the first bed, is disposed on the other side of said partition, so that a heat-exchanging contact between said beds is present and the reaction heat of a first chemical reaction carried out in said first reactor bed is supplied or absorbed by carrying out a second chemical reaction in said second bed.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a grating-interference type displacement meter, and more specifically to that capable of assuring stable interference even when a scale has a uneven surface.
2. Description of the Prior Art
A photoelectric encoder is well known heretofore, which includes a scale on which optical graduations are formed with a given pitch to generate a periodic detection signal. The photoelectric encoder has its resolution defined by the width of a groove of an optical grating and a pitch which is a distance between adjacent grooves of the grating, and defined by characteristics of an electronic-circuit for processing a signal after photoelectric conversion. Such an optical grating is generally formed by etching and hence has the atmost resolution of approximately 4 micro meter in view of final measurement accuracy, and finally practical resolution of approximately 1 micro meter if the electronic circuit is assumed to be used without costing up severely. It is therefore difficult to provide a further accurate optical grating.
In contrast, with the spread of a photoelectric type encoder, it is increasingly required to generate a detection signal at high resolution and with high accuracy.
To further improve the resolution of such a photoelectric type encoder, a grating interference type displacement meter has been proposed, in which fine pitch (typically about 1 micro meter) graduations are formed on a scale by holography and used as a diffraction grating to positively produce diffraction thereon for obtaining a detection signal.
Referring to FIG. 10, a conventional grating interference type displacement meter as disclosed in Japanese Laid-Open Publication No. 47-10034 is illustrated. The grating-interference type displacement meter includes a scale, on which a diffraction grating 10A of a pitch d has been formed, a He - Ne laser light source 12 for emitting a laser beam 14 of a wavelength λ as an optical flux to irradiate the diffraction grating 10A therewith, mirrors 16, 18 for reflecting zeroth-and first-order diffracted optical beams produced by the diffraction grating 10A, respectively, a beam splitter (coarse diffraction grating) 20 for splitting into three equal optical beams a combined beam of a zeroth-order beam of the first order optical beam reflected by the first order side mirror 18 and a first-order beam of the zeroth order optical beam reflected by the zeroth-order side mirror 16, and optical detector elements 22A, 22B and 22C for photoelectrically converting the combined beam splitted by the beam splitter 20, respectively. Herein, the respective elements described above except for the scale constitute an optical detector.
In FIG. 10, polarizers 24, 26 which are inserted into optical paths of the zeroth and first-order optical beams, respectively, have directions of polarizations thereof intersecting perpendicularly to each other, and hence no interference fringe is formed on and around the optical detector 22A which is to receive the central one among the aforementioned three optical beams which are yielded as described above by splitting the combined optical beam into the aforementioned three optical beams. Therefore, a simple additive sum signal, not an interference fringe, is incident upon the optical detector element 22A. The signal is here used as a reference signal Vr.
Additionally, an analyzer 28B, which serves to produce an interference fringe, is disposed just before the optical detector element 22B, which then generates a phase A detection signal φA which would be produced owing the interference fringe.
Further, a quarter wave plate 30 and an analyzer 28C are disposed just before the optical detector element 22C, which then generates a phase B detection signal φB different in its phase by 90° from the phase A detection signal φA.
An incident angle θ of the laser beam 14 and a diffraction angle φ of the first order beam satisfy a relationship:
d(sin θ+sin φ)=λ (1)
In such a grating interference type displacement meter, an optical grating of an 1 micro meter pitch or less can be achieved by manufacturing the diffraction grating 10A by holography for example, thereby assuring resolution of 0.01 micro meter.
However, when the glass surface of the scale 10 including the diffraction grating 10A formed thereon has bad flatness, in the transmission type grating interference type displacement meter as shown in FIG. 10, for example, angles of refraction of the zeroth-and first-order beams are changed and hence those optical beams are deflected as indicated by the arrow A in FIG. 11 (when the flatness of the lower surface of the scale is bad). As a result, directions of propagation of the two optical beams incident upon the optical detector elements 22B, 22C and inclined each other, and wave surfaces of the beams intersecting perpendicularly to these directions exhibit a pattern synthesized into a fringe shape, preventing a uniform interference pattern from being produced between the beams over the whole surface across a cross section on which the beams are superimposed. Accordingly, in such a transmission type grating interference type displacement meter, the flatness of the scale must be kept 5 micro meter/100 mm or less, and further no signal might be detected if the directions of optical axes would be inclined owing to any other factor.
On the contrary, in a reflection type grating interference type displacement meter in which a light source and a detector system are disposed together on one side of a reflection type scale, the light source and the detector system may be disposed on the one side of the scale, so that the reflection type one is suitable for a built-in type scale such as a separate type one. In such a reflection type grating interference type displacement meter, however, diffraction of a reflected light is used, so that displacement of an optical path originating from any inclination of the scale and insufficient flatness of the same is severer than the aforementioned transmission type is, requiring more accurate mounting and adjusting operations, which are difficult in execution.
SUMMARY OF THE INVENTION
In view of the drawbacks of the conventional displacement meters, it is an object of the present invention to provide a grating interference type displacement meter apparatus capable of assuring a stable signal and hence simplifying an alignment needed to mount a detector system by reducing influences due to variations, fine in the magnitude but severe in the influences, resulting from the bad flatness of a scale surface and from pitching (inclination) of the same.
In accordance with one aspect of the present invention, a grating interference type displacement meter apparatus comprises a scale including a diffraction grating formed thereon and a detector composed of a light source for irradiating said diffraction grating with an optical beam emitted therefrom and of an optical detector element for photoelectrically converting a combined beam of a plurality of optical beams produced by said diffraction grating, said detector means generating a periodically-changing detection signal responsibly to a relative displacement thereof with respect to said scale, said apparatus further comprising means for collimating a plurality of the optical beams produced by said diffraction grating before they are combined.
In accordance with the present invention, said means for collimating a plurality of the optical beams produced by said diffraction grating can be a convex lens having the focal point located on a refraction plane or a diffraction plane of said scale.
In accordance with the present invention, said means for collimating a plurality of the optical beams produced by said diffraction grating can be a concave mirror.
In accordance with another aspect of the present invention, a grating interference type displacement meter apparatus like above, further comprises an optical element for splitting the optical beam emitted from said light source such that splitted optical beams enter said diffration grating and a plurality of reflector means for reflecting back respective zeroth-order beams transmitted through said diffraction grating in the same direction respectively, such that those zeroth-order beams reenter said diffraction grating, whereby first-order diffracted beams, which have been produced through said diffraction grating from the zeroth-order reflected beams reentering the diffraction grating from a plurality of said reflector means, are combined.
In the conventional techniques, if a refraction angle (in the transmission type) and a diffraction angle (in the reflection type) would be changed owing to the bad flatness of a scale surface and to any inclination of the scale, two optical beams incident upon the optical detector elements 22B, 22C propagate differently at a certain angle, and hence wave front surfaces intersecting perpendicularly to their directions of propagation are synthesized forming a undesirable fringe pattern, thereby making it impossible to assure uniform interference between the optical beams over the entire surface, in cross section, of superposition of the optical beams. This leads to difficulties that the accuracy of the flatness of the scale must be kept at a high level, and that occurrence of additional inclination between the relative directions of propagation of the optical beams due to any other factor makes it impossible to detect a signal, resulting in any measurement error.
In accordance with a first preferred embodiment of the present invention, as illustrated in FIG. 2, a convex lens 40 is disposed such that its focal point is located on the refraction plane or the diffraction plane of the scale, so that a plurality of optical beams produced by the diffraction grating propagate in parallel to the directions of propagation thereof defined in the design of the apparatus, prior to their combination by a half mirror 50. This enables a stable interference signal to be constructed even when the flatness of the scale is of 15 micro meter/100 mm or more. Additionally, even when the optical axes of the optical beams incident upon the optical detector elements are inclined to each other, owing to any other factor, a stable detection signal can be assured. Herein, a convex mirror may also be available to realize the just-mentioned conditions.
Then, irrespective of the bad flatness of the scale surface and pitching due to variations of alignment upon mounting the scale, the optical beams after transmission through the lens can propagate in parallel to the optical axis as designed to the optical axis as designed at all times. In other words, the optical beams advance along parallel optical beams after transmission through or reflection on the half mirror 50, enabling stable interference to be kept. By making the optical system stable as described above, the affections of the uneven flatness of the scale surface and the pitching can be reduced, thereby assuring a more stable detection signal. Therefore, allowable extents of the flatness of the scale and the alignment upon the mounting of the scale can be improved, allowing the use of an inexpensive scale and simple alignment. Additionally, there is required no severe design of the shape and parallel transmission of the optical beam from the light source.
Particularly, in the reflection type grating interference type displacement meter, in which displacement of the optical path caused by any inclination of the scale, etc., is severer than in the transmission type and critical mounting and adjustment are required, the mounting and adjustment of the scale are more effectually facilitated, and a reflection type grating interference type displacement meter with use of a small-sized light source such as a laser diode for example can be realized.
Here, as illustrated in FIG. 11, the zeroth order optical beam transmitted by the scale 10 is also influenced by the flatness of the scale as the first order beam diffracted by the diffraction grating 10A, and in view of diffraction efficiency the amount of the zeroth order optical beam (about 80%) is very larger than that of the first order one (about 20%).
In accordance with a second preferred embodiment of the present invention, which has been contemplated in view of the just-mentioned aspect of the displacement meter, as illustrated in FIG. 8, the zeroth order optical beams transmitted by the diffraction grating (10) are reflected back in the same direction by a rectangular prism 40 or a triangular prism such as, a corner cube, a cats eye and the like, and are reincident upon the diffraction grating, whereby a plurality of the optical beams produced by the diffraction grating are allowed to propagate parallely to directions of propagation thereof set upon the design of the device.
Then, irrespective of the bad flatness of the scale and the pitching, the optical beams after the diffraction are allowed to propagate in the same direction at all times. The second preferred embodiment also assures a stable reference signal even when the flatness of the scale exceeds 15 micro meter/100 mm, as the first preferred embodiment.
Additionally, when the optical beam emitted from a light source is set so as not to go back to the light source, even if the light source is of such a type as a laser diode wherein it is affected by a returned light, oscillation of the light source is stabilized and hence associated noise can be reduced.
Herein, it is also possible in the prior example shown in FIG. 10 to replace the mirrors 16 and 18 by a rectangular prism for example. In this occasion, however, since the optical beam reflected on the mirror 18 is a first order diffracted one with the amount reduced to about 20% of that of the optical beam emanating from the light source. Accordingly, the amount of a further first order diffracted beam yielded by further diffracting the original first order diffracted beam is reduced to about 4% of that of the optical beam from the light source. This requires a further sensitive optical detector as well as a light source of greater capacity. Against this, since the present invention is adapted to reflect the zeroth order optical beam the amount of the zeroth-first diffracted beam can approach about 16% of the amount of the beam from the light source, thereby improving the response speed of the optical detector as well as miniaturizing the light source.
BRIEF DESCRIPTION OF THE DRAWINGS
The exact nature of this invention, as well as other objects and advantages thereof, will be readily apparent from consideration of the following specification relating to the accompanying drawings, in which like reference characters designate the same or similar parts throughout the figures thereof and wherein:
FIG. 1 is a front view illustrating the construction of a first preferred embodiment of a grating interference type displacement meter apparatus according to the present invention;
FIG. 2 is a view illustrating an optical path for description of the operation of the first preferred embodiment;
FIG. 3 is a front view illustrating the construction of a second preferred embodiment of the present invention;
FIG. 4 is a front view illustrating the construction of a third preferred embodiment of the present invention;
FIG. 5 is a side view illustrating the same;
FIG. 6 is a front view illustrating the construction of a fourth preferred embodiment of the present invention;
FIG. 7 is a front view illustrating the construction of a fifth preferred embodiment of the present invention;
FIG. 8 is a view illustrating an optical path for description of the operation of the fifth preferred embodiment;
FIG. 9 is a side view illustrating a portion of a modified example of the fifth preferred embodiment;
FIG. 10 is a front view illustrating the construction of an illustrative conventional grating interference type displacement meter; and
FIG. 11 is a sectional view illustrating a situation in the conventional example wherein optical beams are deflected owing to the bad flatness of a scale.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the following, preferred embodiments of the present invention will be described with reference to the accompanying drawings.
FIG. 1 illustrates a first preferred embodiment of the present invention. In the first embodiment, a transmission type grating interference type displacement meter includes, as in the aforementioned conventional case, a transmission type scale 10 having a diffraction grating formed thereon, a laser diode (LD) 42 as a light source for emitting a collimated parallel optical beam, and a detector composed of optical detector elements 22A 1 , 22A 2 , 22B and 22C each formed of PIN photodiodes for example, of analyzers 28B, 28C, and of a quarter wave plate 30, whereby a periodically-changing detection signal is generated responsibly to a relative displacement between the scale 10 and the detector, the displacement meter further including a P/S splitter 44 for halving the laser beam 14 emitted from the laser diode 42 conformably to a direction of polarization of the laser beam 14, a pair of mirrors 46A, 46B for directing optical beams so halved to the diffraction grating formed on the scale 10 such that they are symmetrically incident upon the grating at the same diffraction point C and at the same incident angle θ, beam splitters 48A, 48B provided to reflect and separate only first order diffracted optical beams respectively, the optical detector elements 22A 1 , 22A 2 for photoelectrically converting the diffracted optical beams separated by the beam splitters 48A, 48B to yield a reference signal Vr=(Vra+Vrb)/2, a half mirror 50 for recombining the diffracted beams reflected on the beam splitters 48A, 48B, and convex lenses 52A, 52B each disposed between the half mirror 50 and the beam splitters 48A, 48B and each having a focal point thereof at a refraction point of the scale 10.
With such a construction, the two optical beams diffracted by the diffraction grating are transmitted through the convex lenses 52A, 52B prior to the recombination thereof by the half mirror 50, whereby bent optical axes, which might be caused by small, but transversely antisymmetric variations such as insufficient flatness of a scale surface and pitching of the scale, can be corrected without being severely affected by those variations.
In the present embodiment, there has been adopted a transversely symmetrical construction, the so-called multi-stage one wherein the diffracted beams are recombined by the half mirror 50 after once reflected upon the beam splitters 48A, 48B. Accordingly, the diffracted beams enter the optical detector elements 22B, 22C at a substantially predetermined incident angle because of the first order diffracted beams having a common diffraction angle φ, even when the wavelength λ of the emitted beam from the laser diode 42 is varied. Thus, there are also moderated large, but symmetrical variations such as variations of the wavelength of the light source and variations of rolling on the scale and of any gap in the scale, so that the diffracted beams are not affected by such variations. Additionally, there is no fear of any reflected light on the scale 10 surface being directly incident on the optical detector element.
Although in the present embodiment, the convex lenses 52A, 52B were disposed between the beam splitters 48A, 48B and the half mirror 50, they may be disposed without limitation to the above situation between the scale 10 and the beam splitters 48A, 48B. They may be disposed at any position provided there would be satisfied conditions that the position is located on this side of the recombination of the optical beams diffracted by the diffraction grating and their focal points are placed on the reflection plane of the scale.
In succession, a second preferred embodiment of the present invention will be described with reference to FIG. 3.
In the second embodiment, a transmission type grating-interference type displacement meter of the same multi-stage type as in the first embodiment is disclosed, wherein as illustrated in FIG. 3, concave mirrors 54A, 54B are disposed instead of the convex lenses 52A, 52B at positions of the beam splitters 48A, 48B.
Herein, in the second embodiment, a reference signal Vr should be prepared separately using a beam splitter (not shown), etc., disposed at any other position.
Although in the first and second embodiments the present invention was applied to the transmission type grating-interference type displacement meter incorporating the transmission type scale 10, it may also be applicable to a reflection type grating-interference displacement meter incorporating a reflection type scale 60 as illustrated in FIG. 4 for example without limitation to the above illustrative example.
In the following, third and fourth preferred embodiments of the present invention, which are applied to the reflection type grating-interfence displacement meter, will be described.
In the third embodiment, a reflection type grating-interference type displacement meter is disclosed as illustrated in FIG. 4, wherein the convex lenses 52A, 52B are disposed between the beam splitters 48A, 48B and the polarizing plates 24, 26 such that their focal points are located at the diffraction point C of the scale 60.
Additionally, the optical beam 14 emitted from the laser diode 42 as the light source is slantingly incident on the scale 60 as illustrated in FIG. 5, so that a reflected beam on the scale 60 is prevented from being transmitted back to the laser diode 42 and hence automatic power control (APC) of the laser diode 42 is protected from being disturbed owing to such a back light.
Since also in the present embodiment, the optical system is transversely symmetrical, it is resistant to variations of the symmetrical optical path such as variations of the wavelength of the emitted beam from the light source and is capable of moderating the affection of such variations of the wavelength of the emitted beam from the laser diode 42.
Other factors are identical to those of the first embodiment, and hence the description will be omitted.
Successively, the fourth embodiment of the present invention will be described with reference to FIG. 6.
In the fourth embodiment, the same reflection type grating-interference type displacement meter as that in the third embodiment is disclosed, wherein the concave mirrors 54A, 54B are disposed instead of the convex lenses 52A, 52B at the positions of the beam splitters 48A, 48B.
Other factors are identical to those of the third or second embodiment and hence the description will be omitted.
In succession, a fifth preferred embodiment of the present invention will be described with reference to FIG. 7.
In the present embodiment, as illustrated in FIG. 7, a transmission type grating-interference type displacement meter includes, as in the conventional example, a transmission type scale 10, LD (laser diode) 42, and a detector composed of optical detector elements 22A 1 , 22A 2 , 22B, 22C, polarizing plates 24, 26, analyzers 28B, 28C, and a quarter wave plate 30, further including a beam splitter 44 for halving a laser beam 14 emitted from the laser diode 42 such that it is incident upon a diffraction grating formed on the scale 10, rectangular prisms 70A, 70B each for reflecting back respective zeroth-order beams in the same direction, which are transmitted by the diffraction grating on the scale 10 after entering the scale transversely symmetrically at the same incident angle θ with respect to the scale 10 (if θ is set to satisfy θ≅φ, φ is more stable), and directing them such that they reenter the diffraction grating, beam splitters 48A, 48B each for reflecting and separating first-order diffraction beams which have been formed through the diffraction grating from the zeroth-order reflected beams reflected on the rectangular prisms 70A, 70B and allowed to reenter the diffraction grating, the optical detector elements 22A 1 , 22A 2 for photoelectrically converting the diffracted beams separated by the beam splitters 48A, 48B to yield a reference signal Vr=(Vra+Vrb)/2, and a half mirror 50 for recombining the diffracted beams reflected on the beam splitters 48A, 48B.
With such a construction, the respective zeroth-order beams transmitted by the diffraction grating are reflected back in the same direction by the rectangular prisms 70A, 70B, for reentrance onto the diffraction grating. Therefore, as illustrated in FIG. 8, the optical beams, which have been differently refracted by the scale 10 owing to the bad flatness of the same after entering the same, reenter the same at the same incident angle, so that affections of the refraction on the beams are compensated to make equal at all times the diffraction angles φ of the two right and left beams. This assures the first-order diffracted beams propagating in the same direction at all times and hence a stable interference signal whatever the flatness of the scale surface is or whatever scale pitching due to an unsatisfactory alignment of the scale is.
Although in the present embodiment, the rectangular prisms were available as the means for reflecting back the zeroth-order beams transmitted by the diffraction grating, triangular prisms 80 such as corner-cube prisms and cats eyes, etc., may instead be incorporated. In this occasion, the diffraction point may transversely shifted in the vertical direction with respect to the space of FIG. 7, as illustrated in FIG. 9.
Furthermore, although in the above-mentioned embodiments the laser diode 42 was employed as a light source, the kinds of the light source are not limited thereto.
Although certain preferred embodiments have been shown and described, it should be understood that many changes and modifications may be made therein without departing from the scope of the appended claims.
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A grating-interference type displacement meter apparatus is disclosed wherein a convex lens or a concave mirror is disposed such that a focal point thereof is placed on a refraction plane or a diffraction plane of a diffraction grating, or wherein zeroth-order beams transmitted through the diffraction grating are reflected back in the same direction by a rectangular prism or a triangular prism for reentrance thereof onto the diffraction grating. Hereby, a plurality of optical beams produced by the diffraction grating are directed to propagate parallely to directions of propagation thereof defined in its design.
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FIELD OF THE INVENTION
[0001] The present invention relates to N 2 -(3,4-dimethylphenyl)-6-((4-(p-tolyl)piperazin-1-yl)methyl)-1,3,5-triazine-2,4-diamine, useful in the treatment of a condition or disorder associated with nicotinamide adenine dinucleotide phosphate oxidase (Nox). More specifically, the present invention relates to N 2 -(3,4-dimethylphenyl)-6-((4-(p-tolyl)piperazin-1-yl)methyl)-1,3,5-triazine-2,4-diamine as a Nox inhibitor for use in the treatment of various diseases that are caused or driven by elevated Nox activity, in particular Nox4 activity.
BACKGROUND OF THE INVENTION
[0002] The definition of oxidative stress is an in vivo imbalance between the formation and elimination of reactive oxygen. Changes of the normal redox state in the cell or tissues can produce harmful radicals that may damage components of the cellular machinery, including DNA, proteins and lipids. If the cellular components are chemically altered that cause genetic changes, this has generally been considered to promote formation of cancer or other serious diseases.
Sources of Oxygen Radicals—
[0003] Numerous in vivo generators of oxygen radicals (O 2 − , H 2 O 2 and OH − ) that potentially can cause oxidative stress have been identified: complex I and III in the mitochondria and NADPH oxidase, xanthine oxidase, cytochromes P450, metal ions (cobalt, vanadium, chromium, copper and iron) and some organic compounds that can redox cycle.
General Antioxidants—
[0004] There also are numerous endogenously cellular antioxidants such as superoxide dismutase (SOD), catalase, glutathione peroxidase, peroxiredoxins and sulfiredoxin. Vitamins provided by the food are also considered as an important part of the protection of the organism from harmful oxygen radicals, and recent discovery of important antioxidants present in many sources of food has increased the arsenal of antioxidants.
[0005] Antioxidants as Therapeutics—
[0006] It is very clear that some antioxidants can be helpful in preventing diseases and promote health. What is much less clear is what type of antioxidants can be used. Many of the antioxidants present in natural food are redox active. If these types of redox active substances are isolated and provided as complementary pharmaceuticals—this may end up being more harmful than helpful. Clinical trials have shown that untargeted application of antioxidants, which broadly scavenge oxygen radicals, are not only ineffective but may even be harmful. This was illustrated in a study made with sixty-seven randomized trials with 232,550 participants including healthy and patients with various diseases (Bjelakovic G, Nikolova D, Simonetti R G, Gluud C. Cochrane Database Syst Rev. 2008 Jul. 16; (3):CD004183. Epub 2008 Jul. 16).
[0007] Thus general antioxidants that are redox active may actually be adding to the cellular damage, by mediating a harmful redox cycle. Other general antioxidants will harmfully block normal cellular in vivo activity necessary to maintain bodily function.
Source and Role of Reactive Oxygen—
[0008] What has become increasingly clear is that what is causing excessive production and accumulation of reactive oxygen, in a number of pathological conditions, such as inflammation, type 2 diabetes, diabetes complications, polycystic ovary syndrome, stroke, detrimental neurological conditions and cancer, is not generally leaking oxygen radicals such as complex I or III in the mitochondria—rather it is up-regulated powerful producers of oxygen radicals—that are part of the normal cellular signal transduction system. Thus the definition of oxidative stress need not be oxygen radicals that will irreversibly alter DNA, protein or lipids, but instead increasingly interfere, if up regulated with “normal” signal transduction creating an imbalance on a cellular level that eventually may alter other tissues and whole bodily function. A typical example of this is the metabolic syndrome, connected to vascular disease, diabetes 2, stroke, nephropathy, neuropathy, heart failure and stroke with insulin resistance as the initiating factor (Reaven, “Role of insulin resistance in human disease”, Diabetes 37(12), 1988). Insulin resistance in itself is also part of normal bodily function as a tool to direct storage of energy selectively to a suitable receiving organ. However, when metabolic changes occur, such as in overfeeding, or other disturbances such as acromegaly with excess growth hormone production or malfunctioning leptin as in ob/ob-mice, this will induce a harmful condition with an uncontrolled insulin resistance that may cause organ failure connected to the metabolic syndrome. The common denominator to the uncontrolled insulin resistance is overproduction of local and systemic oxygen radicals (Houstis et al., Nature 440, 2006; Katakam et al., J cereb blood Flow Metab, 2012 Jan. 11).
[0009] One of the most interesting candidates for this overproduction is a family of trans-membrane proteins (enzymes), referred to as NADPH oxidase (Nox). There are seven family members of Nox identified (Nox 1-5 and Duox 1-2) that very often are being recognized as a major or key source of reactive oxygen and that also play a major role in a number of cellular events as part of the normal cellular signal transduction system, including proliferation (Brar et al., Am J Physiol Lung Cell Mol Physiol, 282, 2002), growth (Brar et al., Am J Physiol Cell Physiol, 282, 2002), fibrosis (Grewal et al., Am J Physiol, 276, 1999), migration (Sundaresan et al., Science, 270, 1995), apoptosis (Lundqvist-Gustafsson et al., J Leukoc Biol, 65, 1999), differentiation (Steinbeck et al., J Cell Physiol, 176, 1998), cytoskeletal rearrangement (Wu et al., J Virol, 78, 2004) and contraction (Rueckschloss et al., Exp Gerontol, 45, 2010).
NADPH Oxidase and Disease—
[0010] Some genetic conditions with decreased NADPH oxidase activity have been identified—defect Nox2 decreases immunologic response to kill and neutralize microbial attacks (Chronic granulomatous disease)—defect Nox3 in inner ear renders defective gravity perception and dual NADPH oxidase Duox2 having deficient enzymatic activity in the thyroid gland gives rise to hypothyroidism.
[0011] There is however a much larger list of publications that also seems to grow exponentially, that witness of strong evidence that increased Nox activity is part of or even causative of a number of diseases (Lambeth J D, Review Article “ Nox enzymes, ROS, and chronic disease: An example of antagonistic pleiotropy ”, Free Radical Biology & Medicine 43, 2007; Takac I et al., “ The Nox Family of NADPH Oxidases: Friend or Foe of the Vascular System ”, Curr Hypertens Rep. 2011 Nov. 10; Montezano A C, “ Novel Nox homologues in the vasculature: focusing on Nox 4 and Nox 5”, Clin Sci London 2011; Bedard K et al., “ The Nox family of ROS - generating NADPH oxidases: physiology and pathophysiology ” Physiol Rev. 2007; Camici M et al., “ Obesity - related glomerulopathy and podocyte injury: a mini review ”, Front Biosci 2012; Nabeebaccus A et al., “ NADPH oxidases and cardiac remodeling ” Heart Fai Rev. 2011; Kuroda J et al., “ NADPH oxidase and cardiac failure ” J Cardiovasc Transl Res. 2010; Kuroda J et al., “ NADPH oxidase 4 is a major source of oxidative stress in the failing heart ” Proc Natl Acad Sci USA 2010; Maejima Y et al., “ Regulation of myocardial growth and death by NADPH oxidase ” J Mol Cell Cardiol. 2011; Barnes J L et al., “ Myofibroblst differentiation during fibrosis: role of NADPH oxidases ” Kidney international, 2011; Alison Cave “ Selective targeting of NADPH oxidase for cardiovascular protection ” Current Opinion in Pharmacology 2009; Albert van der Vliet “ Nox enzymes in allergic airway inflammation ” Biochimica et Biophysica Acta 1810, 2011; Pendyala S et al., “ Redox regulation of Nox proteins ” Respiratory Physiology & Neurobiology 174, 2010; Nair D et al., “ Intermittent Hypoxia - Induced Cognitive Deficits Are Mediated by NADPH oxidase Activity in a Murine Model of Sleep Apnea ” PLoS ONE, vol. 6, Issue 5, May 2011; Chia-Hung Hsieh et al., “ NADPH oxidase Subunit 4- Mediated Reactive Oxygen species Contribute to Cycling Hypoxia - Promoted Tumor Progression in Glioblastoma Multiforme ” PloS ONE, vol 6, issue 9, September 2011; Sedeek M et al., “ Molecular mechanisms of hypertension: role of nox family NADPH oxidase ” Current Opinion in Nephrology and Hypertension 2009; Augusto C et al., “ Novel Nox homologues in the vasculature: focusing on Nox 4 and Nox 5” Clinical Science 2011; Briones A M et al., “ Differential regulation of Nox 1 , Nox 2 and Nox 4 in vascular smooth muscle cells from WKY and SHR ” Journal of the American Society of Hypertension 5:3, 2011).
[0012] It has been recently shown that the Nox enzymes and particularly Nox 4 are highly involved in pulmonary fibrosis. The function of oxidative stress in fibrosis are well recognized (Kinnula V L, Fattman C L, Tan R J, Oury T D (2005) Oxidative stress in pulmonary fibrosis: a possible role for redox modulatory therapy. Am J Respir Crit Care Med 172:417-422), as there is a substantial and growing body of evidence indicating that oxidative stress plays an important role in the pathological development of lung fibrosis as well as fibrosis in multiple organ systems (Kuwano K, Nakashima N, Inoshima I, Hagimoto N, Fujita M, Yoshimi M, Maeyama T, Hamada N, Watanabe K, Hara N (2003) Oxidative stress in lung epithelial cells from patients with idiopathic interstitial pneumonias. Eur Respir J 21:232-240). Thus, Nox enzymes and particularly Nox4 appear to be involved also in lung infections, acute lung injury, pulmonary arterial hypertension, obstructive lung disorders, fibrotic lung disease, and lung cancer.
NADPH Oxidase Isoenzymes, Similarities, Differences and Function—
[0013] All the seven isoenzymes of NADPH oxidase (identified) are similar in the way of having NADPH and FAD binding site and six trans-membrane domains and in that they include two heme complexes. All the NADPH oxidase forms use the same basic mechanism to generate reactive oxygen, but the subcellular localizations and the modes of actions differ significantly. The reactive oxygen species produced by the enzymatic Nox-family are either superoxide O 2 − or hydrogen peroxide H 2 O 2 .
[0014] Nox1 and 2 are constitutively attached to p22phox and to activate the enzyme complex other components such as Rac, p47phox, p67phox are required for full Nox1 activity. Nox2 needs Rac, p40phox, p47phox and p67phox for full activation. Nox1 and 2 generate O 2 − when activated.
[0015] Nox3 also needs to assemble cytosolic proteins to be active (Cheng et al., J Biol Chem, 279(33), 2004).
[0016] Nox4 is also associated with p22phox, and is constitutively active in this form. Nox4 activity is, however, regulated through expression—not through assembly or ligand activation, which distinguishes this isoform from other isoforms (Serrander et al., Biochem J. 406, 2007). When induced, Nox4 is generally expressed at higher level than Nox1 and 2 (Ago et al., Circulation, 109, 2004). Nox4 seems to mainly generate H 2 O 2 instead of O 2 − as the other Nox-variants (Takac et al., J. Biol. Chem. 286, 2011). This makes this isoform unique because H 2 O 2 has the ability to cross membranes and thus to act at longer distance than O 2 − that has a very short half-life.
[0017] Nox5, Doux1 and Doux2 are activated by Ca 2+ (De Deken, Wang et al., J. Biol Chem., 275(30), 2000).
[0018] Nox4 and Diseases—
[0019] The uniqueness of Nox4 in comparison to the other isoforms is also connected to uniqueness as a therapeutic target as it seems to be involved in a number of different diseases when overexpressed.
[0020] Nox4 is ubiquitously expressed in many cell-types although at a very low level until induced. It is, however mainly found in kidney, endothelial cells, adventitial fibroblasts, placenta, smooth muscle cells, osteoclasts and is the predominant Nox that is expressed in tumors (Chamseddine et al., Am J Physiol Heart Circ Physiol. 285, 2003; Ellmark et al., Cardiovasc Res. 65, 2005; Van Buul et al., Antioxid Redox Signal. 7, 2005; Kawahara et al., BMC Evol Biol. 7, 2007; Krause et al., Jpn J Infect is. 57(5), 2004; Griendling, Antioxid Redox Signal. 8(9), 2006). It was found that Nox4 was overexpressed in the majority of breast cancer cell-lines and primary breast tumors. Overexpression of Nox4 in already transformed breast tumor cells showed increased tumorigenicity, and Nox4 was here identified in the mitochondria. Nox4 was suggested as a target to treat breast cancer (Graham et al., Cancer Biol Ther 10(3), 2010).
[0021] Nox4 mediates oxidative stress and apoptosis caused by TNF-α in cerebral vascular endothelial cells (Basuroy et al., Am J Physiol Cell Physiol vol. 296, 2009). Its adverse effect following ischemic stroke is well demonstrated in animal models and human tissue. Knockdown experiment, of Nox4, dramatically reduced the area of neuronal damage (Sedwick, PLos Biology, vol. 8 issue 9, 2010; Kleinschnitz et al., vol. 8 issue 9, 2010)
[0022] It was demonstrated through knockdown and overexpression studies in both microvascular and umbilical vein endothelial cells that increased Nox4 activity plays an important role in proliferation and migration of endothelial cells (Datla et al., Arterioscler Throm Vasc Biol. 27(11), 2007). Initially it was believed that Nox2 was responsible for the angiogenic defects in diabetes but the focus has shifted more towards Nox4 (Zhang et al., PNAS, 107, 2010; Garriodo-Urbani et al., Plos One 2011; Takac et al., Curr Hypertens Rep, 14, 2012). Nox4 play a key role in epithelial cell death during development of lung fibrosis (Camesecchi et al., Antiox Redox Signal. 1:15(3), 2011).
[0023] It further was demonstrated that siRNA-mediated knockdown of Nox4 significantly reduces NADPH oxidase activity in purified mitochondria from mesangial cells and kidney cortex. The knockdown blocked glucose-induced mitochondrial superoxide generation. It was suggested that Nox4 acts as a central mediator to oxidative stress that may lead to mitochondrial dysfunction and cell injury in diabetes (Block et al., PNAS vol. 106, no. 34, 2009).
[0024] It also was demonstrated that Nox4 was systemically up-regulated at diet-induced obesity in rats (Jiang, redox rep, 16(6), 2011).
[0025] Nox4 has been strongly connected to the pathology in failing hearts. (Nabeebaccus A et al. “NADPH oxidases and cardiac remodeling” Heart Fai Rev. 2011; Kuroda J et al., “NADPH oxidase and cardiac failure Cardiovasc Transl Res. 2010; Kuroda J et al., “NADPH oxidase 4 is a major source of oxidative stress in the failing heart” Proc Natl Acad Sci USA 2010). A connection between increased mitochondrial Nox4 activity and dysfunction of “the aging heart” has been suggested (Tetsuro Ago et al., AGING, December 2010, vol. 2 No 12).
[0026] Extracellular matrix accumulation contributes to the pathology of chronic kidney disease. The growth factor IGF-I activity is a major contributor to this process and Nox4 is a mediator in this process (New et al., Am J Physiol Cell Physiol. 302(1), 2012). The connection between chronic activation of the renin-angiotensin and the progression of kidney damage system is well established with Nox4 and Angiotensin II as collaborators in this process (Chen et al., Mol Cell Biol. 2012).
[0027] From the above, it thus appears that the Nox enzymes have several functions in the living body, and that they may also be involved in various disorders. Examples of such diseases and disorders are cardiovascular disorders, respiratory disorders, metabolism disorders, endocrine disorders, skin disorders, bone disorders, neuroinflammatory and/or neurodegenerative disorders, kidney diseases, reproduction disorders, diseases affecting the eye and/or the lens and/or conditions affecting the inner ear, inflammatory disorders, liver diseases, pain, cancers, allergic disorders, traumatisms, such as traumatic head injury, septic, hemorrhagic and anaphylactic shock, diseases or disorders of the gastrointestinal system, angiogenesis, angiogenesis-dependent conditions. It also appears that especially Nox4 has been found to be involved in such disorders. Consequently, it is considered that compounds capable of inhibiting Nox, and in particular compounds capable of selectively inhibiting Nox4, would be of great interest for use in the treatment of diseases and disorders involving Nox enzymes, and in particular Nox4.
[0028] Several patent applications from GenKyoTex SA relate to various pyrazolo and pyrazoline derivatives for use as Nox inhibitors. Thus, PCT applications WO 2010/035217, WO 2010/035219, WO 2010/035220, WO 2010/035221, WO 2011/036651, WO2011/101804 and WO2011/101805, describe several conditions and disorders related to Nox and provide references to various sources of literature on the subject. The information contained in said applications and in the literature referred to therein is incorporated herein by reference.
[0029] As noted herein above, Nox4 is involved in stroke, among other diseases. Stroke is the second leading cause of death worldwide and survivals often are disabled with serious cognitive difficulties affecting social life as well as the ability to perform work. In addition to the suffering of the patients and the close relatives this also is extremely costly to society and the healthcare system. Without new efficient treatment of stroke patients, the cost to care for stroke victims during the next 45 years will exceed $2.2 trillion in the US only. Stroke is classified into two major categories. Ischemic that causes interruption of blood supply and hemorrhagic that results from rupture of a blood vessel. Both induce rapid loss of brain function caused by disturbances in blood supply. Ischemic stroke is by far the most common form accounting for 87% of the cases, while 9% are due to intracerebral hemorrhage and the remaining 4% are due to subarachnoid hemorrhage.
[0030] The pathophysiology of ischemic stroke is complex and the patient recovery is dependent on the length in time that neuronal tissues are deprived of blood supply. Brain tissues deprived of oxygen for more than three hours will be irreversibly damaged. The pathophysiology includes excitotoxicity mechanisms, inflammatory pathways, oxidative damage, ionic imbalances, apoptosis, angiogenesis and endogenous neuron protection. Additionally when white blood cells re-enter a previously hypo perfused region via returning blood, they can occlude small vessels, producing additional ischemia.
[0031] Different strategies to manage stroke are; to identify risk groups for preventive treatment; development, implantation and dissemination of evidence-based clinical practice guidelines in order to set a standard for stroke management through the continuum of care with early treatment that is fundamental to improve the outcome following an ischemic stroke attack. One of two approved treatments today is IV administration of tissue plasminogen activator (tPA) that will induce thrombolysis, which may remove the clot and restore blood supply to the brain tissue. The other method is to mechanically remove the clot, to restore blood supply. Other approaching methods are in early phase research and some in clinical trials. New potential therapies of interest include administration of neuroprotective agents, cooling of the ischemic brain and the use of stents to revasculate occluded arteries.
[0032] Thus, a method of treatment an ischemic stroke attack generally comprises removing mechanical hinders (blood clots) from the blood flow, e.g. by intravenous administration of tissue plasminogen activator (tPA). It is thought that combining the removal of mechanical hinders from the blood flow with administration, either before or after, of neuroprotective agents, may help saving ischemic neurons in the brain from irreversible injury, including apoptosis. However, as of today no neuroprotective agent has been provided for successful treatment of stroke. It therefore appears that there still is a need for improved treatment of stroke, in particular improved treatment by administration of neuroprotective agents, preferably in combination with the removal of blood clots in the ischemic brain.
[0033] In the international application No. PCT/EP2013/072098, published as WO2014/064118, triazine derivates of the general formula
[0000]
[0000] are disclosed as useful the treatment of a condition or disorder associated with Nox, preferably Nox4.
SUMMARY OF THE INVENTION
[0034] As mentioned herein above, trizazine derivatives have been previously described for use as Nox4 inhibitors. However, the present inventors now have identified a triazine derivative having surprisingly high selectivity for Nox4 over both Nox1 and Nox2, in combination with other surprisingly good properties of importance for a pharmaceutical use, e.g. a surprisingly high kinetic solubility and Caco-2 permeability.
[0035] According to a first aspect, therefore, the compound N 2 -(3,4-dimethylphenyl)-6-((4-(p-tolyl)piperazin-1-yl)methyl)-1,3,5-triazine-2,4-diamine, or pharmaceutically acceptable salt thereof, is provided.
[0036] As noted herein above, the compound of the invention is a Nox4 inhibitor and as such is useful in therapy. Consequently, according to another aspect, the compound N 2 -(3,4-dimethylphenyl)-6-((4-(p-tolyl)piperazin-1-yl)methyl)-1,3,5-triazine-2,4-diamine, or pharmaceutically acceptable salt thereof, is provided for use in therapy.
[0037] In some embodiments, the therapy is directed to treatment of a human patient, i.e. the compound is for human (pharmaceutical) use.
[0038] In some other embodiments, the therapy is directed to the treatment of a non-human mammal, such as a pet animal, i.e. the compound is for veterinary use.
[0039] In another aspect, a pharmaceutical composition is provided, comprising the compound N 2 -(3,4-dimethylphenyl)-6-((4-(p-tolyl)piperazin-1-yl)methyl)-1,3,5-triazine-2,4-diamine, or a pharmaceutically acceptable salt of said compound, and optionally a pharmaceutically acceptable excipient.
[0040] In some embodiments, the pharmaceutical composition is for human use, i.e. for the treatment of a human subject.
[0041] In some other embodiments, the pharmaceutical composition is a veterinary composition, suitable for the treatment of an animal, such as e.g. a dog or a cat.
[0042] According to another aspect, the compound N 2 -(3,4-dimethylphenyl)-6-((4-(p-tolyl)piperazin-1-yl)methyl)-1,3,5-triazine-2,4-diamine, or pharmaceutically acceptable salt thereof, is provided for use in the treatment of diseases associated with, e.g. caused or driven by, elevated Nox activity, more specifically elevated Nox4 activity.
[0043] Examples of such conditions and disorders e.g. are those mentioned herein above as related to or mediated by Nox, for example conditions and disorders selected from endocrine disorders, cardiovascular disorders, respiratory disorders, metabolism disorders, skin disorders, bone disorders, neuroinflammatory and/or neurodegenerative disorders, kidney diseases, reproduction disorders, diseases affecting the eye and/or the lens and/or conditions affecting the inner ear, inflammatory disorders, liver diseases, pain, cancers, allergic disorders, traumatisms, septic, hemorrhagic and anaphylactic shock, diseases or disorders of the gastrointestinal system, abnormal angiogenesis and angiogenesis-dependent conditions, lung infections, acute lung injury, pulmonary arterial hypertension, obstructive lung disorders, and fibrotic lung disease.
[0044] According to one aspect, there is provided a method of inhibiting the activity of Nox, in particular Nox4, in a mammal in need thereof, by administering to said mammal the compound N 2 -(3,4-dimethylphenyl)-6-((4-(p-tolyl)piperazin-1-yl)methyl)-1,3,5-triazine-2,4-diamine, or a pharmaceutically acceptable salt of said compound.
[0045] According to one aspect, the compound of the present invention is for use as neuroprotective agents in the treatment of stroke, e.g. ischemic stroke.
[0046] According to one aspect, the use of a compound as defined herein is provided, for the manufacturing of a medicament for the treatment of any of the disorders mentioned herein.
DETAILED DESCRIPTION OF THE INVENTION
[0047] In general any term used herein shall be given its normal meaning as accepted within the field to which the present invention belongs. For the sake of clarity, however, some definitions will be given herein below, and shall apply throughout the specification and the appended claims, unless otherwise specified or apparent from the context.
[0048] The term “endocrine disorder” refers to disorders of the endocrine system and may be as well endocrine gland hyposecretion as hypersecretion, or tumors of endocrine glands. Diabetes and polycystic ovarian syndrome are examples of endocrine disorders.
[0049] The term “cardiovascular disorder or disease” comprises atherosclerosis, especially diseases or disorders associated with endothelial dysfunction including but not limited to hypertension, cardiovascular complications of Type I or Type II diabetes, intimal hyperplasia, coronary heart disease, cerebral, coronary or arterial vasospasm, endothelial dysfunction, heart failure including congestive heart failure, peripheral artery disease, restenosis, trauma caused by a stent, stroke, ischemic attack, vascular complications such as after organ transplantation, myocardial infarction, hypertension, formation of atherosclerotic plaques, platelet aggregation, angina pectoris, aneurysm, aortic dissection, ischemic heart disease, cardiac hypertrophy, pulmonary embolus, thrombotic events including deep vein thrombosis, injury caused after ischemia by restoration of blood flow or oxygen delivery as in organ transplantation, open heart surgery, angioplasty, hemorrhagic shock, angioplasty of ischemic organs including heart, brain, liver, kidney, retina and bowel.
[0050] The term “respiratory disorder or disease” comprises bronchial asthma, bronchitis, allergic rhinitis, adult respiratory syndrome, cystic fibrosis, lung viral infection (influenza), pulmonary hypertension, idiopathic pulmonary fibrosis and chronic obstructive pulmonary diseases (COPD).
[0051] The term “allergic disorder” includes hay fever and asthma.
[0052] The term “traumatism” includes polytraumatism.
[0053] The term “disease or disorder affecting the metabolism” includes obesity, metabolic syndrome and Type II diabetes.
[0054] The term “skin disease” or disorder” includes psoriasis, eczema, dermatitis, wound healing and scar formation.
[0055] The term “bone disorder” includes osteoporosis, osteoporosis, osteosclerosis, periodontitis, and hyperparathyroidism.
[0056] The term “neurodegenerative disease or disorder” comprises a disease or a state characterized by a central nervous system (CNS) degeneration or alteration, especially at the level of the neurons such as Alzheimer's disease, Parkinson's disease, Huntington's disease, amyotrophic lateral sclerosis, epilepsy and muscular dystrophy. It further comprises neuro-inflammatory and demyelinating states or diseases such as leukoencephalopathies, and leukodystrophies. The term “demyelinating” is referring to a state or a disease of the CNS comprising the degradation of the myelin around the axons. In the context of the invention, the term demyelinating disease is intended to comprise conditions which comprise a process that demyelinate cells such as multiple sclerosis, progressive multifocal leukoencephalopathy (PML), myelopathies, any neuroinflammatory condition involving autoreactive leukocyte within the CNS, congenital metabolic disorder, a neuropathy with abnormal myelination, drug induced demyelination, radiation induced demyelination, a hereditary demyelinating condition, a prion induced demyelinating condition, encephalitis induced demyelination or a spinal cord injury. Preferably, the condition is multiple sclerosis.
[0057] The term “kidney disease or disorder” includes diabetic nephropathy, renal failure, glomerulonephritis, nephrotoxicity of aminoglycosides and platinum compounds and hyperactive bladder. In a particular embodiment, the term according to the invention includes chronic kidney diseases or disorders.
[0058] The term “reproduction disorder or disease” includes erectile dysfunction, fertility disorders, prostatic hypertrophy and benign prostatic hypertrophy.
[0059] The term “disease or disorder affecting the eye and/or the lens” includes cataract including diabetic cataract, re-opacification of the lens post cataract surgery, diabetic and other forms of retinopathy.
[0060] The term “conditions affecting the inner ear” includes presbyacusis, tinnitus, Meniere's disease and other balance problems, utriculolithiasis, vestibular migraine, and noise induced hearing loss and drug induced hearing loss (ototoxicity).
[0061] The term “inflammatory disorder or disease” means inflammatory bowel disease, sepsis, septic shock, adult respiratory distress syndrome, pancreatitis, shock induced by trauma, bronchial asthma, allergic rhinitis, rheumatoid arthritis, chronic rheumatoid arthritis, arteriosclerosis, intracerebral hemorrhage, cerebral infarction, heart failure, myocardial infarction, psoriasis, cystic fibrosis, stroke, acute bronchitis, chronic bronchitis, acute bronchiolitis, chronic bronchiolitis, osteoarthritis, gout, myelitis, ankylosing spondylitis, Reuter syndrome, psoriatic arthritis, spondylarthritis, juvenile arthritis or juvenile ankylosing spondylitis, reactive arthritis, infectious arthritis or arthritis after infection, gonococcal arthritis, syphilitic arthritis, Lyme disease, arthritis induced by “angiitis syndrome,” polyarteritis nodosa, anaphylactic angiitis, Luegenec granulomatosis, rheumatoid polymyalgia, articular cell rheumatism, calcium crystal deposition arthritis, pseudogout, non-arthritic rheumatism, bursitis, tendosynovitis, epicondyle inflammation (tennis elbow), carpal tunnel syndrome, disorders by repetitive use (typing), mixed form of arthritis, neuropathic arthropathy, hemorrhagic arthritis, vascular peliosis, hypertrophic osteoarthropathy, multicentric reticulohistiocytosis, arthritis induced by specific diseases, blood pigmentation, sickle cell disease and other hemoglobin abnormality, hyperlipoproteinemia, dysgammaglobulinemia, hyperparathyroidism, acromegaly, familial Mediterranean fever, Bechet's disease, systemic autoimmune disease erythematosus, multiple sclerosis and Crohn's disease or diseases like relapsing polychondritis, chronic inflammatory bowel diseases (IBD) or the related diseases which require the administration to a mammal in a therapeutic effective dose of a compound expressed by Formula (I) in a sufficient dose to inhibit NADPH oxidase.
[0062] The term “liver diseases or disorders” include liver fibrosis, alcohol induced fibrosis, steatosis and non-alcoholic steatohepatitis.
[0063] The term “arthritis” means acute rheumatic arthritis, chronic rheumatoid arthritis, chlamydial arthritis, chronic absorptive arthritis, anchylous arthritis, arthritis based on bowel disease, filarial arthritis, gonorrheal arthritis, gouty arthritis, hemophilic arthritis, hypertrophic arthritis, juvenile chronic arthritis, Lyme arthritis, neonatal foal arthritis, nodular arthritis, ochronotic arthritis, psoriatic arthritis or suppurative arthritis, or the related diseases which require the administration to a mammal in a therapeutic effective dose of a compound expressed by Formula (I) in a sufficient dose to inhibit NADPH oxidase.
[0064] The term “pain” includes hyperalgesia associated with inflammatory pain.
[0065] The term “cancer” means carcinoma (e.g., fibrosarcoma, myxosarcoma, liposarcoma, chondrosarcoma, osteogenic sarcoma, chordoma, angiosarcoma, endothelium sarcoma, lymphangiosarcoma, lymphangioendothelioma, periosteoma, mesothelioma, Ewing's tumor, leiomyosarcoma, rhabdomyosarcoma, colon carcinoma, pancreatic cancer, breast cancer, ovarian cancer, renal cancer, prostatic carcinoma, squamous cell carcinoma, basal cell carcinoma, adenocarcinoma, sweat gland carcinoma, sebaceous gland carcinoma, papillary carcinoma, papillary adenocarcinoma, cystadenocarcinoma, medullary carcinoma, bronchogenic carcinoma, renal cell carcinoma, hepatocellular carcinoma, cholangiocarcinoma, choriocarcinoma, seminoma, embryonal carcinoma, Wilms' tumor, cervical cancer, orchioncus, lung cancer, small-cell lung cancer, lung adenocarcinoma, bladder cancer or epithelial cancer) or the related diseases which require the administration to a mammal in a therapeutic effective dose of a compound expressed by the Formula (I) in a sufficient dose to inhibit NADPH oxidase.
[0066] The term “disease or disorders of the gastrointestinal system”, includes gastric mucosa disorders ischemic bowel disease management, enteritis/colitis, cancer chemotherapy, or neutropenia.
[0067] The term “angiogenesis” includes sprouting angiogenesis, intussusceptive angiogenesis, vasculogenesis, arteriogenesis and lymphangiogenesis. Angiogenesis is the formation of new blood vessels from pre-existing capillaries or post-capillary venules and occurs in pathological conditions such as cancers, arthritis and inflammation. A large variety of tissues, or organs comprised of organized tissues, can support angiogenesis in disease conditions including skin, muscle, gut, connective tissue, joints, bones and the like tissue in which blood vessels can invade upon angiogenic stimuli. As used herein, the term “angiogenesis-dependent condition” is intended to mean a condition where the process of angiogenesis or vasculogenesis sustains or augments a pathological condition. Vasculogenesis results from the formation of new blood vessels arising from angioblasts which are endothelial cell precursors. Both processes result in new blood vessel formation and are included in the meaning of the term angiogenesis-dependent conditions. Similarly, the term “angiogenesis” as used herein is intended to include de novo formation of vessels such as those arising from vasculogenesis as well as those arising from branching and sprouting of existing vessels, capillaries and venules.
[0068] The term “angiogenesis inhibitory,” means which is effective in the decrease in the extent, amount, or rate of neovascularization. Effecting a decrease in the extent, amount, or rate of endothelial cell proliferation or migration in the tissue is a specific example of inhibiting angiogenesis. Angiogenesis inhibitory activity is particularly useful in the treatment of any cancers as it targets tumor growth process and in the absence of neovascularization of tumor tissue, the tumor tissue does not obtain the required nutrients, slows in growth, ceases additional growth, regresses and ultimately becomes necrotic resulting in killing of the tumor. Further, an angiogenesis inhibitory activity is particularly useful in the treatment of any cancers as it is particularly effective against the formation of metastases because their formation also requires vascularization of a primary tumor so that the metastatic cancer cells can exit the primary tumor and their establishment in a secondary site requires neovascularization to support growth of the metastases.
[0069] As used herein, “treatment” and “treating” and the like generally mean obtaining a desired pharmacological and physiological effect. The effect may be prophylactic in terms of preventing or partially preventing a disease, symptom or condition thereof and/or may be therapeutic in terms of a partial or complete cure of a disease, condition, symptom or adverse effect attributed to the disease. The term “treatment” as used herein covers any treatment of a disease in a mammal, particularly a human, and includes: (a) preventing the disease from occurring in a subject which may be predisposed to the disease but has not yet been diagnosed as having it; (b) inhibiting the disease, i.e., arresting its development; or relieving the disease, i.e., causing regression of the disease and/or its symptoms or conditions.
[0070] The term “subject” as used herein refers to mammals. Mammals contemplated by the present invention include humans and non-human mammals, such as primates, domesticated animals such as farm animals, e.g. cattle, sheep, pigs, horses and the like, as well as pet animals, such as dogs and cats, and the like.
[0071] “An effective amount” refers to an amount of a compound that confers a therapeutic effect on the treated subject. The therapeutic effect may be objective (i.e., measurable by some test or marker) or subjective (i.e., subject gives an indication of or feels an effect).
[0072] The term “inhibitor” used in the context of the invention is defined as a molecule that inhibits completely or partially the activity of Nox, in particular Nox4, and/or inhibits or reduces the generation of reactive oxygen species (ROS).
[0073] “Pharmaceutically acceptable” means being useful in preparing a pharmaceutical composition that is generally safe, non-toxic and neither biologically nor otherwise undesirable and includes being useful for veterinary use as well as human pharmaceutical use.
[0074] The expression “compound of the present invention” should be construed also as referring to a pharmaceutically acceptable salt of the compound N 2 -(3,4-dimethylphenyl)-6-((4-(p-tolyl)piperazin-1-yl)methyl)-1,3,5-triazine-2,4-diamine, unless otherwise indicated or apparent from the context.
[0075] The compound of the present invention is a Nox inhibitor. More specifically, the compound of the present invention is a Nox4 inhibitor. The capacity of inhibiting predominantly one particular Nox isoform, i.e. Nox4, is considered to be an important advantage of the present compound, in view of the fact that Nox isoforms not only are involved in diseases, as Nox4, but also have various important biological functions in the living body.
[0076] Depending on the process conditions compound of the invention is obtained either in neutral or salt form. Acid addition salts of the inventive compound may in a manner known per se be transformed into the free base using basic agents such as alkali or by ion exchange. The free base obtained may also form salts with organic or inorganic acids. Alkali addition salts of the inventive compound may in a manner known per se be transformed into the free acid by using acidic agents such as acid or by ion exchange. The free acid obtained may also form salts with organic or inorganic bases.
[0077] In the preparation of acid or base addition salts, preferably such acids or bases are used which form suitably therapeutically acceptable salts. Examples of such acids are hydrohalogen acids, sulfuric acid, phosphoric acid, nitric acid, aliphatic, alicyclic, aromatic or heterocyclic carboxylic or sulfonic acids, such as formic acid, acetic acid, propionic acid, succinic acid, glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, ascorbic acid, maleic acid, hydroxymaleic acid, pyruvic acid, p-hydroxybenzoic acid, embonic acid, methanesulfonic acid, ethanesulfonic acid, hydroxyethanesulfonic acid, halogenbenzenesulfonic acid, toluenesulfonic acid or naphthalenesulfonic acid. Base addition salts include those derived from inorganic bases, such as ammonium or alkali or alkaline earth metal hydroxides, carbonates, bicarbonates, and the like, and organic bases such as alkoxides, alkyl amides, alkyl and aryl amines, and the like. Examples of bases useful in preparing salts of the present invention include sodium hydroxide, potassium hydroxide, ammonium hydroxide, potassium carbonate, and the like.
[0078] Pharmaceutical formulations are usually prepared by mixing the active substance, i.e. the compound of the invention, or a pharmaceutically acceptable salt thereof, with conventional pharmaceutical excipients. The formulations can be further prepared by known methods such as granulation, compression, microencapsulation, spray coating, etc. The formulations may be prepared by conventional methods in the dosage form of tablets, capsules, granules, powders, syrups, suspensions, suppositories or injections. Liquid formulations may be prepared by dissolving or suspending the active substance in water or other suitable vehicles. Tablets and granules may be coated in a conventional manner.
[0079] For clinical use, the compound of the invention is formulated into pharmaceutical formulations for oral, rectal, parenteral or other mode of administration. These pharmaceutical preparations are a further object of the invention.
[0080] Usually the effective amount of active compound is between 0.1-95% by weight of the preparation, preferably between 0.2-20% by weight in preparations for parenteral use and preferably between 1 and 50% by weight in preparations for oral administration.
[0081] The dose level and frequency of dosage of the specific compound will vary depending on a variety of factors including the potency of the specific compound employed, the metabolic stability and length of action of that compound, the patient's age, body weight, general health, sex, diet, mode and time of administration, rate of excretion, drug combination, the severity of the condition to be treated, and the patient undergoing therapy. The daily dosage may, for example, range from about 0.001 mg to about 100 mg per kilo of body weight, administered singly or multiply in doses, e.g. from about 0.01 mg to about 25 mg each. Normally, such a dosage is given orally but parenteral administration may also be chosen.
[0082] In the preparation of pharmaceutical formulations containing the compound of the present invention in the form of dosage units for oral administration the compound may be mixed with solid, powdered ingredients, such as lactose, saccharose, sorbitol, mannitol, starch, amylopectin, cellulose derivatives, gelatin, or another suitable ingredient, as well as with disintegrating agents and lubricating agents such as magnesium stearate, calcium stearate, sodium stearyl fumarate and polyethylene glycol waxes. The mixture is then processed into granules or pressed into tablets.
[0083] Soft gelatine capsules may be prepared with capsules containing a mixture of the active compound of the invention, vegetable oil, fat, or other suitable vehicle for soft gelatine capsules. Hard gelatine capsules may contain granules of the active compound. Hard gelatine capsules may also contain the inventive compound in combination with solid powdered ingredients such as lactose, saccharose, sorbitol, mannitol, potato starch, corn starch, amylopectin, cellulose derivatives or gelatine.
[0084] Dosage units for rectal administration may be prepared (i) in the form of suppositories which contain the active substance mixed with a neutral fat base; (ii) in the form of a gelatine rectal capsule which contains the active substance in a mixture with a vegetable oil, paraffin oil or other suitable vehicle for gelatine rectal capsules; (iii) in the form of a ready-made micro enema; or (iv) in the form of a dry micro enema formulation to be reconstituted in a suitable solvent just prior to administration.
[0085] Liquid preparations for oral administration may be prepared in the form of syrups or suspensions, e.g. solutions or suspensions containing from 0.2% to 20% by weight of the active ingredient and the remainder consisting of sugar or sugar alcohols and a mixture of ethanol, water, glycerol, propylene glycol and polyethylene glycol. If desired, such liquid preparations may contain colouring agents, flavouring agents, saccharine and carboxymethyl cellulose or other thickening agent. Liquid preparations for oral administration may also be prepared in the form of a dry powder to be reconstituted with a suitable solvent prior to use.
[0086] Solutions for parenteral, e.g. intravenous, administration may be prepared as a solution of a compound of the invention in a pharmaceutically acceptable solvent, preferably in a concentration from 0.1% to 10% by weight. These solutions may also contain stabilizing ingredients and/or buffering ingredients and are dispensed into unit doses in the form of ampoules or vials. Solutions for parenteral administration may also be prepared as a dry preparation to be reconstituted with a suitable solvent extemporaneously before use.
[0087] The compound of the present invention may also be used or administered in combination with one or more additional therapeutically active agents. The components may be in the same formulation or in separate formulations for administration simultaneously or sequentially.
[0088] Accordingly, in a further aspect of the invention, there is provided a combination product comprising:
[0089] (A) the compound of the invention; and
[0090] (B) another therapeutic agent; whereby (A) and (B) is formulated in admixture with a pharmaceutically acceptable excipient.
[0091] Such combination products provide for the administration of the compound of the invention in conjunction with the other therapeutic agent, and may thus be presented either as separate formulations, wherein at least one of those formulations comprises the compound of the invention, and at least one comprises the other therapeutic agent, or may be presented (i.e. formulated) as a combined preparation (i.e. presented as a single formulation including the compound of the invention and the other therapeutic agent).
[0092] Thus, there is further provided:
[0093] (1) a pharmaceutical formulation including the compound of the invention, another therapeutic agent, and a pharmaceutically acceptable excipient, e.g. an adjuvant, diluent or carrier; or
[0094] (2) a kit of parts comprising, as components:
[0095] (a) a pharmaceutical formulation including the compound of the invention, as defined herein, in admixture with a pharmaceutically acceptable excipient, e.g. an adjuvant, diluent or carrier; and
[0096] (b) a pharmaceutical formulation including another therapeutic agent in admixture with a pharmaceutically acceptable excipient, e.g. an adjuvant, diluent or carrier, which components (a) and (b) are each provided in a form that is suitable for administration in conjunction with the other.
[0097] In some particular embodiments, the compound of the invention is used in a combination with an antitumor agent in the treatment of a malignant hyperproliferative disease. Such combination therapy may be particularly useful in cancer chemotherapy, to counteract an anti-apoptotic effect of Nox4 that may lead to tumor resistance to the antitumor agent.
[0098] Thus, there is further provided:
[0099] (1) a pharmaceutical formulation including the compound of the invention, as hereinbefore defined, an antitumor agent, and a pharmaceutically acceptable excipient, e.g. an adjuvant, diluent or carrier; or
[0100] (2) a kit of parts comprising, as components:
[0101] (a) a pharmaceutical formulation including the compound of the invention, as defined herein, in admixture with a pharmaceutically acceptable excipient, e.g. an adjuvant, diluent or carrier; and
[0102] (b) a pharmaceutical formulation including an antitumor agent in admixture with a pharmaceutically acceptable excipient, e.g. an adjuvant, diluent or carrier, which components (a) and (b) are each provided in a form that is suitable for administration in conjunction with the other.
[0103] The components (a) and (b) in any of the above kit of parts may be administered at the same time, in sequence, or separately from each other.
[0104] The compound of the present invention may also be used or administered in combination with other modes of treatment such as irradiation for the treatment of cancer.
[0105] According to one aspect, there is provided a method of inhibiting the activity of Nox, in particular Nox4, in a patient in need thereof, by administering to said patient a therapeutically effective amount of the compound of the invention, as defined herein. The patient may be any mammal, but preferably is a human.
[0106] The patient to be treated may be one suffering from a condition or disorder associated with an elevated activity of Nox, in particular Nox4, or a patient at risk of developing such a condition or disorder. Examples of such conditions and disorders are cardiovascular disorders, respiratory disorders, metabolism disorders, skin disorders, bone disorders, neuroinflammatory and/or neurodegenerative disorders, kidney diseases, reproduction disorders, diseases affecting the eye and/or the lens and/or conditions affecting the inner ear, inflammatory disorders, liver diseases, pain, cancers, allergic disorders, traumatisms, septic, hemorrhagic and anaphylactic shock, diseases or disorders of the gastrointestinal system, angiogenesis, angiogenesis-dependent conditions, lung infections, acute lung injury, pulmonary arterial hypertension, obstructive lung disorders, fibrotic lung disease, and lung cancer.
[0107] In one embodiment, the compound of the present invention is for use in the treatment of stroke. In one particular embodiment, the stroke is ischemic. The compound of the present invention is considered to have neuroprotective activity in the treatment of stroke. Therefore, the compound of the present invention suitably is used in combination with removal of blood clots in the treatment of ischemic stroke. In one particular embodiment, the compound of the present invention is used in combination with tPA in the treatment of ischemic stroke.
[0108] The compound of the invention is useful for the treatment of any mammal subject, e.g. a human or an animal (a non-human mammal).
[0109] In some embodiments, the treated subject is a human. In some other embodiments, the treated subject is a non-human mammal, e.g. a domesticated animal such as a farm animal, a pet animal, or a laboratory animal.
[0110] In some embodiments, the treated non-human mammal is a pet animal. In some embodiments, the pet animal is a dog. In some other embodiments, the pet animal is a cat. In other embodiments, the treated subject is a farm animal, e.g. a cow, or a pig, or a sheep. In other embodiments, the treated subject is a horse.
[0111] The invention will be illustrated by the following, non-limiting Examples.
EXAMPLES
Example 1
Preparation of N 2 -(3,4-dimethylphenyl)-6-((4-(p-tolyl)piperazin-1-yl)methyl)-1,3,5-triazine-2,4-diamine
[0112]
Preparation of 1-carbamimidamido-N-(3,4-dimethylphenyl)methanimidamide hydrochloride (1)
[0113] Cons HCl (2.17 mL, 25.99 mmol) was added to a vial containing 3,4-dimethylaniline (3.00 g, 24.76 mmol) and dicyandiamide (2.18 g, 25.99 mmol) in CH3CN (7.5 mL). After the vial was sealed the reaction was heated at 125° C. for 15 min. After the mixture cooled to approximately 50° C., the biguanide hydrochloride salt began to precipitate. The solid was collected by filtration and washed with CH3CN to give (5.49 g, 92%) of the title compound.
Preparation of 6-(chloromethyl-2-N-(3,4-dimethylphenyl)-1,3,5-triazine-2,4-diamine (2)
[0114] To a solution of NaH (0.91 g, 22.71 mmol) in EtOH (25 mL) was added 1-carbamimidamido-N-(3,4-dimethylphenyl)methanimidamide hydrochloride (5.49 g, 22.71 mmol) and the reaction mixture was stirred at r.t. for 3 h. Ethyl chloroacetate (2.42 mL, 22.71 mmol) was added drop-wise and the reaction mixture was stirred for 4 days. The product that precipitated was collected by filtration, washed with ethanol (3*10 ml) and water (2*10 mL) to give (1.32 g, 22%) of the title compound.
Preparation of N 2 -(3,4-dimethylphenyl)-6-((4-(p-tolyl)piperazin-1-yl)methyl)-1,3,5-triazine-2,4-diamine (3)
[0115] 6-(chloromethyl-2-N-(3,4-dimethylphenyl)-1,3,5-triazine-2,4-diamine (400 mg, 1.52 mmol) and 1-(4-methylphenyl) piperazine (347 mg, 1.97 mmol) was dissolved in acetonitrile (25 mL) and DIPEA (0.53 mL, 3.0 mmol) was added. The reaction mixture was heated at 80° C. for 2 hours and cooled to room temperature. 5 mL of water was added and the reaction mixture was cooled to 0° C. and filtered. The light pink solid was washed with water and dried in vacuo. The solid was redissolved in DCM and washed with 5% NaHCO3. The water phase was washed with DCM (×2) and the combined organic phases were washed with brine, dried (Na2SO4) and concentrated to give 400 mg of the title product as light yellow solid. Yield 65.3%. MS m/z 404 [M+1]+. HPLC purity (98%).
Example 2
Whole Cell Assays to Determine IC50 for Respective Nox Isoform
[0116] The Nox 4 selectivity of the compound of the present invention was compared to those of two compounds (A), (B) exemplified in WO2014/064118, viz. N 2 -(3,4-dimethylphenyl)-6-((4-(3-methoxyphenyl)piperazin-1-yl)methyl)-1,3,5-triazine-2,4-diamine and N 2 -(3-chloro-4-methylphenyl)-6-((4-(3-methoxyphenyl)piperazin-1-yl)methyl)-1,3,5-triazine-2,4-diamine; and to those of two structurally close compounds (C), (D) falling within the scope of WO2014/064118, viz. N 2 -(3,4-dimethylphenyl)-6-((4-(m-tolyl)piperazin-1-yl)methyl)-1,3,5-triazine-2,4-diamine and 6-((4-(4-chlorophenyl)piperazin-1-yl)methyl)-N 2 -(3,4-dimethylphenyl)-1,3,5-triazine-2,4-diamine. The structural formulas of the compounds A-D are shown in Table 1, together with the compound of the invention.
[0000]
TABLE 1
Compound
structural formula
A (prior art)
B (prior art)
C (reference)
D (reference)
inventive
Nox1 Assay
[0117] CHO cells modified to stably express human Nox1 were grown in DMEM/F12 gibco 31331 containing 10% FBS and 1% pen/strep at 37° C. in air with 5% CO 2 . Cells were collected from cultures by Trypsin mediated detachment of adherent cells.
[0118] A luminescence assay was used that measures the production of reactive oxygen species in whole cells. Luminol reacts with superoxide and emits light and light is measured with luminometer (Synergy/2 microplate reader, BioTek).
[0119] Inhibitors were diluted in a compound plate in DMSO (100%) then transferred to Hanks buffer solution and in assay plate DMSO were 2% in all the wells.
[0120] Assay procedure, final well volume 100 μl, 96-well plate: Inhibitors (20 μl) were added, then cell suspension was (100 000 cells/well), incubate 37° C. for 30 min, add PMA (0.9 μM/well) to Luminol reaction mix (Luminol 0.1 mM/well and HRP 3.2 U/well) then this stimulation mix into wells. The plate were then immediately read (steps 5 min each reading) and for 1 h. Data was calculated for the linear part of the curve and IC50 determined.
[0121] Compounds (Nox inhibitors) were diluted at 3× working concentration and titrated from 200 μM to 0.003 μM in 11 steps
Nox2 Assay
[0122] Cells: Human blood was purchased in buffy coat, prepared the same day for isolation of neutrophils, from Labjoy AB, Lund, Sweden. Blood components were separated by density gradient centrifugation using Ficoll-Paque Plus. Plasma, PBMCs and Ficoll were removed before erythrocytes were removed by dextran sedimentation. Remaining erythrocytes were lyses before neutrophils were washed and counted. Isolated neutrophils were kept on ice resuspended in HBSS without Mg and Ca until assayed.
[0123] Buffers: The isoluminol buffer contained Isoluminol (0.175 mg/ml) and HRP fraction II (1.75 U/ml). The buffer was prepared by diluting these ingredients at 4× working concentration in HBSS.
[0124] Procedures: Compounds (Nox inhibitors) were diluted at 4× working concentration and titrated from 100 μM to 0.006 μM in 1:4 steps. PMA was diluted in Isoluminol buffer at 4× working concentration for a final concentration of 30 ng/ml. Compounds had a final DMSO concentration of 1% in the wells; therefore a DMSO control of 1% was included on the plates. 25 μl diluted compound or control/well were added to a white 96-well plate. 25 μl/well of PMA diluted in Isoluminol buffer was added to each well. To non-stimulated control wells only Isoluminol buffer was added. Neutrophils were washed and resuspended at 2×10 6 cells/ml in HBSS with Mg and Ca just before adding 50 μl of the neutrophil cell suspension/well, which was followed by immediate initiation of luminescence measurement. Luminescence was measured using a FluoStar Optima (BMG Labtech). Graphs were performed using Prism 5 for Mac OS X (Prism 5.0 Software, San Diego Calif. USA). Inhibitors were evaluated at 50% inhibition (IC50) in comparison to cell control without inhibitor present
Nox4 Assay
[0125] Cells: HEK (CJ Nox4) stably expressing Nox4 was purchased from Redoxis AB (Lund). The adherent cells were cultivated in RPMI 1640 with L-Glutamine were supplemented with FBS (10%), penicillin (10 U/ml) streptomycin (100 μg/ml) and neomycin (200 μg/ml) at 37° C. in air with 5% CO 2 .
[0126] Hydrogen peroxide produced by Nox4 was measured (fluorescence emission: 590 and excitation: 544) using Amplex red (Molecular Probes) in Fluorescan Ascent plate reader Type 374. Cells were collected from cultures by Trypsin mediated detachment of adherent cells. Cells were seeded in 96-well plates at a density of 50 000 cells in 200 l assay volume. Inhibitors were added for 30 min (37° C.) and then reagents was added to give a final concentration of Amplex Red 35 mM and 0.17 U/ml horseradish peroxidase. Nox4 activity was measured up to 100 min with readings every minute. Inhibition curves of different Nox4 inhibitors were evaluated at 50% inhibition (IC50) in comparison to cell control without inhibitor present. Y-axes: turnover of hydrogen peroxide; x-axes: concentration of inhibitor. Inhibitors were diluted in a compound plate in DMSO (100%) then transferred to Hanks buffer solution and in assay plate DMSO were 2% in all the wells.
[0127] Compounds (Nox inhibitors) were diluted at 3× working concentration and titrated from 200 μM to 0.003 μM in 11 steps. The obtained results are shown in Table 2.
[0000]
TABLE 2
Compound
IC50 Nox1 (μM)
IC50 Nox2 (μM)
IC50 Nox4 (μM)
A
66
1.68
1.68
B
22
17
0.84
C
162
59
1.68
D
200
15
1.68
inventive
66
16
0.67
[0128] As may be seen from Table 2, the inventive compound shows a very low IC50 for Nox4 coupled with a high IC50 for both Nox1 and Nox2.
Example 3
Caco-2 Permeability Assay
[0129] The Caco-2 permeability was measured for compounds A-D and for the inventive compound at a test concentration of from 1 to 10 μM, using the test protocol described by Hubatch et al. in Nature Protocols, 2007, 2, 2111-2119.
[0130] Caco-2 membrane permeability was performed in accordance with published protocols. [Hubatch] Caco-2 cell monolayers (passage 94-105) were grown on permeable filter support and used for transport study on day 21 after seeding. Prior to the experiment a drug solution of 10 μM was prepared and warmed to 37° C.
[0131] The Caco-2 filters were washed with prewarmed HBSS prior to the experiment, and thereafter experiment was started by applying the donor solution on the apical side or basolateral side, depending on which direction that was monitored. The transport experiments were carried out at pH 7.4 in both the apical and basolateral chambers. The experiments were performed at 37° C. and with a stirring rate of 500 rpm. The receiver compartment was sampled at 15, 30, and 60 min, and at 60 min also a final sample from the donor chamber was taken in order to calculate the mass balance of the compound. Directly after the termination of experiment the filter inserts were washed with prewarmed HBSS and the membrane integrity was checked. This was performed by trans-epithelial electrical resistance (TEER) measurement. The experiment was validated by inclusion of the para-cellular marker 14Cmannitoland monitoring its permeability during the experiments. Mannitol is a para-cellular marker used for cell monolayer integrity measurements.
[0132] Test compounds were thus added to either the apical or basolateral side of the Caco-2 cell layer, to measure permeability in the absorptive (apical to basolateral, Papp (a-b)) or secretive (basolateral to apical Papp (a-b) directions, respectively. The efflux is calculated as Papp (b-a) divided by Papp (a-b). The results are presented in Table 3.
[0000]
TABLE 3
Papp (a-b)
MR
Papp (b-a)
MR
Compound
(×10 −6 cm/s)
(%)
(×10 −6 cm/s)
(%)
Efflux
A
35 ± 4.0
17
34 ± 4.0
12
1
B
0.8 ± 0.2
41
43 ± 5.0
41
54
C
2.4 ± 0.1
37
89 ± 27
67
37
D
1.9 ± 0.2
40
33 ± 11
16
17
inventive
12 ± 1.6
13
43 ± 5.8
14
4
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The compound N 2 -(3,4-dimethylphenyl)-6-((4-(p-tolyl)piperazin-1-yl)methyl)-1,3,5-triazine-2,4-diamineor a pharmaceutically acceptable salt of said compound. The compound is useful the treatment of a condition or disorder associated with nicotinamide adenine dinucleotide phosphate oxidaseactivity. A pharmaceutical composition comprising the compound.
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This application claims the benefit under 35 U.S.C.119(e) of U.S. provisional application Ser. No. 61/393,121, filed Oct. 14, 2010.
FIELD OF THE INVENTION
The present invention relates to a lifting device which is suitable for lifting a personal vehicle on a vehicle dolly thereon, and more particularly, the present invention relates to a lifting device including a carriage having track followers for movement along a track and guide followers for guiding alignment of the track followers. Furthermore, the present invention relates to a vehicle dolly which is adjustable for accommodating different types of person vehicles thereon while being readily supported on the lifting device.
BACKGROUND
In storage areas, for example garages and the like, it is desirable to maximize the use of storage space. To accomplish this, it is desirable to store some objects raised above the floor so that additional objects can be stored therebeneath. Examples of lifting devices related to this purpose include U.S. Pat. No. 6,676,233 by Evans et al., U.S. Pat. No. 5,871,070 by Contreras and U.S. Pat. No. 4,184,570 by Edwards. Each of the disclosed devices has some restriction to loading of cargo onto the lifting frame such that the devices are not well suited for readily supporting personal vehicles thereon such as motorcycles, riding mowers, all terrain vehicles and the like.
Vehicle dollies are known for simplifying the transport and handling of personal vehicles, however, the lifting devices described in the above noted patents are not well suited for accommodating known dolly designs. Examples of two motorcycle dollies are disclosed in U.S. Pat. No. 6,287,069 by Oliphant et al and U.S. Pat. No. 6,524,056 by Kloster. Neither of the motorcycle dollies disclosed can be adapted to other vehicle types in an efficient manner nor can known lift designs readily accommodate them.
SUMMARY OF THE INVENTION
According to one aspect of the invention there is provided a lifting device in combination with a vehicle dolly for a personal vehicle wherein the vehicle dolly comprises a dolly frame including at least one wheel track extending in a longitudinal direction between opposing ends of the dolly frame supported on wheels such that the dolly frame is supported for rolling movement along the ground in which said at least one wheel track is arranged for receiving wheels of the personal vehicle rolled thereon, the lifting device comprising:
a mounting frame arranged to be supported on an upright supporting surface;
at least one lifting track extending vertically along the mounting frame; a carriage supported for movement along said at least one lifting track between a lowered position in which a bottom end of the carriage is adjacent to a bottom end of the mounting frame and a raised position in which the bottom end of the carriage is spaced upwardly from the bottom end of the mounting frame;
a lift frame fixed on the carriage for movement therewith along said at least one lifting track, the lift frame extending generally horizontally outward from the bottom end of the carriage so as to be arranged to be received below the said at least one wheel track at a location between the wheels at the opposing ends of the dolly frame.
By providing a lift frame which can be readily accommodated between the wheels of a personal vehicle dolly, the personal vehicle can be readily stored in a raised position relative to the upright supporting wall of a garage or other storage area for example. By arranging the configuration of the carriage to comprise upper and lower track wheels as well as upper and lower guide wheels, the carriage is readily supported for rolling movement along the mounting frame of the lifting device while accommodating very large loads without concern for binding of the carriage relative to the mounting frame. By further providing a lifting frame comprising lifting forks adapted to support a pallet thereon many additional types of cargo can be readily supported on the carriage. the arrangement of the dolly to include rails arranged to be mounted in a first configuration defining a single track or a second configuration defining a pair of tracks allows the dolly to be readily adjusted to accommodate different types of vehicles, including single track motorcycles or dual track all terrain vehicles and riding mowers and the like.
The lift frame may comprise a pair of parallel and spaced apart rails extending perpendicularly outwardly from the mounting frame so as to define a lifting fork arranged for supporting a pallet thereon.
Preferably there is provided a pair of lifting tracks along opposing sides of the mounting frame.
A winch is preferably fixed to the carriage for movement therewith relative to the mounting frame and a winch cable wound onto the winch at a first end, the winch cable extending over an upper pulley supported on a top end of the mounting frame and being anchored at a second end opposite the first end wound onto the winch.
Preferably a ratchet mechanism is provided which includes a plurality of latching surfaces spaced apart in a vertical direction on the mounting frame to define a rack and a pawl pivotally supported on the carriage for pivotal movement between a locking position in which the pawl is arranged for selective engagement with the latching surfaces of the rack such that only downward movement of the carriage relative to the mounting frame is prevented and a released position in which the pawl is prevented from engaging the latching surfaces of the rack. Preferably the pawl is biased towards the locking position. A release cable is preferably coupled to the pawl at a first end and is suspended from the carriage such that pulling an opposing second end of the release cable displaces the pawl into the released position.
According to a second aspect of the present invention there is provided a lifting device comprising:
a mounting frame arranged to be supported on an upright supporting surface;
at least one lifting track extending vertically along the mounting frame, the track comprising an inner bearing surface and an outer bearing surface which are supported on the mounting frame so as to be substantially parallel to the upright supporting surface and such that the inner bearing surface faces the upright supporting surface and the outer bearing surface faces away from the upright supporting surface;
a guide flange extending vertically along the mounting frame and being oriented transversely to the bearing surfaces of said at least one track;
a carriage supported for movement along said at least one track;
an upper track follower supported adjacent a top end of the carriage and being arranged for riding along the inner bearing surface;
a lower track follower supported adjacent a bottom end of the carriage and being arranged for riding along the outer bearing surface;
a pair of upper guide followers supported adjacent the top end of the carriage and being arranged for riding along opposing sides of the guide flange;
a pair of lower guide followers supported adjacent the bottom end of the carriage and being arranged for riding along the opposing sides of the guide flange; and
a lift frame fixed on the carriage for movement therewith along said at least one track, the lift frame extending generally horizontally outward so as to be arranged to support an object for lifting thereon.
Preferably the upper and lower track followers as well as the upper and lower guide followers comprise wheels supported for rolling movement along the bearing surfaces and the sides of the guide flange respectively.
Preferably the guide followers are adjustable relative to the carriage frame in a generally horizontal direction arranged to extend substantially parallel to the upright supporting surface.
Each lifting track preferably comprises a U-shaped channel defined by a first flange defining the inner bearing surface, a second flange defining the outer bearing surface and a base flange joined between the first and second flanges.
According to another aspect of the present invention there is provided a vehicle dolly for a personal vehicle, the vehicle dolly comprising:
a dolly frame extending in a longitudinal direction between opposing front and rear ends, the dolly frame comprising:
a front frame member spanning perpendicularly to the longitudinal direction at the front end of the dolly frame; a rear frame member spanning perpendicularly to the longitudinal direction at the rear end of the dolly frame; and a pair of rails extending in the longitudinal direction between the front frame member and the rear frame member; and
a pair of wheels supported on each of the front and rear frame members at spaced apart positions so as to be arranged to support the dolly frame for rolling movement along the ground;
the pair of rails being arranged to be mounted on the front and rear frame members at a first prescribed spacing so as to be arranged to define a single track arranged to receive wheels of a motorcycle driven thereon; and
the pair of rails being arranged to be mounted on the front and rear frame members at a second prescribed spacing so as to be arranged to define a pair of tracks arranged to receive wheels of a personal all terrain vehicle driven thereon.
The vehicle dolly is preferably used in combination with a pair of elongate panels or boards wherein each rail is arranged to support a respective one of the elongate panels extending along a length thereof in the longitudinal direction in the second prescribed spacing of the rails to define the pair of tracks and wherein the rails are arranged to commonly support one of the elongate panels extending therealong in the longitudinal direction in the first prescribed spacing of the rails to define the single track.
The pair of rails preferably extend overtop of the front and rear frame members in an overlapping configuration therewith with the wheels comprising caster wheels having upright pivot assemblies overtop of which the front and rear frame members are supported.
When there is provided a pair of tie down anchor loops secured to each of the front and rear frame members, preferably each anchor loop being secured to the respective frame member by a common fastener with a respective one of the caster wheels.
One embodiment of the invention will now be described in conjunction with the accompanying drawings in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the lifting device.
FIG. 2 is a front elevational view of the mounting frame.
FIG. 3 is a side elevational view of the mounting frame.
FIG. 4 is a top plan view of a portion of the carriage supported on the mounting frame.
FIG. 5 is a front elevational view of the carriage.
FIG. 6 is a side elevational view of the carriage.
FIG. 7A is a sectional view along the line 7 A- 7 A of FIG. 5 .
FIG. 7B is a sectional view of a portion of the ratchet mechanism along the line 7 B- 7 B of FIG. 5 .
FIG. 8 is a plan view of one of the pairs of guide wheels.
FIG. 9 is a side elevational view of the upper block of upper pulleys.
FIG. 10 is a front elevational view of the upper pulley block.
FIG. 11 is a top plan view of the dolly frame.
FIG. 12 is a side elevational view of the dolly frame.
FIG. 13 is a front elevational view of the dolly frame in the first configuration.
FIG. 14 a front elevational view of the dolly frame in the second configuration.
FIG. 15 is a bottom plan view of the hinge elements connecting one of the ramp sections of the vehicle dolly.
FIG. 16 is a bottom plan view of one of the hinge elements.
FIG. 17 is a side elevational view of one of the hinge elements.
FIG. 18 is an end elevational view of one of the hinge elements.
In the drawings like characters of reference indicate corresponding parts in the different figures.
DETAILED DESCRIPTION
Referring to the accompanying figures there is illustrated a lifting device generally indicated by reference numeral 10 . The lifting device 10 is arranged for mounting onto an upright supporting surface such as the wall of a storage area. In a preferred arrangement, the lifting device is suited for use with a vehicle dolly 12 arranged to support a personal vehicle thereon, for example a motor cycle, an all terrain vehicle or a riding mower.
The lifting device includes a mounting frame 14 defining a vertical mounting plane arranged for mounting parallel against the upright supporting surface. The mounting frame 14 includes two vertical supports 16 extending in the longitudinal direction of the mounting frame along the full height thereof at two laterally opposed sides of the frame. A plurality of horizontal straps 80 of rigid material span in the lateral direction parallel to the mounting plane in fixed connection to the two vertical supports at opposing ends thereof. A crossbar 20 is also provided spanning between the two vertical supports at the top end thereof to define the top end of the mounting frame.
Two tracks 22 are provided extending adjacent respective vertical supports 16 along the opposing sides of the mounting frame. The two tracks span the full height of the mounting frame between top and bottom ends thereof. Each track 22 comprises a U-shaped channel including a first flange 24 which defines an inner bearing surface facing inwardly towards the wall and a second flange 26 defining an outer bearing surface which faces outwardly away from the wall such that the inner and outer bearing surfaces confront one another along the interior of the U-shaped channel. The first and second flanges are joined by a base flange 28 forming the outer side of the channel opposite from the opposing channel.
A guide flange 30 is joined across all of the straps 18 of the mounting frame in fixed connection therewith so as to project perpendicularly outward from the mounting plane of the frame and wall along the full height of the mounting frame. The guide flange 30 is located at an intermediate location in the lateral direction so as to be spaced inwardly from both of the tracks 22 of the mounting frame.
A carriage 32 is supported for rolling movement along the full height of the tracks 22 of the mounting frame. The carriage generally comprises two side plates 34 which are elongate in a vertical direction and which are mounted parallel and spaced apart from one another at opposing sides of the carriage. The side plates are suitably spaced such that the carriage is approximately the full width of the mounting frame while being arranged to be received in between the two tracks 22 of the mounting frame.
An angle 36 is joined to each of the two side plates to also span the full height of the carriage frame. Each angle 36 includes a first flange which is parallel to and in overlapping arrangement with the respective side plate 34 and a second flange which is perpendicular to the first flange and which extends outwardly away from the opposing side plate at the front edge of the respective side plate. In this arrangement, the second flange of the angle 36 is arranged to overlap across the front side of the respective track 22 when the two side plates are received between the tracks.
The carriage 32 further comprises an upper cross bar 38 , a lower cross bar 40 and a middle cross bar 42 which span horizontally between the two side plates adjacent the top end, adjacent the bottom end and at an intermediate location therebetween respectively. The carriage frame further comprises a pulley bar 44 spanning between the top ends of the two side plates to define the top end of the carriage frame.
Two upper track followers 46 are provided on respective opposing sides of the carriage frame adjacent the top end of the carriage frame for rolling movement about a common upper axis oriented in the lateral direction. The wheels defining the upper track followers are arranged for rolling movement within respective ones of the channels forming the tracks. The upper track followers ride along the inner bearing surface when weight is supported on the carriage frame which causes a forward moment to the top end of the carriage frame which urges the upper track followers forwardly against the inner bearing surface.
The carriage similarly comprises lower track followers 48 in the form of a pair of wheels mounted on the respective sides of the carriage frame adjacent the bottom end thereof for rolling movement within respective channels forming the two tracks. The same moment applied to the carriage frame by weight supported thereon urges the lower track followers rearwardly into engagement with the bearing surface inside the channels of the tracks.
The carriage 32 is also provided with a pair of upper guide followers 50 supported on the upper cross bar adjacent the top end of the carriage. The upper guide followers each comprise a wheel with the two wheels being supported on the crossbar for alignment with the guide flange such that the upper guide followers are arranged for rolling movement along opposing sides of the guide flange as the carriage is displaced along the mounting frame between a lowered position adjacent the bottom end thereof and a raised position spaced upwardly therefrom adjacent the top end of the mounting frame.
Each guide follower 50 is supported on a respective threaded rod 42 oriented in the lateral direction such that adjustment of the threaded rod relative to the carriage frame adjusts the position of the respective guide follower 50 in the lateral direction relative to the carriage. By adjusting the position of both guide wheels, the lateral position of the carriage relative to the guide rail can be adjusted at the top end of the carriage which in turn allows for centering alignment of the upper track followers with the respective bearing surfaces of the tracks.
The carriage 32 similarly includes a pair of lower guide followers mounted on the lower cross bar using a similar configuration of threaded rods which permits adjustment in the lateral direction of the position of the guide followers. By mounting the lower guide followers adjacent the bottom end of the carriage, the position of the carriage in the lateral direction can be adjusted relative to the guide flange upon which the pair of guide rollers roll similarly to the upper guide followers so that the lower track followers 48 can be similarly aligned in the lateral direction with the respective bearing surfaces of the tracks.
The carriage includes a lift frame 54 comprised of two rails 56 which are parallel and spaced apart from one another and which project perpendicularly outward from the wall and the mounting plane of the mounting frame 14 . The two rails 56 are anchored to the carriage frame adjacent the two side plates 34 at opposing sides so that the two rails 56 are spaced apart by the full width of the carriage frame so as to be suitably spaced for fitting various commercially available pallets used for transport and handling of various goods.
A pair of strap members 58 are coupled to the two rails 56 respectively to define respective gussets which provide added support to maintain the two rails in a horizontal orientation. Each strap is coupled at a top end to the respective side plate of the carriage frame nearer to the top end than the bottom end thereof while being anchored at an opposing bottom end to the respective rail 56 at a location spaced forwardly from the rear end anchored to the carriage frame. The straps 58 are anchored to the rails closer to the rear end than the forward free ends thereof so as not to interfere with loading of cargo onto the lift frame.
A winch mounting member 60 is mounted to span in the lateral direction between the two rails 56 adjacent to the rear end thereof with the opposing ends of the mounting member 60 overlapping the two rails respectively where they are fastened. A winch 62 is supported on the mounting member by a pair of clamps 64 clamped onto the mounting member at spaced apart positions in the lateral direction. The winch 62 includes an electric motor and a spool 66 onto which a winch cable 68 is wound. The first end of the cable is anchored to the spool for winding thereon. The winch lifts the carriage relative to the mount frame using the cable 68 in cooperation with an upper block comprising a plurality of upper pulleys rotatable about a common upper axis and a lower block 72 comprising a plurality of lower pulleys rotatable about a second lower axis. The upper block is connected to the cross bar 20 at the top of the mounting frame while the lower block 72 is anchored to the pulley bar 44 at the top end of the carriage frame. The cable is alternately wound about upper and lower pulleys of the upper and lower pivot blocks in a block and tackle configuration with the second end of the cable being anchored onto the pulley bar 44 of the carriage. Winding of the cable onto the spool of the winch thus causes the upper and lower blocks to be drawn together such that the top end of the carriage is lifted to the top end of the mounting frame.
The winch further includes a limit switch 74 pivotally supported on the carriage frame so as to be arranged to engage a corresponding stop on the mounting frame when the carriage reaches the top end for automatically turning off the electric motor of the winch 62 once the carriage is fully raised into the raised position.
To prevent the carriage from falling in the event of failure of the winch, a ratchet mechanism is provided which includes a rack 76 on the mounting frame defining a plurality of vertically spaced apart latching surfaces 78 and a pawl 80 pivotally supported on the carriage for cooperation with the rack 76 .
The rack is defined by an elongate member comprising two flanges joined together which span vertically the full height of the mounting frame. The first flange 82 of the rack is joined parallel to the mounting plane of the mounting frame to span across the straps at an intermediate location spaced inwardly from both sides of the mounting frame. The second flange 84 is transverse to the first flange and is oriented to extend outwardly from the mounting plane at an inclination for selective engagement with the pawl 80 on the carriage.
The second flange 84 includes a forward edge which is formed to define a plurality of projections 86 at spaced positions thereon in which the top edge of each projection forms a horizontal shoulder defining a respective latching surface 78 while the bottom edge of the projection is sloped between the inner edge of one latching surface and the outer edge of another latching surface thereabove. Accordingly when the pawl 80 on the carriage is in an engaged position, the sloped bottom portion of each projection causes the pawl to ride over the projection with upward movement of the carriage relative to the mounting frame so that movement towards the raised position is not inhibited by the ratchet mechanism. Alternatively, the pawl is arranged to engage the latching surfaces 78 in a latching configuration therewith so that downward movement of the carriage relative to the mounting frame is resisted in the engaged position.
The pawl 80 is supported on a pivot shaft supported vertically on the cross bars of the carriage frame for rotation about a respective vertical axis so that the free end of the pawl is moveable inwardly towards the mounting frame and towards the engaged position or outwardly away from the mounting frame towards a released position with rotation of the pivot shaft about its upright vertical axis. A crank 90 is fixed onto the pivot shaft at an intermediate location with the free end of the crank being coupled to the cross bar by a suitable biasing member 92 which biases rotation of the pivot shaft to correspond to movement of the pawl from the released position towards the engaged position.
A release cable 94 is provided which is anchored to the pawl 80 at one end and which spans substantially the height of the mounting frame so that even in the raised position a user adjacent the bottom end of the mounting frame can readily grasp the opposing second end of the release cable. Pulling the release cable causes the pawl to be pivoted away from the engaged position towards the released position against the action of the biasing member 92 to allow downward movement of the carriage relative to the mounting frame only as long as the user maintains tension on the release cable.
The vehicle dolly includes a frame which extends in the longitudinal direction between a front end 100 and a rear end 102 . A front frame member 104 spans perpendicularly to the longitudinal direction at the front end and a rear frame member 106 spans perpendicularly to the longitudinal direction at the opposing rear end. Two rails 108 are fastened adjacent opposing ends thereof in an overlapping configuration with the respective front and rear frame members by orienting the two rails to extend in the longitudinal direction. Mounting apertures are provided in each of the front and rear frame members for mounting the rails thereon at different spacings corresponding to different configurations.
In a first mounting configuration shown in FIG. 13 , the two rails are mounted at a first prescribed spacing nearer to one another than the opposing ends of the frame members. In this manner a single elongate panel 110 is provided which spans the full length of the rails for overlapping both rails and commonly defining a single track upon which wheels of a motorcycle may be rolled onto. The elongate panel 110 may comprise a commercially available piece of lumber, for example a 2×10 construction member. The panel is fastened through apertures spaced apart in the longitudinal direction of the rails.
In a second configuration shown in FIG. 14 , the two rails are mounted at a second prescribed spacing greater than the first spacing and greater than the width of the elongate panel such that the two rails are mounted closer to the ends of the frame members than one another. In this instance, each rail mounts a respective panel 110 thereon so that the two rails define a pair of tracks respectively receiving respective wheels of a dual track vehicle thereon such as an all terrain vehicle.
The front and rear frame members are supported on castor wheels 112 having respective vertical axis pivot assemblies 114 . Each end of each of the frame members is mounted in an overlapping configuration overtop of a respective one of the pivot assemblies of a respective castor wheel. In this arrangement the wheels are provided at a sufficient spacing between front and rear ends that the forks of the lift frame can be readily received therebetween. By further overlapping the rails on top of the front and rear frame members which are in turn mounted in overlapping configuration overtop of the pivot assemblies of the castor wheels, a sufficient height is provided to the rails to provide clearance therebelow for receiving the lift frame in use.
The vehicle dolly further comprises a set of tie-down loop anchors 116 in which each anchor comprises a rigid loop having a threaded connector which is arranged to be secured onto a common fastener which secures a respective one of the castor wheels 112 to the respective frame member.
Typically, the castor wheels are mounted at the opposing ends of the respective frame members in either configuration. When using the first configuration with a single track, the front and rear frame members can be shortened in the lateral direction. A set of auxiliary apertures 118 are provided spaced inwardly from each of the ends of each frame member for accommodating the fasteners which commonly mount the castor wheels and the loop anchors 116 onto the respective frame members so that the wheels can be mounted at a narrower spacing when shortening the frame members.
Each of the panels 110 forming either a single track or a pair of tracks is provided with a ramp 120 at the rear end thereof. Each ramp can be formed from the same commercially available wooden piece of lumber, for example a 2×10. A set of four hinge elements 122 is used to attach each ramp 120 to the respective panel 110 .
Two hinge elements 122 are mounted on the end of each of the ramp 120 and the panel 110 at the pivotal connection therebetween. The two hinge elements on each of the ramp 120 and the panel 110 are mounted adjacent respective opposing longitudinally extending sides thereof. Each hinge element 122 includes a mounting flange 124 overlapping the bottom side of the respective ramp or panel and a hinge flange 126 fixed to the mounting flange in perpendicular arrangement therewith for extending upwardly along the respective side of the respective ramp or panel. Fastener apertures in the mounting flange 124 allow suitable fasteners to be used to secure the mounting flange to the bottom side of the ramp or panel adjacent the end thereof. The hinge flange 126 includes a projection at each end thereof which projects in the longitudinal direction beyond the end of the mounting flange. Accordingly at the end of each of the ramp 120 and the panel 110 the hinge flanges define a pair or projections projecting beyond the end of the panel or ramp towards the other one of the panel or ramp in overlapping engagement with corresponding hinge flanges of the other hinge elements. Hinge apertures in the projecting portions of the hinge flange allow fasteners to join the projecting portions together at both sides of the ramp and board to define a common hinge axis extending in the lateral direction.
In use, a user assembles the vehicle dolly in the first or second configuration according to the type of personal vehicle desired to be stored thereon. Commercially available lumber is used to form the panels and the ramps 120 connected thereto. Once a personal vehicle is driven onto the track or tracks, tie down straps are anchored to the anchors 116 for securing the personal vehicle relative to the dolly. The personal vehicle can then be stored in a raised position by lowering the carriage to the lowered position adjacent the ground and loading of the dolly onto the lift carriage. The configuration of the dolly allows rolling movement in a lateral direction so as to permit orientation of the rails extending in the lateral direction of the carriage across the two rails of the lifting frame. Subsequent lifting of the carriage relative to the mounting frame by operating the winch causes the two rails of the vehicle dolly to be supported at spaced apart positions spanning across the two rails of the lifting frame.
As the carriage is raised towards the raised position, the track followers roll along respective bearing surfaces of the tracks while the guide followers roll along opposing sides of the guide flange to maintain alignment of the track followers with the track at top and bottom ends respectively. Continued operation of the winch is permitted until the limit switch on the carriage engages the corresponding stop on the mounting frame at which point operation of the winch ceases and the carriage remains in the raised position. Throughout the lifting motion, the ratchet mechanism remains in the engaged position with the pawl riding over the inclined ramped surfaces of the projections of the rack. In the raised position, the pawl is aligned overtop of an uppermost one of the latching surfaces of the rack to prevent downward movement of the carriage relative to the mounting frame even in the event of failure of the winch.
Since various modifications can be made in my invention as herein above described, and many apparently widely different embodiments of same made within the spirit and scope of the claims without department from such spirit and scope, it is intended that all matter contained in the accompanying specification shall be interpreted as illustrative only and not in a limiting sense.
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A lifting device has a lifting track mounted on a wall and a carriage with a lift frame movable along the track. A dolly with wheels at opposing ends is arranged to support various cargo thereon including personal vehicles such as motorcycles or snowmobiles or other comparably sized objects. The lift frame of the carriage has lift forks arranged to be received a wheel track of the dolly which receives wheels of a personal vehicle thereon. Guide flanges alongside the lifting track are engaged by upper and lower guide followers to prevent binding of the lift frame along the lifting track. The dolly includes longitudinal rails mountable at different lateral distances to accommodate different vehicle wheel configurations.
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TECHNICAL FIELD
[0001] The present invention relates to apparatus for disintegrating food waste and particularly to such apparatus including a rotor to which blades are fixed.
BACKGROUND OF THE INVENTION
[0002] For use in a kitchen a waste disposer must be sufficiently versatile to satisfactorily process not just soft materials or viscous materials (such as fruit or cooked cereals) but also hard and tough materials (such as some vegetables and bones). Particularly in processing these latter materials the duration of grinding required is an important consideration in the design of a disposer.
[0003] Food waste in a conventional food waste disposer is forced by blades on a rotating grinding plate against teeth of a stationary grinding ring. Reduced processing times could be achieved if this action could be improved.
[0004] Additional time is also required, for example, if harder food fragments such as carrot and bone pieces rotate at the same speed as the grinding plate without being ground. This results in increased noise and vibration, as well as residual food left in the grinding chamber after the disposer is turned off. Over time, this residual food may cause unpleasant odours.
[0005] A further problem in designing a food waste disposer is jamming which occurs when hard objects such as bones enter the food waste disposer and get stuck between the blades of the rotating grinding plate and the stationary shredder ring.
[0006] It is an object of the present invention to overcome or substantially ameliorate the above disadvantages or more generally to provide an improved apparatus for disintegrating food waste.
DISCLOSURE OF THE INVENTION
[0007] According to one aspect of the present invention there is provided a food waste disposer comprising:
[0008] a waste receptacle having a base;
[0009] a grinding plate mounted at the base of the waste receptacle for rotation about an axis;
[0010] apertures in the grinding plate for the passage of waste;.
[0011] at least one blade mounted to the grinding plate for travel toward and away from the axis;
[0012] a grinding ring about the periphery of the grinding plate for cooperating with the blade to disintegrate the waste, and
[0013] inner and outer stop means engaging the blade at radially inner and outer travel limits of the blade respectively, the outer stop means engaging the blade as it is thrown outward by rotation of the grinding plate.
[0014] Preferably the blade is slidably engaged with guide means fixed to the grinding plate. The guide means preferably restrain the blade to move linearly, more preferably the guide means restrain the blade to move radially, most preferably the guide means restrain the blade to move radially parallel to a plane of the grinding plate.
[0015] Preferably the blade has at least one tooth having a leading face facing in a direction so as to confront materials to be disintegrated when the grinding plate is rotated, the leading face facing in the direction of rotation of the blade; a receding surface which extends away from the leading face in a direction directed outwardly from a tangent line, the receding surface having shear edges radially outward of the leading face for shearing waste.
[0016] The tooth preferably projects from the grinding plate substantially in the axial direction and includes a receding surface which extends away from the leading face in a direction directed axially outwardly from the leading face.
[0017] Preferably the guide means include upstands formed by stamping of the grinding plate. The blade preferably includes an elongate mounting portion extending in the radial direction from the tooth to an inner abutment, a saddle overlying the mounting portion and fixed to the grinding plate such that the abutment and tooth abut the saddle to limit the travel of the blade and provide the inner and outer stop means respectively.
[0018] Preferably two blades are mounted to the grinding plate for coaxial radial movement on opposing sides of the axis.
[0019] This invention provides a food waste disposer which is effective and efficient in operational use which, compared to comparable prior art disposers reduces processing times, especially for harder food fragments. The disposer is also less prone to jamming and moreover the device has an overall simple design which minimizes manufacturing costs and maximizes performance and reliability.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Preferred forms of the present invention will now be described by way of example with reference to the accompanying drawings, wherein:
[0021] FIG. 1 is a schematic section in an upright plane through a food waste disposer of the present invention;
[0022] FIG. 2 is a pictorial view of the uppermost side of the grinding plate assembly of the disposer of FIG. 1 ;
[0023] FIG. 3 is a pictorial view of the uppermost side: of the grinding plate of the assembly of FIG. 2 ;
[0024] FIGS. 4 a and 4 b are pictorial views of a blade of the grinding plate of the assembly of FIG. 2 ;
[0025] FIG. 5 is a pictorial view of a saddle of the grinding plate assembly of FIG. 2 , and
[0026] FIG. 6 is a pictorial view of a rivet for fastening the saddle.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0027] Referring to the drawings, particularly FIG. 1 , a food waste disposer includes a grinding chamber 1 having an inlet 2 at its upper end and a grinding plate 3 mounted at its base. In use the plane of the grinding plate 3 is substantially horizontal and it is rotated about its upright central axis 4 by a motor/gearbox assembly 5 to which it is connected by a drive shaft 6 . Adjacent the circular periphery 34 of the grinding plate 3 is grinding ring 7 fixed to the housing 8 . The grinding ring 7 includes peripherally spaced teeth 9 which cooperate with the grinding plate 3 to disintegrate the waste.
[0028] As best seen in FIGS. 2 and 3 , two like blades 10 a , 10 b are supported on the planar uppermost face 11 of the grinding plate 3 , each mounted for linear travel toward and away from the axis 4 by upstands 12 a - 12 h formed in the grinding plate 3 and one of the saddles 28 .
[0029] The grinding plate 3 is a metal plate (for instance of stainless steel) and each of the upstands 12 a - 12 h is formed by shearing and bending a section of the plate in a stamping operation. The upstands are arranged in two rows on either side of a radially-extending line 13 that bisects the grinding plate 3 and in sets of four symmetrically positioned either side of a line 14 bisecting the grinding plate perpendicular to line 13 . Guide faces 15 a - 15 d on each of the upstands 12 a - 12 d are coplanar and parallel to the line 13 while respective opposing guide faces 15 e - 15 h of the upstands 12 e - 12 h offset to the other side of line 13 are also coplanar and parallel to the line 13 .
[0030] Each of the blades 10 a , 10 b has an elongate mounting portion 18 extending in the radial direction and having parallel edges 16 a , 16 b that are received between the guide faces 15 a - 15 h . A slot 80 parallel to the edges 16 a , 16 b in the base of the blades 10 a , 10 b reduces the contact area between the blades and the face 11 , leaving the blades 10 a , 10 b supported upon coplanar support surfaces 17 a , 17 b . In this manner the blades 10 a , 10 b are restrained to move radially parallel to a plane of the grinding plate 3 .
[0031] At the outer end of the mounting portion 18 a tooth 19 extends in the axial direction away from the face 11 . The tooth 19 has a leading face 20 facing in the direction of rotation of the blade and aligned perpendicular to the tangent line 21 and to the support surfaces 17 a , 17 b so as to confront materials to be disintegrated when the grinding plate is rotated.
[0032] A receding surface 22 extends away from the leading face 20 to the trailing face 81 in a direction directed outwardly from the tangent line 21 . The receding surface 22 is stepped, having first and second shear edges 24 radially outward of one another and of the leading face 20 for shearing waste.
[0033] The leading edge of the tooth 19 is chamfered to produce a planar chamfer face 26 extending away from the leading face 20 and inclined obliquely to the leading face 20 toward the axial end surface 28 on the axial tip of the tooth 19 . The end surface 28 is planar and substantially parallel to the support surfaces 17 a , 17 b . Extending outwardly from the end surface 28 an upper oblique surface 27 is planar and inclined acutely to the end surface 28 .
[0034] At the inner end of the mounting portion 18 an inner abutment nub 25 is formed, having an abutment face 46 on an outer side thereof. The abutment face 46 is positioned opposite an abutment face 27 formed on the tooth 19 . At radially inner and outer ends of the blades 10 a , 10 b are arcuate surfaces 39 , 41 respectively. The surface 39 is complementary to the cylindrical hub 40 and the surface 41 has the same radius of curvature as the peripheral edge 34 .
[0035] A saddle 28 made, for instance, of corrosion-resistant steel has a symmetrical shape comprising parallel legs 29 joined by a web 30 to form a U-shape. The concave side 31 is complementary to the mounting portion 18 providing a sliding fit therebetween. The saddles 28 are permanently fixed to hold the blades 10 a , 10 b in place by rivets 90 extending through openings 32 a - 32 d in the grinding plate 3 . The nub 25 and tooth 19 provide stop means, the faces 46 , 47 abutting the saddle 28 to limit the travel of the blades 10 a , 10 b.
[0036] Through-extending apertures 36 are provided in the grinding plate 3 for the passage of waste. Two protrusions 35 a , 35 b are formed in diametrically opposite positions in the plate by a stamping operation. The protrusions 35 a , 35 b have a smooth convex surface bounded by an irregular quadrilateral-shaped edge. A projecting lug 37 is formed in like manner to the upstands 12 a - 12 h by shearing and bending a section of the plate in a stamping operation. Notches 38 a - 38 c in the peripheral edge 34 provide additional cutting surfaces. The notches 38 a - 38 c , lug 37 and protrusions 35 a , 35 b , like the blades 10 a , 10 b assist in breaking up the waste and driving it outwardly against the grinding ring 7 .
[0037] When the grinding plate 3 is stationary the blades 10 a , 10 b are free to move radially, for instance, in response to water or waste being directed into the grinding chamber 1 . In operation, rotation of the grinding plate 3 serves to throw the blades 10 a , 10 b outwardly, the nub 25 abutting the saddle 28 in a position where the arcuate surface 41 is radially aligned with the edge 34 adjacent the grinding ring 7 . Material entering the tapering space between the receding face 22 and the grinding ring 9 tends to push the blade inwards, and in addition to the reaction forces acting to disintegrate the waste, clamping action may be provided, the blades holding the waste against the teeth 9 of the grinding ring 7 .
[0038] Aspects of the present invention have been described by way of example only and it should be appreciated that modifications and additions may be made thereto without departing from the scope thereof.
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Blades on a rotating grinding plate force waste against a stationary grinding ring. The blades are mounted on radially aligned guides on the grinding plate, allowing the blades to move freely inwardly and outwardly between opposing stops. The blades are thrown outward by rotation of the grinding plate. A receding face on the blades cooperates with the grinding ring for moving the blades inwardly and for forcing waste against the grinding ring.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. § 119 based upon U.S. Provisional Patent Application No. 60/203,271 filed May 10, 2000.
FIELD OF THE INVENTION
[0002] The present invention generally relates to the fields of oncology, biochemistry, and immunology and to methods of early diagnosis of precancerous or cancerous conditions in a mammal and, more particularly, to a method of diagnosing precancerous or cancerous conditions in a mammal, wherein a biological sample is obtained from said a gastrointestinal site of said mammal to detect the presence of a backleak of signature proteins or carbohydrates indicating tight junctional leakiness at an early stage of a cancerous precancerous condition.
BACKGROUND OF THE INVENTION
[0003] Research has indicated that the tight junctional seal surrounding each epithelial cell in an epithelial tissue is compromised in the process of tumor formation. This has been shown by: 1) the ability of the tumor promoter class of secondary carcinogens to engender tight junctional leakiness through activation of protein kinase C (Mullin and O'Brien, 1986; Mullin et al., 1997); 2) the existence of leaky tight junctions between epithelia of human gastrointestinal tumors (Peralta Soler et al., 1999); and 3) the induction of tight junction leakiness in precancerous rat colon being exposed to primary carcinogens (Peralta Soler et al., 1999). The physiological implication of this leakiness is that it will compromise the barrier function of the entire epithelial tissue. This has in turn very important medical implications for the generation and progression of inflammatory and cancerous states (Mullin, 1998), particularly since proteins such as insulin have been demonstrated to cross these junctions intact (Mullin et al., 1998). Thus, precancerous and cancerous epithelial tight junctions will allow for diffusion of proteins and sugars from the lumen of the upper GI tract (esophagus and stomach) into the bloodstream. In addition however, the intrinsic compartmental physiology of epithelial tissues allows one to take advantage of a naturally occurring diagnostic indicator of leakiness in these tissues, an indicator which can provide a non-invasive early warning to cancerous and precancerous inflammatory states in epithelial tissues.
[0004] All epithelial cells in the body are polar, that is they possess distinct top and bottom surfaces. This structural polarity allows them to perform their two most basic functions: they can reabsorb substances in one direction or secrete other substances in the opposite direction. Secretion of acid into the stomach lumen or reabsorption of sugar from urine are both due to this structural polarity. This vectorial property holds true not just for acids, salts and sugars, but for proteins as well. Gastric epithelia generally secrete digestive enzymes such as trypsin into the lumen of the GI tract, not the bloodstream, whereas the hormones gastrin and secretin, are released in the opposite direction to enter the bloodstream (Mountcastle, Medical Physiology, 1974). This directionality is achieved by the structural polarity of the epithelial cells, but it is maintained by the tight junctional seals preventing back diffusion of substances across the epithelial barrier. As tight junctions become leaky in the process of development of epithelial cancer, backleak of these signature proteins will occur, causing their levels in the opposite fluid compartment to rise.
[0005] The present invention, relates to the early diagnosis of cancer by detection of a backleak of signature proteins in the gastrointestinal tract, considered as a continuum from the mouth to the rectum. Along this “tube” are various proteins and sugars which are vectorially secreted into the GI lumen and are specific not only to the GI tract but to specific sites in the GI tract. Salivary amylase (ptyalin) is a 55,000 molecular weight protein released by cells of the parotid gland into saliva, the first lumen of the GI tract (Dimagno, in Gastroenterology, 1980). It moves down the esophagus into the stomach simply with swallowing. Pepsinogens I and II (40,000 mw) are released into the lumen of the stomach from oxyntic glands. Once these proteins are exposed to the acidity of the lumen of the GI tract, they spontaneously form the smaller and catalytically active protein, pepsin (33,000 mw) (Mountcastle, Medical Physiology, 1974). This enzyme is functional in the stomach and upper intestine. In the lower intestine and colon, the trefoil factor, TFF3 or ITF, is secreted into the lumen. It is a 39 amino acid residue polypeptide which seems to be active in mucosal repair processes (Thim, 1997).
[0006] Tight junctional leakiness between gastrointestinal epithelia in the vicinity of the secretion of these proteins, or downstream of their secretion, will allow for their chronic leak into the bloodstream, raising their level in serum. Therefore, salivary amylase levels in serum have important diagnostic predictive value for esophageal and gastric precancerous conditions, specifically Barett's Esophagus, atrophic gastritis and H. pylorii infection. Serum pepsin levels likewise have diagnostic value in precancerous gastric conditions, such as atrophic gastritis and H. pylorii infection. The secretion of TFF3 (ITF) in the lower intestine and colon makes its serum level predictive of precancerous leaks in the ileum and colon. For all three markers, elevated serum levels of these proteins can serve as low cost, noninvasive indicators whose presence can alert the physician to the need for the more expensive and involved endoscopic or colonoscopic follow-up procedures.
[0007] In addition to detecting leakage of signature proteins into the bloodstream, the present invention relates to detecting cancerous or precancerous conditions by leakage of signature carbohydrates from the epithelium into the bloodstream. Both leakage of signature proteins and leakage of signature carbohydrates serves as the basis for a noninvasive and relatively inexpensive screen for upper GI cancers and for precancerous and cancerous conditions throughout the GI tract. It would also serve to A similar approach could be utilized in a range of other epithelial tissues and cancers.
SUMMARY OF THE INVENTION
[0008] It is an object of the present invention to provide a method of diagnosing precancerous or cancerous conditions in a mammal by detecting the presence of a backleak of at least one signature protein in the gastrointestinal tract of said mammal.
[0009] It is another object of the present invention to provide a method of diagnosing precancerous or cancerous conditions in a mammal by detecting the presence of a backleak of at least one signature carbohydrate in the gastrointestinal tract of said mammal.
[0010] Another object of the present invention to provide a method of diagnosing precancerous or cancerous conditions in a mammal by detecting the presence of a backleak of at least one signature protein in the gastrointestinal tract of said mammal, wherein said signature protein is at least one of the group of trefoil factor, pepsin, and salivary amylase.
[0011] It is yet another object of the present invention to provide a method of diagnosing precancerous or cancerous conditions in a mammal by detecting the presence of a backleak of at least one signature carbohydrate in the gastrointestinal tract of said mammal, wherein said signature carbohydrate is at least one of the group of sucrose and mannitol.
DETAILED DESCRIPTION OF THE INVENTION
[0012] 5 cc peripheral (venous) blood samples are drawn in EGTA-treated tubes to avoid clotting. Samples are immediately centrifuged at room temperature to separate plasma from cells. The supernatant plasma is aliquoted into 1 cc amounts and frozen immediately at −70° C. These aliquots are thawed at time of assay.
[0013] Serum amylase (total) is detected enzymatically. The assay is performed in the presence of an inhibitor, which is selective for specifically the salivary form of the enzyme, resulting in detection of the pancreatic form only. The difference between the total activity and the pancreatic activity is the salivary amylase (Huang and Tietz, 1982 ).
[0014] Pepsin is assayed enzymatically using Folin's phenol reagent. Since pepsinogens in plasma are converted to pepsin upon acidification to pH 2, the assay is in fact a measure of pepsin +pepsinogen. However a second aliquot of each plasma sample is incubated at pH 8 prior to assay, whereupon pepsin will be destroyed, but pepsinogen will be stable. The difference between the total activity and the pepsinogen activity will be pepsin (Herriot, 1955).
[0015] Intestinal-specific trefoil peptide (TFF 3 or ITF) is assayed immunologically.
[0016] Determine if Epithelial Tight Junctional Leakiness Is a Property of Epithelial Tumors in the Upper Gastrointestinal Tract
[0017] Using the same methods with which tight junctional leakiness was observed in tumor epithelia of human colon, tissue is now obtained (by gastrectomy) from patients undergoing stomach surgery for adenocarcinoma. Where the tumor is large enough to permit taking a portion for research purposes, samples are taken of histologically normal mucosa from the edge of the excised tissue alongside portions of mucosa from the very edge of the tumor. Comparative permeability determinations are made electrophysiologically, by radiotracer flux and by use of electron dense dyes in electron microscopy, all techniques which have been published extensively. (Mullin et al., 1997; Peralta Soler et al., 1999; Mullin and McGinn, 1988).
[0018] In addition, the expression and phosphorylation state of the tight junctional protein, occludin, is analyzed in mucosal scrapes from histologically normal gastric mucosa and from mucosa at the edge of tumor.
[0019] Demonstration of the Leakage of Luminal Salivary Amylase and Sucrose Across the GI Barrier in Precancerous States in Humans Across a broad range of endoscopy patients, serum levels of salivary amylase are determined by using well-described enzymatic methods, arranging the results into four clinical groups: 1) grossly normal; 2) precancerous conditions (e.g. Barrett's esophagus, atrophic gastritis); 3) actual carcinomas/adenomas; and 4) ulcerations and other non cancer abnormalities (H. pylori positive tissue). Patients are asked prior to their endoscopy to swallow 200 ml of 0.5 g/ml sucrose. Sucrose leaking across the gastroesophageal mucosa into the bloodstream is analyzed in an overnight urine sample in collaboration with Dr. Jon Meddings of the Univ. of Calgary, Canada. In gastric and esophageal tissue biopsies from these same patients, the level of expression and the phosphorylation state of the tight junctional protein, occludin, is analyzed with a focus on testing for differences among the above four groups.
[0020] The Biomedical Importance of Tight Junction Regulation
[0021] Epithelia, have two key characteristics that seem to define all other more specific traits: 1) cell polarity, creating distinct apical and basal-lateral membrane domains; 2) structural integration into a barrier by means of the gasket-like intercellular sealing strands which are termed the “tight junction” (TJ) or zonula occludens. All other key characteristics of these cells, their binding proteins, receptors, transporters, secretory systems, etc. depend upon these two traits in order to fulfill their function. The most basic processes of nutrient absorption and salt and water balance cannot be achieved without these traits. Without polarity to achieve directionality, and a tight junctional band to maintain polarity and prevent paracellular backleak, there can be no unidirectional transcellular transport, one of, if not the key characteristic of higher life.
[0022] The present invention is predicated in part on the fact that the compromising of one or both of these traits has profound implications for not just the organism and its tissues, but even for the homeostasis of the individual epithelial cells. When one considers that the majority of lethal cancers are epithelial in origin (Fraumeni, et al., 1989), it is unusual that cancer research has not focused more on these two key properties.
[0023] Tight Junction Structure
[0024] With the discovery of the first TJ protein, ZO-1 (Stevenson et al., 1986), morphological approaches to TJ permeability based largely on freeze fracture electron microscopy studies (Pinto da Silva and Kachar, 1982), would now shift to Western immunoblot and immunofluorescence studies. Cingulin (Citi et al., 1988), ZO-2 (Jesaitis and Goodenough, 1994), 7H6 (Zhong et al., 1993), ZO-3 (Haskins et al., 1998) were all identified in the late 1980s and 1990s, as a concept began to emerge that the TJ was not only a complex of proteins, but a complex physically associated with the actin cytoskeleton of the cell (Madara et al., 1986). These proteins were, however, all found to be intracellular and, therefore, could not function as the extracellular barrier situated in the intercellular space.
[0025] The discovery of occludin (Furuse et al., 1993) marked the first of the extracellular proteins to be found. In fact, occludin was a membrane spanning TJ protein whose intracellular portion contained a binding site for ZO-1 (Furuse et al., 1994). Occludin's discovery was followed closely by the claudins (Furuse et al., 1998), which were viewed as extracellular occludin-associated proteins. A picture somewhat like the gears of a clock began to emerge.
[0026] Regulation of Tight Junctions by Tumor Promoting Phorbol Esters
[0027] There is (an) extensive literature indicating that the class of tumor promoters (secondary carcinogens) called phorbol esters, can regulate TJ permeability and assembly. Phorbol esters have been known to increase TJ permeability since the early 1980s. (Ojakian, 1981; Mullin and O'Brien, 1986). This action of phorbol esters was then attributed to PKC activation by studies with a number of structurally distinct tumor promoting Protein Kinase C (PKC) activators such as teleocidin and diacylglycerols. (Mullin et al., 1990; Mullin and McGinn, 1988). In gastrointestinal cell sheets, phorbol esters likewise increase transepithelial permeability. (Hecht et al., 1994). PKC has been shown to mediate the effect of Ca ++ on TJ permeability (Tai et al., 1996 ).
[0028] Although most researchers fixate on the implication of this action of tumor promoters for indicating regulation of TJ permeability by PKC, a key point is frequently missed. This point is that a class of chemicals intricately involved in the processes of chemical carcinogenesis, are very potent mediators of increased TJ leakiness.
[0029] Aberrant Tight Junctions Associated With Tumors and Transformation
[0030] The first published report which indicates altered TJ structure in cancer was actually almost 30 years ago, and showed by using routine transmission electron microscopy that there is loss of electron dense TJ structure as a function of epithelial transformation. (Martinez-Palomo, 1970). Over a decade later, using freeze fracture electron microscopy, a decreased number of TJ strands was observed in transitional carcinoma of the urinary bladder compared with normal mucosa (Saito, 1984). Five years after this, decreased transepithelial impedance was recorded across the colons of mice treated with chemical carcinogens, suggesting increased functional permeability to Na + and Cl − . (Davies et al., 1989). At this same time, inflammatory bowel disease linked with increased colon cancer risk was itself being linked with increased TJ permeability, not only in affected individuals but in first degree relatives as well. (Hollander 1988).
[0031] On a molecular basis, the TJ protein, ZO-1, has been shown to possess significant sequence homology to a septate tumor suppressor protein of Drosophila. A mutation of this protein leads to epithelial tumor formation in larvae. (Woods and Bryant, 1991; Willott et al., 1993). The interaction of the normal APC (adenomatous polyposis coli) colon cancer susceptibility gene product with the cell adhesion protein, beta catenin (Su et al., 1993), raises an interesting possibility that mutation of APC may affect cell adhesion and thereby TJ permeability.
[0032] Findings
[0033] It had been shown 20 years ago (Ojakian, 1981) that the phorbol ester, TPA, was capable of causing transepithelial leakiness to salts in a renal epithelial cell line.
[0034] Once the phorbol esters were found to be activators of the signal transduction intermediate, PKC (Castagna et al., 1982; Nishizuka, 1984), this finding was then used as a springboard by many groups into the regulation of transepithelial permeability by PKC, and later into other signaling elements as well. (reviewed by Schneeberger and Lynch, 1992). Today it is not an exaggeration to say that many view phorbol esters as merely PKC activators and do not consider, or are even unaware of, their related role as tumor promoters.
[0035] One can view Ojakian's 1981 finding in light of the earlier findings which showed that: 1) phorbol esters were among the most powerful tumor promoting agents known (Diamond et al., 1980); and 2) tumor promoters function in epithelial carcinogenesis as second stage carcinogens which produce a nonheritable change in the cells being transformed. (Boutwell, 1974). The action of phorbol esters on epithelial TJs function in the process of epithelial tumorigenesis. Certainly the two key characteristics of epithelia (intrinsic polarity and ability to separate two fluid compartments in vivo) are abrogated in epithelial cancers as described below.
[0036] In the present invention, it was necessary to investigate what types of solutes these phorbol ester-treated epithelial TJs were now leaky to. The physiological and cell biological effects of the TJ leakiness would be in direct association with exactly what types of substances could now cross the epithelial barrier. In a different epithelial cell line (LLC-PK 1 ), it was shown that TPA also caused a rapid, dose dependent decrease in transepithelial electrical resistance (R t ), indicating increased permeability to Na + and Cl − (Mullin and O'Brien, 1986). It was also shown that the paracellular markers D-mannitol (mw 182) and polyethylene glycol (mw 4000) both crossed the TPA-treated epithelial cell sheet much more rapidly than they crossed a control cell sheet, and the electron dense dye, ruthenium red, was able to penetrate TJs of TPA-treated cell sheets, but not corresponding control cultures. (Mullin et al., 1996). In fact, chronic exposure of epithelial cell cultures to TPA (4 days or greater) resulted in polyp-like, multilayered foci, whose junctions were uniquely leaky to ruthenium red, whereas TJs of neighboring morphologically normal, one-cell-layerthick areas were impermeable to the dye. Later studies demonstrated in fact that the TJs became leaky to molecules as large as 2 million mw (Mullin et al., 1997). Most important were the findings that within that molecular weight range, growth factors such as EGF and insulin had over 20-fold increased rates of flux, and that the material coming across the epithelial barrier retained biological activity. (Mullin and McGinn, 1987; Mullin et al., 1999).
[0037] The biological significance here is that luminal fluids of many epithelial tissues contain very high levels of certain growth factors (Barnard et al., 1995; Jorgenson et al., 1990; Nexo et al., 1992; Mroczkowski and Reich, 1993), whereas the receptors for these growth factors are normally found on the abluminal cell surface. (Bishop and Wen, 1994; Muto et al., 1991; Thompson, 1988; Scheving et al., 1989). Therefore if TJs become leaky to such growth factors, this results in epithelial growth factor receptors encountering their ligands at concentrations normally never seen in vivo, in turn resulting in altered states of differentiation and cell cycle regulation. (Mullin, 1997). In the present invention, it was necessary to increase in vivo the concentration of Epidermal Growth Factor (EGF) in rat colonic lumen. This does not produce any observed effect on normal rat colon epithelium. However rat colon which has been treated with the colon carcinogen, dimethylhydrazine, manifests a greater number and size of carcinomas when luminal EGF is increased. This is a direct consequence of the carcinogen's effect on colonic crypt epithelial TJs as described below.
[0038] On a molecular level, there are several published studies showing that the patterns and timing of translocation and downregulation of the alpha isoform of PKC correlate closely with the changes in TJ permeability, suggesting that this specific isoform may govern TJ permeability. (Mullin et al., 1997). Similar results are achieved by molecular overexpression of PKC-alpha. (Rosson et al., 1998). The TJ molecular target of activated PKC led to the conclusion, however, that PKC is further upstream in the signaling pathway regulating TJ permeability than first imagined.
[0039] In approaching the question of molecular targets of PKC which would transduce a signal to a state of increased TJ permeability, occludin was chosen to begin the studies. Unlike ZO-1, occludin is a membrane spanning protein and actually forms part of the TJ barrier. In comparison to claudins, occludin is a larger, more complex protein, and more is known of its structure and interactions. Exposure of epithelial cell sheets to TPA was observed to cause very little change in the localization of occludin as seen by immunofluorescence, whereas the intracellular TJassociated protein, ZO-1, was being down regulated. Western immunoblots likewise showed that occludin was not being down regulated or translocated in association with TPA-induced TJ permeability increase. (Clarke et al., 2000, Appendix B). More important, however, was the finding that occludin's phosphorylation state was changing in association with increased TJ permeability. In fact, whereas it was expected to see an increase in occludin phosphorylation after PKC activation, the opposite was observed, namely a decrease in the threonine phosphorylation state of occludin. This finding led to the conclusion that at least one additional signaling element, a serine/threonine phosphatase, is between PKC and the occludin target. Site directed mutagenesis of conserved threonine residues on the carboxyl terminal end of occludin is necessary in order to better assess whether changes in threonine phosphorylation of occludin regulate TJ permeability.
[0040] Epithelial tissue studies have produced data that is of greater significance to the patient-based studies of this present invention. In a collaboration with Ned Z. Carp, M.D. (Lankenau, Dept. of Surgery) and using colectomy tissue from patients at Lankenau Hospital (F/N-R-92-691), it was shown that the TJs of surface epithelia of human colon carcinomas are uniformly leaky to electron dense dye, whereas those of histologically normal colon mucosa are uniformly impermeable (Peralta Soler et al., 1999, Appendix C). This was likewise true for dimethylhydrazine (DMH)-induced tumors in rat colon.
[0041] Interestingly, surface epithelia of hyperplastic or adenomatous human colon polyps were like normal mucosa, i.e. impermeable to the dye. More important were results which showed that TJ leakiness did in fact precede the onset of tumor formation. First it was observed that aberrant colon crypts increased in number as a function of increased number of weeks of DMH exposure, as numerous investigators have reported. In addition, however, weekly changes in barrier function of DMH-treated colon were examined, with an emphasis on assessing that function by means of electrophysiology (R t ) and transepithelial flux of 14 C-D-mannitol. As the weeks of DMH exposure progressed there was an irregular but significant decline in R t and rise in D-mannitol flux, clearly indicating that TJ leakiness precedes tumor formation (Appendix D).
[0042] Increased barrier leakiness clearly relates to the increased number of aberrant crypts in that barrier. This suggests that the TJs of aberrant crypts are leaky. This proves to be very significant for the overall model since aberrant crypts are generally regarded to be the forerunners of adenomas and carcinomas in the colon mucosa.
[0043] In studies on biopsy tissue obtained from colonoscopy patients at Lankenau Hospital (F/N-R-96-978) (collaboration with James J. Thornton, M.D., Division of Gastroenterology, Lankenau), it was observed that the TJs between colonocytes of patients with Crohn's Disease or ulcerative colitis are significantly leakier than the TJs between colonocytes of histologically normal biopsies from patients without disease (abstract to 2000 Amer. Gastro. Assn. meeting, Gastroenterology 118(4): A803). These procedures, as well as those using the colectomy tissue described above, are very similar to the procedures required here for endoscopy and surgery tissue from patients at Lankenau.
[0044] Experimental Design
[0045] Determine if Epithelial Tight Junctional Leakiness Is a Property of Adenocarcinomas of the Human Upper Gastrointestinal Tract
[0046] In close collaboration with the Departments of General Surgery and Pathology of Lankenau Hospital, this research group has been able to demonstrate that the tight junctions between epithelia of adenocarcinomas of human colon are leaky (relative to the tight junctions of epithelia from colon mucosa more than 10 cm distant from the edge of the tumor. The actual conduct of these studies begins with notification to this research group of upcoming colectomy surgeries. It is then necessary to prepare to receive specimens on the day of that patient's surgery, and notify the pathologist on call that day for frozen sections, that a colectomy for adenocarcinoma is forthcoming. An operating room nurse calls the research lab 5 minutes prior to colon removal. The on-call pathologist and a research group member meet in the frozen sections room, and the pathologist determines if tumor tissue and/or normal mucosa could be taken for research purposes. If this is possible, fresh tumor and normal tissue is transported back to the laboratory in Kreb's Ringer Bicarbonate saline at 4° C.
[0047] The tight junction permeability of this tissue is then analyzed in one of three ways: 1) electrophysiological measurement of transepithelial electrical resistance; 2) transepithelial flux of 14 C-D-mannitol; and/or 3) penetration of the electron dense dye, ruthenium red, from the apical surface into the lateral intercellular space. These methods are described in Peralta Soler et al. (1999) and Mullin et al. (2000) (Appendices C and E) which also detail that tight junctions of tumor epithelia are leaky by each of the above three criteria.
[0048] Demonstration of the Leakage of Luminal Salivary Proteins Across the GI Barrier in Precancerous States in Humans
[0049] It is necessary to functionally verify TJ leakiness in upper GI precancerous states and tumors in humans, and to determine if proteins normally sequestered in the lumen of the upper GI tract can cross the GI barrier at sites where a cancerous or precancerous lesion exists. This forms the basis of a noninvasive early detection system for upper GI cancer.
[0050] Patients coming in for endoscopic have 10 cc of (venous) blood drawn into tubes through an existing line. After centrifugation, the serum supernatant is frozen in 1 ml aliquots at −70° C. The salivary protein, salivary amylase (SA), is initially chosen for study. SA is a 55 kDa protein, immunologically and enzymatically distinct from the pancreatic form. This protein was chosen because it is vectorially secreted (luminally) into a fluid (saliva) which washes down into and over the areas where the TJ leakiness in precancerous lesions can allow for their crossing the gastroesophageal barrier into the bloodstream. Importantly, it is not produced in the area where the tumors will arise, and therefore its blood level cannot be due to tumorigenesis affecting sites of production (as seems to be the case for pep sinogen).
[0051] Salivary amylase can be assayed separately from its pancreatic form by virtue of a specific inhibitor of its activity (Huang and Tietz, 1982. The level of SA in the saliva of the same patients is analyzed by simply analyzing total amylase in sputum samples. SA is surprisingly stable over time in these clinical samples, a factor which aids the accuracy of the tests. Serum is analyzed undiluted. Saliva is diluted 1: 1000 in PBS+1% BSA for analysis of SA.
[0052] Blood levels (and the ratio of blood level/saliva level) of SA is grouped according to whether the patient had a normal endoscopic evaluation, or cancerous/precancerous conditions were observed. For precancerous conditions there is interest in Barrett's esophagus, atrophic gastritis and H. pylori-infected tissue. Patients with active ulcerations of the upper GI tract and conditions of actual upper GI bleeding are not analyzed because here the GI barrier is breached in a macroscopic manner. The interest of the present invention is in the more subtle occurrence of leakiness of epithelial TJs in an otherwise intact epithelium (a condition which will not evidence bleeding).
[0053] A second marker solute is used for gastroesophageal permeability. Patients drink a solution of sucrose (100 gms in 200 ml water) the night before their endoscopy, and collect an overnight urine sample. It has previously been shown that sucrose is an excellent marker for ulceration-type leakiness in the upper GI tract. (Sutherland et al., 1994; Meddings et al., 1993). The reason is that sucrose cannot be transported across cells since it lacks a membrane transporter. Sucrose is normally completely broken down by sucrase/isomaltase on duodenal microvilli, entering enterocytes and the bloodstream as fructose and glucose. Sucrose per se normally is completely absent from the bloodstream. However a defect in the gastric barrier (e.g. ulceration) which would enable sucrose to diffuse undegraded into the bloodstream allows for its subsequent quantitative appearance in blood and then urine. Thus, use of sucrose as an indicator of macroscopic gastric damage (ulcer disease, IBD) can be taken to a more molecular level, namely the leakiness of epithelial TJ seals in precancerous conditions and actual carcinoma. Cell culture models (Mullin et al., 1997) predict that a molecule, such as sucrose, will diffuse through these altered, leaky TJs and enter the bloodstream. Due to sucrose's relatively small size (mw 342 vs. 56,000 for SA), it proves a superior probe to SA in this regard. Endoscopic biopsies of normal and precancerous tissue from distal esophageal and gastric mucosa (corpus region) of these same patients is studied. First, biopsy tissue is mounted in simplified Ussing-type chambers, for overlay of the electron dense dye, ruthenium red, onto the apical surface. This allows for determination of TJ leakiness by observation, in electron micrographs, of the penetration of ruthenium red across the TJ and into the intercellular space, as previously described (Peralta Soler et al., 1999). In addition, use is made of Ussing-type tissue diffusion chambers specially designed for very small (<1 mm) tissue diameters (Harvard Apparatus) that have just recently become available, thereby allowing for transepithelial electrophysiological measurements and radiochemical flux analysis using biopsy samples. Therefore, measurements of R t , as well as e.g. 14 C-mannitol flux studies, can be made on human biopsy tissue as has been done previously with human surgical tissue (colectomy). (Peralta Soler et al., 1999; Mullin et al., 1997).
[0054] In addition to these physiological measurements of TJ permeability in normal versus precancerous tissue, the phosphorylation state of the TJ protein, occludin, is also examined. These studies derive from a recent observation using epithelial cell cultures that as TJ permeability increases, occludin is dephosphorylated at one or more threonine residues. Using techniques already in use, occludin is examined in biopsy tissue. (Clarke et al., 2000 [Appendix B]). Biopsy tissue is immediately placed in homogenization buffer on ice, sonicated, differentially centrifuged, and analyzed by Western immunoblot, probing with anti-occludin and antiphosphothreonine antibodies. This enables determination of whether or not the occludin expression and/or phosphorylation state is altered in precancerous tissue of the esophagus or stomach, as a correlate to changes in TJ permeability in the precancerous state.
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The present invention involves the early diagnosis of cancerous or precancerous conditions in the gastrointestinal tract by detection of a backleak of signature proteins or carbohydrates in a biological sample obtained from the gastrointestinal tract.
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This is a division of application Ser. No. 342,453, filed Jan. 25, 1982, and now U.S. Pat. No. 4,400,340.
BACKGROUND OF THE INVENTION
This invention relates to a method for the preparation of a polymer of dicyclopentadiene (hereinafter referred to as DCPD). In particular, it relates to employing a metathesiscatalyst system to form a high modulus, high impact strength thermoset poly(DCPD) homopolymer. In a preferred embodiment the homopolymer is formed when two solutions, one a catalyst/monomer mixture and the other an activator/monomer mixture, are combined in a reaction injection molding (hereinafter referred to as RIM) machine and then injected into a mold.
Any good thermoset polymer should meet at least two criteria. It should have desirable physical properties and it should lend itself to easy synthesis and forming. Among the most desirable physical properties for many polymers is a combination of high impact strength and high modulus. A standard test for impact strength is the notched Izod impact test, ATSM No. D-256. For an unreinforced theremoset polymer to have good impact strength, its notched Izod impact should be at least 1.5 ft. lb/in. notch. It is desirable that this good impact strength be combined with a modulus of at least about 150,000 psi at ambient temperature. Thermoset polymers with high impact strength and high modulus find useful applications as engineering plastics in such articles of manufacture as automobiles, appliances and sports equipment. Among the critical factors in the synthesis and forming of a thermoset polymer are the conditions required to make the polymer set up or gel. Many thermoset polymers require considerable time, elevated temperature and pressure, or additional steps after the reactants are mixed before the setting is complete.
While some references to poly(DCPD) have been made in the literature, a thermoset homopolymer having high impact strength and high modulus has never been described. Characteristics of thermoset polymers include insolubility in common solvents such as gasoline, naphtha, chlorinated hydrocarbons, and aromatics as well as resistance to flow at elevated temperatures.
Work has been done on the metathesis copolymerization of DCPD with one or more other monomers to produce soluble copolymers. This copolymer formation has resulted in the production of unwanted insoluble by-products. U.S. Pat. No. 4,002,815, for instance, teaches the copolymerization of cyclopentene with DCPD, describes an insoluble by-product and suggests that the by-product could be a gel of a DCPD homopolymer.
Some work, usually in an attempt to produce soluble poly(DCPD's), has been done on the metathesis homopolymerization of DCPD. Japanese unexamined published patent applications KOKAI 53-92000 and 53-111399 disclose soluble poly(DCPD's). Several syntheses of soluble poly(DCPD) have produced insoluble by-products. Takata et al, J. Chem Soc. Japan Ind. Chem. Sect., 69, 711 (1966), discloses the production of an insoluble poly(DCPD) by-product from the Ziegler-Natta catalyzed polymerization of DCPD; Oshika et al, Bulletin of the Chemical Society of Japan, discloses the production of an insoluble polymer when DCPD is polymerized with WCl 6 , AlEt 3 /TiCl 4 or AlEt 3 /MoCl 5 ; and Dall Asta et al, Die Makromolecular Chemie 130, 153 (1969), discloses an insoluble by-product produced when a WCl 6 /AlEt 2 Cl catalyst system is used to form poly(DCPD).
In U.S. Pat. No. 3,627,739, a thermoset poly(DCPD) is the object of synthesis. The poly(DCPD) of U.S. Pat. No. 3,627,739 is brittle, having an Izod impact strength of only 0.78.
Not only is it desirable that the thermoset polymer have high impact strength, but it is also desirable that it be easily synthesized and formed. A RIM process achieves this second goal by in-mold polymerization. The process involves the mixing of two or more low viscosity reactive streams. The combined streams are then injected into a mold where they quickly set up into a solid infusible mass. RIM is especially suited for molding large intricate objects rapidly and in low cost equipment. Because the process requires only low pressures, the molds are inexpensive and easily changed. Furthermore, since the initial materials have low viscosity, massive extruders and molds are not necessary and energy requirements are minimal compared to the injection molding or compression molding commonly used. For a RIM system to be of use with a particular polymer, certain requirements must be met:
(1) The individual streams must be stable and must have a reasonable shelf-life under ambient conditions.
(2) It must be possible to mix the streams thoroughly without their setting up in the mixing head.
(3) When injected into the mold, the materials must set up to a solid system rapidly.
(4) Any additives-fillers, stabilizers, pigments, etc. must be added before the material sets up. Therefore, the additives selected must not interfere with the polymerization reaction.
It can be seen that when developing a RIM process a tradeoff must be made. It is desirable that the polymer set up quickly, but the polymerization cannot be too quick. The components cannot be so reactive that they set up in the mixing head before they can be injected into the mold. Once in the mold, however, the polymer should set up as quickly as possible. It is not desirable that the polymer take a long time or require additional steps to gel completely.
It is known in the prior art to base a RIM system on the combination of two reactive monomers, e.g., the polyol and the diisocyanate monomers employed in a polyurethane system. It is known, but not in the context of a RIM system, to combine two or more reactive parts of a catalyst, where one or both are in solution with the monomer, to form a homopolymer. A process which employs two separate streams based on a two part catalyst system to produce a thermoset polymer in such a manner that the streams can be combined in one place and then rapidly set up in another is unique and is a substantial contribution to the art. U.S. Pat. No. 2,846,426, Larson, claims the combination of two vapor streams, one containing a vaporizable alkylaluminum compound and the other containing a vaporizable compound of Group IV-B, V-B, or VI-B metal, where at least one of the streams contains a gaseous monomer. The vapor streams are combined and a thermoplastic polymer is formed in the same reaction zone. U.S. Pat. No. 3,492,245, Calderon et al, discloses the in-situ formation of a catalyst system containing an organoaluminum compound, a tungsten hexahalide and a hydroxy compound. Again, the reactive components are mixed and the polymerization of an unsaturated alicyclic compound occurs in the same vessel. U.S. Pat. No. 3,931,357, Meyer, teaches a process for forming a soluble graft copolymer of a polydiene or a polyalkenamer and an unsaturated polyolefin rubber which entails combining a stream containing a metathesis catalyst component from a metal of subgroups V through VII of the periodic table with a stream containing an alkyl or a hydride of a metal from main groups I through VII of the periodic table prior to the metathesis reaction proper. Since the copolymer is soluble, there is no requirement that it rapidly set up.
BRIEF DESCRIPTION OF THE INVENTION
This invention encompasses a method for producing a high impact strength, high modulus thermost homopolymer comprising polymerized units of DCPD by using a two part metathesiscatalyst system. The DCPD polymer is a tough, rigid material with high modulus and excellent impact strength. The flexural modulus is in the range of about 150,000 to about 300,000 psi. and the notched Izod impact strength is at least 1.5 ft. lb./in. notch.
The polymer can be synthesized by reacting DCPD with a two part metathesis-catalyst system. The first part of the catalyst system is comprised of a metathesis catalyst, preferably WOCl 4 , WCl 6 or a combination of WCl 6 plus an alcohol or phenol. The second part of the catalyst system is comprised of an activator such as SnBu 4 , AlEt 3 , AlEt 2 Cl, AlEtCl 2 , or similar compounds. In a preferred synthesis, the activator is Et 2 AlCl. Also in the preferred synthesis the activator containing solution includes an ester, ether, ketone or nitrile which serves to moderate the rate of polymerization. Examples of suitable moderators are ethyl benzoate and di-n-butyl ether. In a preferred embodiment the two metathesis-catalyst system components, plus the monomer, form the basis for at least two separate streams which can be mixed in the head of a RIM machine and then injected into a mold where they will quickly set up into a tough, infusible mass. Various additives such as fillers and stabilizers can be added to modify the properties of the thermoset polymer.
DETAILED DESCRIPTION OF THE INVENTION
Dicyclopentadiene can be polymerized in such a manner that the resulting product is a thermoset homopolymer having high impact strength and high modulus. The preferred monomer is commercially available endo-DCPD (3a,4,7,7a-tetrahydro-4,7-methano-1H-idene). The exo-isomer, while not commercially available, can be used just as well. The preferred commercially available material normally has a purity of 96-97%. Commercially available material should be purified in order to prevent impurities from inhibiting the polymerization. The low boiling fraction should be removed. This can be done by stripping away several percent of the unsaturated four to six carbon atom volatiles, i.e., the volatiles distilled below 100° C. at about 90±3 torr. It is often desirable to purify the starting material even further by treatment with silica gel. Additionally, the water content of the starting material should be below about 100 ppm. The presence of water interferes with polymerization by hydrolysis of both the catalyst and the activator components of the catalyst system. For example, water can be removed by azeotropic distillation under reduced pressure. Even after these steps the monomer still contains some impurities. It should be understood, therefore, that throughout this description the term homopolymer refers to the polymer resulting from essentially pure starting material.
The homopolymerization of the purified DCPD is catalyzed by a two part metathesis-catalyst system. One part contains a tungsten containing catalyst, such as a tungsten halide or tungsten oxhyalide, preferably WCl 6 or WOCl 4 . The other part contains an activator such as SnBu 4 or an alkylaluminum compound. The alkylaluminum compound can be an alkylaluminum dihalide or dialkylaluminum halide where the alkyl group contains one to ten carbon atoms. In the preferred activator the alkyl group is ethyl with diethyl aluminum chloride being most preferred.
One part of the catalyst system comprises the tungsten containing catalyst, as described above, preferably in solution with DCPD monomer. The tungsten compound if unmodified, will rapidly polymerize the monomer. Consequently, the tungsten compound should first be suspended in a small amount of a suitable solvent. The solvent must not be susceptible to halogenation by the tungsten compound. Examples of preferred solvents are benzene, toluene, chlorobenzene, dichlorobenzene, and trichlorobenzene. Sufficient solvent should be added so that the tungsten compound concentration is between about 0.1 to 0.7 mole per liter of solvent.
The tungsten compound can be solublized by the addition of a small amount of an alcoholic or a phenolic compound. Phenolic compounds are preferred. Suitable phenolic compounds include phenol, alkyl-phenols, and halogenated phenols, with tert-butyl phenol, tert-octyl phenol and nonyl phenol being most preferred. The preferred molar ratio of tungsten compound/phenolic compound is from about 1:1 to about 1:3. The tungsten compound/phenolic compound solution can be made by adding the phenolic compound to a tungsten compound/organic solvent slurry, stirring the solution and then blowing a stream of a dry inert gas through the solution to remove the hydrogen chloride which is formed. Alternatively, a phenolic salt, such as a lithium or sodium phenoxide, can be added to a tungsten compound/organic solvent slurry, the mixture stirred until essentially all the tungsten compound is dissolved, and the precipitated inorganic salt removed by filtration or centrifugation. All of these steps should be carried out in the absence of moisture and air to prevent deactivation of the catalyst.
To prevent premature polymerization of the tungsten compound/monomer solution, which would occur within a matter of hours, from about 1 to about 5 moles of a Lewis base or a chelating agent can be added per mole of tungsten compound. Preferred chelants include acetylacetones, alkyl acetoacetates, where the alkyl group contains from one to ten carbon atoms; preferred Lewis bases are nitriles and ethers such as benzonitrile and tetrahydrofuran. The improvement in the stability and shelf-life of the tungsten compound/monomer solution is obtained whether the complexing agent is added before or after the phenolic compound. When purified DCPD is added to this catalyst solution it forms a solution which is stable and has a shelf-life of several months.
The other part of the metathesis-catalyst system comprises the activator, as described above, preferably in DCPD monomer. This mixture is storage stable and therefore, unlike the tungsten compound/monomer solution, needs no additives to prolong its shelf-life. If, however, an unmodified activator/monomer solution is mixed with the catalyst/monomer solution, the polymerization would initiate instantaneously and the polymer could set up in the mixing head. The onset of polymerization can be delayed by adding a moderator to the activator/monomer solution. Ethers, esters, ketones and nitriles can act as moderators for the alkylaluminum compounds. Isopropyl ether, di-n-butyl ether, ethyl benzoate, phenylethyl acetate and diisopropyl ketone are preferred. Ethyl benzoate and butyl ether are most preferred. The preferred ratio of the alkylaluminum to moderator is from about 1:1.5 to about 1:5 on a molar basis.
The polymerization time required for gelation is also temperature dependent. As the temperature at which the reaction is carried out is increased the reaction rate will also increase. For every eight degree increase in temperature the reaction rate will approximately double. Consequently, to keep the reaction rate controlled at higher reaction temperatures a less active formulation of the metathesiscatalyst system should be used.
What is ultimately required is that when the catalyst system's components are combined, the resulting DCPD to tungsten compound ratio will be from about 1,000:1 to about 15,000:1 on a molar basis, preferably 2,000:1 and the DCPD to alkylaluminum ratio will be from about 100:1 to about 2000:1 on a molar basis, preferably about 200:1 to about 500:1. To illustrate a preferred combination: sufficient DCPD is added to a 0.1 M tungsten containing catalyst solution prepared as described above, so that the final tungsten compound concentration is 0.007 molar. This corresponds to a DCPD to tungsten compound ratio of 1000:1. Sufficient DCPD is added to the Et 2 AlCl solution, prepared as described above, so that the alkylaluminum concentration is 0.048 M. This corresponds to a DCPD to alkylaluminum ratio of 150:1. If these two streams are mixed in a 1:1 ratio, the final ratio of DCPD to alkylaluminum will be 300:1 and the final ratio of tungsten compound will be 2000:1 and the final ratio of DCPD to alkylaluminum will be 300:1 and the final ratio of tungsten compound to alkylaluminum will be about 1:7. The illustrated combination is not the lowest catalyst level at which moldings can be made, but it is a practical level that provides for excess catalyst if impurities in the system consume some of the catalyst components. A higher alkylaluminum level will not only increase costs and residual chlorine levels but may result in a less satisfactory cure. Too low a tungsten compound concentration results in incomplete conversion. A wide range of alkylaluminum activator to tungsten catalyst formulations produce samples which have good out-of-mold properties such as tear resistance, stiffness, residual odor, and surface properties.
In a preferred synthesis, the poly(DCPD) is made and molded with the RIM process. The two parts of the metathesis-catalyst system are each mixed with DCPD, to form stable solutions which are placed in separates vessels. These containers provide the source for separate streams. The two streams are combined in the RIM machine's mixing head and then injected into a warm mold where they quickly polymerize into a solid, infusible mass. The invention is not intended to be limited to systems employing two streams each containing monomer. It will be obvious to one skilled in the art that there may be situations where it is desirable to have monomer incorporated in just one stream or to employ more than two streams where the additional streams contain monomer and/or additives.
These streams are completely compatible with conventional RIM equipment. Metathesis-catalyzed polymerizations are known to be inhibited by oxygen so it is necessary to store the components under an inert gas but, surprisingly, it is not necessary to blanket the mold with an inert gas. The streams are combined in the mixing head of a RIM machine. Turbulent mixing is easy to achieve because the process involves low molecular weight, rapidly diffusing components. Typically the mixing heads have orifices about 0.032 inch in diameter and a jet velocity of about 400 ft/sec. After being combined the mixture is injected into a mold maintained at 35°-100° C., preferably 50°-70° C. The mold pressure is in the range of about 10-50 psi. A rapid exothermic reaction occurs as the poly(DCPD) sets up. The mold can be opened in as little as 20-30 seconds after the combined streams have been injected. In this short time heat removal is not complete and the polymer is hot and flexible. The polymer can be removed from the mold immediately while hot or after cooling. After the polymer has cooled it will become a rigid solid. The total cycle time may be as low as 0.5 minute. Post-curing is desirable but not essential, to bring the samples to their final stable dimensional states, to minimize residual odors, and to improve final physical properties. Post-curing at about 175° C. for about 15 minutes is usually sufficient.
The product has a flexural modulus of about 150,000 to 300,000 psi and a notched Izod impact resistance of at least about 1.5 ft. lb/in. notch. The homopolymer is insoluble in common solvents such as gasoline, naphthas, chlorinated hydrocarbons and aromatics, resistant to flow at temperatures as high as 350° C. and readily releases from the mold.
Various additives can be included to modify the properties of poly(DCPD). Possible additives include fillers, pigments, antioxidants, light stabilizers and polymeric modifiers. Because of the rapid polymerization time the additives must be incorporated before the DCPD sets up in the mold. It is often desirable that the additives be combined with one or both of the catalyst system's streams before being injected into the mold. Fillers can also be charged to the mold cavity, prior to charging the reaction streams, if the fillers are such that the reaction stream can readily flow around them to fill and the remaining void space in the mole. It is essential that the additives not affect catalytic activity.
One class of possible additives is reinforcing agents or fillers. These are compounds which can increase the polymer's flexural modulus with only a small sacrifice in impact resistance. Possible fillers include glass, wollastonite, mica, carbon black, talc, and calcium carbonate. It is surprising that in spite of the highly polar nature of their surfaces these fillers can be added without appreciably affecting the polymerization rate. From about 5% to 75% by weight may be incorporated. This and all subsequent percentages are based on the weight of the final product. The addition of fillers which have modified surface properties are particularly advantageous. The exact amount of a particular filler to be used in a particular situation will be easily determinable and will depend on the preferences of the practitioner. The addition of fillers also serves to decrease the mold shrinkage of the product. After a short post cure at 150°-200° C. an unfilled product will shrink from about 3.0 to about 3.5% whereas adding 20-25 wt % filler will decrease the shrinkage to 1.5-2% and adding 33 wt % filler will further decrease shrinkage to about 1%.
Since poly(DCPD) contains some unsaturation it may be subject to oxidation. The product can be protected by the incorporation of as much as about 2.0 wt % of a phenolic or amine antioxidant. Preferred antioxidants include 2,6-tertbutyl-p-cresol, N,N'-diphenyl-p-phenylene diamine and tetrakis [methylene(3,5-di-t-butyl-4-hydroxy cinnamate)] methane. While the antioxidant can be added to either or both streams, incorporation into the activator/monomer stream is preferred.
The addition of a elastomer can increase the polymer's impact strength 5-10 fold with only a slight decrease in flexural modulus. The elastomer can be dissolved in either or both of the DCPD streams in the 5-10 wt % range without causing an excessive increase in the solution viscosity. Useful elastomers include natural rubber, butyl rubber, polyisoprene, polybutadiene, polyisobutylene, ethylenepropylene copolymer, styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber and ethylene-propylene diene terpolymers. The amount of elastomer used is determined by its molecular weight and is limited by the viscosity of the streams. The streams cannot be so viscous that adequate mixing is not possible. The Brookfield viscosity of DCPD is about 6 cps at 35° C. Increasing the viscosity to between about 300 cps and about 1000 cps alters the mold filling characteristics of the combined streams. An increase in viscosity reduces leakage from the mold and simplifies the use of fillers by decreasing the settling rates of the solids. An example of a preferred elastomer is styrene-butadiene styrene triblock. Where 10 wt % of this additive is incorporated into the streams not only is the viscosity increased to about 300 cps but the impact strength of the final product also increases. Although the elastomer can be dissolved in either one or both of the streams it is desirable that it be dissolved in both. When the two streams have similar viscosities more uniform mixing is obtained.
EXAMPLES 1 and 2
In Example 1 a 0.1 M solution of a tungsten containing catalyst solution was prepared by adding 20 grams of WCl 6 in 460 ml of dry toluene under a N 2 atmosphere and then adding a solution of 8.2 grams of p-tert-butyl phenol in 30 ml of toluene. The catalyst solution was sparged overnight with nitrogen to remove the HCl generated by the reaction of WCl 6 with the p-tert-butylphenol. In this and in all the following examples phenol is used as a shorthand for p-tert-butylphenol and for simplicity the solution is referred to as WCl 6 /phenol. Then a 0.033 M catalyst/monomer solution was prepared by mixing under nitrogen 10 ml of DCPD, 0.07 ml of benzonitrile and 5 ml of the 0.1 M catalyst solution. An activator/monomer solution was prepared by combining, under nitrogen, 8.6 ml of DCPD, 0.1 ml of isopropyl ether and 0.36 ml of 1.0 M Et 2 AlCl in DCPD.
Polymerization was accomplished by adding 1.1 ml of the 0.033 M catalyst/monomer solution to 8.9 ml of the activator/monomer solution. Both solutions were intially at 25° C. They were vigorously mixed. After a brief induction period and a sharp exotherm was observed. A solid, insoluble polymer was formed. The time that elapsed until rapid polymerization began and the total exotherm of the sample above the starting temperature are shown in Table I.
In Example 2 the above procedure was repeated except that 0.36 ml of 1.0 M EtAlCl 2 was used in place of Et 2 AlCl to prepare the activator solution and the reaction was started at 40° C. A solid, insoluble polymer was formed. The results are shown in Table I.
TABLE I______________________________________ Example 1 Example 2______________________________________DCPD 72 mmol 72 mmolWCl.sub.6 /Phenol 0.036 mmol 0.036 mmolEt.sub.2 AlCl 0.36 mmol --EtAlCl.sub.2 -- 0.36 mmolBenzonitrile 0.04 mmol 0.04 mmolIsopropyl ether 0.72 mmol 0.72 mmolInitial Temperature 25° C. 40° C.Time until exotherm 15 sec. 445 sec.Exotherm 122° C. 147° C.______________________________________
EXAMPLES 3-8
In Examples 3 through 8 the procedure described in Example 1 was repeated except that different moderators were added to the activator/monomer solution. In each example the ratio of moles moderator to moles of Et 2 AlCl was held constant at 2:1. In example 3, di-n-butyl ether was added while in Example 4, diisopropyl ether was used. In Example 5, ethyl benzoate was used while in Example 6, phenylethyl acetate was added. In Example 7, diisopropyl ketone was added. Lastly, in Example 8, tetrahydrofuran was added. In each example the initial temperature was 25° C. (±1° C.). Example 8 was the only case where a solid insoluble polymer was not obtained. The results are listed in Table II.
TABLE II__________________________________________________________________________ Example 3 Example 4 Example 5 Example 6 Example 7 Example 8__________________________________________________________________________DCPD 72 mmol 72 mmol 72 mmol 72 mmol 72 mmol 72 mmolWCl.sub.6 /Phenol 0.036 mmol 0.036 mmol 0.036 mmol 0.036 mmol 0.036 mmol 0.036 mmolEt.sub.2 AlCl 0.36 mmol 0.36 mmol 0.36 mmol 0.36 mmol 0.36 mmol 0.36 mmolDi-n-butyl ether 0.72 mmol -- -- -- -- --Diisopropyl ether -- 0.72 mmol -- -- -- --Ethyl benzoate -- -- 0.72 mmol -- -- --Phenyl ethyl acetate -- -- -- 0.72 mmol -- --Diisopropyl ketone -- -- -- -- 0.72 mmol --Tetrahydrofuran -- -- -- -- -- 0.72 mmolBenzonitrile 0.04 mmol 0.04 mmol 0.04 mmol 0.04 mmol 0.04 mmol 0.04 mmolTime until Exotherm 42 sec. 15 sec. 60 sec. 282 sec. 160 sec. no rxn.Exotherm 153° C. 122° C. 155° C. 157° C. 147° C. --__________________________________________________________________________
EXAMPLES 9-12
In Examples 9 through 12 the activator to catalyst ratios were varied. In Example 9, 0.88 ml of catalyst/monomer solution, described in Example 1 was added to 7.1 ml of DCPD containing sufficient Et 2 AlCl and di-n-butyl ether to give the composition listed in Table III. In Example 10, 0.44 ml of the same catalyst/monomer solution as used in Example 9 was added to 7.5 ml of the same activator/monomer solution used in Example 9, to give the final composition listed in Table III. In Example 11, 4.0 ml of a catalyst/monomer solution prepared by mixing 20 ml of DCPD with 1.5 ml of a 0.1 M WCl 6 /phenol solution, was mixed with 4.0 ml of an activator/monomer solution. In this activator solution there was sufficient Et 2 AlCl to give a DCPD to alkylaluminum ratio of 100:1 and sufficient di-n-butyl ether to give a di-n-butyl ether to aluminum ratio of 2:1. In Example 12, 4.0 ml of the catalyst/monomer solution used in Example 11 was mixed with 2.0 ml of DCPD and 2.0 ml of the activator/monomer solution used in Example 11. In each case a solid, insoluble polymer was formed. The results of these reactions showing a variation in the exotherms due to variations in the Al/W ratio, are listed in Table III.
TABLE III______________________________________ Example 9 Example 10 Example 11 Example 12______________________________________DCPD 57.6 mmol 57.6 mmol 57.6 mmol 57.6 mmolWCl.sub.6 /Phenol 0.029 mmol 0.0145 mmol 0.029 mmol 0.029 mmolEt.sub.2 AlCl 0.29 mmol 0.29 mmol 0.29 mmol 0.145 mmolDi-n-butyl 0.58 mmol 0.58 mmol 0.58 mmol 0.29 mmoletherBenzonitrile 0.033 mmol 0.016 mmol 0.033 mmol 0.033 mmolDCPD/Al 200 200 200 400DCPD/W 2000 4000 2000 2000Al/W 10/1 20/1 10/1 5/1Time to 50 sec. 48 sec. 33 sec. 43 sec.ExothermExotherm 153° C. 120° C. 145° C. 168° C.______________________________________
EXAMPLES 13-15
In Examples 14-15 a small amount of a polar material was added to the catalyst/monomer solution in order to illustrate the effect of polar material on shelf-life. In Example 13, a catalyst/monomer solution was prepared by adding 2.0 ml of a 0.1 M tungsten containing catalyst solution, as described in Example 1, to 20 ml of DCPD in a nitrogen purged tube. This mixture gelled to a non-flowing material within 24 hours. In Example 14, the same procedure was carried out except that 0.03 ml of benzonitrile was added, giving a final benzonitrile to tungsten halide ratio of 1.5:1. This mixture did not gel and was catalytically active after 4 weeks. Example 15 illustrates the result when tetrahydrofuran was added to give a tetrahydrofuran to tungsten halide ratio of 1.5:1. Again, a greatly improved storage stability was observed. The results are listed in Table IV.
TABLE IV______________________________________ Example 13 Example 14 Example 15______________________________________DCPD 130 mmol 130 mmol 130 mmolWCl.sub.6 /Phenol 0.2 mmol 0.2 mmol 0.2 mmolBenzonitrile -- 0.3 mmol --Tetrahydrofuran -- -- 0.3 mmolCondition after gelled low viscosity low viscosity24 hoursCondition after gelled low viscosity low viscosity4 weeksActivity after gelled acceptable acceptable4 weeks______________________________________
EXAMPLES 16-18
In Examples 16-18, the concentration of di-n-butyl ether incorporated into the activator/monomer solution to serve as a moderator was varied. In Example 16, the procedure used in Example 1, was followed with the exception that 0.078 ml of n-butyl ether was substituted for the diisopropyl ether. This gave a final ratio of di-n-butyl ether to alkylaluminum of 1.5:1. In Example 17, the procedure was repeated except that 0.156 ml of di-n-butyl ether was added, giving a final ether/Al ratio of 3:1. In Example 18, sufficient di-n-butyl ether was added to bring the final ether to alkylaluminum ratio to 5:1. All the reactions in Table V were initiated at 25° C. In each case a solid, insoluble polymer was formed. The results of the reactions are listed in Table V.
TABLE V______________________________________ Example 16 Example 17 Example 18______________________________________DCPD 57.6 mmol 57.6 mmol 57.6 mmolWCl.sub.6 /Phenol 0.029 mmol 0.029 mmol 0.029 mmolEt.sub.2 AlCl 0.29 mmol 0.29 mmol 0.29 mmolDi-n-butyl ether 0.43 mmol 0.86 mmol 1.45 mmolBenzonitrile 0.033 mmol 0.033 mmol 0.033 mmolEther/Al 1.5 3.0 5.0Elapsed time 36 sec. 55 sec. 75 sec.until exothermExotherm 150° C. 158° C. 159° C.______________________________________
EXAMPLES 19-21
In Examples 19-21, the level of Et 2 AlCl used in the polymerization of DCPD was varied. In Example 19, 18.5 ml of DCPD was mixed under N 2 with 1.5 ml of a 1.0 M solution of Et 2 AlCl in DCPD and with 0.55 ml of di-n-butyl ether. Then in a N 2 purged tube 8.9 ml of this activator/monomer solution was mixed with 1.1 ml of a catalyst/monomer solution as described in Example 1. In Example 20, 4.5 ml of the activator/monomer solution used in Example 19 was combined with 4.4 ml of DCPD and 1.1 ml of the catalyst/monomer solution used in Example 20. In Example 21, 2.5 ml of the activator/monomer solution used in Example 19 was combined under N 2 with 6.4 ml of DCPD and 1.1 ml of the catalyst/monomer solution used in Example 19. The final compositions of these reaction mixtures are listed in Table VI. All reactions were initiated at 25° C.
TABLE VI______________________________________ Example 19 Example 20 Example 21______________________________________DCPD 72 mmol 72 mmol 72 mmolWCl.sub.6 /Phenol 0.036 mmol 0.036 mmol 0.036 mmolEt.sub.2 AlCl 0.72 mmol 0.36 mmol 0.20 mmolDi-n-butyl ether 1.44 mmol 0.72 mmol 0.40 mmolBenzonitrile 0.04 mmol 0.04 mmol 0.04 mmolDCPD/Al 100 200 360Di-n-butyl 2/1 2/1 2/1ether/AlElapsed time 40 sec. 55 sec. 144 sec.until exothermExotherm 150° C. 151° C. 145° C.______________________________________
EXAMPLES 22-25
The effect of impurities on the catalyst system is illustrated in Examples 22 through 25. In Example 22, a 0.007 M solution of WCl 6 /phenol in DCPD was prepared by mixing under nitrogen 150 ml of DCPD with 10.8 ml of a 0.1 M WCl 6 /phenol solution in toluene and 0.11 ml of benzonitrile. Then 3.0 ml of this solution was mixed under nitrogen with 3 ml of a DCPD solution containing AlEt 2 Cl at a level DCPD to alkylaluminum of 150:1 and di-n-butyl ether at a level of ether to alkylaluminum of 1.5:1.
In Example 23, a 10 ml sample of the catalyst/monomer solution used in Example 22 was mixed with a impurity, 0.036 mmol of H 2 O, added as a dispersion in DCPD. One and one-half hours later, 3 ml of this mixture was mixed under nitrogen with 3.01 of the activator/monomer solution described in Example 22. The reaction was repeated this time combining the activator/monomer solution with the catalyst/monomer solution 18 hours after the H 2 O had been added.
Example 24 was done in the same manner as Example 23 with the exception that 0.036 mmol of tert-butyl hydroperoxide was added to a second 10 ml sample of the catalyst solution rather than H 2 O. The reactivity of the resultant mixture was checked 11/2 and 18 hours after the addition of the impurity. Example 25 was carried out in the same manner with the exception that 0.072 mmol of di-tert-butylperoxide was the impurity added initially to 10 ml sample of the catalyst/monomer solution. In every case a solid, insoluble polymer was formed.
TABLE VII______________________________________ Example 22 Example 23 Example 24 Example 25______________________________________DCPD 43 mmol 43 mmol 43 mmol 43 mmolWCl.sub.6 /Phenol 0.021 mmol 0.021 mmol 0.021 mmol 0.021 mmolH.sub.2 O -- 0.01 mmol -- --tert-butyl- -- -- 0.01 mmol --hydroperoxideDi-tert-butyl- -- -- -- 0.02 mmolperoxideEt.sub.2 AlCl 0.14 mmol 0.14 mmol 0.14 mmol 0.14 mmolAdded 0 0.5/1 0.5/1 1/1Impurity/WInduction 31 sec. 50 sec. 98 sec. 33 sec.Time after11/2 hrs.Exotherm 173° C. 171° C. 168° C. 171° C.after 11/2 hrs.Induction 36 sec. 98 sec. 266 sec. 73 sec.time after 24 hrs.Exotherm 170° C. 170° C. 155° C. 169° C.after 24 hrs.______________________________________
EXAMPLES 26-33
Samples of polymerized DCPD were made by RIM processing using a standard RIM machine supplied by Accuratio Co. of Jeffersonville, Indiana. The following description illustrates the standard procedure for molding samples. First the desired amount of DCPD was charged into two 2 gallon tanks. The tanks are located on different sides of the RIM machine: the tank on the A side is the one to which the activator was later added and the tank on the B side is, the one to which the catalyst was later added. If desired, rubber and/or organic resins were added as a predissolved solution in DCPD. Also solid fillers, if desired, were added.
The tanks were then closed off and inerted with nitrogen. Sufficient Et 2 AlCl was transferred into the A tank to bring the alkylaluminum concentration to 0.048 M and sufficient di-n-butyl ether was added to achieve an ether to alkylaluminum ratio of 1.5:1. Next, sufficient WCl 6 /phenol to bring the concentration of the catalyst in the B side to 0.007 M was added to the B tank. The catalyst was added as a 0.1 M solution in toluene. All transfers were done in a way to preclude the entrance of oxygen or moisture into the system. The materials were then thoroughly blended in their respective tanks.
The mixing of the A stream and the B stream was accomplished using a standard impingement type RIM mixhead. The ratio of the activator/monomer solution mixed with catalyst/monomer solution was 1:1. The impingement mixing was accomplished by passing both the solutions through orifices 0.032" in diameter at a flow rate approximately 80 ml/sec. This required pumping pressure of approximately 1000 psi.
The resulting mixture flowed directly into a mold heated between 50° C. and 60° C. The mold was made out of aluminium and was chrome plated. The mold had a flat cavity which formed a plaque sample 10"×10"×1/8" thick. A clamping force of 1.5 tons was used to keep the mold closed. The finished samples were removed at various times after mold filling ended.
In Example 26, the outlined molding procedure was followed where there was added 10 wt % added styrene-butadienestyrene rubber (Kraton no. 1102 manufactured by Shell Chemical Co). The sample was removed from the mold after 2 minutes. In Example 27 a material of the same composition as Example 26 was produced. This time mold was opened 30 seconds after the combined streams were injected. The surface features of Example 27 were noticably better than those of Example 26. In Examples 28, 10 wt % of a thermally polymerized dicyclopentadiene resin was added in addition to both the catalyst/monomer and the activator/monomer solutions in addition to the styrene-butadiene-styrene rubber.
Various inorganic fillers were incorporated into the DCPD polymer by adding equal amounts to both the catalyst/monomer and the activator/monomer solutions. In Example 29, samples were made containing 33 wt % 1/8" milled glass (P117B grade of Owens Corning Co.). These samples were made by initially slurrying the glass into both solutions the catalyst/monomer and the activator/monomer otherwise, these solutions were indentical to those used in Example 28. In Example 30 a composition consisting of 10 wt % wollastonite was made by adding the filler to a formulation identical to that described in Example 28. In Example 31 the same procedure was followed as in Example 30 except that a 33 wt % level of wollastonite was employed. In Example 32, 25 wt % wollastonite was added to formulation described in Example 27. In each case a solid, insoluble polymer is formed. Representative properties of Examples 26-32 are listed in Table VII.
Example 33 is a RIM processed poly(DCPD) made without any rubber additives.
TABLE VIII__________________________________________________________________________ Example Example Example 26 Example 27 Example 28 Example 29 Example 30 31 Example 33__________________________________________________________________________Resin Composition% cyclopentadiene resin -- -- 10 10 10 10 -- --% Kraton 1102 10 10 10 10 10 10 10 --% DCPD 90 90 80 80 80 80 90 100Filler Compositionwt % 1/8" milled glass -- -- -- 33 -- -- -- --wt % wollastonile -- -- -- -- 10 33 25 --Tensile PropertiesStrength (psi) -- 4,860 5,230 -- 4,700 -- 4,290 5,050Modulus (psi) -- 262,000 257,000 -- 426,000.sup.1 -- 683,000.sup.1 270,000Elongation at yield (%) -- 4.0 4.0 -- 3.0 -- 2.0 3.4Flexural PropertiesStrength (psi) 7,400 8,600 -- 8,200 9,000 8,400 8,300 8,400Modulus (psi) 235,000 250,000 -- 526,000.sup.2 390,000.sup.2 670,000.sup.2 480,000.sup.2 270,000Impact PropertiesNotched Izod (ft #/in. notch) 13.2 10.5 11.0 2.7 2.0 2.9 -- 2.3Plate Impact at 5000"/min. (ft. #)23° C. 21.0 -- -- -- 11.2 -- 11.3 --0° C. 15.7 -- -- -- 12.0 -- 11.8 ---20° C. 12.3 -- -- -- 11.9 -- 12.7 --Heat Deflection Temperature -- .sup. 65° .sup. 64° .sup. 81° .sup. 69° -- .sup. 79° 60°at 264 psi (°C.)Coefficient of Thermal -- 6.0 × -- 3.2 × 5.2 × 10.sup.-5 -- 3.8 --imes. 10.sup.-Expansion (in/in °F.).sup.2 10.sup.-5 10.sup.-5Linear Mold Shrinkage.sup.2 (%) 2.6 3.5 3.1 1.0 1.6 1.0 1.5 --__________________________________________________________________________ .sup.1 Value in the direction parallel to the direction of flow. .sup.2 Value is the average of the values obtained perpendicular to the direction of flow and parallel to the direction of flow.
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A method of making a thermoset polydicyclopentadiene by first combining a plurality of reactant streams, one containing the activator of a metathesis-catalyst system, a second containing the catalyst of a metathesis-catalyst system and at least one containing dicylopentadiene; then immediately injecting this combination into a mold where polymerization results in the formation of a tough, rigid thermoset polymer with high modulus and excellent impact strength.
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TECHNICAL FIELD
The present invention generally relates to test apparatus for wire-type material used for power transmission line, in particular, relates to a winding tester for the wire rod-type specimens with carbon fiber or glass fiber reinforced composites, specifically provides for a winding tester with carbon fiber or glass fiber reinforced composite wire rod-type specimens.
BACKGROUND
Carbon fiber or glass fiber resin is a composite material being made with carbon fiber or glass fiber as reinforcing phase mingled in a resin as matrix phase. It meets the requirements to wire core material of the novel power transmission line in power industry, because of a series of outstanding performance thereof, such as, high specific strength, high specific modulus, high temperature resistance, corrosion resistance, fatigue resistance, and creep resistance, as well as small sag and thermal expansion coefficient, thereby gradually emerging a new configuration of carbon fiber composite core with the center layer of carbon fiber or resin and the coating layer of glass fiber or resin, as time required. It is found that, in subsequent studies, compared with conventional a steel core, the quality and linear expansion coefficient of the carbon fiber or glass fiber composite core equals approximately to ⅕ and 1/12 thereof, respectively. The outer layer, namely coating layer of glass fiber reinforces the wear resistance of the wire rod-type specimens, and is conducive to alleviate the damage generated between the wire rod-type specimens and an aluminum wire. The smooth surface of the wire rod-type specimens enables mating it directly with soft aluminum wire with trapezoidal cross section without processing, that is available for possibility and necessity of its application in transmission overhead line industry, further decrease of the power consumption during transmission, and reduction of 20% quantities of tower rods for land saving, as well as reduction of the metal resource consumption, thus contributing to the implementation of a power grid with environmental protection and power saving of high efficiency.
In order to facilitating the transport and discharge of transmission wire, generally winding its core composite around a disk of reasonable size. For more delivery quantities of wire, it is usually chosen that winding the core composite around the disk in a size as small as possible. However, carbon fiber or glass fiber composite core is configured with high elastic modulus and low elongation that the outer layer of its glass fiber being exposed is prone to cause the exposed surface defects where scratches or damages is not to be promptly detected, the use of the undersized disk may in turn lead to make the wire rod-type specimens damaged or even broken.
There is a need, therefore, for how to quickly and effectively estimate the exposed surface defects of the carbon fiber or glass fiber composite core, and to provide a safe and reasonable radius of curvature for the transport and discharge of the carbon fiber or glass fiber composite core line. A need exists for the primary issue as aforementioned that promotes safe operation of transmission line in new power industry.
SUMMARY
The present invention fulfills the above needs and addresses or alleviates the aforementioned detects in prior art, as well as others, by providing a dedicated winding tester for composite wire rod-type specimens for effectively measuring the minimum winding radius of the wire rod-type specimens being made with carbon fiber or glass fiber reinforced composites in various diameters or textures via automatically gripping specimens, tightly winding, and sequentially proceeding sustained load in time, thereby supplying test data and design consideration in actual use and transport of the wire rod-type specimens being made of carbon fiber or glass fiber reinforced composites.
In one feature of the present invention, the winding tester for composite wire rod-type specimens comprising a shield, a specimen receiver and a winding device being arranged within said shield, as well as a programmable controller being arranged outside the shield, which is characterized in that
the specimen receiver includes a pair of stand seats and a pair of guide mechanisms disposed in front and rear portions between the two stand seats, respectively, each of which includes a bearing, a hand wheel, a polish rod, a pressing plate and a pair of upper guide pulleys and a pair of lower guide pulleys oppositely arranged, wherein the hand wheel passes through the top plate of the bearing and then mates with the pressing plate in screw joint; a rotating spindle of the upper guide pulley is arranged between the two pressing plates with which two ends being penetrated respectively into two vertical grooves set in lateral plates of the bearing; a rotating spindle of the lower guide pulley is arranged between the two lateral plates of the bearing; the polish rod is shafted and connected into the lateral plates of the bearing with which two ends being fixed respectively onto the pair of stand seats, as the polish rod being in parallel with the rotating spindle of the upper guide pulley and the rotating spindle of the lower guide pulley.
the winding device includes a support frame, a drive motor, a winding wheel and a clamp, wherein the drive motor is arranged onto the support frame with which extended end being disposed of a linkage driving shaft on which the winding wheel being disposed; the clamp includes a connector, on which an accommodating slot being formed, being disposed on the winding wheel, a wire rod-type specimens gripping sleeve, on which sleeve bulge a wire rod-type specimens hole being set on one side of the connector, a gasket and a bolt, wherein the sleeve body of the wire rod-type specimens gripping sleeve is disposed within the accommodating slot, the sleeve tail of the wire rod-type specimens gripping sleeve is set with a screw hole, the gasket and the bolt are arranged on the other side of the connector, the bolt mates with the screw hole of the wire rod-type specimens gripping sleeve.
In a preferred embodiment of the winding tester for composite wire rod-type specimens, it features that
1. The specimen receiver enables smoothly feeding the wire-type specimens, whereon the tension maintaining contact, along a predetermined orientation, that the radius of curvature of the specimen equals to the outer diameter of the winding wheel, thereby guaranteeing the accuracy and reliability of the testing process.
2. The advantageous aspects, for example, simplified configuration, eased operation, and automatic feeding, of the winding device of the preferred embodiment in the present invention enables which widely being used for various types of specimens by, such as, regulating the motor speed or the outer diameter of the winding wheel thereof as needed.
3. The preferred embodiment of the winding tester is configured with a programmable controller which can automatically set and control the winding test for various types of the specimens, further calculate and output the test data.
The operating process of the specimen receiver of the preferred embodiment in the present invention features as following that firstly unscrewing to loosen the hand wheels of the front and rear guide mechanisms, and secondly traversing the wire-type specimen out of the space between the upper and lower guide wheels of the front guide mechanism after traversing it into the space between the upper and lower guide wheels of the rear guide mechanism, and then screwing to tighten the hand wheels of the front and rear guide mechanism, thereby clamping the specimen which maintaining a certain tension between the upper and lower guide wheels by pressing the pressing plate down. Proceeding to pull and fix the end of the specimen to the winding device. In winding test process, the specimen may travel between the upper and lower guide wheels, which in turn can be smoothly fed along the determined orientation. As the bearing can rotate around the polish rod, the feeding angle or shaking of the specimen appeared in the feeding process thus can be adjusted by said guide mechanism. At the same time, owing to the pressing plate making merely rolling motion of specimen, whereon the tension maintaining contact, without sliding relative to the guide wheels, the radius of curvature of the specimen equals to the outer diameter of the winding wheel, thereby guaranteeing the accuracy and reliability of the testing process.
In a preferred embodiment of the present invention, the polish rod of the specimen receiver is shafted and connected into the bearing through a ball bearing.
In another preferred embodiment of the present invention, on each stand seat a set of regulating holes vertically arranged are correspondingly set to fasten said polish rod of the rear guide mechanism. Due to the winding tester correspondingly configuring various types of the winding wheel in different diameter according to alternative specifications, it is needed that adjusting the height of the rear guide mechanism for ensuring tangentially pitching each test specimen in the winding wheel in a straight linear state. The rear guide mechanism is fastened to a position at the same height as the front guide mechanism thereof, for feeding the specimen in a horizontal state, where the height of the pitching-in point of the specimen on the winding wheel with a small diameter equals to the feeding height of the front guide mechanism. The rear guide mechanism is fastened into a regulating hole at an upper height than the front guide mechanism thereof, for feeding the specimen in a horizontal state, where the height of the pitching-in point of the specimen on the winding wheel with a large diameter is lower than the feeding height of the front guide mechanism. The regulating hole as mentioned above is disposed according to the individual diameter of winding wheel.
In still another preferred embodiment of the present invention, on each stand seat a vertical guide groove communicated with each regulating hole is further set. It is implemented for a simplified operation that turning the polish rod into a new regulating hole as long as turning it out of the prior hole and moving it into the vertical guide groove among changing the winding wheel with alternative diameter.
In yet another preferred embodiment of the present invention, on each stand seat a vertical regulating groove is set for fastening the polish rod to the rear guide mechanism, which configuration enables steplessly regulating the height of the rear guide mechanism.
The operating process of the winding device of the preferred embodiment in the present invention features as following that passing the specimen through the wire rod-type specimens bore set in the sleeve bulge of the wire rod-type specimens gripping sleeve, fastening the specimen by screwing to tighten the bolt; sequentially, activating the motor to motivate the rotation of the linkage driving shaft, as well as winding wheel for startup of test process; deactivating the motor until the winding wheel having rotated predetermined cycles, then ending the test process; finally, reviewing the surface of specimen to determine whether any flaw or fracture exists therein.
In a preferred embodiment of the present invention, the drive motor of the winding device preferably is an integrated servo motor reducer with compact configuration, or a servo motor with automatic function of control and regulation.
In another preferred embodiment of the present invention, the winding tester correspondingly is configured with various types of the winding wheels in different diameter according to alternative specifications to determine the minimum winding radius of each wire rod-type specimens. The hub of the winding wheel should have enough high intensity to support the centripetal force generated during winding of which, however, plate contacting with the wire rod-type specimens may not have too high intensity to damage the surface layer fiber of the composite wire rod-type specimens so that causes the crack thereof and then affects the test result. The weight of the hub should be small as possible to ease to change. The preferred embodiment of the invention therefore preferably is disposed of the hub with high-intensity MC nylon, and a plurality of thru hole uniformly on the disk surface of a hub of the winding wheel of the winding device without affecting the intensity of the hub, thereby still reaching of ease to change.
In still another preferred embodiment of the present invention, an anti-delinking cap is disposed at the outer periphery of the linkage driving shaft, for preventing the winding wheel falling out during the winding process.
In yet another preferred embodiment of the present invention, a displacement encoder is further on the linkage driving shaft, for transforming the signal representative of the rotation cycle numbers to a electrical signal and outputting the signal to the programmable controller to be calculated, and loading for 30 seconds after reaching of a predetermined value until the test terminates to implement the automatic control of the process.
In alternatively another preferred embodiment of the present invention as shown in FIG. 3 , the two lateral plates 201 of the shield are provided with a bi-layer configuration with an inner layer 202 of metal punching screen and an outer layer 203 of organic glass plate which facilitates observation by the test personnel and prevents the fracture splashing out. The top plate of the shield is a detachable metal plate. At the front of the shield two visual gates, which are provided with material of bi-layer colorless toughened glass with receiving by seal glue therebetween, are arranged for reinforcing the shock resistance of the glass.
In alternatively another preferred embodiment of the present invention, a visual monitoring system is further arranged on the shield, which comprises a monitor disposed outside the shield, a monitor distribution box disposed above the shield, which supplies electric power for said visual monitoring system and stores a recorder for repeating the display, and cameras disposed at four inner corners within the shield which enables visually monitoring the test process, and aligned with the disk surface of the hub of the tester which enables capturing the surface state of the specimen in its circumference direction from four individual directions and visually representing on a display, thereby covering entire winding surface of the specimen. The configuration and operation ensure the test personnel to be safe, but also achieve the real time monitoring and recording of the test process, which in turn enhance the reliability of determination to the damage situation of the specimen.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
FIG. 1 shows a structural schematic diagram of the winding tester for composite wire rod-type specimens of the present invention;
FIG. 2 shows a schematically axonometric diagram of the winding tester for composite wire rod-type specimens of the present invention;
FIG. 3 shows a structural schematic diagram of the each lateral plate of the shield of the present invention;
FIG. 4 shows a structural schematic diagram of the specimen receiver of the present invention;
FIG. 5 shows a schematically axonometric diagram of the specimen receiver of the present invention;
FIG. 6 shows a schematically axonometric diagram of the specimen receiver of the present invention illustrated from another viewpoint;
FIG. 7 shows a structural schematic diagram of a guide mechanism of the specimen receiver of the present invention;
FIG. 8 shows a structural schematic diagram of the specimen receiver, disposed with a winding wheel in a small diameter, of the present invention;
FIG. 9 shows a structural schematic diagram of the specimen receiver, disposed with a winding wheel in a large diameter, of the present invention;
FIG. 10 shows a structural schematic diagram of a preferred embodiment of the specimen receiver, wherein disposed with vertical guide grooves, of the present invention;
FIG. 11 shows a structural schematic diagram of a preferred embodiment of the specimen receiver, wherein disposed with vertical regulating grooves, of the present invention;
FIG. 12 shows a structural schematic diagram of a winding device of the present invention;
FIG. 13 shows a schematic diagram of the left view of the winding device from FIG. 12 ;
FIG. 14 shows a structural schematic diagram of a winding wheel of the winding device of the present invention;
FIG. 15 shows a schematic diagram of the plan view of the winding wheel from FIG. 14 thereof;
FIG. 16 shows a schematic diagram of the rear view of the winding wheel from FIG. 14 thereof;
FIG. 17 shows a structural schematic diagram of a clamp of the winding device of the present invention;
FIG. 18 shows a structural schematic diagram of a front view of the clamp;
FIG. 19 shows a structural schematic diagram of an enlarged section view from A-A dash line direction of FIG. 18 ;
FIG. 20 shows a structural schematic diagram of an assemble and unassemble process of the winding device in the invention;
FIG. 22 shows a structural schematic diagram of a rear view of the programmable controller of the invention;
FIG. 23 shows a schematic drawing of the test process of the invention.
wherein, elements are not to scale so as to more clearly show the details, wherein the like reference numbers indicate like elements throughout the several views, and wherein:
1 —wire-type specimens, 2 —shield, 3 —winding device, 4 —visual gate, 5 —specimen receiver, 6 —programmable controller, 7 —monitor, 8 —camera, 9 —monitor distribution box; 501 —regulating hole, 502 —front guide mechanism, 503 —rear guide mechanism, 504 —bracing plate, 505 —stand seat, 506 —hand wheel, 507 —polish rod, 508 —anti-delinking cap, 509 —ball bearing, 510 —lower guide wheel, 511 —pressing plate, 512 —bearing, 513 —upper guide wheel, 514 —top plate, 515 —lateral plate, 516 —upper rotating spindle, 517 —vertical groove, 518 —lower rotating spindle, 519 —vertical guide groove, 520 —vertical regulating groove, 523 —specimens pitching-in point; 302 —winding wheel, 303 —clamp, 304 —drive motor, 305 —support frame, 306 —anti-delinking cap, 307 —displacement encoder, 308 —linkage driving shaft, 309 —rim, 310 —key slot, 311 —hub, 312 —thru hole, 313 —shaft sleeve, 314 —mounting hole, 315 —connector, 316 —mounting hole, 317 —wire rod-type specimens gripping sleeve, 318 —wire rod-type specimens hole, 319 —screw hole, 320 —accommodating slot, 321 —bolt, 322 —gasket, 323 —key slot, 324 —sleeve bulge, 325 —sleeve body; 601 —human-person interface, 602 —jerk button, 603 —rubber margin foot, 604 —elongated hole.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference now to FIGS. 1 and 2 , a preferred embodiment of the winding tester for composite wire rod-type specimens of the invention comprises a shield 2 , a specimen receiver 5 , and a winding device 3 being arranged within said shield 2 , as well as a programmable controller 6 being arranged outside the shield 2 .
Due to the splash of fiber bundle or fine dust ejected from the composite wire rod-type specimens in the moment of fracture therein, a visual monitoring system is arranged on the shield for protecting the test personnel from injury or inhalation caused by the fracture and for momentarily observing the specimen, which comprises a monitor 7 disposed outside the shield, a monitor distribution box 9 disposed above the shield, which supplies electric power for said visual monitoring system and stores a recorder for repeating the display, and cameras 8 disposed at four inner corners within the shield which enables visually monitoring the test process, and aligned with the disk surface of the hub of the tester which enables capturing the surface state of the specimen in its circumference direction from four individual directions and visually representing on a display, thereby covering entire winding surface of the specimen. The configuration and operation ensure the test personnel to be safe, but also achieve the real time monitoring and recording of the test process, which in turn enhance the reliability of determination to the damage situation of the specimen.
With reference now to FIG. 2 , the top plate 204 of the shield 2 is a removable metal plate. At the front of the shield 2 two visual gates 4 , which are provided with material of bi-layer colorless toughened glass with receiving by seal glue there between, are arranged.
With reference now to FIGS. 4 , 5 and 6 , the specimen receiver 5 of winding tester for composite wire rod-type specimens preferably includes a pair of stand seats 505 and a pair of guide mechanism 502 . 503 disposed in front and rear of the stand seats 505 respectively. A bracing plate 504 is further disposed between said pair of the stand seats 505 .
With reference now to FIG. 7 , each guide mechanism 502 , 503 includes a bearing 512 , a hand wheel 506 , a polish rod 507 , a pressing plate 511 and a pair of upper guide pulleys 513 and a pair of lower guide pulleys 510 oppositely arranged. The bearing 512 is disposed of a top plate 514 and a pair of lateral plates 515 .
The hand wheel 506 disposed on the top passes through the top plate 514 of the bearing 512 and then mates with the pressing plate 511 in screw joint. An upper rotating spindle 516 of the upper guide pulley 513 is arranged onto the pressing plate 511 with which two ends being penetrated into two vertical grooves 517 set at lateral plates 515 of the bearing 512 . A lower rotating spindle 518 of the lower guide pulley 510 is arranged onto lateral plates 515 of the bearing 512 . The polish rod 507 is shafted and connected onto the lateral plates 515 of the bearing 512 with which two ends being fixed onto the pair of stand seats 505 , as the polish rod 507 being in parallel with the upper rotating spindle 516 of the upper guide pulley 513 and the lower rotating spindle 518 of the lower guide pulley 510 .
Firstly, unscrewing in a direction to loosen the hand wheels 506 of the front and rear guide mechanism, thereby moving the upper guide wheel 513 following moving the pressing plate 511 , secondly, traversing the specimen 1 through the space of the upper and lower guide wheels of the front guide mechanism, and then screwing in negative direction to tighten the hand wheels 506 , thereby clamping the specimen which maintaining a certain tension between the upper and lower guide wheels by pressing the pressing plate 511 down until the upper guide wheel 513 compressed the specimen.
In a preferred embodiment of the present invention, the guide wheel portion is used for guiding the carbon fiber wire rod-type specimens, as well as applying frictional resistance thereon.
In another preferred embodiment of the present invention, on each stand seat 505 a set of regulating holes 501 vertically disposed are correspondingly set to fasten said polish rod 507 of the rear guide mechanism 503 .
With reference now to FIG. 8 , due to the winding tester correspondingly configuring various types of the winding wheel in different diameter according to alternative specifications, it is needed that adjusting the height of the rear guide mechanism for ensuring tangentially pitching each test specimen in the winding wheel in a straight linear state. The rear guide mechanism 503 is fastened to a lower regulating hole 501 - 1 at the same height as the front guide mechanism thereof, for feeding the specimen 1 in a horizontal state, where the height of the pitching-in point 523 of the specimen on the winding wheel 302 with a small diameter equals to the feeding height of the front guide mechanism.
With reference now to FIG. 9 , the rear guide mechanism 503 is fastened into a regulating hole 501 - 2 at an upper height than the front guide mechanism thereof, for feeding the specimen 1 in a horizontal state, where the height of the pitching-in point 523 of the specimen on the winding wheel with a large diameter is lower than the feeding height of the front guide mechanism 502 . The regulating hole as mentioned above is disposed according to the individual diameter of winding wheel.
In still another preferred embodiment of the present invention, with reference now to FIG. 10 , on each stand seat 505 a vertical guide groove 519 communicated with each regulating hole 501 is further set. It is implemented for a simplified operation that turning the polish rod into a new regulating hole as long as turning it out of the prior holes and moving it into the vertical guide groove 519 among changing the winding wheel with alternative diameter.
With reference now to FIG. 11 , on each stand seat a vertical regulating groove 520 , altering with the aforementioned regulating holes is set for fastening the polish rod to the rear guide mechanism, which configuration enables steplessly regulating the height of the rear guide mechanism 503 .
In yet another preferred embodiment of the present invention, it allows that controlling the polish rod 507 via a motor-driven moving up and down manner.
With reference now to FIGS. 12 and 13 , a preferred embodiment of the winding device 3 of the invention preferably includes a support frame 305 , a drive motor 304 , a winding wheel 302 and a clamp 303 , wherein the drive motor 304 is arranged onto the support 305 with which extended end being disposed of an linkage driving shaft 308 on which the winding wheel 302 being disposed. A displacement encoder 307 is further on said linkage driving shaft 308 .
the clamp 303 includes a connector 315 , on which an accommodating slot 320 being set, being disposed on the winding wheel 302 , a wire rod-type specimens gripping sleeve 317 , on which sleeve bulge 324 a wire rod-type specimens bore 318 being set on one side of the connector 315 , a gasket 322 and a bolt 321 , wherein the sleeve body 325 is disposed within the accommodating slot 320 , the sleeve tail is set with a screw hole 319 , the gasket 322 and the bolt 321 are arranged on the other side of the connector 315 , the bolt 321 mates with the screw hole 319 of the wire rod-type specimens gripping sleeve 317 .
With reference now to FIGS. 14 , 15 and 16 , the preferred embodiment of the winding wheel 302 preferably is disposed of the hub 311 with high-intensity MC nylon, and 306 thru hole uniformly on the disk surface of the hub of the winding wheel of the winding device without affecting the intensity of the hub, thereby still reaching of decrease the weight thereof and ease to change. Mounting holes 314 are disposed on the hub 311 for mounting the clamp 303 .
With reference now to FIGS. 17 , 18 and 19 , the clamp 303 includes a connector 315 , on which an accommodating slot 320 being set, being disposed on the winding wheel 302 , a wire rod-type specimens gripping sleeve 317 , on which sleeve bulge 324 a wire rod-type specimens bore 318 being set on one side of the connector 315 , a gasket 322 and a bolt 321 , wherein the sleeve body 325 is disposed within the accommodating slot 320 .
In still another preferred embodiment of the present invention, on the sleeve bulge 324 of the wire rod-type specimens gripping sleeve 317 , a wire rod-type specimens bore 318 being set on one side of the connector 315 , the sleeve tail is set with a screw hole 319 , the gasket 322 and the bolt 321 are arranged on the other side of the connector 315 , the bolt 321 mates with the screw hole 319 of the wire rod-type specimens gripping sleeve 317 .
Passing the specimen 1 through the wire rod-type specimens bore 318 set in the sleeve bulge 324 of the wire rod-type specimens gripping sleeve, fastening the specimen by screwing to tighten the bolt 321 during the test process.
In a preferred embodiment of the present invention, as shown in FIG. 20 , the winding tester correspondingly is configured with various types of the winding wheels in different diameter according to alternative specifications to determine the minimum winding radius of each wire rod-type specimens. In the change operation of the winding wheel, firstly removing of the anti-delinking cap 306 , and then mounting the hub to the linkage driving shaft 308 whereon key slots 323 are set for fastening the winding wheel thereon by a keyway coupling, finally, mounting the cap 306 .
In another preferred embodiment of the present invention, the diameter of the linkage driving shaft 308 is 1 mm less than the winding wheel thereof.
With reference now to FIGS. 21 and 22 , the programmable controller 6 of the invention is preferably a pulley controller that facilitates the test personnel timely controlling the tester in any position at time of observation. At the bottom of the pulley controller, four rubber margin feet 603 are disposed, for example, for putting the controller on a desk. At the rear of the controller elongated holes 604 are set for hanging it on the shield. A jerk button 602 is further disposed on the controller for security. A human-person interface 601 is preferably disposed on the controller for setting various parameters.
With reference now to FIG. 23 , the operating process of the tester of the preferred embodiment in the present invention features as following that firstly activating the programmable controller 6 , and then pressing the reset button for unscrewing the winding wheel 302 to the position ease to disposing of the specimen; secondly selecting the appropriate wire rod-type specimens gripping sleeve 317 corresponding to alternative specification of the carbon fiber wire rod-type specimens, traversing the wire rod-type specimens through the space of the upper and lower guide wheels of the front guide mechanism, and then penetrating it into the hole within the wire rod-type specimens gripping sleeve 317 , sequentially screwing to tighten the bolt 321 , thereby clamping the specimen between the upper and lower guide wheels, and then closing the gates 4 after manually screwing to tighten the hand wheels; setting winding cycle number while starting test; ending the test process until the winding wheel having rotated predetermined cycles, finally, reviewing the surface of specimen to determine whether any flaw or fracture exists therein, and then unscrewing to loosen the specimen. The test process can be repeated on a display.
It will be appreciated that the above-described embodiments are merely illustrative, and that those of ordinary skill in the art may readily devise their own implementations and modifications that incorporate the principles of the present invention and fall within the spirit and scope thereof.
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It is provided a dedicated winding tester for composite wire rod-type specimens for effectively measuring the minimum winding radius of the wire rod-type specimens being made with carbon fiber or glass fiber reinforced composites in various diameters or textures via automatically gripping specimens, tightly winding, and sequentially proceeding sustained load in time, thereby supplying test data and design consideration in actual use and transport of the wire rod-type specimens being made of carbon fiber or glass fiber reinforced composites that comprises a shield, a specimen receiver and a winding device being arranged within said shield, as well as a programmable controller being arranged outside the shield.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to building construction devices that provide drainage and reduce cracks within masonry coatings such as stucco. More specifically, the present invention relates to an improved movement control screed that is structured to operate as a control joint for absorbing movement in a masonry coating and also as a weep screed to provide drainage of water from within and behind the masonry coating.
2. Description of Related Art
Expansion control joints and foundation weep screeds are commonly known in the masonry construction arts. FIG. 1 depicts an exemplary expansion control joint 20 in accordance with the known prior art. Expansion control joints are used to break up large areas intended for receiving masonry coatings such as plaster, stucco, and the like, into smaller masonry coated areas for purposes of relieving stress and resisting cracking. The depicted expansion control joint 20 includes metal lath first and second flanges 25 , 30 , and metallic first and second ribs 30 , 32 defined between the first and second flanges 25 , 30 . The metal lath flanges 25 , 30 are typically attached to an exterior wall surface (not shown). First and second masonry coatings 42 , 44 are applied to the exterior wall surface using the first and second ribs 30 , 32 of the expansion control joint 20 as a guide for the applied thickness of the coatings. The first and second ribs 30 , 32 of the expansion control joint 20 are symmetrical and deflectable for absorbing movement between the first and second masonry coatings 42 , 44 during curing or other thermally induced expansion and contraction.
FIG. 2 depicts a foundation weep screed 70 structured in accordance with the known prior art. The foundation weep screed 70 is attached to an exterior wall 54 that is comprised of plywood sheathing 56 and attached to a wall frame 55 just above a concrete building foundation 60 . Foundation weep screeds 70 are commonly produced from sheet metal and positioned at the base of the exterior wall 54 for supporting a masonry coating (not shown) and providing a barrier that prevents water from coming into contact with the exterior wall 54 .
The depicted foundation weep screed 70 is secured to the base of the plywood sheathing 56 . The foundation weep screed 70 includes a flange 72 , and a rib 75 . The rib 75 defines an extending portion 74 for supporting an applied masonry coating and a returning portion 76 . The extending portion of the rib 75 begins generally adjacent the foundation transition 61 and tapers downwardly as shown. A drip edge DE is defined between the extending and returning portions 74 , 76 of the rib 75 . Water resistant building paper 62 is typically positioned over the exterior wall 54 and the flange 72 for directing moisture from behind the masonry coating and over the foundation weep screed 70 . Moisture can get behind the masonry coating at improperly sealed joints (e.g., at doors or windows) or because of cracks that may form in the masonry coating. If left unchecked, such moisture may cause rotting of wooden structures within the wall. Installation of foundation weep screeds 70 as described above create a moisture path extending down the building paper 62 , along the flange 72 , and over the extending portion 74 of the rib 75 to the drip edge DE as shown.
In the wake of severe storms such as hurricanes, many jurisdictions have modified their building codes to require significant reinforcement of first level exterior walls. Typically, this reinforcement is provided by constructing first level exterior walls from reinforced concrete or other similar materials. Such walls provide enhanced wind and impact resistance. However, building codes continue to allow upper floors and roof structures to be made from wood trusses that rest on top of the concrete reinforced exterior walls. In this regard, wall transitions are now defined between dissimilar wall materials (e.g., wood and concrete) used for upper and lower floors. Accordingly, it would be desirable to prevent moisture from entering such wall transitions. It would also be desirable to support masonry coatings applied above and below the wall transitions and to absorb movement of the masonry coatings such as might occur during curing or thermal expansion and contraction of the coatings.
BRIEF SUMMARY OF THE INVENTION
The above needs and other advantages are met by a movement control screed that is structured for installation between first and second masonry coatings applied adjacent to a building wall and that functions both as an expansion control joint and as a weep screed. The movement control screed comprises first and second flanges and, in one embodiment, the first flange defines a planar substantially non-perforated surface for providing a moisture barrier and the second flange defines a substantially perforated surface that is adapted to more readily receive and support an applied masonry coating. At least two ribs defined between the flanges provide the ability for the flanges to move relative to each other and thus accommodate expansion, contraction, or other slight movements between adjoining wall sections. In addition, the ribs provide at least one drip edge to accommodate moisture drainage from behind a masonry coating and therefore the movement control screed also functions as a weep screed.
More specifically, a first rib defines a screed surface extending from the first flange adapted for positioning adjacent at least a portion of a first masonry coating and a second rib defines a screed surface extending from the second flange adapted for positioning adjacent at least a portion of a second masonry coating. In one embodiment, the first flange is deflectable from the second flange for supporting the first and second masonry coatings during relative movement. The screed surface of the first rib may also be deflectable relative to the screed surface of the second rib. Additionally, the screed surface of the first rib may be deflectable relative to the first flange and the screed surface of the second rib may be deflectable relative to the second flange. The above deflection capabilities operate to reduce cracking of the masonry coatings as will be apparent to one of ordinary skill in the art in view of the foregoing disclosure.
In another embodiment of the present invention, the first rib of the movement control screed defines a first screed depth that corresponds to a first masonry coating thickness and the second rib of the movement control screed defines a second screed depth that differs from the first screed depth and corresponds to a second masonry coating thickness. In one embodiment, the first screed depth is larger than the second screed depth. In this regard, first and second masonry coatings having differing thicknesses may be applied on either side of the movement control screed.
Another embodiment of the present invention is directed to a method of installing a movement control screed adjacent a building wall between first and second masonry coatings. The method includes attaching a movement control screed to the building wall wherein the movement control screed comprises a first flange, a second flange, a first rib defining a first screed depth disposed between the first and second flanges, and a second rib defining a second screed depth disposed between the first and second flanges. In one embodiment, the first screed depth is greater than the second screed depth. The method further includes a step of applying a first masonry coating to the building wall at a first masonry coating thickness that substantially corresponds to the first screed depth and applying a second masonry coating to the building wall at a second masonry coating thickness that substantially corresponds to the second screed depth.
The method may also include applying a water resistant layer over the first flange, before the step of applying the first masonry coating, in order to create a moisture path extending from the water resistant layer to the first flange and over the first rib. In addition, the method may include attaching a movement control screed having a first flange that is substantially non-perforated to encourage moisture to flow over and not behind the first flange. In yet another embodiment, the method may include attaching a movement control screed having a second flange that is substantially perforated to more readily receive and support the applied second masonry coating.
BRIEF DESCRIPTION OF THE DRAWINGS
Having thus described the invention in general terms, reference will now be made to the accompanying drawings, which are not necessarily drawn to scale, and wherein:
FIG. 1 is a perspective view of an expansion control joint in accordance with the known prior art;
FIG. 2 is a perspective view of a foundation weep screed in accordance with the known prior art;
FIG. 3 is a perspective view of a movement control screed in accordance with one embodiment of the present invention;
FIG. 4 is a side view of the movement control screed of FIG. 3 installed proximate a wall transition defined between non-masonry and masonry portions of a building wall in accordance with one embodiment of the present invention; and
FIG. 5 depicts a side view of the movement control screed for illustrating a few selected dimensions taken from two exemplary movement control screeds that are structured according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the inventions are shown. Indeed, this invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. Like numbers refer to like elements throughout.
For purposes of the foregoing specification and appended claims the term “masonry coating” refers to a surface covering for walls comprised of plaster, stucco, Portland cement, or other similar materials that are applied wet and then dry into a protective and/or aesthetically pleasing surface.
FIG. 3 depicts a perspective view of a movement control screed 120 in accordance with one embodiment of the present invention. The movement control screed 120 comprises a first flange 132 , a first rib 122 , a second rib 126 , and a second flange 134 . The movement control screed defines a length L and a width W. In the depicted embodiment, the width W appears larger than the length L; however, in practice, the width W of the movement control screed 120 is likely smaller than the length L. The length L of a movement control screed may, for example, correspond generally to the length of an adjacent building wall while the width W of the movement control screed need only be sufficient to cover small areas of the wall above and below a wall transition. For example, in one embodiment, the length L of a movement control screed is approximately ten feet while the width W is approximately six inches. In various embodiments, the length L of the movement control screed need not correspond directly to the length of an adjacent wall as multiple movement control screeds may be placed side-by-side to span the length of the wall. Caulking can be applied between adjoining screeds to assure proper water handling.
In the depicted embodiment, the first flange 132 of the movement control screed 120 is a substantially planar member that is arranged vertically against a building wall (not shown). The first flange 132 includes an attachment portion 133 and a substantially non-perforated portion 131 . The depicted attachment portion 133 defines an aperture 136 for receiving an attaching fastener (not shown) or keying the position of the movement control screed 120 relative to an adjacent movement control screed (not shown) as will be apparent to one of ordinary skill in the art. One or more apertures 136 may be created within the attachment portion 133 during installation of the movement control screed 120 as one or more nails, screws, or other fasteners are used to secure the first flange to the building wall. The substantially non-perforated portion 131 of the first flange 132 operates as a moisture barrier as will be discussed in greater detail below.
The first rib 122 extends from the base of the first flange 132 as shown. In one embodiment, the first rib 122 comprises an extending member 121 , a transition member R 1 , and a returning member 123 . The extending member 121 defines a screed or engagement surface 121 E that is structured to at least partially contact and support a masonry coating (not shown) when the masonry coating is applied. The first rib 122 can act as a screed to guide the application of the masonry coating when it is wet so that the resultant coating has the desired depth or thickness. After drying, the lower edge of the masonry coating may separate from the engagement surface 121 E or the first rib 122 slightly, especially if there is significant contraction of the masonry coating, which can allow water to more readily weep from behind the masonry coating and over the first rib 122 .
A drip angle θ is defined between the first flange 132 and the engagement surface 121 E of the extending member 121 . The drip angle θ is preferably greater than 90 degrees for encouraging moisture to run downwardly along the first flange 132 and on a descending path over the engagement surface 121 E and transition member R 1 of the first rib 122 . In various embodiments, the drip angle θ is between 91 and 145 degrees, preferably between 92 and 120 degrees, and more preferably between 93 and 115 degrees. As will be apparent to one of ordinary skill in the art, providing such drip angles allows water behind the masonry coating to be drawn away from the building wall and to drip harmlessly over the transition member R 1 of the first rib 122 .
In the depicted embodiment, the second rib 126 is positioned immediately below the first rib 122 and above the second flange 134 as shown. The second rib includes an extending member 125 , a transition member R 2 , and a returning member 127 . Although the depicted transitions members R 1 , R 2 define radii between the extending members 121 , 125 and the returning members 123 , 127 of the first and second ribs 122 , 126 other non-radiused transitions are possible. For example, a chamfered, cornered, or pointed transition may be used especially in movement control screeds formed from polymeric materials.
A rib transition 128 is defined between the first rib 122 and the second rib 126 . In the depicted embodiment, the rib transition 128 is a simply defined radius however, in additional embodiments, the rib transition 128 may include one or more flat or planar portions (not shown) for expanding a channel 150 defined between the first and second ribs 122 , 126 .
In various embodiments of the present invention, the returning portion 127 of the second rib defines an engagement surface 127 E that is structured to at least partially contact and support a masonry coating (not shown). In the depicted embodiment, one or more anchor tabs 130 extend from the engagement surface 127 E for further anchoring an adjacent masonry coating.
The depicted second flange 134 extends from the base of the returning portion 127 of the second rib 126 as shown. In one embodiment, the second flange 134 is at least partially perforated by apertures 138 , 139 . One or more of the apertures 139 may be structured to receive fasteners (not shown) for securing the second flange 134 to the wall. Other apertures 138 may be provided simply to define a non-continuous surface that is better adapted to support adhesion with an adjacent masonry coating. In other embodiments, various additional known techniques (e.g., etching, roughing, etc.) may be used to encourage adhesion between the second flange 134 and an adjacent masonry coating.
In various embodiments of the present invention, the first rib 122 defines a first screed depth A and the second rib 126 defines a second screed depth B. In the depicted embodiment, the first screed depth A is larger than the second screed depth B. In this regard, moisture running along the engagement surface 121 E and over the transition portion R 1 of the first rib 122 may be allowed to drip freely from the first rib 122 without impacting the second rib 126 . Providing first and second ribs 122 , 126 of differing screed depths may also provide additional benefits with regard to the application of masonry coatings having differing thicknesses as will be described in greater detail below.
Movement control screeds of various embodiments of the present invention may be manufactured from a variety of materials. For example, all or part of a movement control screed may be produced from metals such as aluminum, zinc, stainless steel, and galvanized steel, molded or extruded polymers and plastics, composites, and other similar materials. Factors influencing material selection are cost, corrosion resistance, regional or geographic environmental factors (e.g., expected humidity, environmental salinity, temperature, etc.), ease of forming, rigidity, and elasticity. The movement control screed depicted in FIG. 3 is manufactured from a polyvinyl chloride (“PVC” ) resin and, thus, provides a deflectable, rigid, low cost, corrosion resistant, masonry coating-supporting article.
FIG. 4 depicts a side section view of a building wall 205 incorporating a movement control screed 220 in accordance with one embodiment of the present invention. This view has been shown with exaggerated clearances between the various components for clarity and ease of understanding. As noted above, it has become common in many areas of the country to construct homes or other dwellings having first floor exterior walls comprised of reinforced concrete or other similar materials and upper floors or roof structures constructed of wood framing. The depicted building wall 205 includes a masonry portion 210 and a non-masonry portion 211 . The non-masonry portion 211 is comprised of framing members 214 including for example, wooden studs, cross-members, and the like, and a plywood sheathing portion 216 . A wall transition 215 is defined between the masonry and non-masonry 210 , 211 portions of the building wall 205 as shown.
Movement control screeds 220 structured in accordance with various embodiments of the present invention may be installed adjacent a building wall 205 proximate the wall transition 215 defined between the masonry and non-masonry portions 210 , 211 . In the depicted embodiment, the movement control screed 220 comprises a first flange 232 , a first rib 222 , a second rib 226 , and a second flange 234 . The depicted first and second flanges 232 , 234 are planar members positioned substantially flush against the non-masonry 211 and masonry 210 portions of the building wall 205 , respectively. More particularly, the first flange 232 is secured to the plywood sheathing 216 of the non-masonry portion 211 of the building wall 205 by fasteners 260 such as nails, screws and the like. In one embodiment, the fasteners 260 are disposed generally through an attachment portion 233 of the first flange 232 thereby defining a substantially non-perforated portion 231 below the attachment portion 233 as shown.
One or more layers of water resistant building paper 212 may be provided over the building wall 205 , the attachment portion 233 of the first flange 232 , and at least a part of the substantially non-perforated portion 231 of the first flange 232 such that any water or moisture running down the building wall 205 drains over and not behind the first flange 232 of the movement control screed 220 . In various embodiments, the movement control screed 220 is mounted such that at least part of the substantially non-perforated portion 231 of the first flange 232 extends a transition distance T below the wall transition 215 defined between the masonry and non-masonry portions 210 , 211 of the building wall 205 . In this regard, the non-perforated portion 231 of the first flange 232 provides a barrier that prevents moisture from entering the wall transition 215 and decaying or otherwise degrading the building wall 205 .
The embodiment depicted in FIG. 4 includes a first rib 222 defining a screed depth that is substantially larger than a screed depth defined by the second rib 226 . As noted above, the first rib 222 extends from the base of the first flange 232 and includes an extending member 221 , a transition member R 1 , and a returning member 223 . The extending member 221 defines a screed or engagement surface 221 E that is structured to at least partially contact and support a first masonry coating 245 . A drip angle θ is defined between the first flange 232 and the engagement surface 221 E of the extending member 221 as shown. As referenced above, the drip angle θ is preferably greater than 90 degrees for encouraging moisture to run downwardly along the first flange 232 and to continue on a descending path over the engagement surface 221 E and transition member R 1 of the first rib 222 . In this regard, moisture is drawn away from the wall and allowed to drip from the transition member R 1 of the first rib 222 .
A first masonry coating 245 is applied to the building wall 205 above the movement control screed 220 . In one embodiment, a metal or plastic lath 213 may be applied over the relatively smooth surfaces of the building paper 212 and first flange 232 to support the first masonry coating 245 . A second masonry coating 255 is applied to the building wall 205 below the movement control screed 220 as shown, and this coating may or may not be applied over lath (not shown) depending on the application. The second rib 226 includes an extending portion 225 , a transition member R 2 , and a returning portion 227 . The returning portion 227 of the second rib 226 includes a screed or engagement surface 227 E that is structured to contact and support at least part of the second masonry coating 255 as shown. In the depicted embodiment, an anchor tab 230 extends from the engagement surface 227 E of the returning portion 227 for anchoring the second masonry coating 255 .
In various embodiments of the present invention, the screed depth of the first rib 222 operates as a guide or screed to define a thickness C for the first masonry coating 245 . The screed depth of the second rib 226 operates as a guide for defining a thickness D for the second masonry coating 255 . In one embodiment, for example, the first and second masonry coatings may be applied at thicknesses sufficient to define first and second outer masonry surfaces that align generally with the outermost points of the transitions members R 1 , R 2 of the first and second ribs 222 , 226 as shown. In other embodiments, the masonry coating may be applied at thicknesses sufficient to define first and second outer masonry surfaces that align generally with guide features defined by or disposed on the first and second ribs (not shown). Such guide features may include reference marks, protuberances, ribs, indentions, bends, or any other visible feature. Accordingly, the “screed depths” referred to in the present application and appending claims would be defined between the first and second flanges and such guide features rather than the first and second flanges and the outermost points of the first and second transition members as shown in FIGS. 3 and 5 .
Conventional building codes allow masonry coatings applied adjacent walls of differing composition (e.g., wood reinforced portions vs. concrete reinforced portions) to have differing acceptable thicknesses. For example, the requisite coating thickness for masonry coatings applied to a reinforced cement wall or wall portion is less than the masonry coating thickness required for masonry coatings applied to wood framed walls or wall portions. Accordingly, in the depicted embodiment, the movement control screed 220 is structured to define a first masonry coating thickness C adjacent the non-masonry portion 211 of the building wall 205 that is greater than the second masonry coating thickness D defined adjacent the masonry portion 210 of the building wall 205 .
As will be apparent to one of ordinary skill in the art, masonry coatings such as stucco or plaster have a measurable coefficient of thermal expansion. If such coatings are applied and rigidly confined, the resulting stresses may produce unsightly cracking. In addition, other factors might cause relative movement between the two sections of masonry coating, such as settling of the building or wind or temperature induced movements between dissimilar (e.g., cement reinforced vs. wood framed, etc.) wall portions. Accordingly, the first flange 232 of the movement control screed 220 may be deflectable from the second flange 234 . The screed or engagement surface 221 E of the first rib 222 may also be deflectable relative to the screed or engagement surface 227 E of the second rib 226 . Additionally, the engagement surface 221 E of the first rib 222 may be deflectable relative to the first flange 232 and the engagement surface 227 E of the second rib 226 may be deflectable from the second flange 234 . The above deflections relieve slight relative movement (whether in the plane at the wall or otherwise) and the resulting masonry coating stresses occurring adjacent the wall transition 215 .
Example Embodiments
FIG. 5 depicts a side view of a movement control screed for illustrating a few selected dimensions taken from several exemplary movement control screeds. Numerical values for the selected dimensions are provided in Table 1 below for illustration purposely only. The precise dimensions of movement control screeds according to various embodiments of the present invention may vary from application to application as will be apparent to one of ordinary skill in the art. Thus, although numerous examples are provided in Table 1 below, multiple additional embodiments of the present invention may include dimensions and numerical values that are not listed in Table 1. The dimensions selected for Table 1 include an exemplary movement control screed width W, a first rib position X, a second rib position Z, and a channel width Y. Exemplary values for a first screed depth A and a second screed depth B are also provided. Notably, the exemplary values for A and B may be reversed to satisfy embodiments in which it is preferred for the second screed depth B to be larger than the first screed depth A. A transition height T is also defined between the wall transition 315 and the rib transition as shown. The dimensions provided in Table 1 are in inches.
TABLE 1
A
B
H
T
X
Y
Z
Example 1
⅞
½
5 13/16
1
3½
9/16
1¾
Example 2
⅞
⅝
5 13/16
1
3½
9/16
1¾
Example 3
½
¼
5 13/16
1
3½
9/16
1¾
Example 4
½
⅜
5 13/16
1
3½
9/16
1¾
Example 5
⅝
¼
5 13/16
1
3½
9/16
1¾
Example 6
⅝
⅜
5 13/16
1
3½
9/16
1¾
Example 7
⅝
½
5 13/16
1
3½
9/16
1¾
Example 8
¾
¼
5 13/16
1
3½
9/16
1¾
Example 9
¾
⅜
5 13/16
1
3½
9/16
1¾
Example 10
¾
½
5 13/16
1
3½
9/16
1¾
Example 11
¾
⅝
5 13/16
1
3½
9/16
1¾
Example 12
⅞
¼
5 13/16
1
3½
9/16
1¾
Example 13
⅞
⅜
5 13/16
1
3½
9/16
1¾
Example 14
⅞
¾
5 13/16
1
3½
9/16
1¾
Example 15
1
¼
5 13/16
1
3½
9/16
1¾
Example 16
1
⅜
5 13/16
1
3½
9/16
1¾
Example 17
1
½
5 13/16
1
3½
9/16
1¾
Example 18
1
⅝
5 13/16
1
3½
9/16
1¾
Example 19
1
¾
5 13/16
1
3½
9/16
1¾
Example 20
1
⅞
5 13/16
1
3½
9/16
1¾
Example 21
9/8
¼
5 13/16
1
3½
9/16
1¾
Example 22
9/8
⅜
5 13/16
1
3½
9/16
1¾
Example 23
9/8
½
5 13/16
1
3½
9/16
1¾
Example 24
9/8
⅝
5 13/16
1
3½
9/16
1¾
Example 25
9/8
¾
5 13/16
1
3½
9/16
1¾
Example 26
9/8
⅞
5 13/16
1
3½
9/16
1¾
Example 27
9/8
1
5 13/16
1
3½
9/16
1¾
Example 28
1¼
¼
5 13/16
1
3½
9/16
1¾
Example 29
1¼
⅜
5 13/16
1
3½
9/16
1¾
Example 30
1¼
½
5 13/16
1
3½
9/16
1¾
Example 31
1¼
⅝
5 13/16
1
3½
9/16
1¾
Example 32
1¼
¾
5 13/16
1
3½
9/16
1¾
Example 33
1¼
⅞
5 13/16
1
3½
9/16
1¾
Example 34
1¼
1
5 13/16
1
3½
9/16
1¾
Example 35
1¼
9/8
5 13/16
1
3½
9/16
1¾
Example 36
1⅜
¼
5 13/16
1
3½
9/16
1¾
Example 37
1⅜
⅜
5 13/16
1
3½
9/16
1¾
Example 38
1⅜
½
5 13/16
1
3½
9/16
1¾
Example 39
1⅜
⅝
5 13/16
1
3½
9/16
1¾
Example 40
1⅜
¾
5 13/16
1
3½
9/16
1¾
Example 41
1⅜
⅞
5 13/16
1
3½
9/16
1¾
Example 42
1⅜
1
5 13/16
1
3½
9/16
1¾
Example 43
1⅜
9/8
5 13/16
1
3½
9/16
1¾
Example 44
1⅜
1¼
5 13/16
1
3½
9/16
1¾
Example 45
1½
¼
5 13/16
1
3½
9/16
1¾
Example 46
1½
⅜
5 13/16
1
3½
9/16
1¾
Example 47
1½
½
5 13/16
1
3½
9/16
1¾
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Many modifications and other embodiments of the invention set forth herein will come to mind to one skilled in the art to which these inventions pertain having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the invention is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
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Various embodiments of the present invention are directed to a movement control screed that is structured for installation between first and second masonry coatings applied adjacent to a building wall. The movement control screed is structured as a control joint for absorbing movement between the first and second masonry coatings and also as a weep screed for accommodating drainage of water from behind the masonry coatings. The movement control screed comprises first and second flanges provided on opposite sides of first and second ribs.
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[0001] This application is a continuation of co-pending U.S. patent application Ser. No. 10/637,245, filed on Aug. 7, 2003, which is a continuation of U.S. patent application Ser. No. 09/829,519, filed on Apr. 9, 2001, now U.S. Pat. No. 6,618,509, which is a continuation of U.S. patent application Ser. No. 09/396,084, filed on Sep. 14, 1999, now U.S. Pat. No. 6,229,917, which is a continuation of U.S. patent application Ser. No. 08/678,427, filed on Jul. 3, 1996, now U.S. Pat. No. 6,011,864.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention generally relates to coding digital video images, and more particularly to reducing loss of image information by automatically adjusting operating parameters utilized in the coding process.
[0004] 2. Description of Background Art
[0005] Digital video systems are becoming increasingly popular, especially in business settings. An example application of a digital video system is a teleconferencing system. Despite their popularity, digital video systems can be extremely expensive in terms of storage and communication costs. The cost of storage and communication is driven by the massive quantity of digital image data which is generated by the system.
[0006] One way to reduce costs or improve performance is to reduce the quantity of digital data used to represent images. Various well known compression techniques have been utilized to reduce the quantity of data used to represent a digitized image. While image compression may reduce some of the costs associated with handling digital image data, the downside is that image quality may suffer.
[0007] A number of compression techniques conventionally involve linear transformation of the digital image, followed by quantization. and coding of transform coefficients. In this way, the quantized and coded signals may be compressed, transmitted, or stored, and subsequently decompressed using an inverse set of operations.
[0008] The Discrete Cosine Transform (DCT) has commonly been used for image compression and decompression. However, because such DCT-based image processing is computationally intensive, various methods have been devised to improve the performance of the transform process.
[0009] The DCT process involves computing a set of coefficients to represent the digital image. One approach used to reduce the time required to perform the transform process is to compute only a subset of the coefficients. The selection of the particular subset of coefficients to be computed is based on detected characteristics of the digital image. While yielding acceptable results, the prior art process of classifying a digital image according to its characteristics and then selecting a subset of coefficients has no mechanism to measure the quality of the transformed image. Furthermore, the selection criteria used to classify an image are fixed such that they cannot be easily adjusted to improve image quality.
[0010] Therefore, to improve the quality of compressed digital images what is needed is a coding system having self-adjusting selection criteria for selecting a transform function.
SUMMARY OF THE INVENTION
[0011] The invention monitors the quality of coded digital images, and based on the monitored quality of the images, updates operating parameters that are used in coding the images.
[0012] A set of predetermined coding functions is available in a video coding system to code a digitized video image. One of the coding functions is selected and applied to the input image. The selection of the coding function is made based upon measured characteristics of the input image and selection criteria which are applied to the measured characteristics. The image is then decoded and the quality of the decoded image is measured. The selection criteria are updated based on the measured quality of the decoded image, whereby for subsequent images coding functions are selected to produce images with a higher quality measure.
[0013] In another aspect of the invention, an historical record is made for the measured characteristics of the images processed by the system. The measured characteristics are correlated with the selected coding function. Periodically, the selection criteria are updated based on the historical record. The historical record provides a broad perspective upon which updating of the selection criteria is based.
[0014] The invention further selects one of a predetermined set of transform functions to code an image. An inverse transform function is selected, independent of the selection of the first transform function, whose application minimally covers the image produced by application of the first transform function. The inverse transform function is then applied to the image, the quality is measured, and the selection criteria are updated as described above. The updating of the selection criteria enables selection of a suitable transform function.
[0015] In still another aspect of the invention, the selection criteria include adjustable thresholds and comparisons of them to measured characteristics of the image to be coded. The measured characteristics are correlated to the selected inverse transform function in the historical record. The respective thresholds are then updated from the historical record of the measured characteristics.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a block diagram of a computer system for encoding video sequences;
[0017] FIG. 2 is a block diagram of a prior art video coding system;
[0018] FIG. 3 is a block diagram of a video coding system which utilizes the present invention;
[0019] FIG. 4 shows the relationship between FIGS. 4A and 4B which together contain a flowchart of the processing performed by the video coding system in utilizing the present invention;
[0020] FIG. 5 shows the EnergyThresholdArray memory map;
[0021] FIG. 6 shows the memory map of a block which is output after the application of the Four-by-Four block transform function;
[0022] FIG. 7 illustrates the memory map of the Decoded Block Quality Array; and
[0023] FIG. 8 illustrates the memory map of the Total Energy histogram.
DETAILED DESCRIPTION
[0024] FIG. 1 is a block diagram of a computer system 100 for encoding video sequences. The exemplary system 100 is a Power Macintosh which is available from Apple Computer, Inc. The system includes a central processing unit (CPU) 102 , an input device 104 such as a keyboard or a mouse, and an output device 106 such as a computer monitor. The system 100 further includes data storage 108 which may consist of magnetic disks and/or tapes, optical storage, or various electronic storage media. The RAM 110 is available for storage of program instructions and data as referenced by the CPU 102 . The functional units of the system 100 are interconnected by a signal bus 112 .
[0025] An operating system program 114 is shown as stored in the RAM 110 to indicate that the program is executable by the CPU 102 , even though only portions of the program may be present in the RAM at a given time. The operating system 114 controls allocation of the resources which are available in the system 100 .
[0026] The system 100 further includes a video input device 116 which is coupled to the bus 112 . The video input device 116 captures and digitizes frames of images presented to a camera portion of the video input device 116 . The video coding system program 118 , represented as being stored in the RAM 110 , compresses the frames of data input by the video input device 116 . The compressed frames may then, depending upon the application, be either stored on the data storage 108 as video frames 120 , or output to a receiving application via the network input/output device 122 .
[0027] FIG. 2 is a block diagram of a prior art video coding system 150 . The video coding system 150 has program modules comprising a color converter 152 , a motion estimator 154 , a transform processor 156 , a classifier 158 , a quantization processor 160 , a lossless coder 162 , an inverse quantization processor 164 , an inverse transform processor 166 , and a motion compensator 168 , the latter three of which provide feedback data to the motion Estimator 154 .
[0028] The color converter 152 receives a frame of a digitized video image via input line 170 and converts the frame from Red-Green-Blue (RGB) format to a luminance-chrominance format such as Yuv. The converted frame is provided as input to a summation element 172 . The second input to the summation element 172 is provided by the motion estimator 154 .
[0029] The motion estimator 154 receives as input a frame from color converter 152 as shown by Line 174 . The previously processed frame is also input to the motion estimator 154 as shown by line 176 . The motion estimator 154 compares the frames to estimate the movement of portions of the image in the frame. The output of the motion estimator 154 is provided to the summation element 172 which outputs a residual frame on line 178 to the transform processor 156 . The residual frame is essentially the difference between the present frame as input on line 174 and the previous frame as input on line 176 .
[0030] The transform processor 156 receives the residual frame from the summation element 172 . The input frame is processed one block at a time, where a block is an m×n array of elements of the input frame. Each element of the block represents a pixel of data In the exemplary embodiment the block size is an 8×8 array of pixel data The input frame is also input to the classifier 158 via line 178 .
[0031] The transform processor 156 applies a Discrete Cosine Transform function to the input block to obtain an output block of coefficients. Background material on transform coding of images may be found in Transform Coding of Images, R. J. Clarke, Academic Press (London), 1985. To save computation time, the transform processor 156 , based on a selection made by the classifier 158 , may compute only a subset of the coefficients of the block. The classifier 158 determines characteristics of the input block, and based on predetermined selection criteria, selects for computation a subset of the coefficients of the block. Note, however, that a block having certain characteristics will result in the computation of all coefficients of a block. The selected subset of coefficients to compute is input to the transform processor 156 as shown by line 182 . The selected subset of coefficients which is selected for computation is hereinafter referred to as the “transform function” or “transform type.”
[0032] Each block of coefficients output by the transform processor 156 is input on line 184 to the quantization processor 160 . The quantization processor 160 reduces the number of bits required to represent each of the coefficients in the block by dividing each coefficient by a predetermined constant The predetermined constant is selected based on the application's required bit transmission rate.
[0033] The block of quantized coefficients is input on line 186 to the lossless coder 162 . The lossless coder 162 codes the block and outputs the coded information on line 188 for storage to data storage 108 , output on network input/output 122 , or output to output device 106 .
[0034] The block of quantized coefficients is also provided as feedback on line 190 to the inverse quantization processor 164 , to the inverse transform processor 166 , and to the motion compensator 168 . The purpose of the feedback data is to permit the motion estimator 154 to perform its estimation by comparing a newly input frame to a frame of the previous image as viewed by an application receiving the output of lossless coder 162 .
[0035] The inverse quantizer 164 multiplies each coefficient of the input quantized block by the same predetermined constant that was used by the quantization processor 160 . The output of the inverse quantizer 164 is provided via line 192 as input to the inverse transform processor 166 .
[0036] The inverse transform processor 166 performs the inverse of the transform function performed by the transform processor 156 and as indicated by the classifier 158 on line 194 . The motion compensator 168 obtains the block of pixels from the previously decoded image which is offset by the motion vectors from the block of interest. The summation element 196 performs a pixel-wise addition of the output of the motion estimator 154 with the incoming block
[0037] FIG. 3 is a block diagram of a video coding system 300 which utilizes the present invention. The elements added to FIG. 2 in FIG. 3 include a forward classifier 302 , a classifier feedback processor 304 , a quality measurement processor 306 , and an inverse classifier 308 .
[0038] The forward classifier 302 selects a transform type, which is indicative of a selectable transform function, based on the characteristics of the block input on line 180 and adjustable selection criteria as provided by the classifier feedback processor 304 on line 310 . Recall from FIG. 2 that the selectable transform function is an indication of the subset of coefficients to compute for the input block. The transform type is input on line 312 to the transform processor 156 .
[0039] The classifier feedback processor 304 provides selection criteria on line 310 to the forward classifier 302 . The selection criteria are adjusted by the classifier feedback processor 304 based on various input data, including: (1) from the forward classifier 302 , the transform type and characteristic values computed for a block as shown by line 314 ; (2) from the quantization processor 160 , the quantization value, Q, on line 316 ; (3) from the motion estimator 154 , motion vectors on line 318 ; (4) from the quality measurement processor 306 , a Peak Signal to Noise Ratio (PSNR) on line 320 ; and (5) from the inverse classifier, an inverse transform type on line 322 . The processing performed by the classifier feedback processor is explained further in the discussion pertaining to the FIGs. that follow.
[0040] Generally, the quality measurement processor 306 measures the quality of the coded images produced by the video coding system 118 for the purpose of improving the quality of subsequent images coded by the system 118 . The quality measurement processor 306 does so by indicating to the classifier feedback processor 304 the PSNR of a block which has been coded and then decoded, relative to the block input for coding. The processing performed by the quality measurement processor 306 is explained further in the discussion pertaining to the FIGs. that follow.
[0041] The inverse classifier 308 selects an inverse transform function for input on line 322 to the classifier feedback processor 304 and for input on line 324 to the inverse transform processor 166 . The inverse classifier 308 selects an inverse transform type independent of the classification performed by the forward classifier 302 . The purpose of the independent selection is decode the block so that the selection criteria used by the forward classifier 302 may be adjusted to improve the image quality of the block output by the transform processor 156 . The processing performed by the inverse classifier 308 is explained further in the discussion pertaining to the FIGs. that follow.
[0042] FIG. 4 shows the relationship between FIGS. 4A and 4B which together form a flowchart of the processing performed by the video coding system 300 in utilizing the present invention.
[0043] In Step 402 , the video coding system 300 performs initialization by associating predetermined transform functions with image characteristics and selection criteria FIG. 5 illustrates how the associations are established in the exemplary system. Briefly, the types of image characteristics and selection criteria utilized include adjustable thresholds of overall energy, horizontal high pass energy, vertical high pass energy, and motion vector magnitudes. The adjustable thresholds and usage thereof are explained in more detail below.
[0044] Step 404 receives an input block whose motion vector has been estimated by the Motion Estimator 154 . A motion vector consists of an x value and a y value, where x is the movement of the image in the block on an x-axis and y is the movement of the image in the block block on a y-axis. The input block is received by the transform processor 156 and the forward classifier 302 , and the motion vector is received by the classifier feedback processor 304 .
[0045] The pseudocode in Table 1 below corresponds to steps 406 and 408 .
TABLE 1 001 ForwardClassification( Q, InputBlock, MotionVectors ) 002 begin 003 004 // Compute characteristics of the input block. 005 energy = ComputeEnergy( InputBlock ); 006 hHPenergy = ComputeHorizHighPassEnergy( InputBlock ); 007 vHPenergy = ComputeVertHighPassEnergy( InputBlock ); 008 mvMag = ComputeMotionVectorMagnitude( MotionVectors ); 009 010 // Loop through each transform type. 011 for transformType = 1:NumberOfTransformTypeTypes-1 012 013 // Select proper thresholds. 014 threshEnergy = EnergyThresholdArray[transformType][Q]; 015 threshHHP = HorizHighPassEnergyThresholdArray[transformType][Q]; 016 threshVHP = VertHighPassEnergyThresholdArray[transformType][Q]; 017 threshMV = MotionVectorMagnitudeThresholdArray[transformType][Q]; 018 019 if energy < threshEnergy and 020 hHPenergy < threshHHP and 021 vHPenergy < threshVHP and 022 mvMag < threshMV 023 then 024 return transformType; 025 end 026 end 027 028 // Since none of the previous transform types work, 029 // select the most general transform type. 030 return DefaultTransformType; 031 032 end
[0046] At step 406 , characteristic values are computed for the input block. Lines 5 - 8 of the pseudocode compute the respective values according to formulae set forth below:
The total energy is the image energy and is computed as the sum of the absolute pixel values. Specifically, where i and j form an index into the input block, x:
total energy=Σ (i,j)εblock |x ( i, j )|
The horizontal high pass energy is computed as the sum of absolute differences of horizontally adjacent pixel values. Specifically:
hHP energy=Σ 0≦i<Blockwidth−1.0≦j<BlockHeight |x ( i, j )− x ( i− 1 ,j)|
The vertical high pass energy is computed as the sum of the absolute differences of vertically adjacent pixel values. Specifically:
vHP energy=Σ 0≦i<Blockwidth, 0≦j<BlockHeight−1 |x ( i, j )− x ( i,j+ 1)|
The motion vector magnitude may be computed as either the sum of the squares of each component, or as the maximum of the two vector components. In the exemplary embodiment either calculation is suitable. Specifically:
mv Mag= x 2 +y 2 or
mv Mag=max( x, y )
[0051] Lines 10 - 30 of the pseudocode of Table 1 correspond to step 408 . Step 408 selects a transform function based on the selection criteria set specified in lines 19-25.
[0052] FIG. 5 shows the EnergyThresholdArray memory map. The memory maps for the HorizHighPassEnergyThresholdArray, the VertHighPassEnergyThresholdArray, and the MotionVectorMagnitudeThresholds are similar in character to the EnergyThresholdArray of FIG. 5 . Therefore, for brevity only the EnergyThresholdArray is illustrated.
[0053] Each of the arrays has t rows, each representing a different transform function, and columns 1 -MAX_Q which represent the constants used by the quantization processor 160 . MAX_Q is a predetermined constant. Each entry in the respective arrays is initially zero, and, during the course of processing is updated by the classifier feedback processor 304 .
[0054] The transform functions utilized in the exemplary system include Zero-block, One-by-Three, Four-by-Four, Four-by-Eight, and Eight-by-Eight.
[0055] FIG. 6 shows the memory map of a block which is output after the application of the Four-by-Four block transform function. The transform processor 156 computes the coefficients for the upper-left four rows and four columns of the block. The computed coefficients are designated as C i,j in the array. The remaining entries in the array are set to zero.
[0056] The Zero-block transform function results in the transform processor 156 setting every entry in the output block to zero. The One-by-Three transform function results in the transform processor 156 computing the coefficients for the first three columns of row one of the input block, and setting the remaining entries to zero. The Four-by-Eight transform function results in the transform processor 156 computing the coefficients for all eight columns of the first four rows of the input block, and setting the remaining entries to zero. The Eight-by-Eight transform function results in the transform processor 156 computing the coefficients for all eight rows and eight columns of the input block. Note that the Eight-by-Eight transform function is the DefaultTransformType as returned by the ForwardClassification pseudocode of Table 1.
[0057] Returning now to FIG. 4A , the transform processor 156 performs step 410 in applying to the input block the transform function selected by the forward classifier 302 . The quantization processor 160 performs Step 412 in quantizing the block received from the transform processor 156 . Control is directed via path 412 p to steps 414 and 416 of FIG. 4B . At step 414 , the lossless coder 162 codes the block and outputs the block to data storage 108 or network input/output 122 .
[0058] Step 416 is performed by the inverse classifier 308 . The pseudocode in Table 2 below sets forth the processing for selecting a transform function that minimally covers the coefficients of the input quantized block.
TABLE 2 001 InverseClassification( QuantizedCoefficientBlock ) 002 begin 003 004 // Determine the locations of the non-zero coefficients. 005 locOfNonZeroCoef 006 = DetermineLocationOfForNonZeroCoefs(QuantizedCoefficientBlock ); 007 008 // Find the transform whose set of coefficients minimally cover the non-zero 009 // coefficints 010 transformType = FindMinimalCoveringTransform( locOfNonZeroCoef ); 011 012 return transformType; 013 014 end
[0059] At lines 5-6 of the InverseClassification pseudocode, the locations of the non-zero entries in the quantized block are identified. Line 10 identifies the inverse transform function (e.g., Zero-by-Zero, One-by-Three, Four-by-Four, Four-by-Eight, or Eight-by-Eight) whose application results in computing all coefficients for the input quantized block and which defines the smallest portion of the 8×8 block (e.g., Zero-by-Zero<One-by-Three<Four-by-Four<Four-by-Eight<Eight-by-Eight).
[0060] The inverse quantization processor 164 inversely quantizes the quantized block at step 418 . Processing continues at step 420 where the inverse transform processor 166 applies the inverse of the transform function selected by the inverse classifier 308 . The decoding process continues at step 422 where the motion compensator 168 undoes the motion estimation applied by the motion estimator 154 .
[0061] The quality measurement processor 306 measures the quality of the decoded block at Step 424 . The exemplary system uses the following calculation to measure decoded block quality (Note that x is the decoded block and {circumflex over (x)} is the original input block):
PSNR = 10 log ( ∑ ( i , j ) ∈ block ( x ( i , j ) - x ^ ( i , j ) ) 2 blocksize * 255 2 )
The quality measurement processor 306 keeps an historical record of decoded block quality values and outputs the decoded block quality on line 320 to the classifier feedback processor 304 .
[0062] FIG. 7 illustrates the memory map of the Decoded Block Quality Array in which historical records of decoded block quality values are kept. For each transform function/quantizer value pair, a historical record is kept of the decoded block quality values. The decoded block quality value may be the average of the PSNR values, the median of the PSNR values, the maximum of the PSNR values, or another suitable statistical measure of the PSNR values. The particular statistical function chosen is driven by application requirements.
[0063] Returning to FIG. 4B , Steps 426 and 428 are performed by the classifier feedback processor 304 . The classifier feedback processor 304 maintains an historical record of characteristic values and quality measures of decoded blocks, as related to the applied inverse transform function applied by the inverse transform processor 166 . At step 426 the historical record is updated. The pseudocode in Table 3 below sets forth the processing for updating the historical record.
TABLE 3 001 procedure UpdateHistograms 002 ( 003 InputBlkCharHist[NumberOfInputBlkCharTypes][NumberOfTransformTypes][MAX_Q], 004 InputBlkCharType, 005 InverseTransformType, 006 Q, 007 ForwardTransformType, 008 InputBlkCharValue, // Comes from the forward classifier. 009 ) 010 011 begin 012 013 // The array ‘NumberOfComputedCoefficients’ is a constant global array. 014 NumCoefInverse = NumberOfComputedCoefficients[InverseTransformType]; 015 NumCoefForward = NumberOfComputedCoefficients[ForwardTransformType]; 016 017 if NumCoefInverse > SomeNiceConstant * NumCoefForward 018 019 // Select the histogram to update. 020 theHistogram = InputBlkCharHist[InputBlkCharType][InverseTransformType][Q] 021 022 / / Update the histogram. 023 theHistogram[InputBlkCharValue]++; 024 025 end 026 027 end
[0064] Inputs to the procedure, UpdateHistograms, include: (1) a histogram designated as InputBlkCharHist [NumberofInputCharTypes][NumberOfTransformTypes][MAX_Q]; (2) a characteristic designated as InputBlkCharType; (3) the inverse transform function designated as InverseTransformType; (4) the quantization value Q; (5) the forward transform function designated as ForwardTranformType; and (6) an input characteristic value designated as InputBlkCharValue.
[0065] FIG. 8 illustrates the memory map of the Total Energy Histogram 472 . The memory maps of the Horizontal High Pass Energy Histogram, the Vertical High Pass Energy Histogram, the Motion Vector Magnitude Histogram are similar in character to the Total Energy Histogram. Therefore, for brevity only the Total Energy Histogram is illustrated. Each of the histograms is singly input to the UpdateHistograms procedure of Table 3 as shown by line 3 of the pseudocode.
[0066] Each of the histograms has a row for each of the available transform functions, and a column for each value in the range of quantization values. Each entry in the array references a one-dimensional array having indices ranging from 0 to a predetermined maximum value. Values in the one-dimensional array are updated as defined by the UpdateHistograms pseudocode of Table 3. The InputBlkCharType which is input to the UpdateHistograms pseudocode specifies which histogram to update.
[0067] Returning now to FIG. 4B , at Step 428 the classifier Feedback processor 304 periodically adjusts the selection criteria used by the forward classifier 302 and then returns control, via control path 428 p, to step 402 to process the next block. In the exemplary embodiment, the selection criteria are adjusted once per second.
[0068] The procedure UpdateThresholds, as set forth in the pseudocode of Table 4 below, updates the selection criteria by selectively updating the various thresholds in the EnergyThresholdArray ( FIG. 5 ), the HorizHighPassEnergyArray, the VertHighPassEnergyArray, and the MotionVectorMagnitudeArray.
TABLE 4 001 procedure UpdateThresholds 002 ( 003 004 InputBlkCharThresh[NumberOfInputBlkCharTypes][NumberOfTransformTypes][MAX_Q], 005 InputBlkCharHist[NumberOfInputBlkCharTypes][NumberOfTransformTypes][MAX_Q], 006 DecodedBlockQuality[[NumberOfTransformTypes][MAX_Q], 007 ) 008 009 begin 010 011 // Loop through each transform type. 012 for TransformType = 1:NumberOfTransformTypes 013 014 // Loop through each quantizer value. 015 for Q = 1:MaxQ 016 017 // Loop through each input block characteristic type 018 for InputBlkCharType = 1:NumberOfInputBlkCharTypes 019 020 // Select the Order-Statistic type. 021 OrderStatisticType = 022 SelectOrderStatistic 023 ( 024 InverseTransformType, 025 Q, 026 InputBlkCharType, 027 DecodedBlockQuality[TransformType][Q] 028 ); 029 030 // Compute the updated threshold. 031 InputBlkCharThresh[InputBlkCharType][ TransformType][Q] = 032 OrderStatistic 033 ( 034 orderStatisticType, 035 InputBlkCharHist[InputBlkCharType][TransformType] [Q] 036 ); 037 038 end 039 end 040 end 041 042 end
[0069] The inputs to the procedure are listed in lines 4-6. The input parameter at line 4 references the threshold arrays (See FIG. 5 ); the input at line 5 references the corresponding histograms (See FIG. 8 ); and the input at line 6 references the Decoded Block Quality Array (See FIG. 7 ).
[0070] As set forth in lines 12-40, each of the threshold arrays is updated by first selecting an order statistic to apply to the respective histogram, and then applying the selected order statistic to the respective histogram. The OrderStatistic function which is initiated on lines 31-36 applies the orderStatisticType to the referenced histogram of characteristic values. The orderStatisticType is a percentage, and the OrderStatistic function computes the characteristic value. To compute the characteristic value. the number of occurrences for all the characteristic values are totaled. and the total is multiplied by the orderStatisticType to obtain an adjusted occurrence total. Then, beginning at the lowest characteristic value in the histogram and proceeding with the following characteristic values, the number of occurrences are totaled until the adjusted occurrence total is reached. The OrderStatistic function then returns the characteristic value at which the adjusted occurrence total was reached.
[0071] The pseudocode for the function SelectOrderStatistic is set forth in Table 5 below.
TABLE 5 001 function SelectOrderStatistic 002 ( 003 TransformType, 004 Q, 005 InputBlkCharType, 006 DecodedBlockQuality 007 ) 008 009 begin 010 011 // The array ‘NumberOfComputedCoefficients’ is a constant global array. 012 NumCoef = NumberOfComputedCoefficients[TransformType]; 013 014 // Depending on the measure being used, select the OrderStatisticType. 015 // Constants k1 - k4 are predetermined. 016 case InputBlkCharType of 017 begin 018 Energy: OrderStatisticType = k1*NumCoef*DecodedBlockQuality; 019 HorizHPEnergy: OrderStatisticType = k2*NumCoef*DecodedBlockQuality; 020 VertHPEnergy: OrderStatisticType = k3*NumCoef*DecodedBlockQuality; 021 MVMagnitude: OrderStatisticType = k4*NumCoef*DecodedBlockQuality; 022 end 023 024 return OrderStatisticType; 025 026 end
[0072] The inputs to the SelectOrderStatistic function are set forth in lines 3-6. The inputs are the transform type, the quantization value, a characteristic type, and a value that indicates the quality of the decoded block.
[0073] The function SelectOrderStatistic returns an OrderStatisticType based upon the input characteristic type, a predetermined constant, the number of coefficients computed for the input transform type, and the input quality value.
[0074] While the foregoing exemplary embodiment of the invention is described in terms of a software implementation, those skilled in the art will recognize that the invention could also be implemented using logic circuits. The exemplary embodiments described herein are for purposes of illustration and are not intended to be limiting. Therefore, those skilled in the art will recognize that other embodiments could be practiced without departing from the scope and spirit of the claims set forth below.
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In a digital signal processing system, a method for selecting a transform function to apply to an input signal based on characteristics of the signal, and for self-adjusting criteria which are used in selecting a transform function to apply to a subsequent signal. Characteristics are obtained from the signal. The characteristics are compared to adjustable criteria which are used in selecting a transform function. Differing criteria are maintained for the different selectable transform functions. A record is maintained of transform functions selected and the particular characteristics that caused the selection. Based on the ability of a transform function to minimally define the coded signal, an inverse transform function is selected to decode the signal. The criteria used in selecting a transform function to apply to a subsequent signal are adjusted based on a quality measure of the decoded signal and the record of selected transform functions.
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TECHNICAL FIELD
[0001] The present invention relates generally to ion implantation dose measurement systems and methods, and more specifically to an in-situ dose measurement system comprising a calorimeter.
BACKGROUND
[0002] In the semiconductor industry, ions are implanted into a workpiece, such as a semiconductor wafer, in order to provide specific characteristics in the workpiece. Various different systems and methodologies are available for implanting the ions; one of which is a plasma immersion ion implantation (PIII) system. In a PIII system, the workpiece is maintained at a predetermined potential, and the implantation is performed in distinct pulses, wherein a large volume of plasma is pulsed for a very short duration. During the pulse, the ions in the plasma are attracted to the workpiece, therein depleting all the ions in the plasma. The plasma is then switched off, allowed to recharge, and then pulsed again. This process is repetitively performed until a desired amount of ions are implanted into the workpiece.
[0003] One of the ongoing problems with a PIII system is the measurement of the implant dose during the implantation, and the associated determination of when the implant should end. When the plasma is pulsed at a relatively high voltage (e.g., 6500V) for a very short duration (e.g., 60 microseconds), the ions in the plasma are accelerated onto the workpiece. In the past, a Faraday cup has been used to measure the dose, however, various shortcomings have been experienced using a Faraday cup to measure the total dose. Another method for measuring the total implant dose is to measure a temperature of a given thermal mass at the beginning of the implant, and measure its temperature at the end of the implant, and then back-calculate the dose using the change in potential energy of the thermal mass. Such a methodology, however, is often adversely affected by various environmental factors, such as radiation loss and conductive loss from electrodes used to make the measurement (e.g., thermocouples, etc.). On low energy implants (e.g., an implant depositing energy on the order of 5 Joules), a relatively low thermal mass is necessitated for such a methodology, thus demanding the thermal resistance to surroundings to be high. Such a scenario is often difficult to achieve. Accordingly, a need exists for a new and more robust measurement system and methodology for measuring dosage of an implantation during implantation.
SUMMARY
[0004] The present invention overcomes the limitations of the prior art by providing a system and method for measuring implant dosage in a plasma emersion implant system utilizing a calorimeter. Accordingly, the following presents a simplified summary of the disclosure in order to provide a basic understanding of some aspects of the invention. This summary is not an extensive overview of the invention. It is intended to neither identify key or critical elements of the invention nor delineate the scope of the invention. Its purpose is to present some concepts of the invention in a simplified form as a prelude to the more detailed description that is presented later.
[0005] In accordance with the present disclosure, an ion implantation system for implanting ions into a workpiece is provided. A process chamber is provided having an energy source configured to produce a plasma of ions within the process chamber. A workpiece support having a support surface configured to position the workpiece within an interior region of the process chamber is configured to expose an implantation surface of the workpiece to the plasma of ions. A pulse generator is in electrical communication with the workpiece support, wherein the pulse generator is configured to apply an electrical pulse to the support, therein attracting ions to the implantation surface of the workpiece and implanting ions into the workpiece. A calorimeter is further associated with the workpiece support, wherein a controller is configured to monitor a signal from the calorimeter and to control the implantation of ions into the workpiece based, at least in part, on the signal from the calorimeter.
[0006] The calorimeter, in one exemplary aspect, comprises a micro-calorimeter, wherein ion implantation deposition energy is measured directly. The micro-calorimeter, for example, measures the deposition energy of ions transmitted through a known aperture area. In one example, the micro-calorimeter comprises a low mass absorption calorimeter, wherein the calorimeter is designed to dissipate approximately a small amount of energy at a controlled temperature greater than an internal temperature of the process chamber. The electronics, for example, are battery powered and communicate to ground through fiber optic links. The batteries, for example, are recharged during workpiece exchange and vacuum recovery periods.
[0007] The above summary is merely intended to give a brief overview of some features of some embodiments of the present invention, and other embodiments may comprise additional and/or different features than the ones mentioned above. In particular, this summary is not to be construed to be limiting the scope of the present application. Thus, to the accomplishment of the foregoing and related ends, the invention comprises the features hereinafter described and particularly pointed out in the claims. The following description and the annexed drawings set forth in detail certain illustrative embodiments of the invention. These embodiments are indicative, however, of a few of the various ways in which the principles of the invention may be employed. 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 drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a block diagram of an ion implantation system according to several aspects of the present disclosure.
[0009] FIG. 2 illustrates a schematic diagram of an ion implantation dose measuring system in accordance with one example of the disclosure.
[0010] FIG. 3 illustrates a graph of a modeled control loop of an ion implantation, according to another exemplary aspect.
[0011] FIG. 4 illustrates a graph of a measured dosage and calorimeter power versus an input dosage, according to another exemplary aspect.
[0012] FIG. 5 illustrates a graph of measurement error versus time from a start of an ion implantation, according to yet another exemplary aspect.
[0013] FIG. 6 illustrates a methodology for controlling a dosage of an ion implantation according to still another aspect.
DETAILED DESCRIPTION
[0014] The present disclosure is directed generally toward a system, apparatus, and method for measuring a dosage of an ion implantation on a workpiece via a utilization of a calorimeter. Accordingly, the present invention will now be described with reference to the drawings, wherein like reference numerals may be used to refer to like elements throughout. It is to be understood that the description of these aspects are merely illustrative and that they should not be interpreted in a limiting sense. 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 will be evident to one skilled in the art, however, that the present invention may be practiced without these specific details. Further, the scope of the invention is not intended to be limited by the embodiments or examples described hereinafter with reference to the accompanying drawings, but is intended to be only limited by the appended claims and equivalents thereof.
[0015] It is also noted that the drawings are provided to give an illustration of some aspects of embodiments of the present disclosure and therefore are to be regarded as schematic only. In particular, the elements shown in the drawings are not necessary to scale with each other, and the placement of various elements in the drawings is chosen to provide a clear understanding of the respective embodiment and is not to be construed as necessarily being a representation of the actual relative locations of the various components in implementations according to an embodiment of the invention. Furthermore, the features of the various embodiments and examples described herein may be combined with each other unless specifically noted otherwise.
[0016] It is also to be understood that in the following description, any direct connection or coupling between functional blocks, devices, components, circuit elements or other physical or functional units shown in the drawings or described herein could also be implemented by an indirect connection or coupling. Furthermore, it is to be appreciated that functional blocks or units shown in the drawings may be implemented as separate features or circuits in one embodiment, and may also or alternatively be fully or partially implemented in a common feature or circuit in another embodiment. For example, several functional blocks may be implemented as software running on a common processor, such as a signal processor. It is further to be understood that any connection which is described as being wire-based in the following specification may also be implemented as a wireless communication, unless noted to the contrary.
[0017] Referring now to the figures, FIG. 1 illustrates an exemplary ion implantation system 100 . In particular, the present disclosure is directed toward a plasma immersion ion implantation (Pill) system 102 , however, the present invention has utility in various other ion implantation systems 100 , such as ion beam-based systems (not shown). As illustrated, the ion implantation system 100 comprises a process chamber 104 , wherein a workpiece support 106 is generally positioned within process chamber. The workpiece support 106 , for example, is configured to provide a surface for holding a workpiece 108 , such as a semiconductor wafer (e.g., a silicon wafer). The workpiece support 106 , for example, may comprise an electrostatic chuck or a mechanical clamping apparatus (not shown) configured to clamp the workpiece 108 about at its periphery to a support surface 110 of the workpiece support. The workpiece support 106 , for example, is at least partially electrically conductive. The workpiece support 106 thus supports the workpiece 108 , while further providing an electrical connection to the workpiece. It should be noted that while the workpiece support 106 is described in the present example as supporting one workpiece 108 , various other configurations are also contemplated, such as a configuration of the workpiece support to concurrently support a plurality of workpieces.
[0018] A load lock 112 is operably coupled to the process chamber 104 , wherein the load lock generally permits an internal environment 114 of the process chamber to be maintained at a predetermined pressure with respect to an external environment 116 (e.g., atmospheric pressure). The load lock 112 thus comprises a valve 118 configured to selectively permit a workpiece 108 to move into and out of the process chamber 104 while maintaining the predetermined pressure within the process chamber. A vacuum pump 120 , for example, is further selectively fluidly coupled to the process chamber 104 via a vacuum valve 122 , wherein the vacuum pump is configured to maintain the internal environment 114 at a reduced pressure. A gas source 124 is further selectively fluidly coupled to the process chamber 104 via a gas source valve 126 , wherein the gas source is configured to supply an ionizable gas to the internal environment 114 of the process chamber.
[0019] In accordance with one example, an energy source 128 is provided above the workpiece support 106 , wherein the energy source is configured to inject energy into the process chamber in order to ionize the gas from the gas source 124 , therein producing a plasma of ions 130 in a plasma region 132 within the process chamber between the energy source and the workpiece support. The energy source 128 , for example, is positioned within the process chamber 104 , or alternatively, is provided along a wall 134 of the process chamber (e.g., a quartz plate, not shown), wherein an RF coil (not shown) operating at a predetermined frequency (e.g., between 2 MHz and 15 MHz) that transmits energy toward the workpiece 108 positioned on the workpiece support 106 .
[0020] RF energy from the energy source 128 thus produces the plasma of ions 130 (also called an ion plasma) from gas molecules that are pumped into the process chamber 104 from the gas source 124 . The pressure within the process chamber 104 , for example, is maintained in the range of 0.2 to 5.0 millitorr. As one example, the gas source 124 provides nitrogen gas into the process chamber 104 , wherein the nitrogen gas is ionized by the RF energy entering the process chamber via the energy source 128 . Accordingly, the RF energy ionizes the gas molecules, therein producing the plasma of ions 130 . It is noted that various other gases, techniques, and/or apparatus known for producing a plasma of ions 130 can be utilized, as all such gases, techniques, and/or apparatus are contemplated as falling within the scope of the present invention.
[0021] In accordance with the present disclosure, once the plasma of ions 130 is set up in the plasma region 132 , the ions are accelerated into contact with the workpiece 108 positioned on the workpiece support 106 . The workpiece support 106 , for example, is at least partially electrically conductive. The plasma of ions 130 , for example, are positively charged, such that an application of an electric field of suitable magnitude and direction in the plasma region 132 will generally cause the ions in the plasma to accelerate toward and impact a surface 136 of the workpiece 108 . In accordance with one example, a pulse generator 138 (also called a modulator) supplies voltage pulses 140 (e.g., less than 10 kV) to the workpiece support 106 , therein biasing workpiece support with respect to conductive inner walls 142 of the process chamber 104 , thus inducing an electric field in the plasma region 132 and accelerating the plasma of ions 130 into the workpiece. The pulse generator 138 , in one example, provides pulses in a range of 100 to 7000 volts, in 1 to 60 microseconds in duration and a pulse repetition rate up to 10 KHz. A controller 144 is further provided to control overall operation of the ion implantation system 100 . For example, the controller 144 is configured to control the pulse generator 138 , supply of gas from the gas source 124 , movement of the workpiece 108 through the load lock 112 , as well as other conditions associated with the ion implantation system 100 .
[0022] It will be appreciated that while specific parameters for the pulse generator 138 and modulation of the voltage pulses 140 are provided as one example, other values and parameters may be utilized, and all such values and parameters are contemplated as falling within the scope of the present invention. The pulse voltage, for example, is selected to implant the positive ions to a desired depth in the workpiece 108 . The number and duration of the pulses are further selected to provide a desired dose of impurity material into the workpiece 108 . The current per pulse is also a function of pulse voltage, gas pressure and species, as well as any variable position of the electrodes. For example, the spacing between the energy source 128 and the workpiece support can be adjusted for various voltages.
[0023] Once the workpiece 108 is implanted with ions, the workpiece is removed from the process chamber 104 via the load lock 112 , wherein further processing or fabrication of the workpiece can be performed. It is highly desirable, however, to tightly control the total energy implanted or deposited on the workpiece 108 during implantation, as resultant devices formed on the workpiece 108 are commonly dependent on proper doping during ion implantation. Accordingly, measurement of the total deposition energy during ion implantation is desirable in order to maintain proper manufacturing yields.
[0024] One method for determining total deposition energy comprises measuring a temperature of a predetermined thermal mass within the process chamber at the beginning of the ion implantation, followed by measuring the temperature of the thermal mass at the end of ion implantation, and then calculating the total energy that is deposited based on the temperature difference of the thermal mass. Such a methodology is moderately effective; however, environmental factors such as radiation losses from the thermal mass and conductive losses from electrodes (e.g., thermocouples, wiring, etc.) used for the temperature measurement can have deleterious effects on the resultant calculation. In low energy implants (e.g., deposits of energy of 5 Joules or less), a relatively low thermal mass is needed, and thermal resistance to surroundings needs to be substantially high.
[0025] Rather than simply measuring temperature differences, however, the present disclosure utilizes calorimetry, therein integrating an amount of power needed to maintain a constant temperature into the determination of the total deposition energy of the ion implantation being performed. Thus, in accordance with the present disclosure, a dosimetry system 146 is provided, where a calorimeter 148 is provided within the process chamber 104 , wherein the calorimeter is generally exposed to the plasma of ions 130 during the implantation. The dosimetry system 146 is illustrated as a schematic 150 in FIG. 2 , wherein the calorimeter 148 comprises of a resistor 152 (e.g., a thick film resistor) formed or positioned over a ceramic substrate 154 (e.g., a 0.5 mm thick alumina substrate). The ceramic substrate 154 thus provides a thermal mass for absorbing energy from the plasma of ions 130 during the implantation. The ceramic substrate 154 , for example, is comprised of alumina (aluminum oxide) or another suitable ceramic material. The calorimeter 148 , for example, further comprises a ring 156 generally encircling the ceramic substrate 154 , wherein one or more wires 158 (e.g., four wires radiating from the ceramic substrate and generally equidistantly spaced about the ceramic substrate) thermally couple the ceramic substrate to the ring. The one or more wires 158 , for example, are comprised of copper or tungsten. The ring 156 , for example, is operably coupled to a thermal cooling apparatus 160 , wherein the thermal cooling apparatus is configured to generally remove heat from the ring. The thermal cooling apparatus 160 , for example, comprises a fluid circulation system (e.g., chilled water) configured to remove heat from the ring 156 .
[0026] Accordingly, the ceramic substrate 154 has a fixed conductive loss through the one or more wires 158 connecting the substrate to the ring 156 that surrounds the ceramic substrate. In accordance with one example, the calorimeter 148 comprises an aperture 162 positioned along the support surface 110 of the workpiece support 106 , wherein the aperture defines an area 164 of the aperture of the calorimeter that is exposed to the plasma of ions 130 .
[0027] The resistor 152 is thus configured to be heated with a predetermined power (e.g., approximately 1 watt) in order to maintain a predetermined constant temperature (e.g., 50 degrees C.) of the calorimeter 148 above ambient temperature. By heating the calorimeter 148 to a constant temperature differential above the ambient temperature of the internal environment 114 of FIG. 1 , a thermal loss is provided to the internal environment, thus providing a constant power loss or “calorimeter constant”. If the power going into the calorimeter is measured during the implantation of ions, the integral of the calorimeter constant over that period of time minus the integral of the power going into the calorimeter 148 will provide the change in energy attributed to the ion implantation, itself.
[0028] In one example, the controller 144 further comprises a PID controller 166 configured to maintain the temperature of the calorimeter 148 at the predetermined constant. Thus, the power delivered to the calorimeter 148 is generally continuously monitored, and a calorimeter constant Kc is updated during periods between implants, thus correcting for variations in ambient temperatures. The calorimeter 148 , for example, is powered via one or more batteries 168 and configured to communicate to the controller 144 via a non-electrically conductive signal transmitter 170 associated with therewith. Thus, the calorimeter 148 is controlled while generally preventing stray capacitance associated with the communication of the signal.
[0029] In one example, the non electrically-conductive signal transmitter 170 comprises a fiber optic signal transmitter 172 , wherein the signal is communicated to the controller via a fiber optic cable 174 . Alternatively, the non electrically-conductive signal transmitter 170 comprises a wireless transmitter (not shown), wherein the signal is communicated to the controller via the wireless transmitter to a wireless receiver (not shown) associated with the controller 144 . The one or more batteries 168 , for example, are configured to be recharged during one or more of a transfer or exchange of workpieces 108 and vacuum recovery periods, wherein the internal environment 114 is stabilized.
[0030] In accordance with another aspect of the present disclosure, the energy or Power P provided to the calorimeter 148 can be stated as:
[0000]
P
=
V
2
R
(
1
)
[0000] where V=voltage provided to the calorimeter to maintain the constant predetermined temperature and R=resistance of the resistor 152 . The measured energy into the calorimeter E c during an implant from time t 0 to t 1 can be written as:
[0000] E c =K C ( t 1 −t 0 )−∫ t 0 t 1 Pdt (2)
[0000] where K C =the calorimeter constant in watts.
[0031] The dosage of the implant Dose (e.g., expressed in ions/cm 2 ) can be written as:
[0000]
Dose
=
E
c
E
b
Aq
(
3
)
[0000] where E b is the ion beam or plasma energy (e.g., expressed in eV), A=the area of the aperture 164 of the calorimeter 148 (e.g., expressed in cm 2 ), and q=the electron charge (e.g., 1.602×10 −19 coulombs).
[0032] Thus, the Dose of the implantation of ions into the workpiece 108 can be finally calculated as:
[0000]
Dose
=
K
c
(
t
1
-
t
0
)
-
∫
t
0
t
1
P
t
E
b
Aq
.
(
4
)
[0033] In accordance with one example, the temperature of the calorimeter 148 is controlled in a tight range (e.g., +/−0.1 degrees C.). In one example, since the PID controller 166 is employed to maintain a predetermined constant (e.g., 50 degrees C.) difference between the calorimeter 148 and its surroundings, environmental factors are automatically compensated for, such as day to day temperature changes. The temperature control equation for the PID controller is:
[0000] P n = P n - 1 + A [ 1 - T n T s ] - B [ 1 - T n - 1 T s ] + C [ ( 1 - T n T s ) - ( 1 - T n - 1 T s ) ] ( 5 ) where:
[0000] A=k i +k p (6)
[0000] B=k p (7)
[0000] C=k d (8)
[0000] and n=a loop counter indexed at a constant frequency.
[0034] A model of the functionality of the dosimetry system 146 will now be described, wherein the thermal response characteristics of the calorimeter 148 are provided for an exemplary implantation of ions. For example, FIG. 3 illustrates a graph 176 of the temperature time response of the dosimetry control system 146 of FIG. 1 from the warm up of the ion implantation system 100 to a stabilization 178 of the PID control and a commencement 180 of the ion implantation. In the present example, the ion implantation was simulated using impulses of 1×10 14 dose, with the impulses spaced 100 msec apart. The dose impulses thus create a disturbance in the control loop, causing the temperature to rise momentarily. In turn, the power supplied to the calorimeter 148 decreases proportionately. As shown in graph 182 of FIG. 4 , the integrator of the PID control measures a drop in heater power 184 (e.g., also called power excursions) and converts it to an implant dose which can be seen in the staircase-like response 186 of accumulated implant dose shown in the graph. Accordingly, the accumulated implant dose D n is used for end-point measurement to control the implantation of ions.
[0035] FIG. 5 is a graph 188 illustrating an error envelope 190 versus implant time, wherein a measurement error 192 is illustrated well within the desired operating range of the system. Each impulse of deposition energy to the calorimeter 148 of FIG. 1 , for example, is reflected as a momentary drop in the applied heater power 184 shown in the graph 182 of FIG. 4 . The PID controller 166 of FIG. 1 , for example, responds relatively slowly to the impulse, thus allowing a momentary rise in calorimeter temperature and causing the input power to drop momentarily. The equation for the power excursions Q n in heater power 184 shown in FIG. 4 is:
[0000] Q n =( Kc−P n )( t n −t n-1 ) (9).
[0000] The equation for the staircase ramp 186 in accumulated implant dose D n is:
[0000]
D
n
=
Q
n
E
b
Aq
+
D
n
-
1
.
(
10
)
[0000] Equations 9 and 10 thus represent the quantization of implant dose as a function of the calorimeter power difference.
[0036] In accordance with another exemplary aspect of the invention, FIG. 6 illustrates an exemplary method 200 for measuring dosage during a plasma emersion ion implantation using a calorimeter. It should be noted that while exemplary methods are illustrated and described herein as a series of acts or events, it will be appreciated that the present invention is not limited by the illustrated ordering of such acts or events, as some steps may occur in different orders and/or concurrently with other steps apart from that shown and described herein, in accordance with the invention. In addition, not all illustrated steps may be required to implement a methodology in accordance with the present invention. Moreover, it will be appreciated that the methods may be implemented in association with the systems illustrated and described herein as well as in association with other systems not illustrated.
[0037] The method 200 of FIG. 6 begins at act 202 , wherein a workpiece is provided on a workpiece support in a process chamber. The workpiece support, for example, comprises a calorimeter, such as the calorimeter 148 of the dosimetry system 146 of FIGS. 1 and 2 . In act 204 of FIG. 6 , a dosage D n of implanted ions (also called a dose counter) is initially set to zero (D n =D 0 =0). A plasma of ions is provided in act 206 , wherein an amount of ions are implanted into the workpiece for a period of time. In act 208 , the dosage D n (e.g., the accumulated amount of ions implanted into the workpiece) is determined via the calorimeter associated with the workpiece support and dosimetry system. For example, the dose D n is updated in act 208 at a rate n that is equal to a clock frequency of the PID controller 166 of FIG. 1 . In act 210 , a determination is made regarding whether the dosage D n has reached a predetermined preset dosage D preset (also called a final implant dose). If the determination in act 210 is such that the preset dosage D preset is achieved (e.g., D n >=D preset ), the implantation is halted and the workpiece is removed from the process chamber in act 212 . If the determination in act 210 is such that the preset dosage D preset has not been achieved, the implantation continues by continuing to provide ions to the workpiece in act 206 . It is noted that a residual error in the dosage D n measurement in act 208 may be seen due to a time delay of the PID controller; however, the residual error is acceptably small, as evidenced in FIG. 5 .
[0038] Although the invention has been shown and described with respect to a certain embodiment or embodiments, it should be noted that the above-described embodiments serve only as examples for implementations of some embodiments of the present invention, and the application of the present invention is not restricted to these embodiments. In particular regard to the various functions performed by the above described components (assemblies, devices, circuits, etc.), the terms (including a reference to a “means”) used to describe such components are intended to correspond, unless otherwise indicated, to any component which performs the specified function of the described component (i.e., that is functionally equivalent), even though not structurally equivalent to the disclosed structure which performs the function in the herein illustrated exemplary embodiments of the invention. In addition, while a particular feature of the invention may have been disclosed with respect to only one of several embodiments, such feature may be combined with one or more other features of the other embodiments as may be desired and advantageous for any given or particular application. Accordingly, the present invention is not to be limited to the above-described embodiments, but is intended to be limited only by the appended claims and equivalents thereof.
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An ion implantation system for implanting ions into a workpiece is provided, having a process chamber and an energy source configured to produce a plasma of ions within the process chamber. A workpiece support having a support surface configured to position the workpiece within an interior region of the process chamber is configured to expose an implantation surface of the workpiece to the plasma of ions. A pulse generator is in electrical communication with the workpiece support, wherein the pulse generator is configured to apply an electrical pulse to the support, therein attracting ions to the implantation surface of the workpiece and implanting ions into the workpiece. A calorimeter is further associated with the workpiece support, wherein a controller is configured to monitor a signal from the calorimeter and to control the implantation of ions into the workpiece based, at least in part, on the signal from the calorimeter.
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BACKGROUND AND FIELD OF THE INVENTION
The invention relates to the field of pillows and, in particular, to a pillow that provides a musical sound to accompany the user as he or she rest and/or falls asleep. It is believed that a pillow that can simultaneously provide the feelings of warmth, sound, and touch to the user will provide a relaxed feeling and allow them to rest or fall asleep peacefully.
The pillow is also shaped to accommodate the size and contour of the user's head so that the pillow molds up to the sides of the face, up to the cheek bone area. The shape varies in proportion to the shape and size of user's head and neck. The neck area of the pillow is elevated in relation to the head portion of the pillow. It is believed that that by supporting the neck and head with the the pillow this will help prevent snoring and early morning "Dry Mouth" feeling, it is also believed to prevent the addition of sleep wrinkles of the face.
PRIOR ART
While there are pillows that do have sound-emitting capabilities, none that applicant is aware of that provide music upon the weight of the user (head or neck) being applied to the pillow and that deactivates the music when the weight is removed from the pillow. In addition, it is believed that the use of a pillow with heat reflective properties is novel with respect to such pillows.
In addition, the use of the particular shape of applicant's pillow is also believed to be unique in the sense that the head molds into the pillow and the pillow is designed in such a way that there is no excessive pressure put on the face of user which prevents the formation of early wrinkles. The elevated support under the neck is also believed to help prevent snoring because it helps keep air passage of the neck (trachea) open.
SUMMARY OF THE INVENTION
The invention is a music-emitting pillow with an oval shaped depression to accommodate the shape of the user's head. The depression is deep enough to partially enclose the user's head when he/she lays their head on the pillow and the top of the pillow should come up to about the top of the cheek bone area of the person. The base of the depression will be elevated so that the neck will be supported and protected from any undue strain.
Inside the pillow is a music emitting device having a weight-activated means for playing music when weight e.g. that of the user's head is placed on the pillow. The music emitting device has a timing means which allows the music to play for a predetermined time, say 30-60 minutes. The weight activated means has a means for turning off the music before the predetermined time in the event that the weight is lifted off the pillow and has a means for restarting the music when the weight is returned. The pillow may be filled with e.g. foam rubber, tightly bound cotton, etc. in order to provide a firm, supporting pillow. The pillow may be covered with a heat reflective material, e.g. mylar for cold weather, illness etc., or with cotton for warmer temperatures.
It is among the objects of the invention to provide a pillow to encourage the user to relax or fall asleep by providing stimulation of the senses of hearing and touch through the use of music as well as heat reflective properties of the surface of the pillow.
Another objective is to provide a pillow that will keep the user's head at a 35-45 degree angle, with respect to the bed, so that the pillow will keep the users' face and neck free from pressure and thus help to prevent early, unsightly, wrinkles to both face and chest.
Another objective is to provide a pillow that can reflect the heat of the neck and provide comfort to the user.
Another objective is to provide a music emitting pillow with a sound emitting device that is constructed on the inside of the pillow in order to avoid the need for speakers on the outside of the pillow which may lead to the discomfort of the user.
Another objective is to provide a music emitting pillow that will emit music when a person's head/neck is laid on the pillow and will stop the music and rewind in response to the head/neck being removed from the pillow in order to restart music.
Another objective is to provide a therapeutic pillow which will enhance muscular relaxation during rest/sleep as well as minimize sagging skin.
Another objective is to provide a pillow with a specially designed protrusion in the pillow that will support the neck of the user and keep the airway in the neck open which should help prevent snoring and prevent discomfort due to arthritis or drafts.
Another objective is to provide a pillow that can support both the neck and head of the user in an upright position with little pressure on the face and thus prevent, or mitigate, the formation of wrinkles in the face during sleep.
Another objective is to provide a pillow that will alleviate stress on the neck and thus reduce the possibility of stiffening of the neck during sleep.
Other objectives of the invention will be readily apparent to those skilled in the art once the invention has been described.
DESCRIPTION OF THE FIGURES
FIG. 1 is a top view of the pillow.
FIG. 2 is a side view of the pillow and user.
FIG. 3 is a side view of the pillow.
FIG. 4 shows a cross section of the pillow in use.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The overall construction of the pillow is as shown in FIG. 1. The pillow should have an outer layer (made of materials e.g. mylar, cloth, etc.) which may be filled with typical cushioning materials found in state of the art pillows such as: cotton, foam, feathers, synthetic materials, etc. in order to produce the overall shape of the pillow.
The inside of the pillow has a music emitting device 8 that has a means for emitting music in response to a weight (such as the user's head/neck) being laid on the pillow. The music emitting device will likely have a tape cassette storage medium for the music. The music emtting device should be in connection with a timing means so that the music will be shut off after a predetermined time, say, 30 or 60 minutes.
The music emitting device will also have a means for turning off and rewinding (in the case of tape cassettes) the music, in response to the weight being removed from the pillow before the predetermined time expires. Again, this may be done by the sensor 10 sending a signal to the music emitter. When the user returns to the pillow, the weight of the neck or head will again activate the music through the sensor.
The music chosen for the pillow should be very relaxing soothing music. Such relaxing music may include by way of example, "New Age" music produced by Valley of the Sun Studios located in Malibu, Calif. 90265. Typical New Age Music includes such examples as: "Upper Astral Suite", which is metaphysical music; "Dawning of the New Age", by Davis Naegele; "Crystal Cave," etc. It is believed that such sounds will relax the mind, body, and soul.
Such a musical device would cover those situations where the user may get up, say, to go to the bathroom, and the music can then begin again when the user puts his head back on the pillow. The weight-sensor in the music emitting device may be nothing more than a unit that sends a signal to the music emitting device in the event that a weight is placed on the pillow or is removed. The music emitter would then operate in an on/off mode where each successive signal changes the mode. The music emitting device can have a switch or sensor 10 that will turn the music off and on when such a signal is sent to it.
In the event that the user gets up the music will turn off in response to the signal sent from the sensor. When the user returns, the signal sent to the music emitter will the activate the music again. In addition, there should also be a means to rewind (in the case of tape cassette storage medium) the recorded music back to start when the music has finished playing.
The overall shape of the pillow is shown in FIG. 1. There is an oval depresssion 20, the bottom 9 of which suports the back of the head. The depression is surrounded for the most part by a head wall 6 that should come up the temple area 12 of the user. At that area where there is no head wall there is an elevated neck channel 5 in connection with the oval depression and is shaped to support the neck 2.
The contour of the pillow helps alleviate pressure on the face as the walls 6 are elevated so that they extend to both sides of the face and head up to the top of the cheek bone 12, arrow I shows the height of the wall in relation to the bottom of the pillow. The wall is, in proportion to user's head as the sides of the user's head are supported during sleep.
The special countour of the pillow provides depressions in the pillow for the support of the head of the user. The depression 20 is preferably oval shaped (or nearly so) and conforms to the shape of the user's head. The neck channel 5 is somewhat raised in relation to the bottom 9 of the oval depression thus giving the neck support and therapeutic stimulation.
Note in FIG. 4 that arrow F shows the height of the bottom 7 of the neck channel in relation to the bottom of the pillow, while arrow G shows the height from the bottom 9 of the oval (head support) depresion to the bottom of the pillow. Height F should be greater than height G. Thus the thickness of the bottom of the pillow at G is about 1-8" and the length of the raised up portion 7 (along line B) should be about 1/2-4".
The neck channel (5) is thus elevated in relation to the head depression and will support the upper trapezius muscle at the back of the neck in order to accommodate the position of the neck 2. The width of the neck channel should be about 2-61/2". The neck will thus be slightly above that of the head when the user lays his/her head in the pillow, face up.
The width of the walls shown as line C should be about 4" and the height shown as line I should be about 6-12".
These depressions 20 and 5 will thus engulf a large portion of the person's head and neck and thus provide a support that will prevent or hinder the user from moving the head and neck. It is preferred that the head depression will be deep enough so that the top of the side walls of this depression will come up to the front of the user's cheek bones and/or the temple area 12. It is believed that this will alleviate stiff necks and snoring. It is believed that many commonly found pillows do not support the neck and this may lead to stiffness of the neck when the user awakes.
The pillow may be covered with a heat reflective covering 30 such as, mylar, for example, that would reflect the body heat of the user and so provide a warming feeling to the head and neck of the user. A heat reflective pillow is believed to provide additional comfort to those with arthritis of the neck which may help to ease the pain. The neck and head depressions will conform around those parts of the user and thus keep a large part of the neck and head out of direct exposure to the air. This is believed to keep the head and neck warm in the event of sweating and/or drafts.
The dimensions of the pillow will vary depending on the user, there may be adult, child and infant sizes of pillows. The depth of the depressions in the pillow may vary. The cushioning material on the inside of the pillow should conform to the shape and size of head and neck, and coming up to the level of the face by the temple area.
The mylar covering may be used in the winter or during times of illness or stress, and there may be a covering of cotton for the summer. The therapeutic pillow, should enhance muscular relaxation during rest/sleep as well as minimize sagging skin because the pillow is shaped in such a way that the head and neck will always be in a 35 to 45 degree angle in relation to the bed (or whatever surface the user is sleeping upon) which keeps the air passages open and may thus prevent snoring.
The pillow should support the head in one position which helps keep ones' skin smooth and relaxed, but not to the point of causing early wrinkles. The support on the neck helps relieve tension and sore necks and will help to keep the air passage open to breath normally.
When an individual is sleeping/resting, the facial muscles and skin relax which may lead to wrinkles during sleep due to pressure on either side of the face. This pillow described herein is designed to prevent that as well as alleviate snoring, temporary blockage of the air passage causes snoring, and dry mouth, the pillow keeps air passage free for normal breathing. The pillow supports the head in a manner that keeps the skin of the head and neck firm without constricting the blood vessels and muscles of the neck and face. The support of the face and neck will also place the skin in a position to be well ventilated during sleep.
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The invention is a music-playing pillow with an internal music playing device. The device has a switch for automatically turning the music on when pressure is applied and turns off when pressure is removed. The pillow has an ovoid shaped depression for the head, consisting of tightly bound cotton material in the interior, which will be elevated on all sides, and up to the cheek bone area, with an elevated portion for the neck to give it warmth, protection and support. The bottom portion of the pillow will end into a "c" shaped curve which will come to either side of the upper trapezius and will support the three basic neck muscles.
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This is a divisional of application Ser. No. 08/412,796 filed on Mar. 29, 1995, now U.S. Pat. No. 5,823,355.
BACKGROUND OF THE INVENTION
The processing of pulp fibers requires several steps before the fibers can be used to manufacture paper. Some of these processes include pressing, washing and liquor extraction. These steps are performed by presses and washers that contain filtering surfaces with openings large enough for some fibers to pass through. The liquor, while flowing through the filtering surface therefore, carries with it a certain amount of fibers.
It is highly desirable to capture the fibers contained in the filtrate as they would otherwise represent loss of usable product and a source of disposal problems. In order to capture the fibers a filtering surface with openings small enough so that only the liquid can go through is required. This permits the collection of fibers. Such a machine is referred to by the present assignee as a Fibresaver Screen. There is a market demand for a screen with openings of 0.004" in diameter, or even smaller. The filtrate of the other machines described above would be fed into this machine in order to recover as many fibers as possible. Typically such a screen may be formed into the shape of a basket or hollow cylinder. Due to the manufacturing process and the economics of manufacturing a screen basket with very small openings the basket thickness cannot exceed a certain value. Usually the smaller the opening, the thinner the basket. For example, a basket with 0.1 millimeter (0.004" ) holes would have a thickness of no more than 1 millimeter (0.04" ). In a production machine of any size a screen basket of this thickness requires a supporting structure in order to handle the loads acting on it without failing.
The foregoing illustrates limitations known to exist in present devices and methods. Thus, it is apparent that it would be advantageous to provide an alternative directed to overcoming one or more of the limitations set forth above. Accordingly, a suitable alternative is provided including features more fully disclosed hereinafter.
SUMMARY OF THE INVENTION
Our initial objective was to remove individual fibers from process liquor efficiently and cost effectively. This required the use of conventional pressure screens using cylindrical screenplates having very small holes. These small holes are cut by an electron beam or equivalent method and for this method of manufacture the plate must be much thinner than is desirable for strength. The holes are closely spaced to maximize capacity which results in very narrow ligaments between holes. Thus the screenplate has low strength, and for typical operating conditions can sustain only a small span between supports. Typical conventional means of reinforcement obstruct flow area and significantly reduce throughput capacity.
All embodiments of the present invention satisfy the initial objective in providing a strong and rigid screen cylinder assembly having maximum unobstructed area. The most frequent use of this invention will likely be in outward flow screen cylinders as described herein; however, an inward flow screen cylinder may adapt the present invention.
In one aspect of the present invention the above is accomplished by providing a support structure for a screen basket having a screen comprising a thin screen; a screen support means having minimum screen contact area to permit maximum flow through the screen; and means for positioning and supporting the screen support means.
The foregoing and other aspects will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawing figures.
BRIEF DESCRIPTION OF THE DRAWING FIGURES
FIG. 1 is a partial longitudinal cross section of a screen basket according to the present invention showing the screen and a supporting structure according to the present invention;
FIG. 2 is a partial longitudinal cross section of a screen and its supporting structure according to an alternative embodiment of the present invention;
FIG. 3 is a cross section taken at Section 3--3 of FIG. 2;
FIG. 4 is a cross section of a second alternative embodiment of the present invention;
FIG. 5 is a partial longitudinal cross section of a third alternative embodiment of the present invention;
FIG. 6 is a partial cross section taken at Section 6--6 of FIG. 5; and
FIG. 7 is a partial longitudinal cross section of a fourth alternative embodiment of the present invention.
DETAILED DESCRIPTION
According to the present invention a first proposed support structure for a vertically oriented screen basket is shown in FIG. 1. Please note the screen axis may be horizontal or vertical in use. In the orientation shown, a number of thin horizontal rings 10 are shown evenly spaced longitudinally about the screening basket 20. The screening basket 20 may, for example, be a cylindrical formed structure of screen material. For a Fibresaver Screen the thickness of the screen may be approximately 1 millimeter (0.04" ) being perforated with closely spaced holes of, for example, 0.1 millimeter (0.004" ) in diameter or even smaller. The rings 10 circumferentially support the screening basket. A number of vertical slotted-ribs 15 position and further support the horizontal rings. The rings and slotted ribs form a support structure in which the screening basket 20 is positioned. The vertical ribs contain slots 17 which are evenly spaced and into which the rings fit for easy assembly and control of the ring spacing. The ring thickness is maintained to a minimum and the vertical ribs are positioned so that they do not come in contact with the basket 20 in order to maximize the open area. The vertical ribs extend from a top mounting flange 22 to a bottom mounting flange 23 and are also further designed to withstand any vertical compression that the basket may be subjected to. Vertical precompression of the basket is sometimes necessary to prevent torsional vibration.
The top and bottom mounting flanges may also be used to mount the screening basket within the Fibresaver drum (not shown). In typical use the fiber containing liquor is introduced into the Fibresaver drum at the top and passes through the central portion of the screen to an outlet at the bottom of the drum. Liquid filtrate extracted from the liquor passes through the screening basket and generally exits a port in the side of the drum. The recovered fiber exits the bottom of the drum in the conventional manner well known to Fibresaver drum technology.
FIG. 2 shows an alternate embodiment for the support structure wherein a rib 11 of substantially triangular cross section is spot welded to a vertical support rib 16 which in turn is disposed between a top and bottom flange 22, 23 respectively. FIG. 3 shows the cross section taken at Section 3--3 of FIG. 2 and shows a suggested radial spacing of the vertical ribs.
FIG. 4 shows a second alternative embodiment wherein vertical ribs 12 are in contact with the screening basket 20. The vertical ribs of this embodiment are supported and evenly spaced by horizontal slotted rings.
A third alternate embodiment is shown in FIGS. 5 and 6. In this configuration the thin perforated screenplate 20 is supported by a series of vertical support rods 25 which in turn are supported by a perforated cylindrical plate support frame 26. As shown in FIG. 5 the screen is attached at its end to a cylindrical spacer 30 for screen support. Vertical support rods 25 are suitably spaced and disposed within the external gap formed between the screen and the cylindrical support frame or plate 26. The support frame 26 may be constructed from a rolled cylindrical plate having relatively large holes or other shaped openings. These openings would be staggered so that they do not line up vertically. In construction the thin screening plate may be attached by electron beam or resistance welding or the like to the series of support rods. The screenplate 20 and rod 25 assembly can be rolled to the required curvature and assembled to the support frame 26 by means of attaching the rods to the support frame. To facilitate this a vertical strip 27 is provided to locate the screen. 15 FIG. 7 shows a fourth alternative embodiment wherein: the principle employed is that wire 30 is wound spirally around a cylindrical screenplate 20 such as to resist bursting (and/or buckling) forces in a radial direction. The pitch of the spiral being selected to suit the permissible unsupported span of the perforated plate. The outer strips 35 provide axial stiffness together with torsional stiffness in both directions to resist buckling and twisting.
The spirally reinforced assembly may be manufactured as follows: using a mandrel to ensure accurate dimensions the screenplate is formed into a cylinder around the mandrel and seam welded; then the top mounting flange 22 and bottom mounting ring (not shown) are weld assembled to the cylinder; next, the reinforcing wire may be wound spirally around the apertured length of the screen cylinder and attached by resistance welding; and finally the relatively wide and thin outer reinforcing strips 35, having been preformed to a spiral shape, are resistance welded to the spiral wires 30 at each crossing and welded to the mounting flanges. Note that a single or multiple start helix may be selected formed or wound to any desired pitch to accomplish the degree of stiffness, stability, and support required.
Compared to a conventional rolled and welded thick screenplate having machined fine slots, the overall radial thickness of the spirally reinforced assembly will not be significantly greater, and the radial dimensional accuracy of the screening surface will be significantly better. That is, it can be physically interchangeable with, and be more accurately made than, a conventional screen cylinder.
Additionally, all embodiments may make the practical use of other, novel thin screenplates. For example, a screenplate requiring very fine slots for the mainline screening of papermaking pulp can be made more precisely and cheaply from thin compared with conventional thick material. Further, for many applications thin screenplates may enable economical use of more wear resistant material which is expensive and/or difficult to manufacture from thick plate. Furthermore, for screening operations in which unconventional shape, orientation and/or pattern of apertures may be required, a thin screenplate permits economical machining by ECM and EDM techniques, and also facilitates economical three dimensional press forming when an irregular surface is required.
Having described our invention in terms of several embodiments above we do not wish to be limited in the scope of our invention except as claimed.
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A support structure for thin screenplates utilized for fine screens in Fibresaving applications for pulp fiber suspensions or the like wherein a support structure having a screen support in minimum screen contact positioned by a support reinforcement and positioning device, assembled to form an integral structure which reduces the stresses and deflections in the thin screenplates occurring in operation.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority to U.S. Provisional Application Ser. No. 61/040,353 entitled “BIOADHESIVE APPLICATOR FOR ENT SURGERY” filed Mar. 28, 2008 by Sean T. Dycus, which is incorporated by reference herein.
BACKGROUND
[0002] 1. Technical Field
[0003] The present invention relates generally to electrosurgical coagulators and, more particularly, to an electrosurgical suction coagulator having a medicinal fluid applicator assembly.
[0004] 2. Description of Related Art
[0005] Electrosurgical suction coagulators that coagulate tissue have been available for some time. Generally, these devices include a conductive suction tube having an insulating coating over all but a most distal portion of the tube so that the distal portion forms a generally annular ablating electrode. A suction source is attached to a proximal portion of the tube for evacuating excess fluid and debris from the surgical site through the distal end of the tube.
[0006] The coagulation of bleeding blood vessels and tissue using electrically conductive suction tubes is a technique, which has been widely used in the medical field, particularly electrosurgery, for some time. Typically, a combination electrocautery and suction device is employed during ear, nose and throat (ENT) surgery whenever excessive blood and tissue debris must be removed from the bleeding site in order to facilitate hemostasis of any bleeding vessels. After removing or treating tissue or organs, such as tonsils or adenoids, a medicinal fluid (e.g., bioadhesive fluid) may be applied to facilitate healing.
[0007] Typically, the user must stop the coagulation and/or the suction procedure, remove the coagulation instrument, insert a bioadhesive applicator and release the bioadhesive material to or into the tissue. If the user decides to perform an additional coagulation and/or suction treatment, the coagulation instrument must be redeployed to the tissue site, thus making it more time consuming for the user and patient and possibly complicating the surgical procedure.
SUMMARY
[0008] The present disclosure relates to an electrosurgical suction coagulator and includes a housing having an elongated electrode and a fluid applicator. The elongated electrode includes distal and proximal ends and is adapted to connect to an energy source, for example, an electrosurgical generator. The proximal end of the elongated electrode is configured to operably couple to a distal end of the housing. Further, the distal end of the elongated electrode is configured to apply energy to tissue. The elongated electrode also includes a lumen defined therethrough, that is operably coupled to a vacuum source. The fluid applicator assembly is operably coupled to the elongated electrode and includes a container defining a reservoir configured to hold a bioadhesive therein. The bioadhesive is selectively dispensable from the container to deliver the bioadhesive to a surgical site.
[0009] In embodiments, the fluid applicator assembly includes a seal or valve to selectively regulate the flow of bioadhesive to the surgical site. Further, the fluid applicator assembly may include a container or bladder that is compressible to expel the bioadhesive from the container to the surgical site. The fluid applicator assembly may include an actuator that is moveable from a first position, wherein the bioadhesive is maintained in the container, to a subsequent position to incrementally dispense the bioadhesive to the surgical site. Such devices may include a plunger or syringe-like assembly.
[0010] In other embodiments, the fluid applicator assembly may include an actuator that is motorized. For example, the actuator may include a motorized screw-like element that forces the bioadhesive from the container to the surgical site. A control switch, that is mounted on the housing, may operate the motorized actuator. The motorized actuator may be adapted to connect to the same electrical energy sources as the electrode or an independent electrical source.
[0011] These and other objects will be more clearly illustrated below by the description of the drawings and the detailed description of the various embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the present disclosure and, together with a general description of the disclosure given above, and the detailed description of the embodiments given below, serve to explain the principles of the present disclosure.
[0013] FIG. 1 is a perspective view of one embodiment of a surgical coagulator in accordance with the present disclosure showing a bioadhesive material applicator assembly (in phantom) disposed within a housing of the surgical coagulator;
[0014] FIG. 2A is a perspective view of the bioadhesive material applicator assembly of FIG. 1 ;
[0015] FIG. 2B is a perspective view of an alternate embodiment of a bioadhesive material applicator assembly;
[0016] FIG. 3A is a side view of a surgical coagulator showing an alternate embodiment of a bioadhesive applicator assembly in accordance with the present disclosure wherein the applicator assembly is disposed outside the housing of the surgical coagulator;
[0017] FIG. 3B is a side view of a surgical coagulator showing an alternate embodiment of a bioadhesive applicator assembly in accordance with the present disclosure having a syringe-like actuating pump for dispelling the bioadhesive to the tissue site; and
[0018] FIG. 3C is a side view of a surgical coagulator showing an alternate embodiment of a bioadhesive applicator assembly in accordance with the present disclosure having a motorized screw-like pump for dispelling the bioadhesive to the tissue site.
DETAILED DESCRIPTION
[0019] Embodiments of the presently disclosed electrosurgical instrument are described in detail with reference to the drawing figures wherein like reference numerals identify similar or identical elements. As used herein, the term “distal” refers to that portion of the instrument, which is further from the user, while the term “proximal” refers to that portion of the instrument, which is closer to the user.
[0020] FIG. 1 sets forth a perspective view of an electrosurgical coagulator according to the present disclosure and is depicted generally as 10 . The electrosurgical coagulator 10 includes a housing 12 having a handle 14 and proximal and distal ends 16 and 18 , respectively. An elongated suction tube electrode 30 is fluidly and electrically coupled to a port or opening 20 defined in the distal end 18 of the housing 12 and extends therefrom. Suction tube electrode 30 may be selectively engageable with housing 12 or integrally formed therewith depending upon a particular purpose.
[0021] The suction tube electrode 30 includes an elongated tubular hollow shaft 32 having proximal and distal ends 34 and 36 , respectively that may, for example, be constructed from a conductive metal that is partially covered by an insulative material to prevent electrical continuity along shaft 32 . The distal end 36 is exposed to include a blunt electrode 38 that is configured and dimensioned to perform various electrosurgical coagulation procedures (e.g., tonsillectomy, adenoidectomy, etc.). The electrode 38 of the distal end 36 may be substantially blunt, rounded or include a pattern of protuberances to facilitate coagulation of tissue at or adjacent the distal end 36 when activated by the user. Suction tube electrode 30 is configured to electrically interface via the hollow shaft 32 to an electrosurgical generator 50 via one or more cables 52 .
[0022] In embodiments, the generator 50 may control the amount of electrosurgical energy delivered to the tissue based on one or more electrical parameters via one or more sensors coupled to a feedback circuit. For example, the generator 50 may regulate, measure, monitor and/or control one or more of the following electrical or electromechanical parameters: electrical intensity, voltage, current, pulse rate, waveform, temperature and/or impedance. A return pad (not shown) may be utilized to complete the electrical circuit through the patient and the generator 50 may be configured to include patient return pad monitoring such as the system commonly sold under the trademark REM™ by Valleylab, Inc., of Boulder, Colo.
[0023] Suction tube electrode 30 includes an aspiration port 38 a defined through the distal end 36 of suction tube electrode 30 . Aspiration port 38 a is configured to facilitate the removal of surgical fluids and debris from the surgical site. In embodiments, the aspiration port 38 a may be disposed through a side of suction tube electrode (not shown). More particularly and as shown in FIG. 1 , the suction tube electrode 30 is connected in fluid communication to a source of negative pressure, i.e., vacuum 60 , which draws air and fluid into the aspiration port 38 a and into the vacuum via hose or tube 62 upon activation by the user. Aspiration port 38 a may be chamfered, beveled or some other advantageous shape to create a smooth fluid stream therethrough and into the suction tube electrode 30 to facilitate fluid or debris removal. Moreover, suction tube electrode 30 may be made from a flexible and/or malleable material to give the user additional control of the coagulator 10 during use.
[0024] Housing 12 of the electrosurgical coagulator 10 also includes one or more control switches 22 a and 22 b which regulate the electrosurgical energy to the suction tube electrode 30 . Either one of the control switches, 22 a or 22 b , disposed on the housing 12 may be utilized to control coagulation of the instrument 10 , while the other control switch may be utilized to control suction of the instrument 10 . In embodiments, a rotating or sliding-type switch may be employed to accomplish this purpose. Moreover, a switch regulator or potentiometer (e.g., a voltage divider network—VDN) may be used to vary the electrosurgical energy and/or the relative suction through tube 30 .
[0025] Coagulator 10 includes a bioadhesive applicator assembly 40 operatively associated with the coagulator 10 . Bioadhesive applicator assembly 40 generally includes a bladder or housing 41 , which defines a reservoir 42 for containing a medicinal fluid 48 (e.g., a bioadhesive material). Reservoir 42 is disposed in fluid communication with a delivery lumen 44 defined between the bladder 41 and the suction tube electrode 30 . Fluid 48 is defined herein to include fluids and gels that are suitable for or compatible with coagulation surgical procedures (e.g., prior to, during or after application of electrical energy). Some examples of medicinal fluids include bioadhesive fluids and gels which are biomaterial surgical sealants and adhesion barriers developed by hydrogel technology focused on adhesion prevention, tissue sealing and hemostatic clinical application, such as gels sold under the trademarks DURASEAL®, SPRAYGEL® and MICROMYST™, manufactured by CONFLUENT® Surgical, Inc. of Waltham, Mass. (a wholly owned subsidiary of U.S. Surgical, a Tyco Healthcare Company). Other bioadhesive examples include hemostatic matrices such as FLOSEAL™ manufactured by Baxter International, Inc. and SURGIFLO™.manufactured by Johnson & Johnson.
[0026] Turning now to FIGS. 2A and 2B , alternative embodiments of the present disclosure are illustrated. The delivery lumen 144 , which includes proximal and distal ends, 144 a and 144 b , respectively, is attached in fluid communication with a distal end 143 of the reservoir 142 such that the delivery lumen 144 and the port 120 (not shown) align. A seal or plug 146 is disposed between the port 120 and the lumen 144 to allow selective expulsion of fluid 48 from reservoir 142 and for preventing fluid 48 from prematurely escaping from the reservoir 142 . Seal 146 is disposed on the proximal end 144 a of delivery lumen 144 in FIG. 2A , while seal 246 may be disposed on the distal end 244 b of delivery lumen 244 . In embodiments, seal 46 , 146 and 246 may be disposed in any suitable location within bioadhesive applicator assembly 40 , 140 and 240 , respectively, such that fluid 48 is contained for selective application within the respective reservoir 42 , 142 and 242 . When pressure is applied by the user, the seal (e.g., seal 46 ) is configured to either break or open to force the bioadhesive material 48 from reservoir 42 . Seal 46 may be a valve, to allow the user to selectively control the expulsion of fluid from reservoir 42 (e.g., duck bill valve, iris valve, etc.).
[0027] As seen in FIGS. 3B-3D , alternative embodiments of electrosurgical coagulator 10 are shown generally as 300 , 400 and 500 . The electrosurgical coagulators 300 , 400 , and 500 are similar to the coagulator 10 and will only be discussed in detail to the extent necessary to identify differences in construction and operation.
[0028] Electrosurgical coagulator 300 includes housing 312 and suction tube electrode 332 that is attached on the distal end 318 of the housing 312 . Suction tube electrode 332 fluidly and electrically couples to housing 312 in a similar fashion as described above, with reference to coagulator 10 . An external fluid applicator assembly 340 , that includes a container, well or bladder 341 defining a reservoir 342 for containing fluid 48 is operatively attached to housing 312 via delivery lumen 344 . The delivery lumen 344 has external and internal segments, 344 a and 344 b , respectively. When the user manually squeezes (e.g., applies pressure) the external fluid applicator assembly 340 (e.g., a squeezable bulb), the fluid 48 contained within reservoir 342 is expelled through the external and internal delivery lumen, 344 a and 344 b , respectively, into the suction tube electrode 332 to the surgical site. A seal 346 is included, which ruptures or regulates the flow of fluid 48 from reservoir 342 .
[0029] FIG. 3B shows an alternate embodiment of a coagulator 400 according to the present disclosure wherein a bioadhesive applicator assembly 440 is disposed within the housing 412 of suction coagulator 400 . The bioadhesive applicator assembly 440 includes a container 443 having a reservoir 442 with a syringe-like or plunger-like actuator 441 for dispensing the fluid 48 from reservoir 442 . More particularly, the plunger-like actuator 441 includes a plunger head 445 that is configured and dimensioned to slidably fit within reservoir 442 . The plunger head 445 is selectively movable from a first configuration wherein the fluid 48 is maintained within reservoir 442 to subsequent positions wherein incremental amounts of fluid 48 are dispensed through lumen 444 and tube 432 to the surgical site. In embodiments, the syringe reservoir 442 may be pre-packaged with a particular medicinal fluid 48 and then inserted within the housing 412 , either by the user or the manufacturer. In embodiments, the user manually operates the plunger head 445 to force the fluid 48 to break and/or open seal 446 similar to the seals described above.
[0030] FIG. 3C shows yet another embodiment of a coagulator 500 according to the present disclosure, which includes a motorized actuator for dispensing fluid 48 to the surgical site. More particularly, the bioadhesive applicator assembly 540 includes a motorized pump or actuator 541 that forces the fluid 48 from reservoir 542 through lumen 544 , into suction tube electrode 532 and to the surgical site, Any suitable motorized pump may be used to drive the fluid 48 to suction tube electrode 532 . Actuator 541 may be powered by the generator 50 ( FIG. 1 ) with one or more controllers or buttons 522 a , 522 b attached therebetween or to the housing 512 . A control wire or connector 560 may connect the button, e.g., 522 a , to the actuator 541 . The motorized applicator assembly 540 may alternatively be separately powered (e.g., battery powered). As shown in FIG. 3D , a screw-like actuator 541 rotates a screw gear 549 that drives fluid 48 from the reservoir 542 through the delivery lumen 544 and a seal 546 . The fluid 48 then flows through the delivery lumen 544 through the suction tube electrode 532 and to the surgical site. The user can selectively regulate the amount of fluid 48 dispensed by controlling the screw 549 or the seal 546 or combinations thereof.
[0031] From the foregoing and with reference to the various figure drawings, those skilled in the art will appreciate that certain modifications can also be made to the present disclosure without departing from the scope of the present disclosure. For example, in embodiments, the coagulator may be manufactured such that the coagulator is disposable, reusable or reposable. Also in embodiments, a variety of different or interchangeable suction tube electrodes could be selectively attached to the distal end of the coagulator housing depending upon a particular purpose or to meet a particular surgical need. Additionally, in other embodiments, the suction coagulator, the electrode, and the fluid applicator assembly may be manually or remotely operated by the user by either a footswitch, or as mentioned above, a controller disposed on the instrument.
[0032] Referring back to FIG. 1 , the suction coagulator 10 is shown having an internal compressible reservoir 42 disposed within the housing 12 . As mentioned above, reservoir 42 may be disposed in any suitable location within the housing 12 . The bottom portion of the housing 12 may be rubberized and integrated with the reservoir 42 , so that when the user manually applies pressure to the reservoir 42 , the bioadhesive fluid 48 is forced out the length of the delivery lumen 44 , through the suction tube electrode 32 and out the aspiration port 38 a for application to the surgical site.
[0033] In addition and although not shown, one or more of the actuators described herein on the bladder shown in FIG. 3B may be configured to provide a small amount of negative pressure (e.g., take in fluid) when release to limit unintentional leakage of additional fluid 48 to the surgical site.
[0034] Although the generator and vacuum are depicted as separate elements in FIG. 1 , a vacuum may be included with the generator in particular embodiments.
[0035] While several embodiments of the disclosure have been shown in the drawings, it is not intended that the disclosure be limited thereto, as it is intended that the disclosure be as broad in scope as the art will allow and that the specification be read likewise. Therefore, the above description should not be construed as limiting, but merely as exemplifications of embodiments. Those skilled in the art will envision other modifications within the scope and spirit of the claims appended hereto.
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The present disclosure relates to an electrosurgical suction coagulator and includes a housing having an elongated electrode and a fluid applicator. The elongated electrode includes distal and proximal ends and is adapted to connect to an energy source, for example, an electrosurgical generator. The proximal end of the elongated electrode is configured to operably couple to a distal end of the housing. Further, the distal end of the elongated electrode is configured to apply energy to tissue. The elongated electrode also includes a lumen defined therethrough, that is operably coupled to a vacuum source. The fluid applicator assembly is operably coupled to the elongated electrode and includes a container defining a reservoir. The reservoir is configured to contain a bioadhesive therein. The selectively dispensable from the container to deliver the bioadhesive to a surgical site.
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REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of U.S. patent application Ser. No. 08/738,034, filed Oct. 24, 1996, now U.S. Pat. No. 5,789,756.
FIELD OF INVENTION
The present invention relates to measuring nanometric distances between objects, particularly an optical apparatus for measuring a gap between a magnetic transducing head and a transparent medium as they move relative to one another. More specifically, the invention relates to an apparatus for measuring the flying height and orientation of a magnetic head with respect to a test disk in a flying-height tester.
BACKGROUND OF THE INVENTION
Most computer systems include a data storage device comprising of a rotating magnetic coated disk and a transducer for reading and writing information stored on the magnetic material of the disk. Such systems are normally characterized by storage density, access speed to data locations, reliability, and data integrity. One of the principal parameters which significantly affects the system characteristics is the position of the magnetic transducing head relative to the rotating disk. The relative air flow between the disk rotating at a high rate and a head biased toward the disk causes the head to fly on an established cushion of air. Generally, the smaller is the head-to-disk spacing the higher is accuracy of transduction of information stored on the disk. The head-to-disk spacing referred to as the "head gap" or a "flying height" for conventional high performance systems is on the order of several tens of nanometers. Flying aerodynamics vary for different heads, disks, rotation speeds resulting in different flying heights and head orientations. Therefore, in the design process, as well as in production, it is important to provide precise control of the flying height and orientation of the head to meet desired performance criteria.
At the present time, several optical techniques are used to measure a nanometric gap between a magnetic head and a rotating magnetic disk.
One measuring method is based on optical interferometry. This method uses a mutual interference effect wherein two optical beams produce lines, bands, or fringes which are either alternately light and dark or variously colored. In order to measure a gap between two objects having nearly parallel mutually facing surfaces, where one of the objects is transparent, a beam of light is directed into the gap to be measured through the body of the transparent object in such a way that the axis of the beam is essentially normal to the facing surfaces. Beams reflected from the surfaces of both objects are superimposed at a detector element and the interference fringes are read. It is known from optics that the detected light intensity depends on the ratio of the path difference between two beams to the radiation wavelength. This relationship is used as a calibration table for gap measurements as the path difference between the beams is twice the gap.
A particular application of optical interferometry for measuring the nanometric gap between a magnetic head and a flat reference disk made of an optically transparent material such as glass is disclosed in U.S. Pat. No. 4,813,782 issued in 1989 to Yagi et al. In the apparatus described in this patent, the operating conditions of a hard disk drive are simulated by rotating a reference disk with a high speed, and a magnetic head to be tested is biased toward the reference disk, e.g., by a spring, and flies above the disk on a dense air cushion. As a disk is rotating, a light beam is directed through the transparent reference disk from the side opposite to the magnetic head. The beams reflected from the surface of the disk and the surface of the head interfere with each other producing interference fringes. These fringes are detected and analyzed for determining the gap between the magnetic head and the reference disk using a calibration curve.
The main drawback of the above method is inaccuracy of the calibration curve near its maximum and minimum points, where measurement accuracy is significantly low due to small changes in the signal with the variation of the gap (so called "flat regions" of the calibration curve). This problem is especially pronounced in systems based on the above principle and intended for measuring head gaps that are much less than one quarter of the optical wavelength. Moreover, commercially available devices are unable to take measurements at several points on the magnetic head at the same time. Therefore, time consuming point-by-point measurements have to be performed in order to obtain a map of surface-to surface proximity.
Another optical method that is used to measure the gap between objects is based on a phenomenon known as "frustrated" total internal reflection. Total internal reflection is observed when electromagnetic radiation (e.g., a light beam) is incident on an interface between two media at an oblique incidence angle. If the radiation propagates from the side of the optically denser of the two media, e.g., the medium having the higher index of refraction of the two referred to below as the first medium, and the incidence angle exceeds (as measured from the propagation axis) a certain critical value that depends on the ratio of the refractive indexes of the two media, all radiation is reflected back to the first medium and none enters the other, or second medium, and the reflection is "total".
However, if the second medium is a thin film, followed by a third medium, which has a higher refractive index than the first medium, a part of the incident radiation is reflected back into the first medium, but a part propagates into the third medium. In other words, the internal reflection is not total and therefore is called a frustrated total internal reflection even though the angle of the incident radiation and the indices of refraction of the first and second media would appear to be appropriate for total internal reflection. In this case of the frustrated total internal reflection, a fraction of radiation reflected back into the first medium depends on a ratio of the thickness of the second medium to the radiation wavelength, a complex refractive index of the third medium, and polarization of the incident radiation. Such systems are more sensitive to the variation of nanometric gaps and therefore are suitable for measuring the "flying height" between a magnetic head above a reference disk with higher accuracy than the apparatuses based on the principle of optical interference.
An apparatus which determines the proximity of a stationary glass surface to another surface using the phenomenon of frustration of total internal reflection is disclosed in U.S. Pat. No. 4,681,451 issued to Guerra et al in 1987. In the apparatus, a glass block is used to substitute a conventional magnetic head. Its spacing from a magnetic disk is then imaged by a video camera detecting intensity distribution of the light reflected back into the glass. The magnetic disk may be rotated to simulate aerodynamic characteristics.
The main disadvantage of this proximity imaging device is its inability to test dynamic behavior and to measure the flying height of an actual magnetic head, as may be needed by a magnetic head manufacturer, or a consumer, for quality control purposes. Even though some of the conditions inside a disk drive can be simulated by executing a replica of the head in glass, the results obtained in this manner are inaccurate. Furthermore, because the size and mass of the optical system required is substantial, the device can not be used to test miniature flying magnetic heads, nor can it exhibit the dynamics of an actual spring mounted head weighing a small fraction of a gram. Thus, the apparatus cannot be used to test the characteristics of an a actual head.
A different apparatus which determines the proximity of a rotating glass surface to another surface using frustrated total internal reflection is disclosed in U.S. Pat. No. 5,257,093 (issued to Mager et al in 1993). In that patent, a device is used to determine the gap between a real magnetic head and a surrogate magnetic disk, represented by a pair of glass lenses. One of the glass lenses may be set into motion to develop aerodynamic characteristics establishing the spacing between the surface of the glass lens and the magnetic head close to the actual device. The stationary second lens with two prisms is used to couple illumination energy into the surface undergoing frustration of the total internal reflection and to view and measure resulting internal reflection for purposes of determining the distance to the head.
Two lenses and two prisms required by this apparatus are physically large and heavy. The apparatus needs complicated alignment of prisms mounted to one of the surfaces. In order to withstand relative motion at several thousand revolutions per minute, these lenses must be fabricated to severe tolerances and must be placed in a strong housing in case they are broken while rotating. Furthermore, the rotating lens is subject to rapid deterioration and, therefore, requires frequent replacement. The replacement is followed by the procedure of full and complicated alignment. Thus, such system is costly, complicated and has a limited scope of application.
The above problem is solved in an apparatus described in a pending U.S. patent application Ser. No. 08/476,626, now U.S. Pat. No. 5,677,805 of the same applicant, incorporated herein by reference. The apparatus described in that application utilizes an extremely simple single flat reference disk made of a transparent material such as glass. Light enters the disk from one side of the disk at an angle to the flat surface higher than the critical angle of the total internal reflection and propagates through the glass. When a magnetic head approaches the flat surface of the disk, frustration of the total internal reflection takes place. It is also known from the field of optics that the phenomenon of the frustrated total internal reflection is always accompanied by so-called photon-tunneling effect. This effect consists in ability of light to penetrate from a first medium to a third medium through a thin a thin second medium. The intensity of the light penetrated through the thin second medium, which in the case under consideration is a gap between the magnetic head and the reference disk, is complementary to the intensity of light reflected back into the reference disk in the case of the aforementioned frustrated total internal reflection.
In the apparatus of U.S. patent application Ser. No. 08/476,626, the proximity of the magnetic head to the disk is measured as intensity of the light that left the disk due to photon tunneling and was scattered by the surface of the magnetic head. As the disk is transparent, the scattered light is measured by a detector located on the side of the disk opposite to the head.
Although this measuring system is extremely simple and inexpensive, it produces a rather weak signal which is difficult to detect on a background of the noise. Such systems are suitable for testing small-batch production of magnetic heads, i.e., for conditions where the manufacture of more sensitive and accurate measurement systems may appear to be economically unjustified.
OBJECTS OF THE INVENTION
It is an object of the present invention to provide an apparatus for measuring a flying height and orientation of a magnetic head relative to a reference medium which is characterized by high accuracy in measuring nanometric gaps on the basis of a frustrated total internal reflection.
Another object of the invention is to provide an apparatus for measuring the gap between the head and the reference disk at several points on the magnetic head at the same time.
Still another object is to obtain a map of a magnetic head to reference disk surface proximity during a short period of time.
Yet another object of the invention is to provide an apparatus which is suitable for testing dynamic behavior and measuring the flying height of an actual magnetic head.
Further object of the invention is to provide an apparatus which is small in size and light in weight, does not need a complicated alignment procedure, and may be manufactured without strict tolerances.
Another object is to provide the aforementioned apparatus which is inexpensive to manufacture and to operate and which has a wide scope of practical application.
Finally, it is an object of the invention to provide an apparatus of the aforementioned type which is characterized by a high signal-to-noise ratio and is suitable for testing magnetic heads in mass production.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic sectional view of the apparatus for measuring a flying height and orientation of a magnetic head with respect to a transparent disk in accordance with one embodiment of the invention.
FIG. 2 is a fragment top view of the apparatus of FIG. 1.
FIG. 3 is a schematic perspective view illustrating essential parts of the apparatus of FIGS. 1 and 2.
FIG. 4 is a schematic perspective view illustrating glass disk and a channel region inside where light is propagated.
FIG. 5a shows a sensing area of the apparatus in the form of a charge coupled device sensor array.
FIG. 5b shows a sensing area of the apparatus in the form of a fast photo-diode system.
FIG. 6 is a view similar to that shown in FIG. 1 but with another embodiment of means for attaching the transparent disk to the electric motor.
FIG. 7 is an alternative form of the invention including an apparatus of the form shown in FIG. 1 augmented by an apparatus of the form shown in U.S. patent application Ser. No. 08/476,626, augmented further by a processing network.
SUMMARY OF THE INVENTION
The invention provides an apparatus for measuring the flying height and orientation of a magnetic head relative to a transparent disk based on frustrated total internal reflection. In a preferred embodiment the apparatus comprises a housing that mounts an electric motor which rotationally supports the aforementioned disk. The disk has tapered lateral surface with light emitting means such as a laser installed on one side of the disk lateral surface and a light detecting means on a side of the disk diametrically opposite to the laser. The light is emitted from the laser and is directed to the disk perpendicular to the tapered lateral surface of the disk. The latter has a tapering angle of 45° so that the light is propagated through the body of the disk nominally with total internal reflection from two parallel surface of the disk into the body of the disk. As a result, when the magnetic head to be tested is absent, the light detecting means shows an area of homogeneous intensity of the reflected light. When, however, the magnetic head approaches to the surface of the disk and is supported during rotation of the disk at a flying height, i.e., on an air cushion, the proximity of the head frustrates the total internal reflection. As a result, the intensity of the reflected light sensed by the detector is reduced. The degree of this reduction can be translated through appropriate electronic means and computer into the value of the flying height. Another form of the invention includes the above described apparatus, augmented by an apparatus of the form disclosed in U.S. patent application Ser. No. 08/476,626, augmented further by a processing network, for example, an averaging network. That dual mode configuration can provide separate measures of flying height for each mode alone, or a single composite measure of the flying height, which may be a weighted or unweighted average of those measures, as desired. Thus, the dual mode or two sub-system apparatus forms a flying height measuring system including the advantages of both of the apparatus described hereinabove and thus disclosed in U.S. patent application Ser. No. 08/476,626. The output signals may be combined and processed to obtain an improved measure of flying height.
DESCRIPTION OF THE PREFERRED EMBODIMENT
An apparatus made in accordance with one embodiment of the invention for measuring a flying height and orientation of a magnetic head with respect to a transparent reference disk is shown in FIGS. 1 through 3. The magnetic head has an index of refraction IR. FIG. 1 is a schematic side sectional view of the apparatus of the invention along the line I--I of FIG. 2, FIG. 2 is a top view of the apparatus of FIG. 1, and FIG. 3 is a perspective view of components of the apparatus of FIGS. 1 and 2.
As can be seen from the drawings, the apparatus has a housing 10 that supports an electric motor 12 with a vertically oriented and upwardly directed output shaft 14 having an axis of rotation Z. A spindle 16 is connected to output shaft 14 and supports a mounting plate 18.
A transparent reference disk 20 is attached to mounting plate 18 by means of four pins 19a, 19b, 19c, and 19d positioned on a rotary drive and support assembly. The disk 20 is extending into correspondingly positioned recesses in the surface 20b. The center of the disk coincides with axis of rotation Z. The pins 19a through 19d are equally displaced from a rotation axis Z leaving the center interior region of disk 20 transparent to propagation of the light. As shown, the pins 19a, 19b, 19c and 19d extend partially through disk 20. Disk 20 is a conic frustum having two parallel surfaces, i.e., a first plane surface 20a and a second plane surface 20b, and a lateral tapered surface 20c between first surface 20a and second surface 20b. In the illustrated embodiment, tapering surface 20c converges in the downward direction at an angle equal to 45° to the planes of first and second surfaces 20a and 20b. The entire surface of disk 20 is polished to optical quality of 1 nm rms or higher. A diameter D1 of first surface 20a of disk 20 and a diameter D2 of second surface 20b of disk 20 are equal to an even number of the disk thicknesses T, and preferably D1-D2=2T. In the preferred embodiment disk 20 is made of glass, preferably, of the type of a glass used as a substrate in conventional magnetic disks. The index of refraction of the disk glass IR1 is about 1.52, where IR1 is less than IR. The disk 20 is optically transparent at least in the channel region 49.
The apparatus also contains an illumination assembly 22 that is secured in housing 10, e.g., by bolts (not shown in the drawing). Illumination assembly 22 consists of a light source such as a laser 24, e.g., a semiconductor diode laser (with the wavelength of 670 nm) driven by a power supply 25 and am associated coupler for coupling light to the interior of disk 20. The coupler includes a collimating lens 26, and a plano-concave lens 28. Laser 24, collimating lens 26, and plano-concave lens 28 are arranged sequentially in the direction of light emitted from laser 24. Plano-concave lens 28 is made of the same material as disk 20. As can be seen from FIG. 2, plano-concave lens 28 has on its surface 28a facing the tapered surface of disk 20 the same curvature as the aforementioned tapered surface 20c. Surface 28a is spaced from tapered surface 20c at a very short distance of about 0.03 to 0.1 mm.
A detector assembly 30 is supported in housing 10 near tapered surface 20c on the side of disk 20 opposite to illumination assembly 22. Detector assembly 30 includes a coupler comprising a plano-concave lens 32, an interference filter 34, and a polarizing filter 36, and a detector 38, all aforementioned elements being arranged sequentially in the direction of propagation of the light from illumination assembly 22. Plano-concave lens 32 is made of the same material as disk 20 and has on its surface 32a facing the tapered surface of disk 20 the same curvature as the aforementioned tapered surface 20c. Surface 32a is spaced from tapered surface 20c at a very short distance of about 0.03 to 0.1 mm. Interference filter 34 passes only the light on the operation wavelength and cuts the light with other wavelengths, i.e., the background light.
In order to increase a signal-to-noise ratio, polarizing filter 36 is arranged to pass to detector only the light which is linearly polarized along the axis perpendicular to the surfaces 20a and 20b. Detector 38 generates a signal representative of light coupled from the disk 20. Detector 38 may be a rectangular charge coupled device (CCD) camera or a set of three fast photodiodes. Detector 38 is connected to a data analyzing unit, e.g., a computer 40 for analyzing output signals of detector 38. Computer has a display unit 42 that shows the results of the analysis, which are generally indicative of the position of the magnetic head relative to surface 20a.
A magnetic head 44 to be tested is mounted on a magnetic head support assembly in which a head loader 46 is fixed in a positioner 48 that allows accurate positioning of the head at any desired point above surface 20a of disk 20 and changing the angle of the head relative to the radius of disk 20--so-called "skew angle" of the magnetic head. The positioner suitable for this purpose may be the one described in U.S. Pat. No. 5,254,946 issued to the same applicant in 1993.
Disk 20 is rotated in a fluid environment A (FIG. 1), such as air, but may alternatively be a liquid contained in the interior of housing 10. It is essential for the material of disk 20 to have refractive index IR1 higher than that of the surrounding environment IR2. In case of air, the refractive index of the environment IR2 is equal approximately to 1.00.
DESCRIPTION OF THE APPARATUS OPERATION
For the beginning of the operation of the apparatus, light source 24 is switched on. As a result, a light from light source 24 passes through collimated lens 26 whereby the light is converted into a collimated light beam B having a diameter D equal to the side length L of surface 20c of disk 20 (FIG. 1). Plano-concave lens 28 allows for the beam to pass through tapered surface 20c in a collimated state (FIG. 2).
As can be seen from FIG. 1, beam B enters disk 20 perpendicular to surface 20c and at an angle of 45° to surfaces 20a and 20b that is higher than the critical angle 41° of total internal reflection from a glass-air interface. In FIG. 1, positions of such interfaces coincide with surfaces 20a and 20b. In other words, in the course of its propagation through the material of disk 20, light beam B undergoes multiple total internal reflections from surfaces 20a and 20b and has a saw-tooth like path. Light beam B propagates in a channel region 49 (FIG. 4) extending along and between overlying diameters of surfaces 20a and 20b.
Because, as has been mentioned above, diameters D1 and D2 of first and second surfaces 20a and 20b of disk 20 are equal to an even number of the disk thicknesses T the light exits disk 20 at the side of detector assembly 30 with the position of the beam on the exit surface being the same as on the entrance surface (FIG. 1). In other words, e.g., a light entering point a 1 on surface 20c on the light source side corresponds to light exit point a 2 on the detector side of surface 20c. Furthermore, the projection of beam B on surface 20a (FIG. 2) is symmetrical with respect to the disk center. As shown in FIG. 1, D1=6T and D2=4T where light beam B reflects three times at surface 20b. In an alternate embodiment where D1=4T and D2=2T, light beam B reflects only one time at surface 20b.
After exiting from disk 20, light beam B sequentially passes through plano-concave lens 32 that keeps it in a collimated state, interference filter 34, polarizing filter 36, and enters detector 38. The latter converts the signals of optical intensity of the beam into electrical signals that are sent to computer 40. Computer 40 analyses the electrical signals and shows the results of the analysis on display 42.
In the case of detector 40 in the form of a CCD sensor array, the results are displayed as a rectangular region 50 corresponding to the configuration of sensing area of the CCD sensor array. This is shown in FIG. 5a. In the event disk 20 is ideal and the light beam is homogeneous, the entire region 50 will have a constant brightness.
A head 44 is then accurately positioned with the use of aforementioned positioning mechanism 48 at a required place above the area of surface 20a corresponding to the projection of propagating beam B on surface 20a (FIG. 2). The magnetic head is then moved toward surface 20a of disk 20. Disk 20 is brought into rotation about central axis Z by motor 12 at a speed of about 4000 rpm, so that a relative air flow supports magnetic head 44 in a floating state on an air cushion, i.e., at a some distance from disk 20. This distance or gap G may be on the order of 20 to 30 nm. When gap G is small enough, frustration of the total internal reflection at the points under the head surface takes place. This decreases the intensity of light reflected from the surface 20a into the body of disk 20 in the area where head 44 is located. As a result, an image of head 44 will be reproduced on computer display 42 with a decrease of brightness in area of head 44 that are closer to surface 20a. These areas of reduced brightness are shown in FIG. 5a as strips 44a and 44b corresponding to projecting portions 44c and 44d of magnetic head 44.
As has been mentioned above, the aforementioned brightness has a functional dependence on a ratio of the gap to the optical wavelength, etc. Therefore the computer output data can be converted into absolute values of gap G.
As disk 20 rotates, for a part of the time, light beam B will be shuttered by pins 19 (FIG. 2). To avoid scattering of light and increase the signal-to-noise ratio, both source 24 and detector 38 are synchronously electronically shuttered for the time intervals when the beam encounters pins 19. For a CCD sensor array, the shuttering can be performed with the use of an electronic shutter that is normally an integral part of a standard CCD camera and therefore is omitted from the description. In the case of a laser source, shuttering can be achieved on a current-modulation principle by means of power supply 25 in a manner known in the art.
OTHER EMBODIMENTS OF THE INVENTION
The apparatus of the invention may have detector 38 in the form of a set of fast photodiodes. One embodiment of such a detector is shown schematically in FIG. 5b in the form of three fast small-area photodiodes P1, P2, and P3 located in specific points corresponding to specific points on surface 20a within the outlines of the projection of head 44 on surface 20a.
The apparatus of the invention with the detector of this embodiment operates in the same manner as the apparatus of the first embodiment, with the exception that the intensities of the light reflected from surface 20a are determined at the aforementioned three specific points. The intensities measured in the aforementioned points are recalculated through the known relationships into the values of gaps at these points. In other words, the measurement at three points provides complete information on the relative position and orientation of head surfaces 44c and 44d with respect to disk surface 20a.
FIG. 6 shows a third embodiment of the invention in which a disk 120 is covered on its bottom surface 120b with a reflection coating 121 and is attached, e.g., by means of an adhesive substance, to a support disk, e.g., another glass disk 123 which in turn is attached to a shaft 130 of an electric motor 132. In this embodiment, the apparatus is free of pins 19a, 19b, 19c, and 19d that shutter the light beam during rotation of the disk. Therefore in this embodiment, there is no need to shutter the detector and the light source. Otherwise, the system operates in the same manner, as described above.
FIG. 7 shows an alternate form of the invention system 110, which is similar to that shown in FIG. 1 but additionally includes a subsystem of the type disclosed in U.S. patent application Ser. No. 08/476,626. In FIG. 7, elements that correspond to elements in FIG. 1 are identified by the same reference numerals, and except for computer 40, those elements function as described above in conjunction with FIG. 1. System 110 further includes a detector 130 and assembly 140 which positions detector 130 to face toward the underside of disk 20, facing and in this embodiment axially aligned with, head 44. The detector 130 and assembly 140 correspond in function to detector 84 and assembly 16 disclosed in U.S. patent application Ser. No. 08/476,626.
Thus as head 44 is moved across the upper (as shown) surface of disk 20, the detector tracks that motion on the underside (as shown) of disk 20. The detector 139 detects the light that passes from the interior of disk 20 across the gap between the top surface of disk 20 and head 44, and is reflected back by head 44 across the gap, through the disk 20 and is incident on detector 130. As in the system disclosed in U.S. patent application Ser. No. 08/476,626, the detector 130 generates a signal representative of this light and transfers that signal to computer 40.
Computer 40 in one mode of operation independently determines separate measures of the gap g from each, the signals transferred by detector 130 and detector 30 (as described in connection with FIG. 1). In another mode, computer 48 combines the determined measures in a predetermined manner to obtain a single composite measure of the gap g. By way of example, the combination may be a simple average of the two independently obtained measures of g, or a weighted average, as desired.
With the form of invention of FIG. 7, the user may selectively determine the mode of operation of computer 40 to optimize the determination of the flying height of head 44 above disk 20.
BROADENING, RAMIFICATIONS, AND SCOPE
Thus it has been shown that the present invention provides an apparatus for measuring a flying height and orientation of a magnetic head relative to transparent medium which is characterized by high accuracy in measuring nanometric gaps on the basis of a frustrated total internal reflection. The apparatus of the invention allows measuring of the gap between the head and the reference disk at several points on the magnetic head at the same time. The invention also allows obtaining of a map of a magnetic head to reference disk surface proximity during a short period of time. The invention makes it possible to test dynamic behavior and measure the flying height of an actual magnetic head. The apparatus of the invention is small in size and light in weight, does not need a complicated alignment procedure, and may be manufactured without strict tolerances. The aforementioned apparatus is inexpensive to manufacture and to operate and has a wide scope of practical application. Finally, the apparatus of the invention is characterized by a high signal-to-noise ratio and is suitable for testing magnetic heads in mass production.
Although the invention has been described by way of practical examples with reference to specific embodiments, it is understood that the scope of practical application of the invention is not limited to these embodiments and that various modifications are possible without departure from the attached claims. For example, light source 24 may be an incandescent source or a light emitting diode, also it may include fiber optics. The lateral tapered surface of the disk may be coated with an antireflecting coating. Lenses 28, 32 and filters 34, 36 may be omitted at the expense of a worse spatial resolution and signal-to-noise ratio. Both CCD sensor array and a set of photodiodes may be combined into an integral system with the use of a beam splitter. In addition, the first and second planes of the disk may be reversed with respect to the position of the head. Furthermore, the angle between the tapering angle of disk 20 and the angle between the light beam B and plane surfaces 20a and 20b of disk 20 may differ from 45° at the expense of a worse signal-to-noise ratio.
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The invention provides an apparatus for measuring the flying height and orientation of a magnetic head (54) relative to a transparent disk (20) based on both frustrated total internal reflection and total internal reflection. The apparatus comprises a housing (10) that mounts an electric motor (12) which rotationally supports the aforementioned disk. The disk (20) has a tapered lateral surface (20c) with light emitting means (22) such as a laser (24) installed on one side of the disk lateral surface and a flat light detecting means (30) on a side of the disk diametrically opposite to the laser. A second light detector (130) is disposed on the other side of the disk (20) from, and opposite the head (54). The light is emitted from the laser (24) and is directed to the disk (20) perpendicular to the tapered lateral surface (20c) of the disk (20). When the magnetic head (44) to be tested is absent, the light detecting means (30) shows an area of homogeneous intensity of the reflected light. When, however, the magnetic head (44) approaches to the surface (20a) of the disk and is supported during rotation of the disk at a flying height, i.e., on an air cushion, the proximity of the head frustrates the total internal reflection. As a result, the intensity of the reflected light sensed by the detector (38) is reduced. The degree of this reduction and that detected by detector (130) can be translated through appropriate electronic means and computer (40) into the value of the flying height.
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FIELD OF THE INVENTION
The present invention relates to a method and apparatus for the continuous regasification of cryogenic fluids and liquefied natural gas (“LNG”) which relies only on ambient air as the heat source. The subject ambient air exchangers continuously heat the cryogenic fluid directly through the heat exchange elements without using an intermediate fluid and without forming ice or frost on the outer surface of the finned tube heat exchange elements.
BACKGROUND OF THE INVENTION
The convenience of transporting and storing industrial gases such as oxygen and nitrogen including LNG is well established. At the use site, the liquefied gas is stored in liquid form at a cryogenic temperature in the range of about −100° F. to −320° F. The liquefied gas is then vaporized and superheated to near ambient temperatures before use. Various heat sources are used to supply the heat for vaporization such as waste process heat, seawater, fired heaters and ambient air. For example, in the case of LNG which is used as a fuel gas, about 2% of the combustion heat of the fuel gas is required for vaporization of the LNG and, for this reason, ambient atmospheric air is a desirable heat source. In Patent Publication U.S. 2010/0043452 A1, Baudat uses water or other intermediate heat transfer fluid loop in which the water or heat transfer fluid is heated as the water is recirculated through an air tower. When the air is too cold, supplemental heat is provided to the process.
The disadvantage of using an intermediate heat transfer fluid loop in any heat transfer process, such as the water loop of Baudat, is that there is a temperature difference loss within each separate fluid (water) loop. These temperature differences are additive that reduce the useful range of the ambient air temperature which may be utilized economically in a process such as Baudat, notwithstanding the added complexity and cost of the apparatus.
In Patent Publication 2007/0214805 A1, Armstrong et al describes a shipboard LNG vaporizer using ambient air and an intermediate heat transfer fluid together with redundant vaporizers to allow for defrost cycles.
In Patent Publication 2010/02505979 A1, Gentry et al describes a heated fluid LNG regasification apparatus.
In Patent Publication 2003/0159800 A1, Nierenberg uses seawater as the heat source for LNG regasification.
In Patent Publication 2007/0214806 A1, Faka continuously regasifies LNG using ambient air together with an intermediate fluid heat transfer loop auxiliary heater wherein the ambient air heater is subjected to a defrost cycle.
In Patent Publication 2011/0030391 A1, Faka employs a mechanical device to remove frost from his continuous ambient air vaporizer and additionally adds an intermediate heat transfer fluid loop.
In Patent Publication 2010/0101240 A1, Mak describes a forced ambient air vaporizer wherein the moist air is dehydrated for subsequent use within his multi-chambered vaporizer system. A temperature control scheme maintains Mak's air above 32° F.; however, no instructions of fin surface temperature where ice may form is discussed in Mak's complicated and costly apparatus.
In Patent Publication 2009/0126372 A1, Faka describes a forced ambient air continuous regasifier that employs a source of heat to intermittently defrost his vaporizer.
Vogler, Jr. et al in U.S. Pat. No. 4,399,660 (1983) describe an ambient air vaporizer with a particularly wide space between their finned tube vaporizer elements to allow for ice growth therein. A steady state frost/ice layer is claimed.
At the AIChE May 2000 spring meeting, Paper #58e, PP 188-196, Bernert further discusses this ice growth problem.
In U.S. Pat. No. 3,293,871 (1966), Tyree, Jr. attaches fins to his vaporizer tubes, said fins being in thermal contact with the tube by suitable means such as soldering. A fan is used to provide a constant stream of ambient air across the fins. Tyree states that although he has ice growth, “it is highly unlikely” for the heat transfer surface to become iced over thus providing defrost means.
In U.S. Pat. No. 5,390,500 (1995), White et al describes various means to manage the ice growth common to ambient air vaporizers. Various concentric tubular assemblies are postulated which rely on flowing or stagnant gas layers combined with internally finned elements partially filled with various filler materials that are in contact with the fluid to be vaporized. It is well known that apparatus used for certain cryogenic liquefied gases such as liquid oxygen should avoid direct contact with such materials. A multiple tube combination is described to complete the apparatus.
In U.S. Pat. No. 3,124,940 (1964), Guelton describes a mechanical defrosting device for a Fan-Ambient air vaporizer thus illustrating an early awareness of the frost/ice formation problem associated with ambient air cryogenic vaporizers.
Booth, in U.S. Pat. No. 2,322,341 (1943), describes an extruded axially-finned aluminum heat exchange element for refrigerants to be evaporated. Such elements are presently used in many different embodiments in cryogenic vaporizers.
In U.S. Pat. No. 3,735,465 (1973), Tibbetts et al describes a finned tube assembly for use in cryogenic vaporizers wherein the extended surface portions are clamped or locked directly onto an elongated tubular member such that “complete contact” is made between the surface to achieve “optimum heat transfer characteristics” and thus “minimizing the thermal contact resistance between the tubing and the hub”. When assembled into a multi-element vaporizer, a fan may be employed. Conversely rather than “minimizing the thermal resistance” of Tibbetts et al, the invention of the present application, as described and claimed, purposely introduces a particular thermal resistance to heat transfer to achieve improved performance.
Similarly to Tibbetts et al, Lutjens et al in U.S. Pat. No. 4,487,256 (1984) describes a clamped fin tube assembly for cryogenic ambient air vaporizers which describes less frosting in the hub area and further that the tube is in intimate contact with the outer sleeve halves to form a common forced ambient air cryogenic vaporizer heat exchange element. Mentioned also is the use of a “thin coating (0.001 inch-0.100 inch) of fluorocarbon or Teflon applied to the” internal cylindrical surface of the hub such that the layer is so thin that even only a temperature drop of 1° or (so) has been encountered across this film, which statement indicates a failure of the prior art to appreciate the nature of the frost growth problem in these vaporizers.
In Patent Application 2007/0214807 A1, Faka employs ambient air with an air heater to prevent icing in similar fashion as Katare does in Patent Application 2007/0250795 A1. In U.S. Pat. No. 8,069,678 B1 (2011), Bernert describes an improved regasification ambient air heat exchange element employing a thermally conductive adhesive to bond the inner fluid tubular conduit to the outer finned hollow bore heat transfer element to improve heat transfer between the ambient air and the cryogenic fluid again, as in Tibbetts above, accepting ice growth as a given to be accommodated with alternate design features.
The reason why atmospheric vaporizers are not used more widely for continuous service is because ice and frost build up on the outside surfaces of the vaporizer that are exposed to the moist ambient air. Not only does the ice inhibit effective vaporizer capacity, the weight of the ice creates a structural problem as well as requiring greater space or larger sized units (for example, in Vogler, Jr. described above) to accomplish a given rate of regasification. Where continuous operation is required, either auxiliary heat or switching redundant modules have been shown in prior art to be necessary.
For the foregoing reasons, there remains a need for a process and apparatus for regasifying or vaporizing cryogenic fluids using only ambient air in direct contact with the cryogenic heat exchange elements which apparatus permits ice-free/frost-free continuous operation of cryogenic fluid vaporizers that use only ambient air as the heat source.
OBJECTS OF THE INVENTION
Accordingly, it is an object of this present invention to provide a cryogenic fluid vaporizer that uses only ambient atmospheric air as the heat source.
It is another object of this invention to provide a cryogenic fluid ambient atmospheric air vaporizer which operates continuously without requiring periodic shutdown for deicing and avoiding the drastic reduction in the operating efficiency characteristic of prior art atmospheric ambient air cryogenic fluid vaporizers.
It is yet another object of this present invention to provide a cryogenic fluid vaporizer using only ambient atmospheric air as the heat source without the use of intermediate heat transfer fluids which ambient air-heated vaporizer operates without frost or ice formation on the heat exchange surface that is in direct contact with the atmospheric ambient air.
Another object of the present invention is to provide a frost-free ambient air cryogenic fluid vaporizer that utilizes a forced air draft means or fan.
Other objects, features and advantages of the invention shall become apparent as the description thereof proceeds when considered in connection with the accompanying illustrative drawings.
SUMMARY OF THE INVENTION
The above and other objects which will be apparent to those skilled in the art are achieved by the present invention which comprises an apparatus for continuously vaporizing a cryogenic fluid by employing only heat absorbed from the ambient atmospheric air, the apparatus comprising a least one or more heat exchange vaporizer elements which are connected together to form an ambient air cryogenic fluid vaporizer. Each heat transfer element is comprised of a central or inner tube contained within an outer tube or central hub with external heat exchange fins. The central tube, which may be of a suitable metal for cryogenic temperature, such as austenitic stainless steel, aluminum, monel or copper, has an outside diameter of from about 0.25 inch to 1.0 inch and preferably about 0.5 inch and is of sufficient thickness to contain the requisite cryogenic fluid supply pressure. The outer tube or central hub with external heat exchange fins into which the central tube is fully inserted has an inside diameter greater than the outside diameter of the central tube such that a gap results between the central tube outer surface and the inside surface of the outer tube or central hub. This gap, which may vary between about 0.005 inch and 0.05 inch and preferably about 0.015 inch, is filled with a thermal barrier material suitable for exposure to cryogenic temperatures which material has a thermal conductivity sufficient to effectively form a thermal barrier to the flow of heat between the cryogenic fluid that flows thru the inner tube and the ambient air which, by either natural or forced draft, flows over and in direct contact with the outer surface of the outer tube having external fins. Preferably, the element is formed of extruded aluminum having a central tubular hub having an internal diameter of about 0.53 inch for the 0.5 inch outside diameter fluid tube described above, and eight to twenty external axial aluminum fins which extend radially outward about three to four inches from the outer tube central hub, said fins being about 0.055 inch to 0.07 inch thick. Such preferred heat exchange vaporizer element would have a surface area ratio of external finned surface area divided by internal liner tube inside surface area of between about 70 to 130, with an overall length varying between four and forty feet.
The thermal barrier material has a relatively low thermal conductivity in the range of between 0.02 BTU/(HR) (FT) (Deg F.) and 0.07 BTU/(HR) (FT) (Deg F.), preferably about 0.05 BTU/(HR) (FT) (Deg F.). The thermal barrier in combination with both the configuration of the heat exchange element providing the above said surface area ratio and the heat transfer characteristics of the other elements of the overall heat exchange process is sufficient to provide a temperature drop from the external ambient air to the internal cryogenic fluid such that the outer finned surface exposed to the air is maintained at or above about 32° F. (the freezing point of water) and thus little or no ice forms on the outer surface of the outer finned tube. Such temperature drop varies based on the temperature of the cryogenic fluid, the temperature of the surrounding ambient air and the heat transfer coefficients of the overall process, for example, in the case of liquid nitrogen, the temperature drop is about 330° F. or in the case of the liquefied natural gas (LNG), the temperature drop is about 270° F.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings which illustrate the best mode presently contemplated for carrying out the present invention:
FIG. 1 is a side elevational view partially broken away of the cryogenic fluid vaporizer heat exchange element in accordance with the present invention;
FIG. 1A is an enlarged detailed view of the circled portion of FIG. 1 ;
FIG. 2 is a cross-sectional view of the heat exchange element taken along Lines 1 - 1 of FIG. 1 ;
FIG. 2A is an enlarged detailed view of the circled portion of FIG. 2 ; and
FIG. 3 is a side elevation view of a cryogenic fluid forced draft ambient atmospheric air vaporizer in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
In FIG. 1 , there is shown a side elevational view partially broken away of the cryogenic fluid ambient atmospheric air vaporizer heat exchange element of the present invention. FIG. 2 is a cross sectional view of the heat exchange element of FIG. 1 taken along the Lines 1 - 1 of FIG. 1 . The particular vaporizer heat exchange element 1 ( FIG. 1 ) comprises a central austenitic stainless steel tube 2 contained within a central tubular hub 3 with fins 4 , said hub with fins being formed of extruded aluminum. The central tube 2 extends the full length of central hub 3 including extended portions 7 and 8 at each end of central hub 3 . The central stainless steel tube 2 has an outside diameter D1 of from about 0.25 inch to about 1.0 inch and preferably about 0.5 inch and being of sufficient thickness to contain the cryogenic fluid supply pressure commonly about 0.049 inch thick to about 0.083 inches thick. The central tubular aluminum hub 3 into which the stainless steel tube 2 is fully inserted has a particular inside diameter greater than the outside diameter of tube 2 in order to form a gap 5 ( FIG. 1A ) between the outside surface of tube 2 and the inside surface of hub 3 . This gap 5 ( FIG. 1A ) may vary between about 0.005 inch and 0.05 inch preferably about 0.015 inch and is filled with thermal barrier material 6 , said thermal barrier material having a thermal conductivity of between about 0.02 BTU/(HR) (FT) (Deg F.) (where BTU is a British thermal unit, HR is hour, FT is feet and Deg F. is degrees Fahrenheit) and 0.07 BTU/(HR) (FT) (Deg F.), preferably about 0.05 BTU/(HR) (FT) (Deg F.). A wide range of thermal barrier material is available such as polyurethane foam sold under the name Stephan Foam 3X250A available from Stephan Chemical Company or alternatively polyimide foam sold under the name Solimide TA-301 available from Evonik Industries.
Ambient air cryogenic vaporizers generally are comprised of a multiplicity of the heat exchange elements 1 of FIG. 1 and are interconnected using manifolds or headers 9 such that the cryogenic fluid 10 is distributed in equal portions 10 A to the multiplicity of elements 1 .
In FIG. 2 is shown a cross-sectional view of the heat exchange element 1 , taken along Lines 1 - 1 of FIG. 1 . In this preferred embodiment, aluminum extrusion 11 is comprised of central tubular hub section 3 and a multiplicity of axial fins 4 which extend axially along the full length of extrusion 11 with such extrusion lengths being between four and forty feet. The fins 4 may number between about eight and twenty fins extending radially outward a distance of between about 2½ inches and 4 inches from central hub 3 . Fins 4 are between about 0.055 inch thick and 0.08 inch thick and may vary in thickness as they radiate outward from hub 3 with the thicker portion 11 A ( FIG. 2 ) at hub 3 and the thinnest portion 11 B ( FIG. 2 ) at the outer fin tip, and the tip may be rounded. Hub fins 4 are integral to central hub 3 and at the connection point 13 ( FIG. 2 ) may be rounded via a filled radius 14 that is common to the extrusion process. More clearly shown in FIG. 2 is gap 5 ( FIG. 1 ) formed between the outer surface of tube 2 and the inner surface of central tubular hub 3 with the gap being filled with thermal barrier material 6 as described above.
In FIG. 3 there is shown a side elevation view partially broken array of a cryogenic fluid ambient atmospheric air vaporizer 24 which, as shown, employs forced air means. In this preferred embodiment, as shown in FIG. 3 , forced draft air fan 20 is used to direct a stream of high velocity ambient atmospheric air 21 ( FIG. 3 ) over a multiplicity of vaporizer heat exchange elements 1 ( FIG. 1 ) said forced draft air stream 21 being forced in either axial direction over the exterior finned surfaces of vaporizer heat exchange elements 1 , said air stream flowing in controlled fashion within outer duct 22 which also passes through forced draft air transition duct 23 .
Cryogenic fluid 10 ( FIG. 3 ) enters manifold or header 9 ( FIG. 3 ) and is evenly distributed as equal fluid portions 10 A ( FIG. 3 ) to the multiplicity of heat exchange elements 1 ( FIG. 3 ) at tube extended end portion 7 of heat exchange element central stainless steel tube 2 ( FIG. 1 ). After being vaporized and superheated passing through stainless steel tube 2 ( FIG. 1 ) of heat exchange elements 1 ( FIG. 3 ), the cryogenic fluid 10 exits said elements at extended tube portions 8 ( FIG. 3 ) and exits vaporizer 24 via exit manifold or header 25 ( FIG. 3 ) as vaporized and super-heated fluid stream 10 B ( FIG. 3 ).
OPERATION OF APPARATUS
Referring to FIGS. 1-3 , the operation of the forced draft ambient atmospheric air cryogenic fluid vaporizer having a multiplicity of heat exchange elements 1 , are assembled together. The elements may number between 1 and about 150 and are enclosed within a forced air outer duct 22 ( FIG. 3 ). A fan 20 ( FIG. 3 ) is provided and attached to said duct 22 by means of transition duct 23 . In operation, said fan provides a forced draft air stream 21 flowing evenly over the exterior finned surface area of said multiplicity of elements 1 , said fan may force air stream 21 in either direction over elements 1 . It is well known that the forced draft air stream may increase the heat transfer rate from the air to the element outer surface significantly over a natural draft vaporizer by as much as ten to twenty times. The heat exchange element 1 of this invention as described above has an exterior finned surface area exposed to the air between about 70 to 130 times the interior surface area of the central stainless steel tube 2 ( FIG. 1 ), said interior surface area being exposed to cryogenic fluid 10 A. In combination, the apparatus can deliver heat from the air to the cryogenic fluid by about 1000 times greater than that of a simple tubular element which has a surface area ratio of about 1.25/1 exposed to natural convection ambient air. Without incorporating the further modification of providing a gap 5 ( FIG. 2A ) and the gap being filled with thermal barrier material 6 as embodied in this invention, frost and ice would form on the exterior surface of the finned elements as is well described in the prior art. Such an undesirable frost or ice layer would clog the heat exchange surface exposed to the ambient air thus making it difficult to achieve a compact, continuously operating cryogenic ambient atmospheric air vaporizer.
Further difficulties are encountered when a frost or ice layer forms on the external surface of the heat exchange element that is exposed to the ambient atmosphere air, which difficulties are inherent in the physical properties of the frost or ice itself. It has been established by those skilled in the art that frost or ice density, such as measured in pounds per cubic feet, is not a constant but will actually vary widely depending upon how, when and at what temperature the frost or ice was formed. Further, it is known that the thermal conductivity of the frost also varies widely in a similar manner. Likewise, the amount of frost as measured by pounds per hour formed on the cryogenic surface exposed to the air varies significantly depending upon the surface temperature of the element surface exposed to the air and the water content (defined as relative humidity) of the air stream. For these reasons, the performance of prior art cryogenic fluid ambient atmospheric air vaporizers will vary widely making predictable performance difficult. For this added reason, the frost-free vaporizer of this invention that has predicable, continuous and steady state performance characteristics is a desirable addition to the prior art.
The cryogenic fluid 10 ( FIGS. 1-3 ) enters manifold header 9 ( FIGS. 1-3 ), is evenly distributed in fluid portions 10 A, is vaporized and super-heated as it travels through central austenitic tubes 2 and exits said vaporizer 24 ( FIG. 3 ) via exit manifold 25 as vaporized and super-heated cryogenic fluid 10 B. With the introduction of thermal barrier material 6 ( FIGS. 1-2 ) to fill gap 5 ( FIGS. 1-2 ), a temperature drop occurs as heat passes from the ambient air through said gap to the cryogenic fluid. Since this insulating barrier gap is at the hub location 3 ( FIGS. 1-2 ) rather than as frost for example, on the external surface of fins 4 ( FIGS. 1-2 ) as, for example, in Vogler, Jr. described above, the significant advantages of the area ratio of between 70 and 130 of this invention combined with the controlled and known low thermal conductivity of said thermal barrier material now make possible a defined, controllable and significant temperature drop from the ambient air to the cryogenic fluid thereby permitting a frost-free ambient atmospheric air cryogenic fluid vaporizer not shown or described in the prior art.
EXAMPLE
Ambient air vaporizer heat exchange elements of prior art vaporizers without the thermal barrier of this instant invention were compared with the elements of FIG. 1 of this invention in a full-scale forced draft ambient air single element vaporizer apparatus essentially as configured in FIG. 3 above. Cryogenic liquid nitrogen at a temperature of about −300° F. was used as the representative cryogenic fluid 10 ( FIG. 1 ). The central extruded aluminum tubular hub 3 ( FIG. 1 ) was sized for a ½ inch outer diameter austenitic stainless steel tube 2 ( FIG. 1 ). The hub fins 4 ( FIG. 1 ) extended about 3⅝ inches radially outward. A forced draft air fan 20 ( FIG. 3 ), an outer duct 22 ( FIG. 3 ) and a transition duct 23 ( FIG. 3 ) completed the model vaporizer 24 ( FIG. 3 ).
For a test of prior art, a stainless steel tube 2 ( FIG. 1 ) was hydro expanded into hub 3 ( FIG. 1 ) to achieve a no gap intimate contact between the inside surface of the central aluminum hub and the outside surface area of the central austenitic stainless steel tube as is standard practice in prior art elements.
In this prior art test, the extruded aluminum hub had twelve fins, which number of fins provides a space between fins for frost growth. When tested with 78° F. entering air from fan 20 ( FIG. 3 ) and using liquid nitrogen entering tube 2 ( FIG. 1 ) at about −300° F.:
1) the frost thickness grew to about 0.4 inches thick on the outside surface of the hub fins 4 ( FIGS. 1-2 ) after 1½ hours of operation; 2) the pressure drop of the forced draft air passing through the outer duct 22 ( FIG. 3 ) increased from 0.5 IN W.C. (inches of water column) at the start, i.e. with no frost on the element to 0.9 IN W.C., after 1½ hours of operation; and 3) the nitrogen gas outlet temperature at location 10 B ( FIG. 3 ) decreased from about 70° F. at the start to about 61° F. after 1½ hours of operation.
This foregoing test confirmed that the vaporizer was building frost and was not operating in a steady state condition at any time and that a shutdown would be required for defrost.
To test a similar vaporizer element provided with the gap 5 and thermal barrier 6 ( FIGS. 1-2 ) of this invention, a similarly dimensioned aluminum extrusion was used in the apparatus, said aluminum extrusion had sixteen fins 4 ( FIG. 2 ) and the stainless steel liner tube 2 ( FIG. 1 ) had a gap 5 ( FIG. 1 ) between the stainless tube 2 and the aluminum tubular hub inside diameter of 0.012 inches and the gap 5 was filled with a thermal barrier material 6 ( FIG. 1 ) of this invention. When tested using cryogenic liquid nitrogen entering at about −300° F. on 80° F. entering air from fan 20 ( FIG. 3 ), no frost or ice formed on the exterior surface or fins 4 of extrusion 3 ( FIG. 1 ). This test was run for about 1 hour under stable operating conditions of 0.9 IN W.C. air duct pressure drop with a constant 78° exit nitrogen gas temperature. The aluminum surface temperature at the outside of the hub measured 32° F., with no water freezing on the surface. The stable operating condition while producing a frost-free vaporizer indicated that since operating conditions were stable, the vaporizer could continue to operate without shutdown for defrost and with a constant exit nitrogen gas temperature.
While there is shown and described herein certain specific structure embodying this invention, it will be manifest to those skilled in the art that various modifications and rearrangements of the parts may be made without departing from the spirit and scope of the underlying inventive concept and that the same is not limited to the particular forms herein shown and described except insofar as indicated by the scope of the appended claims.
DRAWING REFERENCE NUMERALS WORKSHEET
1 . Vaporizer heat exchange element
2 . Central austenitic stainless steel tube
3 . Central aluminum tubular hub
4 . Hub fins
5 . Gap between tube 2 and hub 3
6 . Thermal barrier material
7 . Extended end portion of tube 2
8 . Extended end portion of tube 2
9 . Manifold or header
10 . Cryogenic fluid
10 A. Cryogenic fluid equal portion
10 B. Vaporized and superheated cryogenic fluid
11 . Aluminum extrusion
11 A. Hub fin 4 thickness at hub
11 B. Hub fin 4 thickness at tip
13 . Hub fin 4 connection point to hub 3
14 . Extrusion fillet radius at hub 4
20 . Forced draft air fan
21 . High velocity ambient atmospheric air stream
22 . Forced draft air outer duct
23 . Forced draft air transition duct
24 . Forced draft atmospheric ambient air cryogenic fluid vaporizer
25 . Exit manifold or header
DEFINITIONS
For the purposes of this invention, certain terms used herein are defined as:
1. An ambient atmospheric air cryogenic vaporizer of the invention uses only air directly from the surrounding atmosphere at varying natural ambient temperatures and at the prevailing relative humidity, such air flows over and in direct contact with the exterior surface of the heat exchange elements by either the natural convection heat transfer process, or with the addition of an air moving fan to provide a forced draft or forced air convection heat transfer process. No additional or supplementary energy other than the fan, if used, is required. 2. Continuous vaporization means that the vaporization process may be operated for any desired length of time without shut down or interruption of the process, said vaporization process providing an outlet gas exit temperature which is stable at the given design condition of the apparatus, i.e., a steady state heat exchanger. 3. Cryogenic fluid is any gas, liquid or supercritical fluid having an inlet temperature to the apparatus that is below −100° F. 4. “LNG” means liquefied natural gas commonly used in gaseous form as fuel or fuel gas. 5. Heat source—any medium such as air, water, steam, hot combustion gas, etc. which provides heat to vaporize and/or superheat cryogenic fluid. 6. Indirect heat transfer loop—a closed or open fluid circuit, which may be pumped, of air, water, antifreeze liquid, used to provide the means to utilize various heat sources. 7. Frost/Ice free operation means that when ambient air is used as the heat source and in direct contact with the outside surface of the ambient vaporizer, the moisture (water) in the ambient air does not freeze or precipitate onto the surface of the vaporizer element which is exposed to the air. 8. Thermal conductivity—a material property relating to the ability of a material to transfer heat through the material, commonly expressed as BTU/(HR) (FT) (Deg F.)
Where
BTU=British thermal unit HR=Hour FT=Foot of length Deg F.=Temperature expressed as degree Fahrenheit
9. Area ratio is defined as the heat exchange element outside surface area per foot of length exposed to the ambient air divided by the internal surface area of the cryogenic fluid central tube per foot of length exposed to the cryogenic liquid which ratio is dimensionless. 10. Thermal barrier is defined as a resistance to the flow of heat through the material, thusly being the reciprocal of thermal conductivity of the material. If such a barrier thickness of a certain material is increased by for example, two times, the thermal resistance to the flow of heat would be about two times that of the original thickness. 11. Periodic shutdown due to ice buildup means that the ambient air cryogenic vaporizer is required to have the flow of cryogenic fluid stopped or interrupted so as to allow snow or ice to be removed since such snow or ice would cause non-performance of the vaporizer.
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A cryogenic fluid vaporizer using ambient air comprising a conduit through which the fluid is passed having an outer finned tubular sleeve which includes a thermal insulation barrier between the conduit and the outer finned tubular sleeve. A fan may be included to provide an increased rate of heat transfer from the air to the outer surface of the fins of the tubular sleeve. The combination of the externally finned area and the insulating thermal barrier prevents the information of ice or frost on the exterior surface of the fins during the transfer of heat from the ambient air to the cryogenic fluid providing a frost-free cryogenic ambient air vaporizer for continuous operation.
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FIELD OF INVENTION
[0001] The present invention relates to novel topical formulations of acyclovir in the form of a highly bioadhesive hydrophilic gel, containing low molecular weight hyaluronic acid in association with polyacrylic acid.
BACKGROUND TO THE INVENTION
[0002] Acyclovir is an acyclic analogue of the natural nucleoside 2′-deoxyguanosine which possesses antiviral activity against the Herpes virus, a DNA virus.
[0003] Mild genital and labial herpes infections cause the appearance of local blisters and ulcers of limited size, which may not require any pharmacological treatment, although the first-line treatment for mild herpes infections is local administration of 5% acyclovir.
[0004] Serious genital and labial herpes infections can give rise to extensive blistering and ulceration of the mucous membranes, sometimes accompanied by fever, lymphadenopathy and dysuria, and in some cases may also involve the cervix (Rawls, W. E. (1985). Herpes Simplex viruses. In “Virology” chapter 26, pp 527-561. Ed. Fields B. N., Knipe, D. M., Chanock, R. M., Melnick, J. L., Roizman, B., Raven Press, New York.). The preferred treatment for the said disorder in that case is oral administration of acyclovir (200 mg once a day), always associated with local treatment.
[0005] Acyclovir is administered locally in conventional dosage forms with a dosage pattern of five applications a day; however, this dose is unable to maintain therapeutically effective levels of the drug at the site of action for a long period. Local treatment often fails due to the active physiological removal mechanisms (physiological secretions and/or mechanical stress) which cause incorrect distribution of the drug in the mucocutaneous area affected by the infection, in view of the numerous applications required to maintain efficacious levels of the drug at the site of application.
[0006] To meet therapeutic requirements, formulations containing acyclovir which are intended for topical administration in areas affected by herpes lesions should consequently have good properties of adherence to the mucous membranes and high resistance to physiological removal mechanisms, so as to maintain close, protracted contact between the formulation and the mucosa or epidermis affected by the herpes lesions.
[0007] The mucoadhesive properties of semisolid drug delivery systems are due to the presence of semi-synthetic or natural polymers able to interact with the biological substrates. In contact with aqueous solvents, these polymers form hydrophilic gels characterised by a lattice in which water molecules are trapped.
[0008] Polyacrylic acids (PAA) are synthetic polymers widely used in local drug delivery systems. PAAs are characterised by good mucoadhesive properties and excellent thickening efficiency. Their crosslinked structure and substantial insolubility in water make PAAs suitable for use in controlled drug release systems (Singla A. K. et al., 2000, Drug Dev. Ind. Pharm. 29: 913-924).
[0009] Hyaluronic acid (HA) is a heteropolysaccharide composed of alternate residues of D-glucuronic acid and N-acetyl-D-glucosamine. It is a linear-chain polymer, with a molecular weight that can range between 50,000 and 13×10 6 Da, depending on the source from which it is obtained and the preparation methods used.
[0010] It is a glycosaminoglycan present in nature in the pericellular gels, the synovial fluid of the joints, the vitreous humour and the umbilical cord, and is widely distributed in the extracellular matrix of the connective tissues. HA is believed to perform regulatory and structural functions in the reconstruction of the tissues through modulation of fibroblast proliferation and the inflammatory response (Goa K. L. et al., 1994, Drugs, 47: 536-566).
[0011] HA therefore plays an important role in the biological organism and, together with those described above, also acts as mechanical support for the cells of many tissues such as skin, tendons, muscles and cartilage.
[0012] Mucoadhesive formulations containing synthetic polymers, including polyacrylic acids, and hyaluronic acid have already been disclosed as drug delivery systems in IT 1273742; however, the preferred polymer is Polycarbophil (polyacrylic acid crosslinked with divinyl glycol) in association with high molecular weight hyaluronic acid.
[0013] This invention relates to new topical formulations of acyclovir in the form of hydrophilic gels which are highly bioadhesive due to the presence of hyaluronic acid (with low molecular weight) or derivatives thereof, in association with polyacrylic acid for the treatment of all mucocutaneous lesions caused by Herpes Simplex or Herpes Zoster.
DESCRIPTION OF THE INVENTION
[0014] It has now been found that acyclovir can be advantageously formulated in the form of a hydrophilic gel with ideal viscoelastic and mucoadhesive properties, using vehicles containing salts of hyaluronic acid and/or derivatives thereof, in combination with at least one polyacrylic polymer called Carbopol® or Carbomer®.
[0015] The formulations of the invention are characterised by better release properties, better mucoadhesion properties, and lower leachability than known formulations available on the market. The viscosimetric properties of the gels according to the invention are also compatible with the manufacturing requirements (workability, packaging) and use requirements (extrusion, spreadability) of the product.
[0016] The HA derivatives which can be used in the novel formulations of the invention are listed below:
[0017] 1. HA salified with organic and/or inorganic bases;
[0018] 2. Hyaff®: esters of HA with alcohols in the aliphatic, arylaliphatic, cycloaliphatic, aromatic, cyclic and heterocyclic series, with a percentage of esterification which can vary, depending on the type and length of the alcohol used, from 0.1 to 100% (EP 216453 B1);
[0019] 3. Hyadd®: amides of HA with amines of the aliphatic, arylaliphatic, cycloaliphatic, aromatic, cyclic and heterocyclic series, with an amidation percentage of 1 to 10%, preferably 4% (EP 1095064 B1);
[0020] 4. O-sulphated derivatives of HA up to the 4th degree of sulphation (EP 0702699 B1);
[0021] 5. ACP®: inner esters of HA with an internal esterification percentage ranging between 0.5 and 10%, and preferably 5% (EP 0341745 B1);
[0022] 6. HA deacetylates: they derive from deacetylation of the N-acetyl-glucosamine fraction with a deacetylation percentage preferably between 0.1 and 30%, while all the carboxyl groups of HA can be salified with organic and/or inorganic bases (EP1313772 B1);
[0023] 7. Hyoxx®: percarboxylated derivatives of HA obtained by oxidation of the primary hydroxyl of the N-acetyl-glucosamine fraction with a degree of percarboxylation of between 0.1 and 100%. All the carboxyl groups of HA can be salified with organic and/or inorganic bases (EP1339753).
[0024] The HA used in this invention, as such or in the preparation of its derivatives, may derive from any source, e.g. extraction from cockscombs (EP0138572 B1), fermentation (EP0716688 B1), or a technological process.
[0025] The salts of hyaluronic acid or derivatives thereof are preferably sodium salts of hyaluronic acid with a low molecular weight of between 80,000 and 300,000 Da, depending on the source and manufacturing technique. Hyaluronic acid with a molecular weight of between 90,000 and 230,000 Da is preferably used. The salt of hyaluronic acid or derivatives thereof is present in the formulations according to the invention in the percentage by weight of between 0.1 and 1%, preferably 0.2%.
[0026] The acrylic polymer is preferably Carbopol® 974P or Carbopol® 934P (also called Carbomer® 974P and 934P respectively), available on the market from BF Goodrich, Ohio USA, and is present in the formulations according to the invention in the percentage by weight of between 1 and 5%, preferably 1.5%.
[0027] The percentage by weight of acyclovir can approx. range from 1 to 10%, and is preferably 5%. The formulations according to the invention contain conventional excipients compatible with the topical administration to the skin and mucous membranes. In addition to preservatives (such as parabens), the formulations can contain, for example, glycerol and propylene glycol as wetting agents, polyethylene glycol (such as PEG 400) as solubiliser of the active ingredient, and pH regulators such as triethanolamine.
[0028] The Applicant has surprisingly found that the therapeutic efficacy of the formulations of the invention is particularly advantageous due to the association between low molecular weight hyaluronic acid sodium salt and Carbopol® 974P or Carbopol® 934P, as it produces:
[0029] 1. a significant increase in the mucoadhesive properties of the formulations of the invention compared with the well-known commercial formulation of acyclovir cream (Zovirax®);
[0030] 2. a significant increase in the cumulative amount of drug that permeates into the mucosa compared with acyclovir cream;
[0031] 3. a significant increase in the release of the active ingredient compared with acyclovir cream;
[0032] 4. a significant reduction in the percentage of drug removed from the skin/mucosa by means of physiological removal mechanisms compared with acyclovir cream (“washability” test).
[0033] The tests conducted to prove this finding were performed with formulations based on low molecular weight HA sodium salt (mean molecular weight: 200 KD) and high molecular weight HA sodium salt (mean molecular weight: 1800 KD), in association with Carbopol for the release of the active ingredient acyclovir.
[0034] Gel Preparation
[0035] Hyaluronic acid sodium salt of fermentative origin with a low molecular weight (LMW-HA) of 90-230 KDa (mean molecular weight: 200 KDa), or HA sodium salt (HMW-HA) with a high molecular weight (mean molecular weight: 1800 KDa), or the sulphated derivative of HA or the benzyl ester of HA used for the formulations reported below (HA was not added for the control formulations), was hydrated in bidistilled sterile water, after hot solubilisation of the preservatives methyl p-hydroxybenzoate and propyl p-hydroxybenzoate. PEG 400 and Carbopol® 974P or 934P were added to the solution under magnetic stirring. After complete hydration of the Carbopol®, TEA (triethanolamine) was added to buffer the polymer solution to pH 6.0 so that the Carbopol® gelled. Glycerol, propylene glycol and finally acyclovir were then incorporated, still under stirring. The gel thus obtained was homogenised with an Ultraturrax turbine stirrer (T 25 Janke & Kunkel IKA®-Labortechnick, G) for 5 minutes at the speed of 13,500 rpm.
[0036] Formulation 1:
[0000]
Ingredient
Amount (% w/w)
Acyclovir
5.000
Excipients
Carbopol ® 974P
1.500
Sodium hyaluronate (200 KDa) LMW-HA
1.000
Glycerol
10.000
Propylene glycol
6.675
Polyethylene glycol 400 (PEG 400)
6.675
Methyl-p-hydroxybenzoate
0.080
Propyl-p-hydroxybenzoate
0.020
Purified water
69.05
Triethanolamine
q.s. for pH 6
[0037] Formulation 2:
[0000]
Ingredient
Amount (% w/w)
Acyclovir
5.000
Excipients
Carbopol ® 974P
0.750
Sodium hyaluronate (200 KD) LMW-HA
4.000
Glycerol
10.000
Propylene glycol
6.675
Polyethylene glycol 400 (PEG 400)
6.675
Methyl-p-hydroxybenzoate
0.080
Propyl-p-hydroxybenzoate
0.020
Purified water
66.800
Triethanolamine
q.s. for pH 6
[0038] Formulation 3:
[0000]
TIngredient
Amount (% w/w)
Acyclovir
5.000
Excipients
Carbopol ® 974P
0.750
Sodium hyaluronate (1,800 KD) HMW-
1.000
HA
Glycerol
10.000
Propylene glycol
6.675
Polyethylene glycol 400 (PEG 400)
6.675
Methyl-p-hydroxybenzoate
0.080
Propyl-p-hydroxybenzoate
0.020
Purified water
70.300
Triethanolamine
q.s. for pH 6
[0039] Formulation 4:
[0000]
Ingredient
Amount (% w/w)
Acyclovir
5.000
Excipients
Carbopol ® 974P
1.500
Sodium hyaluronate (200 KD) LMW-HA
0.200
Glycerol
10.000
Propylene glycol
6.675
Triethanolamine
1.325
Polyethylene glycol 400 (PEG 400)
6.675
Methyl-p-hydroxybenzoate
0.200
Propyl-p-hydroxybenzoate
0.020
Purified water
68.405
[0040] Control Formulation (for Formulations 1, 4):
[0000]
Ingredient
Amount (% w/w)
Acyclovir
5.000
Excipients
Carbopol ® 974P
1.500
Glycerol
10.000
Propylene glycol
6.675
Polyethylene glycol 400 (PEG 400)
6.675
Methyl-p-hydroxybenzoate
0.080
Propyl-p-hydroxybenzoate
0.020
Purified water
70.050
Triethanolamine
q.s. for pH 6
[0041] Control Formulation (for Formulations 2-3):
[0000]
Ingredient
Amount (% w/w)
Acyclovir
5.000
Excipients
Carbopol ® 974P
0.750
Glycerol
10.000
Propylene glycol
6.675
Polyethylene glycol 400 (PEG 400)
6.675
Methyl-p-hydroxybenzoate
0.080
Propyl-p-hydroxybenzoate
0.020
Purified water
70.800
Triethanolamine
q.s. for pH 6
[0042] Two further controls were also prepared for Formulation 4 by replacing:
[0043] 1. Carbopol 974 P (1.5% w/w) with Polycarbophil (Noveon®AA-1) (1.5% w/w), and LMW-HA (0.2% w/w) with HMW-HA with a molecular weight of 1×10 6 Da (0.2% w/w), or
[0044] 2. replacing Carbopol 974 P (1.5% w/w) with Polycarbophil (1% w/w) and LMW-HA (0.2% w/w) with HMW-HA with a molecular weight of 1×10 6 Da (0.15% w/w), and adding polyvinyl alcohol (MW 30000-70000) (Sigma-Aldrich) (1.5% w/w).
[0045] These two controls are designed to perform specific mucoadhesion tests by comparison with formulation 4 to demonstrate that the topical compositions according to the invention are more effective than those of the prior art.
[0046] Further formulations containing HA derivatives, described below, were also prepared:
[0047] Formulation Based on O-Sulphated HA Derivative
[0000]
Ingredient
Amount (% w/w)
Acyclovir
5.000
Excipients
Carbopol ® 934P
1.500
O-sulphated HA derivative, grade 3
0.200
Glycerol
10.000
Propylene glycol
6.675
Triethanolamine
1.325
Polyethylene glycol 400 (PEG 400)
6.675
Methyl-p-hydroxybenzoate
0.200
Propyl-p-hydroxybenzoate
0.020
Purified water
68.405
[0048] Formulation Based on HA Benzyl Ester
[0000]
Ingredient
Amount (% w/w)
Acyclovir
5.000
Excipients
Carbopol ® 974P
1.500
50% esterified HA benzyl ester
0.200
Glycerol
10.000
Propylene glycol
6.675
Triethanolamine
1.325
Polyethylene glycol 400 (PEG 400)
6.675
Methyl-p-hydroxybenzoate
0.200
Propyl-p-hydroxybenzoate
0.020
Purified water
68.405
[0049] Characterisation of the Formulations
[0050] Mucoadhesion Measurements
[0051] Mucoadhesion was measured with a tensile stress tester (Ferrari M. C. et al., 1996, Drug Dev. Ind. Pharm. 22: 1223-1230).
[0052] Porcine vaginal mucosa was used as biological substrate.
[0053] The equipment, assembled on a support with a horizontal base, consisted of a load cell with a linearity interval of 0-20 N and sensitivity of ±4 mN, integral with a mobile carriage and connected to a personal computer (IBM AT, IBM, I) via an amplifier.
[0054] A motor fitted with a speed transformer moves a screw which, as it advances, pushes the load cell forward: the movement imparted by the motor is thus transmitted to the mobile carriage through the load cell.
[0055] 100 mg of each formulation was applied to a filter paper disc with a diameter of 16 mm (in the case of FIG. 2 ) or 30 mm (in the case of FIG. 5 ), which was glued to the mobile carriage. A second filter paper disc, of the same diameter, was fixed to the sample holder, and the porcine vaginal mucosa was glued to it with acrylic glue.
[0056] The mobile carriage was placed in contact with the sample holder, and a pre-load of 2500 mN was applied to it. After 3 minutes the pre-load was removed and the carriage moved at a speed of 4 mm/min, until the interface between film and mucosa had completely separated. The movement values and adherence force values obtained from the load cell were acquired and recorded by the computer. A force/movement curve was then constructed, from which the mucoadhesion work parameter was obtained, calculated by the trapezoid rule, as the area underlying the force/movement curve.
[0057] Permeation Test
[0058] A Franz diffusion cell with a 20 mm diameter opening was used for the permeation measurements. The permeation was measured with porcine vaginal mucosa preserved in isotonic phosphate buffer at pH 7.4 until the time of use. The whole mucosa was used, without thinning, so as not to damage the epithelium. 100 mg of each formulation was placed on a circular area of mucosa (diameter 25 mm), which was positioned on an absorbent paper disc to separate the donor compartment from the receptor compartment. An isotonic buffer at pH 7.4 was placed in the receptor compartment to thermostat the mucosa and keep it hydrated. The permeation test was conducted for 5.5 hours. At the end of the test, the tissue was frozen at −20° C. The tissue was then cut into slices 40 μm thick with a cryostat (Leica CM 1510, Leica Microsystems, I). The drug which had permeated the various layers of tissue was extracted according to the method described in Volpato N. M. et al., 1997, J Pharm. Biomed Anal, 16:515-520, and assayed by the HPLC method. The amount of drug in relation to the depth of the tissue, and the total amount of drug recovered from the mucosa, were evaluated. Six replications were performed for each sample.
[0059] “Washability” Test
[0060] The Franz diffusion cell had to be modified in order to perform the washability measurements. The donor compartment used for these measurements was equipped with two side arms to allow the entry and exit of the acetate buffer at pH 5.0, thermostated at 37° C., at a flow rate of 0.2 ml/min, to simulate the vaginal secretions. The donor compartment has an air vent at the tip, which is closed by a screw at the compartment-filling stage.
[0061] Porcine vaginal mucosa approx. 1 cm thick, stored at −20° C., was used as biological substrate. After thawing, the mucosa was laid on a dialysis membrane (cut-off 12-14 kD) and positioned in the donor compartment. 100 mg of each formulation was then placed on a 2 cm 2 area of mucosa. The receptor compartment containing isotonic phosphate buffer at pH 7.4 was used for the sole purpose of keeping the mucosa hydrated and thermostated at the temperature of 37° C. The backflow sample from the donor compartment was collected in a beaker fitted with a magnetic stirring system. 1 ml of backflow buffer was taken up from the beaker at pre-set times (30 minutes) for a total of 5.5 hours, and replaced with 1 ml of fresh buffer. The total amount of drug “washed away” was measured by spectrophotometry, as described in the release test.
[0062] Each sample was analysed in triplicate.
[0063] Release Test
[0064] The release test was performed with a Franz diffusion cell with a 20 mm diameter opening. The system, consisting of an upper donor compartment and a lower “receptor” compartment with a volume of 10 ml, was thermostated with an external jacket at the temperature of 37° C. Acetate buffer at pH 5.0 was used as receptor phase to imitate the vaginal environment. The buffer was degassed before use and stirred during the measurements at a constant speed with a magnetic anchor. The two compartments were separated by a dialysis membrane with a 12-14 kD cut-off. The dialysis membrane was boiled in distilled water for 10 minutes before use and then spread over the opening of the receptor compartment, taking care not to trap air during the operation.
[0065] 100 mg of the formulations tested was applied to a filter paper disc with a constant area (2 cm 2 ), which was laid on the dialysis membrane wetted with the receptor phase to prevent air from being trapped between the two surfaces. The donor compartment was fixed to the receptor compartment with a clip. The upper opening of the donor compartment was closed by a waterproof membrane. At pre-set intervals, for a total of 5.5 hours, 500 μl of receptor phase was taken up with a microsyringe from the centre of the receptor compartment through the sampling arm.
[0066] The volume taken up was replaced with fresh solvent each time. The drug was assayed spectrophotometrically, after suitable dilution of the samples, at the wavelength of 252 nm.
[0067] Three replications were performed for each sample.
[0068] Results
[0069] Permeation Test
[0070] FIG. 1 shows the permeation profiles (in the different layers of the porcine vaginal mucosa) of the acyclovir contained in formulations 1-4 and in the commercial formulation Zovirax®, compared with the respective control formulations measured at the end of the test (5.5 hours). The amount of acyclovir assayed in the first layers relates to a thickness of 0-600 μm. Slices with a depth of up to 5 mm were analysed. The drug was found in the different layers examined in all cases. The amount of drug measured tends to decrease with distance from the surface of the mucosa. Formulation 4 produces a higher drug content in the tissue analysed than formulations 1 and 2, which present almost identical distributions. The commercial formulation, formulation 3 containing high molecular weight HA, and control formulation PAA 1.5, present almost identical profiles, much inferior to the other formulations 1, 2 and 4. Control formulation PAA 0.75 has the lowest distribution profile of all.
[0071] Mucoadhesion Measurements
[0072] FIG. 2 shows the mucoadhesion work values of formulations 1-4 and the commercial formulation. As will be seen, all the formulations present significantly higher mucoadhesion values than the commercial formulation. In particular, formulation 4 presents a much higher value than all the others examined, indicating that the formulation containing low molecular weight HA at the concentration of 0.2%, in combination with 1.5% PAA, presents the best mucoadhesive properties.
[0073] As previously described, topical formulations based on HA and synthetic polymers (including FAA) were already known as controlled drug delivery systems. Patent IT1273742 discloses the use of various kinds of synthetic polymers, polycarbophil and polyvinyl alcohol being selected as the preferred polymers, in combination with HA with a high molecular weight of 1×10 6 Da. To demonstrate that the formulations of the invention are better than known compositions, direct comparisons were conducted between formulation 4 (which presents the best performance in terms of mucoadhesion, washability, release and permeation) and two control formulations similar to formulation 4 but with the replacements described above relating to polycarbophil, the molecular weight of HA, and polyvinyl alcohol. FIG. 5 shows the results obtained by comparing the mucoadhesion work of composition 4 with control formulations 1 and 2, demonstrating its clear superiority in terms of mucoadhesion to the skin/mucosa.
[0074] Release Test
[0075] FIG. 3 shows the mean acyclovir release profiles, obtained in acetate buffer pH 5.0, for formulation 4 and the commercial formulation. It is evident that formulation 4 presents a release profile over time far superior to that of commercial formulation Zovirax®.
[0076] “Washability” Test
[0077] FIG. 4 shows the mean profiles of the acyclovir “washed away” by the formulations tested. Formulation 4 only reaches the value of 90% of drug “washed away” after 5.5 hours, whereas the commercial formulation is totally removed from the mucosa in the first hour after application.
CONCLUSIONS
[0078] The tests conducted clearly demonstrate that the association between low molecular weight hyaluronic acid and Carbopol 974P leads to the formation of highly hydrophilic gels which present the best performances in both the mucoadhesion test and the test of washability, permeation and release of active ingredient, not only compared with the commercial cream formulation Zovirax®, but also compared with formulations containing high molecular weight HA and formulations based on PAA without HA.
[0079] These properties are considered an invaluable index of stability of the drug acyclovir suspended in said new formulations: in fact, only the strong inner structure of the gel of the invention prevents sedimentation of the active ingredient.
[0080] Formulation 4 presents the best performance in terms of mucoadhesion, washability, release and permeation, demonstrating that its ratio between HA concentration (0.2%) and Carbopol concentration (1.5%) is the best among those chosen. The formulation, due to its composition, is consequently able to prolong the release of the drug to the damaged skin/mucosa and to ensure that a larger amount of active ingredient is absorbed. The improved mucoadhesion also allows a lower frequency of administration compared with the cream formulation, with evident advantages of practicality and economy of treatment.
[0081] The therapeutic efficacy of the formulations described above proved particularly advantageous due to the action of hyaluronic acid, which also facilitates healing of the ulcers created locally by viruses by keeping the damaged skin and mucous membranes highly hydrated. The new formulations therefore provide both therapeutic efficacy and the best reconstruction properties for the altered dermis and/or mucosa.
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The invention relates to topical formulations in the form of a bioadhesive hydrophilic gel comprising acyclovir as active ingredient, Sodium hyaluronate and an acrylic polymer. Said formulations improve the local administration of acyclovir in the treatment of herpes infections, because they possess good properties of adherence to the mucosa and high resistance to physiological removal mechanisms.
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FIELD OF THE INVENTION
[0001] The present invention relates to plastic films that have at least one preexisting fragile zone designed to form an oriented tear zone. Such plastic films are notably used in the field of packaging when a part of a container is torn so that its content can be removed.
STATE OF THE ART
[0002] In the present text, the term “welding” should be understood to mean an operation by which two pieces are joined together, with or without a filler material, by causing their edges to melt, so as to obtain a uniform, smooth and very strong joint. The term “weld” should be understood to be the result of welding.
[0003] These days, plastic films are used in many applications and in particular in packaging. The plastic films can be single-layer or multilayer and can be obtained by cast extrusion, extrusion blow-molding, by film coating, by hot lamination or by pasting. They can be printed or neutral.
[0004] One of the problems encountered with films in the state of the art is the difficulty in tearing them (the force required is often high), at least in tearing them in a predefined direction.
[0005] To overcome these defects, various means have been developed:
[0006] 1—In Plastic Film
[0007] Strippability
[0008] Strippability is a way of overcoming the tear problem by opening a bag using the strippability of the welds which are positioned at the edges of the bag. This solution has the drawback of requiring a particular welding film, which is more expensive than the conventional solutions. Also, the resultant product is weaker than in the case of a true weld, which makes it more fragile (when it comes to pressure resistance, for example).
[0009] Oriented Plastic Films
[0010] These films require specific manufacture which significantly increases the price of the film. Their effectiveness when it comes to the orientation of the tear remains relative for most of them. Another drawback lies in the fact that the mechanical properties of the film are greatly modified by this orientation: A greater fragility to impact is generally observed (drop test, for example).
[0011] To sum up, these changes have an effect, first, on the price of the film and, second, on its general behavior (flexibility, strength of the welds, impact resistance, etc.). These two aspects greatly limit the development of these solutions.
[0012] 2—In the Plastic Film Manufacturing Method
[0013] Embrittlement by laser precutting (see, for example, patent applications WO 9829312 and EP 0540184). Laser precutting is used to partially cut a multi-layer plastic film. Its main limitation is that it requires a specific and costly installation. This technology, which has been in existence for a very long time, is little used.
[0014] Embrittlement by mechanical precutting (see, for example, patent application EP 1094013). Precutting is generally done over the entire thickness of the plastic film; in this case, the plastic film is pierced. In the case of a partial cut in the thickness (just one layer, for example), the seal-tightness of the weld becomes difficult to obtain if the welding plastic film is entirely cut. If a bi-oriented layer is entirely cut, there can be a significant loss of mechanical strength.
[0015] Tear oriented by guidance (see, for example, patent application WO 03045816).
[0016] This solution applies only to films that are easy to tear so as to guide the tear.
[0017] These methods do, however, incur industrial overheads mainly associated with investments, additional steps in the method or productivity losses.
[0018] There is consequently a need to remedy the problems of the state of the art explained hereinabove.
GENERAL DESCRIPTION OF THE INVENTION
[0019] The subject matter of the present invention relates to a plastic film comprising a preexisting oriented tear zone. The plastic film according to the invention is characterized in that said zone comprises at least one butt weld joining two parts of the plastic film.
[0020] The term “part” should be understood to mean any surface portion of the film, generally a surface portion positioned in the thickness of the film, in a direction perpendicular to the surface of the film. The “part” is also the surface portion that is in contact with the weld.
[0021] This definition means that, if the weld extends to a depth F that is less than or equal to the thickness of the film, the part also extends to a depth F.
[0022] In the present invention, the weld is advantageously produced by abutting the two parts of the film. The expression “butt weld” should be understood to mean a region in which two films that are not overlaid are joined at their ends, the latter possibly being overlaid, but over a maximum distance of 1 mm.
[0023] According to one embodiment of the invention, the plastic film consists of several overlaid layers. In this case, the weld can join all the layers or only some, even just one of them.
[0024] In a variant of the invention, the weld is located in a region defined by bringing two ends of the plastic film into contact, for example, by winding.
[0025] In another variant of the invention, a slot is produced in the plastic film, the slot having a depth equal to or less than the thickness of the plastic film. Once produced, the slot is totally or partially sealed by welding.
[0026] Regardless of the method used, the welding can be done over all or part of the surface that can be used for this purpose. The depth of the weld can be less than the depth of the slot, whether or not the latter is of a thickness equivalent to that of the plastic film.
[0027] The invention also relates to a method for manufacturing a preexisting oriented tear zone in a plastic film, characterized in that said zone is obtained by attaching two parts of said plastic film by means of a weld.
[0028] Advantageously, the method according to the invention includes the displacement of a plastic film in a direction, the cutting of the plastic film in a direction identical to the direction of movement of the plastic film and the welding of the edges of the resulting slot.
[0029] Finally, the invention also relates to a device for implementing the abovementioned method.
DETAILED DESCRIPTION OF THE INVENTION
[0030] The invention will be better understood hereinbelow from examples illustrated by the following figures:
[0031] FIG. 1 diagrammatically shows a method according to the invention;
[0032] FIG. 2 shows an example of a two-layer plastic film with a welding layer and a non-welding layer;
[0033] FIG. 3 presents a two-layer plastic film similar to that of FIG. 2 , but differing in that the non-welding layer is not cut;
[0034] FIG. 4 presents a structure with a non-cut aluminum layer; and
[0035] FIG. 5 shows a structure with a cut aluminum layer.
[0036] The diagram of FIG. 1 illustrates the linear displacement (arrow) of a plastic film 3 that is first cut, diagrammatically illustrated by a cutting tool 1 , after which the edges of the slot 11 created previously are welded, the welding being diagrammatically illustrated by a welding device 2 .
[0037] On completion of the welding step, the plastic film 3 can undergo another transformation step, for example pasting or film coating. It can also be fashioned on a bag manufacturing or FFS machine. Said step can, moreover, be done in line with the cutting/welding method.
[0038] Advantageously, the welding can be followed by a step (not illustrated) in which the weld is covered with an adhesive tape. This step can take place according to various approaches and/or at various points, in particular:
on the winder at extrusion time on lamination on cutting when the packaging is manufactured, whether this is done on a machine that manufactures preformed bags or an FFS machine that manufactures the bag and fills it in line.
[0044] A device used in the context of the present invention can include a blade that cuts the plastic film as it is continually displaced. This blade is preferably immediately followed by a welding tool, ideally a rotary tool to prevent friction. It is also possible to adapt the method according to the invention for the case of step-by-step pulling of the plastic film. This weld can be produced by heating, by contact, by hot air, by high frequency, by ultrasound, or by any other technique that is available on the market.
[0045] The methods according to the invention in particular allow for the possibility of using the standard films available on the market. They then use steps (cutting, welding, etc.) that are widely known and mastered in the industrial world. Moreover, the invention can be broken down in various ways as illustrated by the following examples:
[0046] FIG. 2 shows a two-layer plastic film 3 with a welding layer 6 and a non-welding layer 5 . In this example, a slot 11 is produced through the two layers 5 , 6 , but only the welding layer 6 is welded. The resulting weld 7 therefore has a height less than that of the two-layer plastic film 3 . The weld zone 7 joins together one end of the film 9 with a second end 10 . The structure according to FIG. 2 can be produced by laser cutting.
[0047] FIG. 3 illustrates the same two-layer structure as FIG. 2 , but differs from the latter in that the non-welding layer 5 has not previously been cut. In this case, the plastic film has a face without a slot or weld, which can offer an esthetic and mechanical advantage.
[0048] The variants of FIGS. 2 and 3 are each of potential interest. The first is more fragile than the second, but may be too fragile for mechanically demanding applications. The second makes it possible to keep the mechanical properties of the packaging intact. Similarly, all kinds of combinations can be used with the standard films available on the market. If the plastic film includes a layer of aluminum, the latter should not be cut in order to preserve the barrier properties of the aluminum. FIG. 4 illustrates a structure with a non-cut aluminum layer 8 . FIG. 5 illustrates a structure with an aluminum layer 8 which has nevertheless been cut. In this second case, ease of tearing has been given priority over the barrier properties of the aluminum layer 8 .
[0049] The choice of the welding material, of the layer or layers to be cut and the setting of the welding parameters (pressure, time, temperature) makes it possible to adjust the ease of tearing.
[0050] The oriented tear in the plastic film can have the desired form (straight or curved). This cut can be continuous or discontinuous (broken line) so as not to excessively embrittle the package.
[0051] This zone can be strengthened with an adhesive tape if necessary. The adhesive can be removed on using the plastic film's tear function. This adhesive can also be used to reseal the packaging.
[0052] As indicated above, the plastic film according to the invention may be known per se. It can be:
a PE a PP a coextruded plastic film of PA/PE type, for example a layered plastic film a laminated plastic film of PET/PE, OPP/PE, OPA/PE, PET/alu/PE, PE/alu/PE, PP/alu/PP, PET/alu/PP type, or any other standard composition.
[0058] Packaging involving a plastic film according to the invention can be used in all fields that require a preexisting tear zone.
[0059] The invention can in particular be used with the following packaging:
bags that stand upright (doypack™, for example), preformed or manufactured on FFS machine; flat bags with three or four welds; bags with resealing ZIP for which the accuracy of the opening is important to the opening/closure functionality; “flowpacks”, satchel bags, or any other film-based packaging can also be advantageously handled in this way.
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The invention relates to a plastic film ( 3 ) including a pre-existing oriented tear zone ( 11, 7 ), characterised in that the zone ( 11, 7 ) comprises a butt weld ( 7 ) which assembles one end of the plastic film ( 9 ) with another end of the plastic film ( 10 ), said weld zone being disposed in the thickness of one or more of the welding layers of the plastic film ( 3 ). The invention also relates to a method and a device for producing said plastic film.
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TECHNICAL FIELD OF THE INVENTION
The present invention relates to a spill resistant container for holding light-weight powders. In particular, the invention relates to a spill resistant container for use with fingerprint dusting powders.
BACKGROUND OF THE INVENTION
This invention relates to a spill resistant container for fingerprint powder. Heretofore, fingerprint powder was placed in an open jar into which an applicating brush was dipped and then surfaces dusted for fingerprints. Conventional latent fingerprint developing powders are very finely divided powdered solid materials which are spread over latent fingerprints in order to bring out the pattern. Various substances have been utilized for powders such as fingerprint developing powder, i.e., powdered metals like aluminum and bronze, dragon's blood powder, a grey powder consisting of a finely ground french chalk and mercury, and black powders employing lamp black, carbon black or a charcoal base. Other materials used include talc and silica. Fingerprint powders may also include pearlescent dyes, florescent dyes and additives to bring out contrast in the print. As the phrase dusting implies, these developing powders are very light weight and easily dispersed. Typical fingerprints powders have a very low bulk density and will rapidly disperse. This characteristic means that powders frequently are spilled or ejected from the container by action of the dipping of the brush into the container, sneezes, gusts of wind, and thus, a host of other motive forces can expel the fingerprint powder from the container. Additionally, jars are frequently dropped or tipped over resulting in the spill of the powder.
Preventing spills or escape of excessive powder is desirable for at least two reasons. The first is to avoid contamination of or obliteration of latent fingerprints by too much dusting powder and the second is to avoid damage by staining furniture, carpets, rugs, etc.
The present invention is advantageous over prior containers. One object of the present invention is to provide a spill resistant container which can effectively trap very light finely divided powders in the event the container is tipped over. Another object of the present invention is to provide a container such that if a container is righted after it has been tipped over the retained powders would flow back to the lowest section of the container. Another object of the present invention is to provide a container designed to allow the easy insertion and removal of an application brush. Another object of the present invention is to provide a surface to wipe the outer edges of the application brush which will return the material to the container. Another object of the present invention is to provide a closure for a standard container to convert it into a spill resistant container.
SUMMARY OF THE INVENTION
The present invention is a spill resistant container having a bottom, and a wall extending upwardly from the bottom which defines a container. A first retaining member is located within the container and is in the form of a elongate passageway which has a first and second end, the second end being attached to the wall of the container at a location spaced apart from the bottom of said container, and the first end of said passageway is spaced apart from the bottom of the container and located between the bottom of the container and the second end of the passageway. In the preferred embodiment, the second end of the passageway is an opening of a larger cross-sectional area than the opening of the first end of the passageway. The container also includes a second retaining member which forms an inwardly extending ridge around the upper end of the container, said ridge being located above the second end of the first retaining member.
In a preferred embodiment, the container has a substantially circular bottom with a cylindrical sidewall extending therefrom to form a container. Positioned within the side wall is a passageway formed by a truncated conical section with the larger end of the conical section oriented such that the smaller end of the conical passageway is spaced apart from the bottom of the container and the upper end of the conical member is the larger opening and is attached to the side wall at a greater distance from the bottom than the lower end. Above the conical section and attached to the side wall extending inwardly is a second retaining member. This member being an inwardly extending wall for a predetermined distance but which does not close off the container.
In another embodiment, to a spill resistant adapter for attachment to standard containers to form a spill resistant container. An adapter is provided which has a member having a mating surface dimensioned to interface with a predetermined container, and an elongate passageway attached to the mating surface which has a lower end and an upper end. The opening at the lower end of the passageway being of a smaller cross-sectional area than the passageway at the upper end. Extending from the member having a mating surface is an inwardly projecting ridge at a predetermined distance. When the adapter is attached to a standard container, such as a commercially available jar which has no internal retention mechanism, the jar can be made spill resistant by attaching the adapter of the present invention to the jar.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of one embodiment of the present invention.
FIG. 2 is a top view of one of the embodiments shown in FIG. 1.
FIG. 3 is a cross-sectional view of an alternate embodiment of the present invention.
FIG. 4 is a cross-sectional view of an embodiment of the invention on its side.
FIG. 5 is an exploded cross-sectional view of another embodiment of the invention.
DETAILED DESCRIPTION
Referring to FIG. 1, there is shown the spill resistant container 10. The container 10 is formed from a bottom 12 and extending side wall 14. In the embodiment shown, the bottom is circular and the side wall is cylindrical forming the shape of a common jar. However, the cross-sectional shape of the device is not critical and the container may be square, rectangular, oval, etc. In the preferred embodiment, the container defines an axis 16 which passes through the bottom and extends vertically. Within the container 10 is a first retaining member 16. First retaining member 16 has a first end 18 and a second end 20. Retaining member 16 forms a elongate passageway. In the preferred embodiment, the elongate passageway has a smaller opening 22 at its first (lower) end and a larger opening 24 at its second (upper) end. Preferably the upper end 20 of elongate passage 16 is connected with side wall 14 at a distance spaced apart from bottom 12. First retaining member 16 may be integrally formed with side wall 14, or may be attached to side wall 14 by suitable means such as friction fit, glue, threaded connection, etc. The container has a second retaining member 26 located above the first end 20 of the first retaining member 16. Retaining member 26 is in an inwardly extending member forming a ridge about the upper portion of the container. The ridge is at any orientation sufficient to prevent escape of powder when the container is laying on its side. A ridge which extends substantially perpendicular to the axis of the container has been found useful. The second retaining member 26 defines an opening 28. In a preferred embodiment opening 28 is of a smaller cross-sectional area than opening 24 at the second end 20 of first retaining member 16. Preferably opening 28 formed by second retaining member 26 is of a larger cross-sectional area than opening 22 at the first end 18 of the first retaining member 16. The height (H) of the container can be suitable to the lower end (first end) 18 height. The height (h 1 ) from the bottom should be of a sufficient distance to allow a predetermined amount of powder to be placed in the container such that the amount of powder will not extend above the first end 18 of the first retaining member 18. The height to the second end (upper end) 20 of the first retaining member can be of any height sufficient to contain the powder when the container is laid on its side. Thus, in the preferred embodiment, the volume for the powder is the volume of the container below the first end of the passageway 18 which will be called the service volume. In the illustrated embodiment, this service volume is the diameter D times height h 1 . This service volume is preferably equal to or less than the capture volume defined by the lower portion of the container below the lower side of opening of the first end of the first retaining member bounded by the bottom side 34 of passageway 18 below the opening, the lower portion of the sidewall below the opening and the lower portion of the bottom below the opening. This capture volume is illustrated in FIG. 4 as the volume below line 33 in the embodiment shown FIG. 4. The capture volume is preferable greater than the service volume by about 10% or more. The capture volume may be less than the service volume. The volume of powder used to charge the device can be less than the service volume and thus less capture volume would be needed to retain the powder; however, to prevent a spill from inadvertent overfilling, the capture volume should be equal to or greater than the service volume.
FIG. 2 is a top view of FIG. 1 and like numbers in FIG. 2 refer to like items in FIG. 1. In FIG. 1 a top 30 can be attached to container 10 by frictional fit, threads, or other mechanisms known in the packaging industry.
In use of container 10, a light-weight powder, such as a fingerprint powder 32, is charged in the can to a distance below the first end 18 of first retaining member 16. A brush to apply fingerprint powder is typically one with a handle with a very pliable brush extending conically from the handle. In use, the brush can be inserted into opening 28 and if the brush is rotated, and pushed downwardly the bristles will be compressed by retaining wall 16. The bristles are then pushed through opening 22 and dabbed into the powder 32. As the brush is withdrawn, it will expand within the passageway formed by the first retaining wall 16. With a larger brush it will completely expand and as is withdrawn through opening 28 in the second retaining member 26 the brush will be slightly constricted. This action will scrape excess fingerprint powder from the edges of the brush which will then fall onto the surface of first retaining member 16 and be funneled back into the bottom of the container 10.
FIG. 3 shows an alternate embodiment of the present invention. In FIG. 3 a standard jar 50 is shown having a bottom 52 and extending side walls 54 at the top of side wall 54 is threaded surface 56. Thus, jar 50 can be your typical consumer jar. The jar can be converted to a spill resistant container of the present invention by providing an adapter 60. Adapter 60 has a wall member 62 dimensioned to mate with a selected predetermined container. Wall member 62 preferably has a mating surface 64 for connecting wall 62 to a predetermined container. In the embodiment shown in the mating surface is thread surface 64. Obviously, the mating surface can be a frictional fit surface, a compressible lip, or a surface designed to frictionally engage the interior surface or exterior of the container. Extending inwardly from wall 62 is first retaining member 66 having a lower end 68 and an upper end 70. Retaining wall 66 forms the first passageway 72 having a opening 74 at the first end 68 of wall 66 and an opening 76 at the second end 70 of wall 66. Also extending from wall 62 is ridge member 78. Ridge 78 is positioned above the first retaining member 66 and extends inwardly a predetermined distance to form opening 80. Wall 62 can also be provided with an outwardly extending lip 82 upon which a snap cover 84 can be applied. Obviously, other mechanism can be supplied on wall 62 to permit the attachment of a lid such as a screw thread surface. Once again in use, a finely divided light weight powder 86 is placed in the container such that the top of the powder does not extend above the lower end 68 of retaining wall 66. The dimensions of the attachment 60 are preferably such that the design provides for a capture volume equal or greater than the service volume of the combined predetermined jar 50 and attachment 60.
The present invention may be made from any suitable material such as glass, plastic, metal or a combination thereof Preferably, the materials of construction are static-free such that powder freely falls to the bottom of the container. Additionally, the inner surfaces of the first retaining member and second retaining member should be smooth so that powder is not unduly retained on those surfaces.
FIG. 4 illustrates the operation of a container. When the container is tipped over the majority of the powder 32 is retained by retaining member 16. However, because these powders are so light and finely divided, it is not unusual for some small portion of the powder 32' to travel through opening 22, however it quickly falls and is retained by a second retaining wall 26. When the can is up-righted powder 32' will flow down the retaining wall 16 into the bottom of the container. Tests have shown that a container having fingerprint powder within it can even be thrown with virtually no escape of powder, no matter how the container lands.
The container and adapter of the present invention can be constricted in a number of ways such as in one piece or multiple pieces. FIG. 5 is an exploded cross-sectional view. The assembled pieces form a spill resistant container 100. The container 100 is made from ajar 102 having a threaded surface 104 at the outside of the top of jar 102. The adapter 106 is constructed of a first retaining wall 108 in the shape of a funnel. Funnel-shaped wall 108 has an opening 110 at the lower end which is smaller than space opening 112. The retaining wall 108 has a mating surface 114 on its upper end. In the illustrated embodiment it is on the outer side of wall 108 and is dimensioned to fit inside jar 102 such that the wall 108 can be held in jar 102 by functional fit or application of an adhesive. At the upper end 116 of wall 108 the wall forms an inner channel 118 for receiving second retaining wall 120 which is a donut shaped piece with an outer edge sized to mate with channel 118 and an opening 124. In manufacture, wall 108 can be blow or injected molded. Second retaining wall 120 can be molded, stamped or cut. Wall 120 can be snapped into channel 118 and held by frictional fit or adhesives. The adapter 106 thus assembled is attached by suitable method. As illustrated the adapter 106 is positioned within jar 102 and held in place by friction, adhesive or other means.
In construction of the device the first retaining member can be funnel-shaped. The angle of divergence of the funnel preferably results in an inclined surface when the jar is upright having sufficient incline to cause powder to slide or roll down to the lower opening freely or when the jar is lightly tapped.
It has been found that a suitable spill resistant container of the invention can be made with an inner diameter of about 31/8 inches, H of about 4 inches, h 1 of about 2 inches, h u of about 2 inches, h 2 of about 2 inches, where the opening at the lower end of the passageway is about 1 inch in diameter. The upper end of the passageway is about the same diameter as the jar, and the second retaining member has an opening about 11/2 inches in diameter.
Modifications and additions to those described above, in relation to preferred embodiments will be apparent to those skilled in the art and such modifications are included within the scope of the below claims.
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A spill resistant container for light weight powders is disclosed. The container has retaining members which allow a fine powder to be retained in the container when the container is dropped or knocked over. The present invention also discloses a top for a common household jar which can be modified to allow for use as a spill resistant container. The container has a first retaining member in the shape of a conical section with the large opening at the upper end, and a second retaining member positioned above the first retaining member.
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This application is a division, of application Ser. No. 577,340, filed Feb. 6, 1984, now U.S. Pat. No. 4,675,043.
DESCRIPTION
FIELD OF THE INVENTION
The present invention relates to the manufacture of profiled elements of a material which can be brought to the viscous state. More particularly, the invention can be applied to the manufacture of fluid dispenser devices such as ink-jet printers, each including a tubular body having a terminal nozzle at one end with an orifice of predetermined cross section.
The object of the invention is to make the manufacture of the profiled elements described above easier and more economical while at the same time giving the finished product good characteristics of precision and reliability.
SUMMARY OF THE INVENTION
In order to achieve this object, the present invention provides a method for the manufacture of fluid dispensing devices including a tubular body having a terminal nozzle at one end with an orifice of predetermined cross-section, characterised in that it includes the steps of:
providing a tubular element, of a material which can be brought to the viscous state by heating and having a transverse profile substantially identical to the transverse profile of the tubular body,
effecting localised heating of an intermediate zone of the tubular element to bring the material in this zone to a viscous state,
causing deformation of the intermediate zone, resulting in a reduction in the cross-section of the internal cavity of the tubular element,
observing, during the heating, variations in the cross-section of the internal cavity of the tubular element in order to identify the condition when the cross-section reaches, at least in a transverse plane of the tubular element, a predetermined value substantially corresponding to the cross-section of the orifice of the nozzle of the dispensing device and
stopping the heating of the tubular element when this condition is reached.
The invention also provides apparatus for the manufacture of fluid dispensing devices comprising a tubular body having at one end a terminal nozzle with an orifice of predetermined cross-section, from tubular elements of material which can be brought to a viscous state by heating, having a profile substantially identical to the transverse profile of the tube of the body, characterised in that it includes:
heating means which can effect localised heating of a zone of each tubular element in order to bring the material constituting the wall of the tubular element itself to the viscous state and reduce its diameter progressively, and
detector means for observing variations in the cross-section of the internal cavity of the said zone of the tubular element during the heating; the detector means being able to identify the condition when the said cross-section reaches, at least in a transverse plane of the tubular element, a predetermined value substantially corresponding to the cross-section of the orifice of the nozzle of the dispensing device and stopping the heating of the zone of the preformed element when the said condition is reached.
The present invention further provides apparatus for the assembly of ink jet printers including an ejector with a tubular body having a nozzle at one end for projecting the ink and an annular transducer fitted onto the ejector with the interposition of a layer of hardenable resinous material in the annular cavity between the ejector and the transducer, characterised in that it includes:
a vacuum source, and
a casing defining at least one fluid-tight chamber connectible to the vacuum source; the casing having an aperture for sealingly receiving the transducer with the ejector mounted within it in an arrangement in which a first end of the annular cavity communicates with the vacuum chamber in the casing and the other end communicates with the external environment, whereby the resinous material introduced into the cavity through the other end is drawn into the cavity itself as a result of the low pressure generated in the chamber of the casing.
A further object of the present invention is to provide apparatus for detecting the size of cylindrical pieces subject to working involving variations of the transverse section of the pieces themselves, characterized in that it includes:
television monitor means which can scan a zone of the piece subject to working and subject to variations in its cross-section in order to produce an image having substantial variations of luminance in correspondence with the sides of the scanned piece; the monitor means generating, for each line of the image, a signal presenting sharp variations of amplitude in response to the substantial variations of luminance, and
measuring means which can derive an indication of the distance between the sides of the scanned piece from the sharp variations in the signal generated by the television monitor means.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be described, purely by way of non-limiting example, with reference to the appended drawings, in which:
FIG. 1 illustrates an ink-jet printer which can be manufactured by means of the method and the apparatus according to the invention;
FIGS. 2 to 7 illustrate schematically the steps of the method according to the invention,
FIG. 8 illustrates first apparatus according to the invention;
FIG. 9 illustrates schematically further apparatus according to the invention;
FIG. 10 is a block schematic diagram of the internal structure of one of the components of FIG. 8;
FIG. 11 illustrates typical changes with time of a signal generated within the block schematic component of FIG. 10, and
FIG. 12 illustrates an alternative form of the apparatus of FIG. 8.
DETAILED DESCRIPTION OF THE INVENTION
In the drawings an ink-jet printer of known type is generally indicated 1 and includes a tubular ejector element 2 onto which a tubular transducer 3 is fitted.
The ejector element 2 is constituted essentially by a capillary tube having a nozzle 4 at one end with a calibrated orifice 5 for projecting the ink. The overall length of the ejector element 2 is about 1.5-2.0 cm and the capillary tube has a diameter of about 1 mm. with a wall thickness of about 5-15 hundredths of a mm. The orifice 5 typically has a diameter of about 5-8 hundredths of a mm. The ejector element 2 is normally made of a vitreous material which can be brought to a viscous state by heating such as, for example, pyrex glass.
The transducer 3 is constituted by a sleeve of piezo-electric material the internal diameter of which is reduced when an excitation voltage pulse is applied between two electrodes 6, 7 connected to respective metallised layers 8 and 9 applied to the outer surface and the inner surface of the transducer 3 respectively.
The annular space between the ejector element 2 and the inner wall of the transducer 3 contains a filling of hardenable resinous material 10 intimately connecting the ejector 2 and the transducer 3 for the transmission of mechanical forces between the transducer 3 and the wall of the ejector element.
When an excitation pulse is applied to the electrodes 6 and 7, the contraction of the transducer 3 causes a corresponding contraction of the wall of the capillary tube. The effect of this contraction is to generate pressure waves within the ink which fills the ejector element 2 in use, which results in the ejection of an ink drop through the orifice 5 of the nozzle 4. A transparent epoxy resin having a low viscosity at ambient temperatures and a low heat generation upon the polymerisation may be used for the connecting layer 10, the polymerisation normally being carried out at ambient or lower temperatures in order to avoid residual stresses after polymerisation. These stresses could in fact result in the ejector element 2 breaking away from the transducer element 3, rendering the printer 1 practically unusable.
One example of a resin of the type mentioned above is the resin sold under the trade name STYCAST 1277 made by Emerson and Cumming.
FIG. 2 illustrates schematically a device of known type for forming glass capillaries from borosilicate glass tubing such as pyrex glass.
In FIG. 2 a pusher member shown at P advances a borosilicate glass tube G into a heating element (muffle) indicated M.
As a result of the heating effect by the element M the glass of the tube G becomes viscous, which makes it possible to achieve, by means of a pair of counterrotating rollers R located downstream of the element M, a drawing action which results in the formation of a glass capillary tube G 1 . A cutter member T, for example a rotary wheel, cuts the capillary tube G 1 successively into pieces each of which is indicated 11.
In FIGS. 3 and 8 a vertical-axis rotary mandrel indicated 12, receives the upper end of one of the tubular pieces 11.
In the same drawings two localised heat sources are shown at 13 which act on an intermediate portion of the capillary tube piece 11 which is rotated about its axis by the mandrel 12, which is driven by a motor 12a.
In the example illustrated in FIG. 8, the sources 13 are constituted by two hydrogen burner nozzles fed by an electrolytic generator 14.
The use of an electrolytic generator avoids the risks resulting from the use of containers such as cylinders of high pressure hydrogen gas or liquid hydrogen.
Instead of the burners 13, however, it is possible to use a heating element similar to the muffle M used in the device illustrated in FIG. 3 or other equivalent heating elements as the localised heat sources 13.
The use of a plurality of localised sources equi-angularly spaced about the vertical axis of rotation of the pieces 11 of glass capillary is, however, considered preferred at present. More particularly, the use of two opposing burner nozzles together with a speed of rotation of the mandrel 12 of about 20 revolutions per minute is considered the optimum at present.
Each of the nozzles 13 is able to effect an angular movement about a horizontal axis which allows the nozzles 13 to be oriented between an angualr working position shown in full outline and indicated A in FIG. 8 and an angular rest position shown in broken outline and indicated B in the same Figure.
In the angular working position A, the nozzles 13 are directed at the tubular piece 11 fixed to the mandrel 12 and cause localised heating of an intermediate zone of the piece 11 indicated 15 and illustrated on a larger scale in FIG. 4.
In the angular rest position B each of the burner nozzles 13 is directed at a respective monitoring thermocouple 16 which detects the operating temperature of the burner and acts, through a control system, not illustrated, on the generator device 14 in order to regulate the heating action achieved by the burner nozzles 13.
In the embodiment illustrated, the positions of the burner nozzles 13 and of the thermocouple 16 are such that, in the angular rest position B, the mouth of each nozzle 13 is at a distance from the respective moitoring thermocouple 16 equal to that between the mouth of the nozzle 13 itself and the zone 15 of the piece 11 subjected to heating in the angular working position A. This facilitates and makes more precise the control of the operating temperature of the burner nozzles 13 themselves.
A reservoir indicated 17 contains a stock of cut pieces 11 of glass capillary each of which constitutes the tubular starting element for the manufacturing of an ejector element 2 of a printer 1 similar to that illustrated in FIG. 1.
The reservoir 17 is disposed above the mandrel 12 and communicates through a vibratory feeder 18 with the axial cavity of the mandrel 12 itself.
The tubular elements (cut pieces) 11 may thus be gravity-fed into the mandrel 12.
The axial fixing position of each preformed element 11 within the mandrel 12 is determined by the bearing of the lower end of the tubular element against a bearing plane 19 located below the mandrel 12.
The bearing plane 19 can be removed from a horizontal working position of engagement with the lower end of the tubular element 11, illustrated in full outline and indicated C in FIG. 8, to a rest position illustrated in broken outline and indicated D in the same Figure.
In the rest position D, the bearing plane 19 lies in a vertical plane in order to allow the fall of the tubular element 11 into an underlying collecting receptacle 20 when the tubular element 11 is disengaged from the mandrel 12.
The orientation of the bearing plane 19 is controlled by an electrical control circuit 21 which also controls the movement of the burner nozzles 13, between their working position A and their rest positions B, and the clamping of the mandrel 12.
The control circuit 21 receives signals from an optical sensor 22 which can detect the presence of a tubular element 11 within the mandrel 12 and a detector circuit 23 connected to a television monitor camera 24 which scans the zone 15 of the tubular element 11 subject to the heating action of the burner nozzles 13. The scanned zone is illuminated by a diffuse light source 24a for example a reflection source. Preferably the camera 24 includes an optical magnification system (microscope) indicated schematically 25 in FIG. 8.
The detector circuit 23 is illustrated schematically in FIG. 10 and will be described in detail below.
With reference now to FIG. 5, a further mandrel N is intended to rotate a tubular element 11 taken from the receptacle 20 of the apparatus of FIG. 8 slowly about a horizontal axis. This element can be seen to be formed of two portions indicated 11a and 11b and corresponding respectively, when the element 11 is mounted on the mandrel 12, to the portion overlying and the portion underlying the intermediate zone 15.
A high velocity rotary cutter wheel is indicated F for separating the two portions 11a and 11b of the element 11 by cutting in a transverse plane indicated 15a.
The axial position of the wheel F is adjustable by means of a control device H controlled by a viewer W which allows the intermediate zone 15 of the element 11 mounted on the mandrel N to be observed and the image thus obtained to be superimposed on an image corresponding to a reference shape V which reproduces the shape of the nozzle 4 of ejector element 2 of the printer 1. In FIG. 6 a rotary plate 26 is shown which effects the lapping of the end face of the portion 11a of the element 11 corresponding to the ejector element 2 of the printer 1.
In FIG. 7 apparatus generally indicated U is shown for the deposition of metal evaporated under vacuum on the end face of the portion 11a of the tubular element 11 as a layer of anit-wetting material which can thus prevent the deposition of ink on the end face.
In use of the apparatus according to the invention, the tubular elements (cut of pieces 11) made by the device illustrated in FIG. 2 are loaded into the reservoir 17.
The vibratory feeder 18, under the control of the circuit 21, introduces the elements 11 sequentially into the mandrel 12 by making them fall into the mandrel 12 in its open position. The falling movement of each element 11 is arrested by the impingement of the lower end of the element 11 against the bearing plane 19 which, at the beginning of each working cycle of each tubular element 11, is in the horizontal working position C.
Immediately the optical sensor 22 detects that a tubular element 11 has been supplied to the mandrel 12, the control circuit 21 initiates the clamping of the mandrel 12 and the tipping of the bearing plane 19 downwardly into its vertical rest position D.
The mandrel 12 is subsequently rotated by means of the motor 12a while the gas nozzles 13 are brought from their angular rest position B in which they are located originally to their working positions A in which the nozzles 13 effect localised heating of the intermediate zone 15 of the tubualr element 11. In their working position A the nozzle 13 must be inclined to the axis of the mandrel in order to avoid the two flames interfering with each other. Preferably this angle is chosen to be about 60°.
As a result of the heating, the vitreous material constituting the wall of the portion 15 becomes viscous whereby, on the basis of known physical laws, the internal diameter and the outer diameter of the intermediate zone 15 of the element 11 are reduced, with a simultaneous increase in the thickness of the wall of the zone itself.
As a result of the heating the intermediate zone 15 of the element 11 thus gradually assumes the deformed hour-glass configuration illustrated schematically in FIG. 4.
The heating of the zone 15 is continued until, as a result of the deformation consequent on the vitreous material constituting the wall of the tubular element 11 changing to the viscous state, the diameter of the internal cavity of the tubular element 11 in the zone 15 reaches a value substantially corresponding to the diameter of the nozzle 5 of the ejector element 2 of the printer 1.
For the purposes of the invention it suffices for this condition to occur solely in a transverse plane of the tubular element 11. However it is preferred, for reasons which will be better described below, to achieve this condition over a certain axial length, of the tubular element itself by a suitable choice of thickness of the tube or variation of the location and inclination of the nozzles 13.
During the heating of the intermediate zone 15 the tubular element 11 is rotated by the mandrel 12 which supports the element 11 itself at its upper end so that the intermediate zone 15 which is being heated keeps its symmetry about its central axis even in the deformed hour glass configuration.
In order for the hour-glass shape to assume the desired length, the length of the tubular element and the position of the nozzles 13 are selected so that the portion 11b of the tubular element 11 beneath the zone 15 subjected to heating has a length such that the strength of the gravitational force on this portion annuls the transverse thrust due to the internal stresses generated in the material in the zone 15 which is in the viscous state or balances them after this zone 15 has been moved vertically by a predetermined amount.
The correct selection of the position of the zone 15 subjected to heating is particularly important since the centrifugal forces resulting from the rotation of the tubular element 11 could have an amplifying effect on deviations of the portion 11b from the axis of the element 11 itself. The weight of the portion 11b must be such as to rectify any deviations caused by the internal stresses along the axis of the tube 11 in the zone 15.
The condition described above establishes a lower limit for the distance between the zone 15 and the lower end of the element 11. The upper limit for this distance is determined by the need to avoid the strength of the gravitational forces acting on the portion 11b being able to bring about excessive axial stretching of the wall of the zone 15 during the heating.
Given the material and the size of the ejector 2 of the printer 1 indicated above, it is preferable to choose value for the distance between the intermediate zone 15 and the lower end of the tubular element 11 of between 40 and 60 mm.
The progressive deformation of the zone 15 subjected to heating may be monitored continuously through the television camera 24 both by observation of the image produced thereby by an operator and through the detector circuit 23.
It is thus possible to discern when the degree of narrowing of the internal cavity of the tubular element has reached the desired level in the zone 15.
At this point it is possible to rotate the burner nozzles 13 towards their rest angular positions B so as to stop the heating by means of a command imparted manually to the control circuit 21 by an operator and by a signal passed to the circuit 21 by the detector circuit 23.
After a brief pause to allow the solidification of the wall of the intermediate zone 15 of the tubular element 11, the mandrel 12 is opened allowing the element 11 with its hour-glass shaped intermediate portion 15 to fall into the collecting receptacle 20.
The bearing plane 19 is then returned to the horizontal position C so as to allow a new tubular element 11 to be fed to the mandrel 12 from the reservoir 17 through the feeder 18 in order to start a new working cycle.
The tubular element 11 taken from the collecting receptacle 20 is transferred to the apparatus illustrated in FIG. 5 in which the lower end 11b of the element, which will be discarded, is mounted on the mandrel N.
It is possible to divide the element 11 into two separate portions by cutting the wall in correspondence with the plane 15a by means of the wheel F the axial position of which relative to the element 11 mounted on the mandrel N can be adjusted through the device H controlled from the viewer W.
The position of the cutting plane 15a is selected by comparison of the profile of the hour-glass zone 15 with the reference shape V which, as indicated above, reproduces the profile of the nozzle 4 of the printer element 1.
It is thus possible to carry out the cutting of the nozzle to a predetermined length with high precision, account being taken of the fact that nozzles which are too short result in the generation of ink drops in association with an excessive number of smaller size spurious droplets (satellites). Nozzles which are too long have too high an hydraulic impedance. The comparison of the zone 15 subject to cutting with the reference V also allows pieces with manufacturing defects to be discarded.
As indicated above, the zone 15 has diameters substantially corresponding to the diameters of the orifice 5 of the nozzle 4 over a certain part of its length. There is thus a field of choice for effecting the cutting of the element 11 in correspondence with an optimum plane 15a having regard to the performance of the ejector device 2.
After the portion 11a of the element 11 has been separated from the portion 11b which is to be discarded, the front face thereof surrounding the nozzle 5 is subjected to lapping as shown schematically in FIG. 6.
The lapping is preferably effected using a tinor lead-based rotary plate 26 to the surface of which is fed a diamond paste with a grain size of less than 1 micron.
At the end of the lapping, each portion 11a is cleaned and after this its internal diameter is checked and any chipping of the wall of the portion itself is looked for.
The portions 11a are subsequently mounted in the apparatus U of FIG. 7 for the vacuum-deposition on the front face thereof which has been lapped of a layer of material (anti-wetting material) for preventing the deposition of the ink on the front face during use as the ejector in an ink jet printer.
In order to apply the layer of anti-wetting material, which is normally a chromium, nickel-chromium and/or cobalt-chromium based material, it is also possible to use cathode sputtering apparatus in which the end faces of the portions 11a act as the targets.
After the deposition of the layer of anti-wetting material each portion 11a, after possible cutting of the end opposite the narrowed end, assumes the final configuration which allows its use, after coupling to a corrisponding transducer 3, as an ejector element 2 in an ink jet printer.
The coupling of the ejector 2 and the transducer element 3 is achieved by means of the apparatus illustrated in FIG. 9 in which a casing is shown generally indicated 40 defining a fluid-tight chamber 41 which can be inspected visually through a transparent wall 42 with the aid of a viewer 43.
The casing 40 may usefully be made of a block of material such as plexiglass in which a blind hole defining the chamber 41 is formed.
The open end of the hole is then sealed by means of a stopper of transparent material such as plexiglass or glass which constitutes the wall 42. The stopper may be shaped like a lens in order to facilitate the optical inspection of the chamber 41.
It is also possible to form a plurality of chambers 41 in a single block of material in the manner described above so as to allow the simultaneous assembly of a plurality of jet printers.
A duct 44 puts the chamber 41 in communication with a vacuum pump 45 which can create a controlled low pressure within the chamber 41 itself.
A further aperture 46 allows the introduction into the chamber 41 of one of the ends of the transducer 3 in which the ejector element 2 is inserted.
The parts and the elements constituting the ejector 2 and the transducer 3 are indicated in FIG. 9 by the same references as used in FIG. 1.
A washer 47 is fitted to the edge of the aperture 46 to ensure sealing between the casing 40 and the outer wall of the transducer 3.
48 indicates an insert of resiliently yieldable material such as the material known as "silastic" which is aligned with the aperture 46.
The arrangement is such that the ejector 2 may be made to slide longitudinally until the nozzle 4 is brought to bear against the insert 48. Under these conditions the orifice 5 of the nozzle 4 is closed and the ejector element 2 is fixed to the casing 4 in a predetermined position.
This allows the adjustment of the axial position of assembly of the transducer 3 on the ejector element 2 very precisely.
This may be achieved, for example, by aligning a reference notch 49 provided on the outer surface of the transducer 3 with the outer edge of the aperture 46.
In the assembled disposition described, the annular cavity between the ejector 2 and the transducer 3 communicates at the end corresponding to the nozzle 4 of the ejector 2 with the chamber 41 and at its opposite end with the external environment.
This cavity may then be filled with resinous material 10 by feeding the material itself into the end of the cavity projecting from the casing 40, adjacent to which a suitable nozzle 60, supplying the resinous material 10, is located, as shown schematically in FIG. 9, the pump 45 being operated simultaneously to create a low pressure within the chamber 41.
As a result of this low pressure, the resinous material 10 is gradually drawn into the cavity. The value of the low pressure within the chamber 41, and consequently the speed with which the material 10 fills the cavity between the ejector 2 and the transducer 3, can be adjusted so as to achieve gradual filling of the cavity itself, avoiding the formation of bubbles or irregular distribution of the material within the filling layer.
Observation of the end of the printer 1 which is within the chamber 41 through the viewer 43 makes it possible to identify when after the chamber between the ejector 2 and the transducer 3 has been filled completely, the resinous material 10 emerges from the end of the cavity corresponding to the nozzle 4.
At this point the pump 45 may be stopped to allow the hardening of the layer of resinous material 10.
This hardening is normally carried out at ambient temperature over a period of about 24 hours. In order to ensure complete hardening it is, however, preferable to subject the device 1 to a final heating phase at a moderate temperature (40°-60° C.) for a period of about 2 hours.
The printer 1, thus completed, can be connected to an ink supply tube indicated P in FIG. 9, of plastics material such as polyvinylchloride.
The connection of the tube P to the ejector element 2 is normally effected by means of a heat-shrinking sleeve (not illustrated) constituted, for example, by a piece of heat-shrinkable tube sold under the trade name RAYCHEM RNF-3000 or a piece of the tube sold under the trade name RAYCHEM UTUM.
FIG. 10 illustrates the internal structure of the detector circuit 23 of FIG. 8.
This circut, together with the television camera 24 is usable in general for monitoring the diameter of cylindrical pieces subjected to working involving variation in the cross section of the pieces themselves. In addition to the formation of the hour-glass shaped zone 15 of the elements 11 the detector circuit 23 may also be used for the manufacture of tubes of plastics material (for example the tube for supplying the ink indicated P in FIG. 9), optical fibres and the like.
FIG. 12 shows schematically a variant of the apparatus of FIG. 2 for manufacturing such a tube. It is formed in an extrusion process by a device 36 including an orifice 37 and a core 38 which roughly define the outer diameter and the inner diameter respectively of the plastics tube P.
The final values assumed by these outer and inner diameters are, however, considerably influenced by the pulling force F exerted, for example by the winding reel 39. The tube P is monitored by a television camera 50, similar to the camera 24 of FIG. 8, which observes the outer diameter, or the inner diameter if the plastics material constituting the tube P is transparent, and provides the feedback signal for an operating mechanism 51 for the winding reel 39 to drive the latter so as to apply a force to the tube P such as to reduce its inner diameter or outer diameter until the value established by the operator is reached.
FIG. 10 shows an oscillator 26 which controls the television camera 24 of FIG. 9 through a horizontal sync generator 27, the camera being oriented so as to scan the portion 15 of the tubular element 11 subjected to heating.
The electrical signal generated by the camera 24 is characterised by variations in amplitude which correspond to the variations in luminance detectable in the scanned visual field.
In the application to the observation of the intermediate zone 15 of the element 11, which is constituted by a transparent vitreous material, these variations in luminance are present at the outer sides and the sides of the internal cavity of the tubular element 11. When the piece observed is made of an opaque material, the said variations in luminance are normally present only at the outer sides of the scanned piece.
In each case the variations in luminance are more easily detectable when the piece to be observed is illuminated with diffuse light such as that produced by the reflected light source 24a of FIG. 8. This avoids the surface of the object observed causing reflections which hinder the detection effected by the camera 24. A squaring amplifier to which the signal produced by the camera 24 is fed is shown at 28.
In the application illustrated in FIG. 8, in which the piece scanned is a tubular element of transparent material, the signal coming from the camera 24 assumes the form illustrated in FIG. 11 for each line of the image and after the squaring operation carried out by the amplifier 28.
In this signal four rectangular pulses can be seen in correspondence with the instants indicated t 1 , t 2 , t 3 , and t 4 .
More particularly, the first and last pulses (t 1 , t 4 ) indicate the presence, in the image produced by the camera 24, of two fringes generated by the total reflection of the light at the glass-air interface in correspondence with the outer sides of the tubular element 11.
The other two pulses (t 2 , t 3 ) correspond to similar fringes located at the sides of the inner cavity of the tubular element 11 itself.
The separation between the "outer" pulses (t 1 , t 4 ) is thus indicative of the outer diameter of the tubular element while the separation between the "inner" pulses (t 2 , t 3 ) indicates the inner diameter of the tubular element with an error due to refraction in the material. This error may be corrected for each time in dependence upon the material by means of a calibration circuit 33 (FIG. 10). For convenience below the signals t 2 , t 3 will be understood as the corrected signals and their separation indicates the diameter of the inner cavity of the tubular element 11 itself.
In an entirely similar manner, the separation between the pulses occurring at the instants t 1 and t 2 and the separation between the pulses occurring at the instants t 3 and t 4 are both indicative of the thickness of the wall region of the tubular element 11 scanned by the camera 24.
Differences between these two values of separation, and any phenomena of overall fluctuation of the position of the pulses, may be indicative of the existence of irregularities or asymmetry in the tubular element 11.
The output signal of the amplifier 28 is fed to a counting and timing block 29 which is synchronised with the scanning action effected by the camera 24 through a frequency signal from the generator 27.
Thus the counting and timing block 29 is able to convert the information relative to the separation of the pulses which appear in the output signal of the squaring amplifier 28 into one or more signals indicative of the transverse dimensions of the piece observed. More particularly, in the embodiment illustrated, the block 29 outputs a signal proportional to the separation between the pulses occurring at the instants t 2 and t 3 .
The output signal indicative of the internal diameter of the tubular element 11 is selected through an external control 31 for passing to a comparator 30 where it is compared with a reference level which is adjustable by means of a detector circuit 23 through the external control 31 according to the internal diameter desired for the nozzle orifice 5 (FIG. 1).
As indicated above, the television camera 24 produces a signal the form of which is illustrated in FIG. 11 for each scanning line of the image. A line counter block 34 is able to select, from all the line signals of an image, that corresponding to the transverse plane and the zone of the tubular element 11 in which it is desired to check the inner diameter of the tubular element. However, when it suffices to determine the operation on the basis of the minimum value of the diameter one may enable the counter 29 to feed to the comparator 30 all the signals generated. It is, however, possible to use various selection criteria in dependence on particular requirements of use. More particularly, when the piece to be formed is made of a material which is opaque to light a signal output by the counter 29 which is proportional to the separation of the signals occurring at the instants t 1 and t 4 (FIG. 11) is selected for passing to the comparator 30 by means of a second external control 35.
When the signal received by the comparator 30 falls below the reference level output of the comparator 30, the comparator 30 itself outputs a signal which is fed to the control circuit 21 to control, as described above, the movement of the burner nozzles 13 to their rest position and the consequent stoppage of the heating of the region 15 of the tubular element 11. This obviously occurs when the diameter of this region has reached a predetermined value selected by operation of the control 31 or 35.
By 32 is shown an anti-noise logic of known type arranged to exclude any spurious signals generated by the counter 29 in a random manner during the scanning. The logic 32 thus allows the counter 29 to output only the signals generated with a certain repetitiveness. For this purpose the logic 32 is interposed between the comparator 30 and the block 29, preventing the erroneous and undesirable switching of the comparator 30 as a result of noise signals coming from the block 29.
Naturally, the principle of the invention remaining the same, constructional details and embodiments may be varied widely with respect to that described and illustrated without thereby departing from the scope of the present invention. For example the control system with the television camera 24 may be used for various applications with or without the microscope and with continuous illumination or stroboscopic illumination. The circuit 23 may also be connected to a visual display screen and possibly to a processing computer.
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The apparatus for manufacturing ink jet glass tubes includes a vertical mandrel which receives the tubes one at a time from a feeder and rotates them relative to a pair of gas nozzles for their heating. The tube is heated in an axially limited intermediary zone so as to form an hour-glass shaped profile.
The profile of the tube is scanned by a television camera which generates two signals indicative of the internal diameter. These are compared electronically with a stored indication of the desired diameter and the two nozzles are rotated into an inactive position when this diameter is reached. The tube is cut along a plane so as to make the profile of the nozzle coincident with a reference profile by a device including an optical device connected to a cutting wheel to permit comparison of the hour-glass profile of the element with the reference profile. The severed end of the tube is then lapped and covered with a non-wettable material. The tubular element is bonded within a piezo-electric transducer, by locating the latter partially in a chamber, after fitting it over the tubular element, while a pump draws an epoxy resin through the chamber and into the space between the transducer and the tubular element.
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BACKGROUND OF THE INVENTION
[0001] This invention relates to a fuel delivery rail assembly for an internal combustion engine, especially for an automotive engine, equipped with an electronic fuel injection system. The fuel delivery rail assembly delivers pressurized fuel supplied from a fuel pump toward intake passages or chambers via associated fuel injectors. The assembly is used to simplify installation of the fuel injectors and the fuel supply passages on the engine. In particular, this invention relates to sectional constructions of a fuel conduit (fuel rail) having a fuel passage therein and connecting constructions between the conduit and sockets for receiving fuel injectors.
[0002] Fuel delivery rails are popularly used for electronic fuel injection systems of gasoline engines. There are two types of fuel delivery rails; one is a return type having a return pipe and another is a non-return (returnless) type. In the return type, fuel is delivered from a conduit having a fuel passage therein to fuel injectors via cylindrical sockets and then residual fuel goes back to a fuel tank via the return pipe. Recently, for economical reasons, use of the non-return type is increasing and new problems are arising therefrom. That is, due to pressure pulsations and shock waves which are caused by reciprocal movements of a fuel pump (plunger pump) and injector spools, the fuel delivery rail and its attachments are vibrated thereby emitting uncomfortable noise.
[0003] U.S. Pat. No. 6,354,273 (Imura et al.) discloses a fuel delivery rail assembly including at least one flat or arcuate flexible absorbing surface. However, in case that one wall of the conduit opposite to the socket mounting wall is providing the absorbing surface, it tends to emit high-frequency noise, which may be caused by mechanical vibratory resonance.
[0004] U.S. Pat. No. 4,660,524 (Bertsch et al.) discloses a fuel supply line having an elastic wall section connected to a rigid wall section.
[0005] U.S. Pat. No. 4,649,884 (Tuckey) discloses a fuel rail having a flexible metal membrane which absorbs pulsations created by injectors.
SUMMARY OF THE INVENTION
[0006] It is an object of the present invention to provide a fuel delivery rail assembly which can reduce the pressure fluctuations within the fuel passages caused by fuel injections, and also to reduce the vibrations caused by fuel reflecting waves (shock waves), to thereby eliminate emission of uncomfortable high-frequency noise.
[0007] A conventional type of fuel delivery rail assembly comprises an elongate conduit having a longitudinal fuel passage therein, a fuel inlet pipe fixed to an end or a side of the conduit, and a plurality of sockets vertically fixed to the conduit adapted to communicate with the fuel passage and so formed as to receive tips of fuel injectors at their open ends.
[0008] According to the characteristics of the invention, one wall of the conduit opposite to the socket mounting wall includes a flat or arcuate flexible absorbing surface. In addition, high-frequency noise suppressing means are applied to the outer surface of the conduit as follows:
[0009] (A) A high-frequency noise suppressing rib is fixed to said one wall across the longitudinal direction of the conduit.
[0010] (B) A high-frequency noise suppressing cavity is formed in said one wall across the longitudinal direction of the conduit.
[0011] (C) A high-frequency noise suppressing clamp is located for holding the socket mounting wall and said absorbing surface between the clamp.
[0012] As a result of the above construction of the invention, in a fuel delivery rail assembly having a fuel conduit made by steel, stainless steel or press materials, it has been found that it becomes possible to eliminate emission of uncomfortable noise including high-frequency noise. These noise are caused by the vibration and pressure pulsations due to the reflecting waves of injections and lack of dampening performance of the conduit.
[0013] In a theoretical principle, when shock waves produced by the fuel injections flow into the fuel inlet of the sockets or flow away therefrom by momentary back streams, the flexible absorbing surface absorbs the shock and pressure pulsations. In addition, when thin plates having small spring constant are deflected and deformed, the space of contents varies, namely expands or shrinks, thereby absorbing pressure fluctuations.
[0014] Further, the high-frequency noise suppressing means work to prevent the absorbing surface from vibrating freely and emitting high-frequency noise. Thus, a high-frequency sound component contained in the noise is minimized and diffusion of high-frequency noise is considerably eliminated.
[0015] Under the continuous experiments, following arrangements are found to be most preferable to obtain best results.
[0016] (1) The rib is fixed near one end or each end of the conduit in its longitudinal direction in order to deviate from the maximum bending position of the absorbing surface.
[0017] (2) The height of the rib is within a range from one half to four times of thickness of said absorbing surface.
[0018] (3) The number of the rib is one to three.
[0019] (4) The depth of the cavity is less than half of the total height of the conduit, and the width of the cavity is less than two times of the total height of the conduit.
[0020] (5) The clamp is located near one end or each end of the conduit in its longitudinal direction.
[0021] (6) The thickness of the absorbing surface is equal to or less than the thickness of other surfaces of the conduit.
[0022] (7) The radius of a curvature at an edge of the absorbing surface is more than two times of the thickness of the absorbing surface.
[0023] In this invention, thickness of each wall of the conduit, ratio of the horizontal size to the vertical size, and the range of clearance between the fuel inlet of the socket and its confronting surface are preferably defined by experiments or calculations such that, especially during idling of the engine, the vibrations and pressure pulsations are minimized.
[0024] Since the present invention is directed essentially to the sectional construction of the conduit and connecting construction of the conduit and the sockets, interchangeability with the prior fuel delivery rails are maintained as far as the mounting dimensions are kept constant.
[0025] Other features and advantages of the invention will become apparent from descriptions of the embodiments, when taken in conjunction with the drawings, in which, like reference numerals refer to like elements in the several views.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] [0026]FIG. 1A is a perspective view, and FIG. 1B is a side view and FIG. 1C is a vertical sectional view of a first type fuel delivery rail assembly according to the invention.
[0027] [0027]FIG. 2 is a perspective view of a modified assembly.
[0028] [0028]FIGS. 3A to 3 C are perspective views of further modified assemblies.
[0029] [0029]FIG. 4 is a perspective view of a second type fuel delivery rail assembly.
[0030] [0030]FIG. 5 is a side view of a third type fuel delivery rail assembly.
[0031] [0031]FIG. 6 is a side view of a modified assembly.
[0032] [0032]FIG. 7A is a perspective view, and FIG. 7B is a vertical sectional view and FIG. 7C is a side elevational view of a further modified embodiment.
[0033] [0033]FIGS. 8A to 8 C are perspective views of further modified assemblies.
[0034] [0034]FIGS. 9A and 9B are vertical sectional views of further modified assemblies.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0035] Referring to FIGS. 1A to 1 C, there is shown a first type embodiment of the present invention, a fuel delivery rail assembly 10 of the so called “top feed type”, adapted to an automotive four-cylinder engine. The fuel conduit (rail) 11 comprised of flat steel pipes extends along a longitudinal direction of a crank shaft (not shown) of an engine.
[0036] At the bottom side of the conduit 11 , four sockets 4 for receiving tips of fuel injectors are located corresponding to the number of cylinders at predetermined angles and distances from each other. To the conduit 11 , two thick and rigid brackets 4 are fixed transversely so as to mount the assembly 10 onto the engine body. Fuel flows along the arrows thereby being discharged from the socket 3 and fuel injectors (not shown) into an air intake passage or cylinders of the engine.
[0037] At the side of the conduit 11 , a fuel inlet pipe 5 is fixed by brazing or welding. Although at an end of the conduit 11 it is possible to provide a fuel return pipe for transferring residual fuel back to a fuel tank, the present invention is directed to a non-return type having fuel pressure pulsation problems, so that the fuel return pipe is not provided.
[0038] As shown in FIG. 1C, the conduit 11 has a flat rectangular section such that a circular steel pipe or stainless steel pipe is pressed into a flat form. The vertical and horizontal dimensions of the conduit 11 can be defined such that each wall thickness is 1.2 mm, the height is 10.2 mm, the width is 28 to 34 mm.
[0039] Based upon the charasteristics of the present invention, one wall 11 a of the conduit 11 opposite to the socket mounting wall 11 b provides a flat flexible absorbing surface 11 a . Since the absorbing surface 11 a faces to the fuel inlet port 13 of the socket 3 , it can absorb shock and vibration during fuel injection timing.
[0040] In addition, two ribs 15 , 16 are fixed to the wall 11 a by brazing or welding across the longitudinal direction of the conduit 11 . The dimensions of each rib 15 , 16 can be defined such that its length is about 80 to 90 percent of the width of the conduit 11 , and its height is within a range about one half (50 percent) to four times (400 percent) of the thickness of the absorbing surface 11 a , and its width is within a range about 30 to 40 percent of the total height of the conduit 11 .
[0041] As it is understood from FIG. 1C, shock waves emitted from a fuel supply port 6 a of the injection nozzle 6 pass through the fuel inlet port 13 of the socket and run againt the absorbing surface 11 a , thereby being dampened. During this action, the ribs 15 , 16 work to minimize a high-frequency sound component from the vibration noise. Thus, diffusion of high-frequency noise is considerably eliminated.
[0042] [0042]FIG. 2 illustrates a fuel delivery rail assembly 20 according to a modified embodiment of the invention. In this embodiment, only one rib 25 is located near the midpoint of the conduit 11 . Further, the fuel inlet pipe 5 is fixed to a distal end of the conduit 11 .
[0043] Depending upon a configuration of the fuel rail, the number of the rib can be selected and optimized by continuous experiments.
[0044] [0044]FIGS. 3A to 3 C illustrate further modified embodiments in which one rib or two ribs are located near one end or each end (both ends) of the conduit 11 . In FIG. 3A, two ribs 26 , 27 are located near each end of the conduit 11 . In FIG. 3B, one rib 26 is located near the free end of the conduit 11 . In FIG. 3C, one rib 27 is located near fuel inlet end of the conduit 11 . According to some experiments, it has been found that the rib position near the end of the conduit 11 can provide the most effective performance.
[0045] Referring to FIG. 4, there is shown a second type embodiment of the present invention, a fuel delivery rail assembly 30 . Based upon the charasteristics of the present invention, one wall 11 a of the conduit 11 opposite to the socket mounting wall provides a flat flexible absorbing surface 11 a . Since the absorbing surface 11 a faces to the fuel inlet port of the socket 3 , it can absorb shock and vibration during fuel injection timing.
[0046] In addition, two cavities 35 , 36 are formed to the wall 11 a across the longitudinal direction of the conduit 11 . The dimensions of each cavity 35 , 36 can be defined such that its length is about 90 to 100 percent of the width of the conduit 11 , and its depth is within a range about 30 to 40 percent of the total height of the conduit 11 , and its width is within a range about 100 to 200 percent of the total height of the conduit 11 .
[0047] The cavities 35 , 36 also work to minimize a high-frequency sound component from the vibration noise. Thus, diffusion of high-frequency noise is considerably eliminated.
[0048] Referring to FIG. 5, there is shown a third type embodiment of the present invention, a fuel delivery rail assembly 40 . Based upon the charasteristics of the present invention, one wall 11 a of the conduit 11 opposite to the socket mounting wall 11 b provides a flat flexible absorbing surface 11 a . Since the absorbing surface 11 a faces to the fuel inlet port 13 of the socket 3 , it can absorb shock and vibration during fuel injection timing.
[0049] In addition, a snap-ring type clamp 45 is located for holding the socket mounting wall 11 b and the absorbing surface 11 a between the clamp 45 . The clamp 45 comprises a semi-circular head 45 a , flat retaining portions 45 b and expanded tails 45 c.
[0050] The clamp 45 also works to minimize a high-frequency sound component from the vibration noise. Thus, diffusion of high-frequency noise is considerably eliminated. The clamp 45 can be made in a removable type as shown in FIG. 5 or made in a rigid type which is fixed to the conduit 11 .
[0051] Referring to FIG. 6, there is shown a modified embodiment of the present invention, a fuel delivery rail assembly 50 . Based upon the charasteristics of the present invention, one wall 11 a of the conduit 11 opposite to the socket mounting wall 11 b provides a flat flexible absorbing surface 11 a . Since the absorbing surface 11 a faces to the fuel inlet port of the socket 3 , it can absorb shock and vibration during fuel injection timing.
[0052] In addition, a rigid U-shape clamp 55 is fixed to the conduit 11 by brazing or welding for holding the socket mounting wall 11 b and the absorbing surface 11 a between the clamp 55 . The width of the clamp 55 along the longitudinal direction of the conduit 11 can be about 12 mm.
[0053] [0053]FIGS. 7A to 7 C illustrate a further modified embodiment in which a rigid C-shape clamp 65 is fixed to the conduit 11 by brazing or welding for holding the socket mounting wall 11 b and the absorbing surface 11 a between the pad portions 65 a of the clamp 65 .
[0054] [0054]FIGS. 8A to 8 C illustrate further modified embodiments in which one clamp or two clamps are located near one end or each end (both ends) of the conduit 11 . In FIG. 8A, two clamps 66 , 67 are fixed to each end of the conduit 11 . In FIG. 8B, one clamp 66 is fixed near the free end of the conduit 11 . In FIG. 8C, one clamp 67 is fixed near the fuel inlet end of the conduit 11 . According to some experiments, it has been found that the clamp position near the end of the conduit 11 can provide the most effective performance.
[0055] [0055]FIGS. 9A and 9B illustrate further modified embodiments in which modified clamps are comprised of end caps 75 , 76 each extending along the longitudinal direction and closing an end portion of the conduit 11 . These clamps 75 , 76 work to prevent the end portions from freely vibrating such that high frequency noise is eliminated. In FIG. 9A, the end cap 75 is connected to the fuel inlet pipe 5 at an end thereof. In FIG. 9B, the end cap 76 is closing the free end of the conduit 11 .
[0056] As shown in FIGS. 9A and 9B, the end caps 75 , 76 are overlapping on the conduit 11 . The dimension of the overlapping portion of the end caps 75 , 76 can be defined such that its wall thickness is about 50 to 400 percent of the thickness of the absorbing surface 11 a , and its overlapping length is within a range about five to twenty times of the thickness of the absorbing surface 11 a.
[0057] Several experiments were done for proving the effects of the inventive clamp associated with an actual engine.
[0058] (1) Fuel delivery rail: width 34 mm, height 10.2 mm, length 300 mm, wall thickness 1.2 mm, material “Japanese industrial standard STKM11A steel pipe”
[0059] (2) Fuel supply pipe from a fuel tank to an engine: outer diameter 8 mm, wall thickness 0.7 mm, material “Japanese industrial standard STKM11A steel pipe”
[0060] (3) Engine: six cylinders gasoline engine
[0061] (4) measuring points: Variations of acceleration were measured by an acceleration pickup which is located under the floor of an automobile near a connecting portion between a steel fuel supply pipe and a connecting plastic hose which is connected to the fuel inlet pipe 5 .
[0062] Under the conventional phase in which the inventive clamp is not located, it was found that peak frequency components exist near 600 Hz and 1.3 kHz. Under the inventive phase in which one clamp is located near the midpoint of the longitudinal conduit, it was found that a vibration level (acceleration) was decreased by 55 percent at 600 Hz, and 30 percent at 1.3 kHz. Under the second inventive phase in which two clamps are located near both ends of the longitudinal conduit, it was found that a vibration level was decreased by 70 percent at 600 Hz, and 45 percent at 1.3 kHz.
[0063] It should be recognized that various modifications are possible within the scope of the invention claimed.
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A fuel delivery rail assembly for supplying fuel to a plurality of fuel injectors in an engine is provided. The assembly comprises an elongate conduit having a longitudinal fuel passage therein, a fuel inlet pipe, and a plurality of sockets. One wall of the conduit opposite to the socket mounting wall includes a flat or arcuate flexible absorbing surface. High-frequency noise suppressing means such as a rib, a cavity or a clamp is applied to the one wall opposite to the absorbing surface. Thus, fuel pressure pulsations and shock waves are reduced by bending of the absorbing surface, and emission of high-frequency noise is eliminated.
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BACKGROND OF THE INVENTION
This invention relates to a method and apparatus for measuring the degree of contamination of liquids, and more particularly to a method and apparatus wherein fine contaminants contained in liquids such as oil utilized in hydraulic actuators, lubricating oil or the like are accumulated on filter papers for determining the degree of contamination.
Such oils are contaminated by foreign matters during their preparation, storage and use. Such contamination causes troubles in precise hydraulic actuators or bearings. Accordingly, it is necessary to measure the degree of contamination of such liquids before or during use thereof in order to know whether the liquids are clean liquids containing contamitants of less than a permissible limit. However, strict control of the degree of contamination of such liquids is usually ignored except in certain field of application.
In the United States of America, with the advance of space navigation engineering, a number of regulations have been established in connection with the degree of purity of liquids, and in Japan some of these regulations have been adopted in certain industries. However, as these regulations require special apparatus and highly trained engineers they are troublesome and uneconomical. Moreover, the methods specified in these regulations make possible a large error if the condition of measuring the degree of contamination of the liquid is not suitable, and such methods lack reproduceability so that in certain cases errors within ± 33% are permitted.
In addition to the advance in space navigation engineering, techniques of a high degree of accuracy have been developed in other fields of engineering, so that it is necessary to control with the same degree of accuracy the quality of the liquids, such as oils utilized to operate various hydraulic actuators and bearing oils used in such fields. To meet such requirements a number of simple methods have been proposed for measuring the purity of liquids. Among these methods, a method wherein light is projected upon a liquid to be examined for causing the light to transmit through or be reflected by the liquid so as to determine the degree of contamination of the liquid in accordance with the quantity of light transmitted or reflected is used most widely. However, with this method, it is extremely difficult to accurately determine the degree of contamination because of the difference in the color of the liquid, change of the liquid color during measurement, variation in the color caused by the presence of contaminants and the coloring of the liquid. For example, the operator often is given an illusion that the liquid under measurement contains a large quantity of cntaminants due to the coloring of the liquid even when the liquid actually contains only a small quantity of the contaminants.
SUMMARY OF THE INVENTION
Accordingly, it is an object of this invention to provide a novel method and apparatus for enabling an unskilled operator to rapidly and accurately determine the degree of contamination of liquids without the difficulties described above.
Another object of this invention is to provide a novel method and apparatus for determining the degree of contamination of liquids which is not affected by the color of the liquids.
Still another object of this invention is to provide a novel method and apparatus capable of determining not only the concentration of the contaminants but also the particle size or particle size distribution of the contaminants.
Yet Yet another object of this invention is to provide an improved apparatus for measuring the degree of contamination of liquids without errors caused by the difference in the characteristics of elements utilized to fabricate the apparatus.
According to one aspect of this invention there is provided a method of measuring the degree of contamination of liquids, characterized in that a liquid containing contaminants is filtered by passing it through a lamination of a plurality of filter papers and that the quantities of the contaminants deposited on the upper and lower filter papers are compared with each other thereby measuring the degree of contamination of the liquid.
According to another aspect of this invention there is provided apparatus for measuring the degree of contamination of liquids, characterized by comprising a filter including a container for receiving a definite quantity of a liquid containing contaminants, a lamination of a plurality of filter papers contained in the container, and a measuring device including a source of light for irradiating upper and lower filter papers taken out of the filter with light having a definite wavelength, photoelectric converting elements responsive to the light reflected by the upper and lower filter papers, respectively, for producing electric signals proportional to the quantities of the contaminants deposited on the upper and lower filter papers, respectively, and a bridge circuit for comparing the electric signals with each other, thus producing a differential output signal corresponding to the degree of contamination of the liquid.
Where the lamination comprises a plurality of filter papers having a different pore size in which the pore size decreases from the upper to the lower, it is possible to determine not only the concentration but also the particle size and particle size distribution of the contaminants.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
FIG. 1 shows a longitudinal section of a filter utilized in this invention;
FIG. 2 is a diagrammatic representation for an optical device utilized in the measuring apparatus and
FIG. 3 is a circuit diagram of a bridge circuit utilized in combination with the optical device shown in FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 of the accompanying drawings shows a filter comprising a cylindrical container 1 made of a material which will not be dissolved by or not chemically react with the liquid to be measured, such as synthetic resins, polyethylene, polypropylene, polyvinyl chloride, glass, etc. A scale 2 is provided on the outer surface of the container 1 to indicate the quantity of the liquid contained therein. The upper end of the container 1 is open and a neck 3 having an inner diameter a little smaller than the filter paper to be used is provided at the lower end. A plurality of sheets of filter paper is inserted into the neck 3 through the lower opening of the container. According to this invention, at least two sheets 4 and 4' of the filter paper are inserted in a superposed relation and a protective disc 5 provided with a plurality of small perforations 5a is disposed below the stack of sheets of filter paper for supporting them when pressure or suction is applied for filtering. Screw threads 6 are formed on the outer surface of the neck 3 to receive a cylindrical cap 7 which is used to clamp the periphery of the sheets of filter paper between a shoulder formed at the lower end of the neck 3 and the protective disc 5.
Before using the container 1, it is washed with clean water to remove any residual contaminant and then dried. A definite quantity of the liquid to be measured is then put in the container and filtered by being passed through the filter paper by pressure suction which is applied through the cylindrical cap 7. After completing the filtering operation, the sheet of filter paper are removed by removing the cap 7 and the protective disc 5 and the condition of the upper filter paper 4 is compared with that of the lower filter paper 4'. It will be clear that most of the contaminant is deposited on the upper sheet of filter paper 4 so that it is possible to determine the quantity of contaminant or the degree of contamination by comparing the conditions of the upper and lower sheets of filter paper.
FIGS. 2 and 3 show apparatus suitable for this purpose. More particularly, as shown in FIG. 2, the upper and lower sheets of filter paper 4 and 4' are illuminated with monochromatic directional light having a wavelength of 7,000A and generated by light sources, for example luminous diodes 10A and 10B through semitransparent reflective mirrors 11A and 11B. The light reflected by the sheets of filter paper 4 and 4' are reflected by reflective mirrors 11A and 11B toward photoelectric converting elements 12A and 12B to generate electric signals directly proportional to the quantities of the contaminants deposited on the upper and lower sheets of filter paper. The photoelectric converting elements may be solar cells, for example. The outputs from the photoelectric converting elements 12A and 12B are amplified by operational amplifiers 13A and 13B, and the outputs thereof are applied to a bridge circuit including resistors R 1a , R 1b , R 2a , R 2b , R fa and R fb and an operational amplifier 14. The output of operational amplifier 14 is applied to an indicating meter 15.
Before measurement, two standard sheets of filter paper (not yet used) are substituted for the sheets of filter paper 4 and 4' shown in FIG. 3. If there is any difference between the characteristics of the light sources 10A, 10B and photoelectric converting elements 12A, 12B and when the bridge circuit is not perfectly balanced, the bridge will produce a differential output. Then, one or both of the feedback resistors R fa , R fb associated with amplifiers 13A and 13B are adjusted to perfectly balance the bridge. Then, sheets of filter paper 4 and 4' are substituted for the standard filter paper sheets. The output of the bridge circuit under these conditions is proportional to the quantity of the contaminants contained in the liquid because most of the contaminants deposits on the upper sheet of filter paper 4 and because upper and lower sheets are colored to the same degree by the liquid. Thus, even when the liquid is colored, its color does not affect in any way the result of measurement and the output from the bridge circuit is directly proportional to the quantity of the contaminants deposited on the upper sheets of filter paper or the difference between the quantities of the contaminants deposited on the upper and lower sheets of filter paper, or the concentration of the contaminants contained in the liquid.
Filter paper made of any suitable material can be used in this invention but it has been found that filter paper made of cellulose ester is suitable. However, filter paper for use in chemical analysis are also satisfactory. The pore size of the filter paper may range from 0.45 to 3.0 microns.
The comparison of the conditions of the two sheets of filter paper can also be made by visual inspection or with a microscope. If three or more sheets of filter paper having different pore sizes are laminated with that having the largest pore size positioned upper most, it is possible to determine not only the quantity of the contaminants but also the particle size or particle size distribution of the contaminants.
With the method of this invention it is possible to limit the permissible error to less than 5%.
While the filter illustrated in FIG. 1 is of the vertical type, it should be understood that it is also possible to use a horizontal type filter, so that the term "upper sheet filter paper" used herein means the sheet of filter paper through which the liquid is first passed.
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Liquid containing contaminants is passed through a lamination of a plurality of filter papers and the quantities of the contaminants deposited on upper and lower filter papers are compared with each other to determine the degree of contamination of the liquid.
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BACKGROUND OF THE INVENTION
The field of the present invention is exhaust timing control devices for two cycle engines.
Japanese utility model laid open No. 51-39112(39112/1976), the disclosure of which is incorporated herein by reference, discloses an exhaust timing control device which controls the initiation of the exhaust cycle in a two cycle engine increase power. This exhaust timing control device is provided with a member which can move to a position on an upper portion of an exhaust port in a two cycle engine. In this position, the member controls the timing edge location of the exhaust port in accordance with the speed of the engine to adjust the exhaust timing.
The aforementioned member itself cooperates closely with the wall of the combustion chamber of the engine. Thus, its operation may be affected by carbon buildup from combustion in the engine, dust in the engine oil, etc.
SUMMARY OF THE INVENTION
The present invention is directed to an exhaust timing control system and method for a two cycle engine which provides for smooth engine operation. An exhaust timing member is controlled to undergo alternating movement between position limits by a timing member drive mechanism when the speed of the engine exceeds a preselected value. The system may then operate responsive to certain engine parameters within the position limits. Thus, a cleaning cycle may be effected along with appropriate exhaust timing control.
A motor may be employed to actuate the timing member which may in turn be controlled by a voltage generator circuit actuated by signals from a CPU within a control circuit. In one aspect of the present invention, the control circuit may include wave shaping, memory, A/D conversion, throttle interface, and ignition key switch setting circuits. In operation, the foregoing circuitry may receive ignition pulse, throttle, and timing member position data input to the control circuit. Through a series of programmed steps the CPU within the control circuit can activate the voltage generator circuit causing the motor, through the timing member driving mechanism, to move the timing member to a desired position.
Accordingly, it is an object of the present invention to provide improved two cycle engine operation. Other and further objects and advantages will appear hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings wherein similar reference characters denote similar elements throughout the several views:
FIG. 1 is a schematic block diagram illustrating an exhaust timing control system according to the present invention;
FIG. 2 is a flow chart illustrating the routine in the CPU of FIG. 1 for adjusting the degree of opening of the timing member;
FIG. 3 is a flow chart illustrating a subroutine function performed for every ignition pulse in the CPU of FIG. 1;
FIG. 4 is a flow chart illustrating an overflow interruption routine;
FIG. 5 is a graph plotting engine torque vs. the rotational speed of the engine, with the exhaust timing member fully open and fully closed; and
FIG. 6 is a block diagram illustrating operating functions of the CPU in FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1, the exhaust control system according to the present invention includes a mechanism 1 for driving an exhaust timing member (not shown) to adjust the position of an upper edge of an exhaust port in a two cycle engine. Means for driving the exhaust timing member include a direct current motor 2. A motor driving voltage V M is supplied to the motor 2 from a control circuit 4 so as to move the exhaust timing member to create the desired port opening. The control circuit 4 determines the motor driving voltage V M from a plurality of inputs. An ignition pulse P Ne obtained from an ignition circuit (not shown) and having a frequency proportional to the rotational frequency of the engine is input to the control circuit 4. The ignition circuit may be, for example, a capacitor discharge type. Also input to the control circuit 4 is a signal TH o from a throttle switch (not shown), activated when the engine throttle is opened to or beyond a preset amount. Additionally, a voltage V.sub.θ from an exhaust timing member position sensor 5 which includes, for example, a potentiometer R is input to the control circuit 4.
The position of the exhaust timing member may include and the control system may differentiate among a first position limit or fully closed position θ s , a middle position θ p and a second position limit or fully open position θ o . The initiation of the exhaust cycle is earliest in the fully open position θ o and is retarded as the exhaust timing member is moved toward the fully closed position θ s . Furthermore, the middle position θ p is not limited to one value. Rather, it may include a plurality of middle positions according to the rotational frequency of the engine irrespective of the throttle setting.
The control circuit 4 includes a microcomputer in which a CPU 10 and memories RAM 11 and ROM 12 or the like are connected in a well known manner via bus lines. The ignition pulse P Ne is processed by a wave shaping circuit 13 having, e.g., a one shot multivibrator and by a flip-flop circuit 14, with the ignition pulse P Ne being received into the CPU 10 as rotational frequency data Ne(N). The throttle signal TH o , in this embodiment reflecting a fully open throttle, is simultaneously supplied to an appropriate port of the CPU 10 via an interface circuit 15.
The exhaust timing member position sensor 5 generates an angular position signal V.sub.θ which indicates, for example, the position or angle of rotation of the electric motor 2, or the displacement from a reference position of an appropriate member of the exhaust timing mechanism 1. The angular position signal V.sub.θ is digitized by an A/D converter 16 and is received into the CPU 10 as data θ v (N) via a bus line.
On the basis of the data Ne(N), TH o , and θ v (N), the CPU 10 determines an optimum opening for the exhaust timing member and supplies command voltage data V o corresponding to this optimum opening to a driving voltage generator circuit 17. The command voltage data V o includes bits which indicate respectively the plus and minus polarity of the voltage and its magnitude. The driving voltage generator circuit 17 generates a motor driving voltage V M supplied to the electric motor 2 on the basis of the data V o . A key switch 18 such as an ignition switch facilitates providing the CPU 10 with commands which set a desired initialized condition in a main routine, as further described hereinafter.
FIG. 2 is a flow chart showing the CPU routine for adjusting the opening of the exhaust timing member. This routine is synchronized with a clock pulse from a self-contained clock generator in the CPU 10.
A power voltage is supplied from a regulated power supply (not shown) to the control circuit 4, for example, by switching on an ignition switch, thereby activating the control circuit 4. The clock pulse is generated from the self-contained clock generator circuit, and the routine is performed with each clock pulse. In this routine, the initialization function is performed immediately after turning on the power supply (step S 1 ). This initialization function is usually carried out in the microcomputer and, for example, includes a function for setting an initial provisional target value for the timing member position θ T (n).
The provisional target position θ T (n) is set from memory (step S 2 ). The provisional target position θ T (n) is either established as part of the initializing function or is calculated in the overflow interrupt routine discussed hereinafter with reference to FIG. 4 as in turn based on the values calculated in the flow chart of FIG. 3. A value θ v (N) of the actual measured exhaust timing member position is then received (step S 3 ). Then, the difference δ(including the plus and minus signs) between θ T (n) and the θ v (N) is derived (step S 4 ), and the absolute value of the difference |δ| and the threshold value δr are compared (step S 5 ). If |δ| is smaller than the threshold value δr, the output voltage data V o is set at zero (step S 6 ) and step S 2 is reentered taking in θ T (n). The threshold value δr is determined within a maximum margin of error including the possibility that θ T (n) and θ v (n) have coincided with each other, and ideally, δr is zero. When |δ|>δr, the opening of the exhaust timing member has not reached the desired position. Accordingly, an output voltage V o having a value proportional to the difference δ (step S 7 ) is generated.
The driving voltage generator circuit 17, when receiving the data V o set by the main routine, drives the electric motor 2 by bringing the value of the motor driving voltage V M to 0, -V M , or +V M , according to the value of Vo (0, -K·δ, +K·δ). The electric motor 2 is then correspondingly stopped, or turns in a reverse or forward direction. The actual position of the exhaust timing member is accordingly changed to the desired position by the operation of the driving mechanism 1. In the driving voltage generator circuit 17, one or the other of the plus and minus power voltages V M or neither may be connected according to the value of V o to the output terminal.
FIG. 3 is a flow chart demonstrating a subroutine performed for every ignition pulse P Ne in the CPU 10. In this routine, a self-contained counter is triggered by the ignition pulse P Ne so as to count the rotational frequency, or speed, of the engine Ne(m) with the data showing a reciprocal of a pulse distance between the ignition pulses P Ne (step S 10 ). Then, a determination is made as to whether or not a self-cleaning complete flag F sc is present (step S 11 ). If F sc =1, the self-cleaning operation is not performed. If the self-cleaning complete flag is not present, F sc =0, the just determined speed Ne(m) is compared with a minimum required engine speed N(sc) beyond idle, for example, 1500 rpm. The self-cleaning operation is then not performed since if Ne(m)<Ne(sc) the rotational speed of the engine is not sufficient. If the self-cleaning operation was to be performed before the rotational speed of the engine is high enough, the fully open state of the exhaust timing member would temporarily occur and the rotational speed of the engine may become unstable.
When Ne(m)≧Ne(sc), the self-cleaning operation is carried out. First, θ v (N) is compared with θ o (step S 13 ). When θ o is not equal to θ v (N), an interim self-cleaning Flag F scl is checked. If the flag F scl is not present, a target position θ TGT is set to θ o (step S 14 ) thereby entering into a return function. Then, when θ v (N) becomes equal to θ o by moving the exhaust timing member open, the target position θ TGT is reset at θ TGT =θ s (step S 15 ). The interim self-cleaning complete flag F scl is then set. A determination is made as to whether θ v (N) is equal to θ s (step S 16 ). Until θ v (N) becomes equal to θ s , the return operation is entered by recognizing the flag F scl and retaining θ TGT =θ s . When θ v (N)=θ s the self-cleaning operation is complete and the self-cleaning complete flag is set, Fsc=1 (step S 17 ), and the control enters into the return operation. Thus, after turning on the power supply and after N(m)≧Ne(sc) the self-cleaning operation is performed.
The self-cleaning complete flags Fsc and Fscl are set to 0 in the initialization step S 1 of the main routine. It is also possible to perform the desired number of the self-cleaning functions in such a manner that the function is performed until a variable K becomes a maximum value by having Fsc taken as K such that K becomes K+1 for every termination of one self-cleaning function cycle.
When F sc =1, the last preceding value Ne(m) of the data of the rotational frequency is compared with a fully closed threshold value Ne s , the speed of the engine at which point the timing member is desired to be fully closed, and it is determined whether the last preceding value Ne(m-1) satisfies the relationship Ne(m-1)<Ne s ≦Ne(m) or not (step S 18 ). When this inequality relationship exists, it is sensed as a moment when the rotational frequency Ne of the engine has exceeded the fully closed threshold value Ne s . In this case, the change in speed, that is, an acceleration (dNe/dt) (Ne s ) of the rotational frequency Ne of the engine is counted at that time (step S 19 ). Here, (dNe/dt)(Ne s ) is represented as ΔNe(Ne s ). Then, the presence or absence of the fully open throttle signal TH o is determined (step S 20 ). In the presence of the signal TH o , the amount of step U sp is selected as the fully open amount of step U spo =U 1 ·ΔNe(Ne s ) (step S 21 ). In the absence of TH o , the amount of step U sp is operated as the first middle opening amount of step U spp1 =U 2 ·ΔNe(Ne s ) and enters into the return function. Here, U 1 , U 2 are constant, preferably with U 1 >U 2 .
When the inequality Ne(m-1)<Ne s ≦N(m) does not exist, the control device decides whether the inequality Ne(m-1)>Ne o ≧Ne(m) is valid or not (step S 23 ). If this inequality is valid, it is a moment when the rotational frequency Ne of the engine is less than the fully open threshold value Ne o . In preparation for closing the timing member, presence of the fully open signal TH o of throttle is determined (step S 24 ). In the presence of TH o , the control device enters into the return function without performing other steps. On the other hand, in the absence of the TH o , the exhaust timing member is adapted to the middle opening position θ p . After counting (dNe/dt) (Ne o )=ΔNe(Ne o ) (step S 25 ), the amount of step U sp is considered as the second middle amount of step, U spp2 =U 3 ·ΔNe(Ne o ) (step S 26 ). Further, U 3 is a constant and as U 2 =U 3 , U spp1 may equal U spp2 .
When the inequality of step S 23 is not valid, the present value of the rotational frequency of the engine Ne(m) is compared with the fully open threshold value Ne o (step S 27 ). When Ne(m) is larger than Ne o , the final target position θ TGT is set at the fully open position data θ o and the amount of step U sp is set at a predetermined value U o1 . Simultaneously, an opening and closing demand flag F RQ is set up and the return function is entered (step S 28 )
When Ne(m) is less than Ne o , Ne(m) is compared with Ne s (step S 29 ). When Ne(m) is less than Ne s , the final target position θ TGT is set at the fully closed position θ s . Simultaneously, F RQ is set up and the amount of step U sp is set a predetermined value U o2 (step S 30 ). If Ne(m) is larger than Ne s , Ne(m) is between the Ne s and the Ne o , and then the presence of the fully open throttle TH o is checked (step S 31 ). When TH o exists, the control device checks whether the timing member is being moved toward full open, that is, whether the conditions of θ TGT =θ o and F RQ =1 are satisfied or not (step S 32 ). If the conditions are valid, the return function is entered without other steps. If it is not valid, the return function is entered as θ TGT =θ o and F RQ =1 (step S 33 ). In the absence of the fully open throttle signal TH o , the opening of the exhaust valve is set to the middle opening position θ p , and the condition of movement to the middle opening position, that is, the condition of θ TGT =θ p and F RQ =1 is established (step S 34 ). If this condition is satisfied, the return function is entered without other steps. If the condition is not satisifed, the return function is entered as θ TGT =θ p and F RQ =1 (step S 35 ). By the aforementioned function modes, the final intended value θ TGT and the amount of step U sp are continuously updated and are always the optimum value for every P Ne pulse.
Alternatively, the provisional target position θ T (n) may be calculated solely on the instantaneous engine speed without including variable timing member response rates responsive to acceleration of the engine.
The flow chart of FIG. 3 is performed by interrupting the main routine with every engine ignition pulse P Ne . A provisional target value setting mode serves to control a function mode which determines a present provisional target value θ T (N). θ T (N) is established by the function mode with respect to the finally intended or final target value θ TGT such that θ T (N) gradually approaches θ TGT . The provisional target value setting mode is performed by an overflow interrupt routine which employs a timer (not shown) to count by means of the clock self-contained in the CPU and which is performs for every desired time.
FIG. 4 is flow chart which shows the overflow interrupt routine for execution of the provisional target value setting mode and the counting mode. First, when the self-contained timer overflows, the control system determines whether the opening and closing demand flag F RQ is present (1) or not (0). If F RQ =0, the routine returns to the CPU routine. If F RQ =1, the provisional target value setting mode is to be performed. The present provisional value θ T (n) and the final target value θ TGT are taken from the memory (step S 41 ). Then, the amount of step U sp therein is received (step S 42 ). By comparing magnitudes of θ TGT and θ T (n) thus taken, a decision is made whether to open or close the timing member (step S 43 ). If θ T (n) is less than θ TGT , the provisional target value is charged by taking θ T (n)+U sp as a final value to increase the provisional target opening degree by the amount of step U sp (step S 44 ). Conversely, if θ T (n) is less than θ TGT , the provisionally aimed opening degree θ T (n) is decreased by the amount of step U sp , as θ T (n+1)=θ T (n)-U sp (step S 45 ).
Then the magnitudes of θ TGT and θ T (n+1) are compared (steps S46, S47). If θ T (n+1) has not reached θ TGT , this mode is terminated); if it has, θ T (n+1) is made equal to θ TGT (step S48), the opening and closing demand flag FRQ is set to zero to release it (step S49) and this mode is terminated.
FIG. 5 shows the relationship of engine torque to engine speed having the positioning of the timing member as a parameter of engine speed. When the engine rapidly accelerates, the timing member experiences prompt actuation and the torque rises smoothly, as shown by the dotted line L. There is no reduction in torque as would be experienced with a conventional engine with one setting or a controlled engine exhaust port with the member controlled to be either fully open or fully closed.
FIG. 6 shows a block diagram which illustrates the operating functions of the CPU 10 shown in the flow charts of FIGS. 2 to 4. Operating means 20 generates the data Ne of rotational frequency on the basis of the ignition pulse P Ne . The data Ne of rotational frequency is compared with the fully open threshold value Ne o and the fully closed threshold value Ne s by means of first and second comparator means 21, 22. The Ne data is differentiated by means of differentiator means 23. Means 24 for setting the final target value sets θ TGT according to the signal from the first and second comparator means 21, 22 and the fully open signal TH o of the throttle. Further, the control device may perform the forced setting of the fully open and fully closed opening upon performing the self-cleaning operation mode, which cooperates with the signal from self-cleaning decision means 25.
Means 27 for setting the step amount operate with the signal from the comparator means 21, 22 and the differentiator means 23. Means 28 for setting the provisional target opening degree sets the provisionally aimed opening θ T according to the step amount U sp from the means 27 for setting the step amount and according to the final target opening degree θ TGT from the means 24 for setting the finally aimed opening degree. Subtraction means 29 computes the difference δ=θ v -θ T between the θ T thus obtained and the real opening degree θ v of the exhaust timing member and supplies this difference to multiplier means 30. The multiplier means 30 calculates V o =K·δ and outputs the result as a driving voltage data V o for the timing member.
The behavior of the circuit shown in the block diagram of FIG. 6 is adapted to actuate at the same parameters as that shown in the flow charts of FIGS. 2 to 4.
Thus, an exhaust timing control device is disclosed for a two cycle engine wherein the opening degree of an exhaust port timing member is adjusted according to the engine operating state to effect optimum exhaust timing and a cleaning cycle is provided to prevent disabling buildups on the member. While embodiments and applications of this invention have been shown and described, it would be apparent to those skilled in the art that many more modifications are possible without departing from the inventive concepts herein. The invention, therefore, is not to be restricted except in the spirit of the appended claims.
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An exhaust timing controller for controlling an exhaust timing member in a two cycle engine includes a control circuit for generating a control signal which actuates a mechanism for moving the exhaust timing member. The control circuit controls the member such that the member is drivable in a range from a fully open position to a fully closed position responsive to certain engine conditions including engine speed. A self cleaning cycle is provided which drives the exhaust timing member first to one position limit and then to the other. This may be performed with initial operation of the engine above a specified engine speed with the position of the exhaust timing member being independent of engine speed during cleaning.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention concerns a method of detecting false locks between a reference signal and a signal to be demodulated by coherent digital demodulation and a device implementing a method of this kind.
2. Description of the Prior Art
A first conventional type microwave receiving system comprises in series after the receive antenna a microwave band filter, a low-noise amplifier and a mixer carrying out transposition to an intermediate frequency by means of a local oscillator. A system of this kind then comprises an intermediate frequency preamplifier, circuits for correcting group delay time and an intermediate frequency amplifier. The intermediate frequency demodulator circuit then restores the baseband signal, the encoded signal being recovered after processing the baseband signal. In receiving systems of this kind the double transposition from the microwave band to the intermediate frequency and then from the intermediate frequency to the baseband entails the use of a set of intermediate frequency circuits, in particular a local oscillator.
A second type of microwave receiving system enables direct demodulation of a received microwave signal with a reduced number of components, the intermediate frequency circuits being eliminated. U.S. Pat. No. 4,559,499 describes a microwave direct demodulation device for demodulating a modulated signal produced by mixing two carriers in phase quadrature each modulated by digital signals; it comprises a modulator circuit the input of which is connected to a received signal input associated with an oscillator operating at the carrier frequency of the received signal and controlled so that the phase of the carrier from the oscillator coincides with the phase of the received signal, the demodulator circuit comprising a separator connected to first inputs of two symmetrical mixers, a coupler introducing a phase shift of 90° into one channel and the outputs of which are connected to second inputs of second mixers, and low-pass filters connected to the outputs of the mixers delivering the demodulated digital signals.
In any coherent demodulation system it is necessary to have a phase reference, obtained by recovering the carrier: the needed information is contained in the phase of this carrier.
Whether demodulation is direct or involves transposition to an intermediate frequency, there occur "false locks" between the reference signal and the signal to be demodulated, resulting in erroneous phase information that cannot normally be corrected. In the case of modulation with four phase states, for example, these false locks are situated at multiples of one quarter the baud rate on either side of the center frequency.
The lower the transmit baud rate the nearer these false locks are to the carrier frequency, so that the stability of the VCO (voltage-controlled oscillator), especially its temperature stability, must be relatively high and therefore possibly difficult to achieve, especially if the baud rate is low and the carrier frequency is high.
If the stability of the VCO (dF/FO) is in the same order of magnitude as the difference between the frequency of the false locks and the carrier frequency FO, phase comparators cannot distinguish true locks from false locks in the search phase (frequency search that must be better than the VGO drift to enable locking).
An object of the invention is to provide a solution to this problem.
SUMMARY OF THE INVENTION
In one aspect, the present invention consists in a method of detecting false locks between a reference signal and an input signal to be demodulated to produce a coherent demodulated signal comprising a number of phase states, the method comprising the steps of:
comparing the level of the input signal at a predetermined moment in the bit period of the input signal after demodulation and before regeneration with the level of the input signal after regeneration, bit by bit, and
optionally correcting the reference signal so as to lock its reference and phase to the input signal.
This method is usable with advantage in all transmission systems using digital modulation processes with 2, 4 or 8 phase states, for example.
To be more specific, the method as described previously is usable with a digitally modulated microwave signal with four phase states.
The method is advantageously independent of the baud rate, the nature of the modulation and the carrier frequency.
The information obtained is advantageously valid irrespective of the coherent demodulation system used: it is therefore possible to use a low baud rate or direct demodulation irrespective of the baud rate.
In another aspect, the present invention consists in a device for detecting false locks in a receiving system comprising a received signal input, a direct demodulation circuit connected to said received signal input and adapted to demodulate said received signal, which is produced by mixing two carriers in phase quadrature modulated by digital signals, to produce demodulated digital signals on two channels, an oscillator adapted to produce a local carrier at the same frequency as the received signal carriers and having a control input by which it is controlled so that the phase of said local carrier is coincident with the phase of said received signal, and a regenerator circuit having two inputs connected to receive respective demodulated digital signals on said two channels and two outputs delivering respective regenerated digital signals on said two channels, said device comprising a phase estimator having two inputs connected to receive said demodulated digital signals on said two channels on the input side of said regenerator circuit and an output delivering a signal dependent on the relative phase of said receive signal carriers and said local carrier, a loop integrator filter having an input connected to said phase estimator output and an output connected to said control input of said oscillator, and a comparator circuit connected between the input and the output of said regenerator circuit on one of said two channels.
The device advantageously provides information enabling the carrier to be recovered where it is modulated with 2, 4 or 8 phase states when intermediate frequency transposition or direct demodulation are used.
In a final aspect, the present invention consists in a receiving system comprising a received signal input, a direct demodulation circuit connected to said received signal input and adapted to demodulate said received signal, which is produced by mixing two carriers in phase quadrature modulated by digital signals, to produce demodulated digital signals on two channels, an oscillator adapted to produce a local carrier at the same frequency as the received signal carriers and having a control input by which it is controlled so that the phase of said local carrier is coincident with the phase of said received signal, a regenerator circuit having two inputs connected to receive respective demodulated digital signals on said two channels, and two outputs delivering respective regenerated digital signals on said two channels, and a device for detecting false locks comprising a phase estimator having two inputs connected to receive said demodulated digital signals on said two channels and an output delivering a signal dependent on the relative phase of said received signal carriers and said local carrier, a loop integrator filter having an input connected to said phase estimator output and an output connected to said control input of said oscillator, and a comparator circuit connected between the input and the output of said regenerator circuit on one of said two channels.
The characteristics and advantages of the invention will emerge from the following description given by way of non-limiting example only with reference to the appended diagramatic drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a receiving system including the device in accordance with the invention.
FIG. 2 is an explanatory diagram.
FIG. 3 shows one embodiment of the device in accordance with the invention.
FIG. 4 shows a series of curves illustrating the operation of the circuit shown in FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The description will refer to direct demodulation with four phase states, but the invention is in no way limited to this type of modulation.
This example has been chosen because direct demodulation at low baud rates accentuates the false lock phenomenon.
FIG. 1 is a block diagram showing one embodiment of the invention in a receiving system.
In this embodiment, the received signal at the input E comprises two carriers in phase quadrature modulated by two synchronous digital signals and forming a signal modulated with four phase states. This circuit also has a local oscillator signal input OL connected to the output of a voltage-controlled oscillator 10.
The local oscillator signal input OL is connected to the input of a 3 dB coupler 11 between the outputs of which there is a phase difference of 90°. The two outputs of the 3 dB coupler are connected to second inputs of two linear mixers 12 and 13 first inputs of which receive the signal from input E. The frequency of the local oscillator is equal to the carrier frequency of the received signal.
The demodulation sequences in the baseband are then applied to the inputs of two automatic gain controlled amplifiers 14 and 15. The outputs of these amplifiers deliver the demodulated digital signals X(t) and Y(t) and are connected to the inputs of a phase estimator circuit 16 the output of which provides an error signal e(t) applied to the input of a loop integrator filter 17 the output of which is connected to the frequency control input of the voltage-controlled oscillator 10.
The demodulated digital signals X(t) and Y(t) are also applied to the inputs of a regenerator circuit 19. The function of this circuit 19 is to deliver rectangular signals derived from the distorted signals available at the output of the demodulator, regeneration being based on estimating, at appropriately chosen times, the rectangular signal that the distorted signal obtained most probably represents.
Regeneration is common to all three types of coherent demodulation and is based on timing recovery.
The timing is recovered from the demodulated signals, by detecting transitions on the X and Y channels, for example. It is used for the digital processing to restore the information content.
A circuit 18 in accordance with the invention compares the input signal after demodulation but before regeneration bit by bit with the same signal after regeneration.
The function of the phase estimator 16 is to produce a stable phase reference so that the various phase jumps embodying the information can be extracted correctly by the demodulator circuit.
In a receiving system using direct demodulation the phase estimator 16 is based on a COSTAS loop demodulator system, for example. In this type of system the error voltage e needed to lock the phase-locked loop is obtained direct from the demodulated signals X(t) and Y(t). It is possible to obtain from these two signals an error signal characteristic of the phase difference between the received carrier and the local oscillator signal.
As described in U.S. Pat. No. 4,559,499 the estimator may be of the "sign of sine 4θ" type, θ being the phase difference between the local carrier supplied by the oscillator 10 and the received carrier.
FIG. 2 is a diagram explaining how an estimator of this kind functions.
Z(t) is the composite signal resulting from the combination at the transmitting end of the two phase quadrature modulated carriers:
Z(t)=ρ(t)[cos (ωot+φ(t))].
Let x(t) and y(t) be the modulation signals on these carriers at transmission; in this example x(t)=y(t) and the modulation phase is φ=π/4. Let X(t) and Y(t) be the demodulated signals on reception on the phase quadrature carriers obtained from the local oscillator, θ being the phase difference between the transmit (PE) and receive (PR) carriers. To estimate this phase difference an error function is computed. If S(t) =X(t)+Y(t) and D(t) =X(t) -Y(t), it is possible to demonstrate that the function X(t)·Y(t)·S(t)·D(t)=+1/2ρ 4 (t) sine 4θ.
This function therefore has an amplitude varying with time and it also varies with θ (sine 4θ). From this function it is possible to obtain an error signal noting that sine 4θ changes sign when θ passes from one π/4 sector into the adjacent sector, in the diagram determined by the orthogonal axes representing the transmitted carriers in phase quadrature giving the values x(t) and y(t) and the bisectors of these axes corresponding to the transmit modulation phases. Let A, B, C . . . H represent these sectors on FIG. 2.
The error function e(t)=sign (+1/2ρ 4 (t) sine 4θ) is positive in sectors A, C, E and G and negative in sectors B, D, F and H.
This sign is the product of the signs of the various components X(t), Y(t), S(t) and D(t). To determine this sign a phase estimator of this kind can use analog multipliers, for example, or a logic circuit implementing the "EXCLUSIVE-OR" function, which is identical to the product sign function.
In the event of false locking of the local carrier, the received signals are erroneous but correspond to a possible state of the signal relative to the phase estimator, whence the necessity for correction as provided for in the method according to the invention.
The proposed device works by comparing the regenerated signal bit by bit with the unregenerated signal in order to obtain information for distinguishing between correct and false locking, so that a correction may be made at the oscillator 10.
This is possible because although the demodulated signals are erroneous they are at the correct baud rate and therefore enable timing recovery.
FIG. 3 shows one embodiment of the false lock detecting device in accordance with the invention.
A first D type flip-flop 20 receives on its input the demodulated unregenerated signal, for example the signal X(t)--this could just as well be the signal Y(t)--and on its clock input the recovered timing signal. A regenerated signal is therefore obtained at the output of this flip-flop.
A second D type flip-flop 21 receives on its input the same input signal--the signal X(t) in this example--and on its clock input the regenerated signal after it has passed through a variable time-delay circuit 22. This flip-flop enables bit by bit comparison of the level of the input signal after regeneration at a predetermined time at the center of the input signal bit period with the level of the same signal before regeneration at the end of the bit period (adjustable by the time-delay τ).
The functioning of a circuit of this kind will now be described with reference to the curves in FIG. 4, in which:
(a) represents the eye diagram synchronized oscilloscope tracing of the input signal (at point A) after limiting and before regeneration in the case of correct locking; the eye being saturated, the transitions on the edges are affected by low amplitude jitter due in particular to the filtering;
(b) represents the eye diagram of the input signal (at point A) after limiting and before regeneration, in the case of false locking; note that the transitions of the eye are subject to significantly higher jitter, the time domain of the transitions on the flanks being much wider; it is therefore sufficient to detect on one of the two flanks of the eye diagram at a time situated in the area of the transitions of case (b) and outside the area of transitions of case (a), to check whether false locking has occurred or not; in this example it is the end of the bit period that is chosen; detection could equally well be done at the start of the bit period;
(c) represents the recovered timing signal (at point B) which is used to regenerate the demodulated signals;
(d) represents the eye diagram of the signal after regeneration in the case of true or false locking --regeneration by pointing of the signal (a) or (b) at the optimum time by the signal (c);
(e) represents the regenerated signal after the time-delay τ (at point D) which aligns the rising edge of the regenerated signal near the flanks of the unregenerated signal in the case of true locking, that is to say at the middle of the transitions in the case of false locking; it is then possible to compare the regenerated signal bit by bit with the unregenerated signal at a time defined by the time-delay τ;
(f) represents the output signal of the second flip-flop 21 in the case of true locking (point E); the pointing of the signal (a) by the signal (e) gives a constant level, the signals (a) and (e) being totally correlated (bit by bit comparison); and
(g) represents the same output signal in the case of false locking (point E); the pointing of the signal (b) by the signal (e) in the middle of the transitions gives at the output of the flip-flop 21 a signal that is random with time (pulse stream); point E (the output of the flip-flop 21) therefore delivers information distinguishing true locking (constant level) from false locking (pulse stream) that can be used as a correcting factor in carrier recovery during the search phase.
It is to be understood that the present invention has been described and shown by way of preferred example only and that its component parts can be replaced by equivalent parts without departing from the scope of the invention.
The above device has been described in connection with a modulated signal with four phase states. This example is obviously not limiting and the receiving system described is applicable to receiving any digitally modulated signal that can be put into the form of two phase quadrature carriers.
The method of the invention is therefore applicable to the coherent digital demodulation of signals that are not situated in the microwave band.
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In a method of detecting false locks between a reference signal and an input signal to be demodulated to produce a coherent demodulated signal comprising a number of phase states, the level of the input signal at a predetermined moment in the bit period of the input signal after demodulation and before regeneration is compared with the level of the input signal after regeneration, bit by bit. The reference signal is optionally corrected so as to lock its reference and phase to the input signal.
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BACKGROUND
[0001] The present embodiments relate to altering the surface area of cylindrical objects, such as for example pipes and tubes, for increasing heat transfer at same.
[0002] It is desirable to increase a surface area of pipes and tubes (collectively “piping”) in order to increase their heat transfer efficiency. Such pipes are used in, for example, heat exchangers and condensers. Known methods include chemical or mechanical joining of fins or wings to existing piping to increase the surface area of said piping to bring about heat transfer efficiency. However, these known processes are labor intensive, which results in increased cost, and are limited in the temperature and the fabrication of the surface area of the piping. For example, the fins which are welded or joined to the piping are usually limited to a lower temperature and are expensive to fabricate due to the exacting tolerances required of the fins.
[0003] In addition, certain alloys cannot be used to fabricate the fins because of the metallurgical or other physical differences between the fins and the base metal used for the existing piping. The physical or molecular differences between the material of the fins and the base metal of the piping may sometimes result in incompatibility of these elements such that the structural integrity of the piping is compromised due to the weakened joint between the components.
[0004] It is also common for fins only to be available in certain repetitive shapes that disallow for novel, particular patterns that could be used to further enhance turbulent or other fluid effects during the heat transfer. While mechanical machining allows almost all types of metals to be machined for the piping, the cost to do so for a myriad of different types of pipes can be unusually expensive, and therefore the related cost for the area to have an increased ratio of surface heat transfer effect by direct machining of said surface is generally prohibitive.
[0005] It would therefore be desirable to have an apparatus and method for use with all types of metallic piping to increase the heat transfer effect at a surface of said piping with minimal labor and material costs.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] For a more complete understanding of the present embodiments, reference may be had to the following description taken in conjunction with the drawing Figures, of which:
[0007] FIG. 1 shows a side view in cross-section of an embodiment of a surface relief apparatus of the present invention;
[0008] FIG. 2 shows an end view in cross-section of another embodiment of a surface relief apparatus;
[0009] FIGS. 3A-3C show portions of top plan views of different surface relief provided by the apparatus of FIGS. 1 and 2 ; and
[0010] FIG. 4 shows an embodiment of a method which may be used to provide surface relief to cylindrical objects such as piping.
DETAILED DESCRIPTION OF THE INVENTION
[0011] Referring to FIG. 1 , an embodiment of a surface relief apparatus of the present invention is shown generally at 10 . The apparatus 10 is used to deposit “resist” on a surface area of cylindrical tubing 12 , such as for example pipes, conduits and other objects of similar construction.
[0012] The apparatus 10 includes at least one printing wheel 14 or alternatively, as shown in FIG. 1 , a pair or a plurality of the printing wheels for coacting with the pipe 12 . If a pair of the printing wheels 14 are used, such pair will be spaced apart a distance sufficient to receive the pipe 12 therebetween for deposition of the resist as describe hereinafter.
[0013] Disposed adjacent to and for coaction with the printing wheel 14 , roller or drum is a reservoir 16 in which is contained a fluid resist 17 for being deposited on a surface 18 of the pipe 12 . Again, it is possible to use one of the reservoirs 16 for a corresponding one of the printing wheels 14 used in the apparatus 10 , as shown for example in FIG. 1 . Each one of the printing wheels 14 has a surface area 20 which is in fluid communication with the reservoir 16 for receipt of the liquid resist on to the surface 20 of the printing wheel. It is possible that either the reservoir 16 or the wheel surface 20 will have the particular pattern that is to be assumed by the resist and transferred onto the surface 18 of the pipe. As the printing wheel 14 rotates, the surface 20 of the wheel is coated with the fluid resist 17 from the reservoir 16 such that the resist is thereafter deposited as a specific pattern on the piping surface 18 .
[0014] At least one bearing 22 or support member is used to support the pipe 12 for introduction adjacent to or between the printing wheels 14 so that deposition of the resist 17 on the surface 18 of the pipe is sufficient and uniform according to the desired application pattern. The bearing 22 or bearings can be roller bearings.
[0015] A direction of travel of the pipe 12 with respect to the apparatus 10 is shown generally by arrow 24 .
[0016] Referring also to FIG. 2 , another embodiment of the surface relief apparatus is shown generally at 26 . In this apparatus 26 , a plurality of the printing wheels 14 are used such that the entire surface 18 of the pipe 12 is covered in the select pattern of the resist 17 to be deposited. Each one of the printing wheels 14 may have its own corresponding reservoir 16 of the fluid resist 17 . Alternatively, each one of the printing wheels 14 is in fluid communication with a common reservoir which functions as a manifold or plenum to supply the fluid resist 17 to each one of the plurality of printing wheels.
[0017] FIGS. 3A-3C show the different patterns or shapes of resist that can be deposited on the surface 18 of the pipe 12 , as for example “microbumps”. A pattern of resist bumps 25 a shown in FIG. 3A , chevrons 25 b shown in FIG. 3B or diagonals 25 c shown in FIG. 3C , can be deposited on the pipe surface 18 . Alternatively, any number of these shapes 25 a - c or a combination of same in a corresponding pattern can be used for deposition on the pipe surface 18 . That is, the patterns shown in FIGS. 3A-3C are formed in relief on the surface 20 of each printing wheel 14 so that the fluid resist 17 is deposited on the elevated pattern for subsequent deposition on the cylindrical tubing 12 . The microbumps may extend, by way of example only, approximately 1 mm above the pipe surface 18 . FIGS. 3A-3C also show for example an area of 1.60, 1.76 and 2.83 square inches, respectively, of the pipe surface 18 having the bump pattern.
[0018] In FIG. 4 , a method is shown generally at 30 for having the pipe 12 etched with surface relief of the patterns from, for example, FIGS. 3A-3C or any other pattern desired, to provide increased surface area and therefore increased heat transfer effect at the pipe surface 18 .
[0019] In operation of the method, a particular type of the pipe 12 is selected 32 for etching. A pipe or tubing cache can be staged in any manner. Thereafter, each one of the pipes 12 are provided to the surface relief apparatus 10 in the step 34 for deposition of the fluid resist 17 in a select pattern on the surface 18 of the pipe. The pattern selected may be that shown in FIGS. 3A-3C , for example. When the pipe 12 emerges from the apparatus 10 , the pipe is subjected to a drying step 36 for drying and stabilizing the resist 17 . Alternatively, if the fluid resist 17 is an epoxy, such may be cured with ultraviolet (UV) or visible light. Thereafter, the pipe 12 is subjected to an etching step 38 which will remove a select amount of the surface 18 of the pipe 12 that is not protected by the fluid resist 17 pattern. After the etching step 38 , the pipe 12 is subjected to a wash 40 for removing or neutralizing the particular etching substance used in the step 38 . The washing can be done with water or deionized water, for example. If an acid etchant is used for the etching 38 , more than likely a neutralizing agent for the acid will have to be used to neutralize any remaining acid on the surface 18 of the pipe 12 . After neutralizing, the pipe surface 18 may also be washed. After the neutralizing and/or washing step 40 , the resist 17 must be removed and this can be done in a removal step 42 which may include heat lamps or other heating elements to burn off and/or dissolve the resist 17 . It is also possible to remove the resist with a chemical treatment to dissolve the resist from the pipe 12 . The result will be that the surface area 18 of the pipe 12 has been etched or worn away except for the particular pattern of microbumps which remain due to the resist 17 deposited during the resist deposition step 34 . Thereafter, the pipe 12 having a new surface relief with a select pattern of, for example, the shapes of FIGS. 3A-3C , and corresponding heat transfer effect will be provided for subsequent processing, such as cutting, bending, painting, graphics, mechanical attachments, etc., or for immediate use by an end user 44 .
[0020] The surface relief apparatus 10 , 26 could alternatively employ either electrostatic, laser or ion deposition of the fluid resist 17 . Photolithography is also possible for deposition of the fluid resist 17 for the step 34 .
[0021] The fluid resist 17 used may be a resin epoxy which would resist a particular etchant chosen. Depending upon the chemistry used in the etchant or wash step 40 , this would determine the type of fluid resist 17 used. For example, during electrolytic etching, a basic inorganic fluid resist 17 may be sufficient. However, if acid etching is used for the etching step 38 , a resin epoxy as the fluid resist 17 could be used at the surface 18 of the pipe 12 . An adhesive polymer may also be used for the resist 17 .
[0022] Similarly, the etchant solution for the step 38 would also be dependant upon the material type of the pipe 12 . For example, if the pipe 12 is high in nickel content, this would require a fluorinated compound (hydrofluoric) etchant, while a sodium hydroxide would be sufficient for etching a stainless steel pipe. A carbon steel or chromium-molybdenum steel could be etched with an electrolytic process containing sodium chloride.
[0023] Regarding the patterns of FIGS. 3A-3C , such as presented are examples only and are not meant to be limiting. It is submitted that a cost-benefit analysis may be performed of the etching solution cost versus the metal of the pipe 12 to be etched. In other words, if the pipe 12 is constructed from a particular material, certain of the patterns for FIGS. 3A-3C would be desirable depending upon convection and radiation requirements of the pipe.
[0024] It will be understood that the embodiments described herein are merely exemplary, and that one skilled in the art may make variations and modifications without departing from the spirit and scope of the invention. All such variations and modifications are intended to be included within the scope of the invention as described and claimed herein. Further, all embodiments disclosed are not necessarily in the alternative, as various embodiments of the invention may be combined to provide the desired result.
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An apparatus for altering a surface of a cylindrical object includes at least one container containing a fluid resist therein and having at least one opening from which the fluid resist is discharged; at least one roller operatively associated with the at least one container and having a surface sized and shaped to be exposed to the at least one opening, the surface area including a pattern of shapes and upon which the fluid resist is deposited; and at least one support member adjacent the at least one roller for supporting the cylindrical object during transit for contacting the at least one roller. A method is also provided.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. application Ser. No. 10/399,801 filed Oct. 6, 2003 now U.S. Pat. No. 6,854,435, now allowed, which is a U.S. National Phase filing under 35 USC 371 based upon PCT Application No. PCT/AU01/01361, filed Oct. 23, 2001, which claims priority to Australian Provisional Application No. PR0931, filed Oct. 23, 2000.
FIELD OF THE INVENTION
This invention relates to camshafts for four stroke internal combustion engines. More particularly it relates to camshafts that cause engine speed variable timing duration of combustion chamber valves.
BACKGROUND OF THE INVENTION
Both petrol and diesel stroke engines typically use a camshaft to control the opening and closing of the engine's intake and exhaust valves. Normally the open period of the valves, usually referred to as the “duration” or “dwell”, is fixed by the valve lobe shape or profile ground onto the lobe of the camshaft when it is manufactured. Normally, this profile cannot be varied without the physical replacement of the camshaft by another with a different profile ground onto its lobes.
On some engines that are described as having variable camshaft timing, the opening and closing points of the valves can be varied but the actual duration or dwell of the valve opening remains fixed. A conventional camshaft that provides a fixed amount of valve opening allows an engine to achieve maximum volumetric efficiency, and hence torque, at only one point in the engine's revolution range. The torque falls off on either side of this point.
A camshaft arrangement which allows the valve opening duration to be varied so as to maximise the torque throughout the engine's revolution range would be very desirable. This fact has long been realised by engine designers and much effort has been expended in the search of a mechanical variable duration system of valve timing. No successful system has been achieved for a mechanical continuously variable system of valve timing duration. Systems which are not continuously variable but operate on a two-stage principle, such as Honda's VTEC system, have been adopted and are highly successful. Much effort is being spent on investigating hydraulic, pneumatic and solenoid systems of variable duration valve timing. Although the main advantage of a variable duration timing camshaft is to improve the torque spread of an engine it could be used to provide throttle-free control of the engine's induction to minimise intake pumping losses and/or to achieve low exhaust emissions.
It has been proposed to use a camshaft having two closely spaced cam lobes in combination with a wider than normal follower, or tappet, that rides on both lobes simultaneously. A mechanism is provided so that the lobes can be aligned to give minimum duration or misaligned to give an increase in duration. If the misalignment does not exceed the angular distance of constant radius of the cam lobe's nose, the follower “sees” the constant radius area as a continuous surface. The main deficiency of these devices is that the useable duration range is limited to twice, measured in degrees of rotation of the crankshaft, that of the angular span of the constant radius at the lobe's nose. The nose is the region of maximum lift of the camshaft lobe. Any attempt to increase the duration past this angular distance results in the follower falling into the gap between the two lobe noses causing unacceptable noise and wear. There have been proposed solutions to this problem, but none have been commercially successful. There is a wide range of possible variations in lobe profiles, style of construction, even using lobes on two separate shafts, and methods of control and actuation of the duration change. However, none of these have provided a successful product.
It would be desirable to have an improved variable duration timing camshaft and even more desirable to have one that could be fitted after market.
SUMMARY OF THE INVENTION
This invention provides in one form a variable duration valve timing camshaft comprising:
a shaft with fixed cam lobes lobe modifying elements that are adapted to move outwardly as the rate of rotation of the camshaft increases thereby cooperating with the lobes to continuously increase the angular distance at constant radius of each fixed valve lobe's nose and wherein the lobe modifying elements are further adapted to move inwards as the rate of rotation of the camshaft decreases thereby continuously decreasing the angular distance of constant radius of each fixed valve lobe's nose until it equals that of the fixed lobe.
Preferably the lobe modifying elements are pivotally connected to the camshaft.
In an alternative form the invention provides an internal combustion engine having a variable duration valve timing camshaft as described above.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1( a ), 1 ( b ), 1 ( c ), 1 ( d ) and 1 ( e ) are schematic views of the assembly of a camshaft.
FIGS. 2( a ), 2 ( b ), 2 ( c ), 2 ( d ), 2 ( e ), 2 ( f ), and 2 g are schematic views of the camshaft in open and closed positions.
FIGS. 3( a ) and 3 ( b ) are schematic views of alternative camshaft arrangements.
DETAILED DESCRIPTION OF THE INVENTION
The preferred lobe is based on the type normally used in engines with a single overhead cam with rockers and inclined valves. Almost every automobile manufacturer makes an engine with this type of valve train. All these camshafts have very similar lobe profiles. These are characterised by having a low lobe lift in comparison to a large base circle diameter and asymmetrical profiles. This is necessary as the rocker ratio varies as the camshaft rotates. The rocker ratio is generally fairly high. This is necessary to give a useable amount of lift at the valve. Sometimes the lift at the valve is as much as twice the lobe lift. All of the above results in a lobe profile which is noticeably “rounded-off” or “snub-nosed” at its point of maximum lift. A typical profile of this type has about 20 degrees of angular span at the nose of the lobe which is very close to having the desired constant radius needed for use in a variable duration arrangement of the present invention.
It has been found that by grinding a small amount (typically 0.25 to 0.50 mm) off the nose of a production camshaft lobe and “blending-in” in the resulting constant radius area with the original profile a satisfactory overall profile can be achieved. In fact we have been able to use the same profile as that of a production camshaft with no apparent adverse effects. A typical general purpose car engine usually has a valve duration of about 250 crankshaft degrees. With a constant radius on the nose of the lobe of 20 degrees (40 crankshaft degrees) a variable duration range of 250 to 290 degrees is possible. Typically a general purpose road engine would not be able to make use of a duration greater than 290 degrees at maximum rotation speed. As the opening and closing areas of the profile remain identical to a standard profile, for that type of engine, and the lobe nose area is only slightly modified wear characteristics, noise are the same or very little different to a standard cam.
Generally, there is a very small window where all the possible parameters come together to produce a workable variable duration camshaft. The art of lobe design is a very critical one and even minor departures from established lobe profiles, that is departures for acceptable rates of lifter acceleration and deceleration and clearances, are likely to cause the mechanism using them to be unsuccessful. A characteristic of this invention is that generally the longer the “base” duration the greater the duration that can be achieved. This can be seen by using the 250 to 290 degree type of basic road cam as an example. If the 290 degree expanded shape was ground on to a lobe as the base or minimum profile, it would have a region of 40 degrees (80 crankshaft degrees) of constant radius which equates to a duration range of 290 to 370 degrees. Durations longer than 360 degrees are virtually unknown. Durations greater than 340 degrees are uncommon even in engines intended only for competition use and never in road use engines. A useable and useful variable duration cam intended only for competition use will have a range of something like 280 to 320 degrees with high lift without departing very much at all from traditional lobe shapes. There is no point in using the available 80 degree duration range. In a similar way it can be seen that the shorter the base duration the shorter the possible duration range is.
The preceding discussion may suggest that this invention is slightly better suited to competition or high performance road use rather than in low-revving industrial petrol engines or diesel engines. The diesel engine however is influenced much more from its camshaft than a petrol engine does. The diesel requires a camshaft with very short duration otherwise it will not generate enough compression pressure to ignite the injected fuel at cranking (starting) revolution speeds or idle speeds. The short duration cam needed seriously hampers the diesel at normal and higher running speeds. It can be seen that even though the diesel is not an ideal subject for this invention, it would probably benefit more from it than a petrol engine and may become the main recipient of camshafts of this type.
As soon as the lobes become even slightly misaligned, the majority of the profile becomes redundant as the follower does not touch it at all. The lobe insert or lobe modifying element uses the minimum amount of the total lobe outline possible which is from the start of the constant radius section to where the lobe base circle begins. The fixed valve lobe is typically mounted on an outer shaft and the lobe modifying elements are fixed to the inner shaft which is coaxial to the outer shaft. The relative angular displacement of the these two shafts is the means by which the duration is varied. If a basic duration of 250 degrees is used (125 camshaft degrees) this means that the minimum segment angular length is 62.5 plus 10 degrees=72.5 degrees. The prototypes have used a segment length of 90 degrees for simplicity and to allow for possible large basic durations more than 250 degrees. Other mechanisms of this type use all of the profile except the basic circle region. Some use the entire profile. Using only the minimum amount of profile on the lobe insert allows the structure to be much more compact and consequently stronger. The aperture in the outer shaft for the insert can be smaller and this weakens the outer shaft to a much lesser extent. It can also be seen that for similar reasons the full lobe profile on the outer shaft does not have to constitute the entire profile. However, for reasons of overall shaft strength and simplicity in manufacture, the complete profile has been used in the prototypes.
The typical method of manufacture and sequence of assembly is shown in FIGS. 1( a ) to 1 ( e ). The lobe segment can be arranged in two basic ways, centrally within the outer shaft lobe ( FIG. 1 d ) or side-by-side ( FIG. 1 e ). Generally, the centrally located lobe segment arrangement requires more width than the side-by-side arrangement. In a purpose designed cylinder head the centrally located segment is to be preferred as the loads on the follower are then symmetrical and there is likely to be more space to accommodate this arrangement. However, the side-by-side arrangement is probably perfectly satisfactory in most applications and because of space restrictions in some cases, it is the more suitable type of layout to use. Many production rockers have a much greater offset between cam lobe and valve stem than that which would result from a side-by-side arrangement of lobe and lobe insert. The outer shaft diameter is made as large as possible to maximise both its strength and that of the inner shaft.
Construction begins in a similar manner to a normal “billet” camshaft (that is, a cam basically machined from a solid piece or billet rather than cast or forged) except that the billet has a hole bored through its entire length. The diameter of this hole is of the order of 24 mm. This hole is for the inner shaft 1 . The outer surface between the locations of where the lobes will be ground is turned to a typical diameter of about 32 mm giving a wall thickness of about 4 mm. This is the outer shaft ( 2 ). At appropriate intervals along the length of this hollow shaft are machined complete circles ( 3 ) of material about 14 to 22 mm wide and of a typical diameter of 48 to 55 mm. These annular sections (or “lobe blanks”) are to become ultimately the cam lobes. Apertures ( 6 ) are then machined through the annular sections to the hole in the middle of the shaft. The location of the apertures, which will finally accommodate the lobe inserts, vary according to whether the lobe segments are contained wholly within the lobes as in FIG. 1( d ) or side-by-side into the lobes as described in FIG. 1( e ). FIG. 1( d ) shows the full lobe FIG. 1( d ) ( 1 ) (mounted on the outer shaft FIG. 1( d ) ( 3 ) containing wholly the slot for the lobe insert ( 7 ) and its locating hole FIG. 1( d ) ( 4 ) in the inner shaft FIG. 1( d ) ( 5 ). Note that the full lobe's width FIG. 1( d ) ( 6 ) tends to be greater than it does with the alternative arrangement shown in FIG. 1( e ). Where FIG. 1( e ) ( 7 ) is the lobe insert and FIG. 1( e ) ( 8 ) the full lobe. The apertures are appropriately circumferentially disposed according to where the cam lobes will ultimately be located. In FIGS. 1( a ), ( b ) and ( c ) for clarity the lobe inserts are shown completely separate from the cam lobes so the aperture is through the outer shaft only. The inner shaft ( 1 ) which runs the full length of the outer shaft ( 2 ) is closely fitted into the outer shaft ( 2 ). The fit is such that although close the inner shaft ( 1 ) can be rotated by hand inside the outer shaft ( 2 ). The inner shaft ( 1 ) has slots ( 4 ) and cylindrical holes ( 5 ) machined into it which line up with the apertures ( 6 ) in the outer shaft/lobe blanks ( 2 )/( 3 ). The segment blank ( 7 ) has a flat-sided section ( 8 ) and a cylindrical stem ( 9 ) the thickness of ( 8 ) being the same as the diameter of the stem ( 9 ), about 8 to 10 mm. The slots ( 4 ) and holes ( 5 ) in the inner shaft ( 1 ) are sized so that ( 8 ) and ( 9 ) are a tight fit in them when assembled. The sides ( 11 ) of the lobe segment blank are angled so that when assembled to the inner and outer shaft they butt up parallel to the edges of the aperture in the outer shaft/lobe blanks. The included angle between the sides is about 20 to 25 degrees less than the angular size of the aperture. This difference in angle is to allow the movement necessary for the variation of the duration. This basically means that it is the same or very similar to the angular span of area of constant radius on the lobe's nose. FIG. 1( b ) shows the lobe segment tightly pressed or pressed and shrunk into the inner shaft through the outer shaft/lobe blank. After assembly a roll pin ( 12 ) is fitted in a hole drilled through the inner shaft ( 1 ) and lobe insert stem ( 9 ). Access to allow this drilling is through the circumferential gap ( 13 ) of 20 to 25 degrees which accommodates the relative allowable movement of the lobe and lobe segment.
FIG. 1( c ) shows the assembly in its finished state after the grinding of the lobe and lobe segment combined profile. The grinding is done with the lobe and lobe segment locked in the position they are shown in FIG. 1( c ), that is, the fully closed or minimum duration position. This is the preferred position in which the grinding is done. After the machining, assembly and grinding is completed the camshaft as a whole unit is surface hardened by nitriding for similar heat treatment. There are also several possible variations whereby the lobe segment could be bolted on and even be made removable. The material used for all components is 4140 or similar grade steel. Although all the prototypes so far have been fully machined there is no reason whey they cannot be at least in part cast or forged especially the outer shaft. There is also the possibility of using sintered powder technology for the lobe segments.
The outer shaft diameter is preferably only about 0.5 mm smaller than the cam lobe's base circle size. Camshafts with a very small shaft bearing diameter generally are not suited to being converted to a variable duration design. Other possible types can have a separate press-in or screw-in stem or lobe segment fixed by a bolt the head of which is later ground off to the correct profile. Most examples have a single piece lobe segment and stem as this allows the greatest stem diameter and overall strength but at the cost of being more difficult to make than other types. In normal applications the outer shaft with its fixed full lobes would lead as the cam rotated, the lobe inserts trailing.
As shown in the drawings, the leading, opening, lobe flank would be full width up to the point where the constant radius region begins, that is, where the aperture of the inset would be located. The object being that the stronger full face of the fixed lobe would be subjected to the inertial loads plus the load from the valve springs. The inserts are only subjected to valve spring loads which rapidly reduce as the normal lobe started to close.
Ideally the total width of the variable lobe would be double that of a normal lobe as used in that type of engine to ensure adequate surface area for the cam lobe follower to bear on. However this is rarely possible due to restrictions on space along the length of the camshaft. “Rarely possible” actually refers to the variable cam system when adapted to an existing production engine and cylinder head. In an engine (or cylinder head) designed specifically to employ this invention it would be much easier to find the required space—especially in twin cam types. This lack of space suggests that the use of a needle-roller bearing follower may be advantageous rather than the much more common sliding type of follower. For the same width roller bearing can withstand greater loads than a sliding type of follower. Even though the prototype engine performed well with the normal sliding type of follower it is expected that the roller follower will be employed in many cases.
It was stated earlier that, although, this particular invention was aimed at the S.O.H.C./ with rockers type of engine, has potential application to all types of valve gear layouts. However, it does suit engines that utilise rockers in their valve train especially those which have a high rocker ratio more than engines that do not have rockers. Thus, overhead cam engines where the valves are directly actuated (via inverted bucket tappets etc) by the camshaft lobes are not very suited to this variable duration camshaft invention. In this type of valve layout the lobe lift is equal to the valve lift. This means that for a reasonably short duration profile (250 degrees for example) the lobe must have a very “pointy” nose—that is a nose with a very short angular span. The only way to obtain a useable span of constant nose radius is to use a camshaft of very large physical size—which is possible but somewhat awkward in practice. To best make use of this invention in an engine with double overhead camshafts short “finger” rockers would usually be needed with an without a roller bearing. Production engines using this type of layout (but with conventional camshafts) are becoming increasingly common in both car and motorcycle engines.
The twin-cam layout has certain advantages compared to a single cam system when used with variable duration camshafts. The basic one is that the rate of increase need not be the same for both intake and exhaust valves. With a single cam the rate of increase must be the same for both the intake and exhaust valves. Another important advantage with a twin cam layout is that the valve overlap, the period when both intake and exhaust valves are open, can be varied independently of the duration variation by the relative rotational displacement of the camshaft with respect to the crankshaft. Many production twin-cam engines already have this capability, usually referred to as ‘variable camshaft timing’, the duration being fixed. If the variable duration camshaft is being used in an application where the main objective is throttle-free engine load control by the late closing of the intake valve, then the layout should be twin can unless the exhaust valve duration is to be fixed in which case a single can system could be used. The now somewhat old-fashioned pushrod operated overhead valve type of engine is generally suited to employ this invention as it has rockers in its valve train. The added inertia of the pushrods, etc, plus the need for fairly high rates of lobe lift, necessary to obtain the desired length of constant radius, and lack of space along the camshaft, especially in “V” type engines, would probably require needle roller bearing cam lobe followers. The pushrod-type engines may be slightly obsolescent but this type of engine is still manufactured in large numbers. Many of these engines, especially the higher performance versions, are equipped with roller Lifters as standard. The typical roller cam profile used in these engines has the desired blunt lobe nose profile which is very similar in shape to the previously described SOHC types but is symmetrical.
The methods of control of the duration in the prototype is by a simple centrifugal mechanism which both controls the appropriate amount of duration for a particular rpm, and actuates the duration change. At the front end, that is, the drive end, of the camshaft both the inner and outer shafts are attached to respective drive flanges. The centrifugal mechanism controls and actuates the relative angular position of these two flanges thereby adjusting the duration of the camshaft. In this example the full lobes advance the same amount that the lobe segments retard which means that the overall centerline of the combined lobe does not change as the duration changes.
The mechanism shown in FIGS. 2( a ), ( b ) and ( c ) are drawings of the device used successfully on the prototype camshaft. This mechanism holds the duration unchanged at 250 degrees from idle to about 3000 rpm, the point of maximum torque of the base 250 degree profile. The static tension on the return spring and the position of the spring's anchorage points, and thus, the amount of leverage of the spring) determines the point at which the duration starts to increase. Above 3000 rpm the duration increases in a roughly linear manner with the rpm until it reaches a maximum of 290 degrees at 6000 rpm. Computer simulations of the test engine have shown that there is little or no gain in power or torque by varying the duration in anything but a linear manner with the rpm. In actual testing it is not really noticeable if the increase in duration is not strictly linear with the rpm but is only roughly so.
Referring to FIGS. 2( a ), 2 ( b ), 2 ( c ), 2 ( d ), 2 ( e ), 2 ( f ) and 2 ( g ) show the component parts of the centrifugal mechanism as used on the prototype variable duration camshafts. FIG. 2( a ) and 2 ( b ) are the front views of the mechanism showing the centrifugal weights ( 15 ) which are mounted on the front of the assembly. FIG. 2( a ) is the fully closed-up position (or minimum duration) and 2 ( b ) is the fully open (or maximum duration) position. The centrifugal weights are fixed to shafts FIG. 2( a ) ( 16 ) by locking pins FIG. 2( b ) ( 17 ) which are pivoted in holes FIG. 2( c ) ( 18 ) in the timing belt pulley. The centrifugal weights return spring is FIG. 2( a ) ( 19 ) the alternative spring anchoring points are shown in FIG. 2( a ) ( 20 ) and the weights limit of travel stop pins are FIG. 2( b )( 21 ). Drive pins FIG. 2( a )( 22 ) in the weights engage in slots FIG. 2( d )( 23 ) in the front drive flange FIG. 2( d ) which is keyed to the inner shaft. The timing belt pulley drawing FIG. 2( c ) shows the holes FIG. 2( c )( 18 ) for the centrifugal weight pivot shaft. The timing belt pulley has a hole in tis centre FIG. 2( c )( 24 ) which fits over a rearward extension of the front drive flange and thus rotably partly locates the timing belt pulley. The centrifugal weight pivot shafts extend through to the rear of the assembly where they are connected to levers FIG. 2( f )( 25 ) locked to the pivot shaft by pins FIG. 2( g )( 26 ). A possible alternative shape for the levers is shown in dashed lines in FIG. 2( f )( 27 ). A degree scale for test purposes is FIG. 2( c )( 28 ) and the timing mark is FIG. 2( c )( 29 ). Drive pins in the levers FIG. 2( f )( 30 ) engage in slots FIG. 2( e )( 31 ). In the rear drive flange FIG. 2( e ) and FIG. 2( g ). The rear drive flange is keyed to the outer shaft. Elongated holes in the drive flanges FIG. ( 2 ( d )( 32 ) allow for the relative movement of the flanges and the pivot shaft.
Arrows FIGS. 2( d ) and 2 ( e ) ( 33 ) indicate direction of camshaft rotation and arrows FIGS. 2( d ) and 2 ( e ) ( 34 ) indicate the direction of flange movement to increase duration. The basic operating principle is as follows. The driving force from the crankshaft is applied to the camshaft belt pulley via the timing belt. This driving force is then applied to the centrifugal weight pivot shaft where it passes through the timing belt pulley. The driving force is then transferred to the drive pins that engage the front and rear drive flanges. The drive pins are offset from the pivot shaft centre of rotation in such a fashion that any rotation of the pivot shaft causes the front and rear drive flanges to move through equal angles but in opposite directions. This is equivalent to saying that the main driving force or torque for the pivot shaft is split into two equal but opposed forces or torques applied to the front and rear drive flanges. The balancing of these two forces was one of the main objectives in the design of the centrifugal mechanism as it allows the actual forces needed to effect duration changes to be very small relative to the force needed to drive the camshaft as a whole. Each of the two weights is linked in the same manner to both drive flanges. As the engine rpm increases above about 2500 or 3000 rpm the static tension on the return spring is overcome by the centrifugal force on the weights and they begin to move outwards thereby rotating the pivot shaft and increasing the duration of the camshaft. Most of the centrifugal force on the weights (of the order of 100 kilograms when the weight limit pins are reached) is used to overcome the return spring tension, very little force is needed to actually change the duration. These large forces compared to actual forces needed to perform the duration change mean that the response time of the duration change when the rpm changes is very fast. In fact there is no discernible time lag in the duration increase or decrease when the rpm varies either up or down.
One of the main aims of the centrifugal system was to make the control and actuating mechanism totally self-contained and not reliant on separate hydraulic pumps, electronics, etc. This is especially important if the variable duration camshaft is being fitted to an existing production engine as an aftermarket item but somewhat less so if the system is being applied to a purpose designed engine/cylinder head. Another important object in the design of the centrifugal mechanism was to link the inner and outer shafts together in such a way that the force needed to drive the advancing lobe is balanced against the force needed to drive the trailing lobe insert, a small force only being needed to increase and decrease the duration. In the testing of the prototype engine this was proven to be the case. Without the return spring fitted the weights move outwards, and increase the duration, as the engine speed rises but when the engine returns to idle the weights slowly return to the closed-up or minimum duration position showing that the force needed to drive the inner and outer shafts are indeed fairly well balanced against each other.
In alternative prototypes the centrifugal mechanism, the weights, springs, etc, can be completely contained within the camshaft drive belt pulley or chain sprocket—as shown in FIGS. 2( a ) and ( b ). This is partly for reasons of safety because if the mechanism failed at high speed, pieces could fly dangerously in all directions. Another proposed improvement is to have the drive to the inner and outer shaft flanges to be by pins engaging curved slots in the flanges. The object of this is to both lower the pin-to-slots wear loads and by changes to the shape of the slots (and/or return spring rates) tailor the rate of increase of duration with rpm to suit particular applications.
An alternative mechanism is shown in FIGS. 3( a ) and 3 ( b ) which has the same basic aims as the one described in FIG. 2 such as the balancing of opposing forces etc. but has it similar principal components arranged into a more suitable design for possible production purposes. The main components are the centrifugal weights ( 40 ), the outer casing ( 41 ) which carries in this sketch a double row chain sprocket and protruding inwards form the casing is a tongue ( 42 ). This tongue ( 42 ) carries the centrifugal weights pivot shaft ( 43 ). The front drive flange ( 44 ) is attached to the inner shaft ( 45 ) and the rear drive flange ( 46 ) is fixed to the outer shaft ( 47 ) by screws. The flange drive pin ( 48 ) located in the weight protrudes at both ends into curved slots ( 49 ) in the front drive flange and ( 50 ) in the rear flange (shown here superimposed for clarity). There are two return springs ( 51 ) which are contained in cylindrical casings ( 52 ) located in holes ( 53 ) bored in the weights. The travel on the weights is limited by the inside surface of the outer casing rathe than by stop pins as previously. The general operating principle is very similar to the previous design, the main difference being the slots in the drive flanges. The curved dashed line ( 53 ) indicates the position of a slot whose centre of curvature is the pivot shaft. If there was a slot in this position movement of the drive pin in the slot would cause no displacement of the drive flange. By having slots as indicated by ( 49 ) and ( 50 ) which have the same starting point and radius but different centres of curvature the appropriate amount of relative movement in the front and rear flanges could be achieved. Variations in the shape of the slots such as straightening or tightening of the curvature (depending on which flange it is) in its outer end could be used to compensate for the excessive duration increase in the upper rpm range. Generally speaking, the shape of the slot can be tailored to give whatever characteristics are desired more easily than with the previous type of mechanism. The return springs are of the compression type rather than the extension type used previously. Compression springs are preferable in this type of application as they are less likely to break if over stressed and they can also be more easily made to have rising spring rates. This newer design also differs from the earlier one in that the sprocket wheel/outer casing is rotatably supported on the edges of the drive flanges whereas in the earlier design the timing belt pulley (the equivalent structure) was supported at its centre on the rearward extension of the front drive flange which in turn was mounted on the inner shaft.
Since modifications within the spirit and scope of the invention may be readily effected by persons skilled in the art, it is to be understood that the invention is not limited to the particular embodiment described, by way of example, hereinabove.
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A variable duration valve timing camshaft is disclosed. The camshaft has a shaft with fixed cam lobes and lobe modifying elements that are adapted to move outwardly as the rate of rotation of the camshaft increases thereby cooperating with the lobes to continuously increase the angular distance at constant radius of each fixed valve lobe's nose. The lobe modifying elements are further adapted to move inwards as the rate of rotation of the camshaft decreases thereby continuously decreasing the angular distance of constant radius of each fixed valve lobe's nose until it equals that of the fixed lobe. The lobe modifying elements are pivotally connected to the camshaft.
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BACKGROUND OF THE INVENTION
[0001] The present invention relates to a speculum for carrying out vaginal surgery, and, more particularly, to a vaginal speculum that has an angular adjustment of the blade angle as well as an adjustable blade length.
[0002] The performance of any vaginal surgery, such as dilation and curettage, hysterectomy, colporrhaphy etc require the use of a vaginal speculum. At the present, the usual vaginal specula are weighted to be self-retaining and have a fixed blade at a fixed angle.
[0003] There are two basic designs with different shapes, with some variation in length and shape of the fixed blade, however, no one speculum design fits all patients and the surgeon may ask for several different specula until one is found suitable for a specific patient, which may simply not always be possible.
[0004] The process imposes a delay to the operation where the surgeon or staff are searching for the proper speculum and often results in choosing a speculum where the weight is often too large and rests against the operating table, causing the speculum to retract poorly and slip out of the patient and fall off the patient
[0005] It would therefore be advantageous to have a vaginal speculum that was adjustable within certain parameters, that is, a vaginal speculum where the length of the blade could be selectively adjusted and where the angle of that blade was adjustable by the surgeon so that the same vaginal speculum could be used on a variety of patients.
SUMMARY OF THE INVENTION
[0006] Accordingly, the present invention relates to a vaginal speculum that can be adjusted, both angularly as well as length-wise, in order to give the physician flexibility in operating on a patient quickly and without the need for a plurality of different specula on hand.
[0007] With the present vaginal speculum, there is a base that is oriented generally vertically and which has a blade that extends outwardly therefrom in generally a horizontal orientation. A plurality of sleeves are available that, in one exemplary embodiment, have slots such that each of the sleeves can be attached to the blade by simply inserting the blade into a slot in a sleeve. In this manner, any one of the plurality of sleeves can be selected by the physician and affixed to the blade.
[0008] Different sleeves are available having different lengths and widths such that the physician can physically examine the particular patient and then select and install the sleeve having the length and/or width that is best suited to that particular patient.
[0009] As a further feature of the present invention, the blade is angularly adjustable with respect to the base such that the physician can set the blade to a specific desired angle extending from the base and lock the blade into that angular orientation.
[0010] In a further embodiment, the vaginal speculum may have two blades, that is, there is a posterior blade and an anterior blade, both extending outwardly and generally aligned with and spaced apart from each other. In the exemplary embodiment, the anterior blade may be adjustable affixed by a sliding manner to the base to vary the space between the posterior and anterior blades and be completely detachable from the base. As such, the user can slide the anterior blade along the base to the desired location and lock the anterior blade to the base at that position, thereby establishing the desired spacing between the anterior and posterior blades.
[0011] The anterior blade may be affixed to the base by means of a mechanical linkage that includes an intermediate section having a loop, such as a C-shape loop, to form an open interior area to allow an instrument to pass through that open area for use on the patient. The vaginal speculum can be used with only the posterior blade, or with both anterior and posterior blades as needed. The sleeves can be interchangeable so as to be slipped onto both the anterior and posterior blades and have different lengths and/or widths and can be comprised of a plastic that is readily disposable.
[0012] These and other features and advantages of the present invention will become more readily apparent during the following detailed description taken in conjunction with the drawings herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a top view of the vaginal speculum of the present invention.
[0014] FIG. 2 is a rear view of the long, vertical weighted base of the vaginal speculum of FIG. 1 ;
[0015] FIG. 3 is a side view of the vaginal speculum of FIG. 1 ;
[0016] FIG. 4 is a perspective view of a sleeve of the present invention;
[0017] FIG. 5 is a side view of the sleeve of FIG. 4 ;
[0018] FIG. 6 is a side view of an alternative embodiment of a vaginal speculum incorporating the present invention and having a posterior blade and an anterior blade;
[0019] FIG. 7 is a rear view of the embodiment of FIG. 6 ;
[0020] FIG. 8 is a top view of the embodiment of FIG. 6 ;
[0021] FIG. 9 is an end view illustrating an alternate embodiment of a sleeve usable with the present invention;
[0022] FIGS. 10A and 10B are end views of a still further alternative embodiment illustrating a sleeve and blade, respectively, usable with the present invention; and
[0023] FIG. 11 is a schematic view of a kit containing a plurality of sleeves useable with a vaginal speculum of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0024] Referring now to FIGS. 1 and 2 , there is shown, a top view of the vaginal speculum 10 of the present invention and a rear view of the base 12 of the vaginal speculum 10 . As can be seen, the base 12 of the vaginal speculum 10 has a bottom surface 14 that is that is adapted to be positioned on a generally planar surface or hanging free. The base 12 is comprised of a base portion 16 and a generally rectangular upper portion 18 . The base portion 16 is preferably heavier at its bottom such that the base portion 16 can taper outwardly toward the bottom surface 14 , that is, the lateral cross section increases in the direction toward the bottom surface 14 of the base portion 16 such that the base portion 16 is weighted at the bottom for stability.
[0025] In an exemplary embodiment, the base portion 16 may be triangular in shape or may be another geometrical configuration, such as square or rectangular in horizontal cross section and a groove 19 may be provided that extends through the upper portion 18 and the base portion 16 to allow for drainage of fluids.
[0026] The base 12 is weighted so as to add stability to the vaginal speculum 10 and may be comprised of a metal, such as stainless steel, however, other materials are suitable for construction of the base 12 , including, but not limited to, a high density plastic. As can be seen, specifically in FIG. 2 , the longitudinal axis I of the base 12 is generally vertical when the vaginal speculum 10 is being used in connection with a patient.
[0027] Extending outwardly from the base 12 is a blade 20 that is rotatably affixed to the base 12 . By that rotational affixation, the blade 20 can be moved from a position where it extends outwardly at about a right angle from the longitudinal axis I of the base 10 , that is, the blade 20 can have a longitudinal axis II that is about 90 degrees from the longitudinal axis I of the base 12 .
[0028] As can be seen, particularly in FIG. 1 , the blade 20 is rotatable affixed to the base 12 such that the blade 20 can be rotated with respect to the base 12 to assume an angle from the base 12 that is desired by the physician using the vaginal speculum 10 . In particular, the mode of affixing the blade 20 to the base 12 can be through the use of a hinge 22 with the blade 20 having a hub 24 that is sandwiched between ears 26 formed on the base 12 such that the blade 20 can be rotatable with respect to the base 12 .
[0029] A locking mechanism 28 can be present in order to control the movement of the blade 12 , that is, one locking mechanism that is illustrated in the exemplary embodiment is by means of a screw 30 that passes through the ears 26 and hub 24 with a threaded device, such as a wing nut 32 threadedly engaged to the free end of the screw 30 .
[0030] As such the locking mechanism can have a locked position wherein the wing nut 32 is forcefully tightened along the screw 30 to pinch the hub 24 between the ears 26 to prevent the movement of the blade 20 and an unlocked position where the wing nut 32 is loosened so as to allow the blade 20 to rotate with respect to the base 12 .
[0031] Accordingly, with the locking mechanism, the physician can move the locking mechanism to the unlocked position, freely move the blade 20 to the desired angular orientation based on the position and anatomy of the patient, and then lock the blade 20 in that position by moving the locking mechanism to its locked position.
[0032] Turning then to FIG. 3 , taken along with FIG. 1 , there is a side view of the vaginal speculum 10 of the present invention and there can be seen a sleeve 34 that is affixed to the blade 20 . The sleeve 34 can be comprised of a plastic material and have a slot 36 that corresponds to the dimensions of the blade 20 such that the sleeve 34 can simply be affixed to the blade 20 by sliding the blade 20 into the slot 36 , thereby affixing the sleeve 34 to the blade 20 .
[0033] Further in FIG. 3 , there can be seen a locking mechanism wherein there is a sliding lock 38 positioned intermediate the base 12 and the blade 20 that, again can be a tightened by means of a screw 30 and wing nut 32 . In the exemplary embodiment of FIG. 3 , there may be grooves acting as teeth to further prevent the movement of the blade 20 when the locking mechanism is in its locked position
[0034] As can be seen, there are grooves serving as base teeth 40 and blade teeth 42 that mesh together when the blade 20 is located in the desired angular orientation such that any relative movement between the base 12 and the blade 20 is prevented in a positive manner.
[0035] Turning then to FIGS. 4 and 5 , there is a perspective view and a side view, respectively, of a sleeve 34 constructed in accordance with the present invention. As can be seen, the sleeve 34 is an elongated configuration having a proximal end 44 and a distal end 46 . The slot 36 can be seen that extends from the proximal end 44 into the sleeve 34 where it ends at a wall 48 .
[0036] The length of the slot 34 is, of course, determined by the length of the blade 20 ( FIG. 1 ) and the internal dimensions of the slot 34 are predetermined so as to fit tightly over the blade 20 while still being removable therefrom In an exemplary embodiment, the overall width of the sleeve 34 is from about 2 cm to about 4 cm with the lengths from about 4 cm to about 15 cm in separate sizes, that is, 2 cm×4 cm, 3 cm×6 cm, to 5 cm to 15 cm in various sizes
[0037] The lateral edges 50 , 52 of the sleeve 34 are upwardly curved and the distal end 46 is also lightly curved upwardly to facilitate the use of the sleeve 34 in carrying out a procedure on the patient.
[0038] Turning then to FIG. 6 , taken along with FIGS. 1 and 2 , there is a side view of an alternative, exemplary embodiment of the vaginal speculum 54 constructed in accordance with the present invention. As can be seen, the vaginal speculum 54 has two blades, that is, there is a posterior blade 56 and an anterior blade 58 . Taking first, the posterior blade 56 , the mounting and function of the posterior blade 56 is basically the same as is shown and described in FIG. 1 and the same identification numbers have been used as in FIG. 1 .
[0039] In brief, there is a base 12 of the vaginal speculum 54 having a bottom surface 14 positioned on a generally planar surface or hanging free and includes a base portion 16 and a generally rectangular upper portion 18 .
[0040] Extending outwardly from the base 12 is the posterior blade 56 that is rotatable affixed to the base 12 in the manner described with respect to the embodiment of FIGS. 1-3 . Again, the angular orientation of the posterior blade 56 with respect to the base 12 is determined and controlled by use of a hinge 22 with the blade 56 having a hub 24 that is sandwiched between ears 26 formed on the base 12 such that the blade 56 can be rotatable with respect to the base 12 .
[0041] A locking mechanism 28 controls the movement of the blade 12 and may be means of a screw 30 that passes through the ears 26 and hub 24 with a threaded device, such as a wing nut 32 threadedly engaged to the free end of the screw 30 .
[0042] Accordingly, by the construction of the hinge 22 and locking mechanism, the physician can move the posterior blade 56 to a desired angular position with respect to the base 12 and simply lock the blade 56 in that position
[0043] As to the anterior blade 58 , it too is affixed to the base 12 and, in the exemplary embodiment of FIG. 6 , there is a mechanical linkage 60 that affixes the anterior blade 58 to the base 12 . The mechanical linkage 60 will be further later explained , however, the mechanical linkage 60 is used to mount the anterior blade 58 to the base 12 and includes a lower flange section 62 that slides vertically along the base 12 . The lower flange section 62 has an elongated slot 64 formed therein and a screw 66 having a large head 68 can pass through the elongated slot 64 to be screwed into a threaded opening 70 in the base 12 .
[0044] As such, the location of the lower flange section 62 , and thus the location of the anterior blade 58 can be adjusted with respect to the base 12 by loosening the screw 66 , vertically moving the lower flange section 62 to the desired location and then tightening the screw 66 in the threaded opening 70 to firmly press the screw head 68 against the lower flange section 62 to affix the lower flange section 62 at the desired location. As can be seen, by adjusting the location of the lower flange section 62 with respect to the base 12 , the space between the poosterior blade 56 and the anterior blade 58 can be adjusted according to the desire of the user.
[0045] Turning to FIG. 7 , taken along with FIG. 6 , the mechanical linkage 60 can be seen more clearly and includes the lower flange section 62 , an upper arm 72 and an intermediate section 74 . The anterior blade 58 extends outwardly from the upper arm 72 and the main body 76 of the intermediate section 74 is designed to be displaced outwardly from the centerline CL of the lower flange section 62 As such there is an open area 78 that is created between the lower flange section 62 and the upper arm 72 that allows the physician to insert and manipulate an instrument on the patient without interference from the mechanical linkage 60 .
[0046] In the exemplary embodiment of FIG. 7 , it can be seen that the intermediate section 74 is a generally C-shaped curved configuration; however, the intermediate section 74 may be other shapes providing there remains the open area 78 to facilitate the introduction of a medical instrument as previously described. In addition, in the illustration of FIG. 7 , the open area 78 is open to the right, as viewed in that Figure which accommodates a right handed physician, however, the open area 78 may also extend to the left to accommodate a left handed physician.
[0047] A sleeve 80 is slipped over the distal end of the anterior blade 58 and the sleeve 80 is held to the anterior blade 58 by a friction fit to the anterior blade 58 in a manner similar to or the same as the sleeve 34 that is affixed to the posterior blade 56 . Both sleeves may the same material and construction and preferable both sleeves are constructed of a plastic material so as to be disposable after a single use.
[0048] Again, with the anterior blade 58 and posterior blade 56 , the sleeves 34 and 80 can be selected from a plurality of sleeves having different lengths and/or widths so that the physician can select and use the appropriate sleeve for the particular patient. For efficiency, the sleeves 34 and 80 may be interchangeable.
[0049] Turning then to FIG. 8 , there is shown a top view of the embodiment of FIG. 6 illustrating the sleeve 80 slipped onto the anterior blade 58 . As described, the sleeve 80 has a slot that is formed therein so the as the sleeve 80 is slipped onto the anterior blade 58 such that the anterior blade 58 enters the slot in a friction fit to allow the sleeve 80 to be affixed to the anterior blade 58 .
[0050] In FIG. 9 , there is shown an alternative sleeve 82 that is usable with the present invention. In particular, it can be seen that the sleeve 82 has a pair of downwardly directed edges 84 so as to form lateral slots 86 that are dimensioned so as to allow the sleeve 82 to be slid onto a blade by sandwiching the blade between the slots 86 to slidingly securing the sleeve 82 to a blade. With this embodiment, it can be seen that the blade does not need to have a slot formed therein.
[0051] In addition, in FIG. 10A and 10B , there is shown a still further alternative exemplary embodiment of the present invention wherein a sleeve 88 is slipped onto a blade 90 . In FIG. 10B , the blade 90 has a projection 92 extending outwardly therefrom that interfits into a corresponding longitudinal slot 94 formed in the slot 89 of sleeve 88 . With this embodiment, the interfitting of the projection 92 of the blade 90 provides lateral stability to the affixation of the blade 90 to the sleeve 88 . While only one projection 92 is shown interfitting into one longitudinal slot 94 , it can be seen that there may be a plurality of projections of differing sizes and shapes that interfit onto a corresponding slot or slots in the sleeve.
[0052] With the present vaginal speculum 10 , therefore, the physician can have a plurality of sleeves 34 ( FIG. 1 ) having different lengths and widths and select the one prior to the operation that best suits the anatomy of the patient after an on site examination of the patient. In particular, the sleeves may be provided in lengths of from 5 cm to about 15 cm in 1 cm increments.
[0053] With a plurality of sleeves available to the physician, there can be a kit 96 shown in FIG. 11 that is located near the physician so that the physician can select the most appropriate sleeve 98 having the desired length or width for each patient such that the vaginal speculum is adaptable to different patients without the need to delay an operation in order to locate a vaginal speculum of the correct length.
[0054] As such, each kit 96 would contain different sleeves 98 of varying lengths and/or widths for selection by the physician after an initial examination of the patient and such kit 96 would be readily accessible to the physician so that the physician could select and attach the desired sleeve 98 to a blade depending on the particular patient.
[0055] Also as a variant of the sleeves 98 , the proximal ends of the sleeves 98 may be open so as to receive a blade therein or may be closed such as where a affixation of the sleeves to a blade is in accordance with FIG. 9 where there is no need for a slot in a sleeve.
[0056] Those skilled in the art will readily recognize numerous adaptations and modifications which can be made to the vaginal speculum of the present invention which will result in an vaginal speculum and method of using the vaginal speculum, yet all of which will fall within the scope and spirit of the present invention as defined in the following claims Accordingly, the invention is to be limited only by the following claims and their equivalents.
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A vaginal speculum comprising a supporting base oriented generally vertically. A blade extends from the base and the angle between the blade and the base is adjustable. A locking system has an unlocked position allowing the blade to be angularly moved with respect to the base and a locked position retaining the blade at that desired angle. The vaginal speculum may also have two blades, a posterior blade having the angular adjustment and an anterior blade adjustably affixed to the base such that the space between the blades may be selectively adjusted by the physician. One or both of the blades may have a plastic sleeves slidably affixed thereto. Preferably, there is a plurality of sleeves of different lengths and/or widths that can be selected and attached to the blades depending on the particular patient. That selection can be made from a kit readily available to the physician.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to night vision devices. More particularly, the present invention relates to night vision devices of the type which removably and relatively movably attach to a support structure secured to a face mask or to a helmet, for example, to thereby be supported in front of at least one eye of the user. As thus supported, the night vision device may be used by the wearer of the helmet or face mask to view a night scene while the user's hands remain free.
2. Related Technology
Conventional night vision devices are known which removably attach to a support structure secured to a helmet or face mask. These conventional night vision devices are relatively movable by manipulation of the support structure to align at least one eye piece of the night vision device with at least one eye of the user. Additionally, the support structure and night vision device are conventionally provided with cooperating structural features which insure that the night vision device is electrically deactivated when it is removed from the support structure. This conventional feature which turns off the night vision device when it is removed from the support structure prevents the battery pack of the device from being inadvertently run down by leaving the device on when it is not in use on the support structure. Also, this feature provides light security so that inadvertent light emissions do not occur.
A conventional night vision device which includes features turning off, or removing electrical power supply to, the night vision device when the latter is moved to a flipped up position is seen in U.S. Pat. No. 4,449,787, issued 22 May 1984, to James H. Burbo, et al. The teaching of the Burbo patent is believed to include the provision of a pair of recesses on a first part of the support structure attached to a helmet. A second part of the support structure is secured to the night vision device and includes a pair of pins receivable into the pair of recesses to pivotally attach and support the night vision device. Electrical contact between the night vision device and its battery pack is made through the engagement of the two parts of the support structure only when the night vision device is pivoted to its use position. Thus, when the night vision device is pivoted upwardly to allow the user unobstructed vision, power supply to the device is interrupted to save energy.
However, the support structure and electrical power interruption features of the Burbo device necessarily result in conduction of electrical power to the night vision device by way of electrical contacts which are exposed. In effect, these exposed contacts are switch contacts because they close and open in response to the pivotal movement of the night vision device between its use and flipped up positions. As a first consideration, such exposed electrical switch contacts are highly subject to damage which can interfere with the conduction of electrical power to the night vision device. Secondly, deterioration of the electrical switch contacts can result from environmental factors. That is, environmental factors may cause corrosion and other deterioration of such exposed contacts, including such undesirable effects as pitting, the formation of nonconductive oxide coatings, and the formation of other films or coatings on the exposed contacts. Of course, all of these environmental effects are detrimental to the reliable conduction of electrical power to the night vision device. The result is that such exposed electrical switch contacts compromise the service reliability of the night vision device, and cause the device to be frail instead of rugged and able to withstand the handling to which such devices are subjected in their use environment.
Another conventional night vision device is known in accord with U.S. Pat. No. 4,672,194, issued 9 Jun. 1987, to William A. Kastendieck, et al. This Kastendieck patent is believed to teach a night vision device which includes a head gear, and a night vision goggle. The goggle includes a power supply circuit having a magnetically-responsive switch in series with a bi-stable latching relay controlling power supply to the image intensifier tube of the goggle. This magnetically-responsive switch is arranged to remain closed, and to keep the power supply relay closed, so long as the switch is subjected to a sufficient magnetic flux. The head gear for the night vision device includes a permanent magnet disposed so that it is close to the magnetically-responsive switch when the goggle is on the head gear. When the goggle is removed from the head gear, the magnetically-responsive switch is moved away from the permanent magnet so that the switch opens, an electrical pulse moves the bi-stable relay to an open condition, and electrical power to the night vision goggle is interrupted. Thus, the goggle is prevented from inadvertently being left on when it is removed from the head gear and is not in use. Also, it is recognized that inadvertently leaving the night vision goggle on when it is not in use can attract the attention of hostile personnel to the phosphor green light emitted from the eyepieces of the goggle.
However, the night vision device according to the Kastendieck patent does not provide for the night vision goggle to be pivoted to a flipped up position while yet supported on the head gear. In order to obtain an unobstructed view with the unaided eyes, a user of the Kastendieck device must remove the night vision goggle from its position on the head gear in front of the user's eyes.
SUMMARY OF THE INVENTION
In view of the above, a primary object for the present invention is to provide a night vision device including a head gear support structure supporting a night vision viewer in a first position in front of at least one of a user's eyes, the night vision viewer being pivotal on the support structure to a second flipped up position above the user's eyes to provide unobstructed natural vision for the user, and the night vision viewer having electrical power supply circuitry including a magnetically-responsive switch maintaining power supply to the night vision viewer only while subjected to a sufficient magnetic flux, and the support structure including a magnet proximate to the magnetically-responsive switch only in the first position of the night vision viewer, whereby pivotal movement of said night vision viewer to the second flipped up position on the support structure causes the magnetically-responsive switch to turn off the night vision viewer.
An advantage of the present invention resides in the improved user safety resulting from automatically turning off the night vision viewer whenever it is flipped to its up position, and thereby extinguishing the green phosphor light emission from the eye piece of the night vision viewer. In this up position of the night vision viewer, the eye piece of the viewer is disposed forwardly toward possibly hostile personnel in front of the user of the night vision device. Were the night vision viewer left on, its green phosphor light emissions could provide an aiming point for hostile personnel.
Additionally, in its flipped up position, the night vision viewer is above the user's line of sight. Thus, even if a warning light were provided on the exterior of the viewer to indicate to the user that the viewer had been left on, this warning light might easily be missed by the user. Additionally, such a warning light could possibly give away the user's position even when the goggle was in its lowered use position.
Additional objects and advantages of the present invention will be apparent from reading the following description of particularly preferred exemplary embodiments of the present invention, taken in conjunction with the following drawing Figures, in which:
DESCRIPTION OF THE DRAWING FIGURES
FIG. 1 provides a fragmentary perspective view of a user wearing a helmet carrying a support structure which supports a night vision viewer in front of the user's eyes;
FIG. 2 is a fragmentary perspective view of the user of FIG. 1, with the night vision viewer flipped up;
FIG. 3 is a side elevation view of the user seen in FIG. 1, at a slightly enlarged scale to better illustrate salient features of the invention;
FIG. 4 is an enlarged fragmentary view of a portion of the night vision device seen in FIGS. 1-3;
FIG. 5 is a fragmentary cross sectional view taken along line 5--5 of FIG. 4;
FIG. 6 is a fragmentary side elevation view taken at line 6--6 of FIG. 4;
FIG. 7 is a fragmentary perspective view similar to that of FIG. 3, but showing an alternative embodiment of the invention which includes a face mask support structure for the night vision viewer;
FIG. 8 is a fragmentary perspective view of a portion of the inventive night vision device seen in FIG. 7;
FIG. 9 provides a fragmentary perspective view of yet another alternative embodiment of the inventive night vision device, in which the night vision viewer is of monocular type; and
FIGS. 10 and 11 provide fragmentary side elevation views of still another alternative embodiment of the present inventive night vision device in which the night vision viewer is of goggle type with a singular objective lens.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring first to FIGS. 1, 2, and 3 in conjunction, an operator 10 is shown using a night vision device 12. The operator 10 wears a helmet 14 carrying a support structure portion 16 of the night vision device 12. This support structure 16 includes a frame 18 secured to the helmet 14 with various straps 20 and having a forwardly and upwardly extending clevis 22. The clevis 22 carries a hinge pin 24 (best seen in FIG. 2) for a flip up mount portion 26 of the support structure 16. Consequently, the flip up mount portion 26 of the support structure 16 is hinged on the clevis 22 for pivotal movement about hinge pin 24. The flip up mount portion 26 carries a carriage 28 and a coupling device 30. A night vision viewer 32 is suspended from the support structure 16 at the coupling device 30. This night vision viewer 32 is of goggle configuration and includes a single objective lens 34, a housing 36, and a pair of eye pieces 38 aligned with respective eyes of the operator 10.
To use the night vision viewer 32, the operator 10 places it in the use position depicted in FIGS. 1, and 3, and looks into eye pieces 38 to see an enhanced image representative of the low-level light from a night time scene which has entered objective lens 34. As those ordinarily skilled in the pertinent arts will appreciate, the night vision viewer 32 includes a power supply in the form of a battery pack (not visible in the drawing Figures), which may be carried on the back of the helmet 14, or carried in a breast pocket of the operator 10. This power supply is connected to the night vision viewer 32 by a power cable (also not illustrated in the drawing Figures). Internally of the night vision viewer, a power supply circuit provides power to an image intensifier tube, which is well known in the pertinent arts, and which supplies to the eye pieces 38 an intensified image in phosphor green light of the night time scene viewed via the objective lens 34. Also, the power supply circuit includes a magnetically-responsive sensor or switch, which is schematically indicated at 40 on FIG. 3. This sensor or switch 40 maintains electrical power supply to the viewer 32 once it is turned on by the operator 10 so long as a magnetic field of sufficient strength is supplied to the switch 40.
However, as is illustrated in FIG. 2, the night vision device 12 allows the operator 10 to flip up the night vision viewer 32 to a second position in which the viewer 32 is above the line of sight of the operator 10. This flipped up position of the night vision viewer allows the operator completely unobstructed vision with unaided eyes. As FIG. 2 clearly shows, however, should the operator 10 forget to turn off the night vision viewer 32 before moving it to its flipped up position, the phosphor green light emitted from the eyepieces 38 would appear to possibly hostile personnel forwardly of the operator 10 as a pair of small green spot lights.
Accordingly, in order to provide the necessary magnetic flux to the switch 40 while at the same time insuring that the magnetic field is removed from the switch 40 when the viewer 32 is pivoted to its flipped up position while still attached to the support structure 16, the latter includes a bracket 42 which hooks under the forward edge of the helmet 14 (best seen in FIGS. 2 and 3). From the bracket 42 depends a flange portion 44, viewing FIGS. 2-6 in conjunction. A pair of laterally spaced apart ears 46 extend oppositely from the flange portion 44 and define respective forwardly extending bores 48 (seen in FIG. 6).
Forwardly from the ears 46 extends a laterally spaced apart pair of yieldable, but shape-retaining support arms 50. The arms 50 are formed of small diameter closed-coil metallic springs 52. At their rear ends 54, the coil springs 52 each threadably receive a respective one of a pair of screw members 56. These screw members 56 have a stem portion 58, as is seen in FIG. 6, which is of a diameter receivable into the spring 52, and defining a screw thread 60 matching the closed-coil helix of this spring. At a forward end 62, each support arm coil spring 52 defines a termination coil 64 which is turned ninety degrees from the remainder of the coil spring to extend forwardly of the support structure 16.
Viewing FIGS. 2-6, and particularly FIG. 5, it is seen that termination coils 64 of the support arm coil springs 52 each receive a respective screw 66 capturing the termination coils 64 against respective ends of a laterally elongate magnet housing 68. Within this magnet housing 68 is disposed a laterally elongate and laterally polarized magnet 70, the magnetic field from which is depicted on FIG. 4 with the numerals 70'.
FIG. 3 illustrates that in the use position of the night vision viewer 32, the magnet housing 68 is located in a recess 72 rearwardly of the coupling device 30, below carriage ways 74 for the carriage 28, and above the housing 36 proximate to the location of switch 40. Thus, when the night vision viewer is located in its use position, as illustrated in FIGS. 1 and 3, the magnetic field 70' from the magnet 70 insures that the viewer 32 remains on once the operator 10 turns it on.
However, when the operator 10 flips up the viewer 32 to its flipped up position depicted in FIG. 2, the yieldable nature of the support arms 50 allows these arms to yield and allow a rearward portion 76 of the flip up mount 26 (seen in FIG. 3) to swing along the arc denoted by the line 78 from the hinge pin 24, past the arms 50 and magnet housing 68. As is easily understood, once the housing 36 of the night vision viewer 32 is a comparatively short distance from its use position along the pivotal movement toward its flipped up position, the magnetic field 70' can not influence switch 40, and the latter effects a shut off of the viewer 32. Consequently, by the time the viewer 32 reaches its flipped up position depicted in FIG. 2, the phosphor green light from the eye pieces 38 has been extinguished.
Thus, the user 10 enjoys a much improved safety in the use of the night vision device 10, while still enjoying the convenience in use which is afforded by a flip up mount. That is, the night vision viewer 32 is immediately available for its next use simply by flipping it down from the position of FIG. 2 to the use position illustrated by FIG. 1. The user 10 need not remove the night vision viewer 32 from its support structure in order to have clear, unobstructed vision with the unaided eyes. Further, the operator 10 need not remember to turn off the viewer 32 each time a view with the unaided eyes is desired. Simply moving the viewer 32 up to its flipped up position will safely extinguish the phosphor green illumination from the eye pieces 38, as well as saving battery power by turning off the viewer 32.
Upon the operator 10 returning the viewer 32 to its flipped down use position, the yieldable nature of the arms 50 allows the rearward portion 76 of the flip up mount 26 to contact the magnet housing 68, and to force this housing and the arms 50 downwardly. Thus, the flip up mount 26, and the housing 36 of viewer 32 can return to their positions illustrated in FIG. 1 and 3. The magnet housing 68 thus returns to the recess 72. In this use position of the viewer, when the operator 10 turns on the viewer 32, the magnetic field 70' by its influence on the switch 40 insures that the viewer stays on until the operator 10 turns it off, or flips it upwardly toward its flipped up position.
FIGS. 7 and 8 depict an alternative embodiment of the present invention. In order to obtain reference numerals for use in describing the embodiment of FIGS. 7 and 8, features which are analogous in structure or function to those depicted and described above are referenced with the same numeral used previously, but with a prime added thereto. Viewing FIGS. 7 and 8 in conjunction, it is seen that a night vision device 12' may be supported on a face mask 80. This face mask 80 may be secured to the head of an operator by use of a plurality of straps, mesh panels, and a chin piece, respectively indicated with the numerals 82, 84, and 86. In the present instance, the face mask 80 carries a frame 18', which includes a forwardly and upwardly extending clevis 22'. On the clevis 22' is carried a flip up mount 26', in all respects the same as the flip up mount 26 described with reference to FIGS. 1-6. This flip up mount 26' carries a night vision viewer 32'.
However, viewing FIGS. 7 and 8, and particularly the latter one of these two Figures, it is seen that the frame 18' carries a pair of laterally spaced apart and depending ears 46'. Forwardly from these ears 46' extends a pair of yieldably shape retaining arms 50', which are embodied as closed coil springs 52'. A laterally extending magnet housing 68' is supported at the forward ends of the arms 50', for interaction with a switch 40' (not depicted in the drawing Figures) of the night vision viewer 32', just as described above with respect to FIGS. 1-6.
FIG. 9 depicts yet another embodiment of the present invention. The embodiment of FIG. 9 is the same in all respects with the embodiment described with reference to FIGS. 1-6, except that the night vision viewer 88 is of a monocular configuration. Accordingly, those features which are familiar because of their introduction and description with reference to FIGS. 1-6 are referenced on FIG. 9 with the same numerals used above. Considering now FIG. 9 it is seen that the operator 10 has configured the night vision viewer 88 to be used with the right-hand eye 90 of the operator. That is, the viewer 88 includes a triangular housing 92 having a pair of dove tailed receptacle 94, one on each of two faces thereof. One of the dove tailed receptacles 94 is received in the coupling device 30 of the flip up mount 26, while the other dove tailed receptacle is not utilized in the depicted configuration of the night vision viewer.
Because of the angulation between the dove tailed receptacles 94, when the depicted one is inserted in the coupling device 30, the viewer hangs in front of the right-hand eye of the operator 10. On the other hand, if the other receptacle 94 is inserted in the coupling device 30, the viewer hangs in front of the left-hand eye of the operator 10. The viewer 88 includes a rotational eye piece shield 96. This shield 96 allows the operator 10 to shield the eye with which the viewer is being used. Accordingly, the embodiment of FIG. 9 allows the operator to have one eye aided by the night vision viewer 88, while the other eye receives an unaided view of the environment around the operator. This combination of night vision and unaided vision has been found to be very beneficial in some circumstances.
As noted on FIG. 9, regardless of which of the dove tailed receptacles 94 is inserted into the coupling device 30, the housing 92 cooperates with the carriage ways 74 to define a recess 72 in which the magnet housing 68 is received. In contrast to the embodiment of FIGS. 1-6 however, the monocular night vision viewer of FIG. 9 includes a magnetically-responsive switch 40 which is offset within the housing 92. This switch is depicted with the dashed lines 98 on FIG. 9. Because of its offset location at the apex of the two sides of housing 92 carrying the mounts 94 this switch is effective to turn off the night vision viewer 88 when it is separated by a sufficient distance from the magnet housing 68, as described above. Thus, regardless of which one of the two possible orientations of the viewer 88 on the coupling device 30 is chosen by the operator 10, the safety advantage of the present invention is fully enjoyed.
Still another embodiment of the present invention is depicted in FIGS. 10 and 11. Again, features of FIGS. 10 and 11 which are analogous in structure or function to those depicted and described above with reference to FIGS. 1-6 are referenced with the same numeral used above, and having a prime added thereto. As is shown in FIG. 10, a support structure 16' may be supported from the head of a operator (not shown) to dispose a goggle type of night vision viewer 32' in front of the eyes of the operator. The support structure 16' includes a clevis 22' to which a flip up mount 26' is hinged at 24'. The night vision viewer 32' includes a magnetically responsive switch 40'.
However, the frame 18' includes a cylindrical magnet housing 102 presenting magnet flux 102', as is best seen in FIG. 11. On the flip up mount 26', a forwardly extending magnetic flux conductor 104 extends into the recess 72' and includes a downwardly turned end portion 106 terminating at an end 108 adjacent to the magnetically responsive switch 40'. The magnetic flux conductor 104 is metallic, and preferably is formed of an alloy known as Permador, supplied by the Carpenter Steel Company. The Permador alloy has a high magnetic flux permeability, while retaining a very low residual magnetism when not supplied with magnetic flux from an external source.
Consequently, when the viewer 32' is in its use position depicted in FIG. 10, the flux conductor 104 is closely associated with magnet housing 102 to receive the magnetic flux 102'. The end 108 is adjacent to the switch 40' so that this switch maintains the viewer turned on. However, as FIG. 11 shows, when the flip up mount 26' with the viewer 32' is moved toward its flipped up position, the conductor 104 is separated from the magnet housing 102. The result is that the switch 40' turns off the viewer 32' as described above.
While the present invention has been depicted, described, and is defined by reference to particularly preferred embodiments of the invention, such reference does not imply a limitation on the invention, and no such limitation is to be inferred. The invention is capable of considerable modification, alteration, and equivalents in form and function, as will occur to those ordinarily skilled in the pertinent arts. For example, the magnetically responsive switch 40 need not itself take the form of a switch. That is, for example, a magnetically responsive semiconductor device or sensor could be substituted for the switch 40 and could be used to effect a power interruption to the viewer 32 when the magnetic field effective on the sensor drops to a predetermined level indicative of pivotal movement of the viewer toward its flipped up position. Accordingly, the depicted and described preferred embodiments of the invention are exemplary only, and are not exhaustive of the scope of the invention. Consequently, the invention is intended to be limited only by the spirit and scope of the appended claims, giving full cognizance to equivalents in all respects.
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A night vision device with improved user safety includes a head gear support structure which suspends a night vision viewer relative to the head and eyes of the user. The head gear includes a flip up mount allowing the user to flip the night vision viewer up and out of the user's line of sight for an unobstructed natural view of the environment. In order both to save battery power, and to prevent the user from inadvertently revealing his position by forgetting to turn off the night vision viewer before flipping it up, the support structure includes a magnetic flux source cooperable with a magnetically-responsive switch of the night vision viewer to maintain the viewer turned on only when the viewer is in its use position. When the viewer is flipped toward its upward position, the switch of the viewer is carried out of magnetic association with the flux source so that the viewer shuts off. Because the viewer remains mounted on the flip up mount during this series of events allowing the user an unobstructed view of the environment, the viewer is immediately available to be flipped downwardly to its use position back into operative association at its switch with the flux source, and to be turned on again for night vision viewing.
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