The invention relates to a non-aqueous laundering machine, methods of using the machine, methods of rinsing, drying and recovery as well as apparatuses for the same.
As defined by Perry's Chemical Engineers' Handbook, 7th edition, liquid extraction is a process for separating components in solution by their distribution between two immiscible phases. Such a process is also referred to as Solvent Extraction, but Solvent Extraction also implies the leaching of a soluble substance from a solid.
The present invention relates to a program of events and ingredients that make it possible to produce a non-aqueous laundering machine that is self contained, automatic and relatively compact that can be used in the home as well as commercially. The machine would offer the consumer the ability not only to launder their traditional fabrics (cotton, polyesters, etc.) at home, but also have the ability to handle delicate fabrics such as dry-clean only fabrics as well. There have been numerous attempts at making a non-aqueous laundering system; however, there have been many limitations associated with such attempts.
Traditional dry-cleaning solvents such as perchloroethylene are not feasible for in-home applications because they suffer from the disadvantage of having perceived environmental and health risks. Fluorinated solvents such as hydrofluoroethers have been posed as potential solvents for such an application. These solvents are environmentally friendly and have high vapor pressures leading to fast drying times, but these solvents don't currently provide the cleaning needed in such a system.
Other solvents have been listed as potential fluids for such an application. Siloxane-based materials, glycol ethers and hydrocarbon-based solvents all have been investigated. Typically, these solvents are combustible fluids but the art teaches some level of soil removal. However, since these solvents are combustible and usually have low vapor pressures, it would be difficult to dry with traditional convection heating systems. The solvents have low vapor pressures making evaporation slow thus increasing the drying time needed for such systems. Currently, the National Fire Protection Association has product codes associated for flammable solvents. These safety codes limit the potential heat such solvents could see or the infrastructure needed to operate the machine. In traditional washer/dryer combination machines, the capacity or load size is limited based on the drying rate. However, with the present invention, the capacity of the machines will be more dependent upon the size of the drum than the size of the load.
The present invention uses some of these aforementioned solvents to clean fabrics without the drying problems associated with these solvents. This is accomplished by using a select rinse fluid that solves many of these drying problems.
U.S. Pat. No. 5,498,266 describes a method using petroleum-based solvent vapors wherein perfluorocarbon vapors are admixed with petroleum solvent vapors to remove the solvents from the fabrics and provide improvements in safety by reducing the likelihood of ignition or explosion of the vapors. However, the long-term stability of these mixtures is unknown but has the potential of separating due to dissociating the separate components.
U.S. Pat. No. 6,045,588 describes a method for washing, drying and recovering using an inert working fluid. Additionally, this application teaches the use of liquid extraction with an inert working fluid along with washing and drying. This new patent application differs from U.S. Pat. No. 6,045,588 in that it describes preferred embodiments to minimize the amount of rinse fluid needed as well as recovery methods, apparatuses and sequences not previously described.
U.S. Pat. No. 6,558,432 describes the use of a pressurized fluid solvent such as carbon dioxide to avoid the drying issues. In accordance with these methods, pressures of about 500 to 1000 psi are required. These conditions would result in larger machines than need be for such an operation. Additionally, this is an immersion process that may require more than one rinse so additional storage capacity is needed.
US20030084588 describes the use of a high vapor pressure, above 3-mm Hg, co-solvent that is subjected to lipophilic fluid containing fabric articles. While a high vapor pressure solvent may be preferred in such a system, US20030084588 fails to disclose potential methods of applying the fluid, when the fluid should be used and methods minimizing the amount of fluid needed. Finally, this patent fails to identify potential recovery strategies for the high vapor pressure co-solvent.
Various perfluorocarbons materials have been employed alone or in combination with cleaning additives for washing printed circuit boards and other electrical substrates, as described for example in U.S. Pat. No. 5,503,681. Spray cleaning of rigid substrates is very different from laundering soft fabric loads. Moreover, cleaning of electrical substrates is performed in high technology manufacturing facilities employing a multi-stage that is not readily adaptable to such a cleaning application.
The first object of the present invention is to devise a complete sequence of non-aqueous laundering operations using a combination of materials that can be economically separated and used over and over again in a self contained non-aqueous laundering machine.
It is a further object of the invention to describe specific processes for introducing the select rinse fluid.
It is an object of the invention to describe techniques and methods for minimizing the amount of select rinse fluid needed and the time that the select rinse fluid should be in contact with the working fluid and fabric articles.
It is a further object of the invention to describe a low temperature drying process that would result in improved fabric care and lower energy requirements for such a non-aqueous laundering machine.
It is still another object of the invention to disclose the advantage of increasing the size of the load to be dried without significantly increasing the drying time as is common with traditional aqueous-based machines and non-aqueous machines using some of these methods.
It is another object of the invention to describe recovery methods and techniques not only for the select rinse fluid, but also additionally for the working fluid and wash liquor.
It is a further object of the invention to describe apparatuses designed to complete the select rinse fluid application, low temperature drying and recovery methods.
It is a further object of the invention that the soils removed are concentrated and disposed of in an environmentally friendly manner.
It is a further object that the materials used are all of a type that avoids explosion and manages flammability hazards.
Further objects and advantages of the invention will become apparent to those skilled in the art to which this invention relates from the following description of the drawings and preferred embodiments that follow:
The present invention provides to a non-aqueous laundering machine for laundering fabric with a non-aqueous wash liquor and a select rinse fluid.
In one aspect of the present invention, an automatic fabric laundering apparatus includes a perforated drum for containing fabrics to be cleaned; first means for supplying a working fluid to said drum; second means for spinning the drum; third means for applying a select rinse fluid to the fabrics such that the select rinse fluid flows through the fabric; fourth means for flowing a drying gas into the container under conditions to vaporize fluids in the fabric; and automatic control means for regulating the times and conditions necessary for the above means to cycle and leave the fabric in essentially a dry condition.
In another aspect of the present invention, a fabric laundering apparatus has a container to hold fabric; storage and dispensing systems for storing and dispensing working fluid, rinse fluid and washing additives; and a recovery system for recovering working fluid and rinse fluid for reuse.
In yet another aspect of the present invention, a fabric laundering apparatus includes a container to hold fabric; a storage and delivery system for the working fluid; a second storage and delivery system for the rinse fluid; a heater to heat fabric to remove fluids from the fabric; and a controller responsive to operate the heater.
Modifications of the machine shown in U.S. patent application Ser. No. 10/699,262, “Non-Aqueous Washing Apparatus”, filed Oct. 31, 2003 now U.S. Pat. No. 7,043,262, has been used to test the efficacy of the washing and recovery operations depicted in the drawings and the specification should be incorporated herein for reference.
A simple electric coil heater (not shown) may be optionally associated with sump 36 so that the wash liquor in the sump may be heated. In various embodiments, it may be desirable to re-circulate heated wash liquor back into the fabric so that the fabric maintains an elevated temperature, or because various washing adjuvant(s) work—or work better—in a heated environment. The heater may also heat the wash liquor to deactivate adjuvant(s) in the wash liquor. Accordingly, the heater may be programmed to activate or deactivate based on the intended use. The heating means is not limited to electric coil heaters.
Wash chamber sump 36 is in fluid communication with a filter 38, such as a coarse lint filter, that is adapted to filter out large particles, such as buttons, paper clips, lint, food, etc. The filter 38 may be consumer accessible to provide for removal, cleaning, and/or replacement.
Accordingly, it may be desirable to locate the filter 38 near the front side of the wash unit 12 and preferably near the bottom so that any passive drainage occurs into the sump 36 and the filter 38. In another embodiment, the filter 38 may also be back-flushed to the reclamation unit 14 so that any contents may be removed from the reclamation unit 14. In another embodiment, the filter can be back-flushed within the wash unit to the sump and then pumped to the reclamation unit. In this regard, consumer interaction with the filter 38 can be intentionally limited.
Filtered wash liquor may then be passed to the reclamation unit 14 for further processing or may be passed to a re-circulation pump 40. Although not shown, a multiway valve may also be positioned between the filter 38 and the pump 40 to direct the wash liquor to the reclamation unit 14 for the further processing. After processing, the wash liquor may be returned to the re-circulation loop at an entry point anywhere along the loop. The re-circulation pump may be controlled to provide continuous operation, pulsed operation, or controlled operation. Returning to the embodiment of
As mentioned above concerning the sump 36, a heater (not shown) may also be associated with the dispenser to modulate the temperature of the dispenser contents. After mixing or heating, if any is to be done, the dispenser contents exit the dispenser via a dispenser outlet 50. Dispenser outlet 50 may be gated to control the outflow of the contents. In this regard, each chamber in the dispenser may be individually gated. The contents exit the dispenser via outlet 50 and enter a fill inlet 52, which is in fluid communication with the wash chamber 26. As shown in
Fill inlet may also include one or more dispensing heads (not shown), such as nozzles or sprayers. The head may be adapted to repel wash liquor or a particular adjuvant so that clogging is avoided or minimized.
Although shown in
In addition, although shown in
With regard to tank construction, if the tank is not uniformly molded, then any seals ought to be tight and resistant to wear, dissolution, leaching, etc. The inside walls of the tank can be microtextured to be very smooth, without substantial surface defects, so that waste fluid entering the tank is easily flowed to the tank bottom. In addition, the inside wall should be easily cleanable. To this end, the tank may include a series of scrapers that periodically scrape the sidewalls and bottom to ensure that little or no waste sticks to the walls and the bottom and that such waste is channeled to the tank outlet. The scrapers may be controlled via programming. Although not shown, the tank outlet may also include a removable particulate filter. Additionally, the tank may include a layer of insulation material that helps sustain the desired temperatures for each systems' heating/cooling mechanisms either within or surrounding the tanks.
The tank outlet is in fluid communication with a high pressure pump 108, which pumps the waste tank contents into a chiller 110, which further cools the waste tank contents. The chiller preferably resides in an insulated box to maintain a cooler environment.
It is also understood that other cooling technologies may be used to cool the waste tank contents as desired. For example, instead of having water cool the compressor system, an air-cooled heat exchanger similar to a radiator can be used. Alternatively, the working fluid may be cooled by moving water through cooling coils, or by thermoelectric devices heaters, expansion valves, cooling towers, or thermo-acoustic devices to, cool the waste tank contents
The permeate flows down to the bottom of the cross flow membrane and exits the membrane 114 and enters a permeate pump 130. This permeate pump 130 pumps the permeate into a permeate filter 132, such as a carbon bed filter. The permeate enters the permeate filter 132 via the permeate filter proximal end 134, travels across the filter media, and exits via the permeate filter distal end 136. The permeate filter is selected for its ability to filter out organic residues, such as odors, fatty acids, dyes, petroleum based products, or the like that are miscible enough with the bulk solvent to pass through the cross flow membrane. Such filters may include activated carbon, alumina, silica gel, diatomaceous earth, aluminosilicates, polyamide resin, hydrogels, zeolites, polystyrene, polyethylene, divinyl benzene and/or molecular sieves. In any embodiment, the permeate may pass over or through several permeate filters, either sequentially or non-sequentially. In addition, the permeate filter may be one or more stacked layers of filter media. Accordingly, the flow may pass through one or more sequential filters and/or one or more stacked and/or unstacked filters. The preferred geometry for liquid and vapor removal for activated carbon is spherical and cylindrical. These systems may have a density between 0.25 to 0.75 g/cm3 with preferred ranges of 0.40 to 0.70 g/cm3. Surface areas may range from 50 to 2500 m2/g with a preferred range of 250 to 1250 m2/g. The particle size may range from 0.05 to 500 μm with a preferred range of 0.1 to 100 μm. A preferred pressure drop across the packed bed would range from 0.05 to 1.0×106 Pa with a preferred range of 0.1 to 1000 Pa. A porosity may range from 0.1 to 0.95 with a preferred range from 0.2 to 0.6.
After the permeate is filtered, the permeate is routed into the clean tank 138, where the permeate, which is now substantially purified working fluid, is stored. The purified working fluid should be greater than 90% free from contaminants with a preferred range of 95% to 99%. As desired, the working fluid is pumped from the clean tank 138 via a fill pump 140 to the wash unit 12.
The cross flow membrane 114 is also selected for its ability to filter out the working fluid as a permeate. Cross flow membranes may be polymer based or ceramic based. The membrane 114 is also selected for its ability to filter out particulates or other large molecular entities. The utility of a cross flow membrane, if polymer based, is a function of, inter alia, the number of hollow fibers in the unit, the channel height (e.g., the diameter of the fiber if cylindrical), length of the fiber, and the pore size of the fiber. Accordingly, it is desirable that the number of fibers is sufficient to generate enough flow through the membrane without significant back up or clogging at the proximal end. The channel height is selected for its ability to permit particulates to pass without significant back up or clogging at the proximal end. The pore size is selected to ensure that the working fluid passes out as permeate without significant other materials passing through as permeate. Accordingly, a preferred membrane would be one that would remove all particulate matter, separate micelles, separate water and other hydrophilic materials, separate hydrophobic materials that are outside the solubility region of the working fluid, and remove bacteria or other microbes. Nano-filtration is a preferred method to remove bacteria and viruses.
Ceramic membranes offer high permeate fluxes, resistance to most solvents, and are relatively rigid structures, which permits easier cleaning. Polymer based membranes offer cost effectiveness, disposability, and relatively easier cleaning. Polymer based membranes may comprise polysulfone, polyethersulfone, and/or methyl esters, or any mixture thereof. Pore sizes for membranes may range from 0.005 to 1.0 micron, with a preferred range of 0.01 to 0.2 microns. Flux ranges for membranes may range from 0.5 to 250 kg/hour of working fluid with a preferred minimum flux of 30 kg/hour (or about 10-5000 kg/m2). Fiber lumen size or channel height may range from 0.05 to 0.5 mm so that particulates may pass through. The dimension of the machine determines the membrane length. For example, the membrane may be long enough that it fits across a diagonal. A length may, preferably, be between 5 to 75 cm, and more preferably 10 to 30 cm. The membrane surface area may be between 10 to 2000 cm2, with 250 to 1500 cm2 and 300 to 750 cm2 being preferred.
The preferred membrane fiber size is dependent upon the molecular weight cutoff for the items that need to be separated. As mentioned earlier, the preferred fiber would be one that would remove all particulate matter, separate micelles, separate water and other hydrophilic materials, separate hydrophobic materials that are outside the solubility region of the working fluid, and remove bacteria or other microbes. The hydrophobic materials are primarily body soils that are mixtures of fatty acids. Some of the smaller chain fatty acids (C12 and C13) have lower molecular weights (200 or below) while some fatty acids exceed 500 for a molecular weight. A preferred surfactant for these systems are silicone surfactants having an average molecular size from 500-20000.
For example, in siloxane based working fluid machines, the fiber should be able to pass molecular weights less than 1000, more preferably less than 500 and most preferably less than 400. In addition, the preferred fibers should be hydrophobic in nature, or have a hydrophobic coating to repel water trying to pass. For the contaminants that pass through the fibers, the absorber and/or absorber filters will remove the remaining contaminants. Some preferred hydrophobic coatings are aluminum oxides, silicone nitrate, silicone carbide and zirconium. Accordingly, an embodiment of the invention resides in a cross flow membrane that is adapted to permit a recovery of the working fluid as a permeate.
Returning to
The dead end filter 144 may be a container that includes an internal filter 146. As concentrate enters the dead end filter 144, the concentrate collects on the internal filter 146. Based on the type of filter used, permeate will pass through the filter 146 and be routed to the waste tank 100 or eventually into the clean tank. The concentrate will remain in the dead end filter. To assist in drawing out remaining liquids from the concentrate so that it passes to the waste tank, a vacuum may be created inside to draw out more liquid. In addition, the dead end filter 144 may include a press that presses down on the concentrate to compact the concentrate and to squeeze liquids through the internal filter 146. The dead end filter 144 may also include one or more choppers or scrapers to scrape down the sides of the filter and to chop up the compacted debris. In this regard, in the next operation of the press, the press recompacts the chopped up debris to further draw out the liquids. The dead end filter may be consumer accessible so that the dead end filter may be cleaned, replaced, or the like; and the remaining debris removed. In addition, the dead end filter may be completed without the assistance of a vacuum, in a low temperature evaporation step or an incineration step. Capturing the concentrate/retentate and then passing a low heat stream of air with similar conditions to the drying air over the filter will complete the low temperature evaporation step. The working fluid will be removed and then routed to the condenser where it will condense and then return to the clean tank.
Another concern that needs to be addressed is the re-use of the filters beds. Some potential means to prevent fouling or to reduce fouling are via chemical addition or cleaning, reducing the temperature and phase changing the water to ice and then catching the ice crystals via a filter mechanism, or coating the membranes with special surfaces to minimize the risk of fouling. A way to regenerate the filters includes but is not limited to the addition of heat, pH, ionic strength, vacuum, mechanical force, electric field and combinations thereof.
A dynamic rinse process is depicted in
In the process depicted in
The processes depicted in
In
In some instances the working fluid and the PRF are immiscible and the miscibility gap could be overcome by a change in temperature or the addition of one or more components. In some instances, it is preferred that the molecular weight of the PRF should be less than the molecular weight of the working fluid.
In any of the aforementioned figures, heating may be supplied at any time to heat the machine, one or more machine components, the fluids, the fabric, air or a combination thereof.
Additionally, apparatuses designed for the PRF should have condensing systems designed to handle multiple fluids. A preferred condensing system will preferentially separate the fluids according to boiling point and vapor pressure. Examples of such condensing systems have been taught in U.S. 20040117919. An example dealing with a PRF would have the PRF condensing, followed by the added water to the system, then a working fluid such as decamethylcyclopentasiloxane or dipropylene glycol n-butyl ether.
The PRF is separated and recovered in step 274. Methods for separating the PRF from the wash liquor include, but are not limited to: fractional distillation, temperature reduction, addition of a flocculating agent, adsorption/absorption, liquid extraction through the use of another additive, filtration, gravimetric separation, osmosis, evaporation, chemisorption or a combination of the aforementioned steps. The final PRF that is recovered and stored for reuse should contain less than 50% by weight of working fluid, more preferably less than 25% and most preferably less than 10%. The PRF and working fluid mixture need not be separated until the concentration of the working fluid exceeds 25% by weight.
Dissolved soils include those items that are dissolved in the working fluid, such as oils, surfactants, detergents, etc. Mechanical and chemical methods or both may remove dissolved soils 276. Mechanical removal includes the use of filters or membranes, such as nano-filtration, ultra-filtration and microfiltration, and/or cross flow membranes. Pervaporation may also be used. Pervaporation is a process in which a liquid stream containing two or more components is placed in contact with one side of a non-porous polymeric membrane while a vacuum or gas purge is applied to the other side. The components in the liquid stream sorb into the membrane, permeate through the membrane, and evaporate into the vapor phase (hence the word pervaporate). The vapor, referred to as “the permeate”, is then condensed. Due to different species in the feed mixture having different affinities for the membrane and different diffusion rates through the membrane, a component at low concentration in the feed can be highly enriched in the permeate. Further, the permeate composition may differ widely from that of the vapor evolved in a free vapor-liquid equilibrium process. Concentration factors range from the single digits to over 1,000, depending on the compounds, the membrane and process conditions.
Chemical separation may include change of state methods, such as temperature reduction (e.g., freeze distillation), temperature increase, pressure increase, flocculation, pH changes and ion exchange resins.
Other removal methods include electric coalescence, absorption, adsorption, endothermic reactions, temperature stratification, third component addition, dielectrophoresis, high performance liquid chromatography, ultrasonic and thermo-acoustic cooling techniques.
Insoluble soils 278 may include water, enzymes, hydrophilic soils, salts, etc. Items may be initially insoluble but may become soluble (or vice versa) during the wash and reclamation processes. For example, adding dissolvers, emulsifiers, soaps, pH shifters, flocculants, etc., may change the characteristic of the item. Other methods of insoluble soil removal include filtration, caking/drying, gravimetric, vortex separation, distillation, freeze distillation and the like.
The step of concentrating impurities 280 may include any of the above steps done that are done to reduce, and thereby purify, the working fluid recovery. Concentrating impurities may involve the use of multiple separation techniques or separation additives to assist in reclamation. It may also involve the use of a specific separation technique that cannot be done until other components are removed.
In some instances, the surfactants may need to be recovered. A potential means for recovering surfactants is through any of the above-mentioned separation techniques and the use of CO2 and pressure.
As used herein, the sanitization step 282 will include the generic principle of attempting to keep the unit relatively clean, sanitary, disinfected, and/or sterile from infectious, pathogenic, pyrogenic, etc. substances. Potentially harmful substances may reside in the unit due to a prior introduction from the fabrics cleaned, or from any other new substance inadvertently added. Because of the desire to retrieve clean clothes from the unit after the cycles are over, the amount of contamination remaining in the clothes ought to be minimized. Accordingly, sanitization may occur due to features inherent in the unit, process steps, or sanitizing agents added. General sanitization techniques include: the addition of glutaraldehyde tanning, formaldehyde tanning at acidic pH, propylene oxide or ethylene oxide treatment, gas plasma sterilization, gamma radiation, electron beam, ultraviolet radiation, peracetic acid sterilization, thermal (heat or cold), chemical (antibiotics, microcides, cations, etc.), and mechanical (acoustic energy, structural disruption, filtration, etc.).
Sanitization can also be achieved by constructing conduits, tanks, pumps, or the like with materials that confer sanitization. For example, these components may be constructed and coated with various chemicals, such as antibiotics, microcides, biocides, enzymes, detergents, oxidizing agents, etc. Coating technology is readily available from catheter medical device coating technology. As such, as fluids are moving through the component, the fluids are in contact with the inner surfaces of the component and the coatings and thereby achieves contact based sanitization. For tanks, the inner surfaces of tanks may be provided with the same types of coatings thereby providing longer exposure of the coating to the fluid because of the extended storage times. Any coating may also permit elution of a sanitizer into the fluid stream. Drug eluting stent technology may be adapted to permit elution of a sanitizer, e.g., elution via a parylene coating.
As was mentioned earlier, modifications of the machine shown in U.S. patent application Ser. No. 10/699,262, “Non-Aqueous Washing Apparatus”, filed Oct. 31, 2003, has been used to test the efficacy of the washing and recovery operations depicted in the drawings. Experiments have been conducted to show the power of the operation and details of such an application.
In one experiment, decamethylcyclopentasiloxane was used as the wash liquor and a commercially available detergent package was used with a 3-kg load of cotton stuffers. The load was washed in the decamethylcyclopentasiloxane/detergent wash liquor for 10 minutes followed by an extraction at 1150 rpm for 7 minutes. The average retention (kg solvent remaining/kg cloth) was 25%. Ethoxynonafluorobutane, HFE-7200, was added to the system and re-circulated for 4 minutes. Another extraction at 1150 rpm at 7 minutes was completed and the fabrics were dried with a low temperature air stream at 60° C. and 150 ft3/min. The retention and drying time were recorded for each sample. Table 1 summarizes the result.
As can be seen in Table 1, the addition of more HFE-7200 improves the extraction efficiency and decreases the drying time needed.
Another test was conducted using a decamethylcyclopentasiloxane/water/detergent mixture washed for 10 minutes and extracted at 1150 rpm for 7 minutes. The resulting retention was measured at 30.0%. An HFE-7200 rinse followed for 4 minutes, followed by the 1150 rpm extraction and followed by the above, described heated drying step. The retention and drying times were recorded and summarized below.
The interesting information from this chart shows that with a consistent volume of HFE-7200, the drying time is not greatly impacted by the size of the load. In a traditional aqueous wash in the same machine, a 3-kg load would take nearly 60 minutes, a 5-kg load 120 minutes and a 6-kg load almost 180 minutes.
Another test was conducted using a spray rinse technique. The fabric load was washed for 10 minutes in the decamethylcyclopentasiloxane/water/detergent mixture followed by a 1150 rpm, 7-minute extraction. HFE-7200 was added to the drum while the clothes were spinning at 300 rpm and the HFE-7200 was re-circulated through the load. A 1150-rpm, 7-minute extraction was completed along with the low temperature drying step described above. The retention and drying times are summarized and recorded below.
In this particular test, the amount of HFE needed has been even further reduced. This rinse method would allow for the most cost-effective solution to the consumer.
Additional experiments involving different working fluids and PRFs have been made. These tests confirm the data given above.
As stated above, the drying temperature for the above operations was around 60° C. In general, fabrics have a tendency to be damaged by temperatures exceeding 60° C. and most inlet air temperatures in traditional dryers may exceed 175° C. In traditional non-aqueous systems, the working fluids of choice usually have flashpoints lower than 100° C. In addition to the high flash points, these working fluids have low vapor pressures and they require higher temperatures for removal from the fabric. The National Fire Protection Association regulates the temperatures to which these working fluids may be heated to 17° C. below the flash point of the solvent.
In addition to temperature, the controller (discussed above) can also be connected to a humidity monitor for monitoring the humidity within the drum to detect an indication of the removal of a predetermined amount of moisture from the container. The controller is responsive to the detection of the removal of predetermined amount of moisture from the container to deactivate the heater in the drying loop.
While, all of the above data was compiled for temperatures that did not exceed 60° C. Additional tests indicate that depending upon energy requirements as well as time restrictions, the temperatures can be lowered further. The PRF removes most of the low vapor pressure working fluid and the use of the PRF with still high vapor pressure can lower drying temperatures still further and/or shorten drying times.
An additional requirement on the PRF is that the fluid is non-flammable. A non-flammable fluid combined with a flammable fluid increases the flash point of the solvent; thereby, increasing the safety associated with the system. The PRF will volatilize more quickly creating a PRF-rich head space above the working fluid; and this greatly reduces fire and explosion hazards due to the wash medium used. While most of the existing codes are set only for commercial machines, the ability to use this apparatus and method in the home can be more easily adapted with the select rinse fluid method. The select rinse fluid method as the capabilities of mitigating the risk associated with the use of cleaning with a flammable solvent.
In preferred embodiments, the working fluid will be selected for being non-aqueous and having the ability to remove soils and clean the fabrics. Such working fluids that fit the criteria are siloxanes and glycol ethers and more specifically decamethylcyclopentasiloxane, dipropylene glycol n-butyl ether, dipropylene glycol tertiary-butyl ether and/or tripropylene glycol methyl ether. Such a fluid will be added to a wash chamber after fabrics have been dispensed for cleaning. The system will run for a time sufficient to clean the fabrics while the working fluid and fabrics are tumbled at a rate sufficient to allow for the clothes to fall on top of one another. The working fluid will be removed from the fabrics through a spin that can range in speed from 600-1700 rpm based on the drum size used. The spin cycle will last for a time sufficient, greater than 2 minutes, where little or no additional working fluid is being removed from the fabrics. A select rinse fluid will be added to the system while the clothes are spinning at a rate of around 300 rpm. The select rinse fluid is selected for its ability to have a lower affinity for the fabrics than the working fluid as well as a lower osmotic force. More specifically, the PRF is a hydrofluoroether, either ethoxynonafluorobutane or methoxynonafluorobutane. The PRF is added while the fabrics are spinning thereby centrifugal force will pull the PRF through the fabrics removing a large portion of the working fluid. This action will take place for a time sufficient to reduce the concentration of working fluid to below 15% by weight of the fabric. The PRF and working fluid are removed by a conventional spinning cycle ranging from 600-1800 rpm. Heated air, preferably less than 80° C., is next introduced into the drum to remove the remaining PRF and working fluid from the fabric. Air is introduced while the fabrics are tumbling in the drum at a rate sufficient to allow air to transport solvent vapors from the surface of the fabrics into the air stream. This air stream is then passed over a condenser medium to remove most of the solvent vapors from the air stream so the air stream can pass over the fabrics again. After the fabrics are dry, they can be removed from the container.
The PRF and working fluid are then passed through a recovery system to separate and purify the fluids as much as possible. In the preferred embodiments, large particulates such as lint will be removed from the system. The recovery system will then pass into a distillation unit. It should be noted that the working fluid collected after the initial wash can be cleaned prior to introduction of the PRF. Most of these technologies have been discussed in U.S. 20040117919 and can be extended to glycol ether containing systems. The distillation unit will be heated to the boiling point of the PRF or to 30° F. below the flash point of the working fluid whichever is lower. The vapors created will be condensed and the PRF will be stored for re-use. The remaining working fluid will undergo a temperature reduction step to remove dissolved contaminants. The solution will pass through a cross-flow filtration membrane to concentrate the remaining contaminants in a smaller volume of working fluid. This concentrated solution will pass through an additional filtration means whereby the remaining working fluid can be evaporated, condensed and then re-used. The non-concentrated stream will pass through a series of adsorption/absorption filters to remove remaining contaminants and then through a sanitizing operation. The contaminants removed from the system will be collected and either discarded after each cycle or collected for a series of cycles and then discarded.
The preferred apparatus for such an operation should contain a myriad of components and can be modular in nature if need be. The apparatus should contain storage containers for the working fluid as well as the select rinse fluid. The apparatus should contain a drum or container for depositing clothes a means for controlling the drum such as a motor, a means for dispensing the working fluid, PRF, washing additives and the likes into the wash chamber, a blower to move air for drying, a heating means for heating the air, the fluids, the fabrics or the drum, a condensing means to remove the solvent vapors from the air stream, a means to add mechanical energy to the drum, means for sensing and a means for recovery.
In a preferred embodiment, the apparatus would be constructed in a manner where the size wouldn't require modifications to place the unit within the home. Additionally, this unit can be constructed and arranged in such a manner to operate as a dual fluid machine (aqueous-based cycles as well as non-aqueous cycles).
In the select rinse fluid (PRF) process of the present invention, it has been accomplished stages of separating the working fluid from the fibers in a series of steps.
The working fluids that are best suited for cleaning all fabrics still have some disadvantages. Most of these fluids have extremely small vapor pressures and generally have flash points. This makes conventional drying processes rather difficult. Select rinse fluids that are miscible with these working fluids can be added during one of the rinses and can remove a substantial amount of the remaining working fluid. These select rinse fluids can then be more easily removed via traditional convection drying processes.
The invention does not stop here; however, in that effective ways of recovery of the PRF are provided. In the preferred embodiments, a combination of working fluids and PRF are selected which are miscible and very different in ways which permit the two to be separated by ways which can be accomplished in simple operations which lend themselves to a complete cycle, which can be performed in the automatic, self-contained non-aqueous laundering machine described.
This application is a Continuation-in-part of application Ser. No. 10/699,159, filed Oct. 31, 2003 now abandoned, and related to patent application docket No. US20040171, entitled “A Method for Laundering Fabric with a Non-Aqueous Working Fluid Using a Select Rings Fluid”; US20040173, entitled “Method and Apparatus Adapted for Recovery and Reuse of Select Rinse Fluid in a Non-Aqueous Wash Apparatus; and US20040174, “Fabric Laundering Using a Select Rinse Fluid and Wash Fluids”, filed concurrently herewith.
Number | Name | Date | Kind |
---|---|---|---|
2107227 | Woodin | Feb 1938 | A |
D120681 | Sutton | May 1940 | S |
2629242 | Hallander | Feb 1953 | A |
2987902 | Mack | Jun 1961 | A |
3085415 | Gosnell | Apr 1963 | A |
3103112 | Behrens et al. | Sep 1963 | A |
3125106 | Brucken et al. | Mar 1964 | A |
3163028 | De Pas et al. | Dec 1964 | A |
3225572 | Robbins et al. | Dec 1965 | A |
3232335 | Kalbfleisch | Feb 1966 | A |
3246493 | Oles | Apr 1966 | A |
3266166 | Heinrich | Aug 1966 | A |
3269539 | Brucken et al. | Aug 1966 | A |
3386796 | Videen | Jun 1968 | A |
3402576 | Krupsky | Sep 1968 | A |
3410118 | Dickey | Nov 1968 | A |
3423311 | Richard Hetherinton, et al. | Jan 1969 | A |
3583181 | Brillet | Jun 1971 | A |
3674650 | Fine | Jul 1972 | A |
3691649 | Pigors, Ernst | Sep 1972 | A |
3733267 | Haase et al. | May 1973 | A |
3805404 | Gould | Apr 1974 | A |
3809924 | Grunow et al. | May 1974 | A |
3930998 | Knopp et al. | Jan 1976 | A |
4004048 | Jackson | Jan 1977 | A |
4032927 | Goshima | Jun 1977 | A |
4042498 | Kennedy | Aug 1977 | A |
4045174 | Fuhring et al. | Aug 1977 | A |
4046700 | Glover | Sep 1977 | A |
4121009 | Chakrabarti | Oct 1978 | A |
4153590 | Mueller | May 1979 | A |
4154003 | Muller | May 1979 | A |
4169856 | Cocuzza et al. | Oct 1979 | A |
4184950 | Bixby | Jan 1980 | A |
4186047 | Salmon | Jan 1980 | A |
4235600 | Capella | Nov 1980 | A |
4247330 | Sanders, Jr. | Jan 1981 | A |
4252546 | Krugmann | Feb 1981 | A |
4331525 | Huba et al. | May 1982 | A |
4388437 | Ona | Jun 1983 | A |
4395488 | Rowe | Jul 1983 | A |
4420398 | Castino | Dec 1983 | A |
4421794 | Kinsley, Jr. | Dec 1983 | A |
4434196 | Robinson et al. | Feb 1984 | A |
4444625 | Smith | Apr 1984 | A |
4457858 | Saran | Jul 1984 | A |
4499621 | Gasser | Feb 1985 | A |
4513590 | Fine | Apr 1985 | A |
4539093 | Friedman et al. | Sep 1985 | A |
4595506 | Kneer | Jun 1986 | A |
4601181 | Privat | Jul 1986 | A |
4610785 | Russell | Sep 1986 | A |
4621438 | Lanciaux | Nov 1986 | A |
4622039 | Merenda | Nov 1986 | A |
4625432 | Baltes | Dec 1986 | A |
4636328 | Flynn et al. | Jan 1987 | A |
4664754 | Caputi et al. | May 1987 | A |
4665929 | Helm | May 1987 | A |
4678587 | Voinche et al. | Jul 1987 | A |
4682424 | Irving | Jul 1987 | A |
4685930 | Kasprzak | Aug 1987 | A |
4708775 | McGregor et al. | Nov 1987 | A |
4708807 | Kemerer | Nov 1987 | A |
4755261 | McCord et al. | Jul 1988 | A |
4761209 | Bonaventura et al. | Aug 1988 | A |
4767537 | Davis | Aug 1988 | A |
4769921 | Kabakov | Sep 1988 | A |
4790910 | Havlik | Dec 1988 | A |
4802253 | Hagiwara | Feb 1989 | A |
4808319 | McNally et al. | Feb 1989 | A |
4818297 | Holzmiiller et al. | Apr 1989 | A |
4830710 | Thompson | May 1989 | A |
4834003 | Reischl et al. | May 1989 | A |
4851123 | Kmishra | Jul 1989 | A |
4857150 | Rival | Aug 1989 | A |
4869872 | Baltes | Sep 1989 | A |
4879888 | Suissa | Nov 1989 | A |
4880533 | Hondulas | Nov 1989 | A |
4904390 | Schweighofer et al. | Feb 1990 | A |
4911761 | McConnell | Mar 1990 | A |
4912793 | Hagiwara | Apr 1990 | A |
4919839 | Durbut | Apr 1990 | A |
4947983 | Jost | Aug 1990 | A |
4961753 | Donkers et al. | Oct 1990 | A |
4980030 | Johnson et al. | Dec 1990 | A |
4984318 | Coindreau-Palau | Jan 1991 | A |
4999398 | Graiver et al. | Mar 1991 | A |
5004000 | Berruex | Apr 1991 | A |
5028326 | Littler et al. | Jul 1991 | A |
5043075 | Dietmar et al. | Aug 1991 | A |
5050259 | Tsubaki et al. | Sep 1991 | A |
5054210 | Schumacher | Oct 1991 | A |
5056174 | Hagiwara | Oct 1991 | A |
5082503 | Slugs | Jan 1992 | A |
5091105 | Madore et al. | Feb 1992 | A |
5093031 | Login et al. | Mar 1992 | A |
5104419 | Funk | Apr 1992 | A |
5104545 | Means et al. | Apr 1992 | A |
5106507 | Klock et al. | Apr 1992 | A |
5112358 | Deal | May 1992 | A |
5116426 | Asano et al. | May 1992 | A |
5116473 | Bostjancic | May 1992 | A |
5118322 | Wasinger et al. | Jun 1992 | A |
5133802 | Maekawa et al. | Jul 1992 | A |
5135656 | Means et al. | Aug 1992 | A |
5143579 | Field et al. | Sep 1992 | A |
5146693 | Dottor et al. | Sep 1992 | A |
5151026 | Anderson et al. | Sep 1992 | A |
5154854 | Zabotto et al. | Oct 1992 | A |
5164030 | Casper | Nov 1992 | A |
5167821 | Tanbo et al. | Dec 1992 | A |
5173200 | Kellett | Dec 1992 | A |
5193560 | Tanaka | Mar 1993 | A |
5199125 | Otto | Apr 1993 | A |
5212272 | Sargent et al. | May 1993 | A |
5232476 | Grant | Aug 1993 | A |
5240507 | Gray | Aug 1993 | A |
5248393 | Schumacher et al. | Sep 1993 | A |
5256557 | Shetty et al. | Oct 1993 | A |
5268150 | Burkitt | Dec 1993 | A |
5269958 | de Jager | Dec 1993 | A |
5273589 | Griswold et al. | Dec 1993 | A |
5284029 | Keuper et al. | Feb 1994 | A |
5287985 | Hatayama | Feb 1994 | A |
5288420 | Mandy | Feb 1994 | A |
5288422 | Basu | Feb 1994 | A |
5290473 | Basu | Mar 1994 | A |
5294644 | Login et al. | Mar 1994 | A |
5300154 | Ferber et al. | Apr 1994 | A |
5300197 | Mitani et al. | Apr 1994 | A |
5304253 | Grant | Apr 1994 | A |
5304320 | Barthelemy et al. | Apr 1994 | A |
5308562 | Wohlfahrt-Laymann | May 1994 | A |
5315727 | Lee | May 1994 | A |
5316690 | Li | May 1994 | A |
5320683 | Samejima | Jun 1994 | A |
5334258 | Osano | Aug 1994 | A |
5340443 | Heinio et al. | Aug 1994 | A |
5340464 | Mickas | Aug 1994 | A |
5342405 | Duncan | Aug 1994 | A |
5344527 | Mickas | Sep 1994 | A |
5346588 | Sixta et al. | Sep 1994 | A |
5354428 | Clark et al. | Oct 1994 | A |
5354480 | Robinson et al. | Oct 1994 | A |
5360547 | Cockett et al. | Nov 1994 | A |
5368649 | Tsukazaki | Nov 1994 | A |
5377705 | Smith | Jan 1995 | A |
5392480 | Ishihara | Feb 1995 | A |
5404732 | Kim | Apr 1995 | A |
5405542 | Trinh et al. | Apr 1995 | A |
5405767 | Shetty | Apr 1995 | A |
5407446 | Sando | Apr 1995 | A |
5419849 | Fields | May 1995 | A |
5421049 | Hendren | Jun 1995 | A |
5423921 | Saal | Jun 1995 | A |
5426955 | Modahl | Jun 1995 | A |
5427858 | Nakamura et al. | Jun 1995 | A |
5431827 | Tatch | Jul 1995 | A |
5439817 | Shetty et al. | Aug 1995 | A |
5443747 | Inada et al. | Aug 1995 | A |
5447171 | Shibano | Sep 1995 | A |
5456856 | Flaningam et al. | Oct 1995 | A |
5460018 | Werner | Oct 1995 | A |
5463819 | Komori | Nov 1995 | A |
5467492 | Chao et al. | Nov 1995 | A |
5480572 | Minor | Jan 1996 | A |
5488842 | Nishioka et al. | Feb 1996 | A |
5490894 | Matsuhisa | Feb 1996 | A |
5492138 | Taricco | Feb 1996 | A |
5493743 | Schneider | Feb 1996 | A |
5494526 | Paranjpe | Feb 1996 | A |
5494600 | Surutzidis et al. | Feb 1996 | A |
5498266 | Takagawa et al. | Mar 1996 | A |
5500096 | Yuan | Mar 1996 | A |
5501811 | Flaningam et al. | Mar 1996 | A |
5503681 | Inada et al. | Apr 1996 | A |
5503756 | Corona, III et al. | Apr 1996 | A |
5504954 | Joo | Apr 1996 | A |
5505985 | Nakamura et al. | Apr 1996 | A |
5511264 | Nishioka et al. | Apr 1996 | A |
5518624 | Filson et al. | May 1996 | A |
5524358 | Matz | Jun 1996 | A |
5536327 | Kaiser | Jul 1996 | A |
5536374 | Spring | Jul 1996 | A |
5537754 | Bachmann et al. | Jul 1996 | A |
5538025 | Gray | Jul 1996 | A |
5538746 | Levy | Jul 1996 | A |
5555641 | Lee | Sep 1996 | A |
5591236 | Roetker | Jan 1997 | A |
5593598 | McGinness et al. | Jan 1997 | A |
5604145 | Hashizume et al. | Feb 1997 | A |
5605882 | Klug et al. | Feb 1997 | A |
5617737 | Christensen et al. | Apr 1997 | A |
5622630 | Romano | Apr 1997 | A |
5625965 | Blissett et al. | May 1997 | A |
5637336 | Kannenberg et al. | Jun 1997 | A |
5644158 | Fujii et al. | Jul 1997 | A |
5645727 | Bhave et al. | Jul 1997 | A |
5649785 | Djerf et al. | Jul 1997 | A |
5653873 | Grossman | Aug 1997 | A |
5656246 | Patapoff et al. | Aug 1997 | A |
5668102 | Severns et al. | Sep 1997 | A |
5676005 | Balliett | Oct 1997 | A |
5689848 | Saal et al. | Nov 1997 | A |
5712240 | Tyerech et al. | Jan 1998 | A |
5759209 | Adler | Jun 1998 | A |
5765403 | Lincoln et al. | Jun 1998 | A |
5773403 | Hijino et al. | Jun 1998 | A |
5776351 | McGinness et al. | Jul 1998 | A |
5776362 | Sato et al. | Jul 1998 | A |
5787537 | Mannillo | Aug 1998 | A |
5789368 | You et al. | Aug 1998 | A |
5799612 | Page | Sep 1998 | A |
5806120 | McEachem | Sep 1998 | A |
5814498 | Mani et al. | Sep 1998 | A |
5814592 | Kahn et al. | Sep 1998 | A |
5814595 | Flynn et al. | Sep 1998 | A |
5824632 | Flaningam et al. | Oct 1998 | A |
5840675 | Yeazell | Nov 1998 | A |
5846435 | Haase | Dec 1998 | A |
5849197 | Taylor et al. | Dec 1998 | A |
5853593 | Miller | Dec 1998 | A |
5858240 | Tardowski et al. | Jan 1999 | A |
5865851 | Sidoti et al. | Feb 1999 | A |
5865852 | Berndt | Feb 1999 | A |
5868937 | Back et al. | Feb 1999 | A |
5876461 | Racette et al. | Mar 1999 | A |
5876685 | Krulik et al. | Mar 1999 | A |
5885366 | Umino et al. | Mar 1999 | A |
5888250 | Hayday et al. | Mar 1999 | A |
5893979 | Held | Apr 1999 | A |
5894061 | Ladouceur | Apr 1999 | A |
5904737 | Preston et al. | May 1999 | A |
5906750 | Haase | May 1999 | A |
5912408 | Trinh et al. | Jun 1999 | A |
5914041 | Chancellor | Jun 1999 | A |
5925469 | Gee | Jul 1999 | A |
5925611 | Flynn et al. | Jul 1999 | A |
5935441 | O'Neill et al. | Aug 1999 | A |
5935525 | Lincoln et al. | Aug 1999 | A |
5942007 | Berndt et al. | Aug 1999 | A |
5954869 | Elfersy et al. | Sep 1999 | A |
5955394 | Kelly | Sep 1999 | A |
5958240 | Hoel | Sep 1999 | A |
5959014 | Liebeskind et al. | Sep 1999 | A |
5960501 | Burdick | Oct 1999 | A |
5960649 | Burdick | Oct 1999 | A |
5962390 | Flynn et al. | Oct 1999 | A |
5972041 | Smith et al. | Oct 1999 | A |
5977040 | Inada et al. | Nov 1999 | A |
5985810 | Inada et al. | Nov 1999 | A |
6006387 | Cooper | Dec 1999 | A |
6010621 | Pattee | Jan 2000 | A |
6013683 | Hill | Jan 2000 | A |
6027651 | Cash | Feb 2000 | A |
6029479 | Pattee | Feb 2000 | A |
6042617 | Berndt | Mar 2000 | A |
6042618 | Berndt | Mar 2000 | A |
6045588 | Estes et al. | Apr 2000 | A |
6056789 | Berndt | May 2000 | A |
6059845 | Berndt | May 2000 | A |
6059971 | Vit et al. | May 2000 | A |
6060108 | Burd et al. | May 2000 | A |
6063135 | Berndt et al. | May 2000 | A |
6063748 | Flynn et al. | May 2000 | A |
6086635 | Berndt et al. | Jul 2000 | A |
6098306 | Ramsey | Aug 2000 | A |
6113815 | Elfersy | Sep 2000 | A |
6115862 | Cooper | Sep 2000 | A |
6120587 | Elfersy | Sep 2000 | A |
6136223 | Collins | Oct 2000 | A |
6136766 | Inada et al. | Oct 2000 | A |
6149980 | Behr et al. | Nov 2000 | A |
6156074 | Hayday et al. | Dec 2000 | A |
6159376 | Lahti | Dec 2000 | A |
6159917 | Baran | Dec 2000 | A |
6168714 | Ilias et al. | Jan 2001 | B1 |
6171346 | Yeazell et al. | Jan 2001 | B1 |
6177399 | Mei et al. | Jan 2001 | B1 |
6190556 | Uhlinger | Feb 2001 | B1 |
6207634 | Meyer et al. | Mar 2001 | B1 |
6216302 | Preston et al. | Apr 2001 | B1 |
6217771 | Boyle et al. | Apr 2001 | B1 |
6221944 | Liebeskind | Apr 2001 | B1 |
6238516 | Watson et al. | May 2001 | B1 |
6238736 | Smith | May 2001 | B1 |
6239097 | Wilson | May 2001 | B1 |
6241779 | Collins | Jun 2001 | B1 |
6241786 | Zarges et al. | Jun 2001 | B1 |
6254838 | Goede | Jul 2001 | B1 |
6254932 | Smith | Jul 2001 | B1 |
6258130 | Murphy | Jul 2001 | B1 |
6258276 | Mika et al. | Jul 2001 | B1 |
6261460 | Benn et al. | Jul 2001 | B1 |
6269667 | Back | Aug 2001 | B1 |
6273919 | Hayday | Aug 2001 | B1 |
6274540 | Scheibel et al. | Aug 2001 | B1 |
6277804 | Kahn et al. | Aug 2001 | B1 |
6281187 | Smerznak | Aug 2001 | B1 |
6288018 | Flynn et al. | Sep 2001 | B1 |
6299779 | Pattee | Oct 2001 | B1 |
6309425 | Murphy | Oct 2001 | B1 |
6309752 | Dams et al. | Oct 2001 | B1 |
6310029 | Kilgour et al. | Oct 2001 | B1 |
6312476 | Perry et al. | Nov 2001 | B1 |
6319406 | Freshour et al. | Nov 2001 | B1 |
6327731 | Back | Dec 2001 | B2 |
6348441 | Aiken et al. | Feb 2002 | B1 |
6350377 | Kollmar et al. | Feb 2002 | B1 |
6365051 | Bader | Apr 2002 | B1 |
6379547 | Larsson | Apr 2002 | B1 |
6384008 | Parry | May 2002 | B1 |
6387186 | Reisig et al. | May 2002 | B1 |
6387241 | Murphy et al. | May 2002 | B1 |
6398840 | Orta-Castro et al. | Jun 2002 | B1 |
6399357 | Winge | Jun 2002 | B1 |
6402956 | Andou et al. | Jun 2002 | B1 |
6416668 | Al-Samadi | Jul 2002 | B1 |
6423230 | Ilias et al. | Jul 2002 | B2 |
6451066 | Estes et al. | Sep 2002 | B2 |
6475968 | Murphy et al. | Nov 2002 | B1 |
6479719 | Kotwica et al. | Nov 2002 | B1 |
6552090 | Behr et al. | Apr 2003 | B1 |
6558432 | Schulte et al. | May 2003 | B2 |
6591638 | Estes et al. | Jul 2003 | B2 |
6653512 | Behr et al. | Nov 2003 | B1 |
6670317 | Severns et al. | Dec 2003 | B2 |
6691536 | Severns et al. | Feb 2004 | B2 |
6734153 | Scheper | May 2004 | B2 |
6736859 | Racette et al. | May 2004 | B2 |
6743262 | Behr et al. | Jun 2004 | B1 |
6746617 | Radomyselski et al. | Jun 2004 | B2 |
6755871 | Damaso et al. | Jun 2004 | B2 |
6766670 | Estes et al. | Jul 2004 | B2 |
6770615 | Aouad et al. | Aug 2004 | B1 |
6811811 | France et al. | Nov 2004 | B2 |
6828295 | Deak et al. | Dec 2004 | B2 |
6840069 | France et al. | Jan 2005 | B2 |
6855173 | Ehrnsperger et al. | Feb 2005 | B2 |
6860998 | Wilde | Mar 2005 | B1 |
6890892 | Scheper et al. | May 2005 | B2 |
6894014 | Deak et al. | May 2005 | B2 |
6898951 | Severns et al. | May 2005 | B2 |
7033985 | Noyes et al. | Apr 2006 | B2 |
20010042275 | Estes et al. | Nov 2001 | A1 |
20010054202 | Severns et al. | Dec 2001 | A1 |
20020004950 | Burns et al. | Jan 2002 | A1 |
20020004952 | Deak et al. | Jan 2002 | A1 |
20020004995 | France et al. | Jan 2002 | A1 |
20020007519 | Noyes et al. | Jan 2002 | A1 |
20020010964 | Deak et al. | Jan 2002 | A1 |
20020010965 | Schulte et al. | Jan 2002 | A1 |
20020013234 | Severns et al. | Jan 2002 | A1 |
20020017493 | Ehrnsperger et al. | Feb 2002 | A1 |
20020029427 | Severns et al. | Mar 2002 | A1 |
20020038480 | Deak et al. | Apr 2002 | A1 |
20020056163 | Estes | May 2002 | A1 |
20020056164 | Estes et al. | May 2002 | A1 |
20020110926 | Kopf-Sill et al. | Aug 2002 | A1 |
20020133886 | Severns et al. | Sep 2002 | A1 |
20030037809 | Favaro | Feb 2003 | A1 |
20030046963 | Scheper et al. | Mar 2003 | A1 |
20030084588 | France et al. | May 2003 | A1 |
20030092592 | Bargaje et al. | May 2003 | A1 |
20030097718 | Evers et al. | May 2003 | A1 |
20030196277 | Hallman et al. | Oct 2003 | A1 |
20030204917 | Estes et al. | Nov 2003 | A1 |
20030226214 | Radomyselski et al. | Dec 2003 | A1 |
20040088795 | Orchowski et al. | May 2004 | A1 |
20040088846 | Murphy et al. | May 2004 | A1 |
20040117919 | Conrad et al. | Jun 2004 | A1 |
20040129032 | Severns et al. | Jul 2004 | A1 |
20040139555 | Conrad | Jul 2004 | A1 |
20050000897 | Radomyselski et al. | Jan 2005 | A1 |
20050037938 | Reinhoudt et al. | Feb 2005 | A1 |
20050043196 | Wright et al. | Feb 2005 | A1 |
20050071928 | Wright et al. | Apr 2005 | A1 |
20050076453 | Lucas et al. | Apr 2005 | A1 |
20050091755 | Conrad et al. | May 2005 | A1 |
20050091756 | Wright | May 2005 | A1 |
20050091757 | Luckman et al. | May 2005 | A1 |
20050092033 | Luckman et al. | May 2005 | A1 |
20050096242 | Luckman et al. | May 2005 | A1 |
20050096243 | Luckman et al. | May 2005 | A1 |
20050126606 | Goedhart et al. | Jun 2005 | A1 |
20050132502 | Goldoni | Jun 2005 | A1 |
20050133462 | Goldini | Jun 2005 | A1 |
20050150059 | Luckman et al. | Jul 2005 | A1 |
20050155393 | Wright et al. | Jul 2005 | A1 |
20050222002 | Luckman et al. | Oct 2005 | A1 |
20050257812 | Wright et al. | Nov 2005 | A1 |
20050263173 | Luckman et al. | Dec 2005 | A1 |
Number | Date | Country |
---|---|---|
0182583 | Nov 1985 | EP |
0182583 | Jul 1991 | EP |
0246007 | Mar 1992 | EP |
6233898 | Aug 1994 | EP |
0707060 | Jul 1998 | EP |
1041189 | Oct 2000 | EP |
1290259 | Mar 2003 | EP |
1528138 | Oct 2004 | EP |
1528139 | Oct 2004 | EP |
1528140 | Oct 2004 | EP |
1528141 | Oct 2004 | EP |
1536052 | Oct 2004 | EP |
1528138 | May 2005 | EP |
1528139 | May 2005 | EP |
153052 | Jun 2005 | EP |
1002318 | Aug 1965 | GB |
1500801 | Feb 1975 | GB |
405064521 | Mar 1993 | JP |
06233898 | Aug 1994 | JP |
WO 9806815 | Feb 1998 | WO |
WO9806818 | Feb 1998 | WO |
WO 9914175 | Mar 1999 | WO |
WO 0106051 | Jan 2001 | WO |
WO 0134613 | May 2001 | WO |
WO 0144256 | Jun 2001 | WO |
WO 0194675 | Dec 2001 | WO |
WO 0194677 | Dec 2001 | WO |
WO 0194680 | Dec 2001 | WO |
WO 0194683 | Dec 2001 | WO |
WO 0194685 | Dec 2001 | WO |
WO0194675 | Dec 2001 | WO |
Number | Date | Country | |
---|---|---|---|
20050092033 A1 | May 2005 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 10699159 | Oct 2003 | US |
Child | 10957485 | US |