US20110169201A1 - Methods of making a mixture for a ptfe membrane with inorganic materials, and compositions related thereto - Google Patents
Methods of making a mixture for a ptfe membrane with inorganic materials, and compositions related thereto Download PDFInfo
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- US20110169201A1 US20110169201A1 US12/877,355 US87735510A US2011169201A1 US 20110169201 A1 US20110169201 A1 US 20110169201A1 US 87735510 A US87735510 A US 87735510A US 2011169201 A1 US2011169201 A1 US 2011169201A1
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- United States
- Prior art keywords
- porous inorganic
- inorganic material
- resin
- weight
- lubricating agent
- Prior art date
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 66
- 229910010272 inorganic material Inorganic materials 0.000 title claims abstract description 48
- 239000011147 inorganic material Substances 0.000 title claims abstract description 48
- 239000012528 membrane Substances 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 65
- 239000011347 resin Substances 0.000 claims abstract description 56
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 239000000314 lubricant Substances 0.000 claims abstract description 47
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 238000003490 calendering Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
- B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F29/00—Mixers with rotating receptacles
- B01F29/60—Mixers with rotating receptacles rotating about a horizontal or inclined axis, e.g. drum mixers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
- B29C69/02—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore of moulding techniques only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/14—Ageing features
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/21—Fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
- B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
Definitions
- Embodiments of the present invention generally relate to making an expanded polytetrafluoroethylene (ePTFE) membrane containing porous inorganic materials.
- ePTFE expanded polytetrafluoroethylene
- PTFE polytetrafluoroethylene
- lubricity e.g., bearings, bushings, etc.
- filters may use discs or sheets.
- Additive-containing PTFE products are known. See, e.g., U.S. Pat. Nos. 5,697,390 to Garrison et al.; 5,827,327 to McHaney et al.; 6,120,532 to Goldfarb; and 6,270,707 to Hori et al.
- a method for making a polytetrafluoroethylene membrane comprising porous inorganic materials may comprise the steps of: (a) mixing a polytetrafluoroethylene resin having a weight, a lubricating agent having a weight, and a porous inorganic material having a weight, wherein the weight of the lubricating agent comprises between 15 and 25 percent of the weight of the polytetrafluoroethylene resin, wherein the weight of the porous inorganic material comprises up to 10 percent of the weight of the polytetrafluoroethylene resin, and wherein the porous inorganic material has at least one dimension less than 100 nm; (b) forming a preform comprising a mixture of the polytetrafluoroethylene resin, the lubricating agent, and the porous inorganic material; (c) extruding the preform to form a tape having a thickness between 1 and 100 mil; (d) calendaring the tape to facilitate evaporation
- a method of incorporating a porous inorganic material into a mixture comprising a polytetrafluoroethylene resin and a lubricating agent may comprise the steps of: (a) mixing the polytetrafluoroethylene resin with the lubricating agent in a V blender for a period of time between 1 and 60 minutes to form a resin/lubricant mixture; (b) wicking the resin/lubricant mixture for a period of time between 1 and 120 hours; and (c) mixing the resin/lubricant mixture with the porous inorganic material in a V blender for a period of time between 1 and 60 minutes; wherein a weight of the lubricating agent comprises between 15 and 25 percent of a weight of the polytetrafluoroethylene resin, wherein a weight of the porous inorganic material comprises up to 10 percent of the weight of the polytetrafluoroethylene resin, and wherein the porous inorganic material has at least one dimension less than 100 n
- composition comprising: a polytetrafluoroethylene resin; a lubricating agent comprising an isoparaffinic solvent; and a porous inorganic material; wherein a weight of the lubricating agent comprises between 15 and percent of a weight of the polytetrafluoroethylene resin; wherein a weight of the porous inorganic material comprises up to 10 percent of the weight of the polytetrafluoroethylene resin; and wherein the porous inorganic material has at least one dimension less than 100 nm and has a specific surface area greater than 50 m 2 /g.
- Certain aspects of the present invention may related to extruding into tape polytetrafluoroethylene (PTFE) that includes porous inorganic materials and/or composites, then converting the extruded PTFE tape into a membrane through biaxial stretching.
- PTFE tape polytetrafluoroethylene
- a combination of PTFE and inorganic porous materials may be prepared by dispersing inorganic porous materials such as activated carbon, carbon nanotubes, zeolites, silicon dioxide, and other nanomaterials into a mixture containing PTFE resin.
- the PTFE composite may be then extruded into tape and converted into a membrane by biaxial stretching.
- a membrane containing porous inorganic particles may have a high porosity/surface area and may be used, at least in some instances, as a catalyst for decontamination.
- membranes containing porous materials may be used in the filtration of toxic gas(ses).
- a dimensionally stable membrane containing porous inorganic materials may be used as a filter media for gas separation and/or liquid separation.
- microporous membrane containing nano- and/or micro-sized complex flow channels on the membrane cell walls for the filtration of gas on a molecular level.
- a PTFE membrane may be chemically inert and typically has a very low surface energy.
- that chemical stability (and/or other beneficial characteristics of a PTFE membrane) may be combined with the nanoporous structure of inorganic materials.
- the adsorption capability of porous inorganic material may be useful in trapping toxic molecules present in the air that contact the PTFE/inorganic material matrix.
- a membrane containing porous materials may be useful as a storage medium for decontaminating toxic treatment agents.
- the PTFE membrane containing inorganic material may be used in the separation and/or purification of gas.
- Ion exchange composite resins may be prepared from membrane containing active porous materials. Large surface area and tunable surface properties may be notable characteristics of such membranes.
- inorganic porous materials may include, for example, any small particle with at least one dimension less than 100 nm. Preferably, the small particles have at least one dimension less than 50 nm, and even more preferably the particles have at least one dimension less than 30 nm.
- Exemplary inorganic porous materials may include activated carbon, carbon nanotubes, carbon fibers, zeolites or other catalysts, silicon dioxide, etc.
- Suitable nanoparticles may have a high surface area to volume (or mass) ratio.
- suitable nanoparticles may have a specific surface area of greater than 10 m 2 /g, greater than 50 m 2 /g, or greater than 90 m 2 /g. In some embodiments, the specific surface area may be about 100 m 2 /g.
- a suitable inorganic porous material may comprise Activated Carbon Nanopowder available from Aldrich Chemical Co.
- Activated nanocarbon may impart properties such as abrasion resistance and/or thermal and electrical conduction and may also improve mechanical properties (e.g., strength, durability, longevity, etc.).
- certain aspects of the present invention relate to a method of making a PTFE membrane containing a porous inorganic material.
- the steps may include one or more of the following steps: (1) mixing PTFE resin with a lubricating agent, then wicking the resin/lubricant mixture; (2) mixing the resin/lubricant mixture with a porous inorganic material (such as an activated nanocarbon); (3) preforming the wet-mixture into a billet; (4) extruding the mixture into tape; (5) calendaring the tape; (6) biaxially stretching the tape to form a membrane; and (7) sintering the membrane to stabilize its microstructure.
- a porous inorganic material such as an activated nanocarbon
- this process may be generally known as a “wet-process” and not a “dry-process” (which generally relies on friction-free air blending in an environment without shear).
- a suitable PTFE resin comprises Dupont Teflon® PTFE 601A, available from E. I. du Pont de Nemours and Co.
- Other PTFE resins may comprise Daikin F107, Dupont 603A, and/or Dupont 60A.
- a suitable lubricating agent includes a hydrocarbon-based liquid, such as the isoparaffinic solvents sold under the Isopar tradename by the ExxonMobil Chemical Co.
- a preferred lubricating agent may comprise Isopar K, Isopar M, and/or Isopar G.
- the PTFE resin powder may be mixed with the lubricating agent in a V blender for between 1 and 60 minutes (preferably about 30 minutes), for example, until the mixture is approximately homogenous.
- the weight percentage of the lubricating agent may range between 15 and 25% (and all subranges therebetween) of weight of the resin. This weight percentage, which is commonly known as the “lube rate,” may vary, for example, depending on the specific processing parameters of the equipment being used in the extrusion process.
- Wicking occurs after mixing, and the resin/lubricant mixture may be held at a temperature of 90° F. for 18 hours.
- the temperature may be higher (e.g., 200° F.) or lower (e.g., 40° F.), and the time may be shorter (e.g., 1 hour) or longer (e.g., 120 hours).
- the wicking may be optional.
- the wicked resin/lubricant mix may then be mixed with porous inorganic material using a V blender, e.g., at ambient temperature for between 1 and 60 minutes, preferably between 15 and 30 minutes.
- the porous inorganic material comprises up to 10 wt % of the PTFE resin. In other embodiments, the porous inorganic material comprises up to 5 wt % of the PTFE resin. In yet further embodiments, the porous inorganic material comprises up to 3 wt % of the PTFE resin.
- the lubricating agent may assist in dispersing the porous inorganic materials.
- the porous inorganic material may be mixed with the resin and/or lubricant in various permutations. For example, they may be all mixed together at the same time, or the lubricant and porous inorganic material may be mixed prior to mixing with the PTFE resin.
- the resin/lubricant/additive mixture may then be preformed, e.g., through charging into a cylinder, then pressed under pressure to form a preform.
- the cylinder may be 50 inches, and the 150 psi of pressure is used to force the mixture into the preform at ambient temperature.
- other process parameters may also be used.
- the preform may then be extruded into tape, e.g., Ram extruder.
- the extrusion occurs at a temperature between 80° F. and 100° F. and at a rate between 80 and 200 in/min.
- the final thickness of the tape may vary between 1 and 100 mil, preferably between 5 and 75 mil, and even more preferably between 10 and 40 mil. Of course, other process parameters may also be used.
- the tape may then be calendared, by passing the mixture through hot calendar rolls to facilitate the obtainment of tape uniformity as well as the evaporation of the lubricating agent.
- the calendaring may occur at a temperature between 300° F. and 400° F. and at a rate between 10 and 20 ft/min.
- the calendar rolls may be 20 inches wide, and calendar rolls may be spaced between 10 and 17 mil apart. Of course, other process parameters may also be used.
- the tape may then be formed into a membrane via tentering.
- the tape is stretched biaxially to form a thin membrane.
- the stretching occurs at a line speed between 30 ft/min and 80 ft/min.
- the stretching occurs multiple times, even in the same direction.
- the tape may be stretched between 1 and 20 times (preferably between 10 and 12 times) in the transverse direction and between 1 and 5 times (preferably 3 times) in the machine direction.
- Various temperatures may be used, e.g., between 150° F. and 800° F., such as, for example, at 200° F., at 500° F., at 650° F., or at 700° F. These temperatures may increase or otherwise vary with the stretch cycles.
- the membrane may be heat treated to stabilize the microstructure of a membrane. This sintering may occur in an oven at a temperature between 400° F. and 750° F., preferably between 650° F. and 750° F., for a period of time between 1 and 120 seconds, and preferably between 10 and 30 seconds.
- the final thickness of the membrane may range between 0.05 and 20 mil (preferably 2 mil).
- Example No. 1 was prepared with 1.9 wt % Activated Carbon Nanopowder (using the weight of the PTFE resin as the basis).
- Example No. 2 was prepared with 3.8 wt % Activated Carbon Nanopowder (using the weight of the PTFE resin as the basis).
- the PTFE resin used was Dupont Teflon® PTFE 601A, and the lubricating agent was Isopar K.
- the resulting membranes were compared to the specifications for two commercially available PTFE membranes from GE Energy: QMO8 and QMO11.
- DuPont 601 A resin fine powder was mixed with 20 wt % of Isopar K using a V blender at ambient condition for about 30 min. The resin/isopar mix was wicked at 90° F. for 24 hours. The wicked PTFE/Isopar mix was blended with 1.9 wt % of activated nanocarbon using a V blender for about 15 min. The resin/isopar/carbon was shaped into cylindrical form (perform) by pressure of 150 psi using a billet press. The perform was extruded into a tape at a temperature 80° F. using a Ram extruder. The isopar was removed from the tape with thickness ⁇ 20 mil by passing it through series of hot calendar rolls at a temperature of 200° F. The tape was stretched biaxially to form a porous PTFE membrane (stretched 2 times in the machine direction and 8 times in the transverse direction). The microstructure of PTFE membrane was stabilized by applying heat at temperature of 680° F.
- the membrane was tested as per product test specifications and compared with GE standard commercialized membrane. It was found that the Nanocarbon additive dispersed uniformly within PTFE matrix and locked in the microstructure.
- Example No. 1 QMO11 QMO8 Lube Rate 20.75 17.5 20.75 (wt % of lubricating agent compared to PTFE resi/n) Average Unit weight (oz/yd 2 ) 0.6 0.4-0.7 0.4-0.6 Air perm (cfm) 0.901 0.2-0.4 1.0-2.5 Mullen (psi) 61 60-120 >25 Thickness (in.) 0.002 — 0.003 Peel Strength MD 0.347 0.2-0.45 >0.2 (lbf/in.) Peel Strength XD 0.343 0.2-0.4 >0.2 (lbf/in.) Tensile Elongation 273% — >100% MD Tensile Elongation XD 103% — >40% IPA Bubble point (psi) 14 — 12-18 MVTR (g/m 2 /24 hrs) 49904 50,000-85,000 >70,000
- DuPont 603 A resin fine powder was mixed with 22 wt % of Isopar M using a V blender at ambient condition for about 20 min. The resin/isopar mix was wicked at 110° F. for 48 hours. The wicked PTFE/Isopar mix was blended with 3.8 wt % of activated nanocarbon using a V blender for about 30 min. The resin/isopar/carbon was shaped into cylindrical form (perform) by applying pressure of 100 psi using a billet press. The perform was extruded into a tape at a temperature 110° F. using a Ram extruder. The isopar was removed from the tape with thickness ⁇ 8 mil by passing it through series of hot Calendar rolls at a temperature of 250° F. The tape was stretched biaxially to form a porous PTFE membrane (stretched 5 times in the machine direction and 12 times in the transverse direction). The microstructure of PTFE membrane was stabilized by applying heat at temperature of 720° F.
- the membrane is tested as per product test specifications and compared with GE standard commercialized membrane. It was found that the Nanocarbon additive dispersed uniformly within PTFE matrix and locked in the microstructure.
- Example No. 2 QMO11 QMO8 Lube Rate 20.75 17.5 20.75 (wt % of lubricating agent compared to PTFE resin) Average Unit weight (oz/yd 2 ) 0.5 0.4-0.7 0.4-0.6 Air perm (cfm) 0.922 0.2-0.4 1.0-2.5 Mullen (psi) 67 60-120 >25 Thickness (in.) 0.002 — 0.003 Peel Strength MD 0.35 0.2-0.45 >0.2 (lbf/in.) Peel Strength XD 0.243 0.2-0.4 >0.2 (lbf/in.) Tensile Elongation 238 — >100% MD Tensile Elongation XD 73 — >40% IPA Bubble point 14 — 12-18 (psi) MVTR (g/m 2 /24 hrs) 52395 50,000-85,000 >70,000
Abstract
Method for making a mixture used in the production of a polytetrafluoroethylene (PTFE) membrane including porous inorganic materials. The mixture includes PTFE resin, a lubricating agent, and a porous inorganic material. The mixture may be further processed to form a PTFE membrane.
Description
- This application is a divisional of application Ser. No. 12/037,501, filed Feb. 26, 2008, the entire contents of which is incorporated herein by reference.
- Embodiments of the present invention generally relate to making an expanded polytetrafluoroethylene (ePTFE) membrane containing porous inorganic materials.
- Materials including polytetrafluoroethylene (PTFE) are known in the art. PTFE has various well-established uses, including, for example, applications requiring lubricity (e.g., bearings, bushings, etc.) and applications requiring a porous membrane. These membrane-related applications may include, for example, filtration, venting, and/or diffusion/barrier applications. Filtration may use discs or sheets.
- Additive-containing PTFE products are known. See, e.g., U.S. Pat. Nos. 5,697,390 to Garrison et al.; 5,827,327 to McHaney et al.; 6,120,532 to Goldfarb; and 6,270,707 to Hori et al.
- In an embodiment of the present invention, there is a method for making a polytetrafluoroethylene membrane comprising porous inorganic materials. The method may comprise the steps of: (a) mixing a polytetrafluoroethylene resin having a weight, a lubricating agent having a weight, and a porous inorganic material having a weight, wherein the weight of the lubricating agent comprises between 15 and 25 percent of the weight of the polytetrafluoroethylene resin, wherein the weight of the porous inorganic material comprises up to 10 percent of the weight of the polytetrafluoroethylene resin, and wherein the porous inorganic material has at least one dimension less than 100 nm; (b) forming a preform comprising a mixture of the polytetrafluoroethylene resin, the lubricating agent, and the porous inorganic material; (c) extruding the preform to form a tape having a thickness between 1 and 100 mil; (d) calendaring the tape to facilitate evaporation of the lubricating agent; (e) tentering the tape through biaxially stretching in a first direction and a second direction perpendicular to the first direction to form a membrane; and (f) sintering the membrane at a temperature between 400° F. and 750° F. for a period of time between 1 and 120 seconds, wherein the membrane after sintering has a thickness between 0.05 and 20 mil.
- In an embodiment of the present invention, there is a method of incorporating a porous inorganic material into a mixture comprising a polytetrafluoroethylene resin and a lubricating agent. The method may comprise the steps of: (a) mixing the polytetrafluoroethylene resin with the lubricating agent in a V blender for a period of time between 1 and 60 minutes to form a resin/lubricant mixture; (b) wicking the resin/lubricant mixture for a period of time between 1 and 120 hours; and (c) mixing the resin/lubricant mixture with the porous inorganic material in a V blender for a period of time between 1 and 60 minutes; wherein a weight of the lubricating agent comprises between 15 and 25 percent of a weight of the polytetrafluoroethylene resin, wherein a weight of the porous inorganic material comprises up to 10 percent of the weight of the polytetrafluoroethylene resin, and wherein the porous inorganic material has at least one dimension less than 100 nm.
- In an embodiment of the present invention, there is a composition comprising: a polytetrafluoroethylene resin; a lubricating agent comprising an isoparaffinic solvent; and a porous inorganic material; wherein a weight of the lubricating agent comprises between 15 and percent of a weight of the polytetrafluoroethylene resin; wherein a weight of the porous inorganic material comprises up to 10 percent of the weight of the polytetrafluoroethylene resin; and wherein the porous inorganic material has at least one dimension less than 100 nm and has a specific surface area greater than 50 m2/g.
- Certain aspects of the present invention may related to extruding into tape polytetrafluoroethylene (PTFE) that includes porous inorganic materials and/or composites, then converting the extruded PTFE tape into a membrane through biaxial stretching.
- In certain embodiments, a combination of PTFE and inorganic porous materials (e.g., composites) may be prepared by dispersing inorganic porous materials such as activated carbon, carbon nanotubes, zeolites, silicon dioxide, and other nanomaterials into a mixture containing PTFE resin. The PTFE composite may be then extruded into tape and converted into a membrane by biaxial stretching.
- A membrane containing porous inorganic particles may have a high porosity/surface area and may be used, at least in some instances, as a catalyst for decontamination. In some embodiments, for example, membranes containing porous materials may be used in the filtration of toxic gas(ses). Furthermore a dimensionally stable membrane containing porous inorganic materials may be used as a filter media for gas separation and/or liquid separation.
- In some exemplary embodiments, for instance, it may be possible to create a microporous membrane containing nano- and/or micro-sized complex flow channels on the membrane cell walls for the filtration of gas on a molecular level.
- A PTFE membrane may be chemically inert and typically has a very low surface energy. In certain embodiments, that chemical stability (and/or other beneficial characteristics of a PTFE membrane) may be combined with the nanoporous structure of inorganic materials. For example, the adsorption capability of porous inorganic material may be useful in trapping toxic molecules present in the air that contact the PTFE/inorganic material matrix. For another example, a membrane containing porous materials may be useful as a storage medium for decontaminating toxic treatment agents.
- In at least some embodiments, the PTFE membrane containing inorganic material may be used in the separation and/or purification of gas. Ion exchange composite resins may be prepared from membrane containing active porous materials. Large surface area and tunable surface properties may be notable characteristics of such membranes.
- In certain embodiments, inorganic porous materials may include, for example, any small particle with at least one dimension less than 100 nm. Preferably, the small particles have at least one dimension less than 50 nm, and even more preferably the particles have at least one dimension less than 30 nm. Exemplary inorganic porous materials may include activated carbon, carbon nanotubes, carbon fibers, zeolites or other catalysts, silicon dioxide, etc. Suitable nanoparticles may have a high surface area to volume (or mass) ratio. For example, suitable nanoparticles may have a specific surface area of greater than 10 m2/g, greater than 50 m2/g, or greater than 90 m2/g. In some embodiments, the specific surface area may be about 100 m2/g. A suitable inorganic porous material may comprise Activated Carbon Nanopowder available from Aldrich Chemical Co.
- Activated nanocarbon, for example, may impart properties such as abrasion resistance and/or thermal and electrical conduction and may also improve mechanical properties (e.g., strength, durability, longevity, etc.).
- In preferred embodiments, certain aspects of the present invention relate to a method of making a PTFE membrane containing a porous inorganic material. In general, the steps may include one or more of the following steps: (1) mixing PTFE resin with a lubricating agent, then wicking the resin/lubricant mixture; (2) mixing the resin/lubricant mixture with a porous inorganic material (such as an activated nanocarbon); (3) preforming the wet-mixture into a billet; (4) extruding the mixture into tape; (5) calendaring the tape; (6) biaxially stretching the tape to form a membrane; and (7) sintering the membrane to stabilize its microstructure.
- Due to the use of a lubricating agent that is removed from the extrudate following the application of heat, this process may be generally known as a “wet-process” and not a “dry-process” (which generally relies on friction-free air blending in an environment without shear).
- In an exemplary embodiment, a suitable PTFE resin comprises Dupont Teflon® PTFE 601A, available from E. I. du Pont de Nemours and Co. Other PTFE resins may comprise Daikin F107, Dupont 603A, and/or Dupont 60A. And in an exemplary embodiment, a suitable lubricating agent includes a hydrocarbon-based liquid, such as the isoparaffinic solvents sold under the Isopar tradename by the ExxonMobil Chemical Co. A preferred lubricating agent may comprise Isopar K, Isopar M, and/or Isopar G. The PTFE resin powder may be mixed with the lubricating agent in a V blender for between 1 and 60 minutes (preferably about 30 minutes), for example, until the mixture is approximately homogenous. In certain embodiments, the weight percentage of the lubricating agent may range between 15 and 25% (and all subranges therebetween) of weight of the resin. This weight percentage, which is commonly known as the “lube rate,” may vary, for example, depending on the specific processing parameters of the equipment being used in the extrusion process.
- Wicking occurs after mixing, and the resin/lubricant mixture may be held at a temperature of 90° F. for 18 hours. In certain embodiments, the temperature may be higher (e.g., 200° F.) or lower (e.g., 40° F.), and the time may be shorter (e.g., 1 hour) or longer (e.g., 120 hours). In other embodiments, the wicking may be optional.
- The wicked resin/lubricant mix may then be mixed with porous inorganic material using a V blender, e.g., at ambient temperature for between 1 and 60 minutes, preferably between 15 and 30 minutes. In some embodiments, the porous inorganic material comprises up to 10 wt % of the PTFE resin. In other embodiments, the porous inorganic material comprises up to 5 wt % of the PTFE resin. In yet further embodiments, the porous inorganic material comprises up to 3 wt % of the PTFE resin.
- In certain embodiments, the lubricating agent may assist in dispersing the porous inorganic materials. In certain embodiments, the porous inorganic material may be mixed with the resin and/or lubricant in various permutations. For example, they may be all mixed together at the same time, or the lubricant and porous inorganic material may be mixed prior to mixing with the PTFE resin.
- The resin/lubricant/additive mixture may then be preformed, e.g., through charging into a cylinder, then pressed under pressure to form a preform. In some embodiments, the cylinder may be 50 inches, and the 150 psi of pressure is used to force the mixture into the preform at ambient temperature. Of course, other process parameters may also be used.
- The preform may then be extruded into tape, e.g., Ram extruder. In some embodiments, the extrusion occurs at a temperature between 80° F. and 100° F. and at a rate between 80 and 200 in/min. The final thickness of the tape may vary between 1 and 100 mil, preferably between 5 and 75 mil, and even more preferably between 10 and 40 mil. Of course, other process parameters may also be used.
- After extrusion, the tape may then be calendared, by passing the mixture through hot calendar rolls to facilitate the obtainment of tape uniformity as well as the evaporation of the lubricating agent. The calendaring may occur at a temperature between 300° F. and 400° F. and at a rate between 10 and 20 ft/min. The calendar rolls may be 20 inches wide, and calendar rolls may be spaced between 10 and 17 mil apart. Of course, other process parameters may also be used.
- After calendaring, the tape may then be formed into a membrane via tentering. During this process, the tape is stretched biaxially to form a thin membrane. Preferably, the stretching occurs at a line speed between 30 ft/min and 80 ft/min. Preferably, the stretching occurs multiple times, even in the same direction. For example, the tape may be stretched between 1 and 20 times (preferably between 10 and 12 times) in the transverse direction and between 1 and 5 times (preferably 3 times) in the machine direction. Various temperatures may be used, e.g., between 150° F. and 800° F., such as, for example, at 200° F., at 500° F., at 650° F., or at 700° F. These temperatures may increase or otherwise vary with the stretch cycles.
- After tentering, the membrane may be heat treated to stabilize the microstructure of a membrane. This sintering may occur in an oven at a temperature between 400° F. and 750° F., preferably between 650° F. and 750° F., for a period of time between 1 and 120 seconds, and preferably between 10 and 30 seconds. The final thickness of the membrane may range between 0.05 and 20 mil (preferably 2 mil).
- Two examples were prepared in accordance with exemplary embodiments of the present invention. Example No. 1 was prepared with 1.9 wt % Activated Carbon Nanopowder (using the weight of the PTFE resin as the basis). Example No. 2 was prepared with 3.8 wt % Activated Carbon Nanopowder (using the weight of the PTFE resin as the basis). The PTFE resin used was Dupont Teflon® PTFE 601A, and the lubricating agent was Isopar K. The resulting membranes were compared to the specifications for two commercially available PTFE membranes from GE Energy: QMO8 and QMO11.
- DuPont 601 A resin fine powder was mixed with 20 wt % of Isopar K using a V blender at ambient condition for about 30 min. The resin/isopar mix was wicked at 90° F. for 24 hours. The wicked PTFE/Isopar mix was blended with 1.9 wt % of activated nanocarbon using a V blender for about 15 min. The resin/isopar/carbon was shaped into cylindrical form (perform) by pressure of 150 psi using a billet press. The perform was extruded into a tape at a temperature 80° F. using a Ram extruder. The isopar was removed from the tape with thickness ˜20 mil by passing it through series of hot calendar rolls at a temperature of 200° F. The tape was stretched biaxially to form a porous PTFE membrane (stretched 2 times in the machine direction and 8 times in the transverse direction). The microstructure of PTFE membrane was stabilized by applying heat at temperature of 680° F.
- The membrane was tested as per product test specifications and compared with GE standard commercialized membrane. It was found that the Nanocarbon additive dispersed uniformly within PTFE matrix and locked in the microstructure.
-
TABLE 1 Comparison of Example No. 1 with specifications for QMO 11 and QMO 8. Membrane Characteristics Example No. 1 QMO11 QMO8 Lube Rate 20.75 17.5 20.75 (wt % of lubricating agent compared to PTFE resi/n) Average Unit weight (oz/yd2) 0.6 0.4-0.7 0.4-0.6 Air perm (cfm) 0.901 0.2-0.4 1.0-2.5 Mullen (psi) 61 60-120 >25 Thickness (in.) 0.002 — 0.003 Peel Strength MD 0.347 0.2-0.45 >0.2 (lbf/in.) Peel Strength XD 0.343 0.2-0.4 >0.2 (lbf/in.) Tensile Elongation 273% — >100% MD Tensile Elongation XD 103% — >40% IPA Bubble point (psi) 14 — 12-18 MVTR (g/m2/24 hrs) 49904 50,000-85,000 >70,000 - DuPont 603 A resin fine powder was mixed with 22 wt % of Isopar M using a V blender at ambient condition for about 20 min. The resin/isopar mix was wicked at 110° F. for 48 hours. The wicked PTFE/Isopar mix was blended with 3.8 wt % of activated nanocarbon using a V blender for about 30 min. The resin/isopar/carbon was shaped into cylindrical form (perform) by applying pressure of 100 psi using a billet press. The perform was extruded into a tape at a temperature 110° F. using a Ram extruder. The isopar was removed from the tape with thickness ˜8 mil by passing it through series of hot Calendar rolls at a temperature of 250° F. The tape was stretched biaxially to form a porous PTFE membrane (stretched 5 times in the machine direction and 12 times in the transverse direction). The microstructure of PTFE membrane was stabilized by applying heat at temperature of 720° F.
- The membrane is tested as per product test specifications and compared with GE standard commercialized membrane. It was found that the Nanocarbon additive dispersed uniformly within PTFE matrix and locked in the microstructure.
-
TABLE 2 Comparison of Example No. 2 with specifications for QMO 11 and QMO 8. Membrane Characteristics Example No. 2 QMO11 QMO8 Lube Rate 20.75 17.5 20.75 (wt % of lubricating agent compared to PTFE resin) Average Unit weight (oz/yd2) 0.5 0.4-0.7 0.4-0.6 Air perm (cfm) 0.922 0.2-0.4 1.0-2.5 Mullen (psi) 67 60-120 >25 Thickness (in.) 0.002 — 0.003 Peel Strength MD 0.35 0.2-0.45 >0.2 (lbf/in.) Peel Strength XD 0.243 0.2-0.4 >0.2 (lbf/in.) Tensile Elongation 238 — >100% MD Tensile Elongation XD 73 — >40% IPA Bubble point 14 — 12-18 (psi) MVTR (g/m2/24 hrs) 52395 50,000-85,000 >70,000 - Tensile strength and elongation were measured using ASTM D5035, and Mullen was measured using ASTM D751-00 Method A, procedure 1.
- All disclosed and claimed numbers and numerical ranges are approximate and include at least some variation and deviation.
- While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (14)
1. A method for making a polytetrafluoroethylene membrane comprising porous inorganic materials, the method comprising the steps of:
(a) mixing a polytetrafluoroethylene resin having a weight, a lubricating agent having a weight, and a porous inorganic material having a weight,
wherein the weight of the lubricating agent comprises between 15 and 25 percent of the weight of the polytetrafluoroethylene resin,
wherein the weight of the porous inorganic material comprises up to 10 percent of the weight of the polytetrafluoroethylene resin, and
wherein the porous inorganic material has at least one dimension less than 100 nm;
(b) forming a preform comprising a mixture of the polytetrafluoroethylene resin, the lubricating agent, and the porous inorganic material;
(c) extruding the preform to form a tape having a thickness between 1 and 100 mil;
(d) calendaring the tape to facilitate evaporation of the lubricating agent;
(e) tentering the tape through biaxially stretching in a first direction and a second direction perpendicular to the first direction to form a membrane; and
(f) sintering the membrane at a temperature between 400° F. and 750° F. for a period of time between 1 and 120 seconds, wherein the membrane after sintering has a thickness between 0.05 and 20 mil.
2. The method of claim 1 , wherein step (a) comprises the steps of:
mixing the polytetrafluoroethylene resin with the lubricating agent in a V blender for a period of time between 1 and 60 minutes to form a resin/lubricant mixture;
wicking the resin/lubricant mixture for a period of time between 1 and 120 hours; and
mixing the resin/lubricant mixture with the porous inorganic material in a V blender for a period of time between 1 and 60 minutes.
3. The method of claim 1 , wherein the lubricating agent comprises an isoparaffinic solvent.
4. The method of claim 2 , wherein the porous inorganic material comprises an activated nanocarbon, a carbon nanotube, a carbon fiber, a zeolite, a catalyst, silicon dioxide, or a mixture thereof.
5. The method of claim 2 , wherein the porous inorganic material has at least one dimension less than 50 nm.
6. The method of claim 2 , wherein the porous inorganic material has at least one dimension less than 30 nm.
7. The method of claim 2 , wherein the porous inorganic material has a specific surface area greater than 10 m2/g.
8. The method of claim 2 , wherein the porous inorganic material has a specific surface area greater than 50 m2/g.
9. The method of claim 2 , wherein the porous inorganic material has a specific surface area greater than 90 m2/g.
10. A method of incorporating a porous inorganic material into a mixture comprising a polytetrafluoroethylene resin and a lubricating agent, the method comprising the steps of:
(a) mixing the polytetrafluoroethylene resin with the lubricating agent in a V blender for a period of time between 1 and 60 minutes to form a resin/lubricant mixture;
(b) wicking the resin/lubricant mixture for a period of time between 1 and 120 hours; and
(c) mixing the resin/lubricant mixture with the porous inorganic material in a V blender for a period of time between 1 and 60 minutes;
wherein a weight of the lubricating agent comprises between 15 and 25 percent of a weight of the polytetrafluoroethylene resin,
wherein a weight of the porous inorganic material comprises up to 10 percent of the weight of the polytetrafluoroethylene resin, and
wherein the porous inorganic material has at least one dimension less than 100 nm.
11. The method of claim 10 , wherein step (b) occurs at a temperature between 40° F. and 200° F.
12. The method of claim 10 , wherein the lubricating agent comprises an isoparaffinic solvent.
13. The method of claim 10 , wherein the porous inorganic material comprises an activated nanocarbon having a specific surface area greater than 90 m2/g and having at least one dimension less than 50 nm.
14.-18. (canceled)
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- 2009-02-16 GB GB0902513.1A patent/GB2458202B/en not_active Expired - Fee Related
- 2009-02-23 DE DE102009003522A patent/DE102009003522A1/en not_active Withdrawn
- 2009-02-26 CN CN200910129199A patent/CN101518951A/en active Pending
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US20090117367A1 (en) * | 2007-09-28 | 2009-05-07 | General Electric Company | Article and associated method |
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JP2015107482A (en) * | 2013-10-23 | 2015-06-11 | ダイキン工業株式会社 | Embossed filter material for air filter, filter pack, air filter unit and manufacturing method for embossed filter material for air filter |
CN107469648A (en) * | 2016-06-07 | 2017-12-15 | 中国科学院大连化学物理研究所 | A kind of preparation method of polytetrafluoroethylhollow hollow fiber composite membrane |
CN108752816A (en) * | 2018-05-04 | 2018-11-06 | 邵春雷 | A kind of polytetrafluoroethylene (PTFE) compound insulating materials and a kind of conducting wire and a kind of wire harness |
CN108677597A (en) * | 2018-05-15 | 2018-10-19 | 昆明纳太科技有限公司 | A kind of micropore PTFE composite carbon nanometer tube paper and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
DE102009003522A1 (en) | 2009-09-17 |
GB2495799B (en) | 2013-07-10 |
GB2458202A (en) | 2009-09-16 |
GB0902513D0 (en) | 2009-04-01 |
US20090212469A1 (en) | 2009-08-27 |
GB2495799A (en) | 2013-04-24 |
US7812081B2 (en) | 2010-10-12 |
GB2458202B (en) | 2013-02-20 |
CN101518951A (en) | 2009-09-02 |
GB201214893D0 (en) | 2012-10-03 |
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