WO1994004334A1 - Dense polytetrafluoroethylene articles and a process for producing them - Google Patents
Dense polytetrafluoroethylene articles and a process for producing them Download PDFInfo
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- WO1994004334A1 WO1994004334A1 PCT/US1992/010674 US9210674W WO9404334A1 WO 1994004334 A1 WO1994004334 A1 WO 1994004334A1 US 9210674 W US9210674 W US 9210674W WO 9404334 A1 WO9404334 A1 WO 9404334A1
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- Prior art keywords
- eptfe
- ptfe
- elastomers
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- layer
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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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
- B29C43/18—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. compression moulding around inserts or for coating articles
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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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
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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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/006—Pressing and sintering powders, granules or fibres
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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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
- B29C43/20—Making multilayered or multicoloured articles
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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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
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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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
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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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
- B29C70/342—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation using isostatic pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D99/00—Subject matter not provided for in other groups of this subclass
- B29D99/0053—Producing sealings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
- B32B37/1018—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure using only vacuum
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J3/00—Diaphragms; Bellows; Bellows pistons
- F16J3/02—Diaphragms
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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
- B29C2791/00—Shaping characteristics in general
- B29C2791/004—Shaping under special conditions
- B29C2791/006—Using vacuum
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- 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
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- 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
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
- B29K2105/0809—Fabrics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/26—Sealing devices, e.g. packaging for pistons or pipe joints
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/755—Membranes, diaphragms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
- Y10T428/1314—Contains fabric, fiber particle, or filament made of glass, ceramic, or sintered, fused, fired, or calcined metal oxide, or metal carbide or other inorganic compound [e.g., fiber glass, mineral fiber, sand, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
- Y10T428/1317—Multilayer [continuous layer]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1355—Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
- Y10T428/1359—Three or more layers [continuous layer]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1376—Foam or porous material containing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/23—Sheet including cover or casing
- Y10T428/233—Foamed or expanded material encased
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/24992—Density or compression of components
Definitions
- This invention relates to new forms of expanded polytetrafluoroethylene which retain the characteristic node and fibril structure of expanded polytetrafluoroethylene; and to a process for making them which involves the bonding and simultaneous densification of individual thin sheets of expanded PTFE using heat, pressure and vacuum.
- Fluoropolymers are characterized by the fact that they are highly inert, paraffinic polymers in which some or all of the ' hydrogen have been replaced by fluorine. Fluoropolymers in general, and polytetrafluoroethylene (PTFE) in particular, have exhibited utility as materials for use in harsh chemical environments which may degrade many conventional polymeric materials. PTFE also has a useful range of temperature from as high as 260°C to as low as near -273°C.
- PTFE exhibits poor mechanical properties, such as low tensile strength and low cold flow properties.
- films of low porosity PTFE made by a skiving process in which solid PTFE films are shaved or split from a thicker article exhibit poor strength and flexibility and thus cannot be combined in a single structure with highly flexible materials such as neoprene rubber.
- These poor mechanical properties limit the use of PTFE in many situations.
- PTFE may be produced in an expanded porous form as taught in U.S. Patent No.3,953,566.
- This material expanded porous polytetrafluoroethylene (ePTFE)
- ePTFE expanded porous polytetrafluoroethylene
- ePTFE cannot be used as a barrier layer to chemicals since it can rapidly absorb through its pores liquids that have a low surface tension, e.g., less than 50 dynes/cm.
- a process that makes films, sheets or forms of various thickness out of densified ePTFE having substantially no porosity maintaining the high strength of the node and fibril structure of ePTFE would therefore have wide utility as a barrier to harsh chemicals.
- Dense ePTFE structures are taught in U.S. Patent No.
- 5,061,561 to Katavama discloses a method to make fibers with high density from ePTFE similar to that used in this invention, however, the method yields a material that is significantly different from that in this invention as evidenced by DSC peaks at 345°C and 380°C.
- Katavama process is different and is applicable only to fine filaments and not to sheets or formed shapes.
- the process is a process for making formed articles of densified ePTFE which comprises placing two or more layers of expanded porous PTFE inside a heat and pressure stable flexible container, evacuating gas from the inside of the container until the pressure in the container is 13 inches of mercury or lower, and preferably 20 inches or less, then subjecting the flexible container to a pressure of between 150-350 psi and a temperature of at least 368°C, preferably between 368°C and 400°C, then cooling the container while reducing the pressure on the container, and retrieving the densified ePTFE.
- the densified PTFE layers can contain one or more reinforcing layers of a fabric material.
- the process is a process for making densified ePTFE films, sheets or formed articles with sufficient thickness and low enough porosity to allow their use as barrier layers either alone or when combined in later constructions with other materials which comprises:
- the process is a process for making reinforced densified ePTFE articles with similar barrier properties as the preceding but having even higher strength in the x and y directions which comprises
- the plates can be a shaped form of suitable metal around which tape is wrapped, and then sealed into the bag and subjected to the conditions above.
- an autoclave chamber can be replaced with a platen press which has been equipped with a vacuum enclosure allowing evacuation of air and gasses from the layers being placed under heat, pressure or both.
- One product of the invention is a material consisting essentially of a sintered, densified, previously-expanded polytetrafluoroethylene, exhibiting remnants of a fibril and node structure as characterized by peaks at about 327°C and about 380°C in a thermogram of differential scanning calorimetry in the course of a temperature rise of 10°C/min, and by having a density of 2.1, preferably 2.14, gm/cc or greater.
- the densified PTFE can contain one or more reinforcing layers of a fabric material, such as fabric of woven expanded porous PTFE fibers.
- Another product of the invention is a pump diaphragm made of a layer of the densified ePTFE laminated to a flexible elastomeric " polymer.
- Figure 1 is a thermogram of Differential Scanning Calorimetry of the inventive material, showing a course of temperature elevation at a rate of 10°C/min.
- Figure 2 depicts a pump diaphragm which is made using a densified product of this invention.
- Figure 3 is a cross-section taken along line 3-3 of Figure 2.
- Figure 4 is a cross-section of a layered construction of the invention in which 40A and 40B are layers of densified PTFE separated by a reinforcing layer 41 of a woven fabric made of expanded porous PTFE fibers. DESCRIPTION OF THE INVENTION
- the process of the invention consists of the bonding and simultaneous densification of a plurality of sheets or tapes comprised of expanded polytetrafluoroethylene (ePTFE) (with or without the reinforcing fabric) such as that described in U.S.
- ePTFE expanded polytetrafluoroethylene
- Patent No. 3,953,566 to Gore incorporated here by reference.
- the process of bonding and densifying under vacuum is novel in that for the first time it allows the elimination of substantially all the pores in the ePTFE while preventing the loss of thickness and/or any substantial change of shape due to flow of the material as occurs in a platen press.
- the node and fibril structure of the original ePTFE as evidenced by DSC peaks at 327°C and at 380°C is retained.
- the ePTFE used is selected to maximize strength in the direction desired for the final article.
- all plies may be expanded in one direction or the plies may be biaxially expanded or be laid up in two or more directions to make a final part with uniform strength in the x-y plane.
- the invention is not limited to the number of plies bonded and densified. Densification may be accomplished at times varying from 15 minutes to over four hours and at temperatures from 330°C to 390°C with pressures as low as 150 psi and as high as 350 psi.
- One skilled in the art will recognize that there exists a relationship between the thickness of the object being formed and the times, temperatures, and pressures most effective.
- the densified ePTFE structure are useful in making composite diaphragms for use in pumps where good flex life is important.
- the ePTFE structure is securely attached to a flexible backing, preferably an elastomer. -o-
- Composite diaphragm 10 in a molded form is depicted.
- Composite diaphragm 10 has a central through hole 11 for attachment of the diaphragm to a means for reciprocating the inventive diaphragm.
- the composite diaphragm is comprised of convex area 12 and concave area 13.
- the shape and placement of the convex and concave areas of the diaphragm are dependent on design requirements of the article in which the diaphragm is placed.
- a molding process can be performed.
- the layers which comprise the inventive diaphragm are arranged in a mold having a desired shape.
- the mold containing the layers is subsequently subjected to a sufficient amount of heat and pressure through press molding, autoclave molding, roto-molding, vacuum forming or thermo-forming processes such that the layers conform to the mold and retain the desired shape upon removal from the mold.
- FIG. 3 a cross-sectional view of the diaphragm in Figure 2 taken along line 3-3 is depicted.
- the composite nature of the diaphragm is more readily apparent.
- Numeral 23 represents the densified ePTFE layer while 22 represenets a flexible elastomeric layer.
- the ribs distribute the forces associated with the reciprocation of the diaphragm resulting in the formation of many shallow radial creases in the ePTFE layer rather than the formation of a few (normally four to eight) deep creases. Since deep radial creases greatly weaken the ePTFE layer, this substantially extends the wear life of the diaphragm. Placement of the ribs in the elastomeric layer, rather than in the ePTFE layer, allows greater freedom of design.
- the flexible polymer is a thermosetting elastomer selected from the class consisting of fluoroelastomers including those containing hydrogen and those not containing hydrogen, perfluoroelasto ers, and fluoroelastomers containing silicone moieties, nitrile elastomers, acrylic elastomers, olefin diene elastomers, chlorosulfonated polyethylene elastomers, polychloroprene elastomers, butyl and halogenated butyl elastomers, styrene- butadiene elastomers, polydiene elastomers and silicone elastomers. It is preferred that the thermosetting elastomers in the above- mentioned class have a flexural elastic modulus (ASTM D790-84a) of less than 1,400 MPa.
- ASTM D790-84a flexural elastic modulus
- the flexible polymer is a thermoplastic elastomer selected from the class consisting of copolyetherester elastomers, polyurethane elastomers, styrene polyolefin block copolymer elastomers, polya ide elastomers, ethylene copolymer elastomers, and thermoplastic elastomers produced by the process of dynamic vulcanization as described in U.S. Patent No.4,130,535 to Coran et al. wherein a blend of a curable elastomer and a plastic results in a thermoplastic elastomeric composition.
- thermoplastic elastomers in the above-mentioned class have a flexural elastic modulus (ASTM D790-84a) of less than 1,400 MPa.
- the flexible polymer is a thermoplastic having a flexural elastic modulus (ASTM D790-84a) less than 1,400 MPa, and selected from the class consisting of fluorinated thermoplastics consisting of copolymers of tetrafluoroethylene, copolymers of vinylidine fluoride, copolymers of chlorotrifluoroethylene, polyolefins, and plasticized polyvinyl chlorides.
- Thermal analysis of a sample is determined through the use of a Differential Scanning Calorimeter. Approximately 10 mg of a sample is placed into the Differential Scanning Calorimeter and the temperature of the sample is increased from 200°C to 400°C at a scan rate of 10°C /min. Density Measurement
- Densities were calculated by weighing samples of known area and measured thickness.
- One half inch wide strip of sample is clamped from the top while a three pound weight is attached to the bottom of the sample.
- the strip is flexed through a radius of 270° at a rate of 278 cycles per minute. Samples were tested until destroyed by cracking.
- Comparative Example B A sample as in Comparative Example B was prepared and placed between die halves in a Carver Model M press and at 330°C at a pressure of 6400 psi for 16 minutes. The resulting piece was milky white except on the edges where it was almost translucent. The sample exhibited 10 % growth in diameter (>20% in area). The density was measured and found to be 2.08 g/cc or 4.35% porosity.
- Example 1 A portion of the sheet of material produced in Example 1 was further processed in the following manner:
- the sheet of material was etched by immersing the sample for thirty seconds in an alkali napthanate solution (Tetra Etch ® etchant available from W. L. Gore & Associates, Inc., Elkton, Maryland). A ten inch diameter circular piece was cut from the etched sheet. A 30% toluene solution of a bonding agent containing an isocyanate (Chemlok 250 available from The Lord Corporation, ' Erie, Pennsylvania), was brushed on one surface of the etched sheet and allowed to dry.
- an alkali napthanate solution Tetra Etch ® etchant available from W. L. Gore & Associates, Inc., Elkton, Maryland.
- a ten inch diameter circular piece was cut from the etched sheet.
- a 30% toluene solution of a bonding agent containing an isocyanate (Chemlok 250 available from The Lord Corporation, ' Erie, Pennsylvania), was brushed on one surface of the etched sheet and allowed to dry.
- Neoprene compound based on Neoprene GK available from E. I. du Pont de Nemours & Co.
- the layer of elastomeric material was adhered to the surface of the etched sheet by placing both layers into a platen press heated to a temperature of 93°C for about thirty seconds while a light pressure is applied thereby forming a diaphragm preform.
- the diaphragm preform was placed in a mold having the desired shape.
- the mold was subsequently placed in a platen press which applied 7580 MPa of pressure at a temperature of 170°C for a period of 20 minutes.
- the mold was allowed to cool to 70°C while still under pressure.
- the resulting diaphragm was removed from the mold and any extra material was trimmed from the diaphragm.
- the diaphragm was placed in a reciprocating pump (Wilden M4 available from Wilden Manufacturing) and driven by 400 N of air pressure against a 127 cm head of water at a rate of 66 cycles per minute. The diaphragm was cycled in the reciprocating pump until the diaphragm developed a hole in one of its layers or such a hole appeared imminent.
- the diaphragm of the instant invention achieved 14,800,000 cycles without a failure.
- a sheet of a woven fabric made from filaments prepared by the method described in U.S. Patent No. 3,962,153 to Gore was sandwiched between eight layers of GORE-TEX membrane having a combined thickness of approximately 0.026 cm and seven layers of GORE-TEX membrane having a combined thickness of approximately .023 cm. This assembly was then placed between caul plates and treated as in Example 1. The resulting sheet was translucent and had a density of 2.23 g/cc.
- a sample was prepared as in sample 3 above but the fabric was coated with an aqueous dispersion of PTFE fine powder, dried and sintered for about five minutes at a temperature between 368 and 380C. The resultant fabric had gained 60% by weight in PTFE by this process. When autoclaved, this sample had a final density of 2.19 g/cc and exhibited higher peel force than example number three indicating that PTFE can act as an adhesive bonding agent in this process.
- Example 1, 3 and 4 material were measured for stress at break and for Mullins Burst strength. As the Table below shows the autoclave process is capable of preparing even further reinforced materials using ePTFE fiber. -12-
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69221509T DE69221509T2 (en) | 1992-08-19 | 1992-12-14 | DENSITY POLYTETRAFLUORETHYLENE ARTICLES AND A PROCESS FOR PRODUCING THEM |
EP93901386A EP0670767B1 (en) | 1992-08-19 | 1992-12-14 | Dense polytetrafluoroethylene articles and a process for producing them |
JP50621494A JP3247382B2 (en) | 1992-08-19 | 1992-12-14 | Dense polytetrafluoroethylene products and methods for their production |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US932,441 | 1992-08-19 | ||
US07/932,441 US5374473A (en) | 1992-08-19 | 1992-08-19 | Dense polytetrafluoroethylene articles |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994004334A1 true WO1994004334A1 (en) | 1994-03-03 |
Family
ID=25462328
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1992/010674 WO1994004334A1 (en) | 1992-08-19 | 1992-12-14 | Dense polytetrafluoroethylene articles and a process for producing them |
Country Status (7)
Country | Link |
---|---|
US (1) | US5374473A (en) |
EP (1) | EP0670767B1 (en) |
JP (1) | JP3247382B2 (en) |
CA (1) | CA2118116C (en) |
DE (1) | DE69221509T2 (en) |
IT (1) | ITTO930621A1 (en) |
WO (1) | WO1994004334A1 (en) |
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Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
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US5466531A (en) * | 1993-08-10 | 1995-11-14 | Textiles Coated International | Polytetrafluoroethylene laminate and method of producing same |
WO1996004133A1 (en) * | 1994-08-03 | 1996-02-15 | Textiles Coated Incorporated | Polytetrafluoroethylene laminate and method of producing same |
AU688788B2 (en) * | 1994-08-03 | 1998-03-19 | Textiles Coated Incorporated | Polytetrafluoroethylene laminate and method of producing same |
EP0955211A3 (en) * | 1998-05-04 | 2002-04-17 | Gore Enterprise Holdings, Inc. | Impact energy absorbing composite materials |
WO2004103699A2 (en) * | 2003-05-16 | 2004-12-02 | Garlock Sealing Technologies, Inc. | Composite plastic material |
WO2004103699A3 (en) * | 2003-05-16 | 2005-02-10 | Garlock Sealing Technologies I | Composite plastic material |
US9650479B2 (en) | 2007-10-04 | 2017-05-16 | W. L. Gore & Associates, Inc. | Dense articles formed from tetrafluoroethylene core shell copolymers and methods of making the same |
US9988506B2 (en) | 2007-10-04 | 2018-06-05 | W. L. Gore & Associates, Inc. | Dense articles formed tetrafluoroethylene core shell copolymers and methods of making the same |
WO2016099914A1 (en) * | 2014-12-19 | 2016-06-23 | W.L. Gore & Associates, Inc. | Dense articles formed from tetrafluroethylene core shell copolymers and methods of making the same |
WO2016099913A1 (en) * | 2014-12-19 | 2016-06-23 | W.L. Gore & Associates, Inc. | Dense articles formed from tetrafluoroethylene core shell copolymers and methods of making the same |
KR20170096176A (en) * | 2014-12-19 | 2017-08-23 | 더블유.엘. 고어 앤드 어소시에이트스, 인코포레이티드 | Dense articles formed from tetrafluoroethylene core shell copolymers and methods of making the same |
KR20170096177A (en) * | 2014-12-19 | 2017-08-23 | 더블유.엘. 고어 앤드 어소시에이트스, 인코포레이티드 | Dense articles formed from tetrafluoroethylene core shell copolymers and methods of making the same |
CN107106730A (en) * | 2014-12-19 | 2017-08-29 | W.L.戈尔及同仁股份有限公司 | Dense product formed by tetrafluoroethene core shell copolymer and preparation method thereof |
CN107108807A (en) * | 2014-12-19 | 2017-08-29 | W.L.戈尔及同仁股份有限公司 | Dense product formed by tetrafluoroethene core shell copolymer and preparation method thereof |
KR102014625B1 (en) | 2014-12-19 | 2019-08-26 | 더블유.엘. 고어 앤드 어소시에이트스, 인코포레이티드 | Dense articles formed from tetrafluoroethylene core shell copolymers and methods of making the same |
KR102014626B1 (en) | 2014-12-19 | 2019-08-26 | 더블유.엘. 고어 앤드 어소시에이트스, 인코포레이티드 | Dense articles formed from tetrafluoroethylene core shell copolymers and methods of making the same |
CN107108807B (en) * | 2014-12-19 | 2020-03-13 | W.L.戈尔及同仁股份有限公司 | Compact articles formed from tetrafluoroethylene core-shell copolymers and methods of making the same |
CN107106730B (en) * | 2014-12-19 | 2020-12-25 | W.L.戈尔及同仁股份有限公司 | Compact articles formed from tetrafluoroethylene core-shell copolymers and methods of making the same |
Also Published As
Publication number | Publication date |
---|---|
ITTO930621A1 (en) | 1994-02-21 |
US5374473A (en) | 1994-12-20 |
CA2118116A1 (en) | 1994-03-03 |
DE69221509D1 (en) | 1997-09-11 |
EP0670767B1 (en) | 1997-08-06 |
JPH08505094A (en) | 1996-06-04 |
CA2118116C (en) | 1999-03-30 |
JP3247382B2 (en) | 2002-01-15 |
DE69221509T2 (en) | 1998-03-12 |
EP0670767A1 (en) | 1995-09-13 |
ITTO930621A0 (en) | 1993-08-18 |
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