Title of Invention	A POROUS COMPOSITE ELEMENT AND A VENTING APPARATUS EMPLOYING THE POROUS COMPOSITE ELEMENT
Abstract	Porous composites comprise a porous membrane having a structure defining a plurality of pores extending therethrough, nonporous discontinuous surface layer affixed to said porous membrane, in which the nonporous discontinuous surface layer forms regions of gas permeability, and regions of gas impermeability, and a coating disposed upon the porous composite which renders at least a portion of the porous composite oleophobic.

Title of Invention

A POROUS COMPOSITE ELEMENT AND A VENTING APPARATUS EMPLOYING THE POROUS COMPOSITE ELEMENT

Abstract

Porous composites comprise a porous membrane having a structure defining a plurality of pores extending therethrough, nonporous discontinuous surface layer affixed to said porous membrane, in which the nonporous discontinuous surface layer forms regions of gas permeability, and regions of gas impermeability, and a coating disposed upon the porous composite which renders at least a portion of the porous composite oleophobic.

Full Text	TITLE POROUS COMPOSITE ARTICLE BACKGROUND Many enclosures require venting to an atmosphere external to an enclosure to relieve any pressure differential between the internal volume of the enclosure and the external atmosphere. Such venting may be required due to temperature fluctuations, altitude changes, and vapor pressure of liquid contained therein. Vents allow the flow of gas for pressure equalization while preventing the entry of liquid and particulate contamination. Market sectors which use porous materials as vents include, but are not limited to automotive, electronics, industrial, medical, and packaging. Expanded PTFE (ePTFE) is a known porous vent material in these applications. However, when these vent materials are exposed to viscous fluids of low surface tension, a loss in gas permeability may be observed. Residual liquid film or droplets remaining on the vent material may restrict the vent area available for gas flow. The fluid can dry and harden on the surface of the vent material, leaving an impermeable film layer on the entire surface, thereby rendering the vent inoperable by eliminating gas permeability. As used in this application, the term "gas permeability" means the property of a material having two sides allowing a gas to move from a first side to the second side when the material is subject to a differential pressure of such, gas across it. Air permeability, for example, can be characterized by Gurley number. There exists a need for a porous material that has adequate air flow after fluid exposure, especially in cases where the vent is exposed to a viscous fluid of low surface tension. SUMMARY In one aspect, a venting apparatus having an opening therein for venting an enclosure and for preventing passage of a liquid is provided. The venting apparatus comprises a porous composite venting element forming a gas-permeable barrier to said liquid, the porous composite venting element comprising a porous membrane having a structure defining a plurality of pores, extending therethrough, and a nonporous discontinuous surface coating. The nonporous discontinuous surface coating blocks at least some of the pores, whereby the porous composite surface has regions of gas permeability and regions of gas impermeability. In another aspect, a porous composite comprising a porous membrane having a structure defining a plurality of pores extending therethrough is provided. A nonporous discontinuous surface layer is affixed to the porous membrane, the nonporous discontinuous surface layer has rents, which form surface regions of gas permeability and surface regions of gas impermeablility. The porous composite has a coating which renders at least a portion of the surface oleophobic. In yet another aspect, a venting apparatus is provided. The venting apparatus has an opening therein for venting an enclosure and for preventing passage of a liquid, and comprising a porous composite venting element forming a gas-permeable barrier to the liquid. The porous composite venting element comprises a porous membrane having a structure defining a plurality of pores extending therethrough, and a nonporous discontinuous surface layer affixed to said porous membrane. The nonporous discontinuous surface layer has rents, whereby the nonporous discontinuous surface layer comprises regions of gas permeability corresponding to the rents. In a still further aspect, a venting apparatus is provided in which the venting apparatus has an opening therein for venting an enclosure. The enclosure defines an internal space and an external space, and the venting apparatus prevents passage of a liquid between the internal space and the external space. The venting apparatus comprises a porous composite venting element forming a liquid-tight, gas-permeable seal of the opening. The porous composite venting element has a liquid face adjacent to the liquid. The porous composite venting element comprises a porous membrane having a structure defining a plurality of pores extending therethrough and a nonporous discontinuous surface covering at least a portion of the liquid face of the porous membrane. The nonporous discontinuous surface blocks at least some of the pores and has openings therein to create surface regions of gas permeability and surface regions of gas impermeability. In another aspect, a venting apparatus has an opening therein for venting an enclosure and prevents passage of a liquid. The venting apparatus comprises a porous composite venting element that forms a gas- permeable barrier to a liquid. The porous composite venting element comprises a porous membrane having a first face and a second face opposite the first face, and a nonporous surface layer affixed to the first face of the porous membrane to form a liquid exposure face. The airflow recovery after liquid exposure to the liquid exposure face of the porous composite venting element exceeds the airflow recovery after liquid exposure to the second face of said porous composite venting element. DESCRIPTION OF THE FIGURES Figure 1 represents a cross sectional view of the venting apparatus. Figure 2 represents a cross sectional view of the porous composite affixed to an opening in a liquid-tight enclosure. Figure 3 represents a cross sectional view of the porous composite having an oleophobic coating affixed to a support layer. Figure 4 is a surface Scanning Electron Micrograph (SEM) of a porous composite made in accordance with Example 1. Figure 5 is a surface Scanning Electron Micrograph (SEM) of a porous composite made in accordance with Example 2. Figure 6 is a Scanning Electron Micrograph (SEM) of a cross section of a porous composite made in accordance with Example 1. Figure 7 is a surface Scanning Electron Micrograph (SEM) of a porous composite made in accordance with Example 5. Figure 8 is a surface Scanning Electron Micrograph (SEM) of a nonporous discontinuous surface layer. Figure 9 represents a cross sectional view of a porous composite having a nonporous discontinuous surface layer on both sides of the porous membrane. Figure 10 represents a cross sectional view of the porous composite affixed over an opening in a liquid-tight enclosure. Figure 11 illustrates a testing apparatus for air flow recovery. DETAILED DESCRIPTION The porous composite articles described herein are useful as venting materials. They provide air flow even after exposure to viscous fluids of low surface tension. As used in this application, the term "viscous fluids of low surface tension' means fluids with a viscosity greater than 50 cP (Centipoise) and surface tension less than 35 mN/m. In applications that involve such fluids, these porous composite articles overcome disadvantages of known venting materials. In certain venting applications, gas permeability of the porous composite after exposure to viscous fluids of low surface tension is desired. Air flow after liquid exposure is referred to hereinafter as air flow recovery. Materials that have high air flow recovery after exposure to such fluids are particularly valuable. The porous composite articles described herein provide excellent air flow recovery after exposure to viscous fluids of low surface tension. The porous composite articles can be used in a venting apparatus. A venting apparatus may include a vent body having an opening therein to allow venting. The porous composite may be affixed to the body to form a liquid- tight, gas-permeable seal of the opening. The venting apparatus may be used in a liquid-tight enclosure. As used in this application, "liquid-tight" means a seal or enclosure that can withstand a water entry pressure of at least 0.5 psi without leakage. Examples include a container for enclosing liquids or an electronic enclosure as in computer disk-drives, automotive engine control units, or automotive head-lamps. As shown in Fig. 1, venting apparatus 40 may include a vent body 42 having a passageway 45 for a gas, and a venting element 43. Venting element 43 may form a gas permeable liquid-tight seal of passageway 45. The vent body 42 may take the form of an insert, cap, or a molded part. In other aspects, as represented in Fig. 2, an enclosure may have a vent body incorporated therein. In simple form, an enclosure may have an opening with a porous composite vent material sealed over it to provide venting. Preferably, the vent body is constructed from polymeric materials, which facilitate easy processing including heat sealing of the porous composite article to the body. This vent body may be constructed in various shapes and forms and installed in any orientation (vertical, horizontal, or inclined at an angle) on to the enclosure. The means for attachment of the vent body to the enclosure depends on the intended venting application. Exemplary attachment means include interference fittings, threads or adhesives. As such, the vent body may incorporate barbs, threads and the like to improve attachment. With reference to Fig. 3, the porous composite article 20 may be comprised of a porous membrane 22 having pores 23, a nonporous discontinuous surface layer 24 that is affixed to the porous membrane, and a coating 28 to provide oleophobic properties. The nonporous discontinuous surface layer 24 blocks at least some of the pores 23 of the porous membrane but has discrete, distributed openings 29 which provide regions of gas permeability. The nonporous discontinuous surface layer improves the air flow recovery of the composite after exposure to viscous fluids of low surface tension. The porous composite can be rendered oleophobic by application of a polymeric coating 28 such that the oil rating of the composite is greater than about 2. Figs. 4 through 7 are scanning electron micrographs (SEM) of representative porous composites. The porous membrane 22 has a structure comprising a plurality of pores 23. The porous membrane can be any porous material that has pores which render the membrane gas permeable. Porous membranes may include but are not limited to, Polyethylene, Polypropylene, Polysulfone, Polyethersulfone, Polyvinylidene Fluoride (PVDF), Cellulose Acetate, Polycarbonate, Ultrahigh molecular weight polyethylene (UHMWPE), and preferably expanded PTFE. The expanded PTFE membranes made in accordance with the teachings in U.S. Patent No. 3,953,566 to Gore are particularly useful. These porous membranes can be uni-axially, bi-axially or radially expanded. The nonporous discontinuous surface layer 24 is affixed to the porous membrane 22 and may provide a discontinuous surface blocking at least some of the pores 23 of the porous membrane 22 at the membrane surface, whereby the porous composite surface has regions of gas permeability and regions of gas impermeability. The nonporous discontinuous surface layer 24 can be made from a wide range of materials including but not limited to thermoplastic materials, thermoset materials, and elastomeric materials. Thermoplastic materials are preferred and may include but are not limited to Polyester, Polyethylene, Polypropylene, Vinylidene Fluoride, tetrafluoroethylene/ hexafluoropropylene copolymers (FEP), tetrafluoroethylene/ perfluoroalkyl vinyl ether copolymers (PFA), chlorotrifluoroethylene (CTFE), and THV (polymer of tetrafluoroethylene, hexaffuoropropylene, vinylidene fluoride). Fluorinated thermoplastic materials such as FEP or PFA are particularly preferred. In one embodiment illustrated by Figs. 4 and 5, the nonporous discontinuous surface layer 24 is a fluorinated thermoplastic that is laminated to a PTFE tape and then co-expanded. Upon expansion, the fluorinated thermoplastic fractures to form a plurality of discrete rents 26. In another embodiment illustrated in Fig. 8, the nonporous discontinuous surface layer 24 comprises a nonporous film 27 having perforations 25. The perforated film is affixed to the porous membrane layer to form a porous composite. In a further embodiment illustrated in Fig. 7, the nonporous discontinuous surface layer 24 comprises a coating of a thermoplastic material. The coating forms a nonporous discontinuous surface layer 24 having openings 29 upon the porous membrane 22. The coating blocks some of the pores 23 to create regions of gas impermeability on the surface of the porous composite. The porous composites can be rendered oleophobic, thereby making them applicable in certain venting applications which require resistance to viscous fluids of low surface tension. As used in this application, the term "oleophobic" means an article with an AATCC Test Method 118-2002 oil rating of greater than about 2. For example, the porous composite may be coated with a solution of perfluorodioxole polymer as described in US Patent No. 5,116,650. The coating may also be applied to at least one of the elements of the porous composite before affixing them together. For example, the porous membrane may be treated with a coating solution to provide oleophobicity before the nonporous discontinuous layer is affixed or applied to it. A nonporous surface layer may be formed by a process of lamination and co-expansion. A nonporous thermoplastic film may be laminated to PTFE and subsequently expanded to form a composite of ePTFE membrane and a nonporous discontinuous surface layer comprised of fluorinated thermoplastic. This process may result in the thermoplastic film fracturing to form rents 26 as shown in Figs. 4 and 5. The thermoplastic may be laminated to the ePTFE by passing the ePTFE and thermoplastic over a surface, such as a roller or plate that is heated to above the melt temperature of the thermoplastic to bond them. The bonded layers can then be expanded uni-axially, bi-axially or radially to form the rents in the thermoplastic surface. The nonporous discontinuous surface layer 24 of polymer in this embodiment can be as thin as 0.5 micron. In a preferred embodiment, FEP is laminated to PTFE and then the laminate is expanded to form a porous composite. With reference to Fig. 8, the nonporous discontinuous surface layer 24 may also be formed by perforating a nonporous film and then bonding it to a porous membrane. The preferred nonporous discontinuous surface layer is polymeric and may comprise a fluorinated thermoplastic film layer such as FEP or PFA. The nonporous polymeric film layer can be perforated using any conventional method, including but not limited to mechanical perforation, or laser drilling. The preferred method is laser drilling. The perforated nonporous discontinuous surface layer can then be affixed to a porous membrane through any conventional method including but not limited to, hot roll lamination, adhesive bonding, or ultrasonic bonding. In another aspect, the perforated nonporous film may be affixed to the PTFE and can be subsequently expanded. In the embodiment illustrated in Fig. 8, a 12.5 micrometer thick sheet of FEP was perforated using a 50 watt laser machine from Universal Laser Systems Inc. (Scottsdale, AZ). The perforations 25 were 0.76 mm in diameter, and the center-center distance between perforations was 1.02 mm. The perforated FEP layer may then be bonded to a porous ePTFE membrane to form the porous composite. Regardless of form or method of construction, the nonporous discontinuous surface layer forms a surface over the porous membrane layer such that some of the pores of the porous membrane are blocked. The nonporous discontinuous surface layer thus has a discontinuous surface with openings therein, whereby the porous composite has regions of gas permeability and regions of gas impermeability. The size and shape of the openings in the nonporous discontinuous surface layer can vary considerably. The porous composite articles may be used as a venting element in venting enclosures. The venting element may be advantageously used to form a liquid-tight seal in an enclosure for containing or excluding liquids. The venting element provides gas permeability necessary for gas expansion, off- gassing of chemicals, and the like. As shown in Fig. 2, venting apparatus 40 may be constructed to have a liquid exposure side 41 and an opposite side 47. A nonporous discontinuous surface layer 24 may be disposed upon the porous membrane 22 to construct a liquid exposure side 41 of the porous composite 20. The liquid exposure side 41 may be oriented towards the interior of an enclosure 32 containing a liquid 38. In these applications (e.g. liquid detergent containers) the liquid is contained, yet the porous composite provides gas permeability. The gas permeability may prevent enclosure deformation or rupture due to thermal cycling, or allow for off gassing of the liquid. In an alternate embodiment illustrated in Fig. 10, in which liquid entry is to be prevented, the liquid exposure side 41 may be oriented towards the outside of the enclosure 32. The opposite side 47 is oriented towards the inside of the enclosure. In such applications, (e.g. electronics enclosures or lighting enclosures) the porous composite may provide gas permeability while preventing liquid entry into the enclosure. In yet another construction illustrated schematically in Fig. 9, both sides of the porous composite may be constructed as liquid exposure sides. Preferably, the air flow recovery of the liquid exposure side exceeds the air flow recovery of the opposite side by a value of at least 1.1%. More preferably, the air flow recovery of the liquid exposure side exceeds the air flow recovery of the opposite side by a value of at least 5%. In embodiments in which the porous composite has two liquid exposure sides, it is preferable that the air flow recovery of the porous composite exceeds the air flow recovery of the porous membrane alone by at least about 5%. In an embodiment, the porous oleophobic composite may have an air flow recovery of at least about 33% when the liquid exposure side of the composite is exposed to viscous fluid of low surface tension. The airflow recovery of this composite when the same viscous fluid of low surface tension is exposed to the opposite side is 0%. More preferably, the porous composite has an air flow recovery of at least about 50% when the liquid exposure side of the composite is exposed to viscous fluid of low surface tension. The airflow recovery of this composite when the same viscous fluid of low surface tension is exposed to the opposite side is 0%. In another embodiment, the porous composite has an air flow recovery of 4% when the liquid exposure side of the composite is exposed to viscous fluid of low surface tension. The airflow recovery of the porous composite when the same viscous fluid of low surface tension is exposed to the opposite side is 0.4%. More preferably, the porous composite has an air flow recovery of 12% when the liquid exposure side of the composite is exposed to viscous fluid of low surface tension. The airflow recovery of the porous composite when the same viscous fluid of low surface tension is exposed to the opposite side is 0.1%. The porous composite can be constructed as a laminate. The laminate may be constructed by supporting the porous composite 20 on a support layer 30, as shown in Fig. 3. Support layer 30 provides structural support and may also aid in attachment of the porous composite 20 to venting enclosure 32 as shown in Fig. 10. Suitable support layers can be in the form of air permeable media like knits, non-wovens, scrims, melt-blowns, woven fabrics, meshes, foams, porous ePTFE membranes, etc. Support layers may be affixed to the porous composite by, for example, hot-roll lamination, adhesives, or ultrasonic bonding. The support layer may be affixed to either side of the porous composite. The present invention will be further described with respect to the non- limiting examples provided below. Test Methods Density Samples die cut to form rectangular sections 2.54 cm by 15.24 cm were measured to determine their mass (using a Mettler-Toledo analytical balance model AG204) and their thickness (using a Kafer FZ1000/30 snap gauge). Using these data, density was calculated with the following formula: in which: p = density (g/cc); m = mass (g); w = width (cm); I = length (cm); and t = thickness (cm). Porosity Porosity was expressed in percent porosity and was determined by subtracting the quotient of the density of the article (described earlier herein) and that of the bulk density of PTFE from 1, then multiplying that value by 100%. For the purposes of this calculation, the bulk density of PTFE was taken to be 2.2 g/cc Air Flow Recovery Figs 11 and 11a illustrate the apparatus used for airflow recovery testing. Vent material 100 is sealed between upper plate 102 and lower plate 104. The plates each include an orifice of diameter 2.54cm. The upper plate incorporates a liquid well 106. The vent material 100 is secured between the plates using a gasket 108 and thumb screws 110. The assembled plates are then secured in an adapter 300 by means of clamps 302, thumb screws 304 and a gasket 306. Adapter 300 includes an air chamber 301 and channel 310 for delivering air to it. A Telydyne Genuine Gurley™ tester (Model Number 4110) is attached to the inlet port 312 of the adapter 300 using the gasket 308. 100 cm3 of air is delivered to the sample at a pressure of 12.4 cm of water and the flow time recorded in seconds. This measurement is Gurley (seconds) before fluid contact. The plate is then removed from the adapter and the vent material is exposed to test fluid by filling liquid well 106 such that the entire surface of the vent material is covered by the fluid. This can be done by using a transfer pipette to add about 2 to 3 cm3 of test fluid to the well 106. After 60 seconds, the plate assembly was tilted ninety degrees. The liquid is allowed to drain off from the vent material for 60 seconds. The plate is then secured in the adapter 300 which is affixed to the Telydyne Genuine Gurley™ tester (Model Number 4110). 100 cm3 of air is allowed to flow through the sample at a pressure of 12.4 cm of water and the flow time recorded in seconds. This measurement is Gurley (seconds) after fluid contact. In cases where airflow did not start after ten minutes in this test, the test was stopped and samples were considered not to recover as denoted by NR for no recovery of airflow. The percentage air flow recovery is then determined by using the equation: Water Entry Pressure As used in this application, the term "water entry pressure" means the pressure required to drive water through a material, such as a membrane, as further described in the test methods contained herein. Water entry pressure provides a test method for water intrusion through membranes or vent bodies. The membrane (or vent body) is placed in a fixture and pressurized with water. A piece of pH paper may be placed on top of the membrane (or vent body) on the non-pressurized side as an indicator of evidence for water entry. The sample is then pressurized in small increments, until a color change in the pH paper indicates the first sign of water entry. The water pressure at breakthrough or entry is recorded as the Water Entry Pressure. Bubble Point The bubble point and mean flow pore size were measured according to the general teachings of ASTM F31 6-03 using a Capillary Flow Porometer (Model CFP 1500 AEXL from Porous Materials Inc., Ithaca, NY). The sample membrane was placed into the sample chamber and wet with SilWick Silicone Fluid (available from Porous Materials Inc.) having a surface tension of 19.1 dynes/cm. The bottom clamp of the sample chamber had a 2.54 cm diameter, 3.175 mm thick porous metal disc insert (Mott Metallurgical, Farmington, CT, 40 micron porous metal disk) and the top clamp of the sample chamber had a 3.175 mm diameter hole. Using the Capwin software version 6.62.1 the following parameters were set as specified in the table immediately below. The values presented for bubble point and mean flow pore size were the average of two measurements. Oil Rating Oil rating testing was conducted in accordance with AATCC Test Method 118-2002. The oil rating of a membrane is the lower of the two ratings obtained when testing the two sides of the membrane. Surface Tension Surface tension of the challenge fluid was measured using a Kruss K12 tensiometer using the Whilhelmy plate method. Kruss Laboratory Desktop Software Version 2.13a was used. Whilhelmy plate immersions were conducted with flamed glass cover slips and the software default dip parameters. Viscosity Viscosity was measured using a Brookfield DVII+ viscometer with a UL low volume spindle and tube accessory. Viscosities are reported in centipoise (cP) for a temperature of 22.5 degrees Celcius, at 30 RPM, and a shear rate of 36.7 second-1. Viscosities were read after five minutes at 30 RPM for samples which had previously been run at the maximum RPM allowed by torque. Challenge Fluids Two representative challenge fluids were formulated and used for air flow recovery testing after fluid exposure. Properties of these fluids are listed in the table below. Challenge Fluid I was used for oleophobic articles with an oil rating of greater than about 2. Challenge Fluid II was used for hydrophobic articles. Challenge Fluid I was prepared in the following manner: A solution of PVP (Polyvinylpyrrolidone, Sigma-Aldrich Chemical, Catalog Number 437190-500G, Molecular Weight = 1,300,000, CAS Number 9003-39-8), and De-ionized water was prepared by mixing the two components and allowing them to stir overnight. Tergitol®TMN6 (Dow Chemical, CAS Number 60828-78-6) was added and the solution was allowed to stir for about one hour and then used immediately for testing. Challenge Fluid II was prepared in the following manner: A solution of Tween® (Mallinckrodt Baker, Inc., Catalog Number X257- 07, CAS Number 9005-65-6), and De-ionized water was prepared by mixing the two components and allowing them to stir overnight. Glycerol (Ultra Pure Grade, MP Biomedicals, Catalog Number 800688) was added and the solution was allowed to stir for about one hour and then used immediately for testing. EXAMPLES EXAMPLE 1 Fine powder of PTFE polymer (Daikin Industries, Ltd., Orangeburg, NY) was blended with Isopar K (Exxon Mobil Corp., Fairfax, VA) in the proportion of 0.25 g/g of fine powder. The lubricated powder was compressed in a cylinder to form a pellet and placed into an oven set at 25°C for approximately 24 hours. Compressed and heated pellets were ram extruded to produce tapes approximately 29 cm wide by 0.635 mm thick. The tape was then calendared between compression rolls to a thickness of 0.20 mm. The tape was then dried in an oven set at 250°C. The dry PTFE tape and a 12.5 urn thick FEP film were layered together and longitudinally expanded between banks of rolls over two heated plates set to a temperature of 300°C. The speed ratio between the second bank of rolls and the first bank of rolls, and hence the expansion ratio on the first plate, was 1.15:1. The speed ratio between the third bank of rolls and the second bank of rolls, and hence the expansion ratio on the second plate, was 1.15:1. The composite FEP laminated PTFE tape was then longitudinally expanded 5:1, through a hot air oven set to a temperature of 320°C. The FEP film bonded to the PTFE tape as it melted and as the two layers expanded, rents were formed in the FEP film. The longitudinally expanded composite was then heat treated through a hot air oven set to a temperature of 360°C. The composite was then expanded transversely at a temperature of approximately 370°C to a ratio of approximately 7:1 and then constrained and heated in an oven set at 370°C for approximately 24 seconds. The porous composite thus produced had a Bubble Point of 6.9 psi. Both sides of the composite were tested for air flow recovery with challenge fluid II. Results are shown in Table I. The composite was treated to render it oleophobic according to the following procedure. A solution was prepared by adding 0.25 weight percent of Teflon AF 1600 (Dupont Fluoroproducts, Wilmington, DE) to PF-5070 Brand Performance Fluid (CAS Number 86508-42-1, 3M) and allowing the fluid to mix overnight. The composite sample was held taut in an embroidery hoop (15.2 cm diameter). A pipette was then used to apply 5 to 6 cm3 of the above solution to the (liquid exposure side) of the composite sample. The composite sample was tilted and rotated such that the solution completely saturated the sample. At this point, the sample became transparent and was visibly wet throughout. The hoop was immediately hung vertically in a hood and allowed to dry overnight. Both sides of the oleophobic composite were then tested for air flow recovery using Challenge Fluid I. The results obtained are shown in Table I. The oil rating was measured to be 5. EXAMPLE 2 Fine powder of PTFE polymer (Daikin Industries, Ltd., Orangeburg, NY) was blended with Isopar K (Exxon Mobil Corp., Fairfax, VA) in the proportion of 0.196 g/g of fine powder. The lubricated powder was compressed in a cylinder to form a pellet and placed into an oven set at 70°C for approximately 12 hours. Compressed and heated pellets were ram extruded to produce tapes approximately 15.2 cm wide by 0.73 mm thick. Two separate rolls of tape were produced and layered together between compression rolls to a thickness of 0.254 mm. The tape was then transversely stretched to 56 cm (i.e., at a ratio of 3.7:1), then dried in an oven set at 250°C. The dry tape was longitudinally expanded between banks of rolls over a heated plate set to a temperature of 340°C. A 12.5 micron thick FEP film was layered onto the PTFE tape prior to expansion over the plate. The speed ratio between the second bank of rolls and the first bank of rolls, and hence the expansion ratio, was 14:1. The FEP film bonded to the PTFE tape as it melted and as the two layers expanded, rents were formed in the FEP film. The longitudinally expanded composite was then expanded transversely at a temperature of approximately 350°C to a ratio of approximately 20:1 and then constrained and heated in an oven set at 380°C for approximately 24 seconds. The porous composite thus produced had a Bubble Point of 30 psi. Both sides of the composite were tested for air flow recovery with challenge fluid II. Results are shown in Table II. The composite was treated to render it oleophobic according to the following procedure. A solution was prepared by adding 0.25 weight percent of Teflon AF 1600 (Dupont Fluoroproducts, Wilmington, DE) to PF-5070 Brand Performance Fluid (CAS Number 86508-42-1, 3M) and allowing the fluid to mix overnight. The composite sample was held taut in an embroidery hoop (15.2 cm diameter). A pipette was then used to apply 5 to 6 cm3 of the above solution to the liquid exposure side of the composite sample. The composite sample was tilted and rotated such that the solution completely saturated the sample. At this point, the sample became transparent and was visibly wet throughout. The hoop was immediately hung vertically in a hood and allowed to dry overnight. Both sides of the oleophobic composite were then tested for air flow recovery using Challenge Fluid I. Results are shown in Table II. The oil rating was measured to be 6. EXAMPLE 3 Fine powder of PTFE polymer (Daikin Industries, Ltd., Orangeburg, NY) was blended with Isopar K (Exxon Mobil Corp., Fairfax, VA) in the proportion of 0.25 g/g of fine powder. The lubricated powder was compressed in a cylinder to form a pellet and placed into an oven set at 25°C for approximately 24 hours. Compressed and heated pellets were ram extruded to produce tapes approximately 29 cm wide by 0.635 mm thick. The tape was then calendared between compression rolls to a thickness of 0.20 mm. The tape was then dried in an oven set at 250°C. The dry PTFE tape and a 12.5 micron thick PFA film were layered together and longitudinally expanded between banks of rolls over two heated plates set to a temperature of 320°C. The speed ratio between the second bank of rolls and the first bank of rolls, and hence the expansion ratio on the first plate, was 1.15:1. The speed ratio between the third bank of rolls and the second bank of rolls, and hence the expansion ratio on the second plate, was 1.15:1. The PFA/ PTFE tape laminate was then longitudinally expanded 8:1, through a hot air oven set to a temperature of 320°C. The longitudinally expanded composite was then heat treated through a hot air oven set to a temperature of 360°C. The composite was then expanded transversely at a temperature of approximately 380°C to a ratio of approximately 2.4:1 and then constrained and heated in an oven set at 380°C for approximately 24 seconds. The porous composite thus produced had a Bubble Point of 0.5 psi. Both sides of the composite were tested for air flow recovery with challenge fluid II. Results are shown in Table III. The composite was treated to render it oleophobic according to the following procedure. A solution was prepared by adding 0.25 weight percent of Teflon AF 1600 (Dupont Fluoroproducts, Wilmington, DE) to PF-5070 Brand Performance Fluid (CAS Number 86508-42-1, 3M) and allowing the fluid to mix overnight. The composite sample was held taut in an embroidery hoop (15.2 cm diameter). A pipette was then used to apply 5 to 6 cm3 of the above solution to the surface liquid exposure side of the composite sample. The composite sample was tilted and rotated such that the solution completely saturated the sample. At this point, the sample became transparent and was visibly wet throughout. The hoop was immediately hung vertically in a hood and allowed to dry overnight. Both sides of the oleophobic composite were then tested for air flow recovery Challenge Fluid 1. The results obtained are shown in Table III. The oil rating was measured to be 6. EXAMPLE 4 A 12.5 micrometer thick sheet of FEP was perforated using a 50 watt laser machine from Universal Laser Systems Inc. (Scottsdale, AZ). Size of the perforations were 0.76 mm in diameter, the center-center distance between perforations was 1.02 mm. The perforated FEP sheet was laminated to an ePTFE membrane (thickness of 22.8 microns, density of 0.39 g/cm3, and bubble point of 8 psi) using a web of co-polyester (Spunfab, Inc. Product Number PE2900-0.6-45W) as an adhesive layer. The materials were laminated together in a heat press (Geo. Knight & Co, MA) using the following conditions: 160 degrees, 60 psi, 3 seconds. The composite was evaluated for air flow recovery using challenge fluid II. Results appear in Table IV. EXAMPLE 5 5 g FEP powder (Product Number 532-8000 from DuPont) was added to a mixture of 47.5g of 2-Propanol (IPA) and 47.5g of HFE-7500 (3M NOVEC (TM) Engineered Fluid). The dispersion was stirred for a few hours until a clear solution was formed. An ePTFE membrane having a thickness of 106 micron, porosity of 64%, and density of 0.78g/cc was coated with this solution using a continuous immersion coating process. In this process, the ePTFE membrane was passed through a first roller and then passed through a bath containing the coating solution using a second immersion roller. After this coating step, the membrane was dried for 4 hours at room temperature in a ventilated hood. A thin layer of FEP particles was left on the surface of the membrane. To melt the particles, the coated membrane was fixed on a tenter frame, and placed in a sinter oven at a temperature of 320°C for 5 minutes. The porous composite thus produced had a nonporous discontinuous surface layer as shown in Figure 7. The porous composite was rendered oleophobic by coating with a solution of 0.75 weight percent Teflon AF1600 (DuPont Fluoroproducts, Wilmington, DE) in solvent PF-5070 (CAS Number 86508-42- 1, 3M) and dried for 6 hours at room temperature in a ventilated hood. We claim: 1. A porous composite comprising: (a) porous membrane having a structure defining a plurality of pores extending therethrough, (b) nonporous discontinuous surface layer affixed to said porous membrane, said nonporous discontinuous surface layer having rents, wherein the rents form regions of gas permeability, and (c) a coating disposed upon wherein at least a portion of the porous composite is rendered oleophobic. 2. The porous composite of claim 1 wherein the said porous membrane comprises expanded PTFE. 3. The porous composite of claim 1 wherein the said microporous membrane comprises UHMWPE. 4. The porous composite of claim 1 wherein the said discontinuous surface layer is less than 5 um thick. 5. The porous composite of claim 1 wherein the said nonporous discontinuous surface layer comprises thermoplastic. 6. The porous composite of claim 1 wherein the said nonporous discontinuous surface layer comprises fluoroplastic. 7. The porous composite of claim 1 wherein the said nonporous discontinuous surface layer comprises FEP. 8. The porous composite of claim 1 wherein said porous composite has an oil rating of greater than about 2. 9. The porous composite of claim 1 wherein the said porous composite is laminated to a support layer. 10. The porous composite of claim 9 wherein the said support layer comprises a nonwoven. 11. The porous composite of claim 9 wherein the said support layer comprises an expanded PTFE membrane. 12. A venting apparatus having an opening therein for venting an enclosure and for preventing passage of a liquid, said venting apparatus comprising a porous composite venting element forming a gas-permeable barrier to said liquid, said porous composite venting element comprising: a) porous membrane having a structure defining a plurality of pores extending therethrough, and b) nonporous discontinuous surface layer affixed to said porous membrane, said nonporous discontinuous surface layer having rents, whereby the nonporous discontinuous surface layer comprises regions of gas permeability corresponding to the rents. 13. The venting apparatus of claim 12 in which the venting element has a liquid exposure side oriented towards the liquid, the liquid exposure side comprising said nonporous discontinuous surface layer. 14. The venting apparatus of claim 12 in which the porous composite venting element has a interior face and an exterior face and wherein the interior face and the exterior face comprise said nonporous discontinuous surface layer. 15. The venting apparatus of claim 12 wherein the said porous membrane comprises expanded PTFE. 16. The venting apparatus of claim 12 wherein the said porous membrane comprises UHMWPE. 17. The venting apparatus of claim 12 wherein the said nonporous discontinuous surface layer comprises thermoplastic. 18. The venting apparatus of claim 12 wherein the said nonporous discontinuous surface layer comprises fluoroplastic. 19. The venting apparatus of claim 12 wherein the said nonporous discontinuous surface layer comprises FEP. 20. The venting apparatus of claim 12 wherein the said porous composite has an oil rating greater than about 2. 21. The venting apparatus of claim 12 wherein the said porous composite is laminated to a support layer. 22. A venting apparatus having an opening therein for venting an enclosure and for preventing passage of a liquid, said venting apparatus comprising: porous composite venting element forming a gas-permeable barrier to said liquid, said porous composite venting element comprising: a) porous membrane having a structure defining a plurality of pores, extending therethrough, b) nonporous discontinuous surface coating said porous membrane, said nonporous discontinuous surface coating blocking at least some of the pores, whereby the porous composite surface has regions of gas permeability and gas impermeability. 23. The porous composite of claim 22 wherein the said nonporous discontinuous surface layer comprises thermoplastic. 24. The porous composite of claim 22 wherein the said nonporous discontinuous surface layer comprises fluoroplastic. 25. The porous composite of claim 22 wherein the said nonporous discontinuous surface layer comprises FEP. 26. A venting apparatus having an opening therein for venting an enclosure, said enclosure defining an internal space and an external space, said venting apparatus preventing passage of a liquid between the internal space and the external space, the venting apparatus comprising: a porous composite venting element forming a liquid-tight, gas-permeable seal of said opening, said porous composite venting element having a liquid face adjacent to the liquid, the porous composite venting element comprising: a) porous membrane having a structure defining a plurality of pores extending therethrough, b) nonporous discontinuous surface covering at least a portion of the liquid face of said porous membrane, said nonporous discontinuous surface blocking at least some of the pores and having openings therein, and whereby the surface of said porous composite has regions of gas permeability and regions of gas impermeability. 27. The venting apparatus of claim 26 wherein the said microporous composite venting element further comprises an oleophobic coating. 28. The venting apparatus of claim 26 wherein said microporous membrane layer is expanded PTFE. 29. The venting apparatus of claim 26 wherein said microporous membrane layer is UHMWPE. 30. The venting apparatus of claim 26 wherein said nonporous discontinuous surface layer comprises thermoplastic. 31. The venting apparatus of claim 26 wherein said nonporous discontinuous surface layer comprises fluoropolymer. 32. The venting apparatus of claim 26 wherein said nonporous discontinuous surface layer comprises FEP. 33. The venting apparatus of claim 26 wherein the said porous composite surface has regions of gas permeability and regions of gas impermeability and wherein the area ratio of gas permeability to gas impermeability is no greater than 0.2: 1. 34.The porous composite of claim 26 wherein the said nonporous discontinuous surface layer is less than 5 um thick. 35. A venting apparatus having an opening therein for venting an enclosure and for preventing passage of a liquid, said venting apparatus comprising: a porous composite venting element forming a gas-permeable barrier to said liquid, said porous composite venting element comprising a porous membrane having a first face and a second face opposite the first face, and a nonporous surface layer affixed to the first face of the porous membrane forming a liquid exposure face of the composite venting element whereby the airflow recovery after liquid exposure to the liquid exposure face of said porous composite venting element exceeds the airflow recovery after liquid exposure to the second face of said porous composite venting element. 36. A venting apparatus of claim 35 wherein the airflow recovery after liquid exposure to the liquid exposure face of said composite exceeds the airflow recovery after liquid exposure to second face of said composite by more than 5%. Porous composites comprise a porous membrane having a structure defining a plurality of pores extending therethrough, nonporous discontinuous surface layer affixed to said porous membrane, in which the nonporous discontinuous surface layer forms regions of gas permeability, and regions of gas impermeability, and a coating disposed upon the porous composite which renders at least a portion of the porous composite oleophobic.

Full Text

TITLE
POROUS COMPOSITE ARTICLE
BACKGROUND
Many enclosures require venting to an atmosphere external to an
enclosure to relieve any pressure differential between the internal volume of
the enclosure and the external atmosphere. Such venting may be required
due to temperature fluctuations, altitude changes, and vapor pressure of liquid
contained therein. Vents allow the flow of gas for pressure equalization while
preventing the entry of liquid and particulate contamination. Market sectors
which use porous materials as vents include, but are not limited to
automotive, electronics, industrial, medical, and packaging. Expanded PTFE
(ePTFE) is a known porous vent material in these applications. However,
when these vent materials are exposed to viscous fluids of low surface
tension, a loss in gas permeability may be observed. Residual liquid film or
droplets remaining on the vent material may restrict the vent area available for
gas flow. The fluid can dry and harden on the surface of the vent material,
leaving an impermeable film layer on the entire surface, thereby rendering the
vent inoperable by eliminating gas permeability. As used in this application,
the term "gas permeability" means the property of a material having two sides
allowing a gas to move from a first side to the second side when the material
is subject to a differential pressure of such, gas across it. Air permeability, for
example, can be characterized by Gurley number.
There exists a need for a porous material that has adequate air flow
after fluid exposure, especially in cases where the vent is exposed to a
viscous fluid of low surface tension.
SUMMARY
In one aspect, a venting apparatus having an opening therein for
venting an enclosure and for preventing passage of a liquid is provided. The
venting apparatus comprises a porous composite venting element forming a
gas-permeable barrier to said liquid, the porous composite venting element
comprising a porous membrane having a structure defining a plurality of
pores, extending therethrough, and a nonporous discontinuous surface
coating. The nonporous discontinuous surface coating blocks at least some
of the pores, whereby the porous composite surface has regions of gas
permeability and regions of gas impermeability.
In another aspect, a porous composite comprising a porous membrane
having a structure defining a plurality of pores extending therethrough is
provided. A nonporous discontinuous surface layer is affixed to the porous
membrane, the nonporous discontinuous surface layer has rents, which form
surface regions of gas permeability and surface regions of gas
impermeablility. The porous composite has a coating which renders at least a
portion of the surface oleophobic.
In yet another aspect, a venting apparatus is provided. The venting
apparatus has an opening therein for venting an enclosure and for preventing
passage of a liquid, and comprising a porous composite venting element
forming a gas-permeable barrier to the liquid. The porous composite venting
element comprises a porous membrane having a structure defining a plurality
of pores extending therethrough, and a nonporous discontinuous surface
layer affixed to said porous membrane. The nonporous discontinuous surface
layer has rents, whereby the nonporous discontinuous surface layer
comprises regions of gas permeability corresponding to the rents.
In a still further aspect, a venting apparatus is provided in which the
venting apparatus has an opening therein for venting an enclosure. The
enclosure defines an internal space and an external space, and the venting
apparatus prevents passage of a liquid between the internal space and the
external space. The venting apparatus comprises a porous composite
venting element forming a liquid-tight, gas-permeable seal of the opening. The
porous composite venting element has a liquid face adjacent to the liquid.
The porous composite venting element comprises a porous membrane having
a structure defining a plurality of pores extending therethrough and a
nonporous discontinuous surface covering at least a portion of the liquid face
of the porous membrane. The nonporous discontinuous surface blocks at
least some of the pores and has openings therein to create surface regions of
gas permeability and surface regions of gas impermeability.
In another aspect, a venting apparatus has an opening therein for
venting an enclosure and prevents passage of a liquid. The venting
apparatus comprises a porous composite venting element that forms a gas-
permeable barrier to a liquid. The porous composite venting element
comprises a porous membrane having a first face and a second face opposite
the first face, and a nonporous surface layer affixed to the first face of the
porous membrane to form a liquid exposure face. The airflow recovery after
liquid exposure to the liquid exposure face of the porous composite venting
element exceeds the airflow recovery after liquid exposure to the second face
of said porous composite venting element.
DESCRIPTION OF THE FIGURES
Figure 1 represents a cross sectional view of the venting apparatus.
Figure 2 represents a cross sectional view of the porous composite
affixed to an opening in a liquid-tight enclosure.
Figure 3 represents a cross sectional view of the porous composite
having an oleophobic coating affixed to a support layer.
Figure 4 is a surface Scanning Electron Micrograph (SEM) of a porous
composite made in accordance with Example 1.
Figure 5 is a surface Scanning Electron Micrograph (SEM) of a porous
composite made in accordance with Example 2.
Figure 6 is a Scanning Electron Micrograph (SEM) of a cross section of
a porous composite made in accordance with Example 1.
Figure 7 is a surface Scanning Electron Micrograph (SEM) of a porous
composite made in accordance with Example 5.
Figure 8 is a surface Scanning Electron Micrograph (SEM) of a
nonporous discontinuous surface layer.
Figure 9 represents a cross sectional view of a porous composite
having a nonporous discontinuous surface layer on both sides of the porous
membrane.
Figure 10 represents a cross sectional view of the porous composite
affixed over an opening in a liquid-tight enclosure.
Figure 11 illustrates a testing apparatus for air flow recovery.
DETAILED DESCRIPTION
The porous composite articles described herein are useful as venting
materials. They provide air flow even after exposure to viscous fluids of low
surface tension. As used in this application, the term "viscous fluids of low
surface tension' means fluids with a viscosity greater than 50 cP (Centipoise)
and surface tension less than 35 mN/m. In applications that involve such
fluids, these porous composite articles overcome disadvantages of known
venting materials.
In certain venting applications, gas permeability of the porous
composite after exposure to viscous fluids of low surface tension is desired.
Air flow after liquid exposure is referred to hereinafter as air flow recovery.
Materials that have high air flow recovery after exposure to such fluids are
particularly valuable. The porous composite articles described herein provide
excellent air flow recovery after exposure to viscous fluids of low surface
tension.
The porous composite articles can be used in a venting apparatus. A
venting apparatus may include a vent body having an opening therein to allow
venting. The porous composite may be affixed to the body to form a liquid-
tight, gas-permeable seal of the opening. The venting apparatus may be used
in a liquid-tight enclosure. As used in this application, "liquid-tight" means a
seal or enclosure that can withstand a water entry pressure of at least 0.5 psi
without leakage. Examples include a container for enclosing liquids or an
electronic enclosure as in computer disk-drives, automotive engine control
units, or automotive head-lamps.
As shown in Fig. 1, venting apparatus 40 may include a vent body 42
having a passageway 45 for a gas, and a venting element 43. Venting
element 43 may form a gas permeable liquid-tight seal of passageway 45.
The vent body 42 may take the form of an insert, cap, or a molded part.
In other aspects, as represented in Fig. 2, an enclosure may have a vent body
incorporated therein. In simple form, an enclosure may have an opening with
a porous composite vent material sealed over it to provide venting.
Preferably, the vent body is constructed from polymeric materials,
which facilitate easy processing including heat sealing of the porous
composite article to the body. This vent body may be constructed in various
shapes and forms and installed in any orientation (vertical, horizontal, or
inclined at an angle) on to the enclosure. The means for attachment of the
vent body to the enclosure depends on the intended venting application.
Exemplary attachment means include interference fittings, threads or
adhesives. As such, the vent body may incorporate barbs, threads and the
like to improve attachment.
With reference to Fig. 3, the porous composite article 20 may be
comprised of a porous membrane 22 having pores 23, a nonporous
discontinuous surface layer 24 that is affixed to the porous membrane, and a
coating 28 to provide oleophobic properties. The nonporous discontinuous
surface layer 24 blocks at least some of the pores 23 of the porous membrane
but has discrete, distributed openings 29 which provide regions of gas
permeability. The nonporous discontinuous surface layer improves the air flow
recovery of the composite after exposure to viscous fluids of low surface
tension. The porous composite can be rendered oleophobic by application of
a polymeric coating 28 such that the oil rating of the composite is greater than
about 2.
Figs. 4 through 7 are scanning electron micrographs (SEM) of
representative porous composites. The porous membrane 22 has a structure
comprising a plurality of pores 23. The porous membrane can be any porous
material that has pores which render the membrane gas permeable. Porous
membranes may include but are not limited to, Polyethylene, Polypropylene,
Polysulfone, Polyethersulfone, Polyvinylidene Fluoride (PVDF), Cellulose
Acetate, Polycarbonate, Ultrahigh molecular weight polyethylene (UHMWPE),
and preferably expanded PTFE. The expanded PTFE membranes made in
accordance with the teachings in U.S. Patent No. 3,953,566 to Gore are
particularly useful. These porous membranes can be uni-axially, bi-axially or
radially expanded.
The nonporous discontinuous surface layer 24 is affixed to the porous
membrane 22 and may provide a discontinuous surface blocking at least
some of the pores 23 of the porous membrane 22 at the membrane surface,
whereby the porous composite surface has regions of gas permeability and
regions of gas impermeability. The nonporous discontinuous surface layer 24
can be made from a wide range of materials including but not limited to
thermoplastic materials, thermoset materials, and elastomeric materials.
Thermoplastic materials are preferred and may include but are not limited to
Polyester, Polyethylene, Polypropylene, Vinylidene Fluoride,
tetrafluoroethylene/ hexafluoropropylene copolymers (FEP),
tetrafluoroethylene/ perfluoroalkyl vinyl ether copolymers (PFA),
chlorotrifluoroethylene (CTFE), and THV (polymer of tetrafluoroethylene,
hexaffuoropropylene, vinylidene fluoride). Fluorinated thermoplastic materials
such as FEP or PFA are particularly preferred.
In one embodiment illustrated by Figs. 4 and 5, the nonporous
discontinuous surface layer 24 is a fluorinated thermoplastic that is laminated
to a PTFE tape and then co-expanded. Upon expansion, the fluorinated
thermoplastic fractures to form a plurality of discrete rents 26. In another
embodiment illustrated in Fig. 8, the nonporous discontinuous surface layer
24 comprises a nonporous film 27 having perforations 25. The perforated film
is affixed to the porous membrane layer to form a porous composite.
In a further embodiment illustrated in Fig. 7, the nonporous
discontinuous surface layer 24 comprises a coating of a thermoplastic
material. The coating forms a nonporous discontinuous surface layer 24
having openings 29 upon the porous membrane 22. The coating blocks some
of the pores 23 to create regions of gas impermeability on the surface of the
porous composite.
The porous composites can be rendered oleophobic, thereby making
them applicable in certain venting applications which require resistance to
viscous fluids of low surface tension. As used in this application, the term
"oleophobic" means an article with an AATCC Test Method 118-2002 oil
rating of greater than about 2. For example, the porous composite may be
coated with a solution of perfluorodioxole polymer as described in US Patent
No. 5,116,650. The coating may also be applied to at least one of the
elements of the porous composite before affixing them together. For
example, the porous membrane may be treated with a coating solution to
provide oleophobicity before the nonporous discontinuous layer is affixed or
applied to it.
A nonporous surface layer may be formed by a process of lamination
and co-expansion. A nonporous thermoplastic film may be laminated to PTFE
and subsequently expanded to form a composite of ePTFE membrane and a
nonporous discontinuous surface layer comprised of fluorinated thermoplastic.
This process may result in the thermoplastic film fracturing to form rents 26 as
shown in Figs. 4 and 5. The thermoplastic may be laminated to the ePTFE by
passing the ePTFE and thermoplastic over a surface, such as a roller or plate
that is heated to above the melt temperature of the thermoplastic to bond
them. The bonded layers can then be expanded uni-axially, bi-axially or
radially to form the rents in the thermoplastic surface. The nonporous
discontinuous surface layer 24 of polymer in this embodiment can be as thin
as 0.5 micron. In a preferred embodiment, FEP is laminated to PTFE and
then the laminate is expanded to form a porous composite.
With reference to Fig. 8, the nonporous discontinuous surface layer 24
may also be formed by perforating a nonporous film and then bonding it to a
porous membrane. The preferred nonporous discontinuous surface layer is
polymeric and may comprise a fluorinated thermoplastic film layer such as
FEP or PFA. The nonporous polymeric film layer can be perforated using any
conventional method, including but not limited to mechanical perforation, or
laser drilling. The preferred method is laser drilling. The perforated
nonporous discontinuous surface layer can then be affixed to a porous
membrane through any conventional method including but not limited to, hot
roll lamination, adhesive bonding, or ultrasonic bonding. In another aspect,
the perforated nonporous film may be affixed to the PTFE and can be
subsequently expanded.
In the embodiment illustrated in Fig. 8, a 12.5 micrometer thick sheet of
FEP was perforated using a 50 watt laser machine from Universal Laser
Systems Inc. (Scottsdale, AZ). The perforations 25 were 0.76 mm in
diameter, and the center-center distance between perforations was 1.02 mm.
The perforated FEP layer may then be bonded to a porous ePTFE membrane
to form the porous composite.
Regardless of form or method of construction, the nonporous
discontinuous surface layer forms a surface over the porous membrane layer
such that some of the pores of the porous membrane are blocked. The
nonporous discontinuous surface layer thus has a discontinuous surface with
openings therein, whereby the porous composite has regions of gas
permeability and regions of gas impermeability. The size and shape of the
openings in the nonporous discontinuous surface layer can vary considerably.
The porous composite articles may be used as a venting element in
venting enclosures. The venting element may be advantageously used to
form a liquid-tight seal in an enclosure for containing or excluding liquids. The
venting element provides gas permeability necessary for gas expansion, off-
gassing of chemicals, and the like. As shown in Fig. 2, venting apparatus 40
may be constructed to have a liquid exposure side 41 and an opposite side
47. A nonporous discontinuous surface layer 24 may be disposed upon the
porous membrane 22 to construct a liquid exposure side 41 of the porous
composite 20. The liquid exposure side 41 may be oriented towards the
interior of an enclosure 32 containing a liquid 38. In these applications (e.g.
liquid detergent containers) the liquid is contained, yet the porous composite
provides gas permeability. The gas permeability may prevent enclosure
deformation or rupture due to thermal cycling, or allow for off gassing of the
liquid. In an alternate embodiment illustrated in Fig. 10, in which liquid entry is
to be prevented, the liquid exposure side 41 may be oriented towards the
outside of the enclosure 32. The opposite side 47 is oriented towards the
inside of the enclosure. In such applications, (e.g. electronics enclosures or
lighting enclosures) the porous composite may provide gas permeability while
preventing liquid entry into the enclosure. In yet another construction
illustrated schematically in Fig. 9, both sides of the porous composite may be
constructed as liquid exposure sides.
Preferably, the air flow recovery of the liquid exposure side exceeds
the air flow recovery of the opposite side by a value of at least 1.1%. More
preferably, the air flow recovery of the liquid exposure side exceeds the air
flow recovery of the opposite side by a value of at least 5%. In embodiments
in which the porous composite has two liquid exposure sides, it is preferable
that the air flow recovery of the porous composite exceeds the air flow
recovery of the porous membrane alone by at least about 5%.
In an embodiment, the porous oleophobic composite may have an air
flow recovery of at least about 33% when the liquid exposure side of the
composite is exposed to viscous fluid of low surface tension. The airflow
recovery of this composite when the same viscous fluid of low surface tension
is exposed to the opposite side is 0%. More preferably, the porous composite
has an air flow recovery of at least about 50% when the liquid exposure side
of the composite is exposed to viscous fluid of low surface tension. The
airflow recovery of this composite when the same viscous fluid of low surface
tension is exposed to the opposite side is 0%.
In another embodiment, the porous composite has an air flow
recovery of 4% when the liquid exposure side of the composite is exposed to
viscous fluid of low surface tension. The airflow recovery of the porous
composite when the same viscous fluid of low surface tension is exposed to
the opposite side is 0.4%. More preferably, the porous composite has an air
flow recovery of 12% when the liquid exposure side of the composite is
exposed to viscous fluid of low surface tension. The airflow recovery of the
porous composite when the same viscous fluid of low surface tension is
exposed to the opposite side is 0.1%.
The porous composite can be constructed as a laminate. The laminate
may be constructed by supporting the porous composite 20 on a support layer
30, as shown in Fig. 3. Support layer 30 provides structural support and may
also aid in attachment of the porous composite 20 to venting enclosure 32 as
shown in Fig. 10. Suitable support layers can be in the form of air permeable
media like knits, non-wovens, scrims, melt-blowns, woven fabrics, meshes,
foams, porous ePTFE membranes, etc. Support layers may be affixed to the
porous composite by, for example, hot-roll lamination, adhesives, or ultrasonic
bonding. The support layer may be affixed to either side of the porous
composite.
The present invention will be further described with respect to the non-
limiting examples provided below.
Test Methods
Density
Samples die cut to form rectangular sections 2.54 cm by 15.24 cm
were measured to determine their mass (using a Mettler-Toledo analytical
balance model AG204) and their thickness (using a Kafer FZ1000/30 snap
gauge). Using these data, density was calculated with the following formula:

in which: p = density (g/cc); m = mass (g); w = width (cm); I = length (cm); and
t = thickness (cm).
Porosity
Porosity was expressed in percent porosity and was determined by
subtracting the quotient of the density of the article (described earlier herein)
and that of the bulk density of PTFE from 1, then multiplying that value by
100%. For the purposes of this calculation, the bulk density of PTFE was
taken to be 2.2 g/cc
Air Flow Recovery
Figs 11 and 11a illustrate the apparatus used for airflow recovery
testing. Vent material 100 is sealed between upper plate 102 and lower plate
104. The plates each include an orifice of diameter 2.54cm. The upper plate
incorporates a liquid well 106. The vent material 100 is secured between the
plates using a gasket 108 and thumb screws 110. The assembled plates are
then secured in an adapter 300 by means of clamps 302, thumb screws 304
and a gasket 306. Adapter 300 includes an air chamber 301 and channel 310
for delivering air to it. A Telydyne Genuine Gurley™ tester (Model Number
4110) is attached to the inlet port 312 of the adapter 300 using the gasket
308.
100 cm3 of air is delivered to the sample at a pressure of 12.4 cm of
water and the flow time recorded in seconds. This measurement is Gurley
(seconds) before fluid contact.
The plate is then removed from the adapter and the vent material is
exposed to test fluid by filling liquid well 106 such that the entire surface of the
vent material is covered by the fluid. This can be done by using a transfer
pipette to add about 2 to 3 cm3 of test fluid to the well 106. After 60 seconds,
the plate assembly was tilted ninety degrees. The liquid is allowed to drain off
from the vent material for 60 seconds. The plate is then secured in the
adapter 300 which is affixed to the Telydyne Genuine Gurley™ tester (Model
Number 4110).
100 cm3 of air is allowed to flow through the sample at a pressure of
12.4 cm of water and the flow time recorded in seconds. This measurement is
Gurley (seconds) after fluid contact. In cases where airflow did not start after
ten minutes in this test, the test was stopped and samples were considered
not to recover as denoted by NR for no recovery of airflow. The percentage air
flow recovery is then determined by using the equation:

Water Entry Pressure
As used in this application, the term "water entry pressure" means the
pressure required to drive water through a material, such as a membrane, as
further described in the test methods contained herein. Water entry pressure
provides a test method for water intrusion through membranes or vent bodies.
The membrane (or vent body) is placed in a fixture and pressurized with
water. A piece of pH paper may be placed on top of the membrane (or vent
body) on the non-pressurized side as an indicator of evidence for water entry.
The sample is then pressurized in small increments, until a color change in
the pH paper indicates the first sign of water entry. The water pressure at
breakthrough or entry is recorded as the Water Entry Pressure.
Bubble Point
The bubble point and mean flow pore size were measured according to
the general teachings of ASTM F31 6-03 using a Capillary Flow Porometer
(Model CFP 1500 AEXL from Porous Materials Inc., Ithaca, NY). The sample
membrane was placed into the sample chamber and wet with SilWick Silicone
Fluid (available from Porous Materials Inc.) having a surface tension of 19.1
dynes/cm. The bottom clamp of the sample chamber had a 2.54 cm
diameter, 3.175 mm thick porous metal disc insert (Mott Metallurgical,
Farmington, CT, 40 micron porous metal disk) and the top clamp of the
sample chamber had a 3.175 mm diameter hole. Using the Capwin software
version 6.62.1 the following parameters were set as specified in the table
immediately below. The values presented for bubble point and mean flow
pore size were the average of two measurements.
Oil Rating
Oil rating testing was conducted in accordance with AATCC Test
Method 118-2002. The oil rating of a membrane is the lower of the two
ratings obtained when testing the two sides of the membrane.
Surface Tension
Surface tension of the challenge fluid was measured using a Kruss K12
tensiometer using the Whilhelmy plate method. Kruss Laboratory Desktop
Software Version 2.13a was used. Whilhelmy plate immersions were
conducted with flamed glass cover slips and the software default dip
parameters.
Viscosity
Viscosity was measured using a Brookfield DVII+ viscometer with a UL
low volume spindle and tube accessory. Viscosities are reported in centipoise
(cP) for a temperature of 22.5 degrees Celcius, at 30 RPM, and a shear rate of
36.7 second-1. Viscosities were read after five minutes at 30 RPM for
samples which had previously been run at the maximum RPM allowed by
torque.
Challenge Fluids
Two representative challenge fluids were formulated and used for air
flow recovery testing after fluid exposure. Properties of these fluids are listed
in the table below. Challenge Fluid I was used for oleophobic articles with an
oil rating of greater than about 2. Challenge Fluid II was used for hydrophobic
articles.
Challenge Fluid I was prepared in the following manner:
A solution of PVP (Polyvinylpyrrolidone, Sigma-Aldrich Chemical,
Catalog Number 437190-500G, Molecular Weight = 1,300,000, CAS Number
9003-39-8), and De-ionized water was prepared by mixing the two
components and allowing them to stir overnight. Tergitol®TMN6 (Dow
Chemical, CAS Number 60828-78-6) was added and the solution was allowed
to stir for about one hour and then used immediately for testing.
Challenge Fluid II was prepared in the following manner:
A solution of Tween® (Mallinckrodt Baker, Inc., Catalog Number X257-
07, CAS Number 9005-65-6), and De-ionized water was prepared by mixing
the two components and allowing them to stir overnight. Glycerol (Ultra Pure
Grade, MP Biomedicals, Catalog Number 800688) was added and the
solution was allowed to stir for about one hour and then used immediately for
testing.

EXAMPLES
EXAMPLE 1
Fine powder of PTFE polymer (Daikin Industries, Ltd., Orangeburg,
NY) was blended with Isopar K (Exxon Mobil Corp., Fairfax, VA) in the
proportion of 0.25 g/g of fine powder. The lubricated powder was compressed
in a cylinder to form a pellet and placed into an oven set at 25°C for
approximately 24 hours. Compressed and heated pellets were ram extruded
to produce tapes approximately 29 cm wide by 0.635 mm thick. The tape was
then calendared between compression rolls to a thickness of 0.20 mm. The
tape was then dried in an oven set at 250°C. The dry PTFE tape and a 12.5
urn thick FEP film were layered together and longitudinally expanded between
banks of rolls over two heated plates set to a temperature of 300°C. The
speed ratio between the second bank of rolls and the first bank of rolls, and
hence the expansion ratio on the first plate, was 1.15:1. The speed ratio
between the third bank of rolls and the second bank of rolls, and hence the
expansion ratio on the second plate, was 1.15:1. The composite FEP
laminated PTFE tape was then longitudinally expanded 5:1, through a hot air
oven set to a temperature of 320°C. The FEP film bonded to the PTFE tape
as it melted and as the two layers expanded, rents were formed in the FEP
film. The longitudinally expanded composite was then heat treated through a
hot air oven set to a temperature of 360°C. The composite was then
expanded transversely at a temperature of approximately 370°C to a ratio of
approximately 7:1 and then constrained and heated in an oven set at 370°C
for approximately 24 seconds.
The porous composite thus produced had a Bubble Point of 6.9 psi.
Both sides of the composite were tested for air flow recovery with challenge
fluid II. Results are shown in Table I.
The composite was treated to render it oleophobic according to the
following procedure. A solution was prepared by adding 0.25 weight percent
of Teflon AF 1600 (Dupont Fluoroproducts, Wilmington, DE) to PF-5070
Brand Performance Fluid (CAS Number 86508-42-1, 3M) and allowing the
fluid to mix overnight. The composite sample was held taut in an embroidery
hoop (15.2 cm diameter). A pipette was then used to apply 5 to 6 cm3 of the
above solution to the (liquid exposure side) of the composite sample. The
composite sample was tilted and rotated such that the solution completely
saturated the sample. At this point, the sample became transparent and was
visibly wet throughout. The hoop was immediately hung vertically in a hood
and allowed to dry overnight. Both sides of the oleophobic composite were
then tested for air flow recovery using Challenge Fluid I. The results obtained
are shown in Table I. The oil rating was measured to be 5.

EXAMPLE 2
Fine powder of PTFE polymer (Daikin Industries, Ltd., Orangeburg,
NY) was blended with Isopar K (Exxon Mobil Corp., Fairfax, VA) in the
proportion of 0.196 g/g of fine powder. The lubricated powder was
compressed in a cylinder to form a pellet and placed into an oven set at 70°C
for approximately 12 hours. Compressed and heated pellets were ram
extruded to produce tapes approximately 15.2 cm wide by 0.73 mm thick.
Two separate rolls of tape were produced and layered together between
compression rolls to a thickness of 0.254 mm. The tape was then
transversely stretched to 56 cm (i.e., at a ratio of 3.7:1), then dried in an oven
set at 250°C. The dry tape was longitudinally expanded between banks of
rolls over a heated plate set to a temperature of 340°C. A 12.5 micron thick
FEP film was layered onto the PTFE tape prior to expansion over the plate.
The speed ratio between the second bank of rolls and the first bank of rolls,
and hence the expansion ratio, was 14:1. The FEP film bonded to the PTFE
tape as it melted and as the two layers expanded, rents were formed in the
FEP film. The longitudinally expanded composite was then expanded
transversely at a temperature of approximately 350°C to a ratio of
approximately 20:1 and then constrained and heated in an oven set at 380°C
for approximately 24 seconds.
The porous composite thus produced had a Bubble Point of 30 psi.
Both sides of the composite were tested for air flow recovery with challenge
fluid II. Results are shown in Table II.
The composite was treated to render it oleophobic according to the
following procedure. A solution was prepared by adding 0.25 weight percent
of Teflon AF 1600 (Dupont Fluoroproducts, Wilmington, DE) to PF-5070
Brand Performance Fluid (CAS Number 86508-42-1, 3M) and allowing the
fluid to mix overnight. The composite sample was held taut in an embroidery
hoop (15.2 cm diameter). A pipette was then used to apply 5 to 6 cm3 of the
above solution to the liquid exposure side of the composite sample. The
composite sample was tilted and rotated such that the solution completely
saturated the sample. At this point, the sample became transparent and was
visibly wet throughout. The hoop was immediately hung vertically in a hood
and allowed to dry overnight. Both sides of the oleophobic composite were
then tested for air flow recovery using Challenge Fluid I. Results are shown in
Table II. The oil rating was measured to be 6.
EXAMPLE 3
Fine powder of PTFE polymer (Daikin Industries, Ltd., Orangeburg,
NY) was blended with Isopar K (Exxon Mobil Corp., Fairfax, VA) in the
proportion of 0.25 g/g of fine powder. The lubricated powder was compressed
in a cylinder to form a pellet and placed into an oven set at 25°C for
approximately 24 hours. Compressed and heated pellets were ram extruded
to produce tapes approximately 29 cm wide by 0.635 mm thick. The tape was
then calendared between compression rolls to a thickness of 0.20 mm. The
tape was then dried in an oven set at 250°C. The dry PTFE tape and a 12.5
micron thick PFA film were layered together and longitudinally expanded
between banks of rolls over two heated plates set to a temperature of 320°C.
The speed ratio between the second bank of rolls and the first bank of rolls,
and hence the expansion ratio on the first plate, was 1.15:1. The speed ratio
between the third bank of rolls and the second bank of rolls, and hence the
expansion ratio on the second plate, was 1.15:1. The PFA/ PTFE tape
laminate was then longitudinally expanded 8:1, through a hot air oven set to a
temperature of 320°C. The longitudinally expanded composite was then heat
treated through a hot air oven set to a temperature of 360°C. The composite
was then expanded transversely at a temperature of approximately 380°C to a
ratio of approximately 2.4:1 and then constrained and heated in an oven set at
380°C for approximately 24 seconds.
The porous composite thus produced had a Bubble Point of 0.5 psi.
Both sides of the composite were tested for air flow recovery with challenge
fluid II. Results are shown in Table III.
The composite was treated to render it oleophobic according to the
following procedure. A solution was prepared by adding 0.25 weight percent
of Teflon AF 1600 (Dupont Fluoroproducts, Wilmington, DE) to PF-5070
Brand Performance Fluid (CAS Number 86508-42-1, 3M) and allowing the
fluid to mix overnight. The composite sample was held taut in an embroidery
hoop (15.2 cm diameter). A pipette was then used to apply 5 to 6 cm3 of the
above solution to the surface liquid exposure side of the composite sample.
The composite sample was tilted and rotated such that the solution
completely saturated the sample. At this point, the sample became
transparent and was visibly wet throughout. The hoop was immediately hung
vertically in a hood and allowed to dry overnight. Both sides of the oleophobic
composite were then tested for air flow recovery Challenge Fluid 1. The
results obtained are shown in Table III. The oil rating was measured to be 6.

EXAMPLE 4
A 12.5 micrometer thick sheet of FEP was perforated using a 50 watt
laser machine from Universal Laser Systems Inc. (Scottsdale, AZ). Size of
the perforations were 0.76 mm in diameter, the center-center distance
between perforations was 1.02 mm. The perforated FEP sheet was laminated
to an ePTFE membrane (thickness of 22.8 microns, density of 0.39 g/cm3,
and bubble point of 8 psi) using a web of co-polyester (Spunfab, Inc. Product
Number PE2900-0.6-45W) as an adhesive layer. The materials were
laminated together in a heat press (Geo. Knight & Co, MA) using the following
conditions: 160 degrees, 60 psi, 3 seconds. The composite was evaluated for
air flow recovery using challenge fluid II. Results appear in Table IV.

EXAMPLE 5
5 g FEP powder (Product Number 532-8000 from DuPont) was added
to a mixture of 47.5g of 2-Propanol (IPA) and 47.5g of HFE-7500 (3M NOVEC
(TM) Engineered Fluid). The dispersion was stirred for a few hours until a
clear solution was formed. An ePTFE membrane having a thickness of 106
micron, porosity of 64%, and density of 0.78g/cc was coated with this solution
using a continuous immersion coating process. In this process, the ePTFE
membrane was passed through a first roller and then passed through a bath
containing the coating solution using a second immersion roller. After this
coating step, the membrane was dried for 4 hours at room temperature in a
ventilated hood. A thin layer of FEP particles was left on the surface of the
membrane. To melt the particles, the coated membrane was fixed on a tenter
frame, and placed in a sinter oven at a temperature of 320°C for 5 minutes.
The porous composite thus produced had a nonporous discontinuous surface
layer as shown in Figure 7. The porous composite was rendered oleophobic
by coating with a solution of 0.75 weight percent Teflon AF1600 (DuPont
Fluoroproducts, Wilmington, DE) in solvent PF-5070 (CAS Number 86508-42-
1, 3M) and dried for 6 hours at room temperature in a ventilated hood.
We claim:
1. A porous composite comprising:
(a) porous membrane having a structure defining a plurality of pores
extending therethrough,
(b) nonporous discontinuous surface layer affixed to said porous
membrane, said nonporous discontinuous surface layer having
rents, wherein the rents form regions of gas permeability, and
(c) a coating disposed upon wherein at least a portion of the porous
composite is rendered oleophobic.
2. The porous composite of claim 1 wherein the said porous membrane
comprises expanded PTFE.
3. The porous composite of claim 1 wherein the said microporous membrane
comprises UHMWPE.
4. The porous composite of claim 1 wherein the said discontinuous surface
layer is less than 5 um thick.
5. The porous composite of claim 1 wherein the said nonporous
discontinuous surface layer comprises thermoplastic.
6. The porous composite of claim 1 wherein the said nonporous
discontinuous surface layer comprises fluoroplastic.
7. The porous composite of claim 1 wherein the said nonporous
discontinuous surface layer comprises FEP.
8. The porous composite of claim 1 wherein said porous composite has an oil
rating of greater than about 2.
9. The porous composite of claim 1 wherein the said porous composite is
laminated to a support layer.
10. The porous composite of claim 9 wherein the said support layer comprises
a nonwoven.
11. The porous composite of claim 9 wherein the said support layer comprises
an expanded PTFE membrane.
12. A venting apparatus having an opening therein for venting an enclosure
and for preventing passage of a liquid, said venting apparatus comprising
a porous composite venting element forming a gas-permeable barrier to
said liquid, said porous composite venting element comprising:
a) porous membrane having a structure defining a plurality of pores
extending therethrough, and
b) nonporous discontinuous surface layer affixed to said porous
membrane, said nonporous discontinuous surface layer having
rents, whereby the nonporous discontinuous surface layer
comprises regions of gas permeability corresponding to the
rents.
13. The venting apparatus of claim 12 in which the venting element has a
liquid exposure side oriented towards the liquid, the liquid exposure side
comprising said nonporous discontinuous surface layer.
14. The venting apparatus of claim 12 in which the porous composite venting
element has a interior face and an exterior face and wherein the interior
face and the exterior face comprise said nonporous discontinuous surface
layer.
15. The venting apparatus of claim 12 wherein the said porous membrane
comprises expanded PTFE.
16. The venting apparatus of claim 12 wherein the said porous membrane
comprises UHMWPE.
17. The venting apparatus of claim 12 wherein the said nonporous
discontinuous surface layer comprises thermoplastic.
18. The venting apparatus of claim 12 wherein the said nonporous
discontinuous surface layer comprises fluoroplastic.
19. The venting apparatus of claim 12 wherein the said nonporous
discontinuous surface layer comprises FEP.
20. The venting apparatus of claim 12 wherein the said porous composite has
an oil rating greater than about 2.
21. The venting apparatus of claim 12 wherein the said porous composite is
laminated to a support layer.
22. A venting apparatus having an opening therein for venting an enclosure
and for preventing passage of a liquid, said venting apparatus comprising:
porous composite venting element forming a gas-permeable barrier to
said liquid, said porous composite venting element comprising:
a) porous membrane having a structure defining a plurality of
pores, extending therethrough,
b) nonporous discontinuous surface coating said porous
membrane, said nonporous discontinuous surface coating
blocking at least some of the pores, whereby the porous
composite surface has regions of gas permeability and gas
impermeability.
23. The porous composite of claim 22 wherein the said nonporous
discontinuous surface layer comprises thermoplastic.
24. The porous composite of claim 22 wherein the said nonporous
discontinuous surface layer comprises fluoroplastic.
25. The porous composite of claim 22 wherein the said nonporous
discontinuous surface layer comprises FEP.
26. A venting apparatus having an opening therein for venting an enclosure,
said enclosure defining an internal space and an external space, said
venting apparatus preventing passage of a liquid between the internal
space and the external space, the venting apparatus comprising:
a porous composite venting element forming a liquid-tight, gas-permeable
seal of said opening, said porous composite venting element having a
liquid face adjacent to the liquid, the porous composite venting element
comprising:
a) porous membrane having a structure defining a plurality of pores
extending therethrough,
b) nonporous discontinuous surface covering at least a portion of the
liquid face of said porous membrane, said nonporous discontinuous
surface blocking at least some of the pores and having openings
therein, and
whereby the surface of said porous composite has regions of gas
permeability and regions of gas impermeability.
27. The venting apparatus of claim 26 wherein the said microporous
composite venting element further comprises an oleophobic coating.
28. The venting apparatus of claim 26 wherein said microporous membrane
layer is expanded PTFE.
29. The venting apparatus of claim 26 wherein said microporous membrane
layer is UHMWPE.
30. The venting apparatus of claim 26 wherein said nonporous discontinuous
surface layer comprises thermoplastic.
31. The venting apparatus of claim 26 wherein said nonporous discontinuous
surface layer comprises fluoropolymer.
32. The venting apparatus of claim 26 wherein said nonporous discontinuous
surface layer comprises FEP.
33. The venting apparatus of claim 26 wherein the said porous composite
surface has regions of gas permeability and regions of gas impermeability
and wherein the area ratio of gas permeability to gas impermeability is no
greater than 0.2: 1.
34.The porous composite of claim 26 wherein the said nonporous
discontinuous surface layer is less than 5 um thick.
35. A venting apparatus having an opening therein for venting an enclosure
and for preventing passage of a liquid, said venting apparatus comprising:
a porous composite venting element forming a gas-permeable barrier to
said liquid, said porous composite venting element comprising a porous
membrane having a first face and a second face opposite the first face,
and a nonporous surface layer affixed to the first face of the porous
membrane forming a liquid exposure face of the composite venting
element
whereby the airflow recovery after liquid exposure to the liquid exposure
face of said porous composite venting element exceeds the airflow
recovery after liquid exposure to the second face of said porous composite
venting element.
36. A venting apparatus of claim 35 wherein the airflow recovery after liquid
exposure to the liquid exposure face of said composite exceeds the
airflow recovery after liquid exposure to second face of said composite by
more than 5%.

Porous composites comprise a porous membrane having a structure defining a plurality of pores extending
therethrough, nonporous discontinuous surface layer affixed to said porous membrane, in which the nonporous discontinuous
surface layer forms regions of gas permeability, and regions of gas impermeability, and a coating disposed upon the porous
composite which renders at least a portion of the porous composite oleophobic.

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Patent Number

268635

Indian Patent Application Number

3739/KOLNP/2009

PG Journal Number

37/2015

Publication Date

11-Sep-2015

Grant Date

09-Sep-2015

Date of Filing

27-Oct-2009

Name of Patentee

GORE ENTERPRISE HOLDINGS, INC.

Applicant Address

551 PAPER MILL ROAD, P.O. BOX 9206, NEWARK, DE 19714-9206 UNITED STATES OF AMERICA

Inventors:

#	Inventor's Name	Inventor's Address
1	BACINO, JOHN, E.	32 SIENNA DRIVE, LANDENBERG, PA 19350 UNITED STATES OF AMERICA
2	HOBSON, ALEX, R.	110 LIBERTY LANE, ELKTON, MD 21921 UNITED STATES OF AMERICA
3	MEINDL, KLAUS	WERNER-VON BRAUN STRASSE II, 85639 PUTZBRUNN GERMANY
4	DIMEO, JOHN, L.	1815 LOVERING AVENUE, WILMINGTON, DE 19806 UNITED STATES OF AMERICA

PCT International Classification Number

B01D71/36; B01D67/00; B01D71/00

PCT International Application Number

PCT/US2008/005182

PCT International Filing date

2008-04-22

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	11/738,761	2007-04-23	U.S.A.