Porous PTFE materials and articles produced therefrom

• US 7,306,729 B2
• Filed: 01/18/2006
• Issued: 12/11/2007
• Est. Priority Date: 07/18/2005
• Status: Active Grant

• Current Assignee: W. L. Gore & Associates (W.L. Gore & Associates)
• Original Assignee: Gore Enterprise Holdings Incorporated (W.L. Gore and Associates)
• Inventors: Hobson, Alex R., Bacino, John E., Strid, Jason J.
• Primary Examiner(s): Menon; Krishnan S.
• Application Number:
  US11/334,243
• Publication Number:
  US 20070012624A1
• Time in Patent Office: 692 Days
• Field of Search: 210/650, 210/500.1, 210/321.6, 210/500.36, 210/500.27, 210/489, 210/640, 428/319.9, 428/318.4, 264/288.8, 264/127, 264/291, 264/294, 96/4, 96/10, 95/45
• US Class Current: 210/500.22
• CPC Class Codes: B01D 2325/0283 Pore size
• CPC Class Codes: B01D 2325/20 Specific permeability or cut-off range
• CPC Class Codes: B01D 2325/24 Mechanical properties, e.g. strength
• CPC Class Codes: B01D 2325/43 Specific optical properties
• CPC Class Codes: B01D 39/1692 Other shaped material, e.g. perforated or porous sheets
• CPC Class Codes: B01D 67/0027 by stretching
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• CPC Class Codes: B01D 71/36 Polytetrafluoroethene
• CPC Class Codes: B32B 2264/0257 Polyolefin particles, e.g. polyethylene or polypropylene homopolymers or ethylene-propylene copolymers
• CPC Class Codes: B32B 2307/414 Translucent
• CPC Class Codes: B32B 2307/54 Yield strength; Tensile strength
• CPC Class Codes: B32B 2307/72 Density
• CPC Class Codes: B32B 2307/724 Permeability to gases, adsorption
• CPC Class Codes: B32B 2307/726 Permeability to liquids, absorption
• CPC Class Codes: B32B 2307/732 Dimensional properties
• CPC Class Codes: B32B 27/12 next to a fibrous or filamentary layer
• CPC Class Codes: B32B 27/322 comprising halogenated polyolefins, e.g. PTFE
• CPC Class Codes: B32B 3/02 characterised by features of form at particular places, e.g. in edge regions non-uniform thickness B32B3/263
• CPC Class Codes: B32B 3/26 characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids foam layer B32B5/18; layer of synthetic resin characterised by fillers that create voids or cavities B32B27/205; characterised by an apertured layer
• CPC Class Codes: B32B 5/022 : Non-woven fabric
• CPC Class Codes: B32B 5/024 : Woven fabric
• CPC Class Codes: B32B 5/026 : Knitted fabric
• CPC Class Codes: B32B 5/16 : characterised by features of a layer formed of particles, e.g. chips, powder or granules layer formed of natural mineral particles B32B19/00; layer being formed of wood fibres, chips or particles B32B21/02
• CPC Class Codes: B32B 5/245 : another layer next to it being a foam layer
• CPC Class Codes: B32B 7/05 : the layers not being connected over the whole surface, e.g. discontinuous connection or patterned connection using interposed adhesives or bonding materials applied in spaced arrangements B32B7/14
• CPC Class Codes: B32B 7/12 : using interposed adhesives or interposed materials with bonding properties
• CPC Class Codes: Y10T 428/249954 : With chemically effective material or specified gas other than air, N, or carbon dioxide in void-containing component
• CPC Class Codes: Y10T 428/269 : including synthetic resin or polymer layer or component
• CPC Class Codes: Y10T 442/2139 : Coating or impregnation specified as porous or permeable to a specific substance [e.g., water vapor, air, etc.]

Abstract

Novel porous PTFE membranes are described possessing a unique combination of high strength, low flow resistance, and small pore size. Additionally, unique constructions with superior filtration and venting properties incorporating porous PTFE membranes are described.

Claims

1. An article comprising

a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said porous PTFE membrane having a Gurley versus bubble point equal to or below the line defined by the equation log (Gurley)=5.13×

10<sup>−

3</sup> (Bubble Point)−

1.26 and a surface area of at least 20 m²/g.

2. The article of claim 1, wherein said extruded lubricated tape is stretched transversely at a ratio of at least 3:

1.

3. The article of claim 1, wherein the ratio of matrix tensile strength in two orthogonal directions is 2:

1 or less.

4. The article of claim 1, wherein the product of matrix tensile strength in two orthogonal directions is greater than 1.3×

10⁵ MPa².

5. The article of claim 1, wherein the product of matrix tensile strength in two orthogonal directions is greater than 1.5×

10⁶ MPa².

6. The article of claim 1, wherein the product of matrix tensile strength in two orthogonal directions is greater than 1.9×

10⁵ MPa².

7. The article of claim 1, wherein said PTFE membrane has a light transmission of greater than 50%.

8. The article of claim 1, wherein the Gurley versus bubble point is equal to or below the line defined by the equation log (Gurley)=5.13×

10<sup>−

3</sup> (Bubble Point)−

1.58.

9. The article of claim 1, wherein the Gurley versus bubble point is equal to or below the line defined by the equation log (Gurley)=5.13×

10<sup>−

3</sup> (Bubble Point)−

2.02.

10. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said porous PTFE membrane having a light transmission of at least 50% and a porosity of at least 50%.

11. The article of claim 10, wherein said extruded lubricated tape is stretched transversely at a ratio of at least 3:

1.

12. The article of claim 10, wherein said porous PTFE membrane has a light transmission of at least 85% and a porosity of at least 75%.

13. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said porous PTFE membrane having a bubble point of at least 448 kPa and a Gurley versus bubble point equal to or below the line defined by the equation log (Gurley)=2.60×

10<sup>−

3</sup> (Bubble Point)−

0.54.

14. The article of claim 13, wherein said extruded lubricated tape is stretched transversely at a ratio of at least 3:

1.

15. The article of claim 13, wherein the Gurley versus bubble point is equal to or below the line defined by the equation log (Gurley)=2.60×

10<sup>−

3</sup> (Bubble Point)−

0.59.

16. The article of claim 13, wherein the Gurley versus bubble point is equal to or below the line defined by the equation log (Gurley)=2.60×

10<sup>−

3</sup> (Bubble Point)−

1.12.

17. A porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said porous PTFE membrane having a product of matrix tensile strengths in two orthogonal directions of at least 1.3×

10⁵ MPa².

18. The article of claim 17, wherein said extruded lubricated tape is stretched transversely at a ratio of at least 3:

1.

19. The article of claim 17, wherein the product of matrix tensile strength in two orthogonal directions is greater than 1.5×

10⁵ MPa².

20. The article of claim 17, wherein the product of matrix tensile strength in two orthogonal directions is greater than 1.9×

10⁵ MPa².

21. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said porous PTFE membrane having a Gurley versus bubble point equal to or below the line defined by the equation log (Gurley)=5.13×

10<sup>−

3</sup> (Bubble Point)−

1.26 and a product of matrix tensile strengths in two orthogonal directions of at least 1.3×

10⁵ MPa².

22. The article of claim 21, wherein said extruded lubricated tape is stretched transversely at a ratio of at least 3:

1.

23. The article of claim 21, wherein the product of matrix tensile strength in two orthogonal directions is greater than 1.5×

10⁵.

24. The article of claim 21, wherein the product of matrix tensile strength in two orthogonal directions is greater than 1.9×

10⁵.

25. The article of claim 21, wherein the Gurley versus bubble point is equal to or below the line defined by the equation log (Gurley)=5.13×

10<sup>−

3</sup> (Bubble Point)−

1.58.

26. The article of claim 21, wherein the Gurley versus bubble point is equal to or below the line defined by the equation log (Gurley)=5.13×

10<sup>−

3</sup> (Bubble Point)−

2.02.

27. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said porous PTFE membrane having a water entry pressure versus Gurley number equal to or above the line defined by the equation WEP=3(Gurley)+2500.

28. The article of claim 27, wherein said extruded lubricated tape is stretched transversely at a ratio of at least 3:

1.

29. The article of claim 27, wherein the water entry pressure versus Gurley is equal to or above the line defined by the equation WEP=3(Gurley)+2900.

30. The article of claim 27, wherein the water entry pressure versus Gurley is equal to or above the line defined by the equation WEP=3(Gurley)+3100.

31. The article of claim 27, wherein the Gurley versus bubble point is equal to or below the line defined by the equation log (Gurley)=5.13×

10<sup>−

3</sup> (Bubble Point)−

1.26.

32. The article of claim 27, wherein the Gurley number is between 1 and 50 seconds.

33. The article of claim 27, wherein the Gurley number is between 5 and 50 seconds.

34. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said porous PTFE membrane having a water flux rate versus bubble point equal to or above the line defined by the equation log (Water Flux Rate)=−

3.5×

10<sup>−

3</sup> (Bubble Point)+1.3.

35. The article of claim 34, wherein extruded PTFE extruded lubricated tape is stretched transversely at a ratio of at least 3:

1.

36. The article of claim 34, having a water flux rate versus bubble point equal to or above the line defined by the equation log (Water Flux Rate)=−

3.5×

10<sup>−

3</sup> (Bubble Point)+1.6.

37. The article of claim 34, having a water flux rate versus bubble point equal to or above the line defined by the equation log (Water Flux Rate)=−

3.5×

10<sup>−

3</sup> (Bubble Point)+2.0.

38. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said porous PTFE membrane having a water flux rate versus mean flow pore size equal to or above the line defined by the equation log (water flux rate)=16.9 (mean flow pore size)−

1.85.

39. The article of claim 38, wherein extruded lubricated tape is stretched transversely at a ratio of at least 3:

1.

40. The article of claim 38, having a water flux rate versus mean flow pore size equal to or above the line defined by the equation log (Water Flux Rate)=16.9 (mean flow pore size)−

1.6.

41. The article of claim 38, having a water flux rate versus mean flow pore size equal to or above the line defined by the equation log (Water Flux Rate)=16.9 (mean flow pore size)−

1.05.

42. An article comprising a composite of at least one porous PTFE membrane and at least one additional layer, said porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said composite having a water flux rate versus bubble point equal to or above the line defined by the equation log (Water Flux Rate)=−

3.5×

10<sup>−

3</sup> (Bubble Point)+1.3.

43. The article of claim 42, wherein said extruded lubricated tape is stretched transversely at a ratio of at least 3:

1.

44. The article of claim 42, having a water flux rate versus bubble point equal to or above the line defined by the equation log (Water Flux Rate)=−

3.5×

10<sup>−

3</sup> (Bubble Point)+1.6.

45. The article of claim 42, having a water flux rate versus bubble point equal to or above the line defined by the equation log (Water Flux Rate)=−

3.5×

10<sup>−

3</sup> (Bubble Point)+2.0.

46. The article of claim 42, wherein said at least 1 additional layer is selected from the group consisting of non-woven, scrim and fabric.

47. The article of claim 42, wherein said at least one additional layer comprises at least one additional layer on each side of the at least one membrane.

48. The article of claim 42, wherein said at least 1 additional layer comprises at least one porous membrane.

49. The article of claim 48, wherein said at least one porous membrane comprises ePTFE.

50. The article of claim 47, wherein said at least one additional layer on each side comprises ePTFE.

51. The article of claim 42 in the form of a filter.

52. The article of claim 42 in the form of a vent.

53. The article of claim 51 in the form of a filter cartridge.

54. An article comprising a composite of at least one porous PTFE membrane and at least one additional layer, said porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said composite further being instantly wettable with water, said composite having a water flux rate versus bubble point equal to or greater than the line defined by the equation log (Water Flux Rate)=−

0.01 (Bubble Point)+1.3.

55. The article of claim 54, wherein said extruded lubricated tape is stretched transversely at a ratio of at least 3:

1.

56. The article of claim 54, having a water flux rate versus bubble point equal to or greater than the line defined by the equation log (Water Flux Rate)=−

0.01 (Bubble Point)+2.48.

57. The article of claim 54, having a water flux rate versus bubble point equal to or greater than the line defined by the equation log (Water Flux Rate)=−

0.01 (Bubble Point)+5.0.

58. The article of claim 54, wherein said at least 1 additional layer is selected from the group consisting of non-woven, scrim and fabric.

59. The article of claim 54, wherein said at least one additional layer comprises at least one additional layer on each side of the at least one membrane.

60. The article of claim 54, wherein said at least 1 additional layer comprises at least one porous membrane.

61. The article of claim 60, wherein said at least one porous membrane comprises ePTFE.

62. The article of claim 59, wherein said at least one additional layer on each side comprises ePTFE.

63. The article of claim 54 in the form of a filter.

64. The article of claim 54 in the form of a vent.

65. The article of claim 63 in the form of a filter cartridge.

66. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said porous PTFE membrane being instantly wettable with water, said membrane having a water flux rate versus bubble point equal to or above the line defined by the equation log (Water Flux Rate)=−

0.01 (Bubble Point)+1.3.

67. The article of claim 66, wherein said extruded lubricated tape is stretched transversely at a ratio of at least 3:

1.

68. The article of claim 66, having a water flux rate versus bubble point equal to or below the line defined by the equation log (Water Flux Rate)=−

0.01 (Bubble Point)+2.48.

69. The article of claim 66, having a water flux rate versus bubble point equal to or below the line defined by the equation log (Water Flux Rate)=−

0.01 (Bubble Point)+5.0.

70. An article comprising at least one porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said porous PTFE membrane having an oleophobic treatment thereon and an oil rating of at least 2, said article having a water entry pressure above 1250 kPa and a Gurley number of greater than 0 and less than 200 seconds.

71. The article of claim 70, wherein said article has an oil rating of at least 3.

72. The article of claim 70, wherein said article has an oil rating of at least 5.

73. The article of claim 70, wherein said article has a water entry pressure above 2000 kPa and a Gurley number of greater than 0 and less than 100 seconds.

74. The article of claim 70, wherein extruded lubricated tape is stretched transversely at a ratio of at least 3:

1.

75. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said porous PTFE membrane having a Gurley versus bubble point equal to or below the line defined by the equation log (Gurley)=5.13×

10<sup>−

3</sup> (Bubble Point)−

1.22 and a light transmission of at least 50%.

76. The article of claim 75, wherein extruded lubricated tape is stretched transversely at a ratio of at least 3:

1.

77. The article of claim 75, wherein the Gurley versus bubble point is equal to or below the line defined by the equation log (Gurley)=5.13×

10<sup>−

3</sup> (Bubble Point)−

1.58.

78. The article of claim 75, wherein the Gurley versus bubble point is equal to or below the line defined by the equation log (Gurley)=5.13×

10<sup>−

3</sup> (Bubble Point)−

2.02.

79. A method of filtering a fluid comprising:

providing a filter comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said porous PTFE membrane having a water flux rate versus bubble point equal to or above the line defined by the equation log (Water Flux Rate)=−

3.5×

10<sup>−

3</sup> (Bubble Point)+1.3; and

flowing a fluid containing particle through said filter;

thereby filtering said particles from said fluid.

80. A method of filtering a fluid comprising:

providing a filter comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said porous PTFE membrane having a water flux rate versus mean flow pore size equal to or above the line defined by the equation log (water flux rate)=16.9 (mean flow pore size)−

1.85; and

flowing a fluid containing contaminants through said filter;

thereby filtering said particles from said fluid.

81. A method of filtering a fluid comprising:

providing a filter comprising a composite of at least one porous PTFE membrane and at least one additional layer, said porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said composite having a water flux rate versus bubble point equal to or above the line defined by the equation log (Water Flux Rate)=−

3.5×

10<sup>−

3</sup> (Bubble Point)+1.3; and

flowing a fluid containing particle through said filter;

thereby filtering said particles from said fluid.

83. The method of claim 81, wherein said filter comprises a hydrophilic composite.

82. A method of filtering a fluid comprising:

providing a filter comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste extrusion process;

stretching the extruded lubricated tape transversely, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape;

then transversely expanding the tape at an expansion ratio of 20;

1 or greater,

said porous PTFE membrane instantly wettable with water, said membrane having a water flux rate versus bubble point equal to or above the line defined by the equation log (Water Flux Rate)=−

0.01 (Bubble Point)+1.3; and

flowing a fluid containing particle through said filter;

thereby filtering said particles from said fluid.

84. An article comprising

a porous PTFE membrane formed by a method comprising:

forming an extruded lubricated tape of PTFE polymer by a paste forming process;

stretching the extruded lubricated tape transversely at a ratio of at least 3;

1, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape at a temperature above 327°

C.;

then transversely expanding the tape at a temperature above 327°

C.,

said porous PTFE membrane having a Gurley versus bubble point equal to or below the line defined by the equation log (Gurley)=5.13×

10<sup>−

3</sup> (Bubble Point)−

1.26 and a surface area of at least 20 m²/g.

85. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste forming process;

stretching the extruded lubricated tape transversely at a ratio of at least 3;

1, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape at a temperature above 327°

C.;

then transversely expanding the tape at a temperature above 327°

C.,

said porous PTFE membrane having a light transmission of at least 50% and a porosity of at least 50%.

86. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste forming process;

stretching the extruded lubricated tape transversely at a ratio of at least 3;

1, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape at a temperature above 327°

C.;

then transversely expanding the tape at a temperature above 327°

C.,

said porous PTFE membrane having a bubble point of at least 448 kPa and a Gurley versus bubble point equal to or below the line defined by the equation log (Gurley)=2.60×

10<sup>−

3</sup> (Bubble Point)−

0.54.

87. A porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste forming process;

stretching the extruded lubricated tape transversely at a ratio of at least 3;

1, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape at a temperature above 327°

C.;

then transversely expanding the tape at a temperature above 327°

C.,

said porous PTFE membrane having a product of matrix tensile strengths in two orthogonal directions of at least 1.3×

10⁵ MPa².

88. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste forming process;

stretching the extruded lubricated tape transversely at a ratio of at least 3;

1, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape at a temperature above 327°

C.;

then transversely expanding the tape at a temperature above 327°

C.,

said porous PTFE membrane having a Gurley versus bubble point equal to or below the line defined by the equation log (Gurley)=5.13×

10<sup>−

3</sup> (Bubble Point)−

1.26 and a product of matrix tensile strengths in two orthogonal directions of at least 1.3×

10⁵ MPa².

89. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste forming process;

stretching the extruded lubricated tape transversely at a ratio of at least 3;

1, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape at a temperature above 327°

C.;

then transversely expanding the tape at a temperature above 327°

C.,

said porous PTFE membrane having a water entry pressure versus Gurley number equal to or above the line defined by the equation WEP=3(Gurley)+2500.

90. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste forming process;

stretching the extruded lubricated tape transversely at a ratio of at least 3;

1, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape at a temperature above 327°

C.;

then transversely expanding the tape at a temperature above 327°

C.,

said porous PTFE membrane having a water flux rate versus bubble point equal to or above the line defined by the equation log (Water Flux Rate)=−

3.5×

10<sup>−

3</sup> (Bubble Point)+1.3.

91. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste forming process;

stretching the extruded lubricated tape transversely at a ratio of at least 3;

1, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape at a temperature above 327°

C.;

then transversely expanding the tape at a temperature above 327°

C.,

said porous PTFE membrane having a water flux rate versus mean flow pore size equal to or above the line defined by the equation log (water flux rate)=16.9 (mean flow pore size)−

1.85.

92. An article comprising a composite of at least one porous PTFE membrane and at least one additional layer, said porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste forming process;

stretching the extruded lubricated tape transversely at a ratio of at least 3;

1, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape at a temperature above 327°

C.;

then transversely expanding the tape at a temperature above 327°

C.,

said composite having a water flux rate versus bubble point equal to or above the line defined by the equation log (Water Flux Rate)=−

3.5×

10<sup>−

3</sup> (Bubble Point)+1.3.

93. An article comprising a composite of at least one porous PTFE membrane and at least one additional layer, said porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste forming process;

stretching the extruded lubricated tape transversely at a ratio of at least 3;

1, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape at a temperature above 327°

C.;

then transversely expanding the tape at a temperature above 327°

C.,

said composite further being instantly wettable with water, said composite having a water flux rate versus bubble point equal to or greater than the line defined by the equation log (Water Flux Rate)=−

0.01 (Bubble Point)+1.3.

94. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste forming process;

stretching the extruded lubricated tape transversely at a ratio of at least 3;

1, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape at a temperature above 327°

C.;

then transversely expanding the tape at a temperature above 327°

C.,

said porous PTFE membrane being instantly wettable with water, said membrane having a water flux rate versus bubble point equal to or above the line defined by the equation log (Water Flux Rate)=−

0.01 (Bubble Point)+1.3.

95. An article comprising at least one porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste forming process;

stretching the extruded lubricated tape transversely at a ratio of at least 3;

1, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape at a temperature above 327°

C.;

then transversely expanding the tape at a temperature above 327°

C.,

said porous PTFE membrane having an oleophobic treatment thereon and an oil rating of at least 2, said article having a water entry pressure above 1250 kPa and a Gurley number of greater than 0 and less than 200 seconds.

96. An article comprising a porous PTFE membrane formed by a method comprising

forming an extruded lubricated tape of PTFE polymer by a paste forming process;

stretching the extruded lubricated tape transversely at a ratio of at least 3;

1, and drying the stretched tape to remove lubricant;

longitudinally expanding the resulting tape at a temperature above 327°

C.;

then transversely expanding the tape at a temperature above 327°

C.,

said porous PTFE membrane having a Gurley versus bubble point equal to or below the line defined by the equation log (Gurley)=5.13×

10<sup>−

3</sup> (Bubble Point)−

1.22 and a light transmission of at least 50%.