Carbon fiber multifilamentary tow which is particularly suited for weaving and/or resin impregnation

• US 4,714,642 A
• Filed: 06/27/1985
• Issued: 12/22/1987
• Est. Priority Date: 08/30/1983
• Status: Expired due to Fees

• Current Assignee: BASF Coatings GmbH (BASF SE), Celanese Corporation, Subject To Agreement Recited See Document For Details.
• Original Assignee: BASF AG (BASF SE)
• Inventors: McAliley, J. Eugene, Daumit, Gene P., Crozier, James R. Jr., Ethridge, Frederick A.
• Primary Examiner(s): Bell, James J.
• Application Number:
  US06/748,781
• Time in Patent Office: 908 Days
• Field of Search: 57/243, 57/250, 428/108, 428/113, 428/114, 428/232, 428/297, 428/260, 428/290, 428/257, 428/408, 428/227, 428/195, 428/196, 428/198, 428/299, 428/109
• US Class Current: 428/113
• CPC Class Codes: D01F 9/22 from polyacrylonitriles
• CPC Class Codes: D03D 15/275 Carbon fibres
• CPC Class Codes: D03D 15/41 with specific twist
• CPC Class Codes: D03D 15/573 Tensile strength
• CPC Class Codes: D03D 9/00 Open-work fabrics
• CPC Class Codes: D10B 2101/12 Carbon; Pitch
• CPC Class Codes: D10B 2321/10 polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
• CPC Class Codes: D10B 2505/00 Industrial
• CPC Class Codes: D10B 2505/02 Reinforcing materials; Prepregs
• CPC Class Codes: Y10T 428/24083 Nonlinear strands or strand-portions
• CPC Class Codes: Y10T 428/24091 with additional layer[s]
• CPC Class Codes: Y10T 428/24124 Fibers
• CPC Class Codes: Y10T 428/24132 including grain, strips, or filamentary elements in different layers or components parallel
• CPC Class Codes: Y10T 428/24826 Spot bonds connect components
• CPC Class Codes: Y10T 428/30 Self-sustaining carbon mass or layer with impregnant or other layer
• CPC Class Codes: Y10T 442/2008 Fabric composed of a fiber or strand which is of specific structural definition
• CPC Class Codes: Y10T 442/2984 Coated or impregnated carbon or carbonaceous fiber fabric

Abstract

An improved multifilamentary tow of carbon fibers is provided which possesses a novel physical configuration that better enables it to undergo impregnation with a matrix-forming resin to form quality composite articles. The individual filaments of the tow are randomly decollimated and commingled with numerous filament cross-over points throughout the length of the multifilamentary tow in order to create a multitude of interstices between adjacent filaments which are well adapted to receive and retain a matrix-forming resin as evidenced by the ability of the filaments when subjected to the flaring test described herein to resist lateral expansion to a width that is as much as three times the original width. The tow commonly comprises approximately 1,000 to 50,000 filaments. Also, the filaments of the tow are substantially continuous and contain at least 70 percent carbon by weight (preferably at least 90 percent carbon by weight). In a preferred embodiment wherein the resistance to lateral expansion is the greatest, the multifilamentary bundles have been found to be capable of being readily woven with no significant productivity loss to form a quality reinforcing fabric while free of a protective size, such as that which has heretofore been required while weaving carbonaceous multifilamentary yarn bundles of the prior art.

Claims

1. A multifilamentary tow of carbonaceous fibrous material which is particularly suited for use as fiber reinforcement in a resin matrix comprising approximately 1,000 to 50,000 adjacent substantially continuous filaments containing at least 70 percent carbon by weight having a length of at least 100 meters, wherein the individual filaments of said multifilamentary tow are randomly decollimated and commingled with numerous filament cross-over points throughout the length of the multifilamentary tow so as to create a multitude of interstices between adjacent filaments which are well adapted to receive and retain a matrixforming resin as evidenced by an ability of the filaments of said multifilamentary tow when subjected to the flaring test described herein while in a substantially untwisted state to resist lateral expansion to a width which is as much as three times the original width as a result of said commingling of adjacent filaments.

2. A multifilamentary tow of carbonaceous fibrous material according to claim 1 which is formed from approximately 3,000 to 12,000 substantially continuous filaments.

3. A multifilamentary tow of carbonaceous fibrous material according to claim 1 which was derived from acrylic filaments.

4. A multifilamentary tow of carbonaceous fibrous material according to claim 1 wherein the filaments contain at least 90 percent carbon by weight.

5. A multifilamentary tow of carbonaceous fibrous material according to claim 1 which has a tensile strength of at least 400,000 psi.

6. A multifilamentary tow of carbonaceous fibrous material according to claim 1 which has a tensile strength of at least 450,000 psi.

7. A multifilamentary tow of carbonaceous fibrous material according to claim 1 which has a tensile strength of at least 500,000 psi.

8. A multifilamentary tow of carbonaceous fibrous material according to claim 1 which has a tensile strength of at least 700,000 psi.

9. A multifilamentary tow of carbonaceous fibrous material according to claim 1 which exhibits an ability of the filaments of said multifilamentary tow when subjected to the flaring test described herein while in a substantially untwisted state to resist lateral expansion to a width which is as much as two times the original width as a result of said commingling of adjacent filaments.

10. A multifilamentary tow of carbonaceous fibrous material according to claim 1 which exhibits an ability of the filaments of said multifilamentary tow when subjected to the flaring test described herein while in a substantially untwisted state to resist lateral expansion to a width which is as much as one and one-half times the original width as a result of said commingling of adjacent filaments.

11. A multifilamentary tow of carbonaceous fibrous material according to claim 1 which exhibits an ability of the filaments of said multifilamentary tow when subjected to the flaring test described herein while in a substantially untwisted state to resist lateral expansion to a width which is as much as one and one-fourth times the original width as a result of said commingling of adjacent filaments.

12. A multifilamentary tow of carbonaceous fibrous material according to claim 1 which exhibits an ability of the filaments of said multifilamentary tow when subjected to the flaring test described herein while in a substantially untwisted state to retain substantially the same width as that originally exhibited as a result of said commingling of adjacent filaments.

13. A multifilamentary tow of carbonaceous fibrous material according to claim 1 which is substantially free of a twist.

14. A multifilamentary tow of carbonaceous fibrous material according to claim 1 which includes a twist.

15. A multifilamentary tow of carbonaceous fibrous material according to claim 1 which is substantially free of a size upon its surface.

16. A multifilamentary tow of carbonaceous fibrous material according to claim 1 which bears a size upon its surface.

17. A multifilamentary tow of carbonaceous fibrous material according to claim 1 wherein the filaments have a denier per filament of approximately 0.2 to 1.5.

18. A multifilamentary tow of carbonaceous fibrous material according to claim 1 wherein said tow has a generally flattened configuration and a width of approximately 0.02 to 2.0 cm. with the greater widths within the range specified commonly being associated with a multifilamentary tow having a larger number of adjacent substantially continuous filaments within the range specified.

19. An improved substantially void-free composite article comprising a solid resinous matrix material and at least a portion of the multifilamentary tow of claim 1 incorporated therein as fibrous reinforcement.

20. A generally flattened multifilamentary tow of a carbonaceous fibrous material which is particularly suited for use as fiber reinforcement in a resin matrix having a width of approximately 0.04 to 1.0 cm. comprising approximately 3,000 to 12,000 adjacent substantially continuous filaments containing at least 90 percent carbon by weight having a length of at least 100 meters, and a tensile strength of at least 400,000 psi, wherein the individual filaments of said multifilamentary tow are randomly decollimated and commingled with numerous filament cross-over points throughout the length of the multifilamentary tow so as to create a multitude of interstices between adjacent filaments which are well adapted to receive and retain a matrixforming resin as evidenced by an ability of the filaments of said multifilamentary tow when subjected to the flaring test described herein while in a substantially unwisted state to resist lateral expansion to a width which is as much as two times the original width as a result of said commingling of adjacent filaments.

21. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 which is formed from approximately 3,000 substantially continuous filaments and has a width of approximately 0.04 to 0.4 cm.

22. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 which is formed from approximately 6,000 substantially continuous filaments and has a width of approximately 0.06 to 0.6 cm.

23. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 which is formed from approximately 12,000 continuous filaments and has a width of approximately 0.1 to 1.0 cm.

24. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 which has a tensile strength of at least 450,000 psi.

25. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 which has a tensile strength of at least 500,000 psi.

26. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 which has a tensile strength of at least 700,000 psi.

27. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 which exhibits an ability of the filaments of said multifilamentary tow when subjected to the flaring test described herein while in a substantially untwisted state to resist lateral expansion to a width which is as much as one and one-half times the original width as a result of said commingling of adjacent filaments.

28. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 which exhibits an ability of the filaments of said multifilamentary tow when subjected to the flaring test described herein while in a substantially untwisted state to resist lateral expansion to a width which is as much as one and one-fourth times the original width as a result of said commingling of adjacent filaments.

29. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 which exhibits an ability of the filaments of said multifilamentary tow when subjected to the flaring test described herein while in a substantially untwisted state to retain substantially the same width as that originally exhibited as a result of said commingling of adjacent filaments.

30. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 which is substantially free of twist.

31. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 which includes a twist.

32. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 which is substantially free of size upon its surface.

33. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 which bears a size upon its surface.

34. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 wherein the filaments have a denier per filament of approximately 0.2 to 1.5.

35. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 wherein the filaments have a denier per filament of approximately 0.3.

36. A generally flattened multifilamentary tow of carbonaceous fibrous material according to claim 20 wherein the filaments have a denier per filament of approximately 0.6.

37. An improved substantially void-free composite article comprising a solid resinous matrix material and at least a portion of the multifilamentary tow of claim 20 incorporated therein as fibrous reinforcement.

38. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material which incorporates a plurality of unsized multifilamentary yarn bundles comprising substantially continuous carbonaceous filaments containing at least 70 percent carbon by weight wherein said multifilamentary yarn bundles are randomly decollimated and commingled with numerous filament cross-over points throughout their lengths so as to create a multitude of interstices between adjacent filaments which are well adapted to receive and retain a matrix-forming resin as evidenced by an ability of the filaments of said yarn bundles when subjected to the flaring test described herein while in a substantially untwisted state to resist lateral expansion to a width which is as much as one and one-half times the original width as a result of said commingling of adjacent filaments.

39. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said multifilamentary yarn bundles are formed from approximately 1,000 to 50,000 substantially continuous filaments.

40. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said multifilamentary yarn bundles are formed from approximately 3,000 to 12,000 substantially continuous filaments.

41. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said substantially continuous carbonaceous filaments contain at least 90 percent carbon by weight.

42. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said substantially continuous carbonaceous filaments were derived from acrylic filaments.

43. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said multifilamentary yarn bundles have a tensile strength of at least 400,000 psi.

44. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said multifilamentary yarn bundles have a tensile strength of at least 450,000 psi.

45. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said multifilamentary yarn bundles have a tensile strength of at least 500,000 psi.

46. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said multifilamentary yarn bundles have a tensile strength of at least 700,000 psi.

47. An improved woven fabric suitable for use as fibrous reinforcement in a resinous material according to claim 38 wherein said multifilamentary yarn bundles are substantially free of a twist.

48. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said multifilamentary yarn bundles possess a twist of approximately 0.1 to 1.0 turn per inch when woven.

49. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said carbonaceous filaments have a denier per filament of approximately 0.2 to 1.5.

50. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said carbonaceous filaments have a denier per filament of approximately 0.3.

51. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said carbonaceous filaments have a denier per filament of approximately 0.6.

52. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said multifilamentary yarn bundles when subjected to the flaring test described herein while in a substantially untwisted state resist lateral expansion to a width which is as much as one and one-fourth times the original width as a result of said commingling of adjacent filaments.

53. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said multifilamentary yarn bundles when subjected to the flaring test described herein while in substantially untwisted state retain substantially the same width as that originally exhibited as a result of said commingling of adjacent filaments.

54. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said multifilamentary yarn bundles are woven in a plain weave configuration.

55. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said multifilamentary yarn bundles are woven in a satin weave configuration.

56. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 55 wherein said multifilamentary yarn bundles are woven in a five harness satin weave construction.

57. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 55 wherein said multifilamentary yarn bundles are woven in an eight harness satin weave configuration.

58. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said multifilamentary yarn bundles were woven while unsized by use of a shuttleless loom.

59. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 58 wherein said multifilamentary yarn bundles were woven while unsized by use of a rapier loom.

60. An improved woven fabric suitable for use as fibrous reinforcement in a resinous matrix material according to claim 38 wherein said multifilamentary yarn bundles were woven while unsized by use of a shuttle loom.

61. An improved woven substantially void-free composite article comprising a solid resinous matrix material and at least one layer of the fabric according to claim 38 incorporated therein as fibrous reinforcement.

62. An improved woven substantially void-free composite article according to claim 61 wherein said solid resinous matrix material is a thermoset resin selected from the group consisting of epoxy resins, polyimide resins, bismaleimide resins, vinylester resins, unsatuted polyester resins, and mixtures of the foregoing.

63. An improved woven substantially void-free composite article according to claim 61 wherein said solid resinous matrix material is a thermoplastic selected from the group consisting of polyether-etherketone resins, polyphenylenesulfide resins, polysulfone resins, saturated polyester resins, polyamide resins, polyamideimide resins, polyetherimide resins, and mixtures of the foregoing.