Superhydrophobic fibers and methods of preparation and use thereof

• US 8,574,713 B2
• Filed: 03/09/2006
• Issued: 11/05/2013
• Est. Priority Date: 03/10/2005
• Status: Expired due to Fees

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Rutledge, Gregory C., Hill, Randal M., Ma, Minglin, Fridrikh, Sergey, Lowery, Joseph L
• Primary Examiner(s): Cole, Elizabeth
• Assistant Examiner(s): SYKES, ALTREV C
• Application Number:
  US11/371,223
• Publication Number:
  US 20060292369A1
• Time in Patent Office: 2,798 Days
• Field of Search: 428/375, 428/292.1, 428/394, 428/364, 524/120, 524/147, 524/151, 524/153, 442/79, 442/80, 442/86, 442/88, 526/348.1, 526/347.2, 528/66, 528/44, 528/28, 528/25, 528/10, 528/34, 528/30, 264/288.4, 264/290.2, 264/341, 264/103, 210/500.21, 210/188, 525/100
• US Class Current: 428/364
• CPC Class Codes: D01D 5/0038 the fibre formed by solvent evaporation, i.e. dry electro-spinning
• CPC Class Codes: D01F 6/42 comprising cyclic compounds containing one carbon-to-carbon double bond in the side chain as major constituent
• CPC Class Codes: D01F 6/92 of polyesters
• CPC Class Codes: D01F 6/96 from other synthetic polymers
• CPC Class Codes: Y10T 428/249924 Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
• CPC Class Codes: Y10T 428/25 Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
• CPC Class Codes: Y10T 428/29 Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
• CPC Class Codes: Y10T 428/2913 Rod, strand, filament or fiber
• CPC Class Codes: Y10T 428/2933 Coated or with bond, impregnation or core
• CPC Class Codes: Y10T 428/2967 Synthetic resin or polymer
• CPC Class Codes: Y10T 442/2164 Coating or impregnation specified as water repellent
• CPC Class Codes: Y10T 442/2172 Also specified as oil repellent
• CPC Class Codes: Y10T 442/2221 Coating or impregnation is specified as water proof
• CPC Class Codes: Y10T 442/2238 Fluorocarbon containing

Abstract

The present invention relates to fibers exhibiting a water contact angle of above 150° and water contact angle hysteresis of below 15°, methods of producing the same, and applications thereof. The present invention further relates to superhydrophobic fiber mats, methods of producing the same, and applications thereof.

Claims

1. A non coated fiber comprising a copolymer, wherein a mat of said fibers exhibits a water contact angle of above 150°

and water contact angle hysteresis of below 15°

, wherein said copolymer comprises a component having a silicon structure and/or wherein said copolymer is fluorinated.

2. The fiber of claim 1, wherein the diameter of said fiber is between 1 nm-5 micron.

3. The fiber of claim 2, wherein said diameter is between 1 nm-500 nm.

4. The fiber of claim 1, wherein said water contact angle is above 160°

.

5. The fiber of claim 1, wherein said fiber is an electrospun fiber.

6. The fiber of claim 1, wherein said fiber exhibits a microphase-separation.

7. The fiber of claim 1, wherein the surface energy of said component is less than about 40 mN/m.

8. The fiber of claim 7, wherein said component segregates to the surface of said fiber.

9. The fiber of claim 1, wherein said silicon structure is a resin, linear, branched, cross-linked, cross-linkable silicone structure or any combination thereof.

10. The fiber of claim 1, wherein said silicon structure is poly-dimethylsiloxane (PDMS).

11. The fiber of claim 1, wherein said copolymer comprises a polyisobutylene, polyolefin, polystyrene, polyacrylate, polyurethane, polyester, polyimide, polyetherimide, any derivative thereof or any combination thereof.

12. The fiber of claim 1, wherein said copolymer comprises a block, graft, star or random copolymer.

13. The fiber of claim 12, wherein said block copolymer comprises poly(styrene-co-dimethylsiloxane) (PS-PDMS).

14. The fiber of claim 12, wherein said fiber comprises poly-dimethylsiloxane (PDMS) blocks non-uniformly dispersed within a polystyrene (PS) matrix.

15. The fiber of claim 14, wherein said poly-dimethylsiloxane (PDMS) blocks segregate to the surface of said fibers.

16. The fiber of claim 12, wherein said block copolymer comprises poly(dimethylsiloxane-co-etherimide).

17. The fiber of claim 1, wherein said fiber exhibits surface roughness properties.

18. A composition or an article of manufacture comprising the fiber of claim 1.

19. A superhydrophobic mat of non coated fibers comprising a copolymer wherein said mat exhibits a water contact angle of above 150°

and water contact angle hysteresis of below 15°

, wherein said copolymer comprises a component having a silicon structure and/or wherein said copolymer is fluorinated.

20. The mat of claim 19, wherein said mat exhibits a water contact angle of above 160°

.

21. The mat of claim 19, wherein said mat exhibits an isotropic nature of said contact angle, contact angle hysteresis or a combination thereof.

22. The mat of claim 19, wherein said mat exhibits a non-isotropic nature of said contact angle, contact angle hysteresis or a combination thereof.

23. The mat of claim 19, wherein the diameter of said fiber is between 1 nm-5 micron.

24. The mat of claim 23, wherein said diameter is between 1 nm-500 nm.

25. The mat of claim 19, wherein said fiber is an electrospun fiber.

26. The mat of claim 19, wherein said fiber exhibits a microphase-separation.

27. The mat of claim 19, wherein the surface energy of said component is less than about 40 mN/m.

28. The mat of claim 27, wherein said component segregates to the surface of said fiber.

29. The mat of claim 19, wherein said silicon structure is a resin, linear, branched, cross-linked, cross-linkable silicone structure or any combination thereof.

30. The mat of claim 19, wherein said silicon structure is poly-dimethylsiloxane (PDMS).

31. The mat of claim 19, wherein said copolymer comprises a polyisobutylene, polyolefin, polystyrene, polyacrylate, polyurethane, polyester, polyamide, polyetherimide, any derivative thereof or any combination thereof.

32. The mat of claim 19, wherein said copolymer comprises a block, graft, star or random copolymer.

33. The mat of claim 32, wherein said block copolymer comprises poly(styrene-co-dimethylsiloxane) (PS-PDMS).

34. The mat of claim 32, wherein said fiber comprises poly-dimethylsiloxane (PDMS) blocks non-uniformly dispersed within a polystyrene (PS) matrix.

35. The mat of claim 34, wherein said poly-dimethylsiloxane (PDMS) blocks segregate to the surface of said fibers.

36. The mat of claim 32, wherein said block copolymer comprises poly(dimethylsiloxane-co-etherimide).

37. The mat of claim 19, wherein said mat exhibits surface roughness properties.

38. The mat of claim 19, wherein said mat exhibits pore size of between 0.1-100 micron.

39. An article of manufacture comprising the mat of claim 19.

40. The article of manufacture of claim 39, wherein said article of manufacture is a waterproof, water resistant or water draining substance.

41. The article of manufacture of claim 39, wherein said article of manufacture is a self-cleaning substance.

42. The article of manufacture of claim 39, wherein said article of manufacture is a coating substance.

43. The article of manufacture of claim 42, wherein said coating reduces drag.

44. The article of manufacture of any one of claims 39-43, wherein said article of manufacture is a fabric.

45. The article of manufacture of claim 44, wherein said fabric is a breathable fabric.

46. The article of manufacture of claim 44, wherein said fabric has a filtration functionality.

47. The article of manufacture of claim 44, wherein said fabric has an absorptive functionality.

48. The article of manufacture of claim 44, wherein said fabric is a non-woven fabric.

49. The article of manufacture of claim 44, wherein said fabric is a waterproof or water resistant fabric.

50. The article of manufacture of any one of claim 39, wherein said article of manufacture is a drug delivery system.

51. The article of manufacture of any one of claim 39, wherein said article of manufacture is a bandage or patch.

52. The article of manufacture of claim 51, wherein said bandage or patch comprise a drug.

53. A method for preparing a non coated fiber or fibers, the method comprising the step of electrospinning a solution comprising a copolymer, wherein said copolymer comprises a component having a silicon structure and/or wherein said copolymer is fluorinated, wherein a mat of said fibers exhibits a water contact angle of above 150°

and water contact angle hysteresis of below 15°

.

54. The method of claim 53, wherein the diameter of said fiber is between 1 nm-5 micron.

55. The method of claim 53, wherein said diameter is between 1 nm-500 nm.

56. The method of claim 53, wherein said water contact angle is above 160°

.

57. The method of claim 53, wherein said fiber exhibits a microphase-separation.

58. The method of claim 53, wherein said component segregates to the surface of said fibers.

59. The method of claim 53, wherein said silicon structure is a resin, linear, branched, cross-linked, cross-linkable silicone structure or any combination thereof.

60. The method of claim 53, wherein said silicon structure is poly-dimethylsiloxane (PDMS).

61. The method of claim 53, wherein said copolymer comprises a polyisobutylene, polyolefin, polystyrene, polyacrylate, polyurethane, polyester, polyamide, any derivative thereof or any combination thereof.

62. The method of claim 53, wherein said copolymer comprises a block, graft, star or random copolymer.

63. The method of claim 62, wherein said block copolymer comprises poly(styrene-co-dimethylsiloxane) (PS-PDMS).

64. The method of claim 63, wherein the concentration of said poly(styrene-co-dimethylsiloxane) (PS-PDMS) in said solution is 21%.

65. The method of claim 53, wherein said fiber comprises poly-dimethylsiloxane (PDMS) blocks non-uniformly dispersed within a polystyrene (PS) matrix.

66. The method of claim 65, wherein said poly-dimethylsiloxane (PDMS) blocks segregate to the surface of said fibers.

67. The method of claim 53, wherein said fiber exhibits surface roughness properties.

68. The method of claim 53, wherein said solution further comprises tetrahydrofuran, diethylformamide, chloroform or a combination thereof.

69. The method of claim 53, wherein said solution further comprises tetrahydrofuran and diethylformamide in a ratio of 3:

1.

70. The method of claim 53, wherein said solution further comprises chloroform and diethylformamide in a ratio of 4:

1.

71. The method of claim 53, further comprising the step of producing a superhydrophobic mat comprising said fibers.

72. The method of claim 71, wherein said mat exhibits surface roughness properties.

73. The mat of claim 71, wherein said mat exhibits pore sizes of between 0.1-100 micron.

74. The method of claim 71, wherein said mat exhibits a non-isotropic nature of said contact angle, contact angle hysteresis or a combination thereof.