Self-repairing, reinforced matrix materials

• US 6,527,849 B2
• Filed: 07/17/2001
• Issued: 03/04/2003
• Est. Priority Date: 06/19/1990
• Status: Expired due to Fees

• Current Assignee: Carolyn M. Dry
• Original Assignee: Carolyn M. Dry
• Inventors: Dry, Carolyn M.
• Primary Examiner(s): Marcheschi, Michael
• Application Number:
  US09/907,378
• Publication Number:
  US 20010050032A1
• Time in Patent Office: 595 Days
• Field of Search: 106/677, 106/711, 106/724, 106/729, 106/823, 106/802, 106/805, 106/676, 106/819, 501/95.1, 753/00, 428/320.2, 428/321.1, 428/321.5, 523/218, 523/219
• US Class Current: 106/677
• CPC Class Codes: A61L 27/48 with macromolecular fillers
• CPC Class Codes: B28B 17/00 Details of, or accessories for, apparatus for shaping the material; Auxiliary measures taken in connection with such shaping moulds B28B7/00; after-treatment B28B11/00; feeding or discharging B28B13/00; arrangements for embedding elements in the material B28B23/00
• CPC Class Codes: B29C 73/163 Sealing compositions or agents, e.g. combined with propellant agents
• CPC Class Codes: B29C 73/22 the article containing elements including a sealing composition, e.g. powder being liberated when the article is damaged
• CPC Class Codes: B32B 15/14 next to a fibrous or filamentary layer
• CPC Class Codes: B32B 15/18 comprising iron or steel B32B15/011, B32B15/012 and B32B15/013 take precedence
• CPC Class Codes: B32B 15/20 comprising aluminium or copper B32B15/016 and B32B15/017 take precedence
• CPC Class Codes: B32B 17/04 bonded with or embedded in a plastic substance
• CPC Class Codes: B32B 17/10036 comprising two outer glass sheets
• CPC Class Codes: B32B 17/10963 specially adapted for repairing the layered products
• CPC Class Codes: B32B 2250/03 3 layers
• CPC Class Codes: B32B 2250/40 Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
• CPC Class Codes: B32B 2307/54 Yield strength; Tensile strength
• CPC Class Codes: B32B 2307/554 Wear resistance
• CPC Class Codes: B32B 2307/762 Self-repairing, self-healing
• CPC Class Codes: B32B 2603/00 Vanes, blades, propellers, rotors with blades
• CPC Class Codes: B32B 2605/18 Aircraft blades, propellers B32B2603/00
• CPC Class Codes: B32B 5/02 characterised by structural features of a fibrous or filamentary layer layer formed of metallic wires B32B15/02; layer formed of natural mineral fibres B32B19/02; layer formed of wood fibres B32B21/02
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C04B 20/0048 Fibrous materials
• CPC Class Codes: C04B 20/0056 : Hollow or porous fibres
• CPC Class Codes: C04B 20/1025 : Fats; Fatty oils; Ester type waxes; Higher fatty acids; Derivatives thereof
• CPC Class Codes: C04B 2103/00 : Function or property of ingredients for mortars, concrete or artificial stone
• CPC Class Codes: C04B 2103/0046 : added as monomers or as oligomers
• CPC Class Codes: C04B 2103/0067 : the ingredients being formed in situ by chemical reactions or conversion of one or more of the compounds of the composition
• CPC Class Codes: C04B 2111/72 : Repairing or restoring existing buildings or building materials
• CPC Class Codes: C04B 22/006 : released by a chemical reaction, e.g. polymer condensation
• CPC Class Codes: C04B 22/085 : containing nitrogen in the anion, e.g. nitrites
• CPC Class Codes: C04B 2235/3217 : Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
• CPC Class Codes: C04B 2235/524 : Non-oxidic, e.g. borides, carbides, silicides or nitrides
• CPC Class Codes: C04B 2235/5284 : Hollow fibers, e.g. nanotubes
• CPC Class Codes: C04B 2235/80 : Phases present in the sintered or melt-cast ceramic products other than the main phase
• CPC Class Codes: C04B 24/08 : Fats; Fatty oils; Ester type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
• CPC Class Codes: C04B 24/282 : Polyurethanes; Polyisocyanates
• CPC Class Codes: C04B 24/32 : Polyethers, e.g. alkylphenol polyglycolether
• CPC Class Codes: C04B 24/42 : Organo-silicon compounds
• CPC Class Codes: C04B 26/02 : Macromolecular compounds
• CPC Class Codes: C04B 26/14 : Polyepoxides
• CPC Class Codes: C04B 28/02 : containing hydraulic cements other than calcium sulfates
• CPC Class Codes: C04B 28/34 : containing cold phosphate binders
• CPC Class Codes: C04B 35/52 : based on carbon, e.g. graphite
• CPC Class Codes: C04B 35/80 : Fibres, filaments, whiskers, platelets, or the like
• CPC Class Codes: C04B 38/0003 : containing continuous channels, e.g. of the "dead-end" type or obtained by pushing bars in the green ceramic product B28B takes precedence
• CPC Class Codes: C04B 40/0028 : Aspects relating to the mixing step of the mortar preparation
• CPC Class Codes: C04B 40/0092 : Temporary binders, mortars or concrete, i.e. materials intended to be destroyed or removed after hardening, e.g. by acid dissolution
• CPC Class Codes: C04B 40/0263 : Hardening promoted by a rise in temperature C04B40/024 takes precedence
• CPC Class Codes: C04B 40/06 : Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
• CPC Class Codes: C04B 40/0633 : Chemical separation of ingredients, e.g. slowly soluble activator
• CPC Class Codes: C04B 40/0641 : Mechanical separation of ingredients, e.g. accelerator in breakable microcapsules
• CPC Class Codes: C04B 40/0675 : Mortars activated by rain, percolating or sucked-up water; Self-healing mortars or concrete
• CPC Class Codes: C08J 3/241 : Preventing premature crosslinking by physical separation of components, e.g. encapsulation
• CPC Class Codes: C08K 7/00 : Use of ingredients characterised by shape
• CPC Class Codes: C08K 7/02 : Fibres or whiskers
• CPC Class Codes: C22C 47/00 : Making alloys containing metallic or non-metallic fibres or filaments
• CPC Class Codes: C22C 47/04 : by coating, e.g. with a protective or activated covering
• CPC Class Codes: C22C 49/00 : Alloys containing metallic or non-metallic fibres or filaments
• CPC Class Codes: C22C 49/14 : characterised by the fibres or filaments
• CPC Class Codes: Y10T 428/249971 : Preformed hollow element-containing
• CPC Class Codes: Y10T 428/249994 : Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
• CPC Class Codes: Y10T 428/249995 : Constituent is in liquid form
• CPC Class Codes: Y10T 428/249997 : Encapsulated liquid

Abstract

Self-repairing, fiber reinforced matrix materials include a matrix material including inorganic as well as organic matrices. Disposed within the matrix are hollow fibers having a selectively releasable modifying agent contained therein. The hollow fibers may be inorganic or organic and of any desired length, wall thickness or cross-sectional configuration. The modifying agent is selected from materials capable of beneficially modifying the matrix fiber composite after curing. The modifying agents are selectively released into the surrounding matrix in use in response to a predetermined stimulus be it internal or externally applied. The hollow fibers may be closed off or even coated to provide a way to keep the modifying agent in the fibers until the appropriate time for selective release occurs. Self-repair, smart fiber matrix composite materials capable of repairing microcracks, releasing corrosion inhibitors or permeability modifiers are described as preferred embodiments in concrete and polymer based shaped articles.

Claims

1. An article comprising:

a matrix material having at least one release vessel disposed therein; and

at least one releasable modifying agent;

wherein said at least one release vessel contains at least one said agent therein until released therefrom; and

wherein the agent is released from the release vessel in the matrix material in response to at least one external stimulus, the agent effective to modify at least a portion of the matrix material.

2. An article according to claim 1, wherein the release vessel is breakable upon fracturing of an adjacent portion of the matrix material.

3. An article according to claim 2, wherein the release vessel has an initial brittleness, the external stimulus modifying at least a portion of the release vessel to make at least said portion more brittleqthan the initial brittleness.

4. An article according to claim 2, wherein the release vessel has an initial brittleness, the release vessel becoming increasingly brittle over time.

5. An article according to claim 3, wherein release vessel becomes more brittle by heat.

6. An article according to claim 1, wherein the release vessel is an elongate fiber comprising a conductive material.

7. An article according to claim 1, wherein the release vessel comprises an organic material.

8. An article according to claim 1, wherein the release vessel comprises straw.

9. An article according to claim 1, wherein the release vessel has an outer diameter which is less than 100 microns.

10. An article according to claim 1, wherein the release vessel is deformable.

11. An article according to claim 10, wherein deformation of the release vessel is effective to squeeze out the modifying agent contained therein.

12. An article according to claim 10, wherein the deformation is effective to change a shape of the matrix.

13. An article according to claim 10, wherein the release vessel is deformable in response to a temperature change.

14. An article according to claim 11, wherein the release vessel comprises a shape memory alloy.

15. An article according to claim 14, where in the release vessel comprises a porous material.

16. An article according to claim 10, wherein the release vessel is deformable in response to electrical stimulation.

17. An article according to claim 10, wherein the release vessel is deformable in response to stress.

18. An article according to claim 1, wherein said release vessel is one of a plurality of release vessels, at least one of the release vessels being disposed inside another.

19. An article according to claim 1, wherein the release vessel comprises a continuous network of hollow fibers.

20. An article according to claim 1, wherein the matrix comprises a metal material having a plurality of voids formed therein.

21. An article according to claim 1, wherein the matrix comprises a shape memory alloy.

22. An article according to claim 21, wherein the matrix has a plurality of voids formed therein.

23. An article according to claim 1, wherein the matrix comprises glass.

24. An article according to claim 1, wherein the matrix material includes a material which reacts with said agent.

25. An article according to claim 24, wherein the agent crosslinks with said material.

26. An article according to claim 24, wherein at least the agent or said material is a catalyst.

27. An article according to claim 1, wherein the released agent cures in situ.

28. An article according to claim 1, wherein only some of said modifying agent is released upon an initial stimulus occurrence to permit at least one subsequent release upon a subsequent stimulus occurrence.

29. An article according to claim 1, wherein the release occurs when said stimulus is an pressure differential delivered to an interior of the release vessel.

30. An article according to claim 1, wherein the agent comprises a repair chemical which enters cracks in the matrix adjacent the release vessel.

31. An article according to claim 30, wherein the agent comprises an adhesive.

32. An article according to claim 31, wherein the agent fills the cracks.

33. An article according to claim 32, wherein the modifying agent is a repair chemical which is expandable upon release.

34. An article according to claim 33, wherein the released modifying agent comprises a foam.

35. An article according to claim 33, wherein the modifying agent is a foaming polyurethane.

36. An article according to claim 1, wherein a component of the matrix material chemically reacts with said agent.

37. An article according to claim 36, wherein the modifying agent exchanges ions with said component.

38. An article according to claim 36, wherein the release of the agent results in a visible signal.

39. An article according to claim 1, wherein the modifying agent comprises an organism.

40. An article according to claim 1, wherein the modifying agent scavenges water.

41. An article according to claim 1, wherein the modifying agent scavenges a chemical in the matrix material.

42. An article according to claim 1, wherein the modifying agent scavenges radioactive materials.

43. An article according to claim 42, wherein the article comprises a container to hold radioactive waste.

44. An article according to claim 1, wherein the modifying agent is a cross linking monomer which causes a polymerization reaction which gives off water to hydrate cement.

45. An article according to claim 1, wherein the agent comprises an antifreeze.

46. An article as according to claim 1, wherein the matrix material has a structure, the released agent modifying the matrix material by building on a site in the structure in a self growing manner.

47. An article according to claim 1, wherein the article comprises a computer chip.

48. An article according to claim 1, wherein the article comprises a self releasing bandage.

49. An article according to claim 1, wherein the article comprises a container.

50. An article according to claim 1, wherein the article comprises an aircraft fuselage.

51. An article according to claim 1, wherein the article comprises a prosthetic device.

52. An article according to claim 51, wherein the prosthetic device comprises a bone.

53. An article according to claim 51, wherein the prosthetic device comprises a joint.

54. An article according to claim 1, wherein the release vessel is made of a piezoelectric material.

55. An article according to claim 54, wherein said at least one external stimulus is an electric potential across at least a portion of said release vessel.

56. An article according to claim 55, wherein the electric potential causes the release vessel to constrict, forcing the agent from the release vessel.

57. An article according to claim 54, wherein stress on the release vessel causes an electric potential across the release vessel.

58. An article according to claim 57, wherein the electric potential is effective to discharge charged ions from the release vessel.

59. An article according to claim 1, wherein the agent is effective to increase the elasticity of the matrix material.

60. An article according to claim 1, wherein the matrix comprises a