Multiple function, self-repairing composites with special adhesives

• US 7,811,666 B2
• Filed: 06/30/2006
• Issued: 10/12/2010
• Est. Priority Date: 07/01/2005
• Status: Active Grant

• Current Assignee: Carolyn Dry
• Original Assignee: Carolyn Dry
• Inventors: Dry, Carolyn
• Primary Examiner(s): Speer; Timothy M
• Application Number:
  US11/428,132
• Publication Number:
  US 20070087198A1
• Time in Patent Office: 1,565 Days
• Field of Search: 106/711, 106/677, 106/676, 106/705, 106/708, 106/717, 106/724, 106/728, 106/802, 106/806, 106/815, 428/408, 428/357, 428/358, 428/364, 428/402, 428/366, 428/370, 428/374, 428/377, 428/378, 428/396
• US Class Current: 428/408
• 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: B29K 2105/06 containing reinforcements, fillers or inserts
• CPC Class Codes: B32B 2250/05 5 or more layers
• CPC Class Codes: B32B 2250/42 Alternating layers, e.g. ABAB(C), AABBAABB(C)
• CPC Class Codes: B32B 2262/101 Glass fibres
• CPC Class Codes: B32B 2307/306 Resistant to heat
• CPC Class Codes: B32B 2307/558 Impact strength, toughness
• CPC Class Codes: B32B 2307/762 Self-repairing, self-healing
• CPC Class Codes: B32B 2419/00 Buildings or parts thereof walls, panels B32B2607/00
• CPC Class Codes: B32B 2457/00 Electrical equipment
• CPC Class Codes: B32B 2603/00 Vanes, blades, propellers, rotors with blades
• CPC Class Codes: B32B 2605/00 Vehicles
• CPC Class Codes: B32B 7/04 Interconnection of layers
• CPC Class Codes: B32B 9/007 comprising carbon, e.g. graphite, composite carbon
• CPC Class Codes: B32B 9/02 comprising animal or vegetable substances , e.g. cork, bamboo, starch
• CPC Class Codes: B32B 9/04 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to a glass layer B32B17/06; layered products with at least two ceramic layers composed mainly of ceramic B32B18/00
• CPC Class Codes: C04B 14/34 Metals , e.g. ferro-silicon
• CPC Class Codes: C04B 14/42 Glass
• CPC Class Codes: C04B 2111/00612 as one or more layers of a layered structure
• CPC Class Codes: C04B 2111/28 Fire resistance, i.e. materials resistant to accidental fires or high temperatures
• CPC Class Codes: C04B 24/24 : Macromolecular compounds C04B24/14 takes precedence; macromolecular compounds comprising sulfonate or sulfate groups C04B24/16
• CPC Class Codes: C04B 28/02 : containing hydraulic cements other than calcium sulfates
• CPC Class Codes: Y10T 428/24744 : Longitudinal or transverse tubular cavity or cell
• CPC Class Codes: Y10T 428/249921 : Web or sheet containing structurally defined element or component
• CPC Class Codes: Y10T 428/249924 : Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
• CPC Class Codes: Y10T 428/249954 : With chemically effective material or specified gas other than air, N, or carbon dioxide in void-containing component
• CPC Class Codes: Y10T 428/249971 : Preformed hollow element-containing
• CPC Class Codes: Y10T 428/249974 : Metal- or silicon-containing element
• 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 428/2902 : Channel shape
• CPC Class Codes: Y10T 428/2913 : Rod, strand, filament or fiber
• CPC Class Codes: Y10T 428/2924 : Composite
• CPC Class Codes: Y10T 428/2971 : Impregnation
• CPC Class Codes: Y10T 428/30 : Self-sustaining carbon mass or layer with impregnant or other layer
• CPC Class Codes: Y10T 428/31678 : Of metal
• CPC Class Codes: Y10T 442/2008 : Fabric composed of a fiber or strand which is of specific structural definition

Abstract

A system for self-repairing matrices such as concrete or cementitous matrices, polymeric matrices, and/or fibrous matrices, including laminates thereof. The system includes repair agents retained in and/or on vessels, such as hollow fibers, within the matrix. Upon impact, the vessel rupture, releasing the chemicals. For multi-layer laminates, the systems provides a total dynamic energetic circulation system that functions as an in situ fluidic system in at least one layer or area. The energy from the impact ruptures the vessels to release the chemical(s), and mixes the chemical(s) and pushes the chemical(s) and/or resulting compound through the matrix. The repair agents can withstand high temperatures, such as the heat of processing of many laminates, e.g., 250-350° F.

Claims

1. A laminate composite comprising:

a matrix;

at least two plies of graphite material; and

at least one self-repair conduit disposed between the at least two plies of graphite material, the self-repair conduit having therein a reactive modifying agent that, when exposed to a temperature of at least 300°

F. for at least one hour, remains reactive.

2. The laminate of claim 1, wherein the composite comprises at least 24 plies of graphite material.

3. The laminate of claim 2, wherein the composite comprises from 24 to 32 plies of graphite material.

4. The laminate of claim 1, wherein the reactive modifying agent, when exposed to a temperature of at least 350°

F. for at least one hour, remains reactive.

5. The laminate of claim 4, wherein the modifying agent, when exposed to a temperature of at least 350°

F. for at least two hours, remains reactive.

6. The laminate of claim 1, further comprising a second conduit having therein a reagent for the modifying agent.

7. The laminate of claim 1, wherein the self-repair conduit comprises a glass fiber.

8. The laminate of claim 1, wherein the self-repair conduit is a channel defined by the matrix.

9. The laminate of claim 1, further comprising a reagent for the modifying agent.

10. The laminate of claim 9, wherein the reagent for the reactive modifying agent is present in the matrix.

11. The laminate of claim 9, wherein the reagent for the modifying agent is present in a second conduit.

12. The laminate of claim 1, wherein the modifying agent reacts in less than one minute after release from the conduit.

13. The laminate of claim 12, wherein the modifying agent reacts in less than 30 seconds after release from the conduit.

14. The laminate of claim 1, wherein the modifying agent repairs the laminate after an impact of from 5 joules to 50 joules to the laminate, the repair resulting in a laminate having at least 80% of the strength the laminate had prior to the impact.

47. A method of making the laminate composite of claim 1, wherein the self-repair conduit is a glass conduit, the method comprising:

treating the glass conduit with at least one of muriatic acid, maleic acid, acetic acid, dichloro silane, and dimethyl silane,

filling the conduit with a reactive agent;

sealing the conduit;

disposing the treated and filled conduit in the matrix to form the composite; and

processing the composite, the processing comprising at least one of heating and applying a vacuum.

48. The method of claim 47, wherein the heating comprises exposing the composite to a temperature of greater than 200°

F. for at least one hour.

49. The method of claim 47 further comprising applying a vacuum while heating the composite.

50. The method of claim 47, wherein the matrix comprises a polymer.

51. The method of claim 47, wherein the reactive agent comprises at least one of an acrylate, alkyl acrylate, methyl methacrylate, cyanoacrylate, acrylic acid, alkyl acrylic acid, olefin, lactone, lactam, styrene, isoprene, butadiene, and epoxy.

52. The method of claim 47, wherein the reactive agent comprises

at least one of an epoxy, epoxy vinyl ester, urethane, and cyanoacrylate, and

at least one of butylated hydroxyanisole, butylated hydroxytoluene, 2-ethylhexyl methacrylate, methylmethacrylate, organic sulfate, sulfite, sulfoxide, sulfinate, hydroquinone, and sulfur dioxide.

53. The method of claim 47 further comprising an additive disposed in the conduit, the additive being selected from the group consisting of cyclic organic sulfate, sulfite, sulfoxide, sulfinate, hydroquinone, butylated hydroxyanisole, butylated hydroxytoluene, methylmethacrylate, nanotubes, and combinations thereof.

15. An article comprising:

a conduit comprising a surrounding wall defining a volume; and

a reactive modifying agent sealed in the volume, the reactive modifying agent, when exposed to a temperature of at least 300°

F. for at least one hour, remains reactive.

16. The article of claim 15, wherein the modifying agent further comprises a color-change additive.

17. The article of claim 15, wherein after reaction of the modifying agent, the reacted modifying agent resists a temperature of at least 250°

F. for at least one hour without degradation.

18. The article of claim 17, wherein the modifying agent repairs damage to a composite from an impact of from 5 joules to 50 joules, the repair resulting in a composite having at least 70% of the strength the composite had prior to the impact.

19. The article of claim 18, wherein the modifying agent repairs damage to a composite from an impact of from 5 joules to 50 joules, the repair resulting in a composite having at least 80% the strength the composite had prior to the impact.

20. The article of claim 15, wherein the modifying agent reacts by one of ROMP (ring-opening metathesis polymerization), Bergman cyclization, Dehls Alder, and Shrock chemistry.

21. A self-repair system for a composite comprising:

a matrix; and

at least one first conduit having retained therein a reactive modifying agent that, in response to an external stimulus, releases from the at least one first conduit and flows in the matrix,

the reactive modifying agent, when exposed to a temperature of at least 300°

F. for a period of one hour, remains reactive.

22. The self-repair system of claim 21, wherein the composite is a laminate.

23. The self-repair system of claim 21, wherein the at least one first conduit comprises nanofibers, electrospun nanotubular fibers, nanotubes, hollow nanowhiskers, fiberglass, cement, asphalt, hydroxyapatite, glass, ceramic, metal, polyolefin, polyester, polycarbonate, polyacrylate, polyarylate, polyamide, polyimide, polyaramide, polyurethane, carbon, graphite, cellulose, nitrocellulose, hydrocarbon, or piezoelectric material.

24. The self-repair system of claim 21, wherein the modifying agent reacts with a reagent present in the matrix.

25. The self-repair system of claim 21 further comprising a second conduit comprising a reagent, the modifying agent reacting with the reagent present in the second conduit when the reagent is released from the second conduit and the modifying agent is released from the first conduit.

26. The self-repair system of claim 25, wherein the at least one first conduit and the second conduit are next to each other.

27. The self-repair system of claim 26, wherein the at least one first conduit and the second conduit are intertwined or twisted.

28. A self-repairing article comprising:

a composite;

a conduit disposed in the composite, the conduit comprising a surrounding wall defining an internal volume; and

a reactive agent disposed in the internal volume of the conduit, the reactive agent, when exposed to a temperature of at least 300°

F. for a period of one hour, remains reactive.

29. The article of claim 28, wherein the conduit comprises a capillary channel, a hollow bead, a hollow optical fiber, tube, pipette, carbon fiber, straw, or a combination thereof.

30. The article of claim 28, wherein the composite comprises a laminate comprising multiple layers, the conduit being disposed between at least two layers of the laminate.

31. The article of claim 28, wherein the composite comprises a matrix, the conduit being disposed within the matrix.

32. The article of claim 28, wherein the conduit releases the reactive agent when exposed to a sufficient external stimulus.

33. The article of claim 28, wherein the reactive agent comprises at least one of an acrylate, alkyl acrylate, methylmethacrylate, cyanoacrylate, acrylic acid, alkyl acrylic acid, olefin, lactone, lactam, styrene, isoprene, butadiene, urethane, and epoxy.

34. The article of claim 28 further comprising an additive disposed in the internal volume of the conduit, the, additive selected from the group consisting of a cyclic organic sulfate, sulfite, sulfoxide, sulfinate, hydroquinone, antioxidant, butylated hydroxyanisole, butylated hydroxytoluene, 2-ethylhexyl methacrylate, sulfur dioxide, triacetone triperoxide, butane, silicon, sodium hydroxide, catalyst, initiator, diol, diamine, amine, nanotubes, UV stabilizer, heat stabilizer, flame retardant, colorant, anticorrosion chemical, anti-freeze material, antimicrobial, odorant, surface-modifying additive, plasticizer, viscosity modifier, and combinations thereof.

35. The article of claim 28, wherein the conduit is a glass tube.

36. The article of claim 35, wherein the tube is treated with at least one of muriatic acid, maleic acid, acetic acid, dichloro silane, and dimethyl silane.

37. The article of claim 28 further comprising a second conduit, wherein the reactive agent comprises a first part and a second part, the first part being disposed in the first conduit and the second part being disposed in the second conduit.

38. The article of claim 37, wherein

the first part comprises

at least one of an acrylate, cyanoacrylate, alkyl acrylate, methyl methacrylate, acrylic acid, alkyl acrylic acid, olefin, lactone, lactam, styrene, isoprene, butadiene, urethane, epoxy vinyl ester, and epoxy, and,

optionally, at least one of cyclic organic sulfate, sulfite, sulfoxide, sulfinate, hydroquinone, antioxidant, butylated hyroxyanisole, butylated hydroxytoluene, 2-ethylhexyl methacrylate, sulfur dioxide, triacetone triperoxide, butane, silicon, nanotubes, and

the second part comprises at least one of methyl methacrylate, nanoclays, an alkaline compound, catalyst, initiator, diol, diamine, and amine, the second part being different from the first part.

39. The article of claim 28, wherein the conduit comprises beads comprising at least one of an epoxy and a cyanoacrylate.

40. The article of claim 28, wherein the composite comprises a cementitious material.

41. The article of claim 28, wherein the composite comprises a polymer matrix.

42. The article of claim 28, wherein the composite comprises an elastomer matrix.

43. The article of claim 42, wherein the reactive agent comprises at least one of epoxy and cyanoacrylate.

44. The article of claim 43 further comprising an additive disposed in the conduit, the additive being selected from the group consisting of a cyclic organic sulfate, sulfite, sulfoxide, sulfinate, hydroquinone, antioxidant, butylated hyroxyanisole, butylated hydroxytoluene, 2-ethylhexyl methacrylate, sulfur dioxide, triacetone triperoxide, butane, silicon, sodium hydroxide, catalyst, initiator, diol, diamine, amine, nanotubes, and combinations thereof.

45. The article of claim 28, wherein the composite comprises layers comprising elastomers and layers comprising a plurality of the conduits, the conduits being in the foam of tubes, the reactive agent being disposed in the tubes.

46. The article of claim 45, wherein the tubes comprise at least one of polymer and metal.