Self-Repairing, Reinforced Matrix Materials

• US 20080053338A1
• Filed: 10/31/2007
• Published: 03/06/2008
• Est. Priority Date: 06/19/1990
• Status: Abandoned Application

• Current Assignee: Carolyn Dry
• Original Assignee: Carolyn Dry
• Inventors: Dry, Carolyn
• Application Number:
  US11/932,720
• Publication Number:
  US 20080053338A1
• Time in Patent Office: Days
• US Class Current: 106/642
• 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 cured matrix material having a modifying agent therein, wherein the modifying agent is capable of beneficially modifying the composite matrix material in response to a stimulus.

2. The article of claim 1 in which the matrix is comprised of cement, concrete, sintered fly ash or bottom ash/phosphoric acid mixtures, ceramic, silicon oxide, titanium oxide, silicon nitride, metals, aluminum, steel, metal alloys, carbon, graphite, asphalt, thermoplastic polymers, thermosetting polymers, thermoplastic elastomers, crosslinkable polymers, curable polymer resin systems, hydroxyapatite, thermoplastic polymers, polyolefins, polyesters, polycarbonates, polyacrylates, polyarylates, polyamides, polyimides, polyaramides, polyurethanes, foaming polyurethanes, curable resin systems, one and two part epoxies, phenolformaldehyde resins, thermoplastic elastomers, rubbery polymers, styrene, butadiene, rubber, neoprene, SEBS, NBR, and EPDM rubbers, viscoelastic materials, latexes, sinterable ceramics, hydroxyapatites, silicas, titanium, carbides, oxides, alumina, iron, lead, copper, steel, bronze, phosphor bronze, brass, alloys, bone, or calcium salts

3. The article of claim 1 wherein the modifying agent comprises at least one of one- and two-part adhesives, one- and two-part epoxy adhesives, cyanoacrylate adhesives, Elmer'"'"'s glue, sealant, siloxane, silica additives, calcium nitrate, polyprolylene glycol, amines and other crosslinkers, epoxy precursors, polymerizable monomers such as methyl methacrylates, styrene or other polymerizable starting materials, acids, bases, and solvents.

4. The article of claim 1 wherein the modifying agent self repairs the matrices by way of cement, fly ash, bottom ash, phosphoric acid, ceramic, silicon oxide, titanium oxide, silicon nitride, metals, aluminum, steel, metal alloys, carbon, graphite, asphalt, thermoplastic polymers, thermosetting polymers, thermoplastic elastomers, crosslinkable polymers, curable polymer resin systems, hydroxyapatite, thermoplastic polymers, polyolefins, polyesters, polycarbonates, polyacrylates, polyarylates, polyamides, polyimides, polyaramides, polyurethanes, foaming polyurethanes, thermosetting and crosslinkable polymers, curable resin systems, one and two part epoxies, phenolformaldehyde resins, thermoplastic elastomers, rubbery polymers, styrene, butadiene, rubber, neoprene, SEBS, NBR, and EPDM rubbers, viscoelastic materials, latexes, sinterable ceramics, hydroxyapatites, silicas, titanium, carbides, oxides, alumina, iron, lead, copper, steel, bronze, phosphor bronze, brass, bone, calcium salts

5. The article of claim 1 further comprising at least one release vessel having the modifying agent therein.

6. The article of claim 5, wherein the release vessel is a hollow particle.

7. The article of claim 1, wherein the article is for an aircraft, automotive, aerospace, or marine application.

8. The article of claim 1, wherein the article resists cracking, corrosion, and oxidation.

9. The article of claim 1, wherein the stimulus is at least one of heating, cooling, loading, impacting, cracking, water infusion, chloride infusion, alkalinity changes, acidity changes, acoustic excitation, low frequency wave excitations, hydrostatic pressure, rolling pressure, light sensitivity, laser excitation, electrical currents, voltages, electrorheological excitation, radiation, or other energetic stimuli.

10. The article of claim 1, wherein the matrix is steel and the stimulus is heat caused by fire or impact caused by earthquake.

13. The article of claim 1, wherein the modifying agent in the hollow particle is a polyolefin.

14. The article of claim 13, wherein the matrix is a laminate structure.

15. The article of claim 14 wherein the polyolefin reacts with a chemical in the laminate structure.

17. The article of claim 1, wherein the hollow release vessel is a hollow particle.

11. An article comprising a cured composite matrix material having a modifying agent in release vessels therein, wherein the modifying agent is capable of beneficially modifying the composite matrix material in response to a stimulus, wherein the cured matrix is a coating.

12. The article of claim 11 wherein the modifying agent comprises at least one of one- and two-part adhesives, one- and two-part epoxy adhesives, cyanoacrylate adhesives, Elmer'"'"'s glue, sealant, siloxane, silica additives, calcium nitrate, polyprolylene glycol, amines, epoxy precursors, polymerizable monomers such as methyl methacrylates, styrene, acids, bases, solvents, cement, fly ash, bottom ash, phosphoric acid, ceramic, silicon oxide, titanium oxide, silicon nitride, metals, aluminum, steel, metal alloys, carbon, graphite, asphalt, thermoplastic polymers, thermosetting polymers, thermoplastic elastomers, crosslinkable polymers, curable polymer resin systems, hydroxyapatite, thermoplastic polymers, polyolefins, polyesters, polycarbonates, polyacrylates, polyarylates, polyamides, polyimides, polyaramides, polyurethanes, foaming polyurethanes, crosslinkable polymers, curable resin systems, one and two part epoxies, phenolformaldehyde resins, thermoplastic elastomers, rubbery polymers, butadiene, rubber, neoprene, SEBS, NBR, and EPDM rubbers, viscoelastic materials, latexes, sinterable ceramics, hydroxyapatites, silicas, titanium, carbides, oxides, alumina, iron, lead, copper, steel, bronze, phosphor bronze, brass, alloys, bone, and calcium salts.

16. The article of claim 11 further comprising at least one hollow release vessel having the modifying agent therein and the vessels are made of fiberglass fibers, cement fibers, asphalt fibers, hydroxyapatite fibers, glass fibers, ceramic fibers, metal fibers, polyolefin fibers, polyester fibers, polyamide fibers, polyaramide fibers, polyimide fibers, carbon fibers, graphite fibers, cellulose fibers, nitrocellulose fibers, hydrocarbon fibers, Goretex™

fibers, Kevlar™

fibers, silicon nitride fibers, polysiloxane, epoxy, hydrocarbon, polytetrafluoroethylene, polyurethane, aramid, polypropylene, or elastomer

18. The article of claim 11, wherein the coating is a paint, membrane, or roofing material.

19. The article of claim 11, wherein the coating is for an aircraft, automotive, aerospace, or marine application.

20. The article of claim 11, wherein the coating resists cracking, corrosion, and oxidation.

21. The article of claim 11, wherein the coating is a heat sensitive coating, a pH sensitive coating, or an ion sensitive coating.

22. The article of claim 11, wherein the external stimulus is at least one of heating, cooling, loading, impacting, cracking, water infusion, chloride infusion, alkalinity changes, acidity changes, acoustic excitation, low frequency wave excitations, hydrostatic pressure, rolling pressure, light sensitivity, laser excitation, electrical currents, voltages, electrorheological excitation, radiation, or other energetic stimuli.

23. The article of claim 11, wherein the matrix metal is steel and the external stimulus is heat caused by fire or impact caused by earthquake.

24. A shaped article comprising a cured composite matrix material having a modifying agent therein, wherein the modifying agent is capable of beneficially modifying the composite matrix material in response to a stimulus, wherein the cured matrix material comprises metal.

25. The article of claim 24, wherein the metal comprises at least one of aluminum, steel, iron, titanium, lead, copper, bronze, phosphor bronze, brass and other alloys.

26. The article of claim 25 wherein the metal is foamed.

27. The article of claim 24, wherein the matrix further comprises polymer.

28. The article of claim 27, wherein the polymer is a foamed polymer.

29. The article of claim 27, wherein the metal and polymer form a sandwich panel.

30. The article of claim 24, wherein the modifying agent comprises charged ions.

31. The article of claim 30, wherein the charged ions are metallic charged ions.

32. The article of claim 26 wherein the modifying agent comprises a metal particle.

33. The article of claim 24, wherein the metal matrix is steel and the stimulus is heat caused by fire or impact caused by earthquake.

34. The article of claim 24, wherein the metal is aluminum and the modifying agent comprises copper.

35. The article of claim 34 wherein the modifying agent comprises copper and another metal.

36. The article of claim 24, wherein the modifying agent comprises copper and the metal matrix comprises at least one of aluminum, steel, iron, titanium, lead, bronze, phosphor bronze, brass and other alloys.

37. The article of claim 24 further comprising at least one hollow release vessel having the modifying agent therein.

38. The article of claim 37 in which the release vessel is a particle.

39. The article of claim 37 wherein the matrix is carbon and alumina and the release vessels are silicon nitride fibers.

40. The article of claim 39, wherein the article is a piston.

41. The article of claim 24, wherein the article is for an aircraft, automotive, aerospace or marine application.

42. A shaped article comprising a cured composite matrix having a modifying agent therein, wherein the modifying agent is capable of beneficially modifying the cured composite material in response to a stimulus, wherein the cured composite matrix comprises polymeric material.

43. The article of claim 42, wherein the polymeric material comprises at least one of a thermosetting or thermoplastic material.

44. The article of claim 42 wherein the modifying agent comprises at least one of polyolefin, polyester, polyamide, polyaramid, polyimide, carbon, graphite, cellulose, nitrocellulose, hydrocarbon, polytetrafluoroethylene, aramid, polypropylene, and elastomer, one- and two-part adhesives, one- and two-part epoxy adhesives, cyanoacrylate adhesives, Elmer'"'"'s glue, acids, bases, solvents, polysiloxanes, and amines.

45. The article of claim 42 further comprising at least one hollow release vessel having the modifying agent therein and selected from fiberglass fibers, cement fibers, asphalt fibers, hydroxyapatite fibers, glass fibers, ceramic fibers, metal fibers, and the like, polyolefin fibers, polyester fibers, polyamide fibers, polyaramide fibers, polyimide fibers, carbon fibers, graphite fibers, cellulose fibers, nitrocellulose fibers, hydrocarbon fibers, Goretex™

fibers, Kevlar™

fibers, piezoelectric and shape memory alloys.

46. The article of claim 42, wherein the hollow release vessel is a hollow particle having modifying agent therein.

47. The article of claim 46, wherein the modifying agent in the hollow particle is a polyolefin.

49. The article of claim 47 wherein the polyolefin reacts with a chemical in the matrix.

50. The article of claim 42, wherein the modifying agent comprises at least one of aluminum, steel, iron, titanium, lead, copper, bronze, phosphor bronze, brass and other alloys.

51. The article of claim 42 wherein the matrix is cured by means of catalysts, crosslinkers, radiation, heat, moisture, cooling, setting up, hardening, rigidifying, curing, or setting to form the shaped article.

52. The article of claim 42 in which the modifying agent is a polymerizable monomer.

53. The article of claim 52 wherein the monomer is methyl methacrylate, styrene, epoxy, siloxane, or amine.

54. A shaped article comprising a cured composite matrix having a modifying agent therein, wherein the modifying agent is capable of beneficially modifying the cured composite material in response to a stimulus, wherein the cured composite matrix comprises a laminate structure.

55. The article of claim 54 wherein the modifying agent is a layer of the laminate.

56. The article of claim 55 wherein the modifying layer of the laminate performs repair of the article.

58. The article of claim 54 further comprising an epoxy precursor material and an amine cross-linking agent.

57. A shaped article comprising a cured composite matrix having a two-part epoxy modifying agent therein, wherein the modifying agent is capable of beneficially modifying the cured composite material in response to a stimulus, wherein the cured composite matrix comprises polymeric material.

59. A shaped article comprising a cured composite matrix having a plurality of hollow vessels and modifying agent therein, wherein the modifying agent is capable of beneficially modifying the cured composite material in response to a stimulus selected from the group of electrical, magnetic, and chemical means.