Self-Repairing, Reinforced Matrix Materials

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.

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.  
     
     
         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.  
     
     
         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.  
     
     
         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  
     
     
         17 . The article of  claim 1 , wherein the hollow release vessel is a hollow particle.  
     
     
         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.  
     
     
         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.  
     
     
         58 . The article of  claim 54  further comprising an epoxy precursor material and an amine cross-linking agent.  
     
     
         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.