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 composite matrix material having a modifying agent in at least one hollow release vessel, 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 and the coating material is an anticorrosion material over metal.  
     
     
         2 . The article of  claim 1 , wherein the hollow release vessel is a hollow particle.  
     
     
         3 . The article of  claim 1  wherein the coating material has more than one release vessel.  
     
     
         4 . The article of  claim 3  wherein an anticorrosion material and an anti-cracking material are in the release vessels.  
     
     
         5 . The article of  claim 4  wherein the vessels have a diameter of less than 100 microns.  
     
     
         6 . The article of  claim 3  wherein the modifying agent is also a dye.  
     
     
         7 . The article of  claim 3  wherein the release vessels comprise fiberglass, cement, asphalt, hydroxyapatite, glass, ceramic, metal, polyolefin, polyester, polycarbonate, polyacrylate, polyarylate, polyamide, polyimide, polyaramide, polyurethane, carbon, graphite, cellulose, nitrocellulose, hydrocarbon, or piezoelectric material.  
     
     
         8 . A corrosion protective coating composition, comprising: 
 a) a coating matrix, and    b) a plurality of hollow vessels within the coating matrix, the vessels containing therein a modifying chemical comprising a self repairing component and a corrosion inhibitor.    
     
     
         9 . The corrosion protective coating composition of  claim 8  wherein the corrosion inhibitor is calcium nitrate.  
     
     
         10 . The corrosion protective coating composition of  claim 8  comprising an epoxy precursor and a amine crosslinking agent.  
     
     
         11 . The corrosion protective coating composition of  claim 8  wherein the coating matrix comprises at least one of polyolefin, polyester, polyamide, polyaramid, polyimide, carbon, graphite, cellulose, nitrocellulose, polysiloxane, epoxy, hydrocarbon, polytetrafluoroethylene, polyurethane, aramid, polypropylene, and elastomer, one- and two-part adhesives, one- and two-part epoxy adhesives, cyanoacrylate adhesives, Elmer's glue, amines, polysiloxanes, one- and two-part adhesives, one- and two-part epoxy adhesives, cyanoacrylate adhesives, sealant, siloxane, silica additives, calcium nitrate, polyprolylene glycol, amines and other crosslinkers, epoxy precursers, 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, 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, phenolformaldehyde resins, rubbery polymers, butadiene, rubber, neoprene, SEBS, NBR, and EPDM rubbers, viscoelastic materials, latexes, sinterable ceramics, hydroxyapatites, silicas, titanium, carbides, oxides, alumina, iron, lead, copper, bronze, phosphor bronze, brass bronze, and calcium salts.  
     
     
         12 . The corrosion protective coating composition of  claim 8  wherein the plurality of vessels includes walls comprising a frangible material having structural integrity.  
     
     
         13 . The corrosion protective coating composition of  claim 12  wherein the frangible vessles are glass, cellulose, polymeric, fiberglass, cement, asphalt, hydroxyapatite, glass, ceramic, metal, polyolefin, polyester, polycarbonate, polyacrylate, polyarylate, polyamide, polyimide, polyaramide, polyurethane, carbon, graphite, cellulose, nitrocellulose, hydrocarbon, or piezoelectric material.  
     
     
         14 . The corrosion protective coating composition of  claim 13  wherein the vessels have a diameter of less than 100 microns.  
     
     
         15 . A corrosion protective coating composition, comprising: 
 (a) a coating matrix;    (b) a plurality of vessels containing a corrosion inhibitor, and    (c) a plurality of vessels containing a self repairing modifying agent, the plurality of vessels being distributed throughout the matrix.    
     
     
         16 . The corrosion protective coating composition of  claim 15  further comprising a plurality of vessels containing a dye.  
     
     
         17 . The corrosion protective coating composition of  claim 15  wherein the coating matrix is selected from the group consisting of epoxy resins, polyester resins, polyurethane resins, resins, resins, acrylic resins and nylon.  
     
     
         18 . The corrosion protective coating of  claim 15  wherein the plurality of vessels includes walls comprising a frangible material having structural integrity.  
     
     
         19 . The corrosion protective coating composition of  claim 18  wherein the frangible material comprises at least one of glass, cellulose, polymeric, fiberglass, cement, asphalt, hydroxyapatite, glass, ceramic, metal, polyolefin, polyester, polycarbonate, polyacrylate, polyarylate, polyamide, polyimide, polyaramide, polyurethane, carbon, graphite, cellulose, nitrocellulose, hydrocarbon, shape memory alloy, magnetostrictive, and piezoelectric material.  
     
     
         20 . The corrosion protective coating composition of  claim 15  wherein the vessels have a diameter of less than 100 microns.  
     
     
         21 . A corrosion protective layer, comprising: 
 (a) a resin matrix, and    (b) a plurality of frangible vessels dispersed in the resin matrix, the vessels containing a fluid modifying agent to effect repair of the protective layer when damaged.    
     
     
         22 . The corrosion protective layer of  claim 21  wherein the modifying agent composition comprises a corrosion inhibitor and a repair agent.  
     
     
         23 . The corrosion protective layer of  claim 22  wherein the repair agent is a dye marker.  
     
     
         24 . The corrosion protective layer of  claim 21  wherein the resin matrix comprises at least one of polyolefin, polyester, polyamide, polyaramid, polyimide, carbon, graphite, hydrocarbon, aramid, polypropylene, and elastomer, latex, one- and two-part adhesives, one- and two-part epoxy adhesives, cyanoacrylate adhesives, Elmer's glue, acids, bases, solvents, polysiloxanes, and amines.