Oriented nanofibers embedded in polymer matrix

Abstract

A method of forming a composite of embedded nanofibers in a polymer matrix is disclosed. The method includes incorporating nanofibers in a plastic matrix forming agglomerates, and uniformly distributing the nanofibers by exposing the agglomerates to hydrodynamic stresses. The hydrodynamic said stresses force the agglomerates to break apart. In combination or additionally elongational flow is used to achieve small diameters and alignment. A nanofiber reinforced polymer composite system is disclosed. The system includes a plurality of nanofibers that are embedded in polymer matrices in micron size fibers. A method for producing nanotube continuous fibers is disclosed. Nanofibers are fibrils with diameters 100 nm, multiwall nanotubes, single wall nanotubes and their various functionalized and derivatized forms. The method includes mixing a nanofiber in a polymer; and inducing an orientation of the nanofibers that enables the nanofibers to be used to enhance mechanical, thermal and electrical properties. Orientation is induced by high shear mixing and elongational flow, singly or in combination. The polymer may be removed from said nanofibers, leaving micron size fibers of aligned nanofibers.

1 . A method for forming a composite of embedded (0-100%) nanofibers in a polymer matrix, comprising: 
 incorporating a plurality of nanofibers in a plastic matrix, said incorporation forming a plurality of agglomerates; and    uniformly distributing said nanofibers by exposing the agglomerates to hydrodynamic stresses, said stresses forcing the agglomerates to break apart.    
     
     
         2 . The method of  claim 1 , further comprising: 
 processing the composite material in a high shear condition using a capillary rheometer or extruder or other fiber spinning processes.    
     
     
         3 . A nanofiber reinforced polymer composite system comprising: 
 a plurality of nanofibers, said nanofibers embedded in polymer matrices in micron size fibers.    
     
     
         4 . A method for producing nanotube continuous fibers, comprising: 
 mixing at least one nanofiber selected from the group consisting of carbon fibrils, multi-walled nanotubes, and single wall nanotubes in a polymer; where these nanofibers may be functionalized or derivatized.    inducing an orientation of the nanofibers that enables said nanofibers to be used to enhance mechanical, thermal and electrical properties.    
     
     
         5 . The method of  claim 4 , further comprising: 
 removing said polymer or binder from said nanofibers, said removal leaving micron size fibers of nanofibers.    
     
     
         14 . The method of  claim 4  wherein said polymer is selected from the group consisting of PP, ABS, PE and UHMW PE.  
     
     
         34 . A composite comprising a network of isotropic dispersions of aligned nanofibers in a polymer matrix for ESD applications.  
     
     
         35 . A composite comprising a network of isotropic dispersions of aligned nanofibers in a polymer matrix for EMURFI applications.  
     
     
         36 . A highly conducting composite comprising isotropic dispersions of aligned nanofibers in a polymer matrix for conducting electrical wire applications.  
     
     
         37 . A composite comprising a isotropic dispersions of aligned nanofibers in a polymer matrix filament for structural applications.  
     
     
         38 . A composite comprising isotropic dispersions of aligned nanofibers in a polymer matrix for thermal applications.  
     
     
         39 . A composite comprising aligned nanofiber reinforced polymer formed by a FDM processing.  
     
     
         40 . FDM components formed from aligned nanofibers in a polymer matrix.  
     
     
         41 . A composite comprising aligned nanofiber reinforced polymer formed by a FDM processing for ESD applications.  
     
     
         42 . A composite comprising aligned nanofiber reinforced polymer formed by a FDM processing for EMLRFI applications.  
     
     
         43 . A composite comprising aligned nanofiber reinforced polymer formed by a FDM processing for thermal applications.  
     
     
         44 . A composite comprising aligned nanofiber reinforced polymer formed by a FDM processing for mechanical applications.  
     
     
         45 . A composite comprising aligned nanofiber reinforced polymer wherein said nanotubes are integrated into a polymer matrix.  
     
     
         46 . The composite of  claim 45  wherein said nanotube integration is by tip attachment and/or side wall functionalization, coincident polymerization, or high shear alignment.  
     
     
         47 . The method of  claim 2  wherein said processing the composite material in a high shear condition using a capillary rheometer or extruder or other fiber spinning processes comprises wet spinning, dry spinning, melt spinning or gel spinning.  
     
     
         48 . A tailored multifunctional reinforced polymer composite system comprising: 
 a plurality of nanofibers, said nanofibers embedded in polymer matrices in micron size fibers.    
     
     
         49 . A multifunctional reinforced polymer composite system comprising a plurality of nanofibers, said nanofibers embedded in polymer matrices in micron size fibers, suitable for further processing to provide composite forms including weaves, mats, plies, filament wound tubing and vessels.  
     
     
         50 . The method of  claim 4  further comprising the steps of: 
 mixing one or more nanofibers selected from said group in a polymer to disperse said nanofibers to the desired range of dispersion and to provide a mix;    processing said mix in a high shear condition;    inducing an orientation of the nanofibers while extruding at least one continuous filament selected from the group consisting of fibers, films, and tapes.    
     
     
         51 . The method of  claim 50  further comprising subjecting said at least one continuous filament to elongational flow.  
     
     
         52 . The method of  claim 50  wherein said mixing and nanofiber dispersion are provided by a Banbury-type mixing.  
     
     
         53 . The method of  claim 50  wherein said mixing and the extruding are accomplished in a multiple zone compounding extruder where the mixing residence is held for sufficient time followed by extrusion of a dispersed nanofiber system.  
     
     
         54 . The method of  claim 51  wherein said mixing and the extruding are accomplished in a multiple zone compounding extruder where the mixing residence is held for sufficient time followed by extrusion of a dispersed nanofiber system.  
     
     
         55 . The method of  claim 4  further comprising the step of purifying as-received single wall nanotubes.  
     
     
         56 . The method of  claim 50  further comprising the step of purifying as-received single wall nanotubes.  
     
     
         57 . The method of  claim 4  further comprising the steps of selecting a polymer in powder form; 
 drying the polymer powder; 
 mixing said powder with said nanofibers in a solvent to form a slurry;  
 drying said slurry to remove all said solvent to form chunks of agglomerated powder with highly dispersed nanofibers.  
   
     
     
         58 . The method of  claim 50  further comprising the steps of selecting a polymer in powder form; 
 drying the polymer powder;    mixing said powder with said nanofibers in a solvent to form a slurry;    drying said slurry to remove all said solvent to form chunks of agglomerated powder with highly dispersed nanofibers.    
     
     
         59 . The method of  claim 57  wherein said solvent is toluene.  
     
     
         60 . The method of  claim 58  wherein said solvent is toluene.  
     
     
         61 . The method of  claim 57  wherein said solvent is dimethyl formamide (DMF).  
     
     
         62 . The method of  claim 58  wherein said solvent is dimethyl formamide (DMF).  
     
     
         63 . Aligned nanofibers packaged in a polymer matrix for subsequent handling and processing formed by: 
 mixing at least one nanofiber selected from said group in a polymer to disperse said nanofibers to the desired range of dispersion;    processing said mix in a high shear condition; 
 inducing an orientation of the nanofibers while extruding at least one continuous filament selected from the group consisting of fibers, films, and tapes.  
   
     
     
         64 . The packaged aligned nanofibers of  claim 65  wherein said formation process further comprises subjecting said extruded filament or filaments to elongational flow.  
     
     
         65 . A woven composite comprising the packaged nanofibers of  claim 63  or  64 .  
     
     
         66 . A laid up composite comprising the packaged nanofibers of  claim 63  or  64 .  
     
     
         67 . A bundled composite comprising the packaged nanofibers of  claim 63  or  64 .  
     
     
         68 . A composite comprising rows of the packaged nanofibers of  claim 63  or  64 .  
     
     
         69 . A composite comprising bundles of the packaged nanofibers of  claim 63  or  64 .  
     
     
         70 . A yarn comprising the packaged nanofibers of claims  63  or  64 .  
     
     
         71 . A thread comprising the packaged nanofibers of  claim 63  or  64 .  
     
     
         72 . The composite of claims  63  through  71  wherein said polymer binder has been removed leaving micron size fibers of only nanofibers.  
     
     
         73 . the composite of claims  63  through  72  wherein said polymer is selected from the group of Acetal, PP, ABS, ASA, PE, PEK, PEEK, PET and UHMW PE.  
     
     
         74 . The composite of claims  63  through  72  wherein said matrix is selected from the group of epoxies and resins.  
     
     
         75 . The method of  claim 4  or  5  further comprising the step of fully integrating said composites by one or more of the processes of integration, dispersion and alignment, derivatization, functionalization, and polymerization so that said nanotubes are part of said matrix.  
     
     
         77 . A fully integrated nanofiber composite comprising the composite of claims  63  through  74  further subjected to one or more of the processes of integration, dispersion and alignment, derivatization, functionalization, and polymerization to integrate said nanofibers into part of said matrix.  
     
     
         78 . The composite of  claim 77  comprising gas permeable polymer for gas sensor applications.  
     
     
         79 . The composite of  claim 77  for electronic, wiring or interconnecting applications.  
     
     
         80 . The composite of  claim 79  comprising 10% byweight of SWNT.  
     
     
         81 . The fully integrated nanofiber composite of  claim 77  further subjected to a toughening process to form a fully integrated toughened nanotube composite surpassing the limits of the rule of mixtures.  
     
     
         82 . The composite of claims  81  wherein said matrix material is PP or nylon.  
     
     
         83 . A shielding material extending to hypervelocity impact applications formed from the composite of  claim 82 .  
     
     
         84 . The method of claims  4 ,  5  or  14  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         85 . The method of claims  50 - 62  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         86 . Aligned nanofibers packaged in a polymer matrix for subsequent handling and processing formed by: 
 mixing one or more nanofibers selected from the group consisting of carbon fibrils, multi-walled nanotubes, and single wall nanotubes in a polymer to disperse said nanofibers to the desired range of dispersion and to provide a mix;    processing said mix in a high shear condition; and    inducing an orientation of the nanofibers while extruding at least one continuous filament selected from the group consisting of fibers, films, and tapes.    
     
     
         87 . The packaged nanofibers of  claim 86  wherein said process further comprises subjecting said at least one continuous filament to elongational flow.  
     
     
         88 . A woven composite comprising the packaged nanofibers of  claim 86 .  
     
     
         89 . A laid up composite comprising the packaged nanofibers of claims  86 .  
     
     
         90 . A bundled composite comprising the packaged nanofibers of  claim 86 .  
     
     
         91 . A composite comprising rows of the packaged nanofibers of  claim 86 .  
     
     
         92 . A composite comprising bundles of the packaged nanofibers of  claim 86 .  
     
     
         93 . A yarn comprising the packaged nanofibers of  claim 86 .  
     
     
         94 . A thread comprising the packaged nanofibers of  claim 86 .  
     
     
         95 . The composite of  claim 86  wherein said polymer has been removed leaving micron size fibers of nanofibers.  
     
     
         96 . The composite of  claim 87  wherein the polymer has been removed leaving micron size fibers of nanofibers.  
     
     
         97 . The composite of  claim 88  wherein said polymer has been removed leaving micron size fibers of nanofibers.  
     
     
         98 . The composite of claims  89  wherein said polymer has been removed leaving micron size fibers of nanofibers.  
     
     
         99 . The composite of  claim 90  wherein said polymer has been removed leaving micron size fibers of nanofibers.  
     
     
         100 . The composite of  claim 91  wherein said polymer has been removed leaving micron size fibers of nanofibers.  
     
     
         101 . The composite of  claim 92  wherein said polymer has been removed leaving micron size fibers of nanofibers.  
     
     
         102 . The composite of  claim 93  wherein said polymer has been removed leaving micron size fibers of nanofibers.  
     
     
         103 . The composite of  claim 94  wherein said polymer has been removed leaving micron size fibers of nanofibers.  
     
     
         104 . The composite of  claim 86  wherein said polymer is selected from the group consisting of Acetal, PP, ABS, ASA, PE, PEK, PEEK, PET and UHMW PE.  
     
     
         105 . The composite of  claim 87  wherein said polymer is selected from the group consisting of Acetal, PP, ABS, ASA, PE, PEK, PEEK, PET and UHMW PE.  
     
     
         106 . The composite of  claim 88  wherein said polymer is selected from the group consisting of Acetal, PP, ABS, ASA, PE, PEK, PEEK, PET and UHMW PE.  
     
     
         107 . The composite of  claim 89  wherein said polymer is selected from the group consisting of Acetal, PP, ABS, ASA, PE, PEK, PEEK, PET and UHMW PE.  
     
     
         108 . The composite of  claim 90  wherein said polymer is selected from the group consisting of Acetal, PP, ABS, ASA, PE, PEK, PEEK, PET and UHMW PE.  
     
     
         109 . The composite of  claim 91  wherein said polymer is selected from the group consisting of Acetal, PP, ABS, ASA, PE, PEK, PEEK, PET and UHMW PE.  
     
     
         110 . The composite of  claim 92  wherein said polymer is selected from the group consisting of Acetal, PP, ABS, ASA, PE, PEK, PEEK, PET and UHMW PE.  
     
     
         111 . The composite of  claim 93  wherein said polymer is selected from the group consisting of Acetal, PP, ABS, ASA, PE, PEK, PEEK, PET and UHMW PE.  
     
     
         112 . The composite of  claim 94  wherein said polymer is selected from the group consisting of Acetal, PP, ABS, ASA, PE, PEK, PEEK, PET and UHMW PE.  
     
     
         113 . The composite of  claim 95  wherein said polymer is selected from the group consisting of Acetal, PP, ABS, ASA, PE, PEK, PEEK, PET and UHMW PE.  
     
     
         114 . The composite of  claim 86  wherein said matrix is selected from the group consisting of epoxies and resins.  
     
     
         115 . The composite of  claim 87  wherein said matrix is selected from the group consisting of epoxies and resins.  
     
     
         116 . The composite of  claim 88  wherein said matrix is selected from the group consisting of epoxies and resins.  
     
     
         117 . The composite of  claim 89  wherein said matrix is selected from the group consisting of epoxies and resins.  
     
     
         118 . The composite of  claim 90  wherein said matrix is selected from the group consisting of epoxies and resins.  
     
     
         119 . The composite of  claim 91  wherein said matrix is selected from the group consisting of epoxies and resins.  
     
     
         120 . The composite of  claim 92  wherein said matrix is selected from the group consisting of epoxies and resins.  
     
     
         121 . The composite of  claim 93  wherein said matrix is selected from the group consisting of epoxies and resins.  
     
     
         122 . The composite of  claim 94  wherein said matrix is selected from the group consisting of epoxies and resins.  
     
     
         123 . The composite of  claim 95  wherein said matrix is selected from the group consisting of epoxies and resins.  
     
     
         124 . The method of  claim 4  further comprising the step of integrating said nanofibers by a process selected from the group consisting of integration, dispersion and alignment, derivatization, functionalization, polymerization, and combinations thereof.  
     
     
         125 . An integrated nanofiber composite comprising the composite of  claim 86  further subjected to a process selected from the group consisting of integration, dispersion and alignment, derivatization, functionalization, polymerization, and combinations thereof.  
     
     
         126 . An integrated nanofiber composite comprising the composite of  claim 87  further subjected to a process selected from the group consisting of integration, dispersion and alignment, derivatization, functionalization, polymerization, and combinations thereof.  
     
     
         127 . An integrated nanofiber composite comprising the composite of  claim 88  further subjected to a process selected from the group consisting of integration, dispersion and alignment, derivatization, functionalization, polymerization, and combinations thereof.  
     
     
         128 . An integrated nanofiber composite comprising the composite of  claim 89  further subjected to a process selected from the group consisting of integration, dispersion and alignment, derivatization, functionalization, polymerization, and combinations thereof.  
     
     
         129 . An integrated nanofiber composite comprising the composite of  claim 90  further subjected to a process selected from the group consisting of integration, dispersion and alignment, derivatization, functionalization, polymerization, and combinations thereof.  
     
     
         130 . An integrated nanofiber composite comprising the composite of  claim 91  further subjected to a process selected from the group consisting of integration, dispersion and alignment, derivatization, functionalization, polymerization, and combinations thereof.  
     
     
         131 . An integrated nanofiber composite comprising the composite of  claim 92  further subjected to a process selected from the group consisting of integration, dispersion and alignment, derivatization, functionalization, polymerization, and combinations thereof.  
     
     
         132 . An integrated nanofiber composite comprising the composite of  claim 93  further subjected to a process selected from the group consisting of integration, dispersion and alignment, derivatization, functionalization, polymerization, and combinations thereof.  
     
     
         133 . An integrated nanofiber composite comprising the composite of  claim 94  further subjected to a process selected from the group consisting of integration, dispersion and alignment, derivatization, functionalization, polymerization, and combinations thereof.  
     
     
         134 . An integrated nanofiber composite comprising the composite of  claim 95  further subjected to a process selected from the group consisting of integration, dispersion and alignment, derivatization, functionalization, polymerization, and combinations thereof.  
     
     
         135 . An integrated nanofiber composite comprising the composite of  claim 104  further subjected to a process selected from the group consisting of integration, dispersion and alignment, derivatization, functionalization, polymerization, and combinations thereof.  
     
     
         136 . An integrated nanofiber composite comprising the composite of  claim 114  further subjected to a process selected from the group consisting of integration, dispersion and alignment, derivatization, functionalization, polymerization, and combinations thereof.  
     
     
         137 . The method of  claim 4  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         138 . The method of  claim 5  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         139 . The method of  claim 14  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         140 . The method of  claim 50  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         141 . The method of  claim 51  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         142 . The method of  claim 52  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         143 . The method of  claim 53  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         144 . The method of  claim 54  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         145 . The method of  claim 55  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         146 . The method of  claim 56  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         147 . The method of  claim 57  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         148 . The method of  claim 58  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         149 . The method of  claim 59  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         150 . The method of  claim 60  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         151 . The method of  claim 61  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         152 . The method of  claim 62  wherein said orientation is induced by fused deposition modeling processing.  
     
     
         153 . The composite of  claim 125  comprising a gas permeable polymer for gas sensor applications.  
     
     
         154 . The composite of  claim 125  for electronic, wiring or interconnecting applications.  
     
     
         155 . The composite of  claim 125  comprising 10 percent by weight of SWNT.  
     
     
         156 . The composite of  claim 125  further subjected to a toughening process to form a toughened nanotube composite surpassing the limits of the rule of mixtures.  
     
     
         157 . The composite of  claim 156  wherein said matrix materials comprise PP or nylon.  
     
     
         158 . A shielding material extending to hypervelocity impact applications formed from the composite of  claim 157 .  
     
     
         159 . The method of  claim 1  wherein the concentration of said nanofibers is in a range of from about 0 to about 100 weight percent.  
     
     
         160 . The method of  claim 1  wherein said composite provides a delivery system for handling said nanofibers.  
     
     
         161 . The method of  claim 1  wherein said composite provides a package for handling said nanofibers.  
     
     
         162 . The method of  claim 1  wherein said polymer comprises a gas permeable polymer that provides for said composite capable of being utilized as a gas sensor.  
     
     
         163 . The method of  claim 1  wherein said nanofibers provide for enhancing the thermophysical characteristics of said polymer.  
     
     
         164 . The method of  claim 1  wherein said nanofibers provide for an increase in the degradation temperature of said polymer.  
     
     
         165 . The method of  claim 1  wherein said nanofibers are linked to a polymer.  
     
     
         166 . The method of  claim 1  wherein said nanofibers are linked together.  
     
     
         167 . The method of  claim 1  wherein said nanofibers are optimized for non-wetted or unbound conditions.  
     
     
         168 . The method of  claim 1  wherein said composite is further chemically treated.  
     
     
         169 . The method of  claim 1  wherein said composite is capable of being used as a wire or electrical interconnect.  
     
     
         170 . The method of  claim 1  wherein said composite achieves conduction via said nanofibers.  
     
     
         171 . The method of  claim 1  wherein said uniformly distributing comprises gel-spinning.  
     
     
         172 . The method of  claim 1  wherein said uniformly distributing comprises the use of a fused deposition modeling system.  
     
     
         173 . The method of  claim 1  wherein said process further comprises quenching.  
     
     
         174 . The method of  claim 1  wherein said composite is used for the production of electrostatic discharge materials by integration.  
     
     
         175 . The method of  claim 1  wherein said nanofibers act as nucleation sites.  
     
     
         176 . The method of  claim 1  wherein said nanofibers affect crystallization of said polymer.  
     
     
         177 . The method of  claim 1  wherein said nanofibers affect the molecule morphology of said polymer.  
     
     
         178 . The method of  claim 1  wherein said process further comprises thinning to help provide for a translucent composite providing for increased visibility.  
     
     
         179 . The method of  claim 1  wherein the toughness of said composite is lower and the strength and rigidity of said composite are higher compared to pure ABS.  
     
     
         180 . The method of  claim 1  wherein a ceramic is used in place of said polymer.  
     
     
         181 . The method of  claim 1  wherein connections are present between said nanofibers and said polymer and further wherein said connections provide for enhanced mechanical properties.  
     
     
         182 . The method of  claim 1  wherein said composite provides for a system having properties similar to Kevlar or ultra-high-density polyethylene.  
     
     
         183 . The method of  claim 1  wherein said polymer comprises a gas permeable polymer and further wherein said gas permeable polymer provides for altering the electrical conduction of said polymer when in contact with a gas.  
     
     
         184 . The method of  claim 1  wherein carbon sheets that mimic nanotubes are used in place of said nanofibers.