Macroscopic ordered assembly of carbon nanotubes

Abstract

The present invention is directed to the creation of macroscopic materials and objects comprising aligned nanotube segments. The invention entails aligning single-wall carbon nanotube (SWNT) segments that are suspended in a fluid medium and then removing the aligned segments from suspension in a way that macroscopic, ordered assemblies of SWNT are formed. The invention is further directed to controlling the natural proclivity of nanotube segments to self assemble into ordered structures by modifying the environment of the nanotubes and the history of that environment prior to and during the process. The materials and objects are “macroscopic” in that they are large enough to be seen without the aid of a microscope or of the dimensions of such objects. These macroscopic, ordered SWNT materials and objects have the remarkable physical, electrical, and chemical properties that SWNT exhibit on the microscopic scale because they are comprised of nanotubes, each of which is aligned in the same direction and in contact with its nearest neighbors. An ordered assembly of closest SWNT also serves as a template for growth of more and larger ordered assemblies. An ordered assembly further serves as a foundation for post processing treatments that modify the assembly internally to specifically enhance selected material properties such as shear strength, tensile strength, compressive strength, toughness, electrical conductivity, and thermal conductivity.

1 - 63 . (canceled)  
     
     
         64 . A method for forming a macroscopic assembly of substantially aligned single-wall carbon nanotubes, comprising: 
 (a) suspending a plurality of single-wall carbon nanotubes in a suspending medium to form a suspension;    (b) subjecting the single-wall carbon nanotubes to an aligning field, whereby the single-wall carbon nanotubes align with the field;    (c) aggregating the aligned single-wall carbon nanotubes while said single-wall carbon nanotubes are subject to the aligning field; and    (d) separating the single-wall carbon nanotubes from the suspending medium.    
     
     
         65 . The method of  claim 64  wherein the suspending medium is oleum.  
     
     
         66 . The method of  claim 64  wherein the suspending medium is selected from the group consisting of dimethylformamide, surfactant and water, sol-gel, and molten metal.  
     
     
         67 . The method of  claim 64  wherein the suspending medium is water and the single-wall carbon nanotubes are bound to chemical compositions which result in the suspension of the single-wall carbon nanotubes in said water.  
     
     
         68 . The method of  claim 67  wherein the chemical compositions are selected from the group consisting of polymers and peptides.  
     
     
         69 . The method of  claim 68  wherein the polymer is polystyrene.  
     
     
         70 . The method of  claim 64  wherein the aligning field is selected from the group consisting of a magnetic field, an electric field, a shear flow field, and combinations thereof.  
     
     
         71 . The method of  claim 64  wherein the aligning field comprises a magnetic field.  
     
     
         72 . The method of  claim 64  wherein said single-wall carbon nanotubes are selected from the group consisting of derivatized single-wall carbon nanotubes, underivatized single-wall carbon nanotubes, and combinations thereof.  
     
     
         73 . The method of  claim 64  wherein the single-wall carbon nanotubes are aggregated by a method selected from the group consisting of (a) filtering the suspension whereby the substantially aligned single-wall carbon nanotubes remain on the filter, (b) adding salt to the suspension, (c) applying an electric field to the suspension; (d) allowing the single-wall carbon nanotubes to settle from the suspension; (e) evaporating the suspending medium; and (f) combinations thereof.  
     
     
         74 . The method of  claim 73  wherein the salt is magnesium chloride.  
     
     
         75 . The method of  claim 64  wherein the macroscopic assembly is in a form selected from the group consisting of ropes, fibers, cables, membranes, arrays, buckypapers, and buckyribbons.  
     
     
         76 . The method of  claim 75  wherein said membranes are at least about 1 micron thick.  
     
     
         77 . The method of  claim 75  wherein said membranes are about 10 microns thick.  
     
     
         78 . The method of  claim 75  wherein said membranes are at least about 10 microns thick.  
     
     
         79 . The method of  claim 75  wherein the single-wall carbon nanotubes in said membrane are parallel to the plane of the membrane.  
     
     
         80 . The method of  claim 75  wherein the single-wall carbon nanotubes in said membrane are perpendicular to the plane of the membrane.  
     
     
         81 . A method for forming a macroscopic assembly of substantially aligned single-wall carbon nanotubes, comprising: 
 (a) suspending a plurality of single-wall carbon nanotubes in a suspending medium to form a suspension;    (b) subjecting the single-wall carbon nanotubes to a magnetic field, whereby the single-wall carbon nanotubes become aligned with the magnetic field;    (c) aggregating the single-wall carbon nanotubes; and    (d) separating the single-wall carbon nanotubes from the suspending medium.    
     
     
         82 . The method of  claim 81  wherein said magnetic field is selected from the group consisting of an alternating current magnetic field and a direct current magnetic field.  
     
     
         83 . The method of  claim 81  wherein said magnetic field is generated by a source selected from the group consisting of a permanent magnet, an electromagnet, a superconducting electromagnet, and an electrical current flowing in a conductive structure.  
     
     
         84 . The method of  claim 81  wherein the magnetic field has a strength of at least about 0.5 Tesla.  
     
     
         85 . The method of  claim 81  wherein said single-wall carbon nanotubes are selected from the group consisting of derivatized single-wall carbon nanotubes, underivatized single-wall carbon nanotubes, and combinations thereof.  
     
     
         86 . The method of  claim 81  wherein the suspending medium is selected from the group consisting of oleum, dimethylformamide, surfactant and water, and sol-gel.  
     
     
         87 . The method of  claim 81  wherein the suspending medium is water and the single-wall carbon nanotubes are bound to chemical compositions which result in the suspension of the single-wall carbon nanotubes in said water.  
     
     
         88 . The method of  claim 87  wherein the chemical compositions are selected from the group consisting of polymers and peptides.  
     
     
         89 . The method of  claim 88  wherein the polymer is polystyrene.  
     
     
         90 . The method of  claim 81  wherein the single-wall carbon nanotubes are caused to come out of suspension by a method selected from the group consisting of (a) filtering the suspension whereby the substantially aligned single-wall carbon nanotubes remain on the filter, (b) adding salt to the suspension, (c) applying an electric field to the suspension; (d) allowing the single-wall carbon nanotubes to settle from the suspension; (e) evaporating the suspending medium; and (f) combinations thereof.  
     
     
         91 . The method of  claim 81  wherein said step of aggregating the single-wall carbon nanotubes occurs while the single-wall carbon nanotubes are subject to the magnetic field.  
     
     
         92 . The method of  claim 90  wherein the salt is magnesium chloride.  
     
     
         93 . The method of  claim 81  wherein the macroscopic assembly is in a form selected from the group consisting ropes, fibers, cables, membranes, arrays, buckypapers, and buckyribbons.  
     
     
         94 . The method of  claim 93  wherein said membranes are at least about 1 micron thick.  
     
     
         95 . The method of  claim 93  wherein said membranes are about 10 microns thick.  
     
     
         96 . The method of  claim 93  wherein said membranes are at least about 10 microns thick.  
     
     
         97 . The method of  claim 93  wherein the single-wall carbon nanotubes in said membrane are parallel to the plane of the membrane.  
     
     
         98 . The method of  claim 93  wherein the single-wall carbon nanotubes in said membrane are perpendicular to the plane of the membrane.  
     
     
         99 . A method for forming a macroscopic ordered assembly of single-wall carbon nanotubes, comprising: 
 (a) suspending a plurality of single-wall carbon nanotubes in a suspending medium to form a suspension;    (b) subjecting the single-wall carbon nanotubes to a shear flow field by extrusion, whereby the single-wall carbon nanotubes become aligned; and    (c) removing the suspending medium from the single-wall carbon nanotubes.    
     
     
         100 . The method of  claim 99  wherein the macroscopic ordered assembly is in a form selected from the group consisting ropes, fibers, cables, membranes, arrays, buckypapers, and buckyribbons.  
     
     
         101 . The method of  claim 100  wherein the ropes are about 0.1 μm in diameter.  
     
     
         102 . The method of  claim 100  wherein the ropes are at least about 0.1 μm in diameter.  
     
     
         103 . The method of  claim 100  wherein the membrane comprises single-wall carbon nanotubes substantially parallel to the plane of the membrane.  
     
     
         104 . The method of  claim 99  wherein the suspending medium is oleum.  
     
     
         105 . The method of  claim 99  wherein the suspending medium is removed by water.  
     
     
         106 . The method of  claim 99  wherein said single-wall carbon nanotubes are selected from the group consisting of derivatized single-wall carbon nanotubes, underivatized single-wall carbon nanotubes, and combinations thereof.  
     
     
         107 . The method of  claim 99  further comprising joining macroscopic ordered assemblies of single-wall carbon nanotubes to make larger assemblies.  
     
     
         108 . The method of  claim 107  wherein the segments of single-wall carbon nanotubes in the macroscopic ordered assemblies are joined either at their ends, their sides or both.  
     
     
         109 . The method of  claim 107  wherein the joining method is selected from the group consisting of chemical cross-linking, heating, energetic particle radiation, electron beam bombardment, and combinations thereof.  
     
     
         110 . The method of  claim 109  wherein said chemical cross-linking is achieved by intercalating a chemical agent into the macroscopic ordered assemblies.  
     
     
         111 . The method of  claim 110  wherein said chemical agent is an acid.  
     
     
         112 . The method of  claim 110  wherein said chemical agent is sulfuric acid.  
     
     
         113 . The method of  claim 109  wherein the temperature of said heating is between about 300° C. and about 1500° C.  
     
     
         114 . The method of  claim 109  wherein the temperature of said heating is between about 900° C. and about 1300° C.  
     
     
         115 . The method of  claim 109  wherein said heating occurs in the presence of hydrogen.  
     
     
         116 . The method of  claim 99  wherein said extrusion occurs in the presence of an aligning field.  
     
     
         117 . A method for assembling single-wall carbon nanotubes on a substrate comprising: 
 (a) providing a plurality of single-wall carbon nanotubes selected from the group consisting of a solution of the single-wall carbon nanotubes and a suspension of the single-wall carbon nanotubes;    (b) subjecting the single-wall carbon nanotubes to an aligning field, whereby the single-wall carbon nanotubes align with the field;    (c) contacting said aligned single-wall carbon nanotubes with a substrate; and    (d) forming a three-dimensional structure of substantially aligned single-wall carbon nanotubes on the substrate.    
     
     
         118 . The method of  claim 117  wherein the single-wall carbon nanotubes are selected from the group consisting of derivatized single-wall carbon nanotubes, underivatized single-wall carbon nanotubes, and combinations thereof.  
     
     
         119 . The method of  claim 118  wherein said derivatized single-wall carbon nanotubes are selected from the group consisting of end-derivatized single-wall carbon nanotubes, side-derivatized single-wall carbon nanotubes, and combinations thereof.  
     
     
         120 . The method of  claim 117  wherein the suspending medium is selected from the group consisting of oleum, dimethylformamide, surfactant and water, sol-gel, and molten metal.  
     
     
         121 . The method of  claim 117  wherein the aligning field is selected from the group consisting of a magnetic field, an electric field, and combinations thereof.  
     
     
         122 . The method of  claim 117  wherein the substrate comprises a component selected from the group consisting of a fiber, a metal, an ordered assembly of single-wall carbon nanotubes, and highly oriented pyrolytic graphite.  
     
     
         123 . The method of  claim 122  wherein the metal substrate is gold.  
     
     
         124 . The method of  claim 122  wherein the fiber substrate is selected from the group consisting of carbon fiber and metal wire.  
     
     
         125 . The method of  claim 117  wherein the single-wall carbon nanotubes are contacted with the substrate by a method selected from the group consisting of chemical bonding, non-covalent bonding, physical contacting, and combinations thereof.  
     
     
         126 . The method of  claim 117  wherein the single-wall carbon nanotubes are contacted with the substrate by a method selected from the group consisting of moving the substrate through the suspending medium, condensing said plurality of single-wall carbon nanotubes on the substrate, and combinations thereof.  
     
     
         127 . The method of  claim 117  wherein the single-wall carbon nanotubes migrate to the substrate.  
     
     
         128 . The method of  claim 117  wherein an electric field is applied to the plurality of single-wall carbon nanotubes.  
     
     
         129 . The method of  claim 117  wherein the single-wall carbon nanotubes are substantially perpendicular to the substrate.  
     
     
         130 . The method of  claim 117  wherein the single-wall carbon nanotubes are substantially parallel to the substrate.  
     
     
         131 . The method of  claim 117  wherein the three-dimensional structure of substantially aligned single-wall carbon nanotubes on a substrate is in a form selected from the group consisting ropes, fibers, cables, membranes, arrays, buckypapers, and buckyribbons.  
     
     
         132 . A method for forming a composite of substantially aligned single-wall carbon nanotubes and a solid matrix material: 
 (a) providing a suspension of single-wall carbon nanotubes in a liquid;    (b) subjecting the single-wall carbon nanotubes to an aligning field, whereby the single-wall carbon nanotubes align with the field; and    (c) converting the liquid to a solid matrix material thereby forming a composite of substantially aligned single-wall carbon nanotubes and solid matrix material.    
     
     
         133 . The method of  claim 132  wherein the liquid is selected from the group consisting of polymer, sol-gel and molten metal.  
     
     
         134 . The method of  claim 133  where said metal is aluminum.  
     
     
         135 . The method of  claim 132  wherein the aligning field is selected from the group consisting of a magnetic field, an electric field, a shear flow field, and combinations thereof.  
     
     
         136 . The method of  claim 132  wherein said single-wall carbon nanotubes are selected from the group consisting of derivatized single-wall carbon nanotubes, underivatized single-wall carbon nanotubes, and combinations thereof.  
     
     
         137 . The method of  claim 132  wherein the liquid is converted to a solid matrix material by cooling.  
     
     
         138 . The method of  claim 132  further comprising removing the solid matrix material from the composite.  
     
     
         139 . The method of  claim 138  wherein the method of removal of the solid matrix material is selected from the group consisting of heating, acid etching and combinations thereof.  
     
     
         140 . The method of  claim 132  wherein the conversion of the liquid to a solid matrix material is in the presence of the aligning field.  
     
     
         141 . A method of forming a macroscopic three-dimensional structure from field-aligned single-wall carbon nanotubes comprising: 
 (a) suspending a plurality of single-wall carbon nanotubes in a suspending medium to form a suspension;    (b) subjecting the single-wall carbon nanotubes to a field that is selected from the group consisting of electric fields, magnetic fields, and shear flow fields, whereby the single-wall carbon nanotubes become aligned substantially parallel with the field; and    (c) modifying the suspension to cause the substantially parallel single-wall carbon nanotubes to aggregate while being subject to the aligning field.    
     
     
         142 . The method of  claim 141  wherein the three dimensional structure of field aligned single-wall carbon nanotubes is in a form selected from the group consisting of ropes, fibers, cables, membranes, arrays, buckypapers, and buckyribbons.  
     
     
         143 . The method of  claim 141  wherein the membrane comprises single-wall carbon nanotubes substantially parallel to the plane of the membrane.  
     
     
         144 . The method of  claim 141  wherein the membrane comprises single-wall carbon nanotubes substantially perpendicular to the plane of the membrane.  
     
     
         145 . The method of  claim 141  further comprising removing the suspending medium from the three-dimensional structure of field-aligned single-wall carbon nanotubes.  
     
     
         146 . The method of  claim 141  wherein the single-wall carbon nanotubes are selected from the group consisting of derivatized single-wall carbon nanotubes, underivatized single-wall carbon nanotubes, and combinations thereof.  
     
     
         147 . The method of  claim 141  wherein modification of the suspension is done by a method selected from the group consisting of (a) filtering the suspension whereby the substantially aligned single-wall carbon nanotubes remain on the filter, (b) adding salt to the suspension, (c) applying an electric field to the suspension; (d) allowing the single-wall carbon nanotubes to settle from the suspension; (e) evaporating the suspending medium; and (f) combinations thereof.  
     
     
         148 . A method of separating different types of single-wall carbon nanotubes comprising the steps of: 
 (a) suspending the plurality of single-wall carbon nanotubes in a suspending medium to form a suspension; and    (b) subjecting the single-wall carbon nanotubes to a magnetic field sufficient to cause the single-wall carbon nanotubes to migrate in different directions due to gradients in the magnetic field whereby the different types of single-wall carbon nanotubes are separated.    
     
     
         149 . The method of  claim 148  wherein the suspending medium is selected from the group consisting of oleum, dimethylformamide, surfactant and water, sol-gel, and molten metal.  
     
     
         150 . The method of  claim 148  wherein the different types of single-wall carbon nanotubes are selected from the group consisting of paramagnetic single-wall carbon nanotubes and diamagnetic single-wall carbon nanotubes.  
     
     
         151 . The method of  claim 148  further comprising the step of removing the single-wall nanotubes from the suspension according to type.  
     
     
         152 . A method for forming a nanotube membrane of substantially aligned single-wall nanotubes, comprising: 
 (a) suspending single-wall carbon nanotubes segments in a surfactant solution;    (b) pumping said solution through a filter assembly;    (c) applying a magnetic field near said filter assembly;    (d) flushing said filter assembly;    (e) drying said filter assembly; and    (f) separating a membrane of substantially aligned single-wall carbon nanotubes from a surface of said filter assembly.    
     
     
         153 . The method of  claim 152  wherein said magnetic field is generated by a magnetic field source selected from the group consisting of permanent magnets, electromagnets, superconducting electromagnets, and electrical currents flowing in a conductive structure.  
     
     
         154 . The method of  claim 152  wherein said magnetic field is generated by a magnetic field source selected from the group consisting of permanent magnets and electromagnets.  
     
     
         155 . The membrane of  claim 152  wherein said membrane is at least about 1 microns thick.  
     
     
         156 . The method of  claim 152  wherein said membrane is about 10 microns thick.  
     
     
         157 . The method of  claim 152  wherein said membrane is at least about 10 microns thick.  
     
     
         158 . The method of  claim 152  wherein said membrane is macroscopic.  
     
     
         159 . A method for forming a macroscopic membrane of substantially aligned single-wall nanotubes, comprising: 
 (a) suspending single-wall carbon nanotubes segments in a suspending agent to form a suspension;    (b) flowing said suspension through a magnetic field whereby the single-wall carbon nanotubes align with the field;    (c) flowing the suspension through a filter whereby the single-wall carbon nanotubes remain on the filter; and    (d) separating a membrane of substantially aligned single-wall carbon nanotubes from a surface of said filter.    
     
     
         160 . The method of  claim 159  further comprising the following steps prior to separating the membrane from the filter: 
 (a) flushing the single-wall carbon nanotubes on said filter; and    (b) drying the single-wall carbon nanotubes on said filter.    
     
     
         161 . The method of  claim 159  wherein said magnetic field is generated by a magnet selected from the group consisting of a permanent magnet, an electromagnet, a superconducting electromagnet or an electrical current flowing in a conductive structure.  
     
     
         162 . The method of  claim 159  wherein said magnetic field is generated by a magnet selected from the group consisting of a permanent magnet and an electromagnet.  
     
     
         163 . The method of  claim 159  wherein the thickness of said membrane is between about 1 and about 10 microns.  
     
     
         164 . An apparatus for forming arrays of substantially aligned single-wall carbon nanotubes, comprising: 
 (a) a source of suspended single-wall carbon nanotubes;    (b) an area for receiving said suspended single-wall carbon nanotubes;    (c) a source of a magnetic field for application to said area; and    (d) a filter for receiving said single-wall carbon nanotubes.    
     
     
         165 . The apparatus of  claim 164  wherein said source of a magnetic field is selected from the group consisting of permanent magnets, electromagnets, superconducting electromagnets, and electrical currents flowing in a conductive structure.  
     
     
         166 . The apparatus of  claim 164  wherein said source of a magnetic field is selected from a group consisting of permanent magnets, electromagnets, and superconducting electromagnets.  
     
     
         167 . The apparatus of  claim 164  wherein said magnetic field has a strength of at least about 0.5 Tesla.  
     
     
         168 . The apparatus of  claim 164  wherein said single-wall carbon nanotubes are suspended in dimethylformamide.  
     
     
         169 . The apparatus of  claim 164  wherein said suspended single-wall carbon nanotubes are forced through said area by high-pressure gas.  
     
     
         170 . The apparatus of  claim 164  wherein said suspended single-wall carbon nanotubes are pulled through said area by a vacuum.  
     
     
         171 . An apparatus for forming arrays of substantially aligned single-wall carbon nanotubes, comprising: 
 (a) a tank;    (b) a positive electrode disposed in said tank;    (c) a negative electrode disposed in said tank;    (d) a filter disposed in said tank near said positive electrode;    (e) a plurality of single-wall carbon nanotubes suspended in a suspending agent in said tank such that said filter is between said single-wall carbon nanotubes and said positive electrode; and    (f) a source of a magnetic field for aligning said single-wall carbon nanotubes; and    wherein said single-wall carbon nanotubes migrate toward said positive electrode in response to the application of a voltage differential and are caught on said filter.    
     
     
         172 . An apparatus for forming macroscopic arrays of substantially aligned single-wall carbon nanotubes, comprising: 
 (a) a reservoir of suspended single-wall carbon nanotubes;    (b) a chamber connected to said reservoir for receiving said single-wall carbon nanotubes and subjected to a magnetic field in which the suspended single-wall carbon nanotubes align with said magnetic field; and    (c) a filter in said chamber for receiving said single-wall carbon nanotubes.    
     
     
         173 . The apparatus of  claim 172  wherein said magnetic field is generated by a magnet selected from a group consisting of a permanent magnet, an electromagnet, a superconducting electromagnet or an electrical current flowing in a conductive structure.  
     
     
         174 . The apparatus of  claim 172  wherein said magnetic field is generated by a magnet selected from a group consisting of a permanent magnet, an electromagnet, and a superconducting electromagnet.  
     
     
         175 . The apparatus of  claim 172  wherein said magnetic field has a strength of at least about 0.5 Tesla.  
     
     
         176 . The apparatus of  claim 172  wherein said single-wall carbon nanotubes are suspended in dimethylformamide.  
     
     
         177 . The apparatus of  claim 172  wherein said suspended single-wall carbon nanotubes are forced through said chamber by high-pressure gas.  
     
     
         178 . The apparatus of  claim 172  wherein said suspended single-wall carbon nanotubes are pulled through said chamber by a vacuum.