Carbon nanotubes possess a number of beneficial properties, such as exceptional strength and electrical conductivity. There is substantial interest in these entities for applications in diverse fields of nanotechnology, electronic devices, optical devices and materials science. Single-wall carbon nanotubes have typically been the most studied for these proposed applications, since these nanotubes tend to offer properties which are not embodied by many of their multi-wall counterparts. The ability to rapidly grow carbon nanotubes in aligned arrays perpendicular to a growth substrate has accelerated development activities for carbon nanotube-based applications. Such perpendicular arrays of vertically aligned carbon nanotubes are sometimes referred to as carpets due to their microscopic resemblance to household carpeting. The ability to form thin, transparent carbon nanotube films has further inspired a host of hypothesized potential applications.
Films of single-wall carbon nanotubes have been prepared through vacuum filtration of solutions of surfactant-suspended single-wall carbon nanotubes. Spin coating of carbon nanotube suspensions has also been utilized to form carbon nanotube films. Exposure to air, liquids, and solvents may alter physical properties of the as-produced carbon nanotubes. Films of aligned multi-wall carbon nanotubes have been produced by drawing multi-wall carbon nanotubes from the side of a vertically aligned multi-wall carbon nanotube array.
Similarly aligned single-wall carbon nanotube films may not currently be produced by the same method due to property differences between aligned arrays of single-wall carbon nanotubes and multi-wall carbon nanotubes.
In order for carbon nanotubes to be utilized in applications and devices, it may be beneficial to separate carbon nanotube arrays and films derived thereof from their growth surfaces. An array of carbon nanotubes may be separated from its growth surface by immersing the as-grown carbon nanotube array in hot water, providing separation based on a thermocapillary effect. Capillary forces present during the drying process may disrupt carbon nanotube alignment and affect physical properties of arrays separated from their growth surfaces in this manner. Mechanical force may also be utilized to separate carbon nanotubes and films derived thereof from their growth surfaces.
In view of the foregoing, development of simple methods for forming single-wall carbon nanotube films from aligned single-walled carbon nanotube arrays would be of considerable utility. Further, methods not requiring a wet chemical processing step for separation of the aligned carbon nanotube arrays and films would be beneficial.
In some aspects, the present disclosure provides a method for producing a carbon nanotube layer. The method comprises compressing an array comprising a plurality of carbon nanotubes. Compressing the array comprises passing a roller over the array.
In other aspects, the present disclosure provides a method for preparing a carbon nanotube layer, wherein the layer comprises a plurality of aligned carbon nanotubes. The method comprises the steps of a) preparing an array comprising a plurality of vertically aligned carbon nanotubes; b) cooling the array in a gaseous mixture comprising a carbon source and H2O; c) compressing the array with a roller to create a carbon nanotube layer, wherein the layer comprises a plurality of aligned carbon nanotubes; and d) treating the layer with an acid.
In another aspect, the present disclosure provides a method for preparing a carbon nanotube layer, wherein the layer comprises a plurality of aligned carbon nanotubes. The method comprises the steps of a) preparing an array comprising a plurality of vertically aligned carbon nanotubes; b) heating the array in a gaseous mixture comprising an etchant; and c) compressing the array with a roller to create a carbon nanotube layer, wherein the layer comprises a plurality of aligned carbon nanotubes.
In still another aspect, the present disclosure provides a method for preparing a carbon nanotube layer, wherein the layer comprises a plurality of aligned carbon nanotubes. The method comprises the steps of: a) preparing a carbon nanotube growth surface, wherein the growth surface comprises an grouping of lines comprising a metallic catalyst; b) growing an array comprising a plurality of vertically aligned carbon nanotubes on the grouping, wherein the height of the plurality of vertically aligned carbon nanotubes is greater than the separation between lines in the grouping; and c) compressing the array with a roller to create a carbon nanotube layer, wherein the layer comprises a plurality of aligned carbon nanotubes.
In yet another aspect, the present disclosure provides a composite material comprising at least one single-wall carbon nanotube layer, wherein the layer comprises a plurality of aligned single-wall carbon nanotubes, and wherein the composite material is prepared by the process comprising the steps of: a) preparing an array comprising a plurality of vertically aligned single-wall carbon nanotubes; b) heating the array in a gaseous mixture comprising an etchant; c) compressing the array with a roller to create a carbon nanotube layer, wherein the layer comprises a plurality of aligned single-wall carbon nanotubes; and d) transferring the layer to a polymer.
The foregoing has outlined rather broadly the features of the present disclosure in order that the detailed description that follows may be better understood. Additional features and advantages of the disclosure will be described hereinafter, which form the subject of the claims.
The foregoing summary as well as the following detailed description of the disclosure will be better understood when read in conjunction with the appended drawings. It should be understood that the disclosure is not limited to the precise arrangements and instrumentalities shown herein. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles and certain embodiments of the present disclosure. For a more complete understanding of the present disclosure, and the advantages thereof, reference is now made to the following descriptions to be taken in conjunction with the accompanying drawings describing a specific embodiment of the disclosure, wherein:
In the following description, certain details are set forth such as specific quantities, sizes, etc. so as to provide a thorough understanding of the present embodiments disclosed herein. However, it will be obvious to those skilled in the art that the present disclosure may be practiced without such specific details. In many cases, details concerning such considerations and the like have been omitted inasmuch as such details are not necessary to obtain a complete understanding of the present disclosure and are within the skills of persons of ordinary skill in the relevant art.
Referring to the drawings in general, it will be understood that the illustrations are for the purpose of describing a particular embodiment of the disclosure and are not intended to be limiting thereto.
While most of the terms used herein will be recognizable to those of skill in the art, the following definitions are nevertheless put forth to aid in the understanding of the present disclosure. It should be understood, however, that when not explicitly defined, terms should be interpreted as adopting a meaning presently accepted by those of skill in the art.
“Array,” as defined herein, comprises a prepared assembly of carbon nanotubes. As used herein, an array of carbon nanotubes refers to carbon nanotube forests and carbon nanotube carpets. Arrays may be formed from patterned growth surfaces.
“Carbon nanotube layer,” as defined herein, refers to a film, ribbon, or sheet of carbon nanotubes.
“Host surface,” as defined herein, comprises a surface to which a carbon nanotube layer is transferred.
In the most general aspects, the present disclosure provides a method for producing a carbon nanotube layer. The method comprises compressing an array, wherein the array comprises a plurality of carbon nanotubes. Compressing the array comprises passing a roller over the array. In some embodiments of the method, the carbon nanotube layer comprises a film. In other embodiments of the method, the carbon nanotube layer comprises a ribbon. In still other embodiments, the carbon nanotube layer comprises a sheet. As illustrated in
The method of compressing an array comprising a plurality of carbon nanotubes is advantageous in that a highly dense layer of carbon nanotubes may be produced from a low density array of carbon nanotubes. In a non-limiting example, an array of carbon nanotubes having a nanotube diameter of about 1 nm and a spacing between nanotubes of about 10 nm can be compressed by a factor of about 25, yielding a nearly full density carbon nanotube film. Prior to compressing, such an array has a density of only about 4% of the maximum possible. One skilled in the art will recognize that the thickness and density of the carbon nanotube layer produced following the compressing step will depend both on the height and spacing of the carbon nanotubes comprising the array. Many proposed applications of carbon nanotube layers are best suited for near full density structures, and the methods disclosed herein provide a simple means to meet that need.
The method for producing a carbon nanotube layer further comprises transferring the carbon nanotube layer to a host surface. Carbon nanotube layers may be transferred to an number of host surfaces, including but not limited to, Cu, Al, Ta, and stainless steel. The host surfaces may include, but are not limited to, foils, films, and blocks. The carbon nanotube layers may also be transferred to polymer films, including thermoplastic and epoxy polymer films, in non-limiting examples. Polymer blocks may also serve as the host surface. Likewise, carbon nanotube layers may be transferred to a polymer precursor, the polymer then being formed after transfer of the carbon nanotube layer. When the carbon nanotube layer is transferred to a polymer, the resultant material comprises a polymer composite comprising carbon nanotubes. In a representative but non-limiting embodiment of the disclosure, carbon nanotube layers may be transferred to a polyethylene film. Carbon nanotube layers may also be transferred to polished surfaces, such as quartz, sapphire, and glass, in non-limiting examples.
In certain embodiments of the method for producing a carbon nanotube layer, the carbon nanotubes comprising the layer are aligned. In some embodiments, the carbon nanotubes are aligned and parallel to the surface of the layer. In certain embodiments, at least a portion of the carbon nanotubes are aligned and parallel to the surface of the layer. According to some embodiments, one or more carbon nanotubes parallel to the surface of the carbon nanotube layer may deviate from the plane of the layer from about 0 degrees to about 20 degrees. According to some embodiments, one or more carbon nanotubes parallel to the surface of the carbon nanotube layer may deviate from the plane of the layer from about 0 degrees to about 10 degrees. According to some embodiments, one or more carbon nanotubes parallel to the surface of the carbon nanotube layer may deviate from the plane of the layer from about 0 degrees to about 5 degrees. Alignment of carbon nanotubes comprising the layer may be determined by alignment of the carbon nanotube array compressed to form the layer. In certain embodiments, the carbon nanotube layer maintains about 99% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 97% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 95% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 90% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 80-90% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 70-80% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 60-70% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 50-60% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 40-50% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 30-40% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 20-30% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 10-20% of the alignment present in the carbon nanotube array. In certain embodiments of the method, transferring the carbon nanotube layer to a host surface maintains alignment of at least a portion of the carbon nanotubes.
Another aspect of the present disclosure is a method for preparing a carbon nanotube layer comprising a plurality of aligned carbon nanotubes. The method comprises the steps of: a) preparing an array comprising a plurality of vertically aligned carbon nanotubes; b) cooling the array in a gaseous mixture comprising a carbon source and H2O; c) compressing the array with a roller to create a carbon nanotube layer, wherein the layer comprises a plurality of aligned carbon nanotubes; and d) treating the layer with an acid. In an embodiment of the method, the layer comprises a film. In another embodiment of the method, the layer comprises a ribbon. In an embodiment of the method, preparing an array, wherein the array comprises a plurality of vertically aligned carbon nanotubes, takes place in the presence of a metallic catalyst (step a). Suitable metallic catalysts for directing carbon nanotube growth may include, but are not limited to, at least one metal selected from Groups 3-12 of the periodic table, the lanthanide elements, and combinations thereof. In an embodiment of the method, the metallic catalyst is Fe deposited on an Al2O3 growth surface. Suitable carbon sources for practicing the method may include, but are not limited to, at least one compound selected from the group consisting of methane, ethane, propane, butane, isobutane, ethylene, propene, 1-butene, cis-2-butene, trans-2-butene, isobutylene, acetylene, propyne, 1-butyne, 2-butyne, benzene, toluene, carbon monoxide, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, cyclopropane, cyclobutane, acetonitrile, propionitrile, butyronitrile, acetone, butanone, formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde. In an embodiment, the carbon source comprises acetylene. In another embodiment of the method, the carbon nanotubes comprise single-wall carbon nanotubes.
In some embodiments of the method, the carbon nanotubes are aligned and parallel to the surface of the layer. In certain embodiments of the method, at least a portion of the carbon nanotubes are aligned and parallel to the surface of the layer. According to some embodiments, one or more carbon nanotubes parallel to the surface of the carbon nanotube layer may deviate from the plane of the layer from about 0 degrees to about 20 degrees. According to some embodiments, one or more carbon nanotubes parallel to the surface of the carbon nanotube layer may deviate from the plane of the layer from about 0 degrees to about 10 degrees. According to some embodiments, one or more carbon nanotubes parallel to the surface of the carbon nanotube layer may deviate from the plane of the layer from about 0 degrees to about 5 degrees. Alignment of carbon nanotubes comprising the layer may be determined by alignment of the carbon nanotube array compressed to form the layer. In certain embodiments, the carbon nanotube layer maintains about 99% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 97% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 95% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 90% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 80-90% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 70-80% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 60-70% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 50-60% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 40-50% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 30-40% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 20-30% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 10-20% of the alignment present in the carbon nanotube array. In certain embodiments of the method, transferring the carbon nanotube layer to a host surface maintains alignment of at least a portion of the carbon nanotubes.
Carbon nanotube films prepared by the method described hereinabove may maintain strong adherence to the growth surface prior to the acid treatment step. Without being bound by mechanism or theory, it is believed that the acid treatment step etches the metallic catalyst particles and results in detachment of the carbon nanotube film from the growth surface. The freestanding carbon nanotube layer is released within a matter of seconds when the as-produced layer is treated with a 1 M HCl etch.
Still another aspect of the present disclosure is a method for preparing a carbon nanotube layer comprising a plurality of aligned carbon nanotubes. The method comprises the steps of a) preparing an array comprising a plurality of vertically aligned carbon nanotubes; b) heating the array in a gaseous mixture comprising an etchant; and c) compressing the array with a roller to create a carbon nanotube layer, wherein the layer comprises a plurality of aligned carbon nanotubes. In an embodiment of the method, the layer comprises a film. In another embodiment of the method, the layer comprises a ribbon. In an embodiment, preparing an array, wherein the array comprises a plurality of vertically aligned carbon nanotubes, takes place in the presence of a metallic catalyst (step a). Suitable metallic catalysts for directing carbon nanotube growth may include, but are not limited to at least one metal selected from Groups 3-12 of the periodic table, the lanthanide elements, and combinations thereof In an embodiment of the method, the metallic catalyst is Fe deposited on an Al2O3 growth surface. Suitable etchants for practicing the method may include at least one component selected from the group, including but not limited to, H2O, H2O2, H2, organic peroxides, and oxidizing acids. In an embodiment of the method, the etchant comprises H2O. In another embodiment of the method, the etchant comprises a mixture comprising H2O and H2. In another embodiment of the method, the carbon nanotubes comprise single-wall carbon nanotubes.
The method of preparing a carbon nanotube layer comprising aligned carbon nanotubes and disclosed immediately hereinabove may be further comprised by transferring the layer (step d). The transferring step may be to a host surface placed on the layer comprising aligned carbon nanotubes following the compressing step. Such host surfaces may include polished host surfaces including, but not limited to, quartz, sapphire, and glass. In an embodiment of the method, the transferring step occurs during the compressing step and the transferring is to a host surface covering the roller. The host surface may cover the roller as a film or a foil in an embodiment. A wide range of host surfaces may be suitable for transfer of the carbon nanotube layer to them. Host surfaces may include, but are not limited to, foils, films, and blocks. Representative host surfaces that may receive carbon nanotube layers when the host surfaces cover the roller may include, but are not limited to, Cu, Al, Ta, and stainless steel foils. The carbon nanotube layers may also be transferred to polymer films, including thermoplastic and epoxy polymer films, in non-limiting examples. Polymer blocks may also serve as the host surface. Likewise, carbon nanotube layers may be transferred to a polymer precursor, the polymer then being formed after transfer of the carbon nanotube layer. In a representative but non-limiting embodiment of the disclosure, carbon nanotube layers may be transferred to a polyethylene film.
In some embodiments, the carbon nanotubes are aligned and parallel to the surface of the layer. In certain embodiments, at least a portion of the carbon nanotubes are aligned and parallel to the surface of the layer. According to some embodiments, one or more carbon nanotubes parallel to the surface of the carbon nanotube layer may deviate from the plane of the layer from about 0 degrees to about 20 degrees. According to some embodiments, one or more carbon nanotubes parallel to the surface of the carbon nanotube layer may deviate from the plane of the layer from about 0 degrees to about 10 degrees. According to some embodiments, one or more carbon nanotubes parallel to the surface of the carbon nanotube layer may deviate from the plane of the layer from about 0 degrees to about 5 degrees. Alignment of carbon nanotubes comprising the layer may be determined by alignment of the carbon nanotube array compressed to form the layer. In certain embodiments, the carbon nanotube layer maintains about 99% of the alignment present in the carbon nanotube array.
In other embodiments, the carbon nanotube layer maintains about 97% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 95% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 90% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 80-90% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 70-80% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 60-70% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 50-60% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 40-50% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 30-40% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 20-30% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 10-20% of the alignment present in the carbon nanotube array. In certain embodiments of the method, transferring the carbon nanotube layer to a host surface maintains alignment of at least a portion of the carbon nanotubes.
Without being bound by theory or mechanism, it is believed that the heating step in an etchant of the method disclosed hereinabove etches the catalyst particles and allows the carbon nanotubes to be easily removed from the growth surface through simple contact and transfer to a host surface. This dry processing method for detaching carbon nanotube layers from the growth surface is advantageous in that it avoids capillary forces during drying. Said capillary forces may lower the alignment factor of the carbon nanotubes comprising a carbon nanotube film released by a wet chemical etch. Such a dry processing treatment is further advantageous in that it may not affect carbon nanotube alignment either before or after the compressing step. It is further distinguishable in that it avoids residual acid, solvent, or surfactant remaining in the film so produced. In an embodiment of the method for dry processing of a carbon nanotube layer, the carbon nanotube array is heated in the presence of an etchant for about 1 minute to about 60 minutes at a temperature of about 500° C. to about 1000° C. In other embodiments, the heating step in the presence of an etchant is conducted for about 2 minutes to about 30 minutes at a temperature of about 600° C. to about 900° C. In still other embodiments, the heating step in the presence of an etchant is conducted for about 3 minutes to about 10 minutes at a temperature of about 700° C. to about 850° C. In an embodiment, the etchant is H2O. Optional inclusion of H2 in the mixture comprising the etchant may be advantageous in certain instances. In a representative, but non-limiting example, the heating of an as-produced carbon nanotube array is conducted at about 775° C. for about 5 minutes in order to prepare the array for compressing and release of the so-produced carbon nanotube film by simple contact with a host surface.
A comparison of the presumptive mechanisms by which heat treatment in the presence of an etchant and acid treatment result in release of carbon nanotube layers from the growth surface is shown in
The dry processing method disclosed hereinabove may provide aligned carbon nanotube films having variable transparency depending on the time the carbon nanotube array is allowed to grow. Further, depending on the temperature at which the carbon nanotube array is grown, arrays comprised of a plurality of single-wall carbon nanotubes or a plurality of double-wall carbon nanotubes may be prepared. Films produced from the single-wall carbon nanotube arrays and double-wall carbon nanotube arrays have variable transparency. Single-wall carbon nanotube arrays were grown at about 765° C. and about 800° C., and double-wall carbon nanotube arrays were grown at about 625° C. Heating of these carbon nanotube arrays in the presence of an etchant at about 775° C. gave carbon nanotube films after compressing that were transferred to a polyethylene host surface.
Yet another aspect of the present disclosure is a method for preparing a layer comprising a plurality of aligned carbon nanotubes. The method comprises the steps of a) preparing a carbon nanotube growth surface, wherein the growth surface comprises a grouping of lines comprising a metallic catalyst; b) growing an array comprising a plurality of vertically aligned carbon nanotubes, wherein growing occurs on the grouping of lines, and wherein the height of the plurality of vertically aligned carbon nanotubes is greater than the separation between lines in the grouping of lines; and c) compressing the array with a roller to create a carbon nanotube layer, wherein the layer comprises a plurality of aligned carbon nanotubes. Lithography offers a means to prepare a patterned growth surface having a grouping of lines comprising the metallic catalyst for carbon nanotube growth. In an embodiment of the method, the layer comprises a film. In another embodiment of the method, the layer comprises a ribbon. Suitable metallic catalysts for directing carbon nanotube growth may include, but are not limited to at least one metal selected from Groups 3-12 of the periodic table, the lanthanide elements, and combinations thereof. In an embodiment of the method, the metallic catalyst is Fe deposited as a grouping of lines on an Al2O3 growth surface. In a representative but non-limiting example of the method disclosed hereinabove, metallic catalyst lines about 2 μm wide and separated by about 50 μm may be used to grow self-supporting aligned carbon nanotube arrays to a height of about 70 μm.
The method disclosed hereinabove may be further comprised by heating the array, wherein the array comprises a plurality of vertically aligned carbon nanotubes, in a gaseous mixture comprising an etchant prior to the compressing step (step c). Suitable etchants for practicing the method may include at least one component selected from the group, including but not limited to, H2O, H2O2, H2, organic peroxides, and oxidizing acids. In an embodiment, the etchant comprises H2O. In another embodiment, the etchant comprises a mixture comprising H2O and H2. In an embodiment of the method, the carbon nanotube array is heated in the presence of an etchant for about 1 minute to about 60 minutes at a temperature of about 500° C. to about 1000° C. In other embodiments, the heating step in the presence of an etchant is conducted for about 2 minutes to about 30 minutes at a temperature of about 600° C. to about 900° C. In still other embodiments, the heating step in the presence of an etchant is conducted for about 3 minutes to about 10 minutes at a temperature of about 700° C. to about 850° C. In certain embodiments of the method, the heating step is conducted in the presence of a mixture comprising H2O and H2 for about 5 minutes at a temperature of about 775° C. The method disclosed hereinabove may also be further comprised by removing the carbon nanotube layer from the growth surface (step d). Removing the carbon nanotube layer may be facilitated as a result of heating in the presence of an etchant or by acid treatment following compression. In embodiments of the method, at least a portion of the carbon nanotubes are aligned following the compressing step.
In some embodiments, the carbon nanotubes are aligned and parallel to the surface of the layer. In certain embodiments, at least a portion of the carbon nanotubes are aligned and parallel to the surface of the layer. According to some embodiments, one or more carbon nanotubes parallel to the surface of the carbon nanotube layer may deviate from the plane of the layer from about 0 degrees to about 20 degrees. According to some embodiments, one or more carbon nanotubes parallel to the surface of the carbon nanotube layer may deviate from the plane of the layer from about 0 degrees to about 10 degrees. According to some embodiments, one or more carbon nanotubes parallel to the surface of the carbon nanotube layer may deviate from the plane of the layer from about 0 degrees to about 5 degrees. Alignment of carbon nanotubes comprising the layer may be determined by alignment of the carbon nanotube array compressed to form the layer. In certain embodiments, the carbon nanotube layer maintains about 99% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 97% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 95% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 90% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 80-90% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 70-80% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 60-70% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 50-60% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 40-50% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 30-40% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 20-30% of the alignment present in the carbon nanotube array. In other embodiments, the carbon nanotube layer maintains about 10-20% of the alignment present in the carbon nanotube array. In certain embodiments of the method, transferring the carbon nanotube layer to a host surface maintains alignment of at least a portion of the carbon nanotubes.
In additional embodiments of the method for forming a carbon nanotube layer, the carbon nanotubes comprise single-wall carbon nanotubes. Carbon nanotube layers comprised of aligned carbon nanotubes, as produced by the method hereinabove, are advantageous in being inherently thin as a result of the spacing between catalyst lines on the patterned growth surface. One skilled in the art will recognize that the spacing between catalyst lines may be varied, along with the height to which the carbon nanotube array is grown, in order to vary the layer thickness and degree of overlap between adjacent carbon nanotube lines.
In an additional aspect, the present disclosure also describes a composite material comprising at least one single-wall carbon nanotube layer, wherein the layer comprises a plurality of aligned single-wall carbon nanotubes, and wherein the composite material is prepared by the process comprising the steps of: a) preparing an array comprising a plurality of vertically aligned single-wall carbon nanotubes; b) heating the array in a gaseous mixture comprising an etchant; c) compressing the array with a roller to create a carbon nanotube layer, wherein the layer comprises a plurality of aligned single-wall carbon nanotubes; and d) transferring the layer to a polymer. Suitable etchants may include at least one component selected from the group, including but not limited to, H2O, H2O2, H2, organic peroxides, and oxidizing acids. In an embodiment of the composite material prepared by the process disclosed hereinabove, the etchant comprises H2O. In another embodiment of the composite material prepared by the process disclosed hereinabove, the etchant comprises a mixture comprising H2O and H2. The composite material prepared by the process disclosed hereinabove may further comprise coating the roller with a polymer film prior to the compressing step (step c). Coating the roller with a polymer film prior to the compressing step may allow transfer of the carbon nanotube layer produced during the compressing step directly to the polymer film. In a further embodiment, the composite material may comprise a laminate composite. In such an embodiment, the composite material prepared by the process disclosed hereinabove further comprises alternating sheets of polymer film and aligned single-wall carbon nanotube layers. Laminate composites may be prepared with the carbon nanotube layers aligned in the same direction. Laminate composites may also be prepared with the carbon nanotube layers arranged in alternating orthogonal layers between sheets of polymer to provide enhanced strength in lateral directions.
In some embodiments of the composite material, the single-wall carbon nanotubes are aligned and parallel to the surface of the layer. In certain embodiments of the composite material, at least a portion of the single-wall carbon nanotubes are aligned and parallel to the surface of the layer. According to some embodiments of the composite material, one or more single-wall carbon nanotubes parallel to the surface of the carbon nanotube layer may deviate from the plane of the layer from about 0 degrees to about 20 degrees. According to some embodiments of the composite material, one or more single-wall carbon nanotubes parallel to the surface of the carbon nanotube layer may deviate from the plane of the layer from about 0 degrees to about 10 degrees. According to some embodiments of the composite material, one or more single-wall carbon nanotubes parallel to the surface of the carbon nanotube layer may deviate from the plane of the layer from about 0 degrees to about 5 degrees. Alignment of single-wall carbon nanotubes comprising the layer may be determined by alignment of the single-wall carbon nanotube array compressed to form the layer. In certain embodiments of the composite material, the single-wall carbon nanotube layer maintains about 99% of the alignment present in the single-wall carbon nanotube array. In other embodiments of the composite material, the single-wall carbon nanotube layer maintains about 97% of the alignment present in the single-wall carbon nanotube array. In other embodiments of the composite material, the single-wall carbon nanotube layer maintains about 95% of the alignment present in the single-wall carbon nanotube array. In other embodiments of the composite material, the single-wall carbon nanotube layer maintains about 90% of the alignment present in the single-wall carbon nanotube array. In other embodiments of the composite material, the single-wall carbon nanotube layer maintains about 80-90% of the alignment present in the single-wall carbon nanotube array. In other embodiments of the composite material, the single-wall carbon nanotube layer maintains about 70-80% of the alignment present in the single-wall carbon nanotube array. In other embodiments of the composite material, the single-wall carbon nanotube layer maintains about 60-70% of the alignment present in the single-wall carbon nanotube array. In other embodiments of the composite material, the single-wall carbon nanotube layer maintains about 50-60% of the alignment present in the single-wall carbon nanotube array. In other embodiments of the composite material, the single-wall carbon nanotube layer maintains about 40-50% of the alignment present in the single-wall carbon nanotube array. In other embodiments of the composite material, the single-wall carbon nanotube layer maintains about 30-40% of the alignment present in the single-wall carbon nanotube array. In other embodiments of the composite material, the single-wall carbon nanotube layer maintains about 20-30% of the alignment present in the single-wall carbon nanotube array. In other embodiments of the composite material, the single-wall carbon nanotube layer maintains about 10-20% of the alignment present in the single-wall carbon nanotube array. In certain embodiments of the method, transferring the single-wall carbon nanotube layer to a polymer maintains alignment of at least a portion of the carbon nanotubes.
The following experimental examples are included to demonstrate particular aspects of the present disclosure. It should be appreciated by those of skill in the art that the methods described in the examples that follow merely represent exemplary embodiments of the disclosure. Those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments described and still obtain a like or similar result without departing from the spirit and scope of the present disclosure.
Measurement of the degree to which the rolling process compresses the carbon nanotube array was studied with a carbon nanotube array grown in a 25 torr atmosphere comprising C2H2, H2O, and H2. Growth of the carbon nanotube array to an average of about 613.6 μm tall was achieved in 30 minutes under these growth conditions. After the compressing step, the resulting carbon nanotube film was partially peeled from the substrate in order to measure its thickness. SEM images of the carbon nanotube array before and after compressing are shown in
Polarized Raman spectroscopy was utilized to verify retention of carbon nanotube alignment in the film following the compressing step. Polarized Raman spectra for a representative single-wall carbon nanotube array and single-wall carbon nanotube film formed by compressing the array are shown in
SEM image 1001 of the above single-wall carbon nanotube array shown in
Physical comparison of the two methods for carbon nanotube film removal was performed. In the wet process, the catalyst is etched away from the growth surface by acid to release the carbon nanotube film. In the dry process, heat treatment with a gaseous etchant provides eventual release of the film after the compressing step. First, a comparison of carbon nanotube arrays either treated with an etchant or not treated with an etchant were studied. In order to study the effect of catalyst-film interactions, two identical single-wall carbon nanotube arrays were produced under the growth conditions (2 mins, 750° C.), except that one of them was heated in a gaseous mixture comprising H2O for 1 minute following growth. The other one was rapidly cooled and removed from the reactor. Following growth, a droplet of water was placed on the top of each single-wall carbon nanotube array and allowed to dry. SEM images of the two arrays after drying are shown in
Investigation of the differences between the two carbon nanotube arrays was also investigated by X-ray Photoelectron Spectroscopy (XPS). In most CVD reactor systems used for preparing carbon nanotube arrays, the catalyst coated growth surface is rapidly inserted in a hot furnace to grow, and then rapidly cooled by removing it out of the furnace while the carbon source gas is still flowing. As the Fe catalyst particle of the present example cools, it forms an Fe—C compound comprising a surface segregated carbon shell surrounding the catalyst due to the difference in surface energy between Fe and C. Following removal from the hot furnace, the carbon nanotubes in the array are fixed to the catalyst particle by C—C bonds to the C shell, which is in turn bound to the catalyst particle through mixed Fe—C bonds. As a result, the initially produced carbon nanotube array is strongly bound to the growth surface. Further, the tight binding explains why the compressing step of an array which has not been heated in the presence of an etchant leaves the carbon nanotube film intact on the growth surface rather than transferred to the roller. Acid treatment removes the Fe catalyst layer from the growth surface and releases the intact carbon nanotube film. When the as-produced carbon nanotube array is exposed at a high temperature (775° C.) to an etchant, the carbon in the catalyst particle is precipitated out and etched away by the H2O, while the catalyst particle is re-oxidized. Mechanical stresses in the film apparently aid in the “pop-off” mechanism of the nanotube array from the oxidized catalyst, explaining the facile removal of carbon nanotube films by contact with another surface. This picture is supported by the XPS data shown in
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this disclosure, and without departing from the spirit and scope thereof, can make various changes and modifications to adapt the disclosure to various usages and conditions. The embodiments described hereinabove are meant to be illustrative only and should not be taken as limiting of the scope of the disclosure, which is defined in the following claims.
This application claims priority to U.S. provisional patent application 60/953,114, filed Jul. 31, 2007, which is incorporated by reference as if written herein in its entirety.
This work was funded by Department of Energy award numbers R14790-489020 and R7A1210416000.
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/US2008/071853 | 7/31/2008 | WO | 00 | 3/7/2011 |