This invention provides a continuous process for the growth of vapor grown carbon fiber (VGCNT) reinforced continuous fiber preforms for the manufacture of articles with useful mechanical, electrical, and thermal characteristics. Continuous fiber preforms are treated with a catalyst or catalyst precursor and processed without vaporization of the preform to yield VGCNT produced in situ resulting in a highly entangled mass of VGCNT infused with the continuous fiber preform. The continuous process disclosed herein provides denser and more uniform carbon nanotubes and provides the opportunity to fine-tune the variables both within an individual preform and between different preforms depending on the characteristics of the carbon nanotubes desired. The resulting continuous fiber preforms are essentially endless and are high in volume fraction of VGCNT and exhibit high surface area useful for many applications. The invention also provides for composites made from the preforms.

This invention provides a continuous process for the growth of vapor grown carbon fiber (VGCNT) reinforced continuous fiber preforms for the manufacture of articles with useful mechanical, electrical, and thermal characteristics. Continuous fiber preforms are treated with a catalyst or catalyst precursor and processed without vaporization of the preform to yield VGCNT produced in situ resulting in a highly entangled mass of VGCNT infused with the continuous fiber preform. The continuous process disclosed herein provides denser and more uniform carbon nanotubes and provides the opportunity to fine-tune the variables both within an individual preform and between different preforms depending on the characteristics of the carbon nanotubes desired. The resulting continuous fiber preforms are essentially endless and are high in volume fraction of VGCNT and exhibit high surface area useful for many applications. The invention also provides for composites made from the preforms.

Method for the preparation of carbon fiber from fiber precursor, wherein the fiber precursor is subjected to a magnetic field of at least 3 Tesla during a carbonization process. The carbonization process is generally conducted at a temperature of at least 400° C. and less than 2200° C., wherein, in particular embodiments, the carbonization process includes a low temperature carbonization step conducted at a temperature of at least or above 400° C. or 500° C. and less than or up to 1000° C., 1100° C., or 1200° C., followed by a high temperature carbonization step conducted at a temperature of at least or above 1200° C. In particular embodiments, particularly in the case of a polyacrylonitrile (PAN) fiber precursor, the resulting carbon fiber may possess a minimum tensile strength of at least 600 ksi, a tensile modulus of at least 30 Msi, and an ultimate elongation of at least 1.5%.

The disclosed materials, methods, and apparatus, provide novel ultra-high temperature materials (UHTM) in fibrous forms/structures; such “fibrous materials” can take various forms, such as individual filaments, short-shaped fiber, tows, ropes, wools, textiles, lattices, nano/microstructures, mesostructured materials, and sponge-like materials. At least four important classes of UHTM materials are disclosed in this invention: (1) carbon, doped-carbon and carbon alloy materials, (2) materials within the boron-carbon-nitride-X system, (3) materials within the silicon-carbon-nitride-X system, and (4) highly-refractory materials within the tantalum-hafnium-carbon-nitride-X and tantalum-hafnium-carbon-boron-nitride-X system. All of these material classes offer compounds/mixtures that melt or sublime at temperatures above 1800° C.—and in some cases are among the highest melting point materials known (exceeding 3000° C.). In many embodiments, the synthesis/fabrication is from gaseous, solid, semi-solid, liquid, critical, and supercritical precursor mixtures using one or more low molar mass precursor(s), in combination with one or more high molar mass precursor(s). Methods for controlling the growth, composition, and structures of UHTM materials through control of the thermal diffusion region are disclosed.

The disclosed materials, methods, and apparatus, provide novel ultra-high temperature materials (UHTM) in fibrous forms/structures; such “fibrous materials” can take various forms, such as individual filaments, short-shaped fiber, tows, ropes, wools, textiles, lattices, nano/microstructures, mesostructured materials, and sponge-like materials. At least four important classes of UHTM materials are disclosed in this invention: (1) carbon, doped-carbon and carbon alloy materials, (2) materials within the boron-carbon-nitride-X system, (3) materials within the silicon-carbon-nitride-X system, and (4) highly-refractory materials within the tantalum-hafnium-carbon-nitride-X and tantalum-hafnium-carbon-boron-nitride-X system. All of these material classes offer compounds/mixtures that melt or sublime at temperatures above 1800° C.—and in some cases are among the highest melting point materials known (exceeding 3000° C.). In many embodiments, the synthesis/fabrication is from gaseous, solid, semi-solid, liquid, critical, and supercritical precursor mixtures using one or more low molar mass precursor(s), in combination with one or more high molar mass precursor(s). Methods for controlling the growth, composition, and structures of UHTM materials through control of the thermal diffusion region are disclosed.

The present invention provides a process for preparing a carbon nanotube sheet, which comprises forming carbon nanotubes; aggregating the carbon nanotubes to form a yarn; treating the yarn with a solvent to enhance the aggregation force; winding the solvent-treated yarn to prepare a sheet preform having a structure in which one yarn is continuously wound; and cutting and/or pressing the sheet preform to prepare a carbon nanotube sheet that comprises an arrangement structure in which one or a plurality of yarns are uniaxially aligned, and a carbon nanotube sheet prepared thereby.

The present invention provides a process for preparing a carbon nanotube sheet, which comprises forming carbon nanotubes; aggregating the carbon nanotubes to form a yarn; treating the yarn with a solvent to enhance the aggregation force; winding the solvent-treated yarn to prepare a sheet preform having a structure in which one yarn is continuously wound; and cutting and/or pressing the sheet preform to prepare a carbon nanotube sheet that comprises an arrangement structure in which one or a plurality of yarns are uniaxially aligned, and a carbon nanotube sheet prepared thereby.

A system for hydrocarbon decomposition comprising a reactor volume, a mechanism to distribute the liquid catalyst as a liquid mist, a distributor to distribute a hydrocarbon reactant, a heat source, a separator to separate the solid product from the liquid catalyst, a re-circulation path and mechanism to re-circulate the liquid catalyst, and an outlet for at least one gaseous product. A system to distribute a liquid to an enclosed volume as a mist has a plurality of orifices designed to break the liquid into a mist. A method to decompose a hydrocarbon reactant includes generating a mist of a liquid catalyst, heating the reactor volume, introducing a hydrocarbon reactant into the reactor volume to produce a solid product and a gaseous product, separating the solid product from the liquid catalyst, removing the solid and gaseous products from the reactor volume, and recirculating the liquid catalyst to the reactor volume.

Generally, the present invention provides methods for the production of materials comprising a plurality of nanostructures such as nanotubes (e.g., carbon nanotubes) and related articles. The plurality of nanostructures may be provided such that their long axes are substantially aligned and, in some cases, continuous from end to end of the sample. For example, in some cases, the nanostructures may be fabricated by uniformly growing the nanostructures on the surface of a substrate, such that the long axes are aligned and non-parallel to the substrate surface. The nanostructures may be, in some instances, substantially perpendicular to the substrate surface. In one set of embodiments, a force with a component normal to the long axes of the nanostructures may be applied to the substantially aligned nanostructures. The application of a force may result in a material comprising a relatively high volume fraction or mass density of nanostructures. In some instances, the application of a force may result in a material comprising relatively closely-spaced nanostructures. The materials described herein may be further processed for use in various applications, such as composite materials (e.g., nanocomposites). For example, a set of aligned nanostructures may be formed, and, after the application of a force, transferred, either in bulk or to another surface, and combined with another material (e.g., to form a nanocomposite) to enhance the properties of the material.

Generally, the present invention provides methods for the production of materials comprising a plurality of nanostructures such as nanotubes (e.g., carbon nanotubes) and related articles. The plurality of nanostructures may be provided such that their long axes are substantially aligned and, in some cases, continuous from end to end of the sample. For example, in some cases, the nanostructures may be fabricated by uniformly growing the nanostructures on the surface of a substrate, such that the long axes are aligned and non-parallel to the substrate surface. The nanostructures may be, in some instances, substantially perpendicular to the substrate surface. In one set of embodiments, a force with a component normal to the long axes of the nanostructures may be applied to the substantially aligned nanostructures. The application of a force may result in a material comprising a relatively high volume fraction or mass density of nanostructures. In some instances, the application of a force may result in a material comprising relatively closely-spaced nanostructures. The materials described herein may be further processed for use in various applications, such as composite materials (e.g., nanocomposites). For example, a set of aligned nanostructures may be formed, and, after the application of a force, transferred, either in bulk or to another surface, and combined with another material (e.g., to form a nanocomposite) to enhance the properties of the material.