WO2019023455A1

WO2019023455A1 - Solid carbon products comprising carbon nanotubes and methods of forming same

Info

Publication number: WO2019023455A1
Application number: PCT/US2018/043902
Authority: WO
Inventors: Randall Smith; Dallas B. Noyes
Original assignee: Seerstone Llc
Priority date: 2017-07-28
Filing date: 2018-07-26
Publication date: 2019-01-31

Abstract

Methods of forming solid carbon products include disposing a plurality of nanotubes in a press, and applying heat to the plurality of carbon nanotubes to form the solid carbon product. Further processing may include sintering the solid carbon product to form a plurality of covalently bonded carbon nanotubes. The solid carbon product includes a plurality of voids between the carbon nanotubes having a median minimum dimension of less than about 100 nm. Some methods include compressing a material comprising carbon nanotubes, heating the compressed material in a non-reactive environment to form covalent bonds between adjacent carbon nanotubes to form a sintered solid carbon product, and cooling the sintered solid carbon product to a temperature at which carbon of the carbon nanotubes do not oxidize prior to removing the resulting solid carbon product for further processing, shipping, or use.

Description

SOLID CARBON PRODUCTS COMPRISING CARBON NANOTUBES

AND METHODS OF FORMING SAME

PRIORITY CLAIM

This application claims priority to U.S. Patent Application Serial No. 15/663,392, filed July

28, 2017, pending, which application is a continuation-in-part of co-pending U.S. Patent Application Serial No. 15/470,587, filed March 27, 2017, which is a divisional of U.S. Patent Application 14/414,232, filed January 12, 2015, now U.S. Patent 9,604,848, issued March 28, 2017, which is a national phase entry under 35 U.S.C. § 371 of International Patent Application PCT/US2013/049719, filed July 9, 2013, designating the United States of America and published in English as International Patent Publication WO 2014/011631 Al on January 16, 2014, which claims the benefit under Article 8 of the Patent Cooperation Treaty to U.S. Provisional Patent Application Serial No. 61/671,022, filed July 12, 2012, for "Solid Carbon Products Comprising Carbon Nanotubes and Methods of Forming Same," the disclosure of each of which is hereby incorporated herein in its entirety by this reference.

TECHNICAL FIELD

Embodiments of the disclosure relate to methods and systems for forming solid carbon products from carbon nanotubes including mixtures of various types of carbon nanotubes and mixtures of carbon nanotubes with other substances.

BACKGROUND

The following documents, each published in the name of Dallas B. Noyes, disclose background information hereto, and each is hereby incorporated herein in its entirety by this reference:

1. U.S. Patent Publication No. 2012/0034150 Al, published February 9, 2012;

2. International Application No. PCT/US2013/000071, filed March 15, 2013;

3. International Application No. PCT/US2013/000072, filed March 15, 2013;

4. International Application No. PCT/US2013/000073, filed March 15, 2013;

5. International Application No. PCT/US2013/000075, filed March 15, 2013;

6. International Application No. PCT/US2013/000076, filed March 15, 2013;

7. International Application No. PCT/US2013/000077, filed March 15, 2013;

8. International Application No. PCT/US2013/000078, filed March 15, 2013;

9. International Application No. PCT/US2013/000079, filed March 15, 2013; and

10. International Application No. PCT/US2013/000081, filed March 15, 2013.

Conventional methods of using CNTs ("carbon nanotubes") or carbon nanofibers in engineering materials generally rely on embedding the CNTs or carbon nanofibers in a matrix material. CNTs are currently processed in a wide variety of composite structures using metals, plastics, thermoset resins, epoxies, and other substances as the matrix to hold the CNTs together, thus creating solid objects. The CNTs act as reinforcing material to improve properties of the materials. Typical objectives of using carbon nanotubes in a matrix are to increase the strength, decrease weight, or to increase electrical and thermal conductivity of the composite.

Methods to make materials composed primarily of carbon nanotubes include spinning the carbon nanotubes into fibers and making "buckyrock." U.S. Patent 6,899,945, issued May 31, 2005, and entitled "Entangled single-wall carbon nanotube solid material and methods for making same" discloses a method for making buckyrock. Buckyrock is a three-dimensional, solid block material including an entangled network of single-wall CNTs. Buckyrock is mechanically strong, tough, and impact resistant with a bulk density of about 0.72 g/cm³ (see Example 3 of U.S. Patent No. 6,899,945). The single-wall CNTs in a buckyrock form are present in a random network. The random network of the CNTs appears to be held in place by Van der Waals forces between the CNTs and by physical entanglement or interference of the CNTs. One type of buckyrock is made by forming a slurry of CNTs in water, slowly removing water from the slurry to create a paste, and allowing the paste to dry very slowly, such that the CNT network of the paste is preserved during solvent evaporation. Buckyrock can be used in various applications requiring lightweight material with mechanical strength, toughness, and impact resistance, such as ballistic protection systems.

Though conventional materials including CNTs have interesting and useful properties, the individual CNTs comprising these materials have significantly different properties. It would therefore beneficial to produce materials having properties more comparable to the properties of individual CNTs.

DISCLOSURE

Methods of forming solid carbon products include pressure compaction methods such as extruding, die pressing, roller pressing, injection molding etc. to form solid shapes comprising a plurality of carbon nanotubes. The carbon nanotubes may optionally be mixed with other substances. Such solid shapes may be further processed by heating in an inert atmosphere to temperatures sufficient to sinter at least some of the CNTs so that covalent bonds form between adjacent CNTs. The methods may include forming a plurality of nanotubes, disposing the plurality of nanotubes in a press, and applying heat and pressure to the plurality of carbon nanotubes to form the solid carbon product. When sintered, the resulting material is a novel composition of matter having two or more CNTs with covalent bonding between them.

The solid carbon products, whether sintered or not, include interlocked CNTs that define a plurality of voids throughout the material. The dimension of the interstitial voids may be controlled by a variety of methods including controlling the characteristic diameter of the CNTs comprising the solid carbon products, the inclusion of other materials that may create voids when removed from the solid carbon products, and the pressure and temperatures at which the solid carbon products are formed.

Sintered solid carbon products include a plurality of covalently bonded carbon nanotubes. In some embodiments, the sintered solid carbon products further include amorphous carbon covalently bonded to other carbon atoms, which may be amorphous carbon or crystalline carbon. Some methods include compressing a material comprising carbon nanotubes, heating the compressed material in a non-reactive environment to form chemical bonds between adjacent carbon nanotubes and form a bonded carbon nanotube structure, and cooling the bonded carbon nanotube structure to a temperature at which carbon of the carbon nanotubes does not react with oxygen.

Other methods include first forming a solid carbon product by compressing a material comprising carbon nanotubes and subsequently placing the resulting solid carbon product into sintering conditions. The sintering conditions may include an inert environment, such as a vacuum or inert atmosphere (e.g., argon or helium). The solid carbon product is heated to a desired temperature for a period of time to induce covalent bonding between adjacent CNTs, after which the object is cooled below the oxidation temperature of carbon in air. The product may then be removed from the sintering conditions.

Such methods may include any of a variety of standard industrial processing methods such as extrusion, die pressing, injection molding, isostatic pressing, and roll pressing. The sintering of the solid carbon products can be performed in a variety of apparatus such as are commonly used in sintered powder metallurgy and sintered ceramic processing. The sintering of the solid carbon products may include any of a variety of means including induction heating, plasma arc discharge, high temperature autoclaves and annealing furnaces, and other related devices and methods as are known in the art.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 through 4 are simplified illustrations of carbon nanotubes;

FIGS. 5 through 9 are simplified cross-sectional views of presses for forming solid carbon products;

FIGS. 10 and 11 are simplified illustrations depicting the structures of linked carbon nanotubes;

FIG. 12 is a graph showing bulk densities of solid carbon products formed by compaction and sintering;

FIG. 13 is simplified illustration of a carbon nanofiber;

FIG. 14 is a simplified illustration illustrating a tool for additively manufacturing a carbon- containing material; FIG. 15 is a simplified flow diagram illustrating a method of additively manufacturing a carbon-containing material;

FIG. 16 is an energy -dispersive spectroscopy (EDS) of a structure formed according to methods described herein; and

FIG. 17 is a picture of the structure of FIG. 16.

MODE(S) FOR CARRYING OUT THE INVENTION

This disclosure includes methods of forming solid carbon products by applying heat and/or pressure to carbon nanotubes, carbon nanofibers, or both. As used herein, the term "solid carbon products" means and includes any material that comprises carbon and may include any material comprising at least one of one or more of carbon nanotubes and one or more carbon nanofibers. Solid carbon products may be useful in various applications, such as filters, reactors, electrical components (e.g., electrodes, wires, batteries), structures (e.g. , beams, frames, pipes), fasteners, molded parts (e.g., gears, bushings, pistons, turbines, turbine blades, engine blocks), etc. Such solid carbon products may exhibit enhanced properties (e.g., strength, electrical or thermal conductivity, specific surface area, porosity, etc.) with respect to conventional materials. This disclosure includes a new class of materials that contain a plurality of CNTs, a plurality of carbon nanofibers, or a combination thereof formed into solid shapes under pressure. When such solid shapes are sintered, covalent bonds form between at least some of the CNTs, the carbon nanofibers, or both forming solid shapes. This material has numerous useful properties.

In other embodiments, solid carbon products may be formed by additive manufacturing. The solid carbon products may be formed to include carbon-carbon covalent bonds between at least some adjacent CNTs and/or carbon nanofibers between at least some of their contact points. In some embodiments, at least some of the carbon of the solid carbon products include amorphous carbon.

As used herein, the term "sintering" means and includes annealing or pyrolizing solid carbon products (e.g., CNTs and/or carbon nanofibers) at temperatures and pressures sufficient to induce carbon-carbon covalent bonding between at least some of the adjacent CNTs and/or carbon nanofibers between at least some of their contact points.

As used herein, the term "catalyst residual" means and includes any non-carbon elements associated with a CNT and/or a carbon nanofiber. Such non-carbon elements may include a nanoparticle of a metal catalyst in the growth tip of CNTs, and metal atoms or groups of atoms randomly or otherwise distributed throughout and on the surfaces of CNTs and/or carbon nanofibers.

As used herein, the term "green" means and includes any solid carbon product that has not been sintered.

CNTs may be created through any method known to the art, including arc discharge, laser ablation, hydrocarbon pyrolysis, the Boudouard reaction, the Bosch reaction and related carbon oxide reduction reactions, or wet chemistry methods (e.g., the Diels-Alder reaction). The methods described herein are applicable to carbon nanotubes regardless of the method of manufacture or synthesis. Carbon nanofibers may be formed through any method known in the art, including deposition from carbon vapor, such as by catalytic chemical vapor deposition (CCVD) wherein carbon is deposited in the presence of a transition metal catalyst on a substrate, or other method of forming carbon nanofibers known in the art.

CNTs may occur as single-wall and multi-wall carbon nanotubes of various diameters ranging from a few nanometers to 100 nanometers in diameter or more. CNTs may have a wide variety of lengths and morphologies, and may occur as substantially parallel "forests", randomly tangled masses, or "pillows" of structured agglomerations. CNTs may also form or be compounded to form many different mixtures of CNTs with various combinations and distribution of the above characteristics (number of walls, diameters, lengths, morphology, orientation, etc.). Various mixtures, when compounded and used to form the solid carbon products described herein, may result in products with specifically engineered properties. For example, the median void size of interstitial spaces between CNTs comprising solid carbon products typically is approximately proportional to the characteristic diameters of the CNTs used in forming the solid carbon products. The median void size influences the overall porosity and density of the solid carbon products.

Various CNT features and configurations are illustrated in FIGS. 1 through 4. FIG. 1 shows a single-wall CNT 100, in which carbon atoms 102 are linked together in the shape of a single cylinder. The carbon atoms 102 are covalently bonded into a hexagonal lattice, and thus form a CNT 100 that appears as a single graphitic layer rolled into the form of a tube. The CNT 100 may be conceptualized as a "rolled graphene sheet" lattice pattern oriented so that the carbon atoms 102 spiral at various angles with regard to the axis of the CNT 100. The angle is called the "chirality" and common named forms include armchair and zigzag, as described in Mildred S. Dresselhaus and Phaedon Avouris, "Introduction to Carbon Materials Research, in Carbon Nanotubes: Synthesis, Structure, Properties, and Applications," 1, 6 (Mildred S. Dresselhaus, Gene Dresselhaus, & Phaedon Avouris, eds., 2001), the entire contents of which are incorporated herein by this reference. Many chiralities are possible; CNTs 100 with different chiralities may exhibit different properties (e.g., CNTs 100 may have either semiconductor or metallic electrical properties).

The CNT 100 has an inside diameter related to the number of carbon atoms 102 in a circumferential cross section. The CNT 100 depicted in FIG. 1 has a zigzag pattern, as shown at the end of the CNT 100. The diameter may also affect properties of the CNT 100. Single-walled CNTs 100 can have many different diameters, such as from approximately 1.0 nm (nanometer) to 10 nm or more. A CNT 100 may have a length from about 10 nm to about 1 μιη (micron), such as from about 20 nm to about 500 nm or from about 50 nm to about 100 nm. CNTs 100 typically have an aspect ratio (i.e., a ratio of the length of the CNT to the diameter of the CNT) of about 100: 1 to 1000: 1 or greater.

CNTs having more than one wall are called multi-wall CNTs. FIG. 2 schematically depicts a multi-wall CNT 120 having multiple graphitic layers 122, 124, 126, 128 arranged generally concentrically about a common axis. Double-walled and triple-walled carbon nanotubes are occasionally described as distinct classes; however, they may be considered as the smallest categories of multi-walled CNTs 120. Diameters of multi-wall CNTs 120 can range from approximately 3 nm to well over 100 nm. Multi-wall CNTs 120 having outside diameters of about 40 nm or more are sometimes referred to as carbon nanofibers in the art.

FIG. 3 depicts two forms of multi-wall CNTs 140, 150. In the CNT 140, one single-wall

CNT 142 is disposed within a larger diameter singe-wall CNT 144, which may in turn be disposed within another even larger diameter single-wall CNT 146. This CNT 140 is similar to the CNT 120 shown in FIG. 2, but includes three single-wall CNTs 142, 144, 146 instead of four. Another form of multi-wall CNTs shown in FIG 3 is CNT 150, which may be conceptualized as a single graphene sheet 152 rolled into tubes.

FIG. 4 schematically depicts a single-wall CNT 180 with an attached nanobud 182. The nanobud 182 has a structure similar to a spherical buckminsterfullerene ("buckyball"), and is bonded to the single-wall CNT 180 by carbon-carbon bonds. As suggested by the structure shown in FIG. 4, modifications may be made to the wall of a single-wall CNT 180 or to the outer wall of a multi-wall CNT. At the point of bonding between the nanobud 182 and the CNT 180, carbon double-bonds can break and result in "holes" in the wall of the CNT 180. These holes may affect the mechanical and electrical properties of the CNT 180. In single-wall CNTs, these holes may introduce a relative weakness when compared to unmodified cylindrical CNTs. In multi-wall CNTs, the outer wall may be affected, but any inner walls likely remain intact.

Carbon nanotubes are typically formed in such a way that a nanoparticle of catalyst is embedded in the growth tip of the carbon nanotube. This catalyst may optionally be removed by mild washing (e.g., by an acid wash). Without being bound to a particular theory, it is believed that if the catalyst is left in place, catalyst atoms become mobilized during the sintering process, and may migrate to the surface or within the pores of the carbon nanotubes. This process may disperse the catalyst atoms randomly, uniformly, or otherwise throughout the solid carbon product mass and may have a significant influence on the properties of the solid carbon product. For example, catalyst material may affect electrical conductivity or the ability to catalyze other chemical reactions.

The catalyst particles may be selected to catalyze other reactions in addition to the formation of solid carbon. Catalyst particles may be any material, such as a transition metal or any compound or alloy thereof. For example, catalyst particles may include nickel, vanadium oxide, palladium, platinum, gold, ruthenium, rhodium, iridium, etc. Because the catalyst particles are attached to or otherwise associated with CNTs, each catalyst particle may be physically separated from other catalyst particles. Thus, the catalyst particles may collectively have a much higher surface area than a bulk material having the same mass of catalyst. Catalyst particles attached to CNTs may therefore be particularly beneficial for decreasing the amount of catalyst material needed to catalyze a reaction and reducing the cost of catalysts. Compressed solid carbon products used as catalysts may, in many applications, benefit from the catalytic activity of both the CNT and the metal catalyst particles embedded in the growth tip of the CNTs.

The CNTs used in the processes herein may be single-wall CNTs, multi-wall CNTs, or combinations thereof, including bi-modally sized combinations of CNTs, mixtures of single-wall and multi-wall CNTs, mixtures of various sizes of single-wall CNTs, mixtures of various sizes of multi- wall CNTs, etc.

FIG. 13 schematically illustrates a carbon nanofiber 350 in accordance with embodiments of the disclosure. As used herein, the term "carbon nanofiber" means and includes a carbon-containing material comprising a solid cylindrical shape substantially free of any voids (e.g., without a hollow central portion). A carbon nanofiber may be similar to a CNT, but may include a solid core rather than a hollow central portion. Carbon nanofibers may exhibit a rod-like shape and may exhibit a greater density than CNTs. In some embodiments, carbon nanofibers may exhibit a greater density than CNTs having the same diameter. Carbon nanofibers may also be in the form of stacked graphene sheets.

The CNTs and the carbon nanofibers may be in forms such as a sheet-molded compound, a pressure-molded compound, or as a pourable liquid. The CNTs and/or the carbon nanofibers may be disposed within a press any other device structured and configured to provide pressure to the material. The press may include an extrusion die, a mold, a cavity, etc. In other embodiments, the CNTs and/or the carbon nanofibers, may be incorporated into a structure comprising the CNTs and/or the carbon nanofibers by additive manufacturing.

For example, in the press 200 shown in FIG. 5, a carbon-containing material (e.g., CNTs and/or carbon nanofibers) 202 may be placed in a hopper 204 configured to feed material through an extrusion die 206. The press 200 includes an extrusion barrel 208 with a screw mechanism 210 connected to a drive motor 212 to carry the carbon-containing material 202 through the extrusion barrel 208 to the extrusion die 206. The extrusion barrel 208 may optionally include means for heating the carbon-containing material 202 as the carbon-containing material 202 passes through the extrusion barrel 208. The extrusion die 206 has an opening with a shape corresponding to the cross-sectional shape of a part to be formed in the press 200. Extrusion dies 206 may be interchangeable, depending on the shape of objects desired. Some possible shapes of extrusion dies 206a, 206b, 206c are shown. For example, the extrusion die 206 may have an opening shaped like a circle, a regular polygon, an irregular polygon, an I-beam, etc. Extrusion dies 206 can be structured to create objects of extruded CNTs of a variety of shapes and sizes: symmetrical or asymmetrical, small to large. The carbon- containing material 202 may optionally be mixed with another material before or within the press 200.

In some embodiments and as shown in the press 220 of FIG. 6, the carbon-containing material 202 is placed into a hopper 224 configured to feed material to a mold 226. The press 220 includes a barrel 228 with a screw mechanism 230 connected to a drive motor 232 to carry the carbon-containing material 202 through the barrel 228 to the mold 226. The barrel 228 may optionally include means for heating the carbon-containing material 202 as the carbon-containing material 202 passes through the barrel 228. The mold 226 has an opening with an interior shape corresponding to the exterior shape of a part to be formed in the press 220. Molds 226 may be interchangeable, depending on the shape of objects desired. Some possible shapes of molds 226a and 226b are shown. For example, the mold 226 may have a shape of a screw or a propeller. The carbon-containing material 202 may optionally be mixed with another material before or within the press 200 to improve flowability, mold release, or other process properties. Such materials may be subsequently removed by suitable means such as etching, pyrolysis, evaporation, etc. The resulting solid carbon product may substantially free of the additional material, and may include essentially carbon and, in some embodiments, residual catalyst material.

In other embodiments and as shown in the press 240 of FIG.7, the carbon-containing material 202 is placed into a body 244 having an interior shape defining an exterior of a product to be formed. The carbon-containing material 202 may be placed between two pistons 246, 248 surrounded by the body 244. The body 244 may have walls 250 defining an interior cavity and configured to allow the pistons 246, 248 to slide freely. In other embodiments, a single piston may be configured to press carbon-containing material against a body.

In an embodiment as shown in the press 260 of FIG. 8, the carbon-containing material 202 is placed within a mold portion 262 having one or more surfaces corresponding to a shape of a product to be formed. One or more additional mold portions 264 are configured to press the carbon-containing material 202 against the mold portion 262, when pressed by pistons 266, 268, as shown in FIG. 9. Together, the mold portions 262, 264 define the shape of the product to be formed.

Pressure is applied to form the carbon-containing material into a cohesive "green" body. For example, the screw mechanisms 210, 230 shown in FIGS. 5 and 6 apply pressure to the carbon-containing material 202 as the carbon-containing material 202 passes through the presses 200, 220. Extrusion through a die 206 as shown in FIG. 5 may be continuous (theoretically producing an infinitely long product) or semi-continuous (producing many pieces). Examples of extruded material include wire, tubing, structural shapes, etc. Molding, as in the press 220 shown in FIG. 6, is the process of manufacturing by shaping pliable raw material (e.g., the carbon-containing material 202) using a rigid pattern (the mold 226). The carbon-containing material 202 may adopt the shape of the mold. The pistons 266, 268 shown in FIGS. 8 and 9 are pressed toward the carbon-containing material 202, forming the carbon-containing material 202 into a green body 270. The resulting green body 270 formed may be held together by relatively weak forces, such that the green body 270 may easily be further shaped (e.g., machined, drilled, etc.), but still holds its shape when handled. Each CNT and/or carbon nanofiber of the carbon-containing material of the green body 270 may each be in physical contact with one or more other CNTs and/or carbon nanofibers.

Heat is applied to green bodies to link the carbon-containing material together into a more cohesive body in which at least some of the adjacent CNTs and/or carbon nanofibers form covalent bonds between other CNTs and/or carbon nanofibers. For example, the carbon-containing material may be heated at a heating rate from about l°C/minute to about 50°C/minute to a temperature of at least 1500°C, 1800°C, 2100°C, 2400°C, 2500°C, 2700°C or even to just below the sublimation temperature of carbon (approximately 3600°C). Pressure may also be applied concurrently with, before, or after heat is applied. For example, the carbon-containing material may be pressed at 10 to 1000 MPa, such as 30 MPa, 60 MPa, 250 MPa, 500 MPa, or 750 MPa. The green bodies may be subjected to a heated inert environment, such as helium or argon, in an annealing furnace. Sintering the carbon-containing material (i.e., subjecting CNTs and/or carbon nanofibers to heat in an oxygen- free environment) apparently creates covalent bonds between the CNTs and/or carbon nanofibers at points of contact. The sintering of the carbon-containing material typically occurs in a non-oxidizing environment, such as a vacuum or inert atmosphere so that the CNTs and/or carbon nanofibers are not oxidized during the sintering. Sintering the carbon-containing material to induce chemical bonding at the contact surfaces may improve desirable material properties such as strength, toughness, impact resistance, electrical conductivity, or thermal conductivity in the solid structure product when compared to the green material. The carbon-containing material may also be sintered in the presence of additional constituents such as metals or ceramics to form composite structures, lubricants to aid processing, or binders (e.g., water, ethanol, polyvinyl alcohol, coal, tar pitch etc.). Materials may be introduced as powders, shavings, liquids, etc. Suitable metals may include, for example, iron, aluminum, titanium, antimony, Babbitt metals, etc. Suitable ceramics may include materials such as oxides (e.g., alumina, beryllia, ceria, zirconia, etc.), carbides, boride, nitrides, silicides, etc. In embodiments in which materials other than CNTs and/or carbon nanotubes are present, covalent bonding occurs between at least some of the CNTs and/or carbon nanofibers, and the additional materials may become locked into a matrix of CNTs and/or carbon nanofibers.

The carbon-containing material in the sintered body may comprise chemical bonds connecting CNTs and/or carbon nanofibers with each other. Chemical bonds, which are generally stronger than physical bonds, impart different properties on the collection of the carbon-containing material than physical bonds. That is, the sintered body may have higher strength, thermal conductivity, electrical conductivity, or other properties than the green body from which it was formed. When single-wall CNTs are covalently bonded to adjacent single-wall CNTs, holes can form on the surface of the CNTs as some of the carbon-carbon bonds break, thus modifying the mechanical and electrical properties of each single-wall CNT. Sintered single-wall CNTs, however, may still typically exceed non-sintered single-wall CNTs in such properties as strength, toughness, impact resistance, electrical conductivity, and thermal conductivity. With multi-wall CNTs, typically only the wall of the outer tube is modified; the internal walls remain intact. Thus, using multi-walled and bi- modally sized CNTs in, for example, extrusion and molding processes, may yield solid structures with properties that, in many respects, exceed practical limitations of single-walled CNTs. Similarly, using carbon nanofibers in, for example, extrusion and molding processes, may yield solid carbon products with properties that, in many respects, exceed practical limitations of carbon nanofiber bound together, such as in a tow or carbon nanofibers.

Sintering appears to cause covalent bonds to form between the walls of CNTs at their contact points and between outer surfaces of carbon nanofibers at their contact points. That is, any given CNT or carbon nanofiber may "cross-link" with an adjacent CNT or carbon nanofiber at the physical point of contact of the two structures. Any given CNT or carbon nanofiber having undergone sintering may be covalently bound to numerous other CNTs (both single-wall CNTs and multi-wall CNTs) and/or carbon nanofibers. This increases the strength of the resulting structure because the CNTs and/or carbon nanofibers do not slide or slip at the bonding points. Unsintered, CNTs (e.g., in buckyrock) and/or carbon nanofibers may slide with respect to each other. Because the covalent bonding caused by sintering may occur at numerous sites in the mass of CNTs and/or carbon nanofibers, the sintered body has significantly increased strength, toughness, impact resistance, and conductivity over convention agglomerations of CNTs and/or carbon nanofibers.

FIG. 10 schematically depicts the cross-linked structure of two covalently bound carbon- containing structures 280, 282 (e.g., CNTs and/or carbon nanofibers) produced by sintering. When sintered, the carbon-containing structures 280, 282 covalently bond at their contact points 284. Each carbon-containing structure may form covalent bonds with some or all of the other carbon-containing structures with which it is in contact during sintering. In some embodiments, the covalent bonds are formed during sintering of the carbon-containing structures 280, 282 at temperatures greater than about 1,600°C. By way of nonlimiting example, due to the internal layering in a multi-wall CNT, covalent boding between the individual walls of the multi-wall CNT is likely to occur under sintering conditions. The heating and optional pressurization of the carbon-containing structures in a sintering process are maintained until the desired level of cross-linking has occurred. The sintered carbon- containing structures are then cooled to a temperature at which the carbon-containing structures will not spontaneously react with oxygen. Thereafter, the mixture may be exposed to air for further processing, storage, packaging, shipment, sale, etc. In another embodiment, a mixture comprising one or more CNTs, one or more carbon nanofibers, or both, is heated in a reactive environment (e.g., in the presence of oxygen, hydrogen, a hydrocarbon, and/or another material). In this embodiment, heat and pressure are maintained as needed until the reactants in the reactive environment have reacted with one another or with the CNTs and/or carbon nanofibers. The product is then cooled. In such a process, the reactants may form additional holes or pores in the CNTs and/or carbon nanofibers, increasing the specific surface area of the sintered body. Alternatively, the reactants may deposit materials on the surface of the CNTs and/or carbon nanofibers without affecting the underlying CNT and/or carbon nanofiber structure.

In another embodiment, the mixture comprising one or more CNTs and/or one or more carbon nanofibers is initially heated and sintered in a nonreactive environment (e.g., in a vacuum, in the presence of helium, or in the presence of argon). Subsequent to sintering, the heat and pressure are changed to suitable reaction conditions and reactants are added to the environment. Such reactants may include a variety of metals (as liquid or vapor), metal carbonyls, silanes, or hydrocarbons. The reaction of the reactants with one another or with the carbon of the one or more CNTs and/or one or more carbon nanofibers may fill some or all of the interstices of the solid carbon product lattice (e.g., the CNT lattice) with products of the reactions. Such processing with additional reactants may in some cases be conducted during sintering, but may also be performed separately. The heat and pressure are maintained until the desired level of reaction (both cross-linking within the CNTs and/or carbon nanofibers, and the reaction between the CNTs and/or carbon nanofibers and the reactant) has occurred. The reacted mixture is then cooled and removed from the reaction environment for further processing, storage, packaging, shipment, sale, etc.

FIG. 11 schematically depicts a mass 300 of covalently bound CNTs 302. The CNTs 302 bind through sintering with other CNTs 302 (multi-wall or single-wall CNTs) through mutual contact points 304, binding the aggregate together into a highly cross-linked structure. The resultant binding may create a material of significant strength, toughness, impact resistance, and electrical and thermal conductivity. Although FIG. 11 has been described as including a mass 300 of covalently bound CNTs 302, the disclosure is not so limited. In other embodiments, the mass 300 may comprise covalently bound carbon nanofibers. In some embodiments, the mass 300 comprises covalently bound carbon nanofibers and covalently bound CNTs. At least some of the CNTs may be covalently bound to other CNTs and to at least some of the carbon nanofibers and at least some of the carbon nanofibers may be covalently bound to at least other carbon nanofibers and to at least some of the CNTs.

During the sintering process, the green body may shrink, corresponding with a decrease in the size of voids among the CNTs and/or carbon nanofibers. However, the sintered body may remain porous due to the porosity of each CNT (i.e., the center of the CNT) and due to voids between and among CNTs and/or carbon nanofibers. The sintered body may have pores or voids having a median minimum dimension of less than about 1 μιη, less than about 500 nm, less than about 100 nm, less than about 50 nm, or even less than about 10 nm. That is, each void may have two or more dimensions (e.g. , a length, a width, and a height, each perpendicular to the others, or a diameter and a length), measured in different directions. The voids need not be regularly shaped. The "minimum dimension" is defined as the minimum of the two or more dimensions of a single void. The "median minimum dimension" is defined as the median of these minimum dimensions for a group of voids.

A sintered body as described herein may have a high specific surface area, due to voids between CNTs and/or carbon nanofibers and within CNTs (i.e., because the CNTs are hollow). For example, a sintered body may have a specific surface area of at least about 100 m²/g, at least about 500 m²/g, at least about 750 m²/g, at least about 900 m²/g, or even at least about 1000 m²/g. The specific surface area can be controlled by the characteristic diameters or mixture of diameters of the CNTs and/or carbon nanofibers used in forming the solid carbon product. For example, small-diameter single-wall CNTs have specific surface areas up to approximately 3000 m²/g, while large-diameter multi-wall CNTs have specific surface areas of approximately 100 m²/g. In some embodiments, the sintered body may be formed from CNTs having at least one property (e.g., a diameter, a density, a specific surface area, a length, etc.) different than an analogous property of at least some carbon nanofibers used to form the sintered body.

A sintered body may have a high electrical conductivity. For example, a sintered body may have an electrical conductivity of at least about 1 x 10⁵ S/m (Siemens per meter), at least about 1 x 10⁶ S/m, at least about 1 x 10⁷ S/m, or even at least about 1 x 10⁸ S/m. The electrical conductivity can be controlled by the types of carbon-containing materials (e.g., CNTs and/or carbon nanofibers) used, the chirality of the carbon-containing materials (e.g., CNTs and/or carbon nanofibers) used, the sintering conditions, and the quantity of resulting covalent bonds in the solid carbon product. For example, single-wall CNTs with a metallic chirality have a much higher electrical conductivity than multi-wall CNTs. As a further example, an increase in the number of covalent bonds appears to correlate with an increase in conductivity.

A sintered body may also have a high thermal conductivity. For example, a sintered body may have a thermal conductivity of at least about 400 W/m-K (watts per meter per Kelvin), at least about 1000 W/m-K, at least about 2000 W/m-K, or even at least about 4000 W/m-K. The thermal conductivity of the resulting solid carbon product may be controlled by the types of carbon-containing material (e.g., CNTs and/or carbon nanofibers) used and the chirality of the carbon-containing material (e.g., CNTs and/or carbon nanofibers used). For example, single-wall CNTs with a metallic chirality have much high thermal conductivity than large multi-wall CNTs.

CNTs and/or nanofibers may alternatively be pressed after the sintering process by, for example, extrusion or molding, as described above with respect to FIGS. 5 through 9. In some embodiments, the sintering process may be part of the formation of the desired object. For example, a section of the extrusion barrel may heat the CNTs and/or carbon nanofibers to the sintering temperature in an inert atmosphere for an appropriate amount of time to cause sintering. Such heating may be, for example, induction heating or plasma arc heating. Thus, sintered CNTs and/or sintered carbon nanofibers may be extruded. The sintered CNTs and/or sintered carbon nanofibers may optionally be mixed with another material such as a metal, a ceramic, or glass. The material may be pressed or pulled through a die under either extreme heat or cold. The material, forced into a given shape, is held in place for a period of time and at sintering temperatures and pressures, and then returned to normal atmospheric conditions. The products may be continuous, such as wires, or may be discrete pieces, such as bolts, propellers, gears, etc. Molding of sintered or sintering CNTs and/or carbon nanofibers typically involves either using the CNT material and/or the carbon nanofiber material in concentrated form (i.e., with minimal impurities) or in forming a moldable composite with another material, such as a metal. The moldable material is placed or poured into a rigid mold, held at a particular temperature and pressure, and then cooled back to normal atmospheric conditions.

In some embodiments, an incremental manufacturing method may be employed wherein, CNTs (either compressed or not) and/or carbon nanofibers are placed in a nonreactive environment, such as in an inert gas autoclave. The CNTs and/or carbon nanofibers are sintered to form covalent bonds between the CNTs and/or carbon nanofibers in the surface layer and the underlying layer. For example, a laser may irradiate a portion of the CNTs and/or carbon nanofibers in a pattern. Additional CNTs and/or carbon nanofibers are deposited over the sintered CNTs and/or carbon nanofibers, and in turn sintered. The sintering process is repeated as many times as necessary to achieve a selected thickness of sintered structure comprising CNTs and/or carbon nanofibers. The sintered CNTs and/or carbon nanofibers are then cooled to a temperature below which the CNTs and/or carbon nanofibers do not react with oxygen or other atmospheric gases. The sintered CNTs and/or carbon nanofibers may then be removed from the nonreactive environment without contaminating the sintered CNTs and/or carbon nanofibers. In some embodiments, the sintered CNTs and/or carbon nanofibers are cooled and removed from the nonreactive environment before deposition of each additional portion of CNTs and/or carbon nanofibers.

In some embodiments, a structure comprising CNTs and/or carbon nanofibers may be formed by additive manufacturing, such as by, for example, selective laser sintering (SLS), laser engineered net shaping, or other 3D printing or additive manufacturing process. In some embodiments, the structure may be formed one layer at a time. FIG. 14 is a cross-sectional view of a tool 400 for additively manufacturing a structure 450. The structure 450 may be disposed on a movable stage 410. In some embodiments, the structure 450 is disposed over a substrate on the movable stage 410. The movable stage 410 may comprise a piston configured to move in a vertical direction (e.g., up and down in the cross-sectional view illustrated in FIG. 14). In some such embodiments, the movable stage 410 may be configured to move closer to (e.g., toward) and away from a laser 402. The movable stage 410 may be disposed between sidewall structures 412. The tool 400 may include one or more powder delivery nozzles 404. The powder delivery nozzles 404 may be configured to provide a powder material over a surface of the structure 450 on the movable stage 410 to form a powder layer 420 thereon. In some embodiments, the powder delivery nozzles 404 may be configured to provide the powder layer 420 to the structure 450 coaxially with the laser radiation from the laser 402. Each of the powder delivery nozzles 404 may be configured to provide a powder material having a different composition than that provided by the other powder delivery nozzles 404. In some embodiments, the powder may be provided from the powder delivery nozzles 404 to the surface of the structure 450 or the substrate by gravity. In other embodiments, the powder may be fed with an inert carrier gas, such as, for example, nitrogen, argon, helium, another inert carrier gas, or combinations thereof. Although FIG. 14 illustrates two powder delivery nozzles 404, the tool 400 may include one powder delivery nozzle 404 or more than two powder delivery nozzles 404 (e.g., three, four, etc.). A shield gas, which may comprise, for example, one or more of the carrier gases (e.g., nitrogen, argon, helium, etc.) configured to shield the powder layer from, for example, oxygen, or to promote layer to layer adhesion, may be provided through one or more shield gas ports 406. Although not shown, the powder delivery nozzles 404 may be operably coupled to a powder source and the shield gas ports 406 may be operably coupled to a shield gas source.

The laser 402 may be configured to direct electromagnetic radiation (e.g., laser radiation) through a lens 408 and to the powder layer 420 over the structure 450. Responsive to exposure to heat provided by the laser radiation, individual particles of the powder layer 420 may form inter-granular bonds with each other and with previously formed layers of the structure 450 previously exposed to the laser radiation.

The lens 408 may comprise a focusing lens and may be positioned to focus laser radiation from the laser 402 a predetermined distance from the laser 402.

The movable stage 410, on which the structure 450 may be disposed, may be configured to move in one or more directions. By way of nonlimiting example, the movable stage 410 may be configured to move in one or more of a z-direction (e.g., up and down in the cross-sectional view of FIG. 14), an x-direction (e.g., left and right in the cross-sectional view of FIG. 14), and a y-direction (e.g., into and out of the plane of the cross-sectional view of FIG. 14). Since the structure 450 is disposed on, or otherwise attached to, the movable stage 410, the structure 450 may be configured to move relative to the laser 402.

In other embodiments, the laser 402 may be configured to move in one or more directions, such as, for example, one or more of the z-direction, the y-direction, and the x-direction. Accordingly, the laser 402 may be configured to move relative to the structure 450 and the movable stage 410.

In use and operation, the powder layer 420 may be formed over an uppermost surface of the structure 450. The powder layer 420 may be exposed to laser radiation from bonds between the powder and the structure 450 (e.g., such as by sintering). Exposing the powder layer 420 to laser radiation may form another layer on the structure 450. As described above, at least one of the laser 402 or the movable stage 410 may be coupled to a suitable drive assembly to move in a horizontal plane (e.g., the x-direction, the y-direction, or both) in a designated pattern and speed to expose selected portions of the powder layer 420 to the laser radiation. After formation of the layer of the structure, the structure 450 may be moved away from the laser 402 (such as by moving the laser 402, moving the movable stage 410, or both) a predetermined distance, which may correspond to a thickness of the previously formed layer of the structure 450. By way of nonlimiting example, the movable stage 410 may be moved away from the laser 402 after forming a layer of the structure 450. Movement of the structure 450 relative to the laser 402 may form a cavity defined by the previously formed layer and the sidewalls 412. Powder may be deposited within the cavity and over the structure 450 by one or more of the powder delivery nozzles 404 to form another powder layer 420 over the previously formed layer of the structure 450. The powder layer 420 may be compacted and subsequently exposed to laser radiation to form another layer of the structure 450. Accordingly, the structure 450 may be formed layer-by -layer.

In some embodiments, the tool 400 may be substantially enclosed, such as with an enclosure 440. The interior of the enclosure 440 may be substantially free of oxygen or other gases that may oxidize or otherwise react with the powders that form the structure 450 during exposure of the powders to the laser radiation. In some embodiments, the interior of the enclosure 440 includes one or more of the shield gases (e.g., argon). In some embodiments, a concentration of oxygen in the enclosure 440 may be less than about 70 ppm, such as less than about 50 ppm, less than about 40 ppm, less than about 20 ppm, or less than about 10 ppm.

Although the tool 400 has been described as including powder delivery nozzles 404, the disclosure is not so limited. In other embodiments, the tool 400 may include a different powder delivery system. By way of nonlimiting example, the tool 400 may include a powder delivery piston located adjacent the movable stage 410 such as in a selective laser sintering (SLS) tool. The powder delivery piston may be configured to introduce one or more powders to a location coplanar with an uppermost surface of the structure 450. A roller may be configured to roll powder from the powder delivery system to a location on the uppermost surface of the structure 450.

FIG. 15 is a simplified flow diagram illustrating a method 500 of forming at least one structure by additive manufacturing, in accordance with embodiments of the disclosure. The method 500 may include act 502 including forming one or more powder mixtures that will be used to additively manufacture a structure; act 504 including introducing the one or more powder mixtures over a substrate to form a powder layer on the substrate; act 506 including selectively exposing at least a portion of the powder layer to laser radiation to form a layer of a structure; and act 508 including repeating cycles of act 504 and act 506 until a net shape of the structure is formed. Act 502 includes forming one or more mixtures of a powder that will be used to additively manufacture at least one structure. In some embodiments, a first powder material is mixed with at least a second, different powder material to form a powder mixture including particles of the first powder material substantially homogeneously dispersed throughout particles of the second powder material.

The first powder material may comprise CNTs, carbon nanofibers, a combination thereof. By way of nonlimiting example, the powder material may comprise single-wall CNTs and multi-wall CNTs, such as the single-wall and the multi-wall CNTs described above. A diameter of particles of the first powder material may be between about 1 nm and about 100 μιη, such as between about 1 nm and about 10 nm, between about 10 nm and about 50 nm, between about 50 nm and about 100 nm, between about 100 nm and about 500 nm, between about 500 nm and about 1 μιη, between about 1 μιη and about 5 μιη, between about 5 μιη and about 10 μιη, between about 10 μιη and about 50 μιη, or between about 50 μιη and about 100 μιη. In some embodiments, the diameter of the particles of the first powder material is between about 1 μιη and about 5 μιη.

The second powder material may comprise one or more materials that may be incorporated into the structure being formed. In some embodiments, the second powder material comprises at least one material selected from the group consisting of at least one metal, at least one ceramic (e.g., a carbide, a nitride, a silicide, an oxide), and at least one other material. By way of nonlimiting example, the second powder material may comprise one or more of aluminum, silicon, phosphorus, sulfur, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, palladium, silver, cadmium, tin, tantalum, tungsten, platinum, and gold, a ceramic (e.g., a carbide (e.g., aluminum carbide, tungsten carbide, cementite, silicon carbide, titanium carbide, boron carbide, etc.), an oxide (e.g., alumina (A1₂0₃), beryllia, ceria, zirconia, etc.) a nitride (e.g., silicon nitride), a silicide (e.g., ferrosilicon (Fe₅Si₂), manganese silicide (MnSi₂), titanium disilicide (TiSi₂), silicon boride (SiB₄, SiB₆), etc.), borides (such as, for example, aluminum diboride (A1B₂), cobalt boride (CoB, C0₂B), nickel boride (NiB), tantalum boride (TaB, TaB₂), titanium boride (TiB₂), tungsten boride (WB), etc.), or combinations thereof.

The first powder material may constitute between about 1 weight percent (1 wt. %) and about 50 weight percent of the powder mixture, such as between about 1 weight percent and about 5 weight percent, between about 5 weight percent and about 10 weight percent, between about 10 weight percent and about 20 weight percent, between about 20 weight percent and about 30 weight percent, between about 30 weight percent and about 40 weight percent, or between about 40 weight percent and about 50 weight percent of the powder mixture.

The second powder material may constitute between about 50 weight percent and about 99 weight percent of the powder mixture, such as between about 50 weight percent and about 60 weight percent, between about 60 weight percent and about 70 weight percent, between about 70 weight percent and about 80 weight percent, between about 80 weight percent and about 90 weight percent, or between about 90 weight percent and about 99 weight percent of the powder mixture.

In some embodiments, particles of the powder mixture may comprise coated particles. One of the first powder material and the second powder material may be coated with the other of the first powder material and the second powder material. By way of nonlimiting example, particles of one or more CNTs and/or carbon nanofibers may be coated with one or more materials of the second powder material (e.g., at least one of one or more of metals and one or more ceramics). In other embodiments, one or more particles of the second powder material may be coated with one or more of CNTs and/or carbon nanofibers. The particles of the powder material may be coated by one or more of atomic layer deposition (ALD), chemical vapor deposition (CVD), or other suitable method. In some such embodiments, forming the one or more powder mixtures may include forming a powder mixture comprising one or more of CNTs and/or carbon nanofibers coated with a second material or a second material coated with one or more of CNTs and/or carbon nanofibers.

Act 504 includes introducing the one or more powder mixtures over a substrate to form a powder layer over the substrate. In some embodiments the first powder material and the second powder material may be disposed over the substrate separately, such as through separate powder delivery nozzles 404 (FIG. 14). In other embodiments, the first powder material and the second powder material may be premixed to a selected composition prior to introducing the powder mixture over the substrate.

Sufficient powder may be provided over the surface of the substrate to form a layer having a thickness between about 10 nm and about 100 μιη, such as between about 10 nm and about 50 nm, between about 50 nm and about 100 nm, between about 100 nm and about 500 nm, between about 500 nm and about 1 μιη, between about 1 μιη and about 5 μιη, or between about 5 μιη and about 10 μιη.

The powder may be provided to the selected locations over the substrate such that a cross- sectional profile of the powder layer exhibits a selected cross-sectional shape and composition of the structure. By way of nonlimiting example, where the structure being formed comprises, for example, an I-beam, the cross-sectional profile of the powder layer formed over the structure may exhibit a cross-sectional profile of the I-beam.

The powder delivery nozzles 404 (FIG. 14) may be controlled by a processor having associated therewith a memory including instructions configured to direct each powder delivery nozzle 404 to locations where powder from the respective powder delivery nozzle 404 should be provided. By way of nonlimiting example, the memory may include data for formation of a selected structure in the form of a computer-aided-design (CAD) model or a computer-aided-manufacturing (CAM) model configured to direct the powder delivery nozzles 404. In other embodiments, the laser 402 (FIG. 14) may be controlled by a processor having the instructions. In some such embodiments, the laser 402 may be configured to scan and expose a selected pattern of the powder layer over the structure to form bonds between selected portions of the powder layer and the uppermost layer of the structure.

Act 506 includes selectively exposing at least a portion of the powder layer to laser radiation, such as portions of the powder layer that are desired to be in the final structure, to form a layer of a structure. Exposing the powder layer to the laser radiation may form inter-granular bonds between adjacent particles of the powder layer and underlying layers of the structure previously formed. In some embodiments, exposing the powder layer to the laser radiation forms carbon-carbon bonds between particles of the powder layer and between particles of the powder layer and underlying particles of the structure previously formed. In some embodiments, such as where the second powder material comprises carbon (e.g., a carbide material), exposing the powder layer to the laser radiation may form carbon-carbon bonds between at least some particles of the first powder material and at least some particles of the second powder material. Exposing the powder layer to the laser radiation may further form metal-metal bonds between particles of the second powder material in the same layer and between particles of the second powder material in adjacent layers.

As described above, at least one of the movable stage 410 (FIG. 14) and the laser 402

(FIG. 14) may be operably coupled to a processor and an associated memory including instructions to move one or both of the movable stage 410 and the laser 402 in the X-Y plane. Accordingly, portions of the powder layer may be selectively exposed to the laser radiation while other portions of the powder layer are unexposed to the laser radiation. In some such embodiments, a shape of the structure being formed may exhibit any selected shape and each layer of the structure may have a different shape than other layers of the structure.

The laser 402 may be any suitable laser configured to provide energy in the form of electromagnetic radiation (e.g., laser radiation) to the powder layer. In some embodiments, the laser 402 is configured to provide electromagnetic radiation having a substantially monochromatic wavelength to the powder layer. By way of nonlimiting example, the laser 402 may comprise a helium-neon laser (having a wavelength of about 632.8 nm), an argon laser (having a wavelength of about 454.6 nm, about 488.0 nm, or about 514.5 nm), a krypton laser (having a wavelength between about 416 nm, about 530.9 nm, about 568.2 nm, 647.1 nm, about 676.4 nm, about 752.5 nm, or about 799.3 nm, a xenon ion laser, a nitrogen laser (having a wavelength of about 337.1 nm), a carbon dioxide laser (having a wavelength of about 10.6 μιη), a carbon monoxide laser (having a wavelength between about 2.6 μιη and about 4.0 μιη or between about 4.8 μιη and about 8.3 μιη), an excimer laser (having a wavelength of about 193 nm, about 248 nm, about 308 nm, or about 353 nm), a fiber laser, or combinations thereof. However, the laser is not so limited and may comprise any suitable laser to provide sufficient energy to the powder layer to form bonds therein. The laser 402 may be configured to provide electromagnetic radiation having a power between about 10 W and about 1 kW, such as between about 10 W and about 50 W, between about 50 W and about 100 W, between about 100 W and about 500 W, or between 500 W and about 1 kW. However, the laser 402 may have a different power and the disclosure is not limited by laser type or power.

Exposing the powder layer to the laser radiation may locally heat the powder layer at regions that are exposed to the laser radiation. In some embodiments, the powder layer may be locally heated to temperatures sufficient to melt at least the second powder material. In some embodiments, the temperature may be between a melting temperature of the second powder material and a melting temperature of carbon (e.g., of carbon nanotube and of carbon nanofibers). In some such embodiments, the temperature may be less than about 3,500°C. By way of nonlimiting example, the temperature may be between about 500°C and about 3,500°C, such as between about 500°C and about 1,000 °C, between about 1,000°C and about 1,500°C, between about 1,500°C and about 2,000°C, between about 2,000°C and about 2,500°C, between about 2,500°C and about 3,000°C, or between about 3,000°C and about 3,500°C. In some embodiments, the temperature may be between about 1,400°C and the sublimation temperature of carbon. In other embodiments, the temperature may be at least about 2, 100°C.

In some embodiments, the second powder material may be selected to exhibit a greater thermal expansion that the first powder material. In some such embodiments, particles of the second powder material may condense or shrink onto particles of the first powder material responsive to cooling after exposure to the laser radiation. Such differences in thermal expansion and cooling of particles of the second powder material may form a physical (e.g., mechanical) bond between particles of the first powder material and particles of the second powder material in the same layer of the structure and in adjacent layers of the structure.

Act 508 includes repeating cycles of act 504 and act 506 until a net shape (i.e., a near final shape) of the structure is formed. After exposing the powder layer to laser radiation to form a layer of the structure, the structure may be moved a predetermined distance from the laser 402 (FIG. 14), which may correspond to a thickness of the layer of the structure previously formed. Another powder layer may be formed over the previously formed layer of the structure. The additional powder layer may exhibit the same or a different cross-sectional shape as previously formed layers of the structure.

The structure may be formed layer-by -layer to form a structure exhibiting a net shape of a final structure. Each layer of the structure may exhibit a different cross-sectional shape than other layers of the structure.

In some embodiments, the structure may be machined, heat treated, or a combination thereof, to a final shape after the additive manufacturing process.

The structure formed according to the method 500 may include one or more of structural members (e.g., beams), fasteners (e.g., screws), moving parts (e.g., propellers, crankshafts, etc.), tubes, channels, plates, electrically conductive members (e.g., electrodes, wires, etc.), a stage of a scanning electron microscope (SEM), or any other structure. FIG. 16 is an energy -dispersive spectroscopy (EDS) of a structure formed according to the method 500 of FIG. 15. The structure comprised a stage of a scanning electron microscope. The structure comprised about 20.3 weight percent (wt. %) carbon, about 6.8 weight percent oxygen, about 0.9 weight percent sodium, about 61.6 weight percent aluminum, and about 10.4 weight percent silicon. The structure comprised about 35.1 atomic percent carbon, about 8.9 atomic percent oxygen, about 0.9 atomic percent sodium, about 47.4 atomic percent aluminum, and about 7.7 atomic percent silicon.

FIG. 17 is picture of the structure of FIG. 16. The structure exhibited covalently bonded carbon atoms. At least some of the carbon atoms were amorphous carbon and at least some of the carbon atoms were crystalline (e.g., graphitic).

In certain embodiments, sintered solid carbon products are formed in a belt-casting operation. A layer of CNTs and/or carbon nanofibers is placed on a moveable belt. The belt moves the CNTs and/or carbon nanofibers into a chamber containing a nonreactive environment. The CNTs and/or carbon nanofibers are sintered in the chamber, then cooled (e.g., in a portion of the chamber), and removed from the chamber. The process may be operated continuously, such as to form a sheet of sintered CNTs and/or carbon nanofibers.

In some embodiments, solid carbon products are further treated by electrodeposition to fill interstices in the solid carbon products with another material. A solution having materials to be deposited is prepared. The solvent of the solution may be water, an organic solvent, or an inorganic solvent. The solute may include a material such as a metal salt, an organic salt, a metalorganic salt, etc. Electroplating solutions are known in the art and not described in detail herein. The solid carbon product to be treated is contacted with the solution, such as by immersing the body in the solution. An electric potential (a direct-current voltage or an alternating-current voltage) is applied to the body to induce electrodeposition of one or more components of the solution. The composition, potential, temperature, and/or pressure are maintained until a selected amount of the material is deposited onto the solid carbon product. The solid carbon product is then removed from the solution and rinsed to remove excess solution.

Solid carbon products formed as described herein each include a plurality of cross-linked CNTs and/or carbon nanofibers. The CNTs define a plurality of voids, which may have a median minimum dimension of less than about 1 μιη, less than about 500 nm, less than about 100 nm, less than about 50 nm, or even less than about 10 nm. Some or all of the carbon-containing material (e.g., the CNTs and/or the carbon nanofibers) may include a metal, such as a metal particle from which the CNTs and/or carbon nanofibers were formed, or a metal coating on the CNTs and/or carbon nanofibers. The solid carbon products may be structural members (e.g., beams), fasteners (e.g., screws), moving parts (e.g. , propellers, crankshafts, etc.), electrically conductive members (e.g. , electrodes, wires, etc.), or any other form. The solid carbon product may include another material dispersed in a continuous matrix surrounding and in contact with the CNTs and/or carbon nanofibers. The solid carbon products may have improved strength, toughness, impact resistance, and electrical and thermal conductivity in comparison to conventional materials.

In some embodiments, the solid carbon products also include other morphologies of carbon, interspersed with or otherwise secured to the CNTs and/or carbon nanofibers. For example, buckyballs may be connected to some of the CNTs and/or carbon nanofibers. As another example, one or more graphene sheets may be formed over all or a portion of a solid carbon product.

Both the compressed solid carbon products and the sintered solid carbon products described herein have a wide variety of potentially useful applications. For example, the compressed solid carbon products may be used as filters, molecular sieves, catalysts, and electrodes in applications where the additional mechanical integrity achieved through sintering is not necessary. The sintered solid carbon products can be used in the applications in which compressed solid carbon products can be used and in a wide variety of additional applications requiring additional mechanical integrity, electrical properties, and other material-property enhancements achieved through sintering.

Sintered solid carbon products may be useful components of armor because of their mechanical integrity, ability to absorb compressive loads with a high spring constant, and ability to dissipate heat. That is, sintered solid carbon products may be used to form projectile-resistant materials, such as armor plates, bullet-proof vests, etc. The light weight of the solid carbon products could improve mission pay loads, increase vehicle range, and alter the center of gravity. For example, armor materials including sintered solid carbon products may be beneficial in preventing injury and death of occupants of vehicles such as Mine Resistant Ambush Protected vehicles ("MRAPs"), which are prone to tipping. Sintered solid carbon products as described herein may be effective in lightweight armament systems such as mortar tubes, gun barrels, cannon barrels, and other components. Sintered solid carbon products may also be beneficial in aerial vehicles, such as aircraft, spacecraft, missiles, etc.

EXAMPLES

Example 1 : Sintering of Compacted CNTs

CNTs were formed as described in U.S. Patent Publication No. 2012/0034150 Al. Samples of approximately 1.0 grams to 1.25 grams of CNTs each were pressed in 15-mm diameter dies using a 100-ton (890-kN) press. The pressed samples were placed in an inert gas furnace (Model 1000-3060- FP20, available from Thermal Technology, LLC, of Santa Rosa, CA) and heated under vacuum at a rate of 25°C until the samples reached 400°C. This temperature was maintained for 30 minutes to allow the samples to outgas any oxygen, water, or other materials present. The furnace was then filled with inert gas (argon or helium) at 3-5 psi (21 to 34 kPa) above atmospheric pressure. The furnace was heated at a rate of 20°C/minute until the sample reached 1500°C. This temperature was maintained for 30 minutes. Heating continued at 5°C/minute to a sintering temperature, which was maintained for a dwell time of 60 minutes. The samples were then cooled at 50°C/minute to 1000°C, after which the furnace was shut down until the samples reached ambient temperature. The sample masses, compaction pressures, and sintering temperatures for the samples are shown in Table 1 below. The inert gas was helium for the samples sintered at 2400°C and was argon for the other samples.

Table 1 : Samples prepared in Example 1

Samples 1 through 18 were harder and more robust than were the samples before the heating process. At the highest sintering temperature of 2400°C (samples 7 through 9), the sintered pellets are flakier than the other sintered samples. All the samples prepared in Example 1 were qualitatively observed to be hard.

Pycnometry tests show that the skeletal density decreases from 2.2 g/cm³ for raw powders and raw compactions to 2.1 g/cm³, 2.08 g/cm³, and 2.05 g/cm³ for the samples sintered at 1800°C, 2100°C, and 2400°C, respectively. Bulk density also decreased after sintering, in almost every case to less than 1.0 g/cm³. Pellet thickness increased 5% to 9% during sintering, with the higher pressure compactions expanding more than the lower pressure compactions. The bulk densities of Samples 1 through 9 are shown in Table 2 and in FIG. 12. Table 2: Properties of samples prepared in Example 1 :

Example 2: Spark Plasma Sintering of CNTs

CNTs were formed as described in U.S. Patent Publication No. 2012/0034150 Al. Graphite foil (available from Mineral Seal Corp., of Tucson, AZ) was lined into 20-mm diameter dies, and 2.0 g to 4.0 g of CNTs were placed over the foil. The samples were placed in a spark plasma sintering (SPS) system (model SPS 25-10, available from Thermal Technology, LLC, of Santa Rosa, CA). An axial pressure of approximately 5 MPa was applied to the CNT samples, and the SPS system was then evacuated to less than 3 mTorr (0.4 Pa). The sample was heated at 150°C/minute to 650°C, and this temperature was maintained for one minute to allow the vacuum pump to re-evacuate any materials out-gassed. The pressure was increased to the compaction pressure of 30 MPa or 57 MPa, while simultaneously increasing the temperature at a rate of 50°C/minute to 1500°C. The temperature and pressure were maintained for one minute. The temperature was then increased at 50°C/minute to the sintering temperature, and maintained for 10 minutes or 20 minutes. After the dwell, the pressure was reduced to 5 MPa, and the sample allowed to cool at 150°C/minute to 1000°C, after which the furnace was shut off until the samples reached ambient temperature.

The sample masses, compaction pressures, compaction rates, sintering temperatures, and dwell times for the samples are shown in Table 2 below.

Table 3: Samples prepared in Example 2:

Sample Mass (g) Compaction Compaction Sintering Dwell time

Pressure (MPa) rate (MPa/min) Temperature (°C) (min)

19 2.449 57 13.0 1800 10

20 3.027 57 13.0 2100 10 21 4.180 57 13.0 1800 20

22 4.210 30 6.0 1800 10

23 4.417 30 6.0 1800 20

The SPS-sintered pellets formed in Example 2 were about 10 mm thick and had bulk densities between 1.3 g/cm³ and 1.5 g/cm³. To illustrate the strength of these samples, sample #20 was planned to be sintered 2100°C, but at about 1900°C, the die broke. The ram traveled significantly, crushing the graphite die. After the test was completed, the die was broken away from the sample. The sample remained visibly intact, though slightly thinner than expected. This would indicate that the sintering occurs at temperatures less than 1900°C, that the strength of SPS-sintered pellets is high, even at extreme temperatures, and that the sintered samples are strong enough to resist an applied force without fracturing.

The bulk densities of the samples with the graphite foil still attached were determined. For the samples weighing about 4 g (i.e., samples #21, #22, and #23), bulk densities were between 1.35 g/cm³ and 1.50 g/cm³. The volume resistivity and electrical conductivity of the samples were also measured. These data are shown in Table 4. The samples are more conductive than amorphous carbon, and nearly as conductive as graphite.

Table 4: Properties of samples prepared in Example 2:

Although the foregoing description contains many specifics, these are not to be construed as limiting the scope of the present invention, but merely as providing certain embodiments. Similarly, other embodiments of the invention may be devised which do not depart from the scope of the present invention. For example, features described herein with reference to one embodiment also may be provided in others of the embodiments described herein. The scope of the invention is, therefore, indicated and limited only by the appended claims and their legal equivalents, rather than by the foregoing description. All additions, deletions, and modifications to the invention, as disclosed herein, which fall within the meaning and scope of the claims, are encompassed by the present invention.

Claims

1. A method of forming a structure comprising solid carbon products by additive manufacturing, the method comprising:

providing a first layer of a powder mixture over a substrate, the powder mixture comprising at least one solid carbon product selected from the group consisting of carbon nanotubes and carbon nanofibers;

exposing the first layer of the powder mixture to electromagnetic radiation from a laser to form a first layer of a structure comprising covalently bonded carbon atoms;

forming a second layer of the powder mixture over the first layer of the structure; and

exposing the second layer of the powder mixture to electromagnetic radiation from the laser to form a second layer of the structure comprising covalently bonded carbon atoms and to form covalent bonds between carbon atoms of the first layer of the structure and carbon atoms of the second layer of the structure.

2. The method of claim 1, further comprising:

selecting the first layer of the powder mixture to comprise carbon nanotubes.

3. The method of claim 1, further comprising:

selecting the first layer of the powder mixture to comprise carbon nanofibers.

4. The method of claim 1, wherein providing a first layer of a powder mixture over a substrate comprises providing a first layer of a powder mixture comprising at least one material selected from the group consisting of a metal material and a ceramic material.

5. The method of claim 4, wherein exposing the first layer of the powder mixture to electromagnetic radiation from a laser comprises forming a mechanical bond between the at least one solid carbon product and the at least one material selected from the group consisting of the metal material and the ceramic material.

6. The method of claim 4, wherein providing a first layer of a powder mixture comprising at least one material selected from the group consisting of a metal material and a ceramic material comprises providing a powder mixture comprising at least one material selected from the group consisting of carbides, oxides, nitrides, silicides, and borides.

7. The method of claim 1, wherein providing a first layer of a powder mixture over a substrate comprises providing a first layer of a powder mixture comprising at least one material selected from the group consisting of aluminum, silicon, phosphorus, sulfur, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, palladium, silver, cadmium, tin, tantalum, tungsten, platinum, and gold.

8. The method of claim 1, wherein providing a first layer of a powder mixture over a substrate comprises selecting the at least one solid carbon product to constitute between about 1 weight percent and about 50 weight percent of the powder mixture.

9. The method of claim 8, wherein providing a first layer of a powder mixture over a substrate comprises providing a powder mixture comprising between about 50 weight percent and about 99 weight percent of at least one of a metal material or a ceramic material over the substrate.

10. The method of claim 1, wherein providing a first layer of a powder mixture over a substrate comprises providing a first layer of a powder mixture having a thickness between about 10 nm and about 100 μιη over the substrate.

11. The method of claim 1, wherein providing a first layer of a powder mixture over a substrate comprises providing the first layer over the substrate such that the first layer exhibits a cross- sectional shape of a structure selected from the group consisting of a beam, a fastener, a propeller, a crankshaft, a gear, a bushing, a piston, a turbine, a turbine blade, and engine block, and an electrically conductive member.

12. The method of claim 1, wherein exposing the first layer of the powder mixture to electromagnetic radiation from a laser comprises exposing the first layer of the powder mixture to at least a melting temperature of a material selected from the group consisting of a metal material and a ceramic material and below a melting temperature of the solid carbon product.

13. The method of claim 1, wherein providing a first layer of a powder mixture over a substrate comprises providing a powder mixture comprising particles selected from the group consisting of carbon nanotubes and carbon nanofibers coated with at least one material selected from the group consisting of a metal material and a ceramic material over the substrate.

14. The method of claim 1, wherein providing a first layer of a powder mixture comprising over a substrate comprises providing a powder mixture comprising particles of a material selected from the group consisting of a metal material and a ceramic material coated with a material selected from the group consisting of carbon nanotubes and carbon nanofibers.

15. The method of claim 1, wherein exposing the first layer of the powder to electromagnetic radiation from a laser comprises melting at least one metal material onto surfaces of particles of the at least one solid carbon product.

16. The method of claim 15, wherein exposing the first layer of the powder to electromagnetic radiation from a laser comprises melting the at least one metal material while the at least one solid carbon product remains in a solid state.