US20210053831A1 - Additively manufacturing structures comprising carbon - Google Patents
Additively manufacturing structures comprising carbon Download PDFInfo
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- US20210053831A1 US20210053831A1 US17/080,566 US202017080566A US2021053831A1 US 20210053831 A1 US20210053831 A1 US 20210053831A1 US 202017080566 A US202017080566 A US 202017080566A US 2021053831 A1 US2021053831 A1 US 2021053831A1
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Definitions
- 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.
- 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.
- 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 ⁇ m, 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 ⁇ m, between about 1 ⁇ m and about 5 ⁇ m, or between about 5 ⁇ m and about 10 ⁇ m.
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
- This application is a divisional of U.S. patent application Ser. No. 15/663,392, filed Jul. 28, 2017, which will issue as U.S. Pat. No. 10,815,124 on Oct. 27, 2020, and is a continuation-in-part of U.S. patent application Ser. No. 15/470,587, filed Mar. 27, 2017, which is a divisional of U.S. patent application Ser. No. 14/414,232, filed Jan. 12, 2015, now U.S. Pat. No. 9,604,848, issued Mar. 28, 2017, which is a national phase entry under 35 U.S.C. § 371 of International Patent Application PCT/US2013/049719, filed Jul. 9, 2013, designating the United States of America and published in English as International Patent Publication WO 2014/011631 A1 on Jan. 16, 2014, which claims the benefit under Article 8 of the Patent Cooperation Treaty to U.S. Provisional Patent Application Ser. No. 61/671,022, filed Jul. 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.
- 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.
- 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 A1, published Feb. 9, 2012;
- 2. International Application No. PCT/US2013/000071, filed Mar.
- 4. International Application No. PCT/US2013/000073, filed Mar. 15, 2013;
- 5. International Application No. PCT/US2013/000075, filed Mar. 15, 2013;
- 6. International Application No. PCT/US2013/000076, filed Mar. 15, 2013;
- 7. International Application No. PCT/US2013/000077, filed Mar. 15, 2013;
- 8. International Application No. PCT/US2013/000078, filed Mar. 15, 2013;
- 9. International Application No. PCT/US2013/000079, filed Mar. 15, 2013; and
- 10. International Application No. PCT/US2013/000081, filed Mar. 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. Pat. No. 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. Pat. 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.
- 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.
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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 ofFIG. 16 . - 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-walled CNT 100, in whichcarbon atoms 102 are linked together in the shape of a single cylinder. Thecarbon atoms 102 are covalently bonded into a hexagonal lattice, and thus form aCNT 100 that appears as a single graphitic layer rolled into the form of a tube. TheCNT 100 may be conceptualized as a “rolled graphene sheet” lattice pattern oriented so that thecarbon atoms 102 spiral at various angles with regard to the axis of theCNT 100. The angle is called the “chirality” and common named forms include armchair and zigzag, as described in Mildred S. Dresselhaus & 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 ofcarbon atoms 102 in a circumferential cross section. TheCNT 100 depicted inFIG. 1 has a zigzag pattern, as shown at the end of theCNT 100. The diameter may also affect properties of theCNT 100. Single-walled CNTs 100 can have many different diameters, such as from approximately 1.0 nm (nanometer) to 10 nm or more. ACNT 100 may have a length from about 10 nm to about 1 μm (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-walled CNTs.
FIG. 2 schematically depicts amulti-walled CNT 120 having multiplegraphitic layers multi-walled CNTs 120. Diameters ofmulti-walled CNTs 120 can range from approximately 3 nm to well over 100 nm.Multi-walled 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 ofmulti-walled CNTs multi-walled CNT 140, one single-walled CNT 142 is disposed within a larger diameter single-walled CNT 144, which may in turn be disposed within another even larger diameter single-walled CNT 146. Thismulti-walled CNT 140 is similar to themulti-walled CNT 120 shown inFIG. 2 , but includes three single-walled CNTs FIG. 3 ismulti-walled CNT 150, which may be conceptualized as asingle graphene sheet 152 rolled into tubes. -
FIG. 4 schematically depicts a single-walled CNT 180 with an attachednanobud 182. Thenanobud 182 has a structure similar to a spherical buckminsterfullerene (“buckyball”), and is bonded to the single-walled CNT 180 by carbon-carbon bonds. As suggested by the structure shown inFIG. 4 , modifications may be made to the wall of a single-walled CNT 180 or to the outer wall of a multi-walled CNT. At the point of bonding between thenanobud 182 and the single-walled CNT 180, carbon double-bonds can break and result in “holes” in the wall of theCNT 180. These holes may affect the mechanical and electrical properties of the single-walled CNT 180. In single-walled CNTs, these holes may introduce a relative weakness when compared to unmodified cylindrical CNTs. In multi-walled 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-walled CNTs, multi-walled CNTs, or combinations thereof, including bi-modally sized combinations of CNTs, mixtures of single-walled and multi-walled CNTs, mixtures of various sizes of single-walled CNTs, mixtures of various sizes of multi-walled CNTs, etc.
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FIG. 13 schematically illustrates acarbon 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 inFIG. 5 , a carbon-containing material (e.g., CNTs and/or carbon nanofibers) 202 may be placed in ahopper 204 configured to feed material through anextrusion die 206. Thepress 200 includes anextrusion barrel 208 with ascrew mechanism 210 connected to adrive motor 212 to carry the carbon-containingmaterial 202 through theextrusion barrel 208 to the extrusion die 206. Theextrusion barrel 208 may optionally include means for heating the carbon-containingmaterial 202 as the carbon-containingmaterial 202 passes through theextrusion 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 thepress 200. Extrusion dies 206 may be interchangeable, depending on the shape of objects desired. Some possible shapes of extrusion dies 206 a, 206 b, 206 c 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-containingmaterial 202 may optionally be mixed with another material before or within thepress 200. - In some embodiments and as shown in the
press 220 ofFIG. 6 , the carbon-containingmaterial 202 is placed into ahopper 224 configured to feed material to amold 226. Thepress 220 includes abarrel 228 with ascrew mechanism 230 connected to adrive motor 232 to carry the carbon-containingmaterial 202 through thebarrel 228 to themold 226. Thebarrel 228 may optionally include means for heating the carbon-containingmaterial 202 as the carbon-containingmaterial 202 passes through thebarrel 228. Themold 226 has an opening with an interior shape corresponding to the exterior shape of a part to be formed in thepress 220.Molds 226 may be interchangeable, depending on the shape of objects desired. Some possible shapes ofmolds mold 226 may have a shape of a screw or a propeller. The carbon-containingmaterial 202 may optionally be mixed with another material before or within thepress 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 ofFIG. 7 , the carbon-containingmaterial 202 is placed into abody 244 having an interior shape defining an exterior of a product to be formed. The carbon-containingmaterial 202 may be placed between twopistons body 244. Thebody 244 may havewalls 250 defining an interior cavity and configured to allow thepistons - In an embodiment as shown in the
press 260 ofFIG. 8 , the carbon-containingmaterial 202 is placed within amold portion 262 having one or more surfaces corresponding to a shape of a product to be formed. One or moreadditional mold portions 264 are configured to press the carbon-containingmaterial 202 against themold portion 262, when pressed bypistons FIG. 9 . Together, themold portions - Pressure is applied to form the carbon-containing material into a cohesive “green” body. For example, the
screw mechanisms FIGS. 5 and 6 apply pressure to the carbon-containingmaterial 202 as the carbon-containingmaterial 202 passes through thepresses die 206 as shown inFIG. 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 thepress 220 shown inFIG. 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-containingmaterial 202 may adopt the shape of the mold. - The
pistons FIGS. 8 and 9 are pressed toward the carbon-containingmaterial 202, forming the carbon-containingmaterial 202 into agreen body 270. The resultinggreen body 270 formed may be held together by relatively weak forces, such that thegreen 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 thegreen 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 1° C./min to about 50° C./min 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-walled CNTs are covalently bonded to adjacent single-walled 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-walled CNT. Sintered single-walled CNTs, however, may still typically exceed non-sintered single-walled CNTs in such properties as strength, toughness, impact resistance, electrical conductivity, and thermal conductivity. With multi-walled 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-walled CNTs and multi-walled 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.
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FIG. 10 schematically depicts the cross-linked structure of two covalently bound carbon-containingstructures 280, 282 (e.g., CNTs and/or carbon nanofibers) produced by sintering. When sintered, the carbon-containingstructures structures - 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.
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FIG. 11 schematically depicts amass 300 of covalently boundCNTs 302. TheCNTs 302 bind through sintering with other CNTs 302 (multi-walled or single-walled 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. AlthoughFIG. 11 has been described as including amass 300 of covalently boundCNTs 302, the disclosure is not so limited. In other embodiments, themass 300 may comprise covalently bound carbon nanofibers. In some embodiments, themass 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 μm, 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-walled CNTs have specific surface areas up to approximately 3000 m2/g, while large-diameter multi-walled 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 1×105 S/m (Siemens per meter), at least about 1×106 S/m, at least about 1×107 S/m, or even at least about 1×108 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-walled CNTs with a metallic chirality have a much higher electrical conductivity than multi-walled 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-walled CNTs with a metallic chirality have much high thermal conductivity than large multi-walled 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 atool 400 for additively manufacturing astructure 450. Thestructure 450 may be disposed on amovable stage 410. In some embodiments, thestructure 450 is disposed over a substrate on themovable stage 410. Themovable stage 410 may comprise a piston configured to move in a vertical direction (e.g., up and down in the cross-sectional view illustrated inFIG. 14 ). In some such embodiments, themovable stage 410 may be configured to move closer to (e.g., toward) and away from alaser 402. Themovable stage 410 may be disposed betweensidewall structures 412. - The
tool 400 may include one or morepowder delivery nozzles 404. Thepowder delivery nozzles 404 may be configured to provide a powder material over a surface of thestructure 450 on themovable stage 410 to form apowder layer 420 thereon. In some embodiments, thepowder delivery nozzles 404 may be configured to provide thepowder layer 420 to thestructure 450 coaxially with the laser radiation from thelaser 402. Each of thepowder delivery nozzles 404 may be configured to provide a powder material having a different composition than that provided by the otherpowder delivery nozzles 404. In some embodiments, the powder may be provided from thepowder delivery nozzles 404 to the surface of thestructure 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. AlthoughFIG. 14 illustrates twopowder delivery nozzles 404, thetool 400 may include onepowder 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 moreshield gas ports 406. Although not shown, thepowder delivery nozzles 404 may be operably coupled to a powder source and theshield 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 alens 408 and to thepowder layer 420 over thestructure 450. Responsive to exposure to heat provided by the laser radiation, individual particles of thepowder layer 420 may form inter-granular bonds with each other and with previously formed layers of thestructure 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 thelaser 402. - The
movable stage 410, on which thestructure 450 may be disposed, may be configured to move in one or more directions. By way of nonlimiting example, themovable 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 ofFIG. 14 ), an x-direction (e.g., left and right in the cross-sectional view ofFIG. 14 ), and a y-direction (e.g., into and out of the plane of the cross-sectional view ofFIG. 14 ). Since thestructure 450 is disposed on, or otherwise attached to, themovable stage 410, thestructure 450 may be configured to move relative to thelaser 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, thelaser 402 may be configured to move relative to thestructure 450 and themovable stage 410. - In use and operation, the
powder layer 420 may be formed over an uppermost surface of thestructure 450. Thepowder layer 420 may be exposed to laser radiation from bonds between the powder and the structure 450 (e.g., such as by sintering). Exposing thepowder layer 420 to laser radiation may form another layer on thestructure 450. As described above, at least one of thelaser 402 or themovable 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 thepowder layer 420 to the laser radiation. After formation of the layer of the structure, thestructure 450 may be moved away from the laser 402 (such as by moving thelaser 402, moving themovable stage 410, or both) a predetermined distance, which may correspond to a thickness of the previously formed layer of thestructure 450. By way of nonlimiting example, themovable stage 410 may be moved away from thelaser 402 after forming a layer of thestructure 450. Movement of thestructure 450 relative to thelaser 402 may form a cavity defined by the previously formed layer and thesidewall structures 412. Powder may be deposited within the cavity and over thestructure 450 by one or more of thepowder delivery nozzles 404 to form anotherpowder layer 420 over the previously formed layer of thestructure 450. Thepowder layer 420 may be compacted and subsequently exposed to laser radiation to form another layer of thestructure 450. Accordingly, thestructure 450 may be formed layer-by-layer. - In some embodiments, the
tool 400 may be substantially enclosed, such as with anenclosure 440. The interior of theenclosure 440 may be substantially free of oxygen or other gases that may oxidize or otherwise react with the powders that form thestructure 450 during exposure of the powders to the laser radiation. In some embodiments, the interior of theenclosure 440 includes one or more of the shield gases (e.g., argon). In some embodiments, a concentration of oxygen in theenclosure 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 includingpowder delivery nozzles 404, the disclosure is not so limited. In other embodiments, thetool 400 may include a different powder delivery system. By way of nonlimiting example, thetool 400 may include a powder delivery piston located adjacent themovable 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 thestructure 450. A roller may be configured to roll powder from the powder delivery system to a location on the uppermost surface of thestructure 450. -
FIG. 15 is a simplified flow diagram illustrating amethod 500 of forming at least one structure by additive manufacturing, in accordance with embodiments of the disclosure. Themethod 500 may includeact 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 ofact 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-walled CNTs and multi-walled CNTs, such as the single-walled and multi-walled CNTs described above. A diameter of particles of the first powder material may be between about 1 nm and about 100 μm, 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 μm, between about 1 μm and about 5 μm, between about 5 μm and about 10 μm, between about 10 μm and about 50 μm, or between about 50 μm and about 100 μm. In some embodiments, the diameter of the particles of the first powder material is between about 1 μm and about 5 μm.
- 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 (Al2O3), 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 (AlB2), cobalt boride (CoB, CO2B), 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 μm, 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 μm, between about 1 μm and about 5 μm, or between about 5 μm and about 10 μm.
- 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 eachpowder delivery nozzle 404 to locations where powder from the respectivepowder 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 thepowder delivery nozzles 404. In other embodiments, the laser 402 (FIG. 14 ) may be controlled by a processor having the instructions. In some such embodiments, thelaser 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 themovable stage 410 and thelaser 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, thelaser 402 is configured to provide electromagnetic radiation having a substantially monochromatic wavelength to the powder layer. By way of nonlimiting example, thelaser 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 μm), a carbon monoxide laser (having a wavelength between about 2.6 μm and about 4.0 μm or between about 4.8 μm and about 8.3 μm), 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. Thelaser 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, thelaser 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 ofact 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 themethod 500 ofFIG. 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 ofFIG. 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 μm, 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 payloads, 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 light-weight 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.
- CNTs were formed as described in U.S. Patent Publication No. 2012/0034150 A1. 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, Calif.) 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./min until the sample reached 1500° C. This temperature was maintained for 30 minutes. Heating continued at 5° C./min to a sintering temperature, which was maintained for a dwell time of 60 minutes. The samples were then cooled at 50° C./min 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 Compaction Sintering Mass Pressure Temperature Sample (g) (MPa) (° C.) 1 1.076 500 1800 2 1.225 750 1800 3 1.176 250 1800 4 1.113 500 2100 5 1.107 750 2100 6 1.147 250 2100 7 1.103 500 2400 8 1.198 750 2400 9 1.121 250 2400 10 1.128 250 1900 11 1.209 500 1900 12 1.212 750 1900 13 1.101 250 2000 14 1.091 500 2000 15 1.225 750 2000 16 1.078 250 1700 17 1.179 500 1700 18 1.157 750 1700 -
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 inFIG. 12 . -
TABLE 2 Properties of samples prepared in Example 1: After Compaction After Sintering Compaction Skeletal Bulk Sintering Skeletal Bulk Pressure Density Density Temperature Density Density Sample (MPa) (g/cc) (g/cc) (° C.) (g/cc) (g/cc) 1 600 2.1992 1.043 1800 2.1095 0.960 2 900 2.2090 1.095 1800 2.0993 0.994 3 300 0.990 1800 2.1131 0.921 4 600 1.063 2100 2.0680 0.971 5 900 1.084 2100 2.0817 0.992 6 300 0.999 2100 2.0829 0.910 7 300 0.985 2400 2.0553 0.932 8 600 1.069 2400 2.0479 1.009 9 900 1.102 2400 2.0666 0.991 - CNTs were formed as described in U.S. Patent Publication No. 2012/0034150 A1. Graphite foil (available from Mineral Seal Corp., of Tucson, Ariz.) 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, Calif.). 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./min 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./min to 1500° C. The temperature and pressure were maintained for one minute. The temperature was then increased at 50° C./min to the sintering temperature, and maintained for 10 min or 20 min. After the dwell, the pressure was reduced to 5 MPa, and the sample allowed to cool at 150° C./min 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: Compaction Compaction Sintering Mass Pressure rate Temperature Dwell time Sample (g) (MPa) (MPa/min) (° 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: Electrical Density Resistance Resistivity Conductivity Sample (g/cm3) (Ω) (Ω · m) (S/m) 19 1.588 2.42 × 10−3 4.98 × 10−5 2.01 × 10−4 20 1.715 2.02 × 10−3 4.77 × 10−5 2.10 × 10−4 21 1.494 3.24 × 10−3 1.23 × 10−4 8.14 × 10−3 22 1.350 3.80 × 10−3 1.62 × 10−4 6.19 × 10−3 23 1.429 3.7 × 10−3 1.57 × 10−4 6.37 × 10−3 - 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 (20)
1. A method of additively manufacturing a structure comprising carbon, the method comprising:
providing a first layer of a solid carbon product in a nonreactive environment;
exposing the solid carbon product to laser radiation to covalently bond at least some carbon atoms of the solid carbon product with other carbon atoms of the solid carbon product;
depositing additional solid carbon product on first layer to form a second layer; and
exposing the additional solid carbon product to laser radiation to covalently bond at least some carbon atoms of the additional solid carbon product to other carbon atoms of the solid carbon product and to at least some carbon atoms of the first layer.
2. The method of claim 1 , wherein providing the first layer of a solid carbon product in a nonreactive environment comprises placing the solid carbon product and a material selected from the group consisting of nickel, vanadium oxide, palladium, platinum, gold, ruthenium, rhodium, and iridium in the nonreactive environment.
3. The method of claim 1 , wherein exposing the solid carbon product to laser radiation comprises exposing a pattern of the solid carbon product to the laser radiation.
4. A method of additively manufacturing a structure comprising at least one of carbon nanotubes and carbon nanofibers, the method comprising:
providing a powder over a substrate to form a first layer of the powder over the substrate, the powder comprising particles of at least one solid carbon product selected from the group consisting of carbon nanotubes and carbon nanofibers and at least one material selected from the group consisting of a metal material and a ceramic material;
exposing the first layer of the powder to laser radiation to form a first layer of a structure comprising inter-granular bonds between particles of the at least one solid carbon product and to form a mechanical bond between the at least one material selected from the group consisting of the metal material and the ceramic material and the at least one solid carbon product;
providing a second layer of the powder over the first layer of the structure; and
exposing the second layer of the powder to laser radiation to form a second layer of the structure and to form inter-granular bonds between the first layer of the structure and the second layer of the structure.
5. The method of claim 4 , further comprising selecting the at least one material to comprise a material selected from the group consisting of at least one carbide, at least one oxide, at least one nitride, at least one silicide, and at least one boride.
6. The method of claim 4 , wherein exposing the first layer of the powder to laser radiation comprises melting at least one metal material onto surfaces of particles of the at least one solid carbon product.
7. The method of claim 6 , wherein exposing the first layer of the powder to laser radiation comprises melting the at least one metal material while the at least one solid carbon product remains in a solid state.
8. The method of claim 4 , further comprising:
providing the substrate on a movable stage; and
moving the movable stage a distance corresponding to a thickness of the first layer of the structure after exposing the first layer of the powder to the laser radiation.
9. The method of claim 4 , wherein providing a powder over a substrate to form a first layer of the powder over the substrate comprises providing a powder comprising the at least one material exhibiting a greater thermal expansion than the at least one solid carbon product.
10. The method of claim 4 , further comprising condensing particles of the at least one material on particles of the at least one solid carbon product after exposing the first layer of the powder to laser radiation.
11. The method of claim 4 , wherein providing a powder over a substrate to form a first layer of the powder over the substrate comprises providing a powder comprising one of the at least one solid carbon product or the at least one material coated with the other of the at least one solid carbon product or the at least one material over the substrate.
12. The method of claim 4 , wherein exposing the first layer of the powder to laser radiation comprises exposing the first layer of the powder to a temperature between about 1,000° C. and about 1,500° C.
13. The method of claim 4 , wherein exposing the first layer of the powder to laser radiation comprises exposing the first layer of the powder to a temperature between about 1,500° C. and about 2,000° C.
14. The method of claim 4 , wherein exposing the first layer of the powder to laser radiation to form a first layer of a structure comprising inter-granular bonds between particles of the at least one solid carbon product comprises forming the first layer of the structure to comprise amorphous carbon.
15. The method of claim 4 , wherein exposing the first layer of the powder to laser radiation to form a first layer of a structure comprising inter-granular bonds between particles of the at least one solid carbon product comprises forming at least some amorphous carbon bonded to crystalline carbon.
16. A method of additively manufacturing a structure comprising carbon, the method comprising:
introducing, to a substrate, a powder comprising particles of a first material coated with a second material, one of the first material and the second material comprising one or both of carbon nanofibers and carbon nanotubes and the other of the first material and the second material comprising a material selected from the group consisting at least one metal and at least one ceramic material;
exposing the powder to laser radiation to form a first layer of a structure comprising inter-granular bonds between the particles of the powder;
introducing additional powder comprising particles of the first material coated with the second material to the first layer of the structure; and
and exposing the additional powder to laser radiation.
17. The method of claim 16 , wherein introducing, to a substrate, a powder comprising particles of a first material coated a second material comprises introducing, to the substrate, particles comprising one or both of carbon nanotubes and carbon nanofibers coated with one or both of at least one metal and at least one ceramic material.
18. The method of claim 16 , wherein introducing, to a substrate, a powder comprising particles of a first material coated a second material comprises introducing, to the substrate, particles comprising one or both of at least one metal and at least one ceramic material coated with one or both of carbon nanotubes and carbon nanofibers.
19. The method of claim 16 , wherein exposing the powder to laser radiation to form a first layer of a structure comprising inter-granular bonds between the particles of the powder comprises forming the first layer of the structure to comprise amorphous carbon.
20. The method of claim 16 , further comprising:
selecting the second material to comprise the material selected from the group consisting of at least one metal and at least one ceramic material; and
selecting the powder to comprise from about 50 weight percent to about 99 weight percent of the second material.
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---|---|---|---|---|
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US11752459B2 (en) | 2016-07-28 | 2023-09-12 | Seerstone Llc | Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same |
WO2019023455A1 (en) * | 2017-07-28 | 2019-01-31 | Seerstone Llc | Solid carbon products comprising carbon nanotubes and methods of forming same |
US11167375B2 (en) | 2018-08-10 | 2021-11-09 | The Research Foundation For The State University Of New York | Additive manufacturing processes and additively manufactured products |
CN115052834A (en) * | 2019-10-28 | 2022-09-13 | 赛尔斯通股份有限公司 | Heat treatment of carbon oxide coke |
JPWO2021106482A1 (en) * | 2019-11-26 | 2021-12-02 | パナソニックIpマネジメント株式会社 | Compressor |
US11930565B1 (en) * | 2021-02-05 | 2024-03-12 | Mainstream Engineering Corporation | Carbon nanotube heater composite tooling apparatus and method of use |
Family Cites Families (385)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3172774A (en) | 1965-03-09 | Method of forming composite graphite coated article | ||
US1478730A (en) | 1922-03-09 | 1923-12-25 | Roy H Brownlee | Special carbon black |
US1746464A (en) | 1925-07-21 | 1930-02-11 | Fischer Franz | Process for the production of paraffin-hydrocarbons with more than one carbon atom |
US1735925A (en) | 1925-08-28 | 1929-11-19 | Selden Co | Process of producing reduction products of carbon dioxide |
US1964744A (en) | 1930-02-20 | 1934-07-03 | William W Odell | Process of making carbon black |
US2429980A (en) | 1942-11-27 | 1947-11-04 | Lion Oil Co | Process of conducting chemical reactions |
US2440424A (en) | 1944-05-04 | 1948-04-27 | Columbian Carbon | Manufacture of carbon black |
US2404869A (en) | 1945-05-10 | 1946-07-30 | Oceanic Tank Proc Corp | Vacuum pumping system |
US2731328A (en) | 1950-05-29 | 1956-01-17 | Phillips Petroleum Co | Carbon black manufacture |
US2811653A (en) | 1953-05-22 | 1957-10-29 | Rca Corp | Semiconductor devices |
US3094634A (en) | 1953-06-30 | 1963-06-18 | Rca Corp | Radioactive batteries |
US2837666A (en) | 1953-07-24 | 1958-06-03 | Ernest G Linder | Radioactive voltage source employing a gaseous dielectric medium |
US2796327A (en) | 1953-08-21 | 1957-06-18 | Phillips Petroleum Co | Process for producing carbon black, acrylonitrile and hydrogen cyanide |
US2745973A (en) | 1953-11-02 | 1956-05-15 | Rca Corp | Radioactive battery employing intrinsic semiconductor |
US2800616A (en) | 1954-04-14 | 1957-07-23 | Gen Electric | Low voltage electrolytic capacitor |
US2976433A (en) | 1954-05-26 | 1961-03-21 | Rca Corp | Radioactive battery employing semiconductors |
US2796331A (en) | 1954-06-09 | 1957-06-18 | Pittsburgh Coke & Chemical Co | Process for making fibrous carbon |
US2819414A (en) | 1954-08-02 | 1958-01-07 | Rca Corp | Radioactive battery employing stacked semi-conducting devices |
US3249830A (en) | 1962-01-09 | 1966-05-03 | Electro Organics Inc | Organic semi-conductor materials and contact rectifier employing the same |
US3378345A (en) | 1965-03-22 | 1968-04-16 | Union Carbide Corp | Process for producing pyrolytic graphite whiskers |
US3488394A (en) | 1966-05-11 | 1970-01-06 | Fmc Corp | Oxidation of olefinic compounds to glycols |
US3634999A (en) | 1970-04-08 | 1972-01-18 | Allied Chem | Method for recovering dust produced in sodium carbonate manufacture |
US3714474A (en) | 1970-10-07 | 1973-01-30 | Ecc Corp | Electron-voltaic effect device |
US3771959A (en) | 1971-10-21 | 1973-11-13 | Nasa | Catalyst cartridge for carbon dioxide reduction unit |
US4126000A (en) | 1972-05-12 | 1978-11-21 | Funk Harald F | System for treating and recovering energy from exhaust gases |
US4200554A (en) | 1974-04-25 | 1980-04-29 | E. I. Du Pont De Nemours & Company | Barium- and ruthenium-containing perovskite catalysts |
US3905748A (en) | 1974-06-24 | 1975-09-16 | Robertshaw Controls Co | Primary control system for furnaces |
US4024420A (en) | 1975-06-27 | 1977-05-17 | General Electric Company | Deep diode atomic battery |
US4197281A (en) | 1975-12-17 | 1980-04-08 | Texaco Development Corporation | Production of ammonia synthesis gas from solid carbonaceous fuels |
US5122332A (en) | 1977-04-13 | 1992-06-16 | Virginia Russell | Protecting organisms and the environment from harmful radiation by controlling such radiation and safely disposing of its energy |
US4710483A (en) | 1977-07-21 | 1987-12-01 | Trw Inc. | Novel carbonaceous material and process for producing a high BTU gas from this material |
US4628143A (en) | 1984-03-12 | 1986-12-09 | Brotz Gregory R | Foamed nuclear cell |
US4746458A (en) | 1984-03-12 | 1988-05-24 | Brotz Gregory R | Photovoltaic material |
US4900368A (en) | 1984-03-12 | 1990-02-13 | Brotz Gregory R | Foamed energy cell |
US4663230A (en) | 1984-12-06 | 1987-05-05 | Hyperion Catalysis International, Inc. | Carbon fibrils, method for producing same and compositions containing same |
US5165909A (en) | 1984-12-06 | 1992-11-24 | Hyperion Catalysis Int'l., Inc. | Carbon fibrils and method for producing same |
US6375917B1 (en) | 1984-12-06 | 2002-04-23 | Hyperion Catalysis International, Inc. | Apparatus for the production of carbon fibrils by catalysis and methods thereof |
US5707916A (en) | 1984-12-06 | 1998-01-13 | Hyperion Catalysis International, Inc. | Carbon fibrils |
US4602477A (en) | 1985-06-05 | 1986-07-29 | Air Products And Chemicals, Inc. | Membrane-aided distillation for carbon dioxide and hydrocarbon separation |
US4727207A (en) | 1986-07-02 | 1988-02-23 | Standard Oil Company | Process for converting methane and/or natural gas to more readily transportable materials |
US4725346A (en) | 1986-07-25 | 1988-02-16 | Ceramatec, Inc. | Electrolyte assembly for oxygen generating device and electrodes therefor |
US5082505A (en) | 1988-12-29 | 1992-01-21 | Cota Albert O | Self-sustaining power module |
US5008579A (en) | 1989-03-03 | 1991-04-16 | E. F. Johnson Co. | Light emitting polymer electrical energy source |
ZA907803B (en) | 1989-09-28 | 1991-07-31 | Hyperion Catalysis Int | Electrochemical cells and preparing carbon fibrils |
DE3937558C2 (en) | 1989-11-11 | 1997-02-13 | Leybold Ag | Cathode sputtering device |
US5149584A (en) | 1990-10-23 | 1992-09-22 | Baker R Terry K | Carbon fiber structures having improved interlaminar properties |
US5413866A (en) | 1990-10-23 | 1995-05-09 | Baker; R. Terry K. | High performance carbon filament structures |
US5133190A (en) | 1991-01-25 | 1992-07-28 | Abdelmalek Fawzy T | Method and apparatus for flue gas cleaning by separation and liquefaction of sulfur dioxide and carbon dioxide |
US5260621A (en) | 1991-03-18 | 1993-11-09 | Spire Corporation | High energy density nuclide-emitter, voltaic-junction battery |
FR2679382B1 (en) | 1991-07-15 | 1996-12-13 | Accumulateurs Fixes | ELECTROCHEMICAL GENERATOR OF HIGH SPECIFIC MASS ENERGY. |
JP2687794B2 (en) | 1991-10-31 | 1997-12-08 | 日本電気株式会社 | Graphite fiber with cylindrical structure |
US20020085974A1 (en) | 1992-01-15 | 2002-07-04 | Hyperion Catalysis International, Inc. | Surface treatment of carbon microfibers |
US5624542A (en) | 1992-05-11 | 1997-04-29 | Gas Research Institute | Enhancement of mechanical properties of ceramic membranes and solid electrolytes |
US5569635A (en) | 1994-05-22 | 1996-10-29 | Hyperion Catalysts, Int'l., Inc. | Catalyst supports, supported catalysts and methods of making and using the same |
EP0641400B1 (en) | 1992-05-22 | 2003-02-12 | Hyperion Catalysis International, Inc. | Improved methods and catalysts for the manufacture of carbon fibrils |
US6159892A (en) | 1992-05-22 | 2000-12-12 | Hyperion Catalysis International, Inc. | Catalyst supports, supported catalysts and methods of making and using the same |
US5531424A (en) | 1993-04-19 | 1996-07-02 | Fior De Venezuela | Fluidized bed direct reduction plant |
IL109497A (en) | 1993-05-05 | 1998-02-22 | Hyperion Catalysis Int | Three-dimensional macroscopic assemblages of randomly oriented carbon fibrils and composites containing same |
US5641466A (en) | 1993-06-03 | 1997-06-24 | Nec Corporation | Method of purifying carbon nanotubes |
US5396141A (en) | 1993-07-30 | 1995-03-07 | Texas Instruments Incorporated | Radioisotope power cells |
DE4338555C1 (en) | 1993-11-08 | 1995-04-13 | Mannesmann Ag | DC arc furnace |
JP3298735B2 (en) | 1994-04-28 | 2002-07-08 | 科学技術振興事業団 | Fullerene complex |
US5572544A (en) | 1994-07-21 | 1996-11-05 | Praxair Technology, Inc. | Electric arc furnace post combustion method |
US6203814B1 (en) | 1994-12-08 | 2001-03-20 | Hyperion Catalysis International, Inc. | Method of making functionalized nanotubes |
US20040202603A1 (en) | 1994-12-08 | 2004-10-14 | Hyperion Catalysis International, Inc. | Functionalized nanotubes |
US5780101A (en) | 1995-02-17 | 1998-07-14 | Arizona Board Of Regents On Behalf Of The University Of Arizona | Method for producing encapsulated nanoparticles and carbon nanotubes using catalytic disproportionation of carbon monoxide |
US5910238A (en) | 1995-06-01 | 1999-06-08 | Technology Management, Inc. | Microspheres for combined oxygen separation, storage and delivery |
US6183714B1 (en) | 1995-09-08 | 2001-02-06 | Rice University | Method of making ropes of single-wall carbon nanotubes |
US5859484A (en) | 1995-11-30 | 1999-01-12 | Ontario Hydro | Radioisotope-powered semiconductor battery |
AU727973B2 (en) | 1996-05-15 | 2001-01-04 | Hyperion Catalysis International Inc. | Rigid porous carbon structures, methods of making, methods of using and products containing same |
JP2000516708A (en) | 1996-08-08 | 2000-12-12 | ウィリアム・マーシュ・ライス・ユニバーシティ | Macroscopically operable nanoscale devices fabricated from nanotube assemblies |
JP3339339B2 (en) | 1996-12-25 | 2002-10-28 | 株式会社島津製作所 | Carbon dioxide fixation device |
US5997832A (en) | 1997-03-07 | 1999-12-07 | President And Fellows Of Harvard College | Preparation of carbide nanorods |
US6683783B1 (en) | 1997-03-07 | 2004-01-27 | William Marsh Rice University | Carbon fibers formed from single-wall carbon nanotubes |
US6221330B1 (en) | 1997-08-04 | 2001-04-24 | Hyperion Catalysis International Inc. | Process for producing single wall nanotubes using unsupported metal catalysts |
JP3415038B2 (en) | 1998-03-25 | 2003-06-09 | 株式会社島津製作所 | Carbon production method |
KR100277881B1 (en) | 1998-06-16 | 2001-02-01 | 김영환 | Transistor |
US6262129B1 (en) | 1998-07-31 | 2001-07-17 | International Business Machines Corporation | Method for producing nanoparticles of transition metals |
US6346189B1 (en) | 1998-08-14 | 2002-02-12 | The Board Of Trustees Of The Leland Stanford Junior University | Carbon nanotube structures made using catalyst islands |
WO2000017101A1 (en) | 1998-09-18 | 2000-03-30 | William Marsh Rice University | Chemical derivatization of single-wall carbon nanotubes to facilitate solvation thereof; and use of derivatized nanotubes |
US6692717B1 (en) | 1999-09-17 | 2004-02-17 | William Marsh Rice University | Catalytic growth of single-wall carbon nanotubes from metal particles |
US7125534B1 (en) | 1998-09-18 | 2006-10-24 | William Marsh Rice University | Catalytic growth of single- and double-wall carbon nanotubes from metal particles |
US6835366B1 (en) | 1998-09-18 | 2004-12-28 | William Marsh Rice University | Chemical derivatization of single-wall carbon nanotubes to facilitate solvation thereof, and use of derivatized nanotubes |
JP3248514B2 (en) | 1998-10-29 | 2002-01-21 | 日本鋼管株式会社 | How to reduce carbon dioxide emissions |
CN100340476C (en) | 1998-11-03 | 2007-10-03 | 威廉马歇莱思大学 | Gas-phase nucleation and growth of single-wall carbon nanotubes from high pressure CO |
US6232706B1 (en) | 1998-11-12 | 2001-05-15 | The Board Of Trustees Of The Leland Stanford Junior University | Self-oriented bundles of carbon nanotubes and method of making same |
DE69929902T2 (en) | 1998-12-04 | 2006-10-19 | Cabot Corp., Boston | METHOD FOR PRODUCING OVEN SOIL |
US6239057B1 (en) | 1999-01-15 | 2001-05-29 | Uop Llc | Catalyst for the conversion of low carbon number aliphatic hydrocarbons to higher carbon number hydrocarbons, process for preparing the catalyst and process using the catalyst |
US6518218B1 (en) | 1999-03-31 | 2003-02-11 | General Electric Company | Catalyst system for producing carbon fibrils |
US6333016B1 (en) | 1999-06-02 | 2001-12-25 | The Board Of Regents Of The University Of Oklahoma | Method of producing carbon nanotubes |
US20030091496A1 (en) | 2001-07-23 | 2003-05-15 | Resasco Daniel E. | Method and catalyst for producing single walled carbon nanotubes |
US6361861B2 (en) | 1999-06-14 | 2002-03-26 | Battelle Memorial Institute | Carbon nanotubes on a substrate |
AU6078700A (en) | 1999-07-21 | 2001-02-13 | Hyperion Catalysis International, Inc. | Methods of oxidizing multiwalled carbon nanotubes |
US6254662B1 (en) | 1999-07-26 | 2001-07-03 | International Business Machines Corporation | Chemical synthesis of monodisperse and magnetic alloy nanocrystal containing thin films |
CA2368043A1 (en) | 1999-10-27 | 2001-05-03 | William Marsh Rice University | Macroscopic ordered assembly of carbon nanotubes |
US6413487B1 (en) | 2000-06-02 | 2002-07-02 | The Board Of Regents Of The University Of Oklahoma | Method and apparatus for producing carbon nanotubes |
US6919064B2 (en) | 2000-06-02 | 2005-07-19 | The Board Of Regents Of The University Of Oklahoma | Process and apparatus for producing single-walled carbon nanotubes |
US6890986B2 (en) | 2000-08-29 | 2005-05-10 | Hitco Carbon Composites, Inc. | Substantially pure bulk pyrocarbon and methods of preparation |
US20020054849A1 (en) | 2000-09-08 | 2002-05-09 | Baker R. Terry K. | Crystalline graphite nanofibers and a process for producing same |
US7592389B2 (en) | 2000-09-08 | 2009-09-22 | Catalytic Materials, Llc | Conductive polymeric structures containing graphite nanofibers having graphite parallel to the growth axis |
KR100382879B1 (en) | 2000-09-22 | 2003-05-09 | 일진나노텍 주식회사 | Method of synthesizing carbon nanotubes and apparatus being used therein. |
WO2002029128A1 (en) | 2000-10-05 | 2002-04-11 | Johns Hopkins University | High performance nanostructured materials and methods of making the same |
KR100604459B1 (en) | 2000-10-06 | 2006-07-26 | 풀러린 인터내셔날 코포레이션 | Double-walled carbon nanotubes and methods for production and application |
US6855301B1 (en) | 2000-10-20 | 2005-02-15 | The Ohio State University | Synthesis method for producing carbon clusters and structured carbon clusters produced thereby |
US6949216B2 (en) * | 2000-11-03 | 2005-09-27 | Lockheed Martin Corporation | Rapid manufacturing of carbon nanotube composite structures |
CN100457609C (en) | 2000-11-13 | 2009-02-04 | 国际商业机器公司 | Manufacturing method and application of single wall carbon nano tube |
US6913789B2 (en) | 2001-01-31 | 2005-07-05 | William Marsh Rice University | Process utilizing pre-formed cluster catalysts for making single-wall carbon nanotubes |
US7052668B2 (en) | 2001-01-31 | 2006-05-30 | William Marsh Rice University | Process utilizing seeds for making single-wall carbon nanotubes |
US20020102193A1 (en) | 2001-01-31 | 2002-08-01 | William Marsh Rice University | Process utilizing two zones for making single-wall carbon nanotubes |
US20020172767A1 (en) | 2001-04-05 | 2002-11-21 | Leonid Grigorian | Chemical vapor deposition growth of single-wall carbon nanotubes |
GB0111875D0 (en) | 2001-05-15 | 2001-07-04 | Univ Cambridge Tech | Synthesis of nanoscaled carbon materials |
US7157068B2 (en) | 2001-05-21 | 2007-01-02 | The Trustees Of Boston College | Varied morphology carbon nanotubes and method for their manufacture |
US20090286675A1 (en) | 2001-05-25 | 2009-11-19 | Tsinghua University | Continuous mass production of carbon nanotubes in a nano-agglomerate fluidized-bed and the reactor |
CN1141250C (en) | 2001-05-25 | 2004-03-10 | 清华大学 | Process and reactor for continuously preparing nm carbon tubes with fluidized bed |
US20050100499A1 (en) | 2001-06-25 | 2005-05-12 | Asao Oya | Carbon nanotube and process for producing the same |
FR2826646B1 (en) | 2001-06-28 | 2004-05-21 | Toulouse Inst Nat Polytech | PROCESS FOR THE SELECTIVE MANUFACTURE OF ORDINATED CARBON NANOTUBES IN FLUIDIZED BED |
GB0120366D0 (en) | 2001-08-22 | 2001-10-17 | Johnson Matthey Plc | Nanostructure synthesis |
US20030059364A1 (en) | 2001-09-21 | 2003-03-27 | Oleg Prilutskiy | Method for poduction of nanostructures |
KR100867281B1 (en) | 2001-10-12 | 2008-11-06 | 재단법인서울대학교산학협력재단 | Synthesis of Monodisperse and Highly-Crystalline Nanoparticles of Metals, Alloys, Metal Oxides, and Multi-metallic Oxides without a Size-selection Process |
SG126710A1 (en) | 2001-10-31 | 2006-11-29 | Univ Singapore | Carbon nanotubes fabrication and hydrogen production |
US7138100B2 (en) | 2001-11-21 | 2006-11-21 | William Marsh Rice Univesity | Process for making single-wall carbon nanotubes utilizing refractory particles |
WO2003045843A1 (en) | 2001-11-28 | 2003-06-05 | National University Corporation Of Nagoya University | Method for preparing hollow nanofiber, hollow nanofiber and catalyst composition for preparing hollow nanofiber |
US6713519B2 (en) | 2001-12-21 | 2004-03-30 | Battelle Memorial Institute | Carbon nanotube-containing catalysts, methods of making, and reactions catalyzed over nanotube catalysts |
US7338648B2 (en) | 2001-12-28 | 2008-03-04 | The Penn State Research Foundation | Method for low temperature synthesis of single wall carbon nanotubes |
US6958572B2 (en) | 2002-02-06 | 2005-10-25 | Ut-Battelle Llc | Controlled non-normal alignment of catalytically grown nanostructures in a large-scale synthesis process |
KR101016763B1 (en) | 2002-02-13 | 2011-02-25 | 도레이 카부시키가이샤 | Process for producing single-walled carbon nanotube |
US7390920B2 (en) | 2002-02-14 | 2008-06-24 | Monsanto Technology Llc | Oxidation catalyst and process |
CN1176014C (en) | 2002-02-22 | 2004-11-17 | 清华大学 | Process for directly synthesizing ultra-long single-wall continuous nano carbon tube |
CA2374848A1 (en) | 2002-03-06 | 2003-09-06 | Centre National De La Recherche Scientifique | A process for the mass production of multiwalled carbon nanotubes |
KR100598751B1 (en) | 2002-03-15 | 2006-07-11 | 오사까 가스 가부시키가이샤 | Iron/Carbon Composite, Carbonaceous Material Comprising the Iron/Carbon Composite, and Process For Producing the Same |
US6899945B2 (en) | 2002-03-19 | 2005-05-31 | William Marsh Rice University | Entangled single-wall carbon nanotube solid material and methods for making same |
US7135160B2 (en) | 2002-04-02 | 2006-11-14 | Carbon Nanotechnologies, Inc. | Spheroidal aggregates comprising single-wall carbon nanotubes and method for making the same |
US6946410B2 (en) | 2002-04-05 | 2005-09-20 | E. I. Du Pont De Nemours And Company | Method for providing nano-structures of uniform length |
US20060165988A1 (en) | 2002-04-09 | 2006-07-27 | Yet-Ming Chiang | Carbon nanoparticles and composite particles and process of manufacture |
US20030194362A1 (en) | 2002-04-12 | 2003-10-16 | Rogers Stephen P. | Chemical reactor and fuel processor utilizing ceramic technology |
US6962685B2 (en) | 2002-04-17 | 2005-11-08 | International Business Machines Corporation | Synthesis of magnetite nanoparticles and the process of forming Fe-based nanomaterials |
GB0211789D0 (en) | 2002-05-22 | 2002-07-03 | Statoil Asa | Process |
US6905544B2 (en) | 2002-06-26 | 2005-06-14 | Mitsubishi Heavy Industries, Ltd. | Manufacturing method for a carbon nanomaterial, a manufacturing apparatus for a carbon nanomaterial, and manufacturing facility for a carbon nanomaterial |
US6855593B2 (en) | 2002-07-11 | 2005-02-15 | International Rectifier Corporation | Trench Schottky barrier diode |
WO2004007364A1 (en) | 2002-07-16 | 2004-01-22 | William Marsh Rice University | Process for functionalizing carbon nanotubes under solvent-free conditions |
GB0216654D0 (en) | 2002-07-17 | 2002-08-28 | Univ Cambridge Tech | CVD Synthesis of carbon nanoutubes |
US7250148B2 (en) | 2002-07-31 | 2007-07-31 | Carbon Nanotechnologies, Inc. | Method for making single-wall carbon nanotubes using supported catalysts |
US20040053440A1 (en) | 2002-08-21 | 2004-03-18 | First Nano, Inc. | Method and apparatus of carbon nanotube fabrication |
CN100411979C (en) | 2002-09-16 | 2008-08-20 | 清华大学 | Carbon nano pipe rpoe and preparation method thereof |
CN1248959C (en) | 2002-09-17 | 2006-04-05 | 清华大学 | Carbon nano pipe array growth method |
AU2003286601A1 (en) | 2002-10-22 | 2004-05-13 | Danny Marshal Day | The production and use of a soil amendment made by the combined production of hydrogen, sequestered carbon and utilizing off gases containing carbon dioxide |
JP3829789B2 (en) | 2002-10-22 | 2006-10-04 | トヨタ自動車株式会社 | Multi-tube carbon nanotube manufacturing method |
AU2003275720A1 (en) | 2002-10-28 | 2004-05-13 | Bussan Nanotech Reserch Institute Inc. | Method and apparatus for heat treatment of powder of fine carbon fiber |
WO2004046102A2 (en) | 2002-11-14 | 2004-06-03 | Catalytic Materials, Llc | Novel graphite nanocatalysts |
AU2003291133A1 (en) | 2002-11-26 | 2004-06-18 | Carbon Nanotechnologies, Inc. | Carbon nanotube particulates, compositions and use thereof |
CN1290763C (en) | 2002-11-29 | 2006-12-20 | 清华大学 | Process for preparing nano-carbon tubes |
US20040265212A1 (en) | 2002-12-06 | 2004-12-30 | Vijay Varadan | Synthesis of coiled carbon nanotubes by microwave chemical vapor deposition |
US20040222080A1 (en) | 2002-12-17 | 2004-11-11 | William Marsh Rice University | Use of microwaves to crosslink carbon nanotubes to facilitate modification |
CN100473601C (en) | 2003-01-23 | 2009-04-01 | 佳能株式会社 | Method for producing nano-carbon materials |
JP3913181B2 (en) | 2003-02-06 | 2007-05-09 | 三菱重工業株式会社 | Carbon nanofiber manufacturing method and manufacturing apparatus |
US7094679B1 (en) | 2003-03-11 | 2006-08-22 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Carbon nanotube interconnect |
CN1286716C (en) | 2003-03-19 | 2006-11-29 | 清华大学 | Method for growing carbon nano tube |
DE10312494A1 (en) | 2003-03-20 | 2004-10-07 | Association pour la Recherche et le Développement des Méthodes et Processus Industriels (Armines) | Carbon nanostructures and methods of making nanotubes, nanofibers, and carbon-based nanostructures |
CN100506691C (en) | 2003-03-24 | 2009-07-01 | 独立行政法人科学技术振兴机构 | High-efficiency synthetic method for carbon nanostructure, apparatus and carbon nanostructure |
US20080008760A1 (en) | 2003-04-14 | 2008-01-10 | Alberto Bianco | Functionalized carbon nanotubes, a process for preparing the same and their use in medicinal chemistry |
WO2004089818A1 (en) | 2003-04-14 | 2004-10-21 | Centre National De La Recherche Scientifique | Functionalized carbon nanotubes, a process for preparing the same and their use in medicinal chemistry |
US7132062B1 (en) | 2003-04-15 | 2006-11-07 | Plasticolors, Inc. | Electrically conductive additive system and method of making same |
JP4413046B2 (en) | 2003-04-25 | 2010-02-10 | 昭和電工株式会社 | Method for producing vapor grown carbon fiber |
JP4379002B2 (en) | 2003-05-30 | 2009-12-09 | 富士ゼロックス株式会社 | Carbon nanotube device manufacturing method and carbon nanotube transfer body |
JP4175182B2 (en) | 2003-06-03 | 2008-11-05 | 三菱化学株式会社 | Carbonaceous fine fiber |
US7169329B2 (en) | 2003-07-07 | 2007-01-30 | The Research Foundation Of State University Of New York | Carbon nanotube adducts and methods of making the same |
US20050025695A1 (en) | 2003-07-28 | 2005-02-03 | Bhabendra Pradhan | Catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures |
JP2007500669A (en) | 2003-07-29 | 2007-01-18 | ウィリアム・マーシュ・ライス・ユニバーシティ | Selective functionalization of carbon nanotubes |
BRPI0413586A (en) | 2003-08-14 | 2006-10-17 | Monsanto Technology Llc | transition metal containing catalysts and process for their preparation and use as oxidation and dehydrogenation catalysts |
KR100537512B1 (en) | 2003-09-01 | 2005-12-19 | 삼성에스디아이 주식회사 | carbon-nano tube structure and manufacturing method thereof and field emitter and display device both adopting the same |
JP4449387B2 (en) | 2003-09-25 | 2010-04-14 | 富士ゼロックス株式会社 | Manufacturing method of composite material |
US7780747B2 (en) | 2003-10-14 | 2010-08-24 | Advanced Technology Materials, Inc. | Apparatus and method for hydrogen generation from gaseous hydride |
US7700065B2 (en) | 2003-11-21 | 2010-04-20 | Mitsubishi Heavy Industries, Ltd. | Carbon nano-fibrous rod, fibrous nanocarbon, and method and apparatus for producing fibrous nanocarbon |
GB0327169D0 (en) | 2003-11-21 | 2003-12-24 | Statoil Asa | Method |
WO2006003482A2 (en) | 2003-12-03 | 2006-01-12 | Honda Motor Co., Ltd. | Method for separating nanotube containing carbonaceous material using cyclones |
US7300642B1 (en) | 2003-12-03 | 2007-11-27 | Rentech, Inc. | Process for the production of ammonia and Fischer-Tropsch liquids |
US7981396B2 (en) | 2003-12-03 | 2011-07-19 | Honda Motor Co., Ltd. | Methods for production of carbon nanostructures |
US7374793B2 (en) | 2003-12-11 | 2008-05-20 | International Business Machines Corporation | Methods and structures for promoting stable synthesis of carbon nanotubes |
US20050147746A1 (en) | 2003-12-30 | 2005-07-07 | Dubin Valery M. | Nanotube growth and device formation |
US20050276743A1 (en) | 2004-01-13 | 2005-12-15 | Jeff Lacombe | Method for fabrication of porous metal templates and growth of carbon nanotubes and utilization thereof |
JP2007523822A (en) | 2004-01-15 | 2007-08-23 | ナノコンプ テクノロジーズ インコーポレイテッド | Systems and methods for the synthesis of elongated length nanostructures |
US20070189953A1 (en) | 2004-01-30 | 2007-08-16 | Centre National De La Recherche Scientifique (Cnrs) | Method for obtaining carbon nanotubes on supports and composites comprising same |
JP4239848B2 (en) | 2004-02-16 | 2009-03-18 | 富士ゼロックス株式会社 | Microwave antenna and manufacturing method thereof |
FI121334B (en) | 2004-03-09 | 2010-10-15 | Canatu Oy | Method and apparatus for making carbon nanotubes |
WO2005113434A1 (en) | 2004-03-25 | 2005-12-01 | William Marsh Rice University | Functionalization of carbon nanotubes in acidic media |
US7740825B2 (en) | 2004-03-31 | 2010-06-22 | Stella Chemifa Corporation | Method for forming a carbon nanotube aggregate |
US7867639B2 (en) | 2004-03-31 | 2011-01-11 | Rochester Institute Of Technology | Alpha voltaic batteries and methods thereof |
US20070253886A1 (en) | 2004-04-06 | 2007-11-01 | Universite De Sherbrooke | Carbon sequestration and dry reforming process and catalysts to produce same |
CA2503655C (en) | 2004-04-06 | 2013-08-06 | Universite De Sherbrooke | Carbon sequestration and dry reforming process and catalysts to produce same |
EP1589131A1 (en) | 2004-04-21 | 2005-10-26 | Stichting Voor De Technische Wetenschappen | Carbon nanofibre composites, preparation and use |
JP4379247B2 (en) | 2004-04-23 | 2009-12-09 | 住友電気工業株式会社 | Method for producing carbon nanostructure |
KR20050104840A (en) | 2004-04-29 | 2005-11-03 | 삼성에스디아이 주식회사 | A carbon nanotube, an emitter comprising the carbon nanotube and an electron emission device comprising the emitter |
US7365289B2 (en) | 2004-05-18 | 2008-04-29 | The United States Of America As Represented By The Department Of Health And Human Services | Production of nanostructures by curie point induction heating |
US20110024697A1 (en) | 2004-05-18 | 2011-02-03 | Board Of Trustees Of The University Of Arkansas | Methods of Producing Carbon Nanotubes and Applications of Same |
US7473873B2 (en) | 2004-05-18 | 2009-01-06 | The Board Of Trustees Of The University Of Arkansas | Apparatus and methods for synthesis of large size batches of carbon nanostructures |
EP1605265A1 (en) | 2004-06-09 | 2005-12-14 | Centre National De La Recherche Scientifique (Cnrs) | Non-covalent complexes comprising carbon nanotubes |
FR2872150B1 (en) | 2004-06-23 | 2006-09-01 | Toulouse Inst Nat Polytech | PROCESS FOR THE SELECTIVE MANUFACTURE OF ORDINATED CARBON NANOTUBES |
KR20070030282A (en) | 2004-06-23 | 2007-03-15 | 하이페리온 커탤리시스 인터내셔널 인코포레이티드 | Functionalized single walled carbon nanotubes |
WO2006017333A2 (en) | 2004-07-13 | 2006-02-16 | William Marsh Rice University | Shortened carbon nanotubes |
US7212147B2 (en) | 2004-07-19 | 2007-05-01 | Alan Ross | Method of agile reduction of radar cross section using electromagnetic channelization |
WO2006135375A2 (en) | 2004-07-21 | 2006-12-21 | The Regents Of The University Of California | Catalytically grown nano-bent nanostructure and method for making the same |
US8178203B2 (en) | 2004-07-27 | 2012-05-15 | National Institute Of Advanced Industrial Science And Technology | Aligned single-walled carbon nanotube aggregate, bulk aligned single-walled carbon nanotube aggregate, and powdered aligned single-walled carbon nanotube aggregate |
EP3181518A1 (en) | 2004-07-27 | 2017-06-21 | National Institute of Advanced Industrial Science and Technology | Aligned single-walled carbon nanotube bulk structure, production process and use |
US20100062229A1 (en) | 2004-07-27 | 2010-03-11 | Kenji Hata | Aligned single-walled carbon nanotube aggregate, bulk aligned single-walled carbon nanotube aggregate, powdered aligned single-walled carbon nanotube aggregate, and production method thereof |
JP2006049435A (en) | 2004-08-02 | 2006-02-16 | Sony Corp | Carbon nanotube and its arrangement method, field effect transistor using the same and its manufacturing method, and semiconductor device |
JP4625980B2 (en) | 2004-08-16 | 2011-02-02 | Dowaエレクトロニクス株式会社 | Method for producing alloy particle powder for magnetic recording medium having fcc structure |
US20060078489A1 (en) | 2004-09-09 | 2006-04-13 | Avetik Harutyunyan | Synthesis of small and narrow diameter distributed carbon single walled nanotubes |
US20060225534A1 (en) | 2004-10-13 | 2006-10-12 | The Research Foundation Of State University Of New York | Production of nickel nanoparticles from a nickel precursor via laser pyrolysis |
US20070116631A1 (en) | 2004-10-18 | 2007-05-24 | The Regents Of The University Of California | Arrays of long carbon nanotubes for fiber spinning |
KR100730119B1 (en) | 2004-11-02 | 2007-06-19 | 삼성에스디아이 주식회사 | Carbon nanosphere having one or more open portion, method for preparing the same, carbon nanosphere impregnated catalyst using the carbon nanosphere and fuel cell adopting the catalyst |
SG157390A1 (en) | 2004-11-10 | 2009-12-29 | Nikon Corp | Carbon nanotube assembly and manufacturing method thereof |
DE102004054959A1 (en) | 2004-11-13 | 2006-05-18 | Bayer Technology Services Gmbh | Catalyst for producing carbon nanotubes by decomposition of gaseous carbon compounds on a heterogeneous catalyst |
US7923403B2 (en) | 2004-11-16 | 2011-04-12 | Hyperion Catalysis International, Inc. | Method for preparing catalysts supported on carbon nanotubes networks |
EP1827681A4 (en) | 2004-11-17 | 2011-05-11 | Hyperion Catalysis Int | Method for preparing catalyst supports and supported catalysts from single walled carbon nanotubes |
US20060104886A1 (en) | 2004-11-17 | 2006-05-18 | Luna Innovations Incorporated | Pure-chirality carbon nanotubes and methods |
US20060204426A1 (en) | 2004-11-17 | 2006-09-14 | Research Foundation Of The City University Of New York | Methods and devices for making carbon nanotubes and compositions thereof |
US7719265B2 (en) | 2004-11-17 | 2010-05-18 | Honda Motor Co., Ltd. | Methods for determining particle size of metal nanocatalyst for growing carbon nanotubes |
US20080014654A1 (en) | 2004-11-19 | 2008-01-17 | William Marsh Rice University | Efficient fluorimetric analyzer for single-walled carbon nanotubes |
US20060141346A1 (en) | 2004-11-23 | 2006-06-29 | Gordon John H | Solid electrolyte thermoelectrochemical system |
WO2006057467A1 (en) | 2004-11-26 | 2006-06-01 | Seoul National University Industry Foundation | Method for large-scale production of monodisperse nanoparticles |
US7842271B2 (en) | 2004-12-07 | 2010-11-30 | Petrik Viktor I | Mass production of carbon nanostructures |
RU2405764C2 (en) | 2004-12-22 | 2010-12-10 | Эксонмобил Кемикэл Пейтентс, Инк. | Production of liquid hydrocarbons from methane |
RU2417974C2 (en) | 2004-12-22 | 2011-05-10 | Эксонмобил Кемикэл Пейтентс Инк. | Synthesis of alkylated aromatic hydrocarbons from methane |
US7871591B2 (en) | 2005-01-11 | 2011-01-18 | Honda Motor Co., Ltd. | Methods for growing long carbon single-walled nanotubes |
FR2881418B1 (en) | 2005-02-03 | 2007-04-27 | Centre Nat Rech Scient | MATERIALS BASED ON NANOFIBRES OR NANOTUBES ENCHEVETRES, THEIR PREPARATION AND USES |
FR2881735B1 (en) | 2005-02-07 | 2008-04-18 | Arkema Sa | PROCESS FOR THE SYNTHESIS OF CARBON NANOTUBES |
US20060191835A1 (en) | 2005-02-28 | 2006-08-31 | Petrik Viktor I | Compositions and methods of remediation devices with nanostructured sorbent |
US7645933B2 (en) | 2005-03-02 | 2010-01-12 | Wisconsin Alumni Research Foundation | Carbon nanotube Schottky barrier photovoltaic cell |
JP4786205B2 (en) | 2005-03-14 | 2011-10-05 | 浜松ホトニクス株式会社 | Carbon nanotube processing method and processing apparatus |
US8529862B2 (en) | 2005-03-29 | 2013-09-10 | Hyperion Catalysis International, Inc. | Method for preparing single walled carbon nanotubes from a metal layer |
US7947247B2 (en) | 2005-03-29 | 2011-05-24 | Hyperion Catalysis International, Inc. | Method for preparing single walled carbon nanotubes from a metal layer |
JP4758130B2 (en) | 2005-04-12 | 2011-08-24 | 国立大学法人北見工業大学 | Method for producing nanocarbon and catalytic reactor for producing nanocarbon |
CN100500555C (en) | 2005-04-15 | 2009-06-17 | 清华大学 | Carbon nanotube array structure and its preparation process |
US20060245996A1 (en) | 2005-04-27 | 2006-11-02 | Peking University | Method of synthesizing single walled carbon nanotubes |
CN101273114A (en) | 2005-04-29 | 2008-09-24 | 海塞特有限责任公司 | System and method for conversion of hydrocarbon materials |
JP5349042B2 (en) | 2005-05-03 | 2013-11-20 | ナノコンプ テクノロジーズ インコーポレイテッド | Carbon composite material and method for producing the same |
US7901654B2 (en) | 2005-05-05 | 2011-03-08 | Honda Motor Co., Ltd. | Synthesis of small diameter single-walled carbon nanotubes |
US20070020168A1 (en) | 2005-05-13 | 2007-01-25 | Board Of Trustees Of Michigan State University | Synthesis of long and well-aligned carbon nanotubes |
US7645497B2 (en) | 2005-06-02 | 2010-01-12 | Eastman Kodak Company | Multi-layer conductor with carbon nanotubes |
US8545790B2 (en) | 2005-06-04 | 2013-10-01 | Gregory Konesky | Cross-linked carbon nanotubes |
WO2008054349A2 (en) | 2005-07-07 | 2008-05-08 | The University Of Maryland | Carbon nanotube structures formed on large free floating substrates |
DE102005032072A1 (en) | 2005-07-08 | 2007-01-11 | Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Gemeinnützige Stiftung e.V. | Carbon nanoparticles, their preparation and their use |
WO2008048227A2 (en) | 2005-08-11 | 2008-04-24 | Kansas State University Research Foundation | Synthetic carbon nanotubes |
US7663288B2 (en) | 2005-08-25 | 2010-02-16 | Cornell Research Foundation, Inc. | Betavoltaic cell |
EP1797950A1 (en) | 2005-12-14 | 2007-06-20 | Nanocyl S.A. | Catalyst for a multi-walled carbon nanotube production process |
FI120195B (en) | 2005-11-16 | 2009-07-31 | Canatu Oy | Carbon nanotubes functionalized with covalently bonded fullerenes, process and apparatus for producing them, and composites thereof |
JP4811712B2 (en) | 2005-11-25 | 2011-11-09 | 独立行政法人産業技術総合研究所 | Carbon nanotube bulk structure and manufacturing method thereof |
WO2008054411A2 (en) | 2005-12-01 | 2008-05-08 | Northeastern University | Directed assembly of carbon nanotubes and nanoparticles using nanotemplates with nanotrenches |
WO2008054416A2 (en) | 2005-12-14 | 2008-05-08 | Carbon Nanotechnologies, Inc. | Gas phase process for growing carbon nanotubes utilizing sequential multiple catalyst injection |
CN100500556C (en) | 2005-12-16 | 2009-06-17 | 清华大学 | Carbon nano-tube filament and its production |
US20070149392A1 (en) | 2005-12-22 | 2007-06-28 | Ku Anthony Y | Reactor for carbon dioxide capture and conversion |
JP2007191840A (en) | 2005-12-22 | 2007-08-02 | Showa Denko Kk | Vapor grown carbon fiber and method for producing the same |
FR2895393B1 (en) | 2005-12-23 | 2008-03-07 | Arkema Sa | PROCESS FOR THE SYNTHESIS OF CARBON NANOTUBES |
WO2007074506A1 (en) | 2005-12-26 | 2007-07-05 | Fujitsu Limited | Method of growing carbon nanotube and carbon nanotube growing system |
US8859048B2 (en) | 2006-01-03 | 2014-10-14 | International Business Machines Corporation | Selective placement of carbon nanotubes through functionalization |
US8202505B2 (en) | 2006-01-06 | 2012-06-19 | National Institute Of Advanced Industrial Science And Technology | Aligned carbon nanotube bulk aggregate, process for producing the same and uses thereof |
US8329135B2 (en) | 2006-01-06 | 2012-12-11 | National Institute Of Advanced Industrial Science And Technology | Aligned carbon nanotube bulk structure having portions different in density |
WO2008016388A2 (en) | 2006-01-30 | 2008-02-07 | Honda Motor Co., Ltd. | Method and apparatus for growth of high quality carbon single-walled nanotubes |
WO2008016390A2 (en) | 2006-01-30 | 2008-02-07 | Honda Motor Co., Ltd. | Catalyst for the growth of carbon single-walled nanotubes |
US8119032B2 (en) | 2006-02-07 | 2012-02-21 | President And Fellows Of Harvard College | Gas-phase functionalization of surfaces including carbon-based surfaces |
US7767114B2 (en) | 2006-02-07 | 2010-08-03 | President And Fellows Of Harvard College | Gas-phase functionalization of carbon nanotubes |
US7569203B2 (en) | 2006-02-21 | 2009-08-04 | Drexel University | Production and uses of carbon suboxides |
JP4678687B2 (en) | 2006-02-24 | 2011-04-27 | 公立大学法人大阪府立大学 | Method and apparatus for producing carbon nanostructure |
WO2008054839A2 (en) | 2006-03-03 | 2008-05-08 | William Marsh Rice University | Carbon nanotube diameter selection by pretreatment of metal catalysts on surfaces |
CN101506413A (en) | 2006-03-03 | 2009-08-12 | 伊利诺伊大学评议会 | Methods of making spatially aligned nanotubes and nanotube arrays |
EP1837306B1 (en) | 2006-03-20 | 2011-07-20 | Research Institute of Petroleum Industry (RIPI) | Continuous process for producing carbon nanotubes |
KR20080113269A (en) | 2006-03-29 | 2008-12-29 | 하이페리온 커탤리시스 인터내셔널 인코포레이티드 | Method for preparing uniform single walled carbon nanotubes |
DE102006017695A1 (en) | 2006-04-15 | 2007-10-18 | Bayer Technology Services Gmbh | Process for producing carbon nanotubes in a fluidized bed |
US7659437B2 (en) | 2006-04-21 | 2010-02-09 | Exxonmobil Chemical Patents Inc. | Process for methane conversion |
KR101355038B1 (en) | 2006-04-24 | 2014-01-24 | 도꾸리쯔교세이호진 상교기쥬쯔 소고겡뀨죠 | Single-walled carbon nanotube, carbon fiber aggregate containing the single-walled carbon nanotube, and method for production of the single-walled carbon nanotube or the carbon fiber aggregate |
TW200804613A (en) | 2006-04-28 | 2008-01-16 | Univ California | Synthesis of pure nanotubes from nanotubes |
US7601294B2 (en) | 2006-05-02 | 2009-10-13 | Babcock & Wilcox Technical Services Y-12, Llc | High volume production of nanostructured materials |
US8268281B2 (en) | 2006-05-12 | 2012-09-18 | Honda Motor Co., Ltd. | Dry powder injector for industrial production of carbon single walled nanotubes (SWNTs) |
JP2007313621A (en) | 2006-05-29 | 2007-12-06 | Kanai Juyo Kogyo Co Ltd | Polishing roll and its manufacturing method |
US20080233402A1 (en) | 2006-06-08 | 2008-09-25 | Sid Richardson Carbon & Gasoline Co. | Carbon black with attached carbon nanotubes and method of manufacture |
CN104163413B (en) | 2006-08-30 | 2016-08-24 | 西北大学 | Monodisperse single-walled carbon nanotube colony and manufacture method thereof |
WO2008039496A2 (en) | 2006-09-27 | 2008-04-03 | The Trustees Of Columbia University | Growth and applications of ultralong carbon nanotubes |
EP2084105A4 (en) | 2006-10-18 | 2011-07-27 | Agency Science Tech & Res | Method of functionalizing a carbon material |
US8753602B2 (en) | 2006-10-19 | 2014-06-17 | University Of Cincinnati | Composite catalyst and method for manufacturing carbon nanostructured materials |
JP5140989B2 (en) | 2006-10-26 | 2013-02-13 | ソニー株式会社 | Single-walled carbon nanotube heterojunction manufacturing method and semiconductor device manufacturing method |
CN100450922C (en) | 2006-11-10 | 2009-01-14 | 清华大学 | Ultralong orientational carbon nano-tube filament/film and its preparation method |
JP5157147B2 (en) | 2006-12-08 | 2013-03-06 | 株式会社デンソー | Carbon nanotube manufacturing apparatus and manufacturing method thereof |
US20080134942A1 (en) | 2006-12-12 | 2008-06-12 | Matthew Brenner | Carbon Nanotube-Fiber Reinforced Cement And Concrete |
EP2102136A1 (en) | 2006-12-19 | 2009-09-23 | BP Oil International Limited | Process for converting methane into a higher alkane mixture. |
KR100824301B1 (en) | 2006-12-21 | 2008-04-22 | 세메스 주식회사 | Reaction chamber, and apparatus and system of collecting carbon nano tube having the same |
US9005755B2 (en) | 2007-01-03 | 2015-04-14 | Applied Nanostructured Solutions, Llc | CNS-infused carbon nanomaterials and process therefor |
KR100829555B1 (en) | 2007-01-25 | 2008-05-14 | 삼성에스디아이 주식회사 | A carbon nanotube, a support catalyst, a method for preparing the support catalyst and a fuel cell comprising the support catalyst |
US7794797B2 (en) | 2007-01-30 | 2010-09-14 | Cfd Research Corporation | Synthesis of carbon nanotubes by selectively heating catalyst |
US20090056802A1 (en) | 2007-02-16 | 2009-03-05 | Eli Michael Rabani | Practical method and means for mechanosynthesis and assembly of precise nanostructures and materials including diamond, programmable systems for performing same; devices and systems produced thereby, and applications thereof |
WO2008102813A1 (en) | 2007-02-20 | 2008-08-28 | National Institute Of Advanced Industrial Science And Technology | Beam-like material comprising carbon nanotube, and method for production thereof |
CN101049927B (en) | 2007-04-18 | 2010-11-10 | 清华大学 | Method for producing Nano carbon tubes continuously and equipment |
JP5301793B2 (en) | 2007-05-07 | 2013-09-25 | 国立大学法人北海道大学 | Fine carbon fiber aggregate for redispersion and method for producing the same |
EP1990449B1 (en) | 2007-05-11 | 2012-07-11 | Grupo Antolin-Ingenieria, S.A. | Carbon nanofibers and procedure for obtaining said nanofibers |
JP5596540B2 (en) | 2007-05-31 | 2014-09-24 | ジ アドミニストレイターズ オブ ザ チューレン エデュケイショナル ファンド | Method for forming stable functional nanoparticles |
JP2010528974A (en) | 2007-06-06 | 2010-08-26 | リンデ・エルエルシー | Integrated process for carbon monoxide generation for carbon nanomaterial generation |
US20080305030A1 (en) | 2007-06-06 | 2008-12-11 | Mckeigue Kevin | Integrated processes for generating carbon monoxide for carbon nanomaterial production |
US20080305029A1 (en) | 2007-06-06 | 2008-12-11 | Mckeigue Kevin | Integrated processes for generating carbon monoxide for carbon nanomaterial production |
US20080305028A1 (en) | 2007-06-06 | 2008-12-11 | Mckeigue Kevin | Integrated processes for generating carbon monoxide for carbon nanomaterial production |
JP4692520B2 (en) | 2007-06-13 | 2011-06-01 | 株式会社デンソー | Carbon nanotube manufacturing method |
US20090004075A1 (en) | 2007-06-26 | 2009-01-01 | Viko System Co., Ltd. | Apparatus for mass production of carbon nanotubes using high-frequency heating furnace |
JP5266907B2 (en) | 2007-06-29 | 2013-08-21 | 東レ株式会社 | Carbon nanotube aggregate, dispersion and conductive film |
US8314044B2 (en) | 2007-08-17 | 2012-11-20 | Juzer Jangbarwala | Fibrous composite catalytic structures and their use in chemical reactors |
DE102007044031A1 (en) | 2007-09-14 | 2009-03-19 | Bayer Materialscience Ag | Carbon nanotube powder, carbon nanotubes and methods of making same |
KR100933028B1 (en) | 2007-09-28 | 2009-12-21 | 세메스 주식회사 | Carbon nanotube manufacturing facility and manufacturing method of carbon nanotube using the same |
US20110053020A1 (en) | 2007-11-09 | 2011-03-03 | Washington State University Research Foundation | Catalysts and related methods |
US20090136413A1 (en) | 2007-11-15 | 2009-05-28 | Zhongrui Li | Method for enhanced synthesis of carbon nanostructures |
CN101873994B (en) | 2007-11-30 | 2013-03-20 | 东丽株式会社 | Carbon nanotube assembly and process for producing the same |
US8178049B2 (en) | 2007-12-26 | 2012-05-15 | Nikkiso Co., Ltd. | Carbon nanotube or carbon nanofiber production apparatus and recovery apparatus |
US20090191352A1 (en) | 2008-01-24 | 2009-07-30 | Nanodynamics, Inc. | Combustion-Assisted Substrate Deposition Method For Producing Carbon Nanosubstances |
US20090227460A1 (en) | 2008-03-07 | 2009-09-10 | Dow Agrosciences Llc | Stabilized oil-in-water emulsions including meptyl dinocap |
KR101543052B1 (en) | 2008-03-07 | 2015-08-07 | 히타치가세이가부시끼가이샤 | Carbon nano-tube manufacturing method and carbon nano-tube manufacturing apparatus |
US20110039124A1 (en) | 2008-03-25 | 2011-02-17 | Toray Industries, Inc. | Conductive composite and method for producing the same |
KR101034579B1 (en) | 2008-03-28 | 2011-05-12 | 한화케미칼 주식회사 | Continuous methods and apparatus of functionalizing Carbon Nanotube |
GB0805837D0 (en) | 2008-03-31 | 2008-06-04 | Qinetiq Ltd | Chemical Vapour Deposition Process |
AU2009233885B2 (en) | 2008-04-09 | 2013-05-30 | Riehl-Johnson Holdings, Llc | Method for production of carbon nanostructures |
JP5179979B2 (en) | 2008-04-16 | 2013-04-10 | 日信工業株式会社 | Carbon nanofiber and method for producing the same, method for producing carbon fiber composite material using carbon nanofiber, and carbon fiber composite material |
WO2009128349A1 (en) | 2008-04-16 | 2009-10-22 | 日本ゼオン株式会社 | Equipment and method for producing orientated carbon nano-tube aggregates |
US20100081568A1 (en) | 2008-04-21 | 2010-04-01 | Lockheed Martin Corporation | Methods for producing carbon nanotubes with controlled chirality and diameter and products therefrom |
EP2307311A1 (en) | 2008-06-30 | 2011-04-13 | Showa Denko K.K. | Process for producing carbon nanomaterial and system for producing carbon nanomaterial |
EP2301993A4 (en) | 2008-07-10 | 2012-07-25 | Nissin Kogyo Kk | Carbon nanofiber, process for producing the same, and carbon fiber composite material |
KR101497412B1 (en) | 2008-07-16 | 2015-03-02 | 주식회사 뉴파워 프라즈마 | Heat sink with compound material having covalent bond carbon nanotube |
WO2010014650A2 (en) | 2008-07-29 | 2010-02-04 | Honda Motor Co., Ltd. | Preferential growth of single-walled carbon nanotubes with metallic conductivity |
CN101712468B (en) | 2008-09-30 | 2014-08-20 | 清华大学 | Carbon nanotube composite material and preparation method thereof |
KR101007183B1 (en) | 2008-10-23 | 2011-01-12 | 제일모직주식회사 | Supported Catalyst for Synthesizing Carbon Nanotubes, Method for Preparing thereof and Carbon Nanotube Using the Same |
US8086154B2 (en) * | 2008-10-23 | 2011-12-27 | Xerox Corporation | Nanomaterial heating element for fusing applications |
WO2010055861A1 (en) | 2008-11-14 | 2010-05-20 | ジェイパワー・エンテック株式会社 | Lock hopper |
US8617270B2 (en) | 2008-12-03 | 2013-12-31 | Kellogg Brown & Root Llc | Systems and methods for improving ammonia synthesis efficiency |
US8709373B2 (en) | 2008-12-11 | 2014-04-29 | William Marsh Rice University | Strongly bound carbon nanotube arrays directly grown on substrates and methods for production thereof |
JP5355062B2 (en) | 2008-12-15 | 2013-11-27 | 東洋エンジニアリング株式会社 | Co-production method of methanol and ammonia |
US20100160155A1 (en) | 2008-12-22 | 2010-06-24 | Kangning Liang | Carbon Nanotubes with Nano-Sized Particles Adhered thereto and Method of Preparing Same |
KR101226522B1 (en) | 2008-12-22 | 2013-01-25 | 제일모직주식회사 | Supported Catalyst with Solid Sphere Structure, Method for Preparing Thereof and Carbon Nanotube Using the Same |
KR100969860B1 (en) | 2008-12-29 | 2010-07-13 | 금호석유화학 주식회사 | Catalyst compositions for preparing carbon nanotube |
US8318250B2 (en) | 2009-02-13 | 2012-11-27 | Babcock & Wilcox Technical Services Y-12, Llc | Anchored nanostructure materials and method of fabrication |
WO2010091704A1 (en) | 2009-02-16 | 2010-08-19 | Bayer International Sa | A compound material comprising a metal and nano particles and a method for producing the same |
KR101074027B1 (en) | 2009-03-03 | 2011-10-17 | 한국과학기술연구원 | Graphene composite nanofiber and the preparation method thereof |
KR100969861B1 (en) | 2009-03-13 | 2010-07-13 | 금호석유화학 주식회사 | Catalysts for preparing carbon nanotube comprising multi component support materials containing amorphous si particles and the bulk scale preparation of carbon nanotube using the same |
EP2419553A4 (en) | 2009-04-17 | 2014-03-12 | Seerstone Llc | Method for producing solid carbon by reducing carbon oxides |
WO2010124263A2 (en) | 2009-04-24 | 2010-10-28 | Old Dominion University Research Foundation | Electroosmotic pump |
KR101038750B1 (en) | 2009-05-20 | 2011-06-03 | 한국에너지기술연구원 | Carbon nanotubes catalysts having metal nano-particle catalyst supported on inner channel of carbon nanotube and preparation method thereof |
US8454923B2 (en) | 2009-06-10 | 2013-06-04 | Carbon Solutions, Inc. | Continuous extraction technique for the purification of carbon nanomaterials |
JP5647435B2 (en) | 2009-06-11 | 2014-12-24 | Dowaホールディングス株式会社 | Carbon nanotube and method for producing the same |
EP2444370A4 (en) | 2009-06-17 | 2015-04-29 | Nat Inst Of Advanced Ind Scien | Method for producing carbon nanotube assembly having high specific surface area |
KR20120041198A (en) | 2009-06-18 | 2012-04-30 | 타타 스틸 리미티드 | A process of direct low-temperature growth of carbon nanotubes (cnt) and fibers (cnf) on a steel strip |
US20110014368A1 (en) | 2009-07-14 | 2011-01-20 | Cfd Research Corporation | Carbon nanotube growth at reduced temperature via catalytic oxidation |
CN106829925A (en) | 2009-07-17 | 2017-06-13 | 西南纳米科技公司 | Catalyst And Method for preparing multi-walled carbon nano-tubes |
US8257678B2 (en) | 2009-07-31 | 2012-09-04 | Massachusetts Institute Of Technology | Systems and methods related to the formation of carbon-based nanostructures |
US8487392B2 (en) | 2009-08-06 | 2013-07-16 | Widetronix, Inc. | High power density betavoltaic battery |
DE102009038464A1 (en) | 2009-08-21 | 2011-02-24 | Bayer Materialscience Ag | Carbon nanotubes agglomerate |
US20120258374A1 (en) | 2009-09-10 | 2012-10-11 | The University Western Australia | Process for Producing Hydrogen from Hydrocarbons |
RU2414296C1 (en) | 2009-10-29 | 2011-03-20 | Инфра Текнолоджиз Лтд. | Catalyst for synthesis of hydrocarbons from co and h2 and preparation method thereof |
US8293204B2 (en) | 2009-12-19 | 2012-10-23 | Abbas Ali Khodadadi | Carbon nanotubes continuous synthesis process using iron floating catalysts and MgO particles for CVD of methane in a fluidized bed reactor |
US8225704B2 (en) | 2010-01-16 | 2012-07-24 | Nanoridge Materials, Inc. | Armor with transformed nanotube material |
EP2404869A1 (en) | 2010-07-06 | 2012-01-11 | Ammonia Casale S.A. | Process for producing ammonia synthesis gas |
US8596047B2 (en) | 2011-07-25 | 2013-12-03 | King Fahd University Of Petroleum And Minerals | Vehicle electrocatalyzer for recycling carbon dioxide to fuel hydrocarbons |
TW201341609A (en) | 2011-12-12 | 2013-10-16 | Exxonmobil Upstream Res Co | Methods and system for forming carbon nanotubes |
US9567219B2 (en) | 2011-12-12 | 2017-02-14 | Exxonmobil Upstream Research Company | Method and systems for forming carbon nanotubes |
US20130154438A1 (en) | 2011-12-20 | 2013-06-20 | Marvin Tan Xing Haw | Power-Scalable Betavoltaic Battery |
WO2013158158A1 (en) | 2012-04-16 | 2013-10-24 | Seerstone Llc | Methods for treating an offgas containing carbon oxides |
CN104271498B (en) | 2012-04-16 | 2017-10-24 | 赛尔斯通股份有限公司 | The method and structure of oxycarbide is reduced with non-iron catalyst |
WO2013158160A1 (en) | 2012-04-16 | 2013-10-24 | Seerstone Llc | Method for producing solid carbon by reducing carbon dioxide |
NO2749379T3 (en) | 2012-04-16 | 2018-07-28 | ||
JP2015520717A (en) | 2012-04-16 | 2015-07-23 | シーアストーン リミテッド ライアビリティ カンパニー | Method for using a metal catalyst in a carbon oxide catalytic converter |
MX354526B (en) | 2012-04-16 | 2018-03-07 | Seerstone Llc | Methods and systems for capturing and sequestering carbon and for reducing the mass of carbon oxides in a waste gas stream. |
US20150064092A1 (en) | 2012-04-16 | 2015-03-05 | Seerstone Llc | Methods and reactors for producing solid carbon nanotubes, solid carbon clusters, and forests |
TW201410596A (en) | 2012-04-17 | 2014-03-16 | 艾克頌美孚上游研究公司 | Feedstocks for forming carbon allotropes |
TW201400407A (en) | 2012-04-18 | 2014-01-01 | Exxonmobil Upstream Res Co | Generating catalysts for forming carbon allotropes |
TWI627130B (en) | 2012-04-18 | 2018-06-21 | 美商艾克頌美孚上游研究公司 | Removing carbon nanotubes from a continuous reactor effluent |
TWI570072B (en) | 2012-04-18 | 2017-02-11 | 艾克頌美孚上游研究公司 | Removing carbon nanotubes from a water stream |
CN104284862A (en) | 2012-04-23 | 2015-01-14 | 赛尔斯通股份有限公司 | Carbon nanotubes having a bimodal size distribution |
US9896341B2 (en) | 2012-04-23 | 2018-02-20 | Seerstone Llc | Methods of forming carbon nanotubes having a bimodal size distribution |
US10815124B2 (en) | 2012-07-12 | 2020-10-27 | Seerstone Llc | Solid carbon products comprising carbon nanotubes and methods of forming same |
US9604848B2 (en) | 2012-07-12 | 2017-03-28 | Seerstone Llc | Solid carbon products comprising carbon nanotubes and methods of forming same |
JP6025979B2 (en) | 2012-07-13 | 2016-11-16 | シーアストーン リミテッド ライアビリティ カンパニー | Methods and systems for forming ammonia and solid carbon products |
US9779845B2 (en) | 2012-07-18 | 2017-10-03 | Seerstone Llc | Primary voltaic sources including nanofiber Schottky barrier arrays and methods of forming same |
US9165694B2 (en) * | 2012-10-01 | 2015-10-20 | The Board Of Trustees Of The Leland Stanford Junior University | Nanowire apparatuses and methods |
MX2015006893A (en) | 2012-11-29 | 2016-01-25 | Seerstone Llc | Reactors and methods for producing solid carbon materials. |
WO2014151135A2 (en) | 2013-03-15 | 2014-09-25 | Seerstone Llc | Direct combustion heating |
WO2014151942A1 (en) | 2013-03-15 | 2014-09-25 | Seerstone Llc | Compositions of matter comprising nanocatalyst structures, systems comprising nanocatalyst structures, and related methods |
EP3129133A4 (en) | 2013-03-15 | 2018-01-10 | Seerstone LLC | Systems for producing solid carbon by reducing carbon oxides |
WO2014151119A2 (en) | 2013-03-15 | 2014-09-25 | Seerstone Llc | Electrodes comprising nanostructured carbon |
EP3113880A4 (en) | 2013-03-15 | 2018-05-16 | Seerstone LLC | Carbon oxide reduction with intermetallic and carbide catalysts |
WO2014150944A1 (en) | 2013-03-15 | 2014-09-25 | Seerstone Llc | Methods of producing hydrogen and solid carbon |
EP3129338A4 (en) | 2013-03-15 | 2018-01-17 | Seerstone LLC | Methods and systems for forming a hydrocarbon product |
WO2014151138A1 (en) | 2013-03-15 | 2014-09-25 | Seerstone Llc | Reactors, systems, and methods for forming solid products |
EP3122459A4 (en) | 2013-03-15 | 2018-01-10 | Seerstone LLC | Methods and systems for forming catalytic assemblies, and related catalytic assemblies |
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