• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    METHOD FOR PREPARING GRAPHENIC CARBON PARTICLES, GRAPHENIC CARBON PARTICLES AND APPARATUS TO PRODUCE GRAPHENIC CARBON PARTICLES. A method for producing graphene carbon particles is described. The method includes introducing a hydrocarbon precursor material in a thermal zone (20), heating the hydrocarbon precursor material in the thermal zone to form the graphene carbon particles of the hydrocarbon precursor material, and collecting the graphene carbon particles. The hydrocarbon precursor material may comprise a hydrocarbon and / or methane capable of forming a kind of two-carbon fragment. An apparatus (20) for carrying out such a method and the graphene particles produced by the method are also described.
    公开号:BR112014007540B1
    申请号:R112014007540-9
    申请日:2012-09-28
    公开日:2020-12-29
    发明作者:Cheng-Hung Hung；Noel R. Vanier
    申请人:Ppg Industries Ohio, Inc；
    IPC主号:
    专利说明:

    Technical field
    [001] The present invention relates to graphene carbon particles and, more particularly, to the production of such particles using hydrocarbon precursor materials. Prior art
    [002] Graphene is an allotrope of carbon containing an atom-thick structure. The planar structure comprises sp2 hybridized carbon atoms, densely packed in a honeycomb-like crystal lattice. The graphical materials resemble this ideal structure in that they have, on average, only a few planar sheets stacked of carbon atoms with sp hybridization of one atom in thickness. Summary of the Invention
    [003] One aspect of the present invention is to provide a method for preparing graphene carbon particles comprising introducing a hydrocarbon precursor material in a thermal zone, heating the hydrocarbon precursor material in the thermal zone to a temperature of at least 1,000 ° C to form graphene carbon particles from the hydrocarbon precursor material and collect the graphene carbon particles.
    [004] Another aspect of the present invention is to provide an apparatus for preparing graphene carbon particles comprising a source of hydrocarbon precursor material, a plasma chamber, and at least one supply line for releasing the hydrocarbon precursor material into the chamber of plasma.
    [005] These and other aspects of the present invention will be apparent from the description below. Brief description of the drawings
    [006] Figure 1 is a schematic flow diagram illustrating a method for forming graphene carbon particles from a hydrocarbon precursor material according to an embodiment of the present invention;
    [007] Figure 2 is a partially schematic longitudinal sectional view of a plasma system for producing graphene carbon particles according to an embodiment of the present invention;
    [008] Figure 3 is a graph of Raman exchange versus reflectance for a sample of graphene carbon particles produced with a n-propanol hydrocarbon precursor material according to an embodiment of the present invention;
    [009] Figures 4 and 5 are TEM micrographs of the graphene carbon particles corresponding to Figure 3;
    [010] Figure 6 is a graph of Raman exchange versus reflectance for a sample of graphene carbon particles produced with an ethanol precursor material;
    [011] Figures 7 and 8 are TEM micrographs of the graphene carbon particles corresponding to Figure 6;
    [012] Figure 9 is a graph of Raman exchange versus reflectance for a sample of carbon particles produced with an isopropanol precursor material;
    [013] Figures 10 and 11 are TEM micrographs of the carbon particles corresponding to Figure 9;
    [014] Figure 12 is a graph of Raman exchange versus reflectance for a sample of carbon particles produced with a precursor material of n-butanol;
    [015] Figures 13 and 14 are TEM micrographs of the carbon particles corresponding to Figure 12;
    [016] Figure 15 is a graph of Raman exchange versus reflectance for a sample of carbon particles produced with a precursor material of n-pentanol;
    [017] Figures 16 and 17 are TEM micrographs of the carbon particles corresponding to Figure 15;
    [018] Figure 18 is a graph of Raman exchange versus reflectance for a sample of carbon particles produced with a n-hexane precursor material;
    [019] Figures 19 and 20 are TEM micrographs of the carbon particles corresponding to Figure 18;
    [020] Figure 21 is a graph of Raman exchange versus reflectance for a sample of graphene carbon particles produced with a methane precursor material in accordance with an embodiment of the present invention; and
    [021] Figure 22 is a TEM micrograph of the graphene carbon particles corresponding to Figure 21. Detailed Description
    [022] Certain embodiments of the present invention are directed to methods and apparatus for preparing graphene carbon particles, as well as graphene carbon particles produced by such methods and apparatus. As used herein, the term "graphene carbon particles" means carbon particles containing structures comprising one or more layers of planar sheets of carbon atoms showing sp hybridization with an atom of thickness, densely packed in a crystalline lattice similar to a hive. The average number of layers stacked can be less than 100, for example, less than 50. In certain embodiments, the average number of layers stacked is 30 or less. The graphene carbon particles can, however, be substantially flat, and at least a portion of the planar sheets may be substantially curved, curly or wrinkled. The particles typically do not have a spheroidal or equiaxial morphology.
    [023] In certain embodiments, the graphene carbon particles prepared according to the present invention have a thickness, measured perpendicular to that of the carbon atom layers, up to 10 nanometers, such as up to 5 nanometers, or, in certain embodiments, up to 3 or 1 nanometer. In certain embodiments, the graphene carbon particles can have layers 1 to 10, 20 or 30 atoms thick or more.
    [024] In certain embodiments, the graphene carbon particles have a width and length measured parallel to the layers of carbon atoms, of at least 50 nanometers, as well as of more than 100 nanometers, in some cases, of more than 100 nanometers to 500 nanometers, or more than 100 nanometers to 200 nanometers. Graphene carbon particles can be provided in the form of ultra-thin sheets, platelets or sheets with relatively high aspect ratios (aspect ratio being defined as the ratio of the longest dimension of a particle to the shortest dimension of the particle) greater than 3 : 1, such as greater than 10: 1.
    [025] In certain embodiments, graphene carbon particles have relatively low oxygen content. For example, graphene carbon particles may, even though they have a maximum thickness of 5, or a maximum of 2 nanometers, have an oxygen content of up to 2 percent by atomic weight, such as up to 1.5 or 1 percent atomic weight, or up to 0.6 percent atomic weight, such as about 0.5 percent atomic weight. The oxygen content of graphene carbon particles can be determined using X-ray Photoelectronic Spectroscopy, as described in D.R. Dreyer et al., Chem. Soc. Rev. 39, 228-240 (2010).
    [026] In certain embodiments, the graphene carbon particles have a specific B.E.T. at least 50 square meters per gram, such as 70 to 1000 square meters per gram, or, in some cases, 200 to 1000 square meters per gram or 200 to 400 square meters per gram. As used herein, the term “specific surface area B.E.T.” refers to a specific surface area determined by nitrogen adsorption, according to the ASTM 3663-78 standard based on the Brunauer-Emmett-Teller method, described in the journal “The Journal of the American Chemical Society”, 60, 309 ( 1938).
    [027] In certain embodiments, the graphene carbon particles have a 2D / G peak Raman spectroscopy ratio of at least 1.1, for example, at least 1.2 or 1.3. As used herein, the term "2D / G peak ratio" refers to the ratio of the 2D peak intensity at 2692 cm-1 to the peak G intensity at 1,580 cm-1.
    [028] In certain embodiments, the graphene carbon particles have a relatively low bulk density. For example, graphene carbon particles are characterized by having an apparent density (tapped density) of less than 0.2 g / cm3, such as up to 0.1 g / cm3. For the purposes of the present invention, the apparent density of the graphene carbon particles is determined by placing 0.4 gram of the graphene carbon particles in a glass measuring cylinder with a readable graduated line. The cylinder is lifted approximately 1 inch and tapped 100 times, the base of the cylinder being tapped against a hard surface, to allow the graphene carbon particles to settle inside the cylinder. The particle volume is then measured and the apparent density calculated by dividing 0.4 grams by the measured volume, the apparent density being expressed in terms of g / cm3.
    [029] In certain embodiments, the graphene carbon particles have a compressed density and a percentage density less than the compressed density and the percentage density of graphite powder and certain types of substantially flat graphene carbon particles. Lower compressed density and percent densification are believed to contribute to better dispersion and / or rheological properties than graphene carbon particles that exhibit higher percent density and densification. In certain embodiments, the compressed density of the graphene carbon particles is equal to or less than 0.9, such as less than 0.8, less than 0.7, such as from 0.6 to 0.7. In certain embodiments, the percent densification of the graphene carbon particles is less than 40%, such as less than 30%, such as 25 to 30%.
    [030] For the purposes of the present invention, the compressed density of graphene carbon particles is calculated from a measured thickness of a given particle mass after compression. Specifically, the measured thickness is determined by subjecting 0.1 gram of the graphene carbon particles to the cold press under 15,000 pounds of force in a 1.3 cm matrix for 45 minutes, where the contact pressure is 500 MPa. The compressed density of the graphene carbon particles is then calculated from their measured thickness according to the following equation: Compressed density (g / cm3) = 0.1 gram II * (1.3 cm / 2) 2 * (thickness In cm)
    [031] The percent densification of the graphene carbon particles is then determined as the ratio of the compressed density calculated from the graphene carbon particles, as determined above, to 2.2 g / cm3, which is the density of the graphite.
    [032] In certain embodiments, graphene carbon particles have an apparent net conductivity measured of at least 100 microSiemens, such as at least 120 microSiemens, such as at least 140 microSiemens immediately after mixing and at later points in time, such like 10 minutes, or 20 minutes, or 30 minutes, or 40 minutes. For the purposes of the present invention, the apparent net conductivity of the graphene carbon particles is determined as described below. First, a sample comprising 0.5% solution of graphene carbon particles in butyl cellosolve is sonified for 30 minutes with a tank-type (bath) sonifier. Immediately after sonication, the sample is placed in a standard calibrated electrolytic conductivity cell (K = 1). A Fisher Scientific AB30 conductivity meter is introduced into the sample to measure its conductivity. Conductivity is plotted in approximately 40 minutes.
    [033] According to certain embodiments, percolation, defined as long-range interconnectivity, occurs between conductive graphene carbon particles. Such percolation can reduce the resistivity of the materials in which the graphene particles are dispersed. Conductive graphene particles can occupy a minimum volume in a composite matrix, in such a way that the particles form a continuous or almost continuous grid. In this case, the aspect ratios of the graphene carbon particles can affect the minimum volume required for percolation. In addition, the surface energy of the graphene carbon particles can be equal to or similar to the surface energy of the matrix material. On the other hand, particles can tend to flocculate or decompose ("demix") as they are processed.
    [034] According to embodiments of the invention, graphene carbon particles are produced with hydrocarbon precursor materials that are heated to high temperatures in a thermal zone. Hydrocarbon precursor materials can be any organic molecule that contains carbon and hydrogen and that has a molecular structure that, when heated to high temperatures in inert conditions, as described here, produces a kind of two-carbon fragment, that is, a species containing two carbon atoms joined together. The two-carbon fragment species may comprise carbon alone or, in certain embodiments, may include at least one hydrogen atom. Without binding to any specific theory, at high temperatures in the thermal zone, decomposition occurs, and the carbon atoms may be totally or partially lost. The remaining two-carbon fragment species form graphene carbon particles with relatively high product yields according to embodiments of the invention.
    [035] In certain embodiments, small molecule hydrocarbon precursor materials that produce two-carbon fragment species during the heat treatment process are used to produce high-quality graphene carbon particles. Examples of hydrocarbon precursor materials include n-propanol, ethane, ethylene, acetylene, vinyl chloride, 1,2-dichloroethane, allyl alcohol, propionaldehyde, vinyl bromide, and the like. Other feed materials that produce two-carbon fragment species in thermolysis can also be used. The structures of some hydrocarbon precursors capable of forming two-carbon fragment species are shown below.


    [036] According to the embodiments of the invention, graphene carbon particles are produced from methane precursor materials that are heated to high temperatures in a thermal zone. As used herein, the term "methane precursor material" means a material comprising significant amounts of methane, typically at least 50 weight percent methane. For example, the methane precursor material may comprise gaseous or liquid methane, at least 95 or 99 percent pure or more. In certain embodiments, the methane precursor can have a purity of at least 99.9 or 99.99 percent. In one embodiment, the methane precursor can be provided in the form of natural gas.
    [037] Without being bound by any specific theory, in the high temperatures of the thermal zone, the decomposition and pyrolysis of methane may involve the formulation of two carbon fragment species:

    [038] In certain embodiments, low concentrations of feed materials or additional dopants comprising atoms of B, N, O, F, Al, Si, P, S and / or Li can be introduced into the thermal zone to produce doped graphene containing low atom levels or doping atoms. Doping feed materials comprise less than 15 weight percent relative to the methane concentration. The functionalization or doping of graphene can also be carried out by introducing these dopants or reactive organic molecules in a colder area of the process, such as at or near the cooling site. For example, a low concentration of oxygen introduced in the cooling stage can result in graphene functionalization with hydroxyl, epoxy and / or carboxyl groups.
    [039] Figure 1 is a flow diagram illustrating certain embodiments of the methods of the present invention. At least one hydrocarbon precursor material selected in accordance with the present invention is provided as a feed material. According to certain methods of the present invention, the hydrocarbon precursor feed materials are contacted with an inert carrier gas. Inert carrier gases include, but are not restricted to, argon, nitrogen, helium, nitrogen and their combinations.
    [040] Then, according to certain embodiments of the present invention, the hydrogen precursor materials are heated in a thermal zone, for example, by a plasma system. In certain embodiments, hydrogen precursor materials are heated to a temperature ranging from 1,000 ° C to 20,000 ° C, such as 1,200 ° C to 10,000 ° C. For example, the temperature of the thermal zone can vary from 1,500 to 8,000 ° C, such as from 2,000 to 5,000 ° C, or it can vary from more than 3,500 ° C to 10,000 ° C. Although the thermal zone can be generated by a plasma system according to embodiments of the present invention, it is understood that any other suitable heating system can be used to create the thermal zone, such as various types of furnaces, including electrically heated tubular furnaces. and the like.
    [041] In certain methods of the present invention, the gas stream is contacted with one or more rapid cooling streams that are injected into the plasma chamber through at least one rapid cooling current injection port. For example, rapid cooling streams are injected at flow rates and injection angles that result in the cooling streams colliding with each other within the gaseous stream. The rapid cooling stream can cool the gas stream to facilitate formation or to control the particle size or morphology of the graphene carbon particles. Materials suitable for use in fast-cooling streams include, but are not restricted to inert gases, such as argon, hydrogen, helium, nitrogen and the like.
    [042] In certain embodiments, the specific flow rates and injection angles of the various cooling streams may vary, and may impact each other on the gas stream resulting in rapid cooling of the gas stream. For example, rapid cooling streams can mainly cool the gas stream through dilution, rather than adiabatic expansion, thus causing rapid cooling of the gas stream before, during and / or after the formation of graphene carbon particles. Such rapid cooling can occur in certain embodiments before the particles are passed through a convergent member, such as a convergent-divergent nozzle, as described below.
    [043] In certain embodiments of the invention, after contacting the gaseous product stream with the rapid cooling streams, the ultrafine particles can be passed through a converging member, the plasma system being designed to minimize its fouling. In certain embodiments, the convergent member comprises a convergent-divergent nozzle (De Laval). In these embodiments, although the convergent-divergent nozzle can act to cool the product stream to a certain degree, the cooling streams play a large role in cooling, so that a substantial amount of the graphene carbon particles are formed upstream of the nozzle. In these embodiments, the convergent-divergent nozzle can act mainly as a choke, a position that allows the reactor to operate at higher pressures, thus increasing the residence time of the materials contained therein.
    [044] As noted in Figure 1, in certain embodiments of the present invention, after the graphene carbon particles emanate from the plasma system, they are collected. Any suitable medium can be used to separate graphene carbon particles from the gas stream, such as, for example, a bag filter, cyclonic separator or deposition on a substrate.
    [045] According to embodiments of the invention, relatively high product yields are obtained. For example, the weight of the collected graphical particles can be at least 10 or 12 percent of the hydrocarbon precursor material that is fed into the plasma system.
    [046] Figure 2 is a partially schematic cross-sectional diagram of an apparatus for producing graphene carbon particles according to certain embodiments of the present invention. A plasma chamber 20 is provided and includes a feed inlet 50 which, in the embodiment shown in Figure 2, is used to introduce the hydrocarbon precursor material into the plasma chamber 20. In another embodiment, the feed inlet 50 can be replaced by separate entries (not shown) for the feed material. At least one carrier gas supply inlet 14 is also provided, through which the conductive gas flows in the direction of the arrow 30 into the plasma chamber 20. The conductive gas and the hydrocarbon precursor material form a gas stream that flows up to the plasma 29. A cooling inlet 23 and a cooling outlet 25 may be present for a double-walled plasma chamber 20. In these embodiments, the refrigerant flow is indicated by arrows 32 and 34.
    [047] In the embodiment shown in Figure 2, a plasma torch is provided. The torch 21 can thermally decompose or vaporize the feed materials in or near the plasma 29, as the plasma is released through the entrance of the plasma chamber 20. As seen in Figure 2, the feed materials are, in certain embodiments , injected downstream of the place where the arc connects to the annular anode 13 of the generator or plasma torch.
    [048] Plasma is a high temperature luminous gas, at least partially (from 1 to 100%) ionized. Plasma is composed of gas atoms, gas ions, and electrons. A thermal plasma can be created by passing a gas through an electric arc. The electric arc quickly heats the gas through resistive and radioactive heating to very high temperatures within microseconds of passage through the arc. Plasma is often luminous at temperatures above 9,000 K.
    [049] A plasma can be produced with any variety of gases. This can produce excellent control over the occurrence of any chemical reactions that occur in the plasma, as the gas can be inert, such as argon, helium, nitrogen, hydrogen or similar. Such inert gases can be used to produce graphene carbon particles, in accordance with the present invention. In Figure 2, the plasma gas supply inlet is shown at 31.
    [050] As the gaseous product stream emanates from the plasma 29 it proceeds towards the outlet of the plasma chamber 20. An additional current can optionally be injected into the reaction chamber before the injection of the cooling streams. A supply inlet for the additional current is shown in Figure 2 at 33.
    [051] As can be seen in Figure 2, in certain embodiments of the present invention, the gas stream is contacted with a plurality of cooling currents that enter the plasma chamber 20 in the direction of the arrows 41 through a plurality of injection ports of cooling current 40 located along the circumference of the plasma chamber 20. As previously indicated, the specific flow rate and the injection angle of the cooling streams can result in collision of the rapid cooling streams 41 with each other within the gas stream. , in some cases at or near the center of the gas stream, resulting in rapid cooling of the gas stream to control the particle size and / or morphology of the graphene carbon particles. This can result in rapid cooling of the gas stream through dilution.
    [052] In certain methods of the present invention, contacting the gas stream with the cooling streams can result in the formation and / or control of the size or morphology of the graphene carbon particles, which are then passed through and through a converging member. As used herein, the term “converging member” refers to a device that restricts the flow of a flow through it, thereby controlling the residence time of the flow in the plasma chamber due to the pressure differential upstream and downstream of the limb convergent.
    [053] In certain embodiments, the convergent member comprises a convergent-divergent nozzle (De Laval), as illustrated in Figure 2, which is positioned at the outlet of the plasma chamber 20. The convergent section or upstream of the nozzle, or that is, the convergent member, restricts the passage of gas and controls the residence time of the materials in the plasma chamber 20. It is believed that the contraction that occurs in the transverse size of the current, as it passes through the convergent portion of the nozzle 22 , alters the movement of at least part of the flow in random directions, including rotating and vibrating movements, to a straight line movement parallel to the geometric axis of the plasma chamber. In certain embodiments, the dimensions of the plasma chamber 20 and the material flow are selected to obtain sonic velocity at the neck of the restricted nozzle.
    [054] As the flow confined current enters the divergent or downstream portion of the nozzle 22, it undergoes an ultra-fast pressure reduction as a result of the gradual increase in volume along the conical outlet walls of the nozzle. By the appropriate selection of nozzle dimensions, the plasma chamber 20 can be operated at atmospheric pressure, or at a pressure slightly below atmospheric, or, in some cases, under a pressurized condition, to obtain the desired residence time, while the chamber 26 downstream of the nozzle 22 can be maintained at a vacuum pressure by operating a vacuum producing device, such as a vacuum pump 60. After passing through the nozzle 22, the graphene carbon particles can then enter a cooling chamber 26.
    [055] Although the nozzle shown in Figure 2 includes a converging portion and a diverging portion downstream, other nozzle configurations can be used. For example, the diverging downstream portion can be replaced by a straight portion. Rapid cooling currents can be introduced at or near the transition from the converging portion to the straight portion.
    [056] As is evident in Figure 2, in certain embodiments of the present invention, the graphene carbon particles can flow from the cooling chamber 26 to a collection station 27 via cooling section 45, which may comprise, for example, a tube jacketed cooling system. In certain embodiments, the collection station 27 comprises a bag filter or other collection means. A downstream purifier 28 can be used, if desired, to condense and collect material within the flow, prior to its entry into the vacuum pump 60.
    [057] In certain embodiments, the residence times for materials in the plasma chamber 20 are in the order of milliseconds. Hydrocarbon precursor materials can be injected under pressure (such as 1 to 300 psi) through a small orifice to obtain sufficient speed for penetration and mixing with the plasma. In addition, in many cases, the current is injected perpendicularly (90 ° angle) to the flow of plasma gases. In some cases, positive or negative deviations from the 90 ° angle by up to 30 ° may be desirable.
    [058] The high temperature of the plasma can quickly decompose and / or vaporize the feed materials. There may be a substantial difference in temperature gradients and gas flow patterns over the length of the plasma chamber 20. It is believed that, at the plasma arc inlet, the flow is turbulent and that there may be a high temperature gradient. , for example, temperatures of up to 20,000 K on the geometric axis of the chamber up to about 375K on the walls of the chamber. At the neck of the nozzle, it is believed that the flow is laminar and that there is a low temperature gradient due to its restricted open area.
    [059] The plasma chamber is often constructed of water-cooled stainless steel, nickel, titanium, copper, aluminum or other appropriate materials. The plasma chamber can also be constructed of ceramic materials, to withstand a harsh chemical and harsh environment.
    [060] The walls of the plasma chamber can be internally heated through a combination of radiation, convection and conduction. In certain embodiments, cooling the plasma chamber walls prevents unwanted melting and / or corrosion of their surfaces. The system used to control this cooling must keep the walls at a temperature as high as permitted by the selected wall material, which is often inert to the materials in the plasma chamber at the expected wall temperatures. This is also true with respect to the nozzle walls, which can be subjected to heat by convection and conduction.
    [061] The length of the plasma chamber is often determined experimentally using first an elongated tube within which the user can determine the target threshold temperature. The plasma chamber can then be designed long enough that the materials have sufficient residence time at high temperature to achieve equilibrium and complete the formation of the desired end products.
    [062] The internal diameter of the plasma chamber 20 can be determined by the properties of plasma fluid and mobile gas stream. It must be large enough to allow the necessary gas flow, although not so large as to allow the formation of recirculating eddies or stagnant areas along the chamber walls. Such harmful flow patterns can cool the gases prematurely and precipitate unwanted products. In many cases, the inner diameter of the plasma chamber 20 is greater than 100% of the plasma diameter at the inlet end of the plasma chamber.
    [063] In certain embodiments, the converging section of the nozzle has a diameter change with a high aspect ratio that keeps transitions smooth to a first inclined angle (such as> 45 °) and then to smaller angles (such as <45 ° degrees) leading into the nozzle neck. The purpose of the nozzle neck is often to compress the gases and obtain sonic velocities in the flow. The speeds obtained in the neck of the nozzle and in the divergent section of the nozzle downstream are controlled by the pressure differential between the plasma chamber and the downstream section of the divergent section of the nozzle. For this purpose, negative pressure downstream or positive pressure upstream can be applied. A convergent-divergent nozzle of the type suitable for use in the present invention is described in U.S. Patent No. RE37,853 column 9, line 65 to col. 11, line 32, the part of which is incorporated herein by reference.
    [064] The following examples are intended to illustrate certain embodiments of the present invention, and not to restrict its scope. Example 1
    [065] Graphene carbon particles were produced using a DC thermal plasma reactor system similar to that shown in Figure 2. The main reactor system included a DC plasma torch (Plasma Sprayer Model SG-100 from Praxair Technology, Inc. Dambury, Connecticut), operated on 60 standard liters per minute of argon-bearing gas and 26 kilowatts of energy supplied to the torch. Precursor of n-propanol (from Alfa Aesar, Ward Hill, Massachusetts) was fed to the reactor at a rate of 12 grams per minute through a gas assisted liquid nebulizer, located about 0.5 ”downstream of the outlet. plasma torch. In the nebulizer, 15 standard liters per minute of argon were released to aid in the atomization of liquid precursors. After a 14 ”long reactor section, a plurality of cooling current injection ports were provided which included nozzles with 6 1/8” diameter, located 60 ° from each other radially. The argon cooling gas was injected through the rapid cooling current injection ports at a rate of 185 standard liters per minute. The particles produced were collected in a bag filter. The collected solid material was 13 percent by weight of the feed material, corresponding to a 13 percent yield. Particle morphology analysis using Raman analysis and high resolution transmission electron microscopy (TEM) indicates the formation of a graphene layer structure with an average thickness less than 3.6 nm. The Raman graph shown in Figure 3 shows that graphene carbon particles were formed due to the sharp and high peak at 2692 on the graph versus smaller peaks at 1348 and 1580. The TEM image in Figure 4 shows the graphical particles in the form of a thin plate , while the TEM image with the largest magnification in Figure 5 shows a profile view of one of the platelets with several stacked atomic layers. Example 2
    [066] Example 1 was repeated, except that ethanol with the molecular structure shown below was used as the feed material (from Alfa Aesar, Ward Hill, Massachusetts).

    [067] The collected solid material had only 1 percent by weight of the feed material, corresponding to 1 percent yield. The Raman and TEM analysis of the particle morphology, illustrated in Figures 6-8, indicates the formation of a graphene layer structure. Example 3
    [068] Example 1 was repeated, except that isopropane, with the molecular structure shown below, was used as feed material (from Alfa Aesar, Ward Hill, Massachusetts).

    [069] The collected solid material had 5 percent by weight of the feed material, corresponding to 5 percent yield. The Raman and TEM analysis of particle morphology, as illustrated in Figures 9-11, indicates that the particles do not have a graphical layer structure. Specifically, the Raman chart includes a non-distinct and spread peak in the 2692 region, and significant peaks in the 1348 and 1587 regions. As shown in the TEM images in Figures 10 and 11, the particles tend not to have a plaque shape. Example 4
    [070] Example 1 was repeated, with the exception that n-butanol with the molecular structure shown below, was used as feed material (from Alfa Aesar, Ward Hill, Massachusetts).

    [071] The solid material collected was 9 percent by weight of the feed material, corresponding to a 9 percent yield. The Raman and TEM analysis of particle morphology, as shown in Figures 12-14, indicates the non-formation of a predominantly graphene structure, that is, the particles comprise a mixture of crystalline spheroidal structures with structures of graphene layer. Example 5
    [072] Example 1 was repeated, except that n-pentanol was used as the feed material (from Alfa Aesar, Ward Hill, Massachusetts). The collected solid material was 12 percent by weight of the feed material, corresponding to a 12 percent yield. The Raman and TEM analysis of particle morphology, as shown in Figures 15-17, indicates the non-formation of a predominantly graphene structure, that is, the particles comprise a mixture of crystalline spheroidal structures with structures of graphene layer. Example 6
    [073] Example 1 was repeated, with the exception that diethyl ketone was used as the feed material (from Alfa Aesar, Ward Hill, Massachusetts). The collected solid material was 13 percent by weight of the feed material, corresponding to a 13 percent yield. The Raman and TEM analysis of particle morphology, indicates the non-formation of a predominantly graphene structure, that is, the particles comprise a mixture of crystalline spheroidal structures with structures of graphene layer. Example 7
    [074] Example 1 was repeated, with the exception that propargyl alcohol was used as the food material (from Alfa Aesar, Ward Hill, Massachusetts). The collected solid material was 12 percent by weight of the feed material, corresponding to a 12 percent yield. The Raman and TEM analysis of particle morphology, indicates that the particles did not have a graphene layer structure. Example 8
    [075] Example 1 was repeated, with the exception that n-hexane was used as feed material (from Alfa Aesar, Ward Hill, Massachusetts). The collected solid material was 30 percent by weight of the feed material, corresponding to a 30 percent yield. The Raman and TEM analysis of particle morphology, as shown in Figures 18-20, indicates that the particles did not have a graphical layer structure. Example 9
    [076] Example 1 was repeated, with the exception that solid naphthalene particles were used as feed material (from Alfa Aesar, Ward Hill, Massachusetts). The Raman and TEM analysis of particle morphology, indicates that the particles did not have a graphene layer structure. Example 10
    [077] Example 1 was repeated, except that benzene was used as the feed material (from Alfa Aesar, Ward Hill, Massachusetts). The collected solid material was 67 percent by weight of the feed material, corresponding to a 67 percent yield. The Raman and TEM analysis of particle morphology, indicates that the particles did not have a graphene layer structure. Example 11
    [078] The graphene carbon particles were produced using a DC thermal plasma reactor system similar to that shown in Figure 2. The main reactor system included a DC plasma torch (Praxair Technology Plasma Sprayer Model SG-100, Inc. Dambury, Connecticut), operated on 60 standard liters per minute of argon-bearing gas and 26 kilowatts of energy supplied to the torch. Methane precursor from Airgas Great Lakes, Independent, Ohio, was fed to the reactor at a speed of 5 liters, located about 0.5 ”downstream of the plasma torch outlet. After a 14 ”long reactor section, a plurality of cooling current injection ports were provided which included nozzles with 6 1/8” diameter, located 60 ° from each other radially. The argon cooling gas was injected through the rapid cooling current injection ports at a rate of 185 standard liters per minute. The particles produced were collected in a bag filter. The collected solid material was 75 percent by weight of the feed material, corresponding to a 100 percent carbon conversion efficiency. Particle morphology analysis using Raman analysis and high resolution transmission electron microscopy (TEM) indicates the formation of a graphene layer structure with an average thickness less than 3.6 nm. The Raman graph shown in Figure 21 shows that graphene carbon particles were formed due to the sharp and high peak at 2692 on the graph versus smaller peaks at 1348 and 1580. The TEM image in Figure 22 shows the graphical particles in the form of a thin plate . The specific surface area B.E.T. The measurement of the material produced was 270 square meters per gram using a Gemini analyzer model 2360 from Micromeritics Instrument Corp., Norcross, Georgia.
    [079] It is understood that the invention can assume several alternative variations and step sequences, except when expressly specified otherwise. In addition, except in any operational examples, or when otherwise indicated, all figures expressing, for example, quantities of ingredients used in the report and claims, should be considered as modified, in all cases, by the term "about" . Consequently, unless otherwise indicated, the numerical parameters set out in the report and attached claims, are approximations that may vary, depending on the desired properties to be obtained by the present invention. At a minimum, and not as an attempt to restrict the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in light of the number of significant digits cited and applying common rounding techniques.
    [080] Despite the fact that the numerical ranges and parameters that establish the broad scope of the invention are approximations, the numerical values cited in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective test measurements.
    [081] Likewise, it is understood that any numerical range mentioned here is intended to cover all the sub-ranges included therein. For example, a range of “1 to 10” is intended to include all sub-ranges between (and inclusive) the minimum quoted value of 1 and the maximum quoted value of 10, that is, having a minimum value equal to or greater than 1 and a value maximum equal to or less than 10.
    [082] In the present application, the use of the singular includes the plural and the plural includes the singular, unless specifically mentioned otherwise. In addition, in this application, the use of "or" means "and / or", unless specifically stated otherwise, even though "and / or" may be explicitly used in certain cases.
    [083] It will be appreciated by those skilled in the art, what modifications can be made to the invention without departing from the concepts mentioned in the description below. Such modifications should be considered as included in the following claims, unless the claims, by their language, expressly express otherwise. Consequently, the specific embodiments described here in detail are for illustrative purposes only, and are not intended to restrict the broad scope of the appended claims and any and all equivalents thereof.
    权利要求:
    Claims (15)
    [0001]
    1. Method for preparing graphene carbon particles, characterized by the fact that it comprises: - introducing a hydrocarbon precursor material capable of forming a kind of two-carbon fragment or a hydrocarbon precursor material comprising methane in a thermal zone; - heat the hydrocarbon precursor material in the thermal zone (2) to a temperature in the range of 3,500 ° C to 20,000 ° C to form particles of graphene carbon from the hydrocarbon precursor material; and - to collect graphene carbon particles, with graphene carbon particles having an average aspect ratio greater than 3: 1.
    [0002]
    2. Method according to claim 1, characterized in that the hydrocarbon precursor material comprises n-propanol, ethane, ethylene, acetylene, vinyl chloride, 1,2-dichloroethane, allelic alcohol, propionaldehyde or vinyl bromide
    [0003]
    3. Method according to claim 1, characterized in that the hydrocarbon precursor material comprises n-propanol.
    [0004]
    4. Method according to claim 1, characterized in that the hydrocarbon precursor material comprises methane.
    [0005]
    Method according to any one of claims 1 to 4, characterized in that the thermal zone (20) is maintained at a temperature greater than 3,500 to 10,000 ° C.
    [0006]
    Method according to any one of claims 1 to 5, characterized in that the thermal zone (20) is in an inert atmosphere.
    [0007]
    Method according to any one of claims 1 to 6, characterized in that the thermal zone (20) comprises a plasma (29).
    [0008]
    8. Method, according to claim 7, characterized in that it also comprises introducing an inert gas into the plasma (29).
    [0009]
    Method according to claim 8, characterized in that the inert gas and the hydrocarbon precursor material are introduced into the plasma (29) together.
    [0010]
    Method according to claim 8, characterized in that the inert gas is introduced into the plasma (29) separately from the hydrocarbon precursor.
    [0011]
    11. Method according to claim 8, characterized in that the inert gas comprises argon, hydrogen, helium or nitrogen.
    [0012]
    12. Method according to any one of claims 1 to 11, characterized in that the graphene carbon particles have an average of 30 carbon atom layers or less.
    [0013]
    13. Method according to any one of claims 1 to 12, characterized in that the graphene carbon particles are less than 10 mm thick.
    [0014]
    Method according to any one of claims 1 to 13, characterized in that the harvested graphical particles have a weight that is at least 10 percent of the weight of the hydrocarbon precursor material.
    [0015]
    15. Method according to any of claims 1 to 14, characterized in that the graphene carbon particles have a specific B.E.T. at least 50 square meters per gram.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014007540B1|2020-12-29|method for preparing graphene carbon particles
    US20200230566A1|2020-07-23|Method and device to synthesize boron nitride nanotubes and related nanoparticles
    Kim et al.2014|Hydrogen-catalyzed, pilot-scale production of small-diameter boron nitride nanotubes and their macroscopic assemblies
    Yu et al.2010|Vertically aligned boron nitride nanosheets: chemical vapor synthesis, ultraviolet light emission, and superhydrophobicity
    Faraji et al.2014|Structural annealing of carbon coated aligned multi-walled carbon nanotube sheets
    WO2008105895A2|2008-09-04|Production of ultrafine boron carbide particles utilizing liquid feed materials
    Musso et al.2008|Fluid dynamic analysis of gas flow in a thermal-CVD system designed for growth of carbon nanotubes
    Wang et al.2019|Continuous synthesis of graphene nano-flakes by a magnetically rotating arc at atmospheric pressure
    Liu et al.2014|Synthesis of structure controlled carbon nanomaterials by AC arc plasma process
    Klimov et al.2014|Some aspects of the synthesis of multiwalled carbon nanotubes by chemical vapor deposition and characteristics of the material obtained
    Abdullayeva et al.2015|Characterization of high quality carbon nanotubes synthesized via Aerosol-CVD
    Zhang et al.2016|Large-scale synthesis of novel vertically-aligned helical carbon nanotube arrays
    Amirov et al.2015|Synthesis of graphene-like materials by pyrolysis of hydrocarbons in thermal plasma and their properties
    WO2009051888A1|2009-04-23|Doped ultrafine metal carbide particles
    Selbmann et al.2008|A parametric study of the synthesis and purification of single-walled carbon nanotubes using the high-pressure carbon monoxide process
    US20190300370A1|2019-10-03|Graphenic carbon particles
    Patel et al.2014|Synthesis and microstructure analysis of aligned carbon nanotube/pyrocarbon composites
    Moise et al.2016|High-quality carbon nanomaterials synthesized by excimer laser ablation
    Li et al.2017|Reducing dimensions of nanocarbons in electric arc plasma via rapid flow treatment
    Cochon et al.1999|A continuous wave CO 2 laser reactor for nanotubes synthesis
    Kumar2021|Synthesis Methods for Carbon-Based Materials
    Shavelkina et al.2017|Application of low-temperature plasma for the synthesis of hydrogenated graphene |
    Fulcheri et al.2004|Plasma processing of carbon nanomaterials
    Wattanaprayoon2011|Graphite exfoliation by supercritical carbon dioxide extraction
    Karmakar2017|Unveiling the mystery of nucleation and growth of carbon nanotube and layered graphene inside carbon arc-discharge
    同族专利:
    公开号 | 公开日
    IN2014DN02472A|2015-05-15|
    KR101593347B1|2016-02-11|
    JP2014528897A|2014-10-30|
    JP5943438B2|2016-07-05|
    US8486364B2|2013-07-16|
    US8486363B2|2013-07-16|
    US20130084236A1|2013-04-04|
    CA2850515C|2016-12-13|
    CN104010965B|2016-08-24|
    RU2014117529A|2015-11-10|
    CN104010965A|2014-08-27|
    US9221688B2|2015-12-29|
    WO2013049498A1|2013-04-04|
    EP2760788A1|2014-08-06|
    US20140227165A1|2014-08-14|
    US20130084237A1|2013-04-04|
    KR20140089526A|2014-07-15|
    CA2850515A1|2013-04-04|
    MX341013B|2016-08-03|
    RU2591942C2|2016-07-20|
    MX2014003762A|2014-07-24|
    US20150259211A9|2015-09-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4851262A|1987-05-27|1989-07-25|Carnegie-Mellon University|Method of making carbide, nitride and boride powders|
    US5369241A|1991-02-22|1994-11-29|Idaho Research Foundation|Plasma production of ultra-fine ceramic carbides|
    NO176885C|1992-04-07|1995-06-14|Kvaerner Eng|Use of pure carbon in the form of carbon particles as anode material for aluminum production|
    FR2701267B1|1993-02-05|1995-04-07|Schwob Yvan|Process for the production of carbonaceous soot with defined microstructures.|
    JPH07187633A|1993-12-28|1995-07-25|Univ Nagoya|Synthetic method of fullerenes by high frequency plasma|
    US5749937A|1995-03-14|1998-05-12|Lockheed Idaho Technologies Company|Fast quench reactor and method|
    US6821500B2|1995-03-14|2004-11-23|Bechtel Bwxt Idaho, Llc|Thermal synthesis apparatus and process|
    US5905000A|1996-09-03|1999-05-18|Nanomaterials Research Corporation|Nanostructured ion conducting solid electrolytes|
    US5851507A|1996-09-03|1998-12-22|Nanomaterials Research Corporation|Integrated thermal process for the continuous synthesis of nanoscale powders|
    US5788738A|1996-09-03|1998-08-04|Nanomaterials Research Corporation|Method of producing nanoscale powders by quenching of vapors|
    US5989648A|1997-05-06|1999-11-23|The Penn State Research Foundation|Plasma generation of supported metal catalysts|
    FR2764280B1|1997-06-06|1999-07-16|Yvan Alfred Schwob|PROCESS FOR THE MANUFACTURE OF CARBON 60|
    US5984997A|1997-08-29|1999-11-16|Nanomaterials Research Corporation|Combustion of emulsions: A method and process for producing fine powders|
    US6344271B1|1998-11-06|2002-02-05|Nanoenergy Corporation|Materials and products using nanostructured non-stoichiometric substances|
    US6716525B1|1998-11-06|2004-04-06|Tapesh Yadav|Nano-dispersed catalysts particles|
    US6569397B1|2000-02-15|2003-05-27|Tapesh Yadav|Very high purity fine powders and methods to produce such powders|
    EP1129990A1|2000-02-25|2001-09-05|Lucent Technologies Inc.|Process for controlled growth of carbon nanotubes|
    US6719821B2|2001-02-12|2004-04-13|Nanoproducts Corporation|Precursors of engineered powders|
    US6652967B2|2001-08-08|2003-11-25|Nanoproducts Corporation|Nano-dispersed powders and methods for their manufacture|
    US6689192B1|2001-12-13|2004-02-10|The Regents Of The University Of California|Method for producing metallic nanoparticles|
    US6669823B1|2002-06-17|2003-12-30|Nanophase Technologies Corporation|Process for preparing nanostructured materials of controlled surface chemistry|
    US7071258B1|2002-10-21|2006-07-04|Nanotek Instruments, Inc.|Nano-scaled graphene plates|
    US20050271574A1|2004-06-03|2005-12-08|Jang Bor Z|Process for producing nano-scaled graphene plates|
    US20060093885A1|2004-08-20|2006-05-04|Krusic Paul J|Compositions containing functionalized carbon materials|
    US7842271B2|2004-12-07|2010-11-30|Petrik Viktor I|Mass production of carbon nanostructures|
    US20070045116A1|2005-08-26|2007-03-01|Cheng-Hung Hung|Electrodepositable coating compositions and related methods|
    US7658901B2|2005-10-14|2010-02-09|The Trustees Of Princeton University|Thermally exfoliated graphite oxide|
    US20100072430A1|2005-10-14|2010-03-25|Gergely John S|Compositions of carbon nanosheets and process to make the same|
    JP2007268692A|2006-03-31|2007-10-18|Fujitsu Ltd|Carbon nanotube connected body, its manufacturing method, and element and method for detecting target|
    WO2007117503A2|2006-04-07|2007-10-18|The Trustees Of Columbia University In The City Of New York|Preparing nanoparticles and carbon nanotubes|
    US7754184B2|2006-06-08|2010-07-13|Directa Plus Srl|Production of nano-structures|
    US20100314788A1|2006-08-18|2010-12-16|Cheng-Hung Hung|Production of Ultrafine Particles in a Plasma System Having Controlled Pressure Zones|
    US7776303B2|2006-08-30|2010-08-17|Ppg Industries Ohio, Inc.|Production of ultrafine metal carbide particles utilizing polymeric feed materials|
    US20110070426A1|2006-08-30|2011-03-24|Vanier Noel R|Sintering aids for boron carbide ultrafine particles|
    US7635458B1|2006-08-30|2009-12-22|Ppg Industries Ohio, Inc.|Production of ultrafine boron carbide particles utilizing liquid feed materials|
    US7785492B1|2006-09-26|2010-08-31|Nanotek Instruments, Inc.|Mass production of nano-scaled platelets and products|
    US7745528B2|2006-10-06|2010-06-29|The Trustees Of Princeton University|Functional graphene-rubber nanocomposites|
    US7892514B2|2007-02-22|2011-02-22|Nanotek Instruments, Inc.|Method of producing nano-scaled graphene and inorganic platelets and their nanocomposites|
    US20090022649A1|2007-07-19|2009-01-22|Aruna Zhamu|Method for producing ultra-thin nano-scaled graphene platelets|
    US7824741B2|2007-08-31|2010-11-02|Micron Technology, Inc.|Method of forming a carbon-containing material|
    KR20090026568A|2007-09-10|2009-03-13|삼성전자주식회사|Graphene sheet and process for preparing the same|
    CN102066245B|2007-10-19|2014-07-16|卧龙岗大学|Process for the preparation of graphene|
    KR100923304B1|2007-10-29|2009-10-23|삼성전자주식회사|Graphene sheet and process for preparing the same|
    KR101344493B1|2007-12-17|2013-12-24|삼성전자주식회사|Single crystalline graphene sheet and process for preparing the same|
    US7790285B2|2007-12-17|2010-09-07|Nanotek Instruments, Inc.|Nano-scaled graphene platelets with a high length-to-width aspect ratio|
    US8883114B2|2007-12-26|2014-11-11|Nanotek Instruments, Inc.|Production of ultra-thin nano-scaled graphene platelets from meso-carbon micro-beads|
    US9546092B2|2008-02-05|2017-01-17|The Trustees Of Princeton University|Functionalized graphene sheets having high carbon to oxygen ratios|
    US7923491B2|2008-08-08|2011-04-12|Exxonmobil Chemical Patents Inc.|Graphite nanocomposites|
    KR101040967B1|2008-08-22|2011-06-16|한국과학기술연구원|Method for preparing graphene ribbon|
    US8114375B2|2008-09-03|2012-02-14|Nanotek Instruments, Inc.|Process for producing dispersible nano graphene platelets from oxidized graphite|
    US20100055017A1|2008-09-03|2010-03-04|Ppg Industries Ohio, Inc.|Methods for the production of ultrafine metal carbide particles and hydrogen|
    US20100126660A1|2008-10-30|2010-05-27|O'hara David|Method of making graphene sheets and applicatios thereor|
    EP2408956B1|2009-03-16|2016-03-16|Kordsa Global Endustriyel Iplik Ve Kord Bezi Sanayi Ve Ticaret A.S.|Tire cords|
    FR2943660B1|2009-03-25|2011-04-29|Commissariat Energie Atomique|GRAPHENE PRODUCTION PROCESS|
    US8568851B2|2009-03-31|2013-10-29|Nec Corporation|Method for manufacturing optical information recording medium, and optical information recording medium|
    KR101611410B1|2009-04-07|2016-04-11|삼성전자주식회사|Manufacturing method of graphene|
    US20100301212A1|2009-05-18|2010-12-02|The Regents Of The University Of California|Substrate-free gas-phase synthesis of graphene sheets|
    US20100323113A1|2009-06-18|2010-12-23|Ramappa Deepak A|Method to Synthesize Graphene|
    GB0913011D0|2009-07-27|2009-09-02|Univ Durham|Graphene|
    US8227386B2|2009-08-18|2012-07-24|GM Global Technology Operations LLC|Nanographene layers and particles and lubricants incorporating the same|
    US7999027B2|2009-08-20|2011-08-16|Nanotek Instruments, Inc.|Pristine nano graphene-modified tires|
    GB201000743D0|2010-01-18|2010-03-03|Univ Manchester|Graphene polymer composite|
    JP2011178617A|2010-03-02|2011-09-15|Panasonic Corp|Method for forming graphene film|
    KR101187810B1|2010-09-17|2012-10-05|탑나노시스|Transparent conductive sheet including anti-reflection layer and the method for manufacturing the same|
    WO2013166414A2|2012-05-03|2013-11-07|Ppg Industries Ohio, Inc.|Adhesive compositions containing graphenic carbon particles|
    DE102011003619A1|2011-02-03|2012-08-09|Bayer Materialscience Aktiengesellschaft|Multi-layer lacquer system, useful for preventing fouling by fouling organisms, comprises optionally third lacquer composition of diamine components, isocyanate components and defoamer in organic solvent|
    KR101856214B1|2011-07-28|2018-06-25|엘지이노텍 주식회사|Conducting film and manufacturing method of the same|
    US8486363B2|2011-09-30|2013-07-16|Ppg Industries Ohio, Inc.|Production of graphenic carbon particles utilizing hydrocarbon precursor materials|
    US20130296479A1|2012-05-03|2013-11-07|Ppg Industries Ohio, Inc.|Rubber formulations including graphenic carbon particles|
    US20130337258A1|2012-06-19|2013-12-19|Ppg Industries Ohio, Inc.|Coated sheet materials having high solar reflective index and corrosion resistance, and methods of making same|US8796361B2|2010-11-19|2014-08-05|Ppg Industries Ohio, Inc.|Adhesive compositions containing graphenic carbon particles|
    US20140150970A1|2010-11-19|2014-06-05|Ppg Industries Ohio, Inc.|Structural adhesive compositions|
    US9475946B2|2011-09-30|2016-10-25|Ppg Industries Ohio, Inc.|Graphenic carbon particle co-dispersions and methods of making same|
    US9988551B2|2011-09-30|2018-06-05|Ppg Industries Ohio, Inc.|Black pigments comprising graphenic carbon particles|
    US10763490B2|2011-09-30|2020-09-01|Ppg Industries Ohio, Inc.|Methods of coating an electrically conductive substrate and related electrodepositable compositions including graphenic carbon particles|
    US9938416B2|2011-09-30|2018-04-10|Ppg Industries Ohio, Inc.|Absorptive pigments comprising graphenic carbon particles|
    US8486363B2|2011-09-30|2013-07-16|Ppg Industries Ohio, Inc.|Production of graphenic carbon particles utilizing hydrocarbon precursor materials|
    US10240052B2|2011-09-30|2019-03-26|Ppg Industries Ohio, Inc.|Supercapacitor electrodes including graphenic carbon particles|
    US9761903B2|2011-09-30|2017-09-12|Ppg Industries Ohio, Inc.|Lithium ion battery electrodes including graphenic carbon particles|
    US9832818B2|2011-09-30|2017-11-28|Ppg Industries Ohio, Inc.|Resistive heating coatings containing graphenic carbon particles|
    CN107004829A|2014-10-31|2017-08-01|Ppg工业俄亥俄公司|Include the lithium ion battery electrode of graphene carbon particle|
    US10294375B2|2011-09-30|2019-05-21|Ppg Industries Ohio, Inc.|Electrically conductive coatings containing graphenic carbon particles|
    WO2016070068A1|2014-10-31|2016-05-06|Ppg Industries Ohio, Inc.|Resistive heating coatings containing graphene carbon particles and use of such coatings for low energy curing|
    KR102238443B1|2016-09-08|2021-04-09|피피지 인더스트리즈 오하이오 인코포레이티드|Method for coating an electrically conductive substrate, and a related electrodepositable composition comprising graphene carbon particles|
    MY171697A|2012-09-28|2019-10-23|Ppg Ind Ohio Inc|Electrically conductive coatings containing graphenic carbon particles|
    US20130296479A1|2012-05-03|2013-11-07|Ppg Industries Ohio, Inc.|Rubber formulations including graphenic carbon particles|
    US9574094B2|2013-12-09|2017-02-21|Ppg Industries Ohio, Inc.|Graphenic carbon particle dispersions and methods of making same|
    US10370539B2|2014-01-30|2019-08-06|Monolith Materials, Inc.|System for high temperature chemical processing|
    US10100200B2|2014-01-30|2018-10-16|Monolith Materials, Inc.|Use of feedstock in carbon black plasma process|
    US10138378B2|2014-01-30|2018-11-27|Monolith Materials, Inc.|Plasma gas throat assembly and method|
    US9574086B2|2014-01-31|2017-02-21|Monolith Materials, Inc.|Plasma reactor|
    US9385374B2|2014-04-01|2016-07-05|Ppg Industries Ohio, Inc.|Electrode binder composition for lithium ion electrical storage devices|
    GB201410639D0|2014-06-13|2014-07-30|Fgv Cambridge Nanosystems Ltd|Apparatus and method for plasma synthesis of graphitic products including graphene|
    US20160016143A1|2014-07-16|2016-01-21|Korea Institute Of Energy Research|APPARATUS FOR MANUFACTURING Si-BASED NANO-PARTICLES USING PLASMA|
    PT3213333T|2014-10-31|2020-09-18|Ppg Ind Ohio Inc|Supercapacitor electrodes including graphenic carbon particles|
    PL3253904T3|2015-02-03|2021-01-11|Monolith Materials, Inc.|Regenerative cooling method and apparatus|
    CN104961127A|2015-07-23|2015-10-07|合肥开尔纳米能源科技股份有限公司|Method for preparing nano graphene powder by plasma chemical vapor synthesis|
    CA3033947A1|2015-09-09|2017-03-16|Monolith Materials, Inc.|Circular few layer graphene|
    KR20180094843A|2015-09-14|2018-08-24|모놀리스 머티어리얼스 인코포레이티드|Carbon black prepared from natural gas|
    US10351661B2|2015-12-10|2019-07-16|Ppg Industries Ohio, Inc.|Method for producing an aminimide|
    US10377928B2|2015-12-10|2019-08-13|Ppg Industries Ohio, Inc.|Structural adhesive compositions|
    TWI648423B|2016-03-08|2019-01-21|財團法人工業技術研究院|Metal-doped graphene and growth method of the same|
    CN105692604A|2016-03-24|2016-06-22|浙江极力动力新能源有限公司|Method for preparing powder graphene from gas phase plasma|
    KR101820820B1|2016-04-15|2018-01-22|주식회사 제이오|Method for measuring thickness of graphite|
    EP3448553A4|2016-04-29|2019-12-11|Monolith Materials, Inc.|Secondary heat addition to particle production process and apparatus|
    PT109387B|2016-05-13|2021-12-14|Inst Superior Tecnico|PROCESS AND SYSTEM FOR THE SELECTIVE PRODUCTION OF AUTONOMOUS TWO-DIMENSIONAL NANOSTRUCTURES USING PLASMA TECHNOLOGY|
    WO2018112623A1|2016-12-21|2018-06-28|Raymor Industries Inc.|Plasma processes for producing graphene nanosheets|
    EP3580172A4|2017-02-10|2020-12-23|Raymor Industries Inc.|Graphenic carbon nanoparticles having a low polyaromatic hydrocarbon concentration and processes of making same|
    LU100335B1|2017-07-18|2019-01-28|Luxembourg Inst Science & Tech List|Plasma device for depositing functional composite film comprising crystallized particles embedded in a matrix and method of deposition thereof|
    US10434490B2|2017-08-08|2019-10-08|H Quest Vanguard, Inc.|Microwave-induced non-thermal plasma conversion of hydrocarbons|
    US9987611B1|2017-08-08|2018-06-05|H Quest Vanguard, Inc.|Non-thermal plasma conversion of hydrocarbons|
    CA3130338A1|2019-02-20|2020-08-27|Ppg Industries Ohio, Inc.|Dispersions containing graphenic carbon nanoparticles and dispersant resins|
    US20200317918A1|2019-04-05|2020-10-08|Prc-Desoto International, Inc.|Controlling cure rate using polythioether synergists|
    US20210095131A1|2019-08-16|2021-04-01|Ppg Industries Ohio, Inc.|Silica-Graphenic Carbon Composite Particles and Elastomeric Materials Including Such Particles|
    法律状态:
    2018-05-02| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2019-11-26| B06G| Technical and formal requirements: other requirements [chapter 6.7 patent gazette]|
    2020-06-16| B15K| Others concerning applications: alteration of classification|Free format text: A CLASSIFICACAO ANTERIOR ERA: C01B 31/04 Ipc: C01B 32/184 (2017.01), B82Y 40/00 (2011.01), B82Y |
    2020-06-23| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-12-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/09/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/249,315|2011-09-30|
    US13/249,315|US8486363B2|2011-09-30|2011-09-30|Production of graphenic carbon particles utilizing hydrocarbon precursor materials|
    US13/309,894|US8486364B2|2011-09-30|2011-12-02|Production of graphenic carbon particles utilizing methane precursor material|
    US13/309,894|2011-12-02|
    PCT/US2012/057811|WO2013049498A1|2011-09-30|2012-09-28|Production of graphenic carbon particles utilizing hydrocarbon precursor materials|
    [返回顶部]