Production of graphenic carbon particles utilizing hydrocarbon precursor materials

(54) Title: PRODUCTION OF GRAPIIENIC CARBON PARTICLES UTILIZING HYDROCARBON PRECURSOR MATERIALS wo 2013/049498 Al llllllllllllllllllillllllllllllllllllllllllllllll^

<img file="IN2472DEN2014A_D0001.tif" />

FIG. 1 (57) Abstract: A method is disclosed for making grapheme carbon particles. The method includes introducing a hydrocarbon precursor material into a thermal zone (20), heating the hydrocarbon precursor material in the thermal zone to form the graphenic carbon particles from the hydrocarbon precursor material, and collecting the grapheme carbon particles. The hydrocarbon precursor material may comprise a hydrocarbon and/or methane capable of forming a two-carbon-fragment species. Apparatus (20) for performing such a method, and grapheme particles produced by the method, are also disclosed.

WO 2013/049498 Al ΙΙΙΙΜΙΙΗΙΙΙΜ

TR), OAPl (BF, BJ, CF, CG, Cl, CM, GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG).

Declarations under Rule 4.17:

— as to applicant's entitlement to apply for and he granted a patent (Rule 4. J 7(H)) as to the applicant's entitlement to claim the priority of the earlier application (Rule 4.17(iii))

Published:

— with international search report (Art. 21(3)) ~~ before the expiration of the lime limit for amending the claims and to be republished in the event of receipt of amendments (Rule 48.2(h))

FORM 2

THE PATENTS ACT, 1970 (39 of 1970) &amp;

The Patent Rules, 2003

COMPLETE SPECIFICATION (See section 10 and rule 13)

TITLE OF THE INVENTION “PRODUCTION OF GRAPHENIC CARBON PARTICLES UTILIZING HYDROCARBON PRECURSOR MATERIALS”

We, PPG INDUSTRIES OHIO, INC., a corporation organized under the laws of State of Delaware, United States of America, of 3800 West 143rd Street, Cleveland, Ohio 44111, United States of America.

The following specification particularly describes the nature of the invention and the manner in which it is performed:

WO 2013/049498

PCT/US2012/057811

PRODUCTION OF GRAPHENIC CARBON PARTICLES UTILIZING HYDROCARBON PRECURSOR MATERIALS

HELD OF THE INVENTION [0001] The present invention relates to grapheme carbon particles, and more particularly relates to the production of such particles utilizing hydrocarbon precursor materials.

BACKGROUND INFORMATION [0002] Graphene is an allotrope of carbon having a structure that is one atom thick. The planar structure comprises sp²-bondcd carbon atoms that arc densely packed in a honeycomb crystal lattice. Grapheme materials approach this ideal structure by having on average only a few one-atom-thick planar sheets of sp²-bonded carbon atoms stacked together.

SUMMARY OF THE INVENTION [0003] An aspect of the present invention is to provide a method for making grapheme carbon particles comprising introducing a hydrocarbon precursor material into a thermal zone, heating the hydrocarbon precursor material in the thermal zone to a temperature of at least l,000°C to form the grapheme carbon particles from thc hydrocarbon precursor material, and collecting the grapheme carbon particles.

[0004] Another aspect of the present invention is to provide an apparatus for making grapheme carbon particles comprising a source of hydrocarbon precursor material, a plasma chamber, and at least one feed line for delivering the hydrocarbon precursor material to the plasma chamber.

[0005] These and other aspects of thc present invention will be more apparent from the following description.

BRIEF DESCRIPTION OF THE DRAWINGS [0006] Fig. 1 is a schematic flow diagram illustrating a method of forming grapheme carbon particles from a hydrocarbon precursor material in accordance with an embodiment of the present invention.

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PCT/US2012/057811 [0007] Fig. 2 is a partially schematic longitudinal section view of a plasma system for producing graphenic carbon particles in accordance with an embodiment of the present invention.

[0008] Fig. 3 is a plot of Raman shift versus reflectance for a sample of graphenic carbon particles produced from an n-propanol hydrocarbon precursor material in accordance with an embodiment of the present invention.

[0009] Figs. 4 and 5 are TEM micrographs of the graphenic carbon particles corresponding to Fig. 3.

[0010] Fig. 6 is a plot of Raman shift versus reflectance for a sample of graphenic carbon particles produced from an ethanol precursor material.

[0011] Figs. 7 and 8 are TEM micrographs of the graphenic carbon particles corresponding to Fig. 6.

[0012] Fig. 9 is a plot of Raman shift versus reflectance for a sample of carbon particles produced from an iso-propanol precursor material.

[0013] Figs. 10 and 11 are TEM micrographs of the carbon particles corresponding to Fig. 9.

[0014] Fig. 12 is a plot of Raman shift versus reflectance for a sample of carbon particles produced from an n-butanol precursor material.

[0015] Figs. 13 and 14 are TEM micrographs of the carbon particles corresponding to Fig. 12.

[0016] Fig. 15 is a plot of Raman shift versus reflectance for a sample of carbon particles produced from an n-pentanol precursor material.

[0017] Figs. 16 and 17 are TEM micrographs of the carbon particles corresponding to Fig. 15.

[0018] Fig. 18 is a plot of Raman shift versus reflectance for a sample of carbon particles produced from an n-hexane precursor material.

[0019] Figs. 19 and 20 are TEM micrographs ofthe carbon particles corresponding to Fig. 18, [0020] Fig. 21 is a plot of Raman shift versus reflectance for a sample of graphenic carbon particles produced from a methane precursor material in accordance with an embodiment of the present invention.

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PCT/US2012/057811 [0021] Fig. 22 is a TEM micrograph of the grapheme carbon particles corresponding to Fig. 21.

DETAILED DESCRIPTION [0022] Certain embodiments of the present invention are directed to methods and apparatus for making graphenic carbon particles, as well as the grapheme carbon particles produced by such methods and apparatus. As used herein, the term “graphenic carbon particles means carbon particles having structures comprising one or more layers of one-atom-thick planar sheets of sp²-bonded carbon atoms that are densely packed in a honeycomb crystal lattice. The average number of stacked layers may be less than 100, for example, less than 50. In certain embodiments, the average number of stacked layers is 30 or less. The graphenic carbon particles may be substantially flat, however, at least a portion of the planar sheets may be substantially curved, curled or buckled. The particles typically do not have a spheroidal or equiaxed morphology.

[0023] In certain embodiments, the graphenic carbon particles made in accordance with the present invention have a thickness, measured in a direction perpendicular to the carbon atom layers, of no more than 10 nanometers, such as no more than 5 nanometers, or, in certain embodiments, no more than 3 or 1 nanometers. In certain embodiments, the graphenic carbon particles may be from 1 atom layer to 10, 20 or 30 atom layers thick, or more.

[0024] In certain embodiments, the graphenic carbon particles have a width and length, measured in a direction parallel to the carbon atoms layers, of at least 50 nanometers, such as more than 100 nanometers, in some cases more than 100 nanometers up to 500 nanometers, or more than 100 nanometers up to 200 nanometers. The graphenic carbon particles may be provided in the form of ultrathin flakes, platelets or sheets having 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) of greater than 3:1, such as greater than 10:1.

[0025] In certain embodiments, the graphenic carbon particles have relatively low oxygen content. For example, the graphenic carbon particles may, even when having a thickness of no more than 5 or no more than 2 nanometers, have an oxygen

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PCT/US2012/0578U content of no more than 2 atomic weight percent, such as no more than 1.5 or 1 atomic weight percent, or no more than 0.6 atomic weight, such as about 0.5 atomic weight percent. The oxygen content of the grapheme carbon particles can be determined using X-ray Photoelcctron Spectroscopy, such as is described in D. R. Dreyer et al., Chem. Soc. Rev. 39, 228-240 (2010).

[0026] In certain embodiments, the grapheme carbon particles have a B.E.T. specific surface area of at least 50 square meters per gram, such as 70 to 10(X) square meters per gram, or, in some cases. 200 to 1000 square meters per grams or 200 to 400 square meters per gram. As used herein, the term ‘ B E T. specific surface area” refers to a specific surface area determined by nitrogen adsorption according to the ASTMD 3663-78 standard based on the Brunauer-Emmett-Teller method described in the periodical ‘The Journal ofthe American Chemical Society”. 60, 309 (1938).

[0027] In certain embodiments, the grapheme carbon particles have a Raman spectroscopy 2D/G peak ratio of al least 1.1, for example, al least 1.2 or 1.3. As used herein, the term “2D/G peak ratio” refers to the ratio of the intensity of the 2D peak at 2692 ctn¹ to the intensity of the G peak at 1,580 cm'¹.

[0028] In certain embodiments, the grapheme carbon particles have a relatively low bulk density. For example, the grapheme carbon particles are characterized by having a bulk density (tap density) of less than 0.2 g/cm³, such as no more than 0.1 g/cm³. For the purposes of the present invention, the bulk density of the grapheme carbon particles is determined by placing 0.4 grams of the grapheme carbon particles in a glass measuring cylinder having a readable scale. The cylinder is raised approximately one-inch and tapped 100 times, by striking the base of the cylinder onto a hard surface, to allow the grapheme carbon particles to settle within the cylinder. The volume of the particles is then measured, and the bulk density is calculated by dividing 0.4 grams by the measured volume, wherein the bulk density is expressed in terms of g/cm³.

[0029] In certain embodiments, the grapheme carbon particles have a compressed density and a percent densification that is less than the compressed density and percent densification of graphite powder and certain types of substantially flat grapheme carbon particles. Lower compressed density and lower percent densification are each currently believed to contribute to better dispersion and/or rheological

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PCT/US2012/057811 properties than grapheme carbon particles exhibiting higher compressed density and higher percent densilication. In certain embodiments, the compressed density of the grapheme carbon particles is 0.9 or less, 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 grapheme carbon particles is less than 40%, such as less than 30%, such as from 25 to 30%.

[0030] For purposes of the present invention, tlie compressed density of grapheme carbon particles is calculated front a measured thickness of a given mass of the particles after compression. Specifically, the measured thickness is determined by subjecting 0.1 grams of the graphenic carbon particles to cold press under 15,000 pound of force in a 1,3 centimeter die for 45 minutes, wherein the contact pressure is 500 MPa. The compressed density of the graphenic carbon particles is then calculated from this measured thickness according to the following equation:

Compressed Density (g/cm³) = _____________0.1 grams________________ n*(1.3cm/2)'*(measured thickness in cm) [0031] The percent densification of the graphenic carbon particles is then determined as the ratio of the calculated compressed density ofthe graphenic carbon particles, as determined above, to 2.2 g/cm³, which is the density of graphite, [0032] In certain embodiments, the graphenic carbon particles have a measured bulk liquid conductivity 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 as at 10 minutes, or 20 minutes, or 30 minutes, or 40 minutes. For the purposes of the present invention, the bulk liquid conductivity of the graphenic carbon particles is determined as follows. First, a sample comprising a 0.5% solution of graphenic carbon particles in butyl cellosolve is sonicated for 30 minutes with a bath sonicator. Immediately following sonication, the sample is placed in a standard calibrated electrolytic conductivity cell (K= 1). A Fisher Scientific AB 30 conductivity meter is introduced to the sample to measure the conductivity of the sample. The conductivity is plotted over the course of about 40 minutes.

[0033] In accordance with certain embodiments, percolation, defined as long range interconnectivity, occurs between the conductive graphenic carbon particles.

Such percolation may reduce the resistivity of the materials in which the graphenic

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PCT/US2012/057811 particles are dispersed. The conductive grapheme particles may occupy a minimum volume within a composite matrix such that lhe particles form a continuous, or nearly continuous, network. In such a case, the aspect ratios of the grapheme carbon particles may affect the minimum volume required for percolation. Furthermore, the surface energy of the grapheme carbon particles may be the same or similar to the surface energy of the matrix material. Otherwise, the particles may tend to flocculate or demix as they are processed.

[0034] In accordance with embodiments of the invention, the grapheme carbon particles are produced from hydrocarbon precursor materials that are heated to high temperatures in a thermal zone. The hydrocarbon precursor materials may be any organic molecule that contains carbon and hydrogen, and has a molecular structure which, when heated to the elevated temperatures under inert conditions as described herein, yields a two-carbon-fragment species, i.e., a species having two carbon atoms bonded together. The two-carbon-fragment species may comprise carbon alone or, in certain embodiments, may include at least one hydrogen atom. While not intending to be bound by any particular theory, at the high thermal zone temperatures, decomposition occurs and rhe hydrogen atoms may be entirely or partially lost. The remaining two-carbon-fragment species form grapheme carbon particles with relatively high product yields in accordance with embodiments ofthe invention.

[0035] In certain embodiments, small molecule hydrocarbon precursor materials that produce two-carbon-fragment species during the thermal treatment process are used to produce high quality graphenic 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 yield two-carbon-fragnicnt species on thermolysis may also be used. The structures of some hydrocarbon precursors capable of forming twocarbon-fragment species are shown below.

Η ΗH

I II

H—C--CC—OH

I II

Η η H (n-propanol)

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PCT/US2012/057811

Η Η

II

H—C--CH

II

Η h (ethane)

<img file="IN2472DEN2014A_D0002.tif" />

<img file="IN2472DEN2014A_D0003.tif" />

<img file="IN2472DEN2014A_D0004.tif" />

<img file="IN2472DEN2014A_D0005.tif" />

<img file="IN2472DEN2014A_D0006.tif" />

(ethylene)

H—c=c—H (acetylene)

<img file="IN2472DEN2014A_D0007.tif" />

<img file="IN2472DEN2014A_D0008.tif" />

(vinyl chloride)

ΗH

II

Cl—cC Cl

II

Η H (1,2-dichloroethane)

Η ΗH

I —II

C--CC—OH

Η H (allyl alcohol) [0036] In accordance with embodiments of the invention, the grapheme 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 of at least 95 or 99 percent purity or higher. In certain embodiments, the methane precursor may have a purity of at least 99.9 or 99.99 percent. In an embodiment, the methane precursor may be provided in the form of natural gas.

WO 2013/049498

PCT/US2012/057811 [0037] While not intending to be bound by any particular theory, at the high thermal zone temperatures, decomposition or pyrolysis of methane may involve the formulation of two-carbon-fragment species:

CH4 CH₃ + Η' CH₄ + Η’ -&gt; CHj + H₂CH₃ + CH₃ -5 c₂h₆c₂h₆ y· C₂H₄ + H₂c₂h₄ c₂h₃ + h₂ [0038] In certain embodiments, low concentrations of additional feed materials or dopants comprising atoms of B, N, O, F, Al, Si, P, S and/or Li may be introduced in the thermal zone to produce doped graphene containing low levels of the doping atom or atoms. The dopant feed materials typically comprise less than 15 weight percent relative to the concentration of methane. Functionalization or doping of the graphene may also be effected by introducing these dopants or reactive organic molecules at a cooler zone ofthe process such as at or near the quench location. For example, a low concentration of oxygen introduced at the quench stage could result in functionalization of the graphene with hydroxyl, epoxy and/or carboxyl groups.

[0039] Fig. 1 is a flow diagram depicting 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. In accordance with certain methods of the present invention, the hydrocarbon precursor feed materials are contacted with an inert carrier gas. Suitable inert carrier gases include, but are not limited to, argon, hydrogen, helium, nitrogen and combinations thereof.

[0040] Next, in accordance with 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, the hydrogen precursor materials are heated to a temperature ranging from l,000°C to 20,000°C, such as l,200°Cto 10,000°C. For example, the temperature ofthe thermal zone may range from 1,5(K&gt; to 8,000Τ, such as from 2,000 to 5,000°C, or may range from greater than 3.5OO°C to 10,000ⁿC. Although the thermal zone may be generated by a plasma system in accordance with embodiments of the present invention, it is to be understood that any other suitable

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PCT/US2012/057811 heating system may be used (o create the thermal zone, such as various types of furnaces including electrically heated lube furnaces and the like.

[0041] In certain methods of the present invention, the gaseous stream is contacted with one or more quench streams that are injected into the plasma chamber through al least one quench stream injection port. For example, the quench streams are injected at flow rates and injection angles that result in impingement of the quench streams with each other within the gaseous stream. The quench stream may cool the gaseous stream to facilitate the formation or control the particle size or morphology of the graphenic carbon particles. Materials suitable for use in the quench streams include, but are not limited to, inert gases such as argon, hydrogen, helium, nitrogen and lhe like.

[0042] In certain embodiments, the particular flow rales and injection angles of the various quench streams may vary, and may impinge with each other within the gaseous stream to result in the rapid cooling of the gaseous stream. For example, the quench streams may primarily cool the gaseous stream through dilution, rather than adiabatic expansion, thereby causing a rapid quenching of the gaseous stream, before, during and/or after the formation of the graphenic carbon particles. Such quenching may occur in certain embodiments prior to passing the particles into and through a converging member, such as a converging-diverging nozzle, as described below.

[0043] In certain embodiments of the invention, after contacting the gaseous product stream with the quench streams, the ultrafine particles may be passed through a converging member, wherein the plasma system is designed to minimize the fouling thereof. In certain embodiments, the converging member comprises a convergingdiverging (De Laval) nozzle. In these embodiments, while the con verging-diverging nozzle may act to cool the product stream to some degree, the quench streams perform much of the cooling so that a substantial amount of the graphenic carbon particles are formed upstream of the nozzle. In these embodiments, the converging-diverging nozzle may primarily act as a choke position that permits operation of the reactor at higher pressures, thereby increasing the residence time of the materials therein.

[0044] As is seen in Fig. 1, in certain embodiments of the present invention, after (he graphenic carbon particles exit the plasma system, they are collected. Any

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PCT/US2012/0578U suitable means may be used to separate the graphenic carbon particles from the gas flow, such as, for example, a bag filter, cyclone separator or deposition on a substrate.

[0045] In accordance with embodiments of the invention, relatively high product yields are achieved. For example, the weight of the collected graphenic particles may be at least 10 or 12 percent ofthe weight ofthe hydrocarbon precursor material that is fed to the plasma system.

[0046] Fig. 2 is a partially schematic sectional diagram of an apparatus for producing graphenic carbon particles in accordance with certain embodiments ofthe present invention. A plasma chamber 20 is provided that includes a feed inlet 50 which, in the embodiment shown in Fig. 2, is used to introduce the hydrocarbon precursor material into the plasma chamber 20. In another embodiment, the feed inlet 50 may be replaced with separate inlets (not shown) for the feed material. Also provided is at least one carrier gas feed inlet 14, through which a carrier gas flows in the direction of arrow 30 into the plasma chamber 20. The carrier gas and hydrocarbon precursor material form a gas-stream wliich flows towards plasma 29. A cooling inlet 23 and outlet 25 may be present for a double-walled plasma chamber 20. In these embodiments, coolant flow is indicated by arrows 32 and 34.

[0047] In the embodiment shown in Fig. 2, a plasma torch 21 is provided. The torch 21 may thermally decompose or vaporize the feed materials within or near the plasma 29 as the stream is delivered through the inlet of the plasma chamber 20. As is seen in Fig. 2, the feed materials arc, in certain embodiments, injected downstream of the location where the arc attaches to the annular anode 13 of the plasma generator or torch.

[0048] A plasma is a high temperature luminous gas which is at least partially (1 to 100%) ionized. A plasma is made up of gas atoms, gas ions, and electrons. A thermal plasma can be created by passing a gas tlirough an electric arc. The electric arc will rapidly heat the gas by resistive and radiative heating to very high temperatures within microseconds of passing tlirough the arc. The plasma is often luminous at temperatures above 9,000 K.

[0049] Λ plasma can be produced with any of a variety of gases. This can give excellent control over the occurrence of any chemical reactions taking place in the plasma, as the gas may be inert, such as argon, helium, nitrogen, hydrogen or the like.

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PCT/US2012/057811

Such inert gases may be used to produce grapheme carbon particles in accordance with the present invention. In Fig. 2, the plasma gas feed inlet is depicted al 31.

[0050] As the gaseous product stream exits the plasma 29 it proceeds towards the outlet of the plasma chamber 20. An additional stream can optionally be injected into lhe reaction chamber prior to lhe injection of the quench streams. A supply inlet for the additional stream is shown in Fig. 2 at 33.

[0051] As is seen in Fig. 2, in certain embodiments of the present invention, the gaseous stream is contacted with a plurality of quench streams which enter the plasma chamber 20 in the direction of arrows 41 through a plurality of quench stream injection ports 40 located along the circumference of the plasma chamber 20. As previously indicated, the particular flow rate and injection angle of the quench streams may result in impingement of the quench streams 41 with each other within the gaseous stream, in some cases at or near the center of the gaseous stream, to result in the rapid cooling of the gaseous stream to control lhe particle size and/or morphology of the grapheme carbon particles. This may result in a quenching of the gaseous stream through dilution.

[0052] In certain methods of the present invention, contacting (he gaseous stream with the quench streams may result in the formation and/or control of the size or morphology of the grapheme carbon particles, which are then passed into and through a converging member. As used herein, the term “converging member” refers to a device that restricts passage of a flow therethrough, thereby controlling the residence time of the flow in the plasma chamber due to pressure differential upstream and downstream of the converging member.

[0053] In certain embodiments, the converging member comprises a converging-diverging (De Laval) nozzle, such as (hat depicted in Fig. 2, which is positioned within the outlet of the plasma chamber 20. The converging or upstream section of the nozzle, i.e., the converging member, reslricts gas passage and controls the residence time ofthe materials within the plasma chamber 20. It is believed that the contraction that occurs in the cross sectional size of the stream as it passes through the converging portion of nozzle 22 changes the motion of at least some of the flow from random directions, including rotational and vibrational motions, to a straight line motion parallel to the plasma chamber axis. In certain embodiments, the dimensions of

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PCT/US2012/057811 the plasma chamber 20 and the material flow are selected to achieve sonic velocity within the restricted nozzle throat.

[0054] As the confined stream of flow enters the diverging or downstream portion of the nozzle 22, it is subjected to an ultra fast decrease in pressure as a result of a gradual increase in volume along the conical walls of the nozzle exit. By proper selection of nozzle dimensions, the plasma chamber 20 can be operated at atmosplreric pressure, or slightly less than atmospheric pressure, or, in some cases, at a pressurized condition, to achieve the desired residence time, while the chamber 26 downstream of the nozzle 22 may be maintained at a vacuum pressure by operation of a vacuum producing device, such as a vacuum pump 60. Following passage through nozzle 22, the grapheme carbon particles may then enter a cool down chamber 26.

[0055] Although the nozzle shown in Fig. 2 includes a converging portion and a downstream diverging portion, other nozzle configurations may be used. For example, the downstream diverging portion may be replaced with a straight portion. Quench streams may be introduced at or near the transition from the converging portion to the straight portion.

[0056] As is apparent from Fig. 2, in certain embodiments of the present invention, the grapheme carbon particles may flow from cool down chamber 26 to a collection station 27 via a cooling section 45, which may comprise, for example, a jacketed cooling tube. In certain embodiments, the collection station 27 comprises a bag filter or other collection means. A downstream scrubber 28 may be used if desired to condense and collect material within the flow prior to the flow entering vacuum pump 60.

[0057] In certain embodiments, the residence times for materials within the plasma chamber 20 are on the order of milliseconds. Thc hydrocarbon precursor materials may be injected under pressure (such as from 1 to 300 psi) through a small orifice to achieve sufficient velocity to penetrate and mix with the plasma. In addition, in many cases the injected stream is injected normal (90° angle) to the flow of the plasma gases. In some cases, positive or negative deviations from the 90° angle by as much as 30° may be desired.

[0058] The high temperature of the plasma may rapidly decompose and/or vaporize the feed materials. There can be a substantial difference in temperature

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PCT/US2012/057811 gradients and gaseous flow patterns along the length of the plasma chamber 20. It is believed that, at the plasma arc inlet, flow is turbulent and there may be a high temperature gradient, e.g., from temperatures of up to about 20,000 K at the axis of the chamber to about 375 K at the chamber walls. At the nozzle throat, it is believed, the flow is laminar and there is a very low temperature gradient across its restricted open area.

[0059] The plasma chamber is often constructed of water cooled stainless steel, nickel, titanium, copper, aluminum, or other suitable materials. The plasma chamber can also be constructed of ceramic materials to withstand a vigorous chemical and thermal environment.

[0060] The plasma chamber walls may be internally heated by a combination of radiation, convection and conduction. In certain embodiments, cooling of the plasma chamber walls prevents unwanted melting and/or corrosion at their surfaces. The system used to control such cooling should maintain the walls at as high a temperature as can be permitted by the selected wall material, which often is inert to the materials within the plasma chamber at the expected wall temperatures. This is true also with regard to the nozzle walls, which may be subjected to heat by convection and conduction.

[0061] The length of the plasma chamber is often determined experimentally by first using an elongated tube within which the user can locate the target threshold temperature. The plasma chamber can then be designed long enough so that the materials have sufficient residence time at the high temperature to reach an equilibrium state and complete the formation of the desired end products.

[0062] The inside diameter of the plasma chamber 20 may be determined by the fluid properties of the plasma and moving gaseous stream. It should be sufficiently great to permit necessary gaseous flow, but not so large that recirculating eddys or stagnant zones are formed along the walls of the chamber. Such detrimental flow patterns can cool the gases prematurely and precipitate unwanted products. In many cases, the inside diameter of the plasma chamber 20 is more than 100% of the plasma diameter at the inlet end of the plasma chamber.

[0063] In certain embodiments, the converging section of the nozzle has a high aspect ratio change in diameter that maintains smooth transitions to a first steep angle

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PCT/US2012/057811 (such as &gt; 45°) and then to lesser angles (such as &lt; 45° degree.) leading into rhe nozzle throat. The purpose ofthe nozzle throat is often to compress the gases and achieve sonic velocities in the flow. The velocities achieved in the nozzle throat and in the downstream diverging section of the nozzle are controlled by the pressure differential between the plasma chamber and the section downstream of the diverging section of the nozzle. Negative pressure can be applied downstream or positive pressure applied upstream for this purpose. A converging-diverging nozzle of the type suitable for use in the present invention is described in United States Patent No. RE37.853 at col. 9, line 65 to coL 11, line 32, the cited portion of which being incorporated by reference herein.

[0064] The following examples are intended to illustrate certain embodiments of the present invention, and are not intended to Limit the scope of the invention.

Example 1 [0065] Grapheme carbon particles were produced using a DC thermal plasma reactor system similar to that shown in Fig. 2. The main reactor system included a DC plasma torch (Model SG-100 Plasma Spray Gun commercially available from Praxair Technology, Inc., Danbury, Connecticut) operated with 60 standard liters per minute of argon carrier gas and 26 kilowatts of power delivered to the torch. N-propanol precursor (commercially available 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 inch down stream of the plasma torch outlet. At the nebulizer, 15 standard liters per minute of argon were delivered to assist in atomization of the liquid precursors. Following a 14 inch long reactor section, a plurality of quench stream injection ports were provided that included 6 1/8 inch diameter nozzles located 60° apart radially. Quench argon gas was injected through (he quench stream injection ports at a rate of 185 standard Liters per minute. The produced particles were collected in a bag filter. The solid material collected was 13 weight percent ofthe feed material, corresponding to a 13 percent yield. Analysis of particle morphology using Raman analysis and high resolution transmission electron microscopy (TEM) indicates the formation of a grapheme layer structure with average thickness of less than 3.6 nm. The Raman plot shown in Fig. 3 demonstrates that grapheme carbon particles were

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PCT/LS2012/057811 formed by virtue of the sharp and tall peak at 2692 on the plot versus shorter peaks at 1348 and 1580. The TEM image of Fig. 4 shows the thin plate-like graphenic particles, while the higher magnification TEM image of Fig. 5 shows an edge view of one of the platelets having several stacked atomic layers.

Example 2 [0066] Example 1 was repeated, except ethanol having the molecular structure shown below was used as the feed material (commercially available from Alfa Aesar, Ward Hill, Massachusetts).

ΗH

II

H---C---COH

II

Η H (ethanol)

The solid material collected was only 1 weight percent of the feed material, corresponding to a 1 percent yield. Raman and TEM analysis of the particle morphology as illustrated in Figs. 6-8 indicates the formation of a graphenic layer structure.

Example 3 [0067] Example 1 was repeated, except iso-propanol having the molecular structure shown below was used as the feed material (commercially available from Alfa

<td> Aesar, Ward Hill, Massachusetts),</td><td></td><td></td>

<td> H 1</td><td> H 1</td><td> H 1</td>

H—C--C--C—H

I I I

H OH H (iso-propanol)

The solid material collected was 5 weight percent of the feed material, corresponding to a 5 percent yield. Raman and TEM analysis of particle morphology as illustrated in Figs. 9-11 indicates the particles do not have a graphenic layer structure. Specifically, the Raman plot includes a non-distinct and spread out peak in the 2692 region, and significant peaks in the 1348 and 1587 regions. As shown in the TEM images of Figs. 10 and 11, the particles tend to be non-platc-likc.

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PC17US2012/057811

Example 4 [0068] Example I was repeated, except n-butanol having the molecular structure shown below was used as the feed material (commercially available from Alfa Aesar, Ward Hill, Massachusetts).

Η Η Η H

Illi

H—C--C--C--C--OH

Illi Η Η Η H (n-butanol)

The solid material collected was 9 weight percent of the feed material, corresponding to a 9 percent yield. Raman and TEM analysis of particle morphology as shown in Figs. 12-14 indicates that a predominantly graphcnic structure is not formed, i.e., the particles comprise a mixture of crystalline spheroidal structures with grapheme layer structures.

Example 5 [0069] Example 1 was repeated, except n-pentanol was used as the feed material (commercially available from Alfa Aesar, Ward Hill, Massachusetts). The solid material collected was 12 weight percent of the feed material, corresponding to a percent yield. Raman and TEM analysis of particle morphology as shown in Figs. 15-17 indicates that a predominantly grapheme structure is not formed, i.e., the particles comprise a mixture of crystalline spheroidal structures with grapheme layer structures.

Example 6 [0070] Example 1 was repeated, except diethyl ketone was used as the feed material (commercially available from Alla Aesar, Ward Hill, Massachusells). The solid material collected was 13 weight percent ofthe feed material, corresponding to a percent yield. Raman and TEM analysis of particle morphology indicates that a predominantly grapheme structure is not formed, i.e., the particles comprise a mixture of crystalline spheroidal structures with grapheme layer structures.

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Example 7 [0071] Example 1 was repeated, except propargyl alcohol was used as the feed material (commercially available from Alfa Aesar, Ward Hill, Massachusetts). The solid material collected was 12 weight percent of the feed material, corresponding to a 12 percent yield. Raman and TEM analysis of particle morphology indicates the particles do not have a graphenic layer structure.

Example 8 [0072] Example 1 was repeated, except n-hexane was used as the feed material (commercially available from Alfa Aesar, Ward Hill, Massachusetts). The solid material collected was 30 weight percent of the feed material, corresponding to a 30 percent yield. Raman and TEM analysis of particle morphology as shown in Figs. 1820 indicates the particles do not have a graphenic layer structure.

Example 9 [0073] Example 1 was repeated, except that solid naphalene particles was used as the feed material (commercially available front Alfa Aesar, Ward Hill, Massachusetts). Raman and TEM analysis of particle morphology indicates the particles do not have a graphenic layer structure.

Example 10 [0074] Example 1 was repeated, except benzene was used as the feed material (commercially available from Alfa Aesar, Ward Hill, Massachusetts). The solid material collected was 67 weight percent of the feed material, corresponding to a 67 percent yield. Raman and TEM analysis of particle morphology indicates the particles do not have a graphenic layer structure.

Example 11 [0075] Graphenic carbon particles were produced using a DC thermal plasma reactor system similar to that shown in Fig. 2. The main reactor system included a DC plasma torch (Model SG-100 Plasma Spray Gun commercially available from Praxair Technology, Inc., Danbury, Connecticut) operated with 60 standard liters per minute

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PCT/US2012/057811 of argon carrier gas and 26 kilowatts of power delivered to the torch. Methane precursor gas, commercially available from Airgas Great Lakes, Independent, Ohio, was fed to the reactor at a rate of 5 standard liters per minute about 0.5 inch downstream of the plasma torch outlet. Following a 14 inch long reactor section, a plurality of quench stream injection ports were provided that included 6 1/8 inch diameter nozzles located 60° apart radially. Quench argon gas was injected through the quench stream injection ports at a rate of 185 standard liters per minute. The produced particles were collected in a bag filler. The total solid material collected was 75 weight percent of the feed material, corresponding to a 100 percent carbon conversion efficiency. Analysis of particle morphology using Raman analysis and high resolution transmission electron microscopy (TEM) indicates the formation of a grapheme layer structure with average thickness of less than 3.6 nm. The Raman plot shown in Fig. 21 demonstrates that grapheme carbon particles were formed by virtue of the sharp and tall peak at 2692 on the plot versus shorter peaks at 1348 and 1580. The TEM image of Fig. 22 shows the thin plate-like grapheme particles. The measured B.E.T. specific surface area of the produced material was 270 square meters per gram using a Gemini model 2360 analyzer available from Micromeritics Instrument Corp., Norcross, Georgia.

[0076] It is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0077] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in

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PCT/US2012/057811 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 testing measurements.

[0078] Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of “1 to 10” is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.

[0079] In this application, the use of the singular includes the plural and plural encompasses singular, unless specifically stated 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 instances.

[0080] It will be readily appreciated by those skilled in the art that modifications may be made to the invention without departing from the concepts disclosed in the foregoing description. Such modifications are to be considered as included within the following claims unless the claims, by their language, expressly state otherwise. Accordingly, the particular embodiments described in detail herein are illustrative only and are not limiting to the scope of the invention which is to be given the full breadth of the appended claims and any and all equivalents thereof.

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