Carbon black from natural gas

Abstract
Carbon nanoparticles made in a one step process. A method of making carbon black nanoparticles is described, including adding a hydrocarbon to a heated gas to produce carbon nanoparticles that are less than 1 micron volume equivalent sphere and have an Lc greater than 3.0 nm. Elastomer composites containing such particles are also described.
Description
TECHNICAL FIELD

The field of art to which this invention generally pertains is methods and apparatus for making use of electrical energy to affect chemical changes.


BACKGROUND

There are many processes that can be used and have been used over the years to produce carbon black. The energy sources used to produce such carbon blacks over the years have, in large part, been closely connected to the raw materials used to convert hydrocarbon containing materials into carbon black. Residual refinery oils and natural gas have long been a resource for the production of carbon black. Energy sources have evolved over time in chemical processes such as carbon black production from simple flame, to oil furnace, to plasma, to name a few. As in all manufacturing, there is a constant search for more efficient and effective ways to produce such products, and new and improved products. Varying flow rates and other conditions of energy sources, varying flow rates and other conditions of raw materials, increasing speed of production, increasing yields, reducing manufacturing equipment wear characteristics, etc. have all been, and continue to be, part of this search over the years.


The embodiments described herein meet the challenges described above, and additionally attain more efficient and effective manufacturing process.


BRIEF SUMMARY

Carbon nanoparticles are described including carbon nanoparticles that are less than 1 micron volume equivalent sphere and have an Lc greater than 3.0 nanometers (nm).


Additional embodiments include: the carbon nanoparticle described above where the volume equivalent sphere is less than 700 nm; the carbon nanoparticle described above where the d002 is less than 0.35 nm; the carbon nanoparticles described above including a fullerene-like surface structure; the carbon nanoparticle described above where the particles have 0.2% hydrogen or less by weight as produced; the carbon nanoparticles described above where the particles have 0.4% oxygen or less by weight as produced; the carbon nanoparticles described above where the particles have 0.3% sulfur or less by weight as produced.


Elastomer composites containing the carbon nanoparticles described above compounded therein and additionally containing sulfur, are also described.


Additional embodiments include: the composite described above where the strain required to stretch the elastomer composite 300% of the original length is at least 90% of the reference carbon black elastomer composite value; the composite described above where the tan delta at 0° C. is at least 90% of the reference carbon black elastomer composite value; the composite described above where the tan delta at 60° C. is less than 110% of the reference carbon black elastomer composite value; the composite described above where the tan delta at 60° C. is less than 95% of the reference carbon black elastomer composite value.


A method of making carbon nanoparticles in a one step process is also described including adding a hydrocarbon to a heated gas to produce carbon nanoparticles that are less than 1 micron volume equivalent sphere and have an Lc greater than 3.0 nm.


Additional embodiments include: the method described above where the hydrocarbon has been mixed with a hot gas to effect removal of hydrogen from the hydrocarbon; the method described above where the nanoparticles are produced in an oxygen free atmosphere; the method described above where the hydrocarbon is natural gas; the method described above where the yield of carbon nanoparticles is at least 90%; the methods described above additionally including the use of one or more heat exchangers, filters, degas chambers, and/or backend equipment; the method described above where the backend equipment includes one or more of a pelletizer, a binder mixing tank connected to the pelletizer, and/or a dryer connected to the pelletizer.


These and additional embodiments are further described below.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 demonstrates a flow chart of a process described herein.



FIGS. 2, 3 and 4 depict various apparatus for carrying out processes described herein.



FIGS. 5 and 6 show typical Transmission Electron Micrograph (TEM) images of carbon nanoparticle produced by processes herein.





DETAILED DESCRIPTION

The particulars shown herein are by way of example and for purposes of illustrative discussion of the various embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of the invention. In this regard, no attempt is made to show details of the invention in more detail than is necessary for a fundamental understanding of the invention, the description making apparent to those skilled in the art how the several forms of the invention may be embodied in practice.


The present invention will now be described by reference to more detailed embodiments. This invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.


Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for describing particular embodiments only and is not intended to be limiting of the invention. As used in the description of the invention and the appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. All publications, patent applications, patents, and other references mentioned herein are expressly incorporated by reference in their entirety.


Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth 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 sought 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 be construed in light of the number of significant digits and ordinary rounding approaches.


Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.


Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.



FIG. 1 shows that the process begins through the addition of hydrocarbon to hot gas. FIGS. 2, 3 and 4 show different methods of combining the hot gas and the hydrocarbon precursor. The hot gas is typically a stream of hot gas that is at an average temperature of over 2200° C. The hot gas will typically be comprised of greater than 50% hydrogen by volume.


The hydrocarbon feedstock used include any chemical within the formula CnHx or CnHxOy, where n is an integer, x is between 1n and 2n+2, and y is between 0 and n. For example, simple hydrocarbons such as methane, ethane, propane, butane, etc. can be used. Aromatic feedstocks such as benzene, toluene, methyl naphthalene, pyrolysis fuel oil, coal tar, coal, heavy oil, oil, bio-oil, bio-diesel, other biologically derived hydrocarbons, or the like can be used. Also, unsaturated hydrocarbon feedstocks can also be used, such as ethylene, acetylene, butadiene, styrene and the like. Oxygenated hydrocarbons such as ethanol, methanol, propanol, phenol, ketones, ethers, esters, and similar compounds are also acceptable feedstocks. The above should be viewed as non-limiting examples of acceptable hydrocarbon feedstocks which can additionally be combined and/or mixed with other acceptable components. The use of the term hydrocarbon feedstock herein, refers to feedstocks where the majority of the feedstock is hydrocarbon in nature. For example, natural gas would be a preferred hydrocarbon feedstock for the processes described herein.


Heat can also be provided through latent radiant heat from the wall of the reactor. This can either occur through heating of the walls via an external energy source or through the heating of the walls from the hot gas. The heat is transferred from the hot gas to the hydrocarbon feedstock. This will occur immediately upon addition of the hydrocarbon feedstock to the hot gas in the reactor or the reaction zone (102). The hydrocarbon will begin to crack and decompose before being fully converted into carbon black.


The process described herein is substantially free of atmospheric oxygen. The process is designed to include heating a gas that is comprised of 50% or greater by volume hydrogen and then adding this hot gas to a hydrocarbon (101). The process includes one or more of the steps of heating the gas, adding hydrocarbon to the hot gas, and can additional include the use of one or more of a heat exchanger (103), filter (104), degas chamber (105), and backend (106). The backend can optionally include one or more of a pelletizer, a binder mixing tank connected to the pelletizer, and a dryer connected to the pelletizer. These components are shown schematically in FIG. 1. With the exception of the degas unit, conventional pieces of equipment used in the carbon black industry to perform these functions can be used, as demonstrated, for example, by U.S. Pat. Nos. 3,981,659; 3,309,780; and 3,307,923, the disclosures of which are herein incorporated by reference. The degas unit which can be used is also described in commonly assigned, copending U.S. provisional patent application Ser. No. 62/111,346, Carbon Black Generating System, the entirety of which is incorporated by reference herein.



FIG. 2 shows a schematic representation of an embodiment of a typical apparatus described herein. Plasma gas (201) such as oxygen, nitrogen, argon, helium, air, hydrogen, carbon monoxide, hydrocarbon (e.g. methane, ethane) etc. (used alone or in mixtures of two or more) is injected into an annulus created by two electrodes that are positioned in the upper chamber in a concentric fashion. Plasma forming electrodes are arranged with an inner (202) and outer (203) electrode and a sufficiently large voltage is applied between the two electrodes. Electrodes are typically made of copper, tungsten, graphite, molybdenum, silver etc. The thus-formed plasma then enters into the reaction zone where it reacts/interacts with a hydrocarbon feedstock that is fed at the hydrocarbon injector (205) to generate a carbon black product. The walls of the vessel can withstand the plasma forming temperatures, with graphite being the preferred material of construction. And the hydrocarbon injector(s) (205) can be located anywhere on a plane at or near the throat (206) below the converging region (207) or further downstream of the throat in the diverging region (208) of the reactor. The hydrocarbon injector tips are arranged concentrically around the injection plane and there can be at least 6 injectors and up to 18 tips of this sort, or a slot, as non-limiting examples.



FIG. 3 shows another embodiment of a typical apparatus described herein. This is a two dimensional cutout of a reactor that utilizes inner (301) and outer electrodes (302) that consist of concentric rings of electrically conductive material, preferably graphite. Plasma gas (307) can flow through the annulus between the two electrodes where the arc will then excite the gas into the plasma state. The arc is controlled through the use of a magnetic field which moves the arc in a circular fashion rapidly around the electrode tips. In this example, the hydrocarbon is injected at the hydrocarbon injector (303) tip (304) through the center of the concentric electrodes via a hydrocarbon injector that can be optionally water cooled. The hydrocarbon injector tip can be placed to a point above the bottom plane of the electrodes, or it can be below the plane, or at the same height as the plane. Optionally, there are converging regions (305) leading to a narrowing of the reactor and then diverging regions (306) downstream of the converging region.



FIG. 4 shows another embodiment of an apparatus described herein. Hot gas is generated in the upper portion of the reactor either through the use of three or more AC electrodes, through the use of concentric DC electrodes as shown in FIGS. 2 and 3, or through the use of a resistive heater, more detail of which can be found in commonly assigned, U.S. Patent Application Ser. No. 62/209,017, High Temperature Heat Integration Method Of Making Carbon Black, the disclosure of which is herein incorporated by reference. The hot gas (401) is comprised of at least 50% hydrogen by volume that is at least 2400° C. The hydrocarbon injector (402) can be water cooled and enters from the side of the reactor and then turns into an axial position in regard to hot gas flow. The hydrocarbon injector tip (403) can be one opening or a plurality of openings that can inject hydrocarbons in clockwise or counter clockwise flow patterns to optimize mixing. Optionally, there are converging regions (404) leading to a narrowing of the reactor and then diverging regions (405) downstream of the converging region.



FIGS. 5 and 6 are Transmission Electron Micrograph (TEM) images of typical carbon nanoparticle produced by the above processes. The surface active sites (501 and 601) are unique to these high temperature techniques and are not found in furnace carbon black samples. Only some representative surface active sites are labelled.


In its early years, carbon black was made from oil and tar via the lamp or thermal process. In the mid-19th century, the channel process which utilized the impingement of natural gas on hot iron channels became the main method of manufacture of carbon black. In the early 1940s, the furnace process came to the forefront which utilizes a heavy oil such as pyrolysis fuel oil (PFO) to manufacture carbon black in an oxygen lean combustion environment at carbon yields of approximately 40-50%.


Plasma based synthesis of carbon black utilizing natural gas has both cost and pollution reducing advantages over the furnace process. The process is clean, emitting near zero local CO2, and zero SOx—compared to multiple tons of CO2 for the furnace process, with tens of kilograms of NOx and SOx for every ton of carbon black produced. Although the plasma technique has been attempted many times throughout the last century, there have been no long term viable commercial production enterprises based on this process.


A one step process as described herein contains the reactants and products up until a degas step has been completed to remove the hydrogen that has been produced from the cracking of, for example, methane. Hydrogen is a highly combustible gas and must be separated from the as-produced carbon nanoparticles in order to manipulate the carbon nanoparticles. A degas is considered to be complete if the hydrogen level has been reduced to less than 20 percent by volume.


An oxygen free atmosphere is deemed to possess less than 5% oxygen by volume for the examples stated herein. Preferably, the oxygen free atmosphere is less than 3% or less than 1% oxygen.


In the past, plasma generator designs have not been able to meet the power, corrosion resistance, and continuous operation requirements to produce carbon black because of such things as the insufficient unit power of their basic components and the tendency of these components to decay when exposed to hydrogen plasma, resulting in lost reactor time, increased capital costs, and uneconomically produced carbon black, among other things. For more details concerning methods of heating hydrocarbons rapidly to form carbon nanoparticles and hydrogen please see the following commonly assigned, copending U.S. patent applications, the disclosures of which are herein incorporated by reference: Ser. No. 62/111,317, Carbon Black Combustible Gas Separation; Ser. No. 14/591,541, Use Of Feedstock In Carbon Black Plasma Process; Ser. No. 14/601,761, Plasma Gas Throat Assembly And Method; Ser. No. 14/601,793, Plasma Reactor; Ser. No. 62/198,431, DC Plasma Torch Electrical Power Design Method And Apparatus; Ser. No. 14/591,528, Integration Of Plasma And Hydrogen Process With Combined Cycle Power Plant, Simple Cycle Power Plant, And Steam Reformer; Ser. No. 62/202,498, Method Of Making Carbon Black; Ser. No. 14/610,299, Plasma Torch Design; Ser. No. 14/591,476, System For High Temperature Chemical Processing; Ser. No. 62/198,486, Method Of Making Carbon Black Including Thermal Transfer Gas; Ser. No. 62/111,341, Regenerative Cooling Method And Apparatus.


In addition, there have never been satisfactory rubber performance results of carbon nanoparticles produced in a plasma. When compounded into rubber, plasma based carbon nanoparticles have been substandard in performance when compared to furnace based carbon black. This is part of the reason that plasma produced carbon nanoparticles have never been adopted and mass produced. The processes and systems described herein can successfully generate quality carbon nanoparticles that can reinforce elastomer compounds.


Elastomer as defined herein refers to a class of polymers that are related to natural rubber that have both viscous and elastic components or viscoelasticity. Some example elastomers are natural rubber (NR), styrene butadiene rubber (SBR), polybutadiene, polyisobutylene, polyisoprene, nitrile rubber, ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), silicone rubber, fluoroelastomers, amongst other classes that can be found in “The Science and Technology of Rubber” (Mark, Erman, and Roland, Fourth Edition, Academic Press, ©2013).


Reinforcement of elastomer is defined as an increase in tensile strength, tear resistance, abrasion resistance, and modulus to increase beyond the values expected from simple particle-matrix theory. In other words, the carbon nanoparticle, be it carbon black or some other carbon nanoparticle, enables the stiffening of the gummy elastomer so that it can be more useful in applications such as tires, door seals, rubber hoses, etc.


A carbon nanoparticle is any particle which is 90% or greater carbon, has a surface area greater than 5 m2/g (square meters per gram), and the volume equivalent sphere possesses a diameter of less than 1 micron (displacement of liquid is equivalent to a 1 micron sphere or less per particle). This can be comprised of many different shapes including disks, bowls, cones, aggregated disks, few layer graphene (FLG), ellipsoidal, aggregated ellipsoidal, spheres, and aggregated spheres (e.g. carbon black), as non-limiting examples. The carbon nanoparticles can also comprise a plurality of these particle shapes. When using the definition of carbon nanoparticles, it is assumed that at least 90% of the particles in any given sample on a number basis fall within the confines of this definition.


Dibutyl phthalate (DBP) absorption measures the relative structure of carbon black by determining the amount of DBP a given mass of carbon black can absorb before reaching a specified viscous paste. Thermal blacks have the lowest DBP numbers (32-47 ml/100 g) (milliliters per gram) of any carbon black, indicating very little particle aggregation or structure. DBP is typically measured by following ASTM D2414-12. The nitrogen surface area (N2SA) and statistical thickness surface area (STSA) are measured via ASTM D6556-10.


Crystallinity of the carbon nanoparticle can be measured via X-Ray Crystal Diffractometry (XRD). Specifically for the measurements described herein, Cu K alpha radiation is used at a voltage of 40 kV (kilovolts) and a current of 44 mA (milliamps). The scan rate is 1.3 degrees/minute from 2 theta equal 12 to 90 degrees. The 002 peak of graphite is analyzed using the Scherrer equation to obtain Lc (lattice constant) and d002 (the lattice spacing of the 002 peak of graphite) values reported herein. Briefly, larger Lc values correspond to greater degree of crystallinity. Smaller lattice spacing (d002) values correspond to higher crystallinity or a more graphite like lattice structure. Larger lattice spacing (d002) of 0.36 nm or larger is indicative of turbostratic carbon which is common for carbon black samples produced via the furnace process. Elemental analysis is measured via devices manufactured by Leco and the results are given as percentage of the total sample.


Styrene butadiene rubber specimens were prepared according to ASTM D3191. ASTM D412 and ASTM D2240 were utilized to measure tensile properties and Shore A Hardness. Tangent delta was measured using TA Instruments RSA G2 device at a temperature range of −100 C to 100 C at a heating rate of 4 C/minute a strain of 0.5% and a frequency of 10 Hz.









TABLE 1







Physical Characteristics of Samples.

















N2SA
STSA
DBP
Lc
d002






Name
(m2/g)
(m2/g)
(mL/100 g)
(nm)
(nm)
S
H
N
O



















N234
121
119
124
2.2
0.366
1.05
0.32
0.23
1.75


N234
125
130
118
2.9
0.358
0.70
0.03
0.08
0.2


@1200


N550
38.8
38.4
120
2.5
0.359
2.10
0.27
0.12
0.87


N762
26.2
25.6
65
2.6
0.358
1.57
0.26
0.08
0.52


M762
24.5
26.5
70
6.8
0.347
0.13
0.09
0.16
0.16


M550
45.6
48.8
135
6.9
0.346
0.15
0.09
0.2
0.11
















TABLE 2







Elastomer composite performance values.















Tensile
Elongation
Durometer




300%
Strength
at Break
Shore



Name
(psi)
(psi)
(%)
Hardness







N234
3265
3507
326
75



N234
1235
3036
589
68



@1200C



N762
1527
2870
496
63



M762
1547
2609
437
64



N550
2101
3161
450
58



M550
2136
3033
401
58

















TABLE 3







Tan delta values for elastomer composites.













Tan
Tan
Tan




Delta
Delta
Delta



Sample
60° C.
40° C.
0° C.







N762
0.1197
0.1329
0.1745



M762
0.1106
0.1226
0.1747



N550
0.1416
0.1553
0.2028



M550
0.1325
0.1456
0.1995










Samples of competitor grades of N234, N550, and N762 carbon blacks were obtained. These samples were made via the furnace process with a heavy oil. N234 was heat treated in an inert atmosphere at 1200° C. and is labelled in the tables as “N234 @ 1200 C”. M550 and M762 are designations given to Monolith carbon nanoparticles produced via mixing hot gas with natural gas as described herein.


Example 1
Manufacture of M762

Samples were manufactured using a setup similar to that shown in FIG. 3 where a hydrocarbon injector is inserted into the center of two concentric electrodes. The injector tip is 14 inches above the plane of the electrodes and the electrodes are operating at 650 kW. The plasma temperature was 2900° C. and the fully mixed reaction temperature was 2100° C. The hydrogen flow rate in the annulus between the electrodes was 90 Nm3/hr (normal cubic meters/hour) and the shield flow around the outside of the electrodes was 242 Nm3/hr. Natural gas was injected at a rate of 88 kg/hour. Yield of carbon nanoparticles based upon methane conversion rate was greater than 95%.


Example 2
Manufacture of M550

Samples were manufactured using a setup similar to that shown in FIG. 3 where a hydrocarbon injector is inserted into the center of two concentric electrodes. The injector tip is 14 inches above the plane of the electrodes and the electrodes are operating at 850 kW. The plasma temperature was 2900° C. and the fully mixed reaction temperature was 2100° C. The hydrogen flow rate in the annulus between the electrodes was 235 Nm3/hr (normal cubic meters/hour) and the shield flow around the outside of the electrodes was 192 Nm3/hr. Natural gas was injected at a rate of 103 kg/hour. Yield of carbon nanoparticles based upon methane conversion rate was greater than 94%.


Typical carbon black as currently made by the furnace process is made in a very similar fashion worldwide. Variation in hydrogen content, oxygen content, sulfur content and crystallinity is very minimal between different plants and different manufacturers. Grades are determined by the N2SA and by the DBP values. Only very minor differences can be determined due to differences in surface activity or crystallinity as all of the furnace blacks are very similar in these characteristics. Reference carbon black is a carbon black material as made in the furnace process that has values of N2SA and DBP within 20% of the carbon nanoparticles produced by the process described herein. In Table 1, the specific values of the reference furnace carbon black (labelled with “N” prefix) can be found and compared to the experimental grades that are labelled with an “M” prefix.


The importance of crystallinity and surface activity is paramount as can be seen in the examples from Tables 1 and 2. Through the heat treatment of N234 to only 1200° C., the reinforcement capability of the carbon black has been completely eliminated. The hydrogen content is lower and the crystallinity is higher. Both of these factors point to lower performance of the carbon black as a reinforcing agent according to various literature sources (for example, “The Science and Technology of Rubber” cited above and “Carbon Black Elastomer Interaction” Rubber Chemistry and Technology, 1991, pages 19-39—the disclosures of which both are herein incorporated by reference).


Specifically, the modulus at 300% has decreased from 3265 psi to 1235 psi (pounds per square inch). The elongation at break has increased from 326% to 589% indicating that the rubber composite test specimen with the heat treated N234 behaves almost as though there were no carbon black filler present. The specimen is not stiff and behaves as the raw rubber gum would behave in terms of ability to stretch and force required to pull the specimen to 3 times the original length. The increased crystallinity, decreased d002, decreased hydrogen content all point to a less active surface, even though the N2SA and DBP are almost unchanged. The composites also typically contain about 0.5% to about 4% by weight sulfur.


For Monolith samples, even though the crystallinity is more than double that of the furnace black counterpart, the hydrogen content is one-third that of the furnace black counterpart and there is more than 10 times less sulfur present, the samples reinforce rubber quite well.


This is a surprising result that runs counterintuitive to current thought in carbon black reinforcement science. One possibility to these strong results is the existence of “fullerene-like” moieties in the carbon black produced in the process described herein. Fullerene-like structures may be formed by the introduction of defects into a graphene sheet. The defects may form one or more pentagonal, heptagonal or other kind of rings, or a combination thereof, to create one or more fullerene-like structures. The defects may introduce curvature to the graphene sheet. These types of surface active species are observed in FIGS. 5 and 6. For more information about fullerene like moieties, please see “The Impact of a Fullerene-Like Concept in Carbon Black Science”, Carbon, 2002, pages 157-162the disclosure of which is incorporated by reference herein. In this paper it is proposed to radiate already manufactured carbon black with plasma gas, however, it was not conceived to be possible until now that fullerene-like moieties (referred to as “surface active sites” (501 and 601) in FIGS. 5 and 6) could be manufactured in one step from a hydrocarbon precursor.


Increasing tan delta at 0° C. correlates to improved wet traction, while lowering tan delta at 60° C. correlates to improved rolling resistance. Generally, conventional tread rubber compounds that optimize tan delta at one temperature negatively impact tan delta at the other temperature. It is therefore surprising that the M550 and M762 (given above in Table 3) show the same performance for tan delta at 0° C. and improved performance at 60° C. when compared to reference furnace carbon black. This should correspond to better rolling resistance in tire tread grades of carbon black while maintaining wet grip performance.


Thus, the scope of the invention shall include all modifications and variations that may fall within the scope of the attached claims. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.

Claims
  • 1. An elastomer composite containing carbon nanoparticles that are less than 1 micron volume equivalent sphere diameter and have a lattice constant (Lc) greater than 3.0 nanometers (nm) compounded therein.
  • 2. The elastomer composite of claim 1, wherein the volume equivalent sphere diameter is less than 700 nm.
  • 3. The elastomer composite of claim 1, wherein a lattice spacing of the 002 peak of graphite (d002) is less than 0.35 nm.
  • 4. The elastomer composite of claim 1, including a fullerene-like surface structure.
  • 5. The elastomer composite of claim 1, wherein the carbon nanoparticles have 0.2% hydrogen or less by weight as produced.
  • 6. The elastomer composite of claim 1, wherein the carbon nanoparticles have 0.4% oxygen or less by weight as produced.
  • 7. The elastomer composite of claim 1, wherein the carbon nanoparticles have 0.3% sulfur or less by weight as produced.
  • 8. The elastomer composite of claim 1, wherein strain required to stretch the elastomer composite 300% of the original length is at least 90% of a reference carbon black elastomer composite value.
  • 9. The elastomer composite of claim 1, wherein tan delta at 0° C. is at least 90% of a reference carbon black elastomer composite value.
  • 10. The elastomer composite of claim 1, wherein tan delta at 60° C. is less than 110% of a reference carbon black elastomer composite value.
  • 11. The elastomer composite of claim 1, wherein tan delta at 60° C. is less than 95% of a reference carbon black elastomer composite value.
  • 12. A method of making carbon nanoparticles in a one step process comprising adding a hydrocarbon to a heated gas to produce carbon nanoparticles that are less than 1 micron volume equivalent sphere diameter and have an Lc greater than 3.0 nm.
  • 13. The method of claim 12 wherein the hydrocarbon has been mixed with a hot gas to effect removal of hydrogen from the hydrocarbons.
  • 14. The method of claim 12 wherein the nanoparticles are produced in an oxygen free atmosphere.
  • 15. The method of claim 12 wherein the hydrocarbon is natural gas.
  • 16. The method of claim 12 wherein the yield of carbon nanoparticles is at least 90%.
  • 17. The method of claim 12 additionally including the use of one or more heat exchangers, filters, degas chambers, and/or backend equipment.
  • 18. The method of claim 17 wherein the backend equipment includes one or more of a pelletizer, a binder mixing tank connected to the pelletizer and/or a dryer connected to the pelletizer.
  • 19. The elastomer composite of claim 4, wherein the fullerene-like surface structure includes one or more defects that introduce curvature to a graphene sheet of the carbon nanoparticles.
  • 20. The elastomer composite of claim 1, further comprising sulfur.
CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional Application No. 62/218,137 filed Sep. 14, 2015, the disclosure of which is expressly incorporated by reference herein in its entirety.

US Referenced Citations (244)
Number Name Date Kind
1339225 Rose May 1920 A
1536612 Lewis May 1925 A
1597277 Jakowsky Aug 1926 A
2062358 Frolich Sep 1932 A
2002003 Eisenhut et al. May 1935 A
2039312 Goldman et al. May 1936 A
2393106 Johnson et al. Jan 1946 A
2557143 Royster Jun 1951 A
2572851 Gardner et al. Oct 1951 A
2603669 Chappell Jul 1952 A
2616842 Sheer et al. Nov 1952 A
2785964 Pollock Mar 1957 A
2850403 Day Sep 1958 A
2851403 Hale Sep 1958 A
2897071 Gilbert Jul 1959 A
2951143 Anderson et al. Aug 1960 A
3009783 Sheer et al. Nov 1961 A
3073769 Doukas Jan 1963 A
3288696 Orbach Nov 1966 A
3307923 Ruble Mar 1967 A
3309780 Goins Mar 1967 A
3331664 Jordan Jul 1967 A
3344051 Latham, Jr. Sep 1967 A
3308164 Johnson Oct 1968 A
3408164 Johnson Oct 1968 A
3409403 Bjornson et al. Nov 1968 A
3420632 Ryan Jan 1969 A
3431074 Jordan Mar 1969 A
3464793 Jordan et al. Sep 1969 A
3619140 Morgan et al. Nov 1971 A
3637974 Tajbl et al. Jan 1972 A
3673375 Camacho Jun 1972 A
3725103 Jordan et al. Apr 1973 A
3922335 Jordan et al. Nov 1975 A
3981654 Rood et al. Sep 1976 A
3981659 Myers Sep 1976 A
3984743 Horie Oct 1976 A
4028072 Braun et al. Jun 1977 A
4035336 Jordan et al. Jul 1977 A
4057396 Matovich Nov 1977 A
4075160 Mills et al. Feb 1978 A
4101639 Surovikin et al. Jul 1978 A
4199545 Matovich Apr 1980 A
4282199 Lamond et al. Aug 1981 A
4289949 Raaness et al. Sep 1981 A
4317001 Silver et al. Feb 1982 A
4372937 Johnson Feb 1983 A
4404178 Johnson et al. Sep 1983 A
4452771 Hunt Jun 1984 A
4431624 Casperson Aug 1984 A
4472172 Sheer et al. Sep 1984 A
4543470 Santen et al. Sep 1985 A
4553981 Fuderer Nov 1985 A
4601887 Dorn et al. Jul 1986 A
4678888 Camacho et al. Jul 1987 A
4689199 Eckert et al. Aug 1987 A
4755371 Dickerson Jul 1988 A
4765964 Gravley et al. Aug 1988 A
4787320 Raaness et al. Nov 1988 A
4864096 Wolf et al. Sep 1989 A
4977305 Severance, Jr. Dec 1990 A
5039312 Hollis, Jr. et al. Aug 1991 A
5045667 Iceland et al. Sep 1991 A
5046145 Drouet Sep 1991 A
5105123 Ballou Apr 1992 A
5147998 Tsantrizos et al. Sep 1992 A
5206880 Olsson Apr 1993 A
5352289 Weaver et al. Oct 1994 A
5399957 Vierboom et al. Mar 1995 A
5427762 Steinberg et al. Jun 1995 A
5476826 Greenwald et al. Dec 1995 A
5481080 Lynum et al. Jan 1996 A
5486674 Lynum et al. Jan 1996 A
5500501 Lynum et al. Mar 1996 A
5527518 Lynum Jun 1996 A
5593644 Norman et al. Jan 1997 A
5604424 Shuttleworth Feb 1997 A
5611947 Vavruska Mar 1997 A
5673285 Wittle et al. Sep 1997 A
5717293 Sellers Feb 1998 A
5725616 Lynum et al. Mar 1998 A
5749937 Detering et al. May 1998 A
5935293 Detering et al. Aug 1999 A
5951960 Lynum et al. Sep 1999 A
5989512 Lynum et al. Nov 1999 A
5997837 Lynum et al. Dec 1999 A
6068827 Lynum et al. May 2000 A
6099696 Schwob et al. Aug 2000 A
6188187 Harlan Feb 2001 B1
6197274 Mahmud et al. Mar 2001 B1
6277350 Gerspacher Aug 2001 B1
6358375 Schwob Mar 2002 B1
6380507 Childs Apr 2002 B1
6395197 Detering et al. May 2002 B1
6403697 Mitsunaga et al. Jun 2002 B1
6441084 Lee et al. Aug 2002 B1
6442950 Tung Sep 2002 B1
6444727 Yamada et al. Sep 2002 B1
6602920 Hall et al. Aug 2003 B2
6703580 Brunet et al. Mar 2004 B2
6773689 Lynum et al. Aug 2004 B1
6955707 Ezell et al. Oct 2005 B2
7167240 Stagg Jan 2007 B2
7294314 Graham Nov 2007 B2
7312415 Ohmi et al. Dec 2007 B2
7360309 Vaidyanathan et al. Apr 2008 B2
7431909 Rumpf et al. Oct 2008 B1
7452514 Fabry et al. Nov 2008 B2
7462343 Lynum et al. Dec 2008 B2
7563525 Ennis Jul 2009 B2
7655209 Rumpf et al. Feb 2010 B2
7777151 Kuo Aug 2010 B2
7968191 Hampden-Smith et al. Jun 2011 B2
8147765 Muradov et al. Apr 2012 B2
8221689 Boutot et al. Jul 2012 B2
8257452 Menzel Sep 2012 B2
8277739 Monsen et al. Oct 2012 B2
8323793 Hamby et al. Dec 2012 B2
8443741 Chapman et al. May 2013 B2
8471170 Li et al. Jun 2013 B2
8486364 Vanier et al. Jul 2013 B2
8501148 Belmont et al. Aug 2013 B2
8581147 Kooken et al. Nov 2013 B2
8710136 Yurovskaya et al. Apr 2014 B2
8771386 Licht et al. Jul 2014 B2
8784617 Novoselov et al. Jul 2014 B2
8850826 Ennis Oct 2014 B2
8871173 Nester et al. Oct 2014 B2
8911596 Vancina Dec 2014 B2
9095835 Skoptsov et al. Aug 2015 B2
9315735 Cole et al. Apr 2016 B2
9445488 Foret Sep 2016 B2
9574086 Johnson et al. Feb 2017 B2
10100200 Johnson et al. Oct 2018 B2
10138378 Hoermman et al. Nov 2018 B2
10370539 Johnson et al. Aug 2019 B2
20010029888 Sindarrajan et al. Oct 2001 A1
20010039797 Cheng Nov 2001 A1
20020000085 Hall et al. Jan 2002 A1
20020050323 Moisan et al. May 2002 A1
20020051903 Masuko et al. May 2002 A1
20020157559 Brunet et al. Oct 2002 A1
20030103858 Baran et al. Jun 2003 A1
20030152184 Shehane et al. Aug 2003 A1
20040047779 Denison Mar 2004 A1
20040071626 Smith et al. Apr 2004 A1
20040081862 Herman Apr 2004 A1
20040148860 Fletcher Aug 2004 A1
20040168904 Anazawa et al. Sep 2004 A1
20040211760 Delzenne et al. Oct 2004 A1
20040216559 Kim et al. Nov 2004 A1
20040247509 Newby Dec 2004 A1
20050063892 Tandon et al. Mar 2005 A1
20050079119 Kawakami et al. Apr 2005 A1
20050230240 Dubrovsky et al. Oct 2005 A1
20060034748 Lewis et al. Feb 2006 A1
20060037244 Clawson Feb 2006 A1
20060068987 Bollepalli et al. Mar 2006 A1
20060107789 Deegan et al. May 2006 A1
20060155157 Zarrinpashne et al. Jul 2006 A1
20060226538 Kawata Oct 2006 A1
20060239890 Chang et al. Oct 2006 A1
20070140004 Marotta et al. Jun 2007 A1
20070183959 Charlier et al. Aug 2007 A1
20070270511 Melnichuk et al. Nov 2007 A1
20070293405 Zhang et al. Dec 2007 A1
20080041829 Blutke et al. Feb 2008 A1
20080121624 Belashchenko et al. May 2008 A1
20080159947 Yurovskaya et al. Jul 2008 A1
20080169183 Hertel et al. Jul 2008 A1
20080182298 Day Jul 2008 A1
20080226538 Rumpf et al. Sep 2008 A1
20080279749 Probst et al. Nov 2008 A1
20080292533 Belmont et al. Nov 2008 A1
20090014423 Li et al. Jan 2009 A1
20090090282 Gold et al. Apr 2009 A1
20090142250 Fabry et al. Jun 2009 A1
20090155157 Stenger et al. Jun 2009 A1
20090173252 Nakata et al. Jul 2009 A1
20090208751 Green et al. Aug 2009 A1
20090230098 Salsich et al. Sep 2009 A1
20100147188 Mamak et al. Jun 2010 A1
20100249353 Macintosh et al. Sep 2010 A1
20110036014 Tsangaris et al. Feb 2011 A1
20110071692 D'Amato et al. Mar 2011 A1
20110071962 Lim Mar 2011 A1
20110076608 Bergemann et al. Mar 2011 A1
20110138766 Elkady et al. Jun 2011 A1
20110155703 Winn Jun 2011 A1
20110180513 Luhrs et al. Jul 2011 A1
20110239542 Liu et al. Oct 2011 A1
20120018402 Carducci et al. Jan 2012 A1
20120025693 Wang et al. Feb 2012 A1
20120201266 Boulos et al. Aug 2012 A1
20120232173 Juranitch et al. Sep 2012 A1
20120292794 Prabhu et al. Nov 2012 A1
20130039841 Nester et al. Feb 2013 A1
20130062195 Samaranayake et al. Mar 2013 A1
20130062196 Sin Mar 2013 A1
20130092525 Li et al. Apr 2013 A1
20130194840 Huselstein et al. Aug 2013 A1
20130292363 Hwang et al. Nov 2013 A1
20130323614 Chapman et al. Dec 2013 A1
20130340651 Wampler et al. Dec 2013 A1
20140000488 Sekiyama et al. Jan 2014 A1
20140057166 Yokoyama et al. Feb 2014 A1
20140131324 Shipulski et al. May 2014 A1
20140190179 Barker et al. Jul 2014 A1
20140224706 Do et al. Aug 2014 A1
20140227165 Hung et al. Aug 2014 A1
20140248442 Luizi et al. Sep 2014 A1
20140290532 Rodriguez et al. Oct 2014 A1
20140294716 Susekov et al. Oct 2014 A1
20140339478 Probst et al. Nov 2014 A1
20140357092 Singh Dec 2014 A1
20140373752 Hassinen et al. Dec 2014 A2
20150004516 Kim et al. Jan 2015 A1
20150044516 Kyrlidis et al. Feb 2015 A1
20150056516 Hellring et al. Feb 2015 A1
20150064099 Nester et al. Mar 2015 A1
20150180346 Yuzurihara et al. Jun 2015 A1
20150210856 Johnson et al. Jul 2015 A1
20150210857 Johnson et al. Jul 2015 A1
20150210858 Hoermann et al. Jul 2015 A1
20150211378 Johnson et al. Jul 2015 A1
20150217940 Si et al. Aug 2015 A1
20150218383 Johnson et al. Aug 2015 A1
20150223314 Hoermann et al. Aug 2015 A1
20150252168 Schuck et al. Sep 2015 A1
20160030856 Kaplan et al. Feb 2016 A1
20160210856 Assenbaum et al. Jul 2016 A1
20160243518 Spitzl Aug 2016 A1
20160293959 Blizanac et al. Oct 2016 A1
20170034898 Moss et al. Feb 2017 A1
20170037253 Hardman et al. Feb 2017 A1
20170058128 Johnson et al. Mar 2017 A1
20170066923 Hardman et al. Mar 2017 A1
20170073522 Hardman et al. Mar 2017 A1
20170349758 Johnson Dec 2017 A1
20180015438 Taylor et al. Jan 2018 A1
20180016441 Taylor et al. Jan 2018 A1
20180022925 Hardman et al. Jan 2018 A1
20190048200 Johnson et al. Feb 2019 A1
20190100658 Taylor et al. Apr 2019 A1
Foreign Referenced Citations (91)
Number Date Country
2897071 Nov 1972 AU
830378 Dec 1969 CA
964405 Mar 1975 CA
2 353 752 Jan 2003 CA
2 621 749 Aug 2009 CA
203269847 Nov 2013 CH
1458966 Nov 2003 CN
1644650 Jul 2005 CN
101092691 Dec 2007 CN
102007186 Apr 2011 CN
102060281 May 2011 CN
102108216 Jun 2011 CN
102993788 Mar 2013 CN
103160149 Jun 2013 CN
103391678 Nov 2013 CN
211457 Jul 1984 DE
198 07 224 Aug 1999 DE
200300389 Dec 2003 EA
0325689 Aug 1989 EP
0 616 600 Sep 1994 EP
0 635 044 Feb 1996 EP
0 635 043 Jun 1996 EP
0 861 300 Sep 1998 EP
1017622 Jul 2000 EP
1088854 Apr 2001 EP
1188801 Mar 2002 EP
2 891 434 Mar 2007 FR
395893 Jul 1933 GB
987498 Mar 1965 GB
1068519 May 1967 GB
1 400 266 Jul 1975 GB
1 492 346 Nov 1977 GB
2419883 May 2006 GB
H04228270 Aug 1992 JP
6-322615 Nov 1994 JP
H09316645 Dec 1997 JP
H11123562 May 1999 JP
2001253974 Sep 2001 JP
2004-300334 Oct 2004 JP
2005-243410 Sep 2005 JP
2005235709 Sep 2005 JP
10-2008-105344 Dec 2008 KR
2014-0075261 Jun 2014 KR
2425795 Aug 2011 RU
2488984 Jul 2013 RU
200418933 Oct 2004 TW
2017027385 Feb 1917 WO
9312031 Jun 1993 WO
9318094 Sep 1993 WO
9320153 Oct 1993 WO
WO-9320152 Oct 1993 WO
9323331 Nov 1993 WO
1994008747 Apr 1994 WO
9703133 Jan 1997 WO
WO-9813428 Apr 1998 WO
WO-0018682 Apr 2000 WO
WO-0224819 Mar 2002 WO
WO-03014018 Feb 2003 WO
WO-2004083119 Sep 2004 WO
2 937 029 Apr 2010 WO
2012015313 Feb 2012 WO
2012067546 May 2012 WO
2012094743 Jul 2012 WO
2012149170 Nov 2012 WO
2013134093 Sep 2013 WO
2013184074 Dec 2013 WO
2013185219 Dec 2013 WO
2014000108 Jan 2014 WO
2014012169 Jan 2014 WO
2015049008 Apr 2015 WO
WO-2015051893 Apr 2015 WO
WO-2015093947 Jun 2015 WO
2015116797 Aug 2015 WO
2015116798 Aug 2015 WO
2015116800 Aug 2015 WO
2015116807 Aug 2015 WO
2015116811 Aug 2015 WO
2015116943 Aug 2015 WO
2016012367 Jan 2016 WO
WO-2016014641 Jan 2016 WO
2016126598 Aug 2016 WO
2016126599 Aug 2016 WO
2016126600 Aug 2016 WO
2017019683 Feb 2017 WO
2017034980 Mar 2017 WO
2017044594 Mar 2017 WO
2017048621 Mar 2017 WO
2017190015 Nov 2017 WO
2017190045 Nov 2017 WO
WO-2018165483 Sep 2018 WO
WO-2018195460 Oct 2018 WO
Non-Patent Literature Citations (149)
Entry
Gago et al., Trends in Fullerene Research, Published by Nova Science Publishers, Inc. (2007), pp. 1-46.
Non-Final Office Action dated May 2, 2017 in U.S. Appl. No. 14/610,299.
Ex Parte Quayle Action dated May 19, 2017 in U.S. Appl. No. 14/601,761.
Extended European Search Report from EP Application No. 15742910.1 dated Jul. 18, 2017.
Supplementary Partial European Search Report from EP Application No. 15743214.7 dated Sep. 12, 2017.
ISR and Written Opinion from PCT/US2017/030139, dated Jul. 19, 2017.
ISR and Written Opinion from PCT/US2017/030179, dated Jul. 27, 2017.
Reese, J. (2017). Resurgence in American manufacturing will be led by the rubber and tire industry. Rubber World. 255. 18-21 and 23.
Non-Final Office Action dated Feb. 27, 2017 in U.S. Appl. No. 14/591,476.
Extended European Search Report from EP Application No. 15743214.7 dated Jan. 16, 2018.
Chiesa P, Lozza G, Mazzocchi L. Using Hydrogen as Gas Turbine Fuel. ASME. J. Eng. Gas Turbines Power. 2005;127(1):73-80. doi:10.1115/1.1787513.
Tsujikawa, Y., and T. Sawada. “Analysis of a gas turbine and steam turbine combined cycle with liquefied hydrogen as fuel.” International Journal of Hydrogen Energy 7.6 (1982): 499-505.
Search report from RU2016135213, dated Feb. 12, 2018.
Non-Final Office Action dated Jan. 16, 2018 in U.S. Appl. No. 14/591,528.
Bakken, Jon Arne, et al. “Thermal plasma process development in Norway.” Pure and applied Chemistry 70.6 (1998): 1223-1228.
Polman, E. A., J. C. De Laat, and M. Crowther. “Reduction of CO2 emissions by adding hydrogen to natural gas.” IEA Green House Gas R&D programme (2003).
Verfondern, K., “Nuclear Energy for Hydrogen Production”, Schriften des Forschungzentrum Julich, vol. 58, 2007.
U.S. Environmental Protection Agency, “Guide to Industrial Assessments for Pollution Prevention and Energy Efficiency,” EPA 625/R-99/003, 1999.
Breeze, P. “Raising steam plant efficiency—Pushing the steam cycle boundaries.” PEI Magazine 20.4 (2012).
Final Office Action dated Oct. 13, 2017 in U.S. Appl. No. 14/591,476.
Final Office Action dated Oct. 13, 2017 in U.S. Appl. No. 14/591,541.
Notice of Allowance dated Jan. 18, 2018 in U.S. Appl. No. 14/601,761.
Correced Notice of Allowance dated Feb. 9, 2018 in U.S. Appl. No. 14/601,761.
Final Office Action dated Sep. 19, 2017 in U.S. Appl. No. 15/221,088.
Non-Final Office Action dated Jan. 9, 2018 in U.S. Appl. No. 15/259.884.
Non-Final Office Action dated Apr. 20, 2018 in U.S. Appl. No. 15/221,088.
ISR and Written Opinion from PCT/US2015/013482, dated Jun. 17, 2015.
ISR and Written Opinion from PCT/US2015/013505, dated May 11, 2015.
ISR and Written Opinion from PCT/US2015/013487, dated Jun. 16, 2015.
Donnet, Basal and Wang, “Carbon Black”, New York: Marcel Dekker, 1993 pp. 46, 47 and 54.
Boehm, HP, “Some Aspects of Surface Chemistry of Carbon Blacks and Other Carbons”, Carbon 1994, p. 759.
“Carbon Black Elastomer Interaction” Rubber Chemistry and Technology, 1991, pp. 19-39.
“The Impact of a Fullerene-Like Concept in Carbon Black Science”, Carbon, 2002, pp. 157-162.
ISR and Written Opinion from PCT/US2015/013510, dated Apr. 22, 2015.
ISR and Written Opinion from PCT/US2016/015939, dated Jun. 3, 2016.
ISR and Written Opinion from PCT/US2016/015941, dated Feb. 22, 2016.
ISR and Written Opinion from PCT/US2016/015942, dated Apr. 11, 2016.
ISR and Written Opinion from PCT/US2016/044039, dated Oct. 6, 2016.
ISR and Written Opinion from PCT/US2016/045793, dated Oct. 18, 2016.
ISR and Written Opinion from PCT/US2016/050728, dated Nov. 18, 2016.
ISR and Written Opinion from PCT/US2016/051261, dated Nov. 18, 2016.
ISR and Written Opinion from PCT/US2015/013484, dated Apr. 22, 2015.
AP 42, Fifth Edition, vol. I, Chapter 6: Organic Chemical Process Industry, Section 6.1: Carbon Black.
Fulcheri, et al. “Plasma processing: a step towards the production of new grades of carbon black.” Carbon 40.2 (2002): 169-176.
Grivei, et al. A clean process for carbon nanoparticles and hydrogen production from plasma hydrocarbon cracking. Publishable Report, European Commission JOULE III Programme, Project No. JOE3-CT97-0057, circa 2000.
Fabry, et al. “Carbon black processing by thermal plasma. Analysis of the particle formation mechanism.” Chemical Engineering Science 56.6 (2001): 2123-2132.
Pristavita, et al. “Carbon nanoparticle production by inductively coupled thermal plasmas: controlling the thermal history of particle nucleation.” Plasma Chemistry and Plasma Processing 31.6 (2011): 851-866.
Cho, et al. “Conversion of natural gas to hydrogen and carbon black by plasma and application of plasma black.” Symposia—American Chemical Society, Div. Fuel Chem. vol. 49. 2004.
Pristavita, et al. “Carbon blacks produced by thermal plasma: the influence of the reactor geometry on the product morphology.” Plasma Chemistry and Plasma Processing 30.2 (2010): 267-279.
Pristavita, et al. “Volatile Compounds Present in Carbon Blacks Produced by Thermal Plasmas.” Plasma Chemistry and Plasma Processing 31.6 (2011): 839-850.
Garberg, et al. “A transmission electron microscope and electron diffraction study of carbon nanodisks.” Carbon 46.12 (2008): 1535-1543.
Knaapila, et al. “Directed assembly of carbon nanocones into wires with an epoxy coating in thin films by a combination of electric field alignment and subsequent pyrolysis.” Carbon 49.10 (2011): 3171-3178.
Krishnan, et al. “Graphitic cones and the nucleation of curved carbon surfaces.” Nature 388.6641 (1997): 451-454.
Høyer, et al. “Microelectromechanical strain and pressure sensors based on electric field aligned carbon cone and carbon black particles in a silicone elastomer matrix.” Journal of Applied Physics 112.9 (2012): 094324.
Naess, Stine Nalum, et al. “Carbon nanocones: wall structure and morphology.” Science and Technology of advanced materials (2016), 7 pages.
Fulcheri, et al. “From methane to hydrogen, carbon black and water.” International journal of hydrogen energy 20.3 (1995): 197-202.
ISR and Written Opinion from PCT/US2016/047769, dated Dec. 30, 2016.
D.L. Sun, F. Wang, R.Y. Hong, C.R. Xie, Preparation of carbon black via arc discharge plasma enhanced by thermal pyrolysis, Diamond & Related Materials (2015), doi: 10.1016/j.diamond.2015.11.004, 47 pages.
ISR and Written Opinion from PCT/US2015/013794, dated Jun. 19, 2015.
Biscoe, et al., An X-Ray study of carbon black. Journal of Applied physics, 1942; 13: 364-371.
Co-pending U.S. Appl. No. 16/180,635, filed Nov. 5, 2018.
EP16847102.7 Extended European Search Report dated Jul. 5, 2019.
U.S. Appl. No. 15/241,771 Office Action dated Mar. 13, 2019.
U.S. Appl. No. 15/259,884 Office Action dated May 31, 2019.
Co-pending U.S. Appl. No. 16/097,035, filed Oct. 26, 2018.
Co-pending U.S. Appl. No. 16/563,008, filed Sep. 6, 2019.
Co-pending U.S. Appl. No. 16/807,550, filed Mar. 3, 2020.
Donnet, et al., Observation of Plasma-Treated Carbon Black Surfaces by Scanning Tunnelling Microscopy. Carbon (1994) 32(2): 199-206.
EP16845031.0 Extended European Search Report dated Mar. 18, 2019.
EP17790549.4 Extended European Search Report dated Nov. 26, 2019.
EP17790570.0 Extended European Search Report dated Nov. 8, 2019.
Extended European Search Report for EP Application No. 16747055.8, dated Jun. 27, 2018.
Extended European Search Report for EP Application No. 16747056.6 dated Jun. 27, 2018.
Extended European Search Report for EP Application No. 16747057.4 dated Oct. 9, 2018.
Extended European Search Report for EP Application No. 16835697.0 dated Nov. 28, 2018.
Gago, et al., Growth mechanisms and structure of fullerene-like carbon-based thin films: superelastic materials for tribological applications. Trends in Fullerene Research, Published by Nova Science Publishers, Inc. (2007): 1-46.
Hernandez, et al. Comparison of carbon nanotubes and nanodisks as percolative fillers in electrically conductive composites. Scripta Materialia 58 (2008) 69-72.
International Preliminary Report on Patentability for Application No. PCT/US2015/013482 dated Aug. 2, 2016.
International Preliminary Report on Patentability for Application No. PCT/US2015/013484 dated Aug. 2, 2016.
International Preliminary Report on Patentability for Application No. PCT/US2015/013487 dated Aug. 2, 2016.
International Preliminary Report on Patentability for Application No. PCT/US2015/013505 dated Aug. 2, 2016.
International Preliminary Report on Patentability for Application No. PCT/US2015/013510 dated Aug. 2, 2016.
International Preliminary Report on Patentability for Application No. PCT/US2017/030139 dated Oct. 30, 2018.
International Preliminary Report on Patentability for Application No. PCT/US2017/030179 dated Oct. 30, 2018.
International Search Report and Written Opinion for Application No. PCT/US2018/021627 dated May 31, 2018.
International Search Report and Written Opinion for Application No. PCT/US2018/028619 dated Aug. 9, 2018.
International Search Report and Written Opinion for Application No. PCT/US2018/048374 dated Nov. 21, 2018.
International Search Report and Written Opinion for Application No. PCT/US2018/048378 dated Dec. 20, 2018.
International Search Report and Written Opinion for Application No. PCT/US2018/048381 dated Dec. 14, 2018.
International Search Report for Application No. PCT/US2015/13482 dated Jun. 17, 2015.
International Search Report for Application No. PCT/US2015/13487 dated Jun. 16, 2015.
Larouche, et al.,Nitrogen Functionalization of Carbon Black in a Thermo-Convective Plasma Reactor. Plasma Chem Plasma Process (2011) 31: 635-647.
Medalia, et al., Tinting Strength of Carbon Black. Journal of Colloid and Interface Science 40.2. (1972).
Partial International Search Report for Application No. PCT/US2018/028619 dated Jun. 18, 2018.
PCT/US2018/021627 International Search Report and Written Opinion dated May 31, 2018.
PCT/US2018/028619 International Search Report and Written Opinion dated Aug. 9, 2018.
PCT/US2018/048374 International Search Report and Written Opinion dated Nov. 21, 2018.
PCT/US2018/057401 International Search Report and Written Opinion dated Feb. 15, 2019.
PCT/US2018/064538 International Search Report and Written Opinion dated Feb. 19, 2019.
PCT/US2019/025632 International Search Report and Written Opinion dated Jun. 24, 2019.
Reynolds, Electrode Resistance: How Important is Surface Area. Oct. 10, 2016. p. 3 para[0001]; Figure 3; Retrieved from http://electrotishing.net/2016/10/10/electrode-resistance-how-important-is-surface-area/ on May 8, 2018.
Translation of Official Notification of RU Application No. 2016135213 dated Feb. 12, 2018.
U.S. Appl. No. 14/591,541 Notice of Allowance dated Sep. 17, 2018.
U.S. Appl. No. 14/591,528 Office Action dated Jan. 17, 2019.
U.S. Appl. No. 15/548,346 Office Action dated Oct. 22, 2019.
U.S. Appl. No. 15/548,348 Office Action dated Apr. 25, 2019.
U.S. Appl. No. 14/591,476 Notice of Allowance dated Mar. 20, 2019.
U.S. Appl. No. 14/591,476 Office Action dated Jul. 11, 2016.
U.S. Appl. No. 14/591,476 Office Action dated Jun. 7, 2018.
U.S. Appl. No. 14/591,476 Office Action dated Mar. 16, 2016.
U.S. Appl. No. 14/591,528 Office Action dated Oct. 28, 2019.
U.S. Appl. No. 14/591,541 Notice of Allowance dated Jun. 7, 2018.
U.S. Appl. No. 14/591,541 Office Action dated Feb. 22, 2017.
U.S. Appl. No. 14/591,541 Office Action dated Jul. 14, 2016.
U.S. Appl. No. 14/591,541 Office Action dated Mar. 16, 2016.
U.S. Appl. No. 14/601,761 Notice of Allowance dated Feb. 9, 2018.
U.S. Appl. No. 14/601,761 Notice of Allowance dated Jun. 19, 2018.
U.S. Appl. No. 14/601,761 Notice of Allowance dated Oct. 11, 2018.
U.S. Appl. No. 14/601,761 Notice of Allowance dated Sep. 17, 2018.
U.S. Appl. No. 14/601,761 Office Action dated Apr. 14, 2016.
U.S. Appl. No. 14/601,761 Office Action dated Oct. 19, 2016.
U.S. Appl. No. 14/601,793 Notice of Allowance dated Oct. 7, 2016.
U.S. Appl. No. 14/601,793 Office Action dated Apr. 13, 2016.
U.S. Appl. No. 14/601,793 Office Action dated dated Aug. 3, 2016.
U.S. Appl. No. 14/610,299 Notice of Allowance dated Feb. 20, 2020.
U.S. Appl. No. 14/610,299 Office Action dated Sep. 25, 2018.
U.S. Appl. No. 15/221,088 Office Action dated Dec. 23, 2016.
U.S. Appl. No. 15/221,088 Office Action dated Dec. 4, 2019.
U.S. Appl. No. 15/221,088 Office Action dated Mar. 7, 2019.
U.S. Appl. No. 15/229,608 Office Action dated Apr. 8, 2019.
U.S. Appl. No. 15/229,608 Office Action dated Oct. 25, 2019.
U.S. Appl. No. 15/241,771 Office Action dated Jul. 6, 2018.
U.S. Appl. No. 15/241,771 Office Action dated Sep. 25, 2019.
U.S. Appl. No. 15/259,884 Office Action dated Feb. 25, 2020.
U.S. Appl. No. 15/259,884 Office Action dated Jan. 9, 2018.
U.S. Appl. No. 15/259,884 Office Action dated Oct. 11, 2018.
U.S. Appl. No. 15/410,283 Office Action dated Jan. 16, 2020.
U.S. Appl. No. 15/410,283 Office Action dated Jun. 7, 2018.
U.S. Appl. No. 15/410,283 Office Action dated Mar. 12, 2019.
U.S. Appl. No. 15/548,348 Notice of Allowance dated Dec. 12, 2019.
U.S. Appl. No. 15/548,352 Office Action dated Jan. 31, 2020.
U.S. Appl. No. 15/548,352 Office Action dated May 9, 2019.
U.S. Appl. No. 15/548,352 Office Action dated Oct. 10, 2018.
U.S. Appl. No. 16/159,144 Office Action dated Mar. 26, 2020.
Wikipedia, Heating Element. Oct. 14, 2016. p. 1 para[0001]. Retrieved from https://en.wikipedia.org/w/index.php?title=Heating_element&oldid=744277540 on May 9, 2018.
Wikipedia, Joule Heating. Jan. 15, 2017. p. 1 para[0002]. Retrieved from https://en.wikipedia.org/w/index . Dhp?title=Joule_heating&oldid=760136650 on May 9, 2018.
U.S. Appl. No. 15/229,608 Office Action dated May 15, 2020.
U.S. Appl. No. 15/241,771 Office Action dated May 1, 2020.
U.S. Appl. No. 15/548,346 Office Action dated May 4, 2020.
Related Publications (1)
Number Date Country
20170073522 A1 Mar 2017 US
Provisional Applications (1)
Number Date Country
62218137 Sep 2015 US