Carbon particle composition and method for producing the same

Abstract

This disclosure provides compositions comprising carbon particles such as carbon black. The compositions may comprise rubber, for example, rubber usable in tires, and carbon black as a filler compound. The carbon black filler compound may comprise carbon black particles produced by thermal plasma methane pyrolysis and one or more binders configured to pelletize the carbon black particles.

Description

[Technical Field]

[0001] cross reference This application relates to U.S. Provisional Patent Application No. 63 / 471,461, filed on June 6, 2023, whose entire disclosure is expressly incorporated herein by reference, and claims the benefit of priority under 119(e) of the U.S. Patent Act. [Background technology]

[0002] There is a significant industrial need for more environmentally friendly fillers for the rubber compositions used in tires. In line with the global social movement for more sustainable products, major tire manufacturers have announced specific targets to reduce carbon emissions associated with tire products and increase the use of sustainable materials by a certain date. For example, some of the world's top tire manufacturers have set targets to produce tires from 100% sustainable materials and to achieve net-zero carbon emissions (carbon neutrality) by 2050. Particulate fillers used in tire rubber compositions account for approximately 25% of the tire's weight, and such fillers are primarily furnace carbon black of various grades. Carbon black produced using the furnace process (hereinafter referred to as "furnace carbon black" or "furnace black") generates substantially harmful emissions, including several tons of carbon dioxide (CO2) and tens of kilograms of nitrogen oxides (NOx) and sulfur oxides (SOx). An alternative process, namely the pyrolysis of end-of-life tires, results in a carbon filler material that is substantially inferior to virgin furnace carbon black when compounded into rubber compounds for vehicle tires. Bio-based materials containing the pyrolysis products have been investigated as fillers for potential use in tires, but these materials also impart inferior properties to furnace carbon black to rubber compounding and are not produced on a scale large enough to supply the tire industry.

[0003] Furthermore, to improve productivity and reduce energy consumption in manufacturing, it is necessary to increase the thermal conductivity of the rubber composition used in tires to facilitate faster curing (vulcanization) of tire components. Higher thermal conductivity of tire compounds is particularly desirable in the manufacture of heavy-duty tires for heavy trucks, construction and mining equipment, tractors, and other heavy-duty vehicles. Increased thermal conductivity also helps to improve tire durability by improving heat transfer and counteracting viscoelastic heat generation during tire use. Tire rubber compounds are hysteresis viscoelastic materials that dissipate mechanical deformation that generates heat (viscoelastic heat generation). Heat that is not transferred from the material by heat transfer causes a rise in temperature; therefore, this creates a strong driving force in the tire industry to improve heat transfer of tire compositions by increasing thermal conductivity. With a certain degree of hysteresis (dissipation) and a certain degree of associated heat generation, high thermal conductivity reduces the temperature of dynamically deforming tire components. The rate of fatigue cracking, wear, and degradation of tire compositions decreases as the temperature decreases. Improved tire durability from lower operating temperatures results in safer tires and a longer tire life, the latter having a positive environmental effect.

[0004] Currently, there are no low-emission solutions that substantially increase the thermal conductivity of tire compositions without adversely affecting other tire performance characteristics. While several specialty fillers with high thermal conductivity exist, such as boron nitride, these are non-reinforcing fillers and contain micrometer-sized particles that negatively impact mechanical stiffness (reinforcement), durability, and other properties when used to replace conventional fillers such as furnace carbon black and precipitated silica.

[0005] Embodiments described herein satisfy the above-mentioned problems. Accordingly, this disclosure provides a solution to mitigate climate change through the capture, storage, and / or sequestration of greenhouse gases (e.g., CO2 and methane) by producing carbon black fillers using a non-combustion (low-emission) thermal plasma process, and / or converting methane into carbon black fillers for use in tire rubber compositions and rubber articles, thereby reducing greenhouse gas emissions, reducing and / or preventing additional greenhouse gas emissions, and / or mitigating climate change in the manufacture of goods. [Overview of the Initiative]

[0006] This disclosure provides compositions comprising carbon particles, such as carbon black particles, and methods for producing them. The carbon particles may be produced via a thermal plasma process (e.g., thermal decomposition of methane). The carbon particles may be pelletized by contacting them with a binder. The pelletized carbon particles may be compounded with rubber, such as rubber compounding for use in tires.

[0007] In one embodiment, the disclosure provides a rubber article in which at least 2% by weight of a plasma carbon black filler is compounded therein. The rubber article may be a tire component such as an inner liner, sidewall, subtread, bead skim, wire skim, tread, or body price skim.

[0008] In some embodiments, the rubber article may also contain at least 10% by weight of natural rubber, butadiene rubber, halobutyl, butyl rubber, isoprene rubber, chloroprene rubber, EPDM, and / or synthetic elastomers.

[0009] In some embodiments, the rubber article may also contain precipitated silica, recovered carbon, furnace carbon black, graphene, lignin, carbon nanotubes, and / or clay. In some embodiments, the ratio of plasma carbon black filler to precipitated silica, recovered carbon, furnace carbon black, graphene, lignin, carbon nanotubes, or clay may be in the range of 1:10 to 10:1. In some embodiments, precipitated silica, recovered carbon, or furnace carbon black may be present in the range of 15 phr to 60 phr.

[0010] In some embodiments, a rubber article containing a furnace carbon black filler may have improved (increased) thermal conductivity compared to another rubber article of the same type that does not contain a plasma carbon black filler. In various embodiments, the improved thermal conductivity may be at least 0.33 W / mK or at least 5% or at least 20% greater than the thermal conductivity of other (non-plasma carbon black) rubber articles.

[0011] In some embodiments, the rubber article may contain at least 0.2% by weight of MBT (mercaptobenzothiazole) or MBTS (2,2'-dibenzothiadyl disulfide). In some embodiments, the rubber article may contain sulfur in the range of about 0.05 to 5% by weight.

[0012] In some embodiments, the rubber article may have improved diffusion compared to a second rubber article of the same type that includes a furnace carbon black filler and does not include a plasma carbon black filler.

[0013] In some embodiments, the rubber article contains furnace carbon black in a weight percentage of no more than 20% of the plasma carbon black filler in the rubber article, and may have a reduced viscoelastic loss tangent (tanδ) compared to a second rubber article of the same type that does not contain the plasma carbon black filler. In some embodiments, the reduced viscoelastic loss tangent (tanδ) may be at least 2% lower than the viscoelastic loss tangent of the second rubber article.

[0014] In another embodiment, the disclosure provides carbon particles produced via a thermal plasma process, which may have a spherical equivalent diameter of less than 1 micrometer, a lattice constant (Lc) greater than 3 nanometers (nm), and a deviation of less than 20% between the measured aggregate diameter and the calculated aggregate diameter, as measured by centrifugal particle sedimentation (CPS), where the measured aggregate diameter is the Z-mean value measured by dynamic light scattering (DLS), and the calculated aggregate diameter (Da) is determined by the equation [Da=(2540+(71*OAN)) / STSA].

[0015] In some embodiments, the carbon particles may contain silane added to the carbon particles after they have been pelletized and dried. In some embodiments, the silicon content of the carbon particles may be greater than 0.05%, but may be less than 1%.

[0016] In another embodiment, the Disclosure provides a rubber article comprising an elastomer composition, wherein the elastomer composition comprises a plasma carbon black filler having (i) a comparative statistical thickness surface area (STSA) and comparative oil absorption (OAN) of a comparative furnace carbon black filler that are within 15% of the STSA and OAN of a comparative furnace carbon black filler, and (ii) a thermal conductivity at least 10% higher than the comparative thermal conductivity of a comparative elastomer composition comprising a comparative furnace carbon black filler.

[0017] In another aspect, the present disclosure provides a rubber article comprising an elastomer composition, wherein the elastomer composition has a 100% tensile stress at elongation (M100), a calculated average aggregate diameter (Da), or a Shore A hardness within 15% of the comparative M100, Da, or Shore A hardness of a comparative elastomer composition comprising a furnace carbon black filler, and (ii) a thermal conductivity that is at least 10% higher than the comparative thermal conductivity of the comparative elastomer composition, and comprises a plasma carbon black filler.

[0018] In another aspect, the present disclosure provides a tire comprising two sidewalls, two bead skims, and a tread, wherein each sidewall is configured such that one of the two bead skims is connected to the tread, and at least one of the two sidewalls, the two bead regions, and the tread comprises thermal plasma carbon black.

[0019] Further aspects and advantages of the present disclosure will become readily apparent to those skilled in the art from the following detailed description, which merely illustrates exemplary embodiments of the present disclosure. As will be understood, the present disclosure is capable of other different embodiments and some of its details are capable of modification in various obvious respects without departing from the present disclosure. Accordingly, the drawings and description are to be regarded as illustrative in nature and not restrictive.

[0020] Incorporation by Reference All publications, patents, and patent applications mentioned herein are incorporated herein by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference. If the publications and patents or patent applications incorporated by reference conflict with the disclosure contained herein, the present specification will supersede and / or prevail over such conflicting material.

[0021] Novel features of the present invention are specifically described in the appended claims. A better understanding of the features and advantages of this disclosure will be obtained by referring to the following detailed description of exemplary embodiments in which the principles of this disclosure are utilized, and to the appended drawings (hereinafter also referred to as "Figure" and "FIG."). [Brief explanation of the drawing]

[0022] [Figure 1] A schematic diagram shows a method for producing a carbon particle composition according to one or more embodiments of the present disclosure. [Figure 2] A schematic diagram of an exemplary apparatus that can be used to provide carbon particles according to one or more embodiments of this disclosure is shown. [Figure 3] A schematic diagram of an exemplary apparatus that can be used to provide carbon particles according to one or more embodiments of this disclosure is shown. [Figure 4] A schematic diagram of an exemplary apparatus that can be used to provide carbon particles according to one or more embodiments of this disclosure is shown. [Figure 5] A schematic diagram of an exemplary system that can be used to provide carbon particles according to one or more embodiments of this disclosure is shown. [Figure 6] A schematic diagram of an exemplary system that can be used to provide plasma carbon black according to one or more embodiments of this disclosure is shown. [Figure 7] A schematic diagram of an exemplary process that can be used to provide plasma carbon black according to one or more embodiments of this disclosure is shown. [Figure 8] The following are schematic diagrams illustrating exemplary cross-sections of vehicle tires according to one or more embodiments of the present disclosure. [Figure 9] The graphs illustrate the thermal conductivity correlated with the oil absorption amount (OAN) of sidewall formulations, with various examples of furnace carbon black and plasma carbon black according to one or more embodiments of the present disclosure compounded therein. [Figure 10]The graphs show exemplary thermal conductivity correlated with the nitrogen surface area (N2SA) of sidewall formulations, with various examples of furnace carbon black and plasma carbon black according to one or more embodiments of the present disclosure compounded therein. [Figure 11] The graphs show exemplary thermal conductivity correlated with the OAN and Compression Oil Absorption (COAN) of inner liner formulations, with various examples of furnace carbon black and plasma carbon black according to one or more embodiments of the present disclosure compounded therein. [Figure 12] The graphs show exemplary values ​​of thermal conductivity correlated with Shore A hardness for body-price-skim formulations having varying carbon black filler amounts (43, 50, and 57 phr), in which furnace carbon black and various examples of plasma carbon black according to one or more embodiments of the present disclosure are compounded. [Figure 13] The graphs illustrate the thermal conductivity (k) correlated with the 100% modulus (M100) of body-price skim formulations having various carbon black filler amounts (43, 50, and 57 phr), in which furnace carbon black and various examples of plasma carbon black according to one or more embodiments of the present disclosure are compounded. [Figure 14] The graphs illustrate the thermal conductivity (k) correlated with the 300% modulus (M300) of body-price skim formulations having various carbon black filler amounts (43, 50, and 57 phr), in which furnace carbon black and various examples of plasma carbon black according to one or more embodiments of the present disclosure are compounded. [Figure 15] Exemplary stress-versus-strain graphs of body-price skim formulations in which furnace carbon black and various examples of plasma carbon black (baseline and modifications 1-4) according to one or more embodiments of the present disclosure are compounded therein are shown. [Figure 16]The graphs show exemplary thermal conductivity correlated with the OAN and COAN of tread formulations, with various examples of furnace carbon black and plasma carbon black according to one or more embodiments of the present disclosure compounded therein. [Figure 17] The graphs illustrate the thermal conductivity correlated with the Z-mean aggregate diameter of tread formulations, with various examples of furnace carbon black and plasma carbon black according to one or more embodiments of the present disclosure compounded therein. [Modes for carrying out the invention]

[0023] While various embodiments of this disclosure are shown and described herein, those skilled in the art will understand that such embodiments are provided only as examples. Those skilled in the art will be able to conceive of countless variations, modifications, and alternatives without departing from this disclosure. It should be understood that various alternatives may be adopted to the embodiments described herein.

[0024] If the terms “at least,” “greater than,” or “greater than or equal to” precede the first number in a series of two or more numbers, then the terms “at least,” “greater than,” or “greater than or equal to” apply to each number in that series. For example, 1, 2, or 3 or more is equivalent to 1 or more, 2 or more, or 3 or more.

[0025] If the terms "not greater than," "less than," or "less than or equal to" precede the first number in a series of two or more numbers, then those terms apply to each number in that series. For example, 3, 2, or 1 or less is equivalent to 3 or less, 2 or less, or 1 or less.

[0026] In certain embodiments of this specification, numerical ranges are contemplated. Where a range exists, the range includes its endpoints. Additionally, all partial ranges and values ​​within a range exist as if explicitly written. The terms “about” or “approximately” may mean within an acceptable margin of error for a particular value, which may vary in part depending on how the value is measured or determined, such as the limitations of the measurement system. For example, “about” may mean within or above one standard deviation, according to convention in the art. Alternatively, “about” may mean a range of up to 20%, up to 10%, up to 5%, or up to 1% of a particular value. Where specific values ​​are given herein, unless otherwise specified, the term “about” may be assumed to mean within an acceptable margin of error for the specific value.

[0027] Carbon black production utilizing thermal plasma processes (e.g., methane pyrolysis) to decompose hydrocarbon raw materials may offer advantages over furnace processes in terms of reduced cost and pollution. Plasma-based carbon black production processes can be low-emission, releasing nearly zero localized carbon dioxide (CO2) and nearly zero amounts of sulfur dioxide (SOx) and nitrogen oxides (NOx) per ton of carbon black produced, compared to several tons of CO2 and tens of kilograms of NOx and SOx in furnace processes. Plasma pyrolysis of methane may be described in U.S. Patent No. 10,808,097, incorporated herein by reference.

[0028] Hydrocarbon raw materials are, n H x or C n H x O yHydrocarbon feedstocks may include any chemical substance within the formula, where n is an integer, x is (i) between 1 and 2n+2, or (ii) less than 1 for fuels such as coal, coal tar, and pyrolytic fuel oil, and y is between 0 and n. Hydrocarbon feedstocks may include, for example, simple hydrocarbons (e.g., methane, ethane, propane, butane), aromatic feedstocks (e.g., benzene, toluene, xylene, methylnaphthalene, pyrolytic fuel oil, coal tar, coal, heavy oil, petroleum, bio-oil, biodiesel, and other bio-derived hydrocarbons), unsaturated hydrocarbons (e.g., ethylene, acetylene, butadiene, styrene), oxygenated hydrocarbons (e.g., ethanol, methanol, propanol, phenol, ketones, ethers, esters), or any combination thereof. Hydrocarbon feedstocks may include or may be natural gas. Sustainable hydrocarbon feedstocks may also be derived from biomaterials or fossil fuels (e.g., at least 1.35*10 -14 Compared to the C14:C12 ratio, raw materials containing at least 10% biological material with a significant amount of carbon-14 (C14) can be used. Examples of sustainable raw materials include renewable natural gas produced from landfills, untreated sewage, fertilizers, livestock, or other sources, as well as raw materials produced from the pyrolysis of end-of-life tires in the form of gaseous hydrocarbon mixtures, liquid hydrocarbon mixtures, and / or carbonaceous solids. Other sustainable hydrocarbon raw materials that do not contain C14 include processed end-of-life plastics that can be used to produce aliphatic and aromatic hydrocarbons suitable for use in gaseous or liquid forms. These non-limiting examples of acceptable raw materials do not need to have only hydrocarbon components (i.e., do not need to be 100% or more hydrocarbons) and may be further combined and / or mixed with other components, for example, to ensure that an amount of sustainable hydrocarbon raw material is used in a thermal plasma process.

[0029] Figure 1 shows an exemplary method for producing a carbon particle composition 100 according to one or more embodiments of the present disclosure. Method 100 may include generating plasma in a reactor using one or more electrodes (operation 110), and injecting hydrocarbons into the reactor, or gases into hydrocarbons in the reactor, through one or more injectors, thereby producing carbon particles (operation 120). The term “carbon particles” may refer to particles containing carbon. Method 100 may include processing the carbon particles to produce plasma carbon black (operation 130). “Plasma carbon black” (also referred to herein as “plasma black,” “thermal plasma black,” or “thermal plasma carbon black”) refers to the carbon black produced from operations 100–130, which may collectively be referred to as “thermal plasma processes.”

[0030] Operations 110, 120, and 130 of Figure 1 are further described with reference to schematic diagrams of exemplary apparatus and / or systems that can be used to provide carbon black particles, as shown in Figures 2, 3, 4, and 7. Figure 2 shows a schematic diagram of an exemplary apparatus 200. A heat transfer gas (e.g., plasma gas) 201, which may contain one or more of, for example, nitrogen, argon, helium, hydrogen, carbon monoxide, hydrocarbons (e.g., methane, ethane, unsaturated), air, oxygen, etc., can be injected into an annular portion created by electrodes located in a concentric manner in the upper chamber. The plasma-forming electrodes may comprise an internal electrode 202 and an external electrode 203. The heat transfer gas may also be injected inside the internal electrode 202 and outside the external electrode 203. A sufficiently large voltage can be applied between the two electrodes. The electrodes may contain or be made from copper, tungsten, graphite, molybdenum, silver, etc. The plasma thus formed may enter a reaction zone in which it can react / interact with hydrocarbon feedstock supplied by hydrocarbon injectors 205 to produce carbon particles. The walls of the vessel (including, or composed of, refractory material, graphite, cooling, etc.) can withstand the plasma formation temperature. The hydrocarbon injectors 205 may be located in or near the throat 206 below the converging region 207 of the reactor, or somewhere on the plane further downstream of the throat 206 in the diverging region 208. The hydrocarbon injector tips may be arranged concentrically around the injection plane, for example. In non-limiting examples, there may be at least six injectors and at least 18 tips, or slots, or continuous slots of this kind.

[0031] Figure 3 shows a schematic diagram of another example of the apparatus 300, comprising an internal electrode 301 and an external electrode 302, respectively, including a concentric ring of a conductive material (e.g., graphite). A heat transfer gas (e.g., plasma gas) 307 may flow through the annular portion between the two electrodes, where an arc may excite the gas into a plasma state. The arc may be controlled through the use of a magnetic field, thereby allowing the arc to move rapidly in a circular manner around the electrode tips. In this example, hydrocarbons may be injected into the hydrocarbon injector 303 through the center of the concentric electrodes (e.g., at the hydrocarbon injector tip 304). In some examples, the hydrocarbon injector 303 may be water-cooled, for example. The hydrocarbon injector tip may be located at a point on the bottom surface of the electrodes, or below a plane, or on the same plane (e.g., at the same height as the plane). In some implementations, the apparatus may include a converging region(s) 305 leading to a narrowing of the reactor, and then a diverging region(s) 306 downstream of the converging region(s).

[0032] Figure 4 shows a schematic diagram of another example of apparatus 400. In this example, the heat transfer gas 401 may be generated at the top of the reactor by using three or more AC electrodes, by using concentric DC electrodes (e.g., as shown in Figures 2 and 3), or by using a resistor or induction heater. The heat transfer gas may contain at least about 50 volume% hydrogen, which may be at least about 1,800°C. The hydrocarbon injector 402 may be cooled (e.g., water cooled). The hydrocarbon injector 402 may enter from the side of the reactor (e.g., in a preferred position as shown or otherwise described herein) and then be reoriented to an axial position relative to the heat transfer gas (hot gas) flow. The hydrocarbon injector tip 403 may contain or contain one or more openings (e.g., hydrocarbons may be injected in a clockwise or counterclockwise flow pattern (e.g., to optimize mixing)). The reactor may include a convergence region 404. Converging regions(s) 404 may lead to reactor constriction and / or diverging regions(s) 405 downstream of the convergent region(s). See, for example, commonly assigned International Patent Publication No. 2017 / 044594 ("CIRCULAR FEW LAYER GRAPHENE") and WO2017 / 048621 ("CARBON BLACK FROM NATURAL GAS"), which are incorporated herein by reference, respectively.

[0033] The exemplary reactor apparatus shown in Figures 2, 3, and 4 has a vertical orientation with a downward flow, but an upward flow or horizontal reactor orientation may be used.

[0034] Silicon additives can be supplied to the high-temperature zone of a thermal plasma reactor during particle formation. For example, silicon additives may be present in the hydrocarbon, hydrogen, and silicon additive effluent stream at less than 1% (e.g., less than 0.5%) in terms of moles of silicon per mole of carbon atoms. Silicon atoms can be supplied through solid addition, gaseous injection, or liquid injection. The use of silicon provides a lower reaction temperature, which can result in higher energy efficiency and lower power consumption. Silicon can be present in the final pelletized carbon black product as elemental silicon, silicon carbide, or silicon oxide, or a mixture thereof (e.g., silicon oxycarbide). The addition of silicon species can result in an increase in ash content in carbon particles of 0.01% to 0.05% to over 0.2% but less than 1.5%.

[0035] Figure 5 schematically shows an exemplary system 500 that can be used to provide carbon particles according to one or more embodiments of the present disclosure. The apparatus may be configured to enable, for example, heat generation (e.g., heating) 505, injection 510, and reaction 515. For example, the apparatus may comprise one or more constant diameter regions / sections, one or more converging regions / sections, one or more diverging regions / sections, one or more inserts or other additional components, or any combination thereof. Such regions / sections, and / or inserts or other additional components, may be combined in various ways to perform heat generation (e.g., heating) 505, injection 510, and reaction 515. Such implementations may include, but are not limited to, configurations described in relation to the schematic diagrams of Figures 2, 3, and 4. For example, the region / section in which heat generation 505 is performed may or may not be separated by a throat from the reaction region / section in which reaction 515 is performed, and the injection 510 may or may not be downstream of heat generation 505.

[0036] Returning to Figure 1, the method or system of the present disclosure may include processing carbon particles to produce plasma carbon black (operation 130), the processing of which may include or use one or more of the following: a heat exchanger (e.g., connected to a reactor), a main filter (e.g., connected to a heat exchanger), a degassing (e.g., product insertion) device (e.g., a chamber) (e.g., connected to a filter), and a backend. Operation 130 in Figure 1 is further described with reference to Figures 6 and 7, which show schematic diagrams of exemplary systems and processes that can be used to provide plasma carbon black according to embodiments of the present disclosure.

[0037] Figure 6 shows an example of a system 600 configured to perform the processes of the present disclosure. The system may comprise a thermally activated chamber (e.g., a plasma chamber) 605, a throat and / or other regions 610, and a reactor 615 (generally related to operations 110 and 120 in Figure 1), as well as a heat exchanger 620, a filter 625, a degasser (e.g., a degasser chamber) 630, a backend 635, or a combination thereof (generally related to operation 130 in Figure 1).

[0038] Figure 7 shows an example flowchart of process 700. The process may be initiated by a method of heat generation in the heat generator 701. The process may include one or more steps of heating a gas (e.g., a heat transfer gas), adding hydrocarbons to the hot gas, and passing the flow through the reactor 702 (e.g., as described in relation to Figures 2 to 5) to produce carbon particles. The process may also include using one or more of the following: a heat exchanger 703, a filter 704, a degasser (e.g., a degasser chamber) 705, and a backend 706. The hot gas may be a flow of hot gas at an average temperature of at least about 1,800°C. In some implementations, the processes described herein may not contain substantially any oxygen from the atmosphere. The process may include heating a gas (e.g., containing 50% or more by volume of hydrogen) and then adding this hot gas to hydrocarbons in 701. Heat (e.g., also) may be supplied through latent heat radiation from the reactor walls. This can occur through heating the walls via energy supplied from an external source, or through heating the walls from a hot gas. Heat can be transferred from the hot gas to the hydrocarbon feedstock, and this heat transfer can occur immediately after the hydrocarbon feedstock is added to the hot gas in the reactor or reaction zone 702. The hydrocarbons may begin to crack and decompose before being completely converted into carbon particles. The reaction products can be cooled after production.

[0039] The systems of this disclosure may be configured to perform a closed process, for example, using a closed particle-generating reactor. The system (process) may include one or more of the following: a heat generator (e.g., a plasma generator) over the throat and / or other areas (e.g., as described in relation to Figures 2 to 5), a thermal activation chamber (e.g., a plasma chamber), a reactor or reaction chamber, a main filter (e.g., as described in relation to Figures 6 to 7), and / or a degassing chamber. These components may not substantially contain oxygen and other atmospheric gases. The process (or a part thereof) may allow only a given atmosphere. For example, oxygen may be excluded or added in a controlled amount, for example, less than about 5 volume percent, in a closed process.

[0040] Referring to the exemplary thermal plasma system and process schematic diagrams in Figures 6 and 7, carbon particles (e.g., plasma carbon black particles) may be generated in the admixture of the high-temperature gas effluent flow containing flammable gas that comes into contact with a heat exchanger (e.g., 620 or 703) and exits the reactor (e.g., 615 or 702). The high-temperature gas effluent flow containing flammable gas (e.g., then) may pass through a filter (e.g., 625 or 704), on which substantially all of the carbon particles (e.g., carbon black particles) may be captured. The gas (e.g., then) may pass through a degasser (e.g., 630 or 705), in which the amount of flammable gas is reduced to less than about 10 volume percent. The flammable gas may or may contain hydrogen. Carbon particles (e.g., plasma carbon black particles) then enter the backend (e.g., 635 or 706), are mixed with water containing a binder, and are subsequently formed into pellets, after which most of the water may be removed in a dryer.

[0041] The reaction products may be cooled using a quench (not shown). For example, a quench containing a large amount of hydrogen gas may be used. The quench may be injected into the reactor portion of the process.

[0042] A heat exchanger (e.g., 620 or 703) may be used to cool the process gas. In the heat exchanger, the process gas can be exposed to a large surface area and therefore cooled, while the product flow can be transported simultaneously. Due to the high temperature of the plasma process of this disclosure, the heat exchange may be more efficient than, for example, a furnace process. The heat exchanger may be configured as described, for example, in International Patent Publication No. 2016 / 126599 ("CARBON BLACK GENERATING SYSTEM") and No. 2017 / 034980 ("HIGH TEMPERATURE HEAT INTEGRATION METHOD OF MAKING CARBON BLACK"), which are incorporated herein by reference. In a given configuration, the energy removed may depend, for example, on the operating conditions and / or the grade of plasma carbon black. Carbon particles may be generated in the effluent flow with and / or in the effluent mixture of the high-temperature gas flow that exits the reactor and comes into contact with the heat exchanger. The heat exchanger can reduce the thermal energy of the gas and carbon particle effluent flows by using carbon particles with a thermal energy of over approximately 5000 kilojoules / kilogram (kJ / kg).

[0043] The gas and carbon particulate flow can then pass through a filter (e.g., 625 or 704), which may allow more than 50% of the gas to pass through and capture substantially all of the carbon parts on the filter. At least about 98% by weight of carbon parts may be captured on the filter.

[0044] The carbon particles can be degassed (e.g., 630 or 705). Hydrogen and / or other flammable gases can be separated from the pores and / or interstitial spaces of the carbon particle production stream (e.g., in a plasma torch reactor system or other systems for producing carbon particles that produce gases, which are formed in order to form carbon particles containing more than about 40% flammable gas). The one-step process may contain reactants and products until a degassing step is completed to remove flammable gases (plural) (e.g., hydrogen) produced from the decomposition of hydrocarbon feedstocks (e.g., methane). To manipulate the carbon particles, hydrogen, a highly flammable gas, can be separated from the as-produced carbon particles. Such flammable gases can be removed, for example, by varying the pressure (pressure swing method) or temperature (temperature swing method), or by discharging the generated carbon particles into an upward-flowing inert gas stream (backflow method) (for example, by replacing the flammable gas with an inert gas, thereby safely obtaining carbon particles for processing in downstream equipment), (for example, to a safe level where explosions cannot occur, or to create an inert environment). The inert gas may be, for example, nitrogen, noble gases (helium, neon, argon, krypton, xenon, etc.), vapor, or carbon dioxide, or any combination thereof. Flammable gases (e.g., hydrogen) can also be removed from the carbon particles by diffusion (e.g., placement in a filter over time), by flowing the gas through a large amount of carbon particles or through fluidized carbon particles (e.g., in a fluidized bed), or by dilution with an inert gas (e.g., argon). In some examples, removing flammable gases may mean reducing the flammable gases to an acceptable volume percentage. For example, degassing may be considered complete when the hydrogen level has been reduced to less than 20 volume percent (or other amounts). Degassing (e.g., 630 or 705) may be, for example, as described in the jointly assigned International Patent Publication 2016 / 126599 ("CARBON BLACK GENERATING SYSTEM"), which is incorporated herein by reference.

[0045] The reactor backend (e.g., 635 or 706) may include, for example, one or more of the following: a pelletizer (e.g., connected to a degasser), a binder mixing (e.g., binder and water) tank (e.g., connected to the pelletizer), a dryer (e.g., connected to the pelletizer), and / or a bagger. Non-limiting examples of other components may include a conveying process, process filters, cyclones, classifiers, hammer mills, and / or other size reduction equipment (e.g., for reducing the proportion of grid in the product). Components may be added or removed. See also, for example, U.S. Patent No. 3,981,659 “APPARATUS FOR DRYING CARBON BLACK PELLETS”, U.S. Patent No. 3,309,780 “PROCESS AND APPARATUS FOR DRYING WET PARTICULATE SOLIDS”, and U.S. Patent No. 3,307,923 “PROCESS AND APPARATUS FOR MAKING CARBON BLACK”, each of which is incorporated herein by reference.

[0046] An example of a pelletizer can be found in U.S. Patent Publication 2012 / 0292794, “PROCESS FOR THE PREPARATION OF CARBON BLACK PELLETS,” which is incorporated herein by reference. In a pelletizer, water, a binder, and carbon particles (e.g., carbon black) may be added together in a pin-type pelletizer, processed through the pelletizer, and then dried. The binder:carbon particle ratio may be less than about 0.1:1, and the water:carbon particle ratio may be in the range of about 0.1:1 to about 3:1. Carbon particles with low dibutyl phthalate (DBP) absorption may require less water to produce pellets of acceptable quality, and therefore less heat may be needed. The pelletizing medium (e.g., water) may be heated (e.g., so that the carbon enters the dryer at a higher temperature). Alternatively, the process may use a dry pelletizing process in which a rotating drum densens the product. The pelletizer may use an oil pelletizing process, for example, as found in U.S. Patent No. 8,323,793, “PELLETIZATION OF PYROLYZED RUBBER PRODUCTS”, which is incorporated herein by reference. A binder oil (e.g., at least one of highly aromatic oils, naphthenic oils, and paraffinic oils) and carbon particles may be added together in the pelletizer. The binder oil may be added together with the carbon particles to a mixer (e.g., up to about 15% by weight) to form pelletized carbon particles (e.g., pelletized carbon black). Alternatively, a binder that does not contain distilled water and ash (e.g., sugar, polyethylene glycol, and / or polyoxyethylene (e.g., polymers of ethylene oxide such as Tween® 80 and / or Tween® 20 materials)) may be used.

[0047] A dryer can be an indirect rotary dryer (e.g., indirectly calcined or heated by heat exchange with one or more fluids in the system instead of combustion). The dryer may heat the carbon particles (e.g., pelletized) using one or more of air, process gas, and purge gas. In some examples, only purge gas may be used. In some examples, air with or without purge gas may be used. In some examples, process gas with or without purge gas may be used. In some examples, air with or without purge gas and process gas may be used. The dryer can be configured for forward or reverse flow action (e.g., by purge gas). The dryer can also be a vibrating fluidized bed with a vibrating tray conveyor through which a hot gas flows through perforations or holes in a tray and comes into contact with the carbon pellets being dried. The vibration of the tray, combined with the fluidization of the carbon pellets, allows for the forward transport of the pellets once dried, as well as the creation of different zones where the temperature of the hot gas can be varied to result in a controlled drying protocol. High-temperature gases can be electrically heated via resistive or plasma-based processes, thereby eliminating the need for combustion and, consequently, the potential CO2 emissions from the drying process.

[0048] The reactor (e.g., 615 or 702) may operate at atmospheric pressure (about 0 bar) or above atmospheric pressure (about 0 bar), for example, in the range of about 0 bar to about 100 bar or more, for example, about 0 to 10 bar, about 0 to 20 bar, about 1 to 10 bar, about 1 to 50 bar, etc., more examples of which can be found in International Patent Publication 2016 / 028658 ("SYSTEMS AND METHODS FOR ELECTRIC PROCESSING"), which is incorporated herein by reference. For example, the reactor may operate at pressures in the range of about 1.1 bar to about 4 bar. Carbon particles formed in a reactor operating at higher pressures may have a smaller surface area than carbon particles formed in a reactor operating at lower pressures.

[0049] Returning to Figure 1, in some cases, process 100 may produce hydrogen. For example, in the production of carbon black particles using a thermal plasma process, hydrogen gas can also be produced. The hydrogen can be discarded or collected as an additional product of the process. Hydrogen and carbon particles can be produced in a once-through, i.e., single-stage process. For example, hydrogen and carbon particles can be produced simultaneously (e.g., a process operation that produces carbon particles can also produce hydrogen). In this example, hydrogen and plasma carbon black can be produced in a single operation of the reactor (e.g., the same hydrocarbon decomposition operation). A single-stage process may offer increased reaction efficiency (e.g., efficiency of heat transfer from plasma to raw materials), may allow cost savings due to the types of materials that can be used for construction and maintenance, and / or may have a high-density (e.g., optically high-density) field of carbon particles in or near the plasma arc (e.g., may offer increased heat transfer to the carbon particles and decreased heat transfer to the reactor walls). In some cases, hydrogen and carbon particles can be produced in a multi-stage (e.g., two-stage, three-stage, etc.) process. For example, a two-stage process may include a first injection of hydrocarbons and a second injection of hydrocarbons. Multistage processes can reduce fouling in the reactor or on the electrodes by decreasing the amount of hydrocarbons in a given region of the reactor, allow for additional process operations between stages (e.g., water injection to remove fouling from the reactor without the need to shut down the reactor or disable the plasma), and / or provide increased mixing of the raw materials into the plasma gas due to an increase in the velocity and momentum of the plasma gas.

[0050] The surface area of ​​carbon particles can be increased by using one or more additives. One or more additives can be added to hydrocarbons before, during, or after they are injected into the reactor. One or more additives can be injected into the reactor before the plasma is introduced. Examples of additives, but not limited to, include hydrocarbons (e.g., hydrocarbon gases), silicon-containing compounds (e.g., siloxanes, silanes, etc.), aromatic additives (e.g., benzene, xylene, polycyclic aromatic hydrocarbons, etc.), or any combination thereof.

[0051] The systems and methods described herein may be integrated with, mounted on, or used with one or more computer systems. One or more computer systems may be configured or operable to perform methods described elsewhere in this specification, or may be operable to monitor the status of systems described elsewhere in this specification. For example, one or more computer systems may be used to monitor the temperature of a product or equipment at various points in the process, to control or monitor process conditions such as non-hydrogen gas, hydrocarbon feedstock, or separated gas flow rates, to control or monitor inlet or outlet gas concentrations, to control or monitor pretreatment or post-reactor conditions, or any combination thereof. One or more computer systems may be configured or can monitor effective current values ​​and voltages for plasma phases (e.g., each of the three phases for a three-phase system), gas flow rates at inputs and outputs, input and output water temperatures in systems with water-cooled loops, water flow rates per loop in systems with water-cooled loops, or any combination thereof. One or more computer systems may further monitor the internal reactor wall temperature at different locations within the reactor, for example, using optical pyrometers and Type C thermocouples (e.g., tungsten / rhenium thermocouples). The average reactor temperature may be used as an estimate of the average reaction temperature.

[0052] Referring to Figure 1, after the plasma carbon black is generated (through operations 110, 120, and 130 discussed above), the plasma carbon black may be mixed with polymers and other components to produce a plasma carbon black filler for compounding into a tire rubber composition (operation 140) as a component of a tire, as described in the following paragraphs and examples.

[0053] The systems and methods described herein (e.g., thermal plasma processes) may be used to produce improved carbon particles (e.g., carbon black) for a variety of purposes, including use in pigments and / or elastomer composites of tires and / or tire components (e.g., as fillers in polymers). The carbon particles may have a set of properties or a combination of properties. As described herein, for example, in the jointly assigned International Patent Publication No. 2018 / 195460 ("PARTICLE SYSTEMS AND METHODS"), incorporated herein by reference, carbon particles may have a given shape, size(s) or size distribution, density, crystallinity, surface functionality (e.g., (surface) hydrophilicity content), surface acid group content, water content, elemental analysis (e.g., oxygen content, hydrogen content, sulfur content, nitrogen content, carbon content, etc.), water diffusion pressure, surface area (e.g., nitrogen surface area (N2SA), statistical thickness surface area (STSA), STSA / N2SA ratio), structure (e.g., expressed in terms of dibutyl phthalate (DBP) absorption, where larger DBP values ​​may correspond to higher structural degrees), and other properties. In addition, as further described below, properties to be measured may include toluene extract (TOTE) transmittance, centrifugal particle sedimentation assay (CPS) number mean, and dynamic light scattering (DLS) Z mean aggregate diameter. Some modifications and / or adjustments to the systems and methods described herein may be necessary to achieve some and / or combinations of particle properties.

[0054] Carbon black can have a given surface area. The surface area can refer to, for example, the nitrogen surface area (N2SA) and / or the statistical thickness surface area (STSA), as further described below. In some examples, the surface area excluding internal pores can be about 10 m 2 / g (square meters per gram) to about 300 m 2 / g. In some examples, the surface area excluding internal pores can be about 15 m 2 / g to about 300 m 2 / g. In some examples, the surface area excluding internal pores can be about 15 m 2 / g to about 150 m 2 / g. The surface area (e.g., N2SA and / or STSA) can be, for example, about 5, 10, 20, 30, 50, 80, 100, 120, 150, 180, 200, 250, 300, or 400 m 2 / g or more. Alternatively, or in addition, the surface area (e.g., N2SA and / or STSA) can be, for example, about 400, 300, 250, 200, 180, 150, 120, 100, 80, 50, 30, 20, 10, or 5 m 2 / g or less. The surface area (e.g., N2SA and / or STSA) can be within a range defined by any two of the aforementioned values. For example, N2SA or STSA can be in the range of about 15 m 2 / g to about 200 m 2 / g. STSA and N2SA can be different.

[0055] Carbon black can have a given structure. The structure can be represented in terms of the oil absorption number (OAN), as further described below. The structure (e.g., OAN) can be, for example, about 32, 40, 50, 80, 100, 120, 150, 180, 200, or 250 mL / 100 g (milliliters per 100 grams, or 10 -5 m 3It may be greater than or equal to ( / kg). Alternatively, or in addition, the structure (e.g., OAN) may be less than or equal to approximately 250, 200, 180, 150, 120, 100, 80, 50, or 40 mL / 100g. The structure (e.g., OAN) may be within the range defined by any two of the aforementioned values. For example, OAN may be in the range of approximately 32 mL / 100g to approximately 250 mL / 100g, or approximately 50 mL / 100g to approximately 180 mL / 100g.

[0056] Carbon particles (e.g., carbon black) can be classified into grades. For example, ASTM D1765, incorporated herein by reference, provides a standard classification system for carbon black used in rubber products (see, e.g., N550, N660, N326, and others, where the prefix "N" indicates the typical curing rate of furnace black). ASTM grading is based on certain measurement parameters (e.g., surface area(s) N2SA and / or STSA, oil absorption (OAN), oil absorption of compressed samples ("compressed OAN" or COAN"), etc.), as further described below. Carbon black particles (e.g., carbon black) derived from the thermal plasma process of this disclosure may be of any grade or may be of no grade at all.

[0057] Generally, considering the same N2SA and OAN, COAN and STSA may be higher in plasma carbon black compared to furnace carbon black. The lattice constant (Lc) or crystallinity, as measured by powder X-ray diffraction (XRD), may be higher in plasma carbon black compared to furnace carbon black.

[0058] The colloidal properties of plasma carbon black samples ("M" samples) compared to furnace carbon black of various grades ("N" samples) are given in Tables 1 and 2 below. [Table 1] [Table 2]

[0059] For use in tires and other critical applications, the colloidal properties of carbon black grades must be clearly defined and reproducible. Table 1 lists surface area and structural data that can be considered predictive of how carbon black particles will function in rubber compounds. Specifically, Table 1 lists STSA (Statistical Thickness Surface Area) values ​​measured via ASTM D6556 (e.g., ASTM D6556-10), OAN and COAN (Oil Absorption and Compression OAN) values ​​measured via ASTM D2414 (e.g., ASTM D2414-09) and ASTM D3493, respectively, 325 mesh grid values ​​measured via ASTM D1514 water-washed grit test through a 325 wire mesh screen, TOTE measured via ASTM D1618-99, and pH values ​​measured via ASTM D1512. Table 1 also lists DLS and CPS data, where the DLS Z-mean gives the average hydrodynamic particle size (e.g., diameter) calculated using the Einstein-Stokes equation with correlation coefficients calculated using detectors that measure the collective migration velocity of particles, and CPS determines the mass or corresponding volume of equivalent spheres by using Mie scattering to count aggregate particles as they are passed through a gradient viscosity solution and centrifuged.

[0060] The data in Table 1 show that plasma carbon black has larger particle size results compared to furnace carbon black, as measured by DLS and CPS, regardless of whether STSA decreases (M660) or increases (M772, M550), or OAN increases (M660, M772) or remains stable (M550). For example, both the hydrodynamic radius (DLS) and equivalent sphere (CPS) are larger for plasma grade M660 than for the furnace grade N660 counterpart, increasing by 38% and 17%, respectively. For the three plasma grades tested, the DLS increase ranged from 3% to 38% above the corresponding furnace grade, and the CPS increase ranged from 17% to 32%. The increase in the DLS Z mean value or the increase in the CPS value between the plasma carbon black of this disclosure and the corresponding furnace black grade may be, for example, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, in between, or greater. This slight colloidal difference in particle size is intentional, and the important aspect for new carbon black manufacturers is not necessarily to match across colloidal properties, but rather to match (or exceed) the in-rubber performance properties of the corresponding furnace carbon black. Nevertheless, for use in tires, as described in the systems and methods of this disclosure, it is desirable to repeatedly manufacture the same STSA and OAN that match the DLS and CPS.

[0061] Table 2 lists the measured (weight percent) elemental analysis results for oxygen (O), nitrogen (N), hydrogen (H), and sulfur (S) in each sample, as well as the results of X-ray crystal diffraction (XRD) analysis of the graphite 002 peak using Scherrer's equation to obtain Lc (lattice constant or "crystallinity" as used herein) and d002 (lattice plane spacing of the graphite 002 peak) values. Larger Lc values ​​may correspond to higher crystallinity. Smaller d002 values ​​may correspond to higher crystallinity or a more graphite-like lattice structure, but larger d002 values ​​(e.g., greater than about 0.35 or 0.36 nm) may indicate turbid carbon (e.g., this is common in carbon black samples produced via furnace processes). Here, the measured crystallinity (Lc) values ​​of plasma carbon black samples that are superior to the corresponding furnace carbon black samples are in the range of 2.5 to greater than 3.1 times. The increase in crystallinity between the plasma carbon black of this disclosure and the corresponding furnace black grade may be, for example, 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, or more.

[0062] Table 3 shows equation D a =(2540+(71*OAN)) / STSA(where, D a The DLS Z-mean value (Table 1) and the calculated Z-mean value are compared according to the calculation Z-mean value (where (aggregate diameter) is the calculated Z-mean value). [Table 3]

[0063] The plasma carbon black of this disclosure exhibits a low deviation (ranging from 1.2 to 4.4 percent) compared to the corresponding furnace black grade, which differs from the calculated Z mean by at least 21% (up to 29.8%). The deviation between the measured Z mean and the calculated Z mean can be 0%, 1%, 2%, 3%, 4%, 5%, and up to 15% or more. The remarkably low deviation between the measured Z mean and the calculated Z mean of the plasma carbon black of this disclosure compared to the corresponding furnace carbon black grade indicates that the plasma carbon black is composed of unique carbon black particles that share certain colloidal and rubber performance characteristics with furnace black.

[0064] The plasma carbon black fillers of this disclosure may have specific utility in various tire rubber compositions, as further described below. In one example, plasma carbon black may be mixed with a polymer (e.g., elastomer polymer and / or rubber) and other components to produce a plasma carbon black filler for compounding into a tire rubber composition. In one example, the plasma carbon black filler may be compounded into a tire rubber composition. Thus, a tire rubber composition may include a plasma carbon black filler, which may include carbon black particles produced by a thermal plasma process and a binder used to pelletize the carbon black particles.

[0065] In some embodiments, the elastomer of the tire rubber composition may be or may include natural rubber, synthetic elastomers, or synthetic polymers (e.g., polybutadiene (butadiene rubber), polyisobutylene (butyl rubber), polyisoprene, nitrile rubber, halobutyl, ethylene propylene rubber, ethylene propylene diene rubber, silicone rubber, fluoroelastomers, etc.).

[0066] In some embodiments, the tire rubber composition may include a compounded plasma carbon black filler therein, the plasma carbon black filler comprising carbon black particles produced by a thermal plasma process, silica nanoparticles as trace filler components incorporated to form a mixture of carbon black particles and silica particles, and a binder used to pelletize the mixture of carbon black particles and silica particles. The carbon black particles and / or silica particles may be in the form of one or more molecules, nanoparticles (e.g., particles with a size of a sphere or smaller than about 2 micrometers in volume), particles (e.g., particles with a size of up to about 10 micrometers, 50 micrometers, 100 micrometers, 150 micrometers, or larger), or any combination thereof.

[0067] In some embodiments, the tire rubber composition may include a compounded plasma carbon black filler therein, the plasma carbon black filler comprising plasma carbon black particles produced by a thermal plasma process, furnace carbon black particles as a trace filler component incorporated to form a mixture of plasma carbon black particles and furnace carbon black particles, and a binder used to pelletize the mixture of plasma carbon black particles and furnace carbon black particles.

[0068] Plasma carbon black fillers can be classified according to the following scheme: Class A (e.g., no trace filler components), Class B (e.g., incorporating silica particles as trace or major filler components), and Class C (e.g., incorporating furnace carbon black particles as trace or major filler components). Class A can be further classified into types A1 (e.g., no binder), A2 (e.g., standard binder), and A3 (e.g., special binder). Class B can be further classified into types B1 (e.g., no binder), B2 (e.g., standard binder), and B3 (e.g., special binder). Class C can be further classified into types C1 (e.g., no binder), C2 (e.g., standard binder), and C3 (e.g., special binder).

[0069] For example, in carbon black fillers without a binder (e.g., types A1, B1, and C1), water alone may be used in the pelletizing process carried out in a pin flocculant. For example, in carbon black fillers containing a standard binder (e.g., types A2, B2, and C2), a standard binder material may be used in the pelletizing process carried out in a pin flocculant. Examples of standard binder materials for carbon black pelletizing include various sugars, molasses, lignosulfonates, poly(ethylene glycol) (PEG), Tween® 80 (polysorbate 80), and / or similar. The binder may be one of these individually, or a mixture of various combinations of these standard binder materials. The fill level of the standard binder compared to carbon black may be, for example, in the range of about 0.1% to 4% or about 0.2% to 0.6%.

[0070] Special binders may be used in certain examples of the plasma carbon black fillers disclosed herein (e.g., types A3, B3, and C3), and the special binders are applied to the pelletization process carried out in a pin agglomeration facility.

[0071] A fourth class of plasma carbon black fillers may be class D, which can be further classified as types D1 (e.g., no binder), D2 (e.g., standard binder), and D3 (e.g., special binder) of any combination of thermal plasma carbon black combined with recovered carbon. Recovered carbon refers to carbon recovered from the thermal decomposition of used tires, which may be, for example, approximately 85% carbon and 15% ash. The ash may consist of silica, zinc oxide, zinc sulfide, various metals and their oxides, as well as other impurities present in the tire. Although it is a difficult starting material to produce high-quality tire products, by using a mixture of recovered carbon from end-of-life tires and thermal plasma carbon black, tires can be made into a recyclable product (which can be even more beneficial in terms of environmental carbon footprint). Before being combined with plasma carbon black, the recovered carbon may be treated, for example, by extracting the ash using an acid or base or other means (sublimation), or by breaking down the larger particles using any number of grinding techniques such as ball mills, jet mills, and / or such.

[0072] Any of these supplies of filler materials (e.g., classes A to D above), as well as other fillers (e.g., rubber-grade clay used in certain tire components), can be co-pelletized with thermal plasma carbon black particles.

[0073] Plasma carbon black filler can be filled into tire rubber compositions or formulations (e.g., for rubber articles) of the Disclosure together with one or more other fillers, such as furnace carbon black, precipitated silica, recovered carbon, or other filler materials. The total filler material in a tire rubber composition for rubber articles may be, for example, 0.1, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, or 90 percent by weight or more. The total filler material in a tire rubber composition for rubber articles may be, for example, 90, 8, 70, 60, 50, 40, 30, 20, 10, 5, 1, or 0.1 percent by weight or less. The filler material may be present in or filled into a tire rubber composition or formulation within the range defined by any two of the aforementioned values. For example, the total filler material may be present in the range of about 30 to about 70 percent by weight. The weight percentage may be the total weight percentage (e.g., the weight percentage of the total composition including plasma carbon black and other fillers). Various fillers (e.g., precipitated silica, furnace carbon black, recovered carbon, and / or such) can either be co-pelletized with carbon particles produced by a thermal plasma process, or added as separate components and mixed in the rubber compound.

[0074] Tire rubber compositions (e.g., for rubber articles) can be made by combining plasma carbon black filler with other fillers—e.g., silica (class B), furnace carbon black (class C), and / or recovered carbon (class D)—in various ratios of plasma carbon black filler to other filler materials. For example, the ratio of plasma carbon black filler to one or more of silica (e.g., precipitated silica), furnace carbon black, or recovered carbon may be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:20, 1:50, 1:100 or less, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 20:1, 50:1, 100:1 or more, or any ratio in between.

[0075] In types A3, B3, C3, and D3, the special binder mixture may contain any number of binder additives. For example, the additive mixture may contain one or more carboxylate salts. The carboxylate salt may be or may contain any hydrocarbon having a carboxylate or carboxylic acid moiety. The salt of a carboxylic acid may be, for example, one of the classes of organic compounds, in which a carbon atom in the organic compound may (i) be bonded to an oxygen atom by a double bond, (ii) a hydrogen atom may be bonded to a hydroxyl group replaced by a metal, metalloid, etc., and (iii) a fourth bond of the carbon atom may be bonded to another carbon or hydrogen atom. The carboxylate salt may contain anions (e.g., the carboxylate-containing moiety of the salt) and cations (e.g., one or more counterions of the anion). Examples of carboxylate salt anions include, but are not limited to, citrate, acetate, propionate, oxalate, phthalate, oleate, maleate, maleate, sulfanylate, trithiocyanurate, stearate, acrylate, methacrylate, dibutylphthalate, fumarate, lactate, ethylenediaminetetraacetate, benzoate, aminobenzoate, periodate, and polymers containing carboxylates (e.g., polyacrylate, polybutadiene / maleate copolymer, etc.). Examples of carboxylate salt cations include, but are not limited to, hydrogen, alkali metals (e.g., lithium, sodium, potassium, rubidium, etc.), alkaline earth metals (magnesium, calcium, barium, etc.), tin, zirconium, vanadium, chromium, manganese, iron, cobalt, nickel, zinc, organic cations (e.g., carbon-containing cations), other polyatomic cation species (e.g., ammonium, tetramethylammonium, trimethylammonium, triethylammonium, tetrabutylammonium, guanidinium, other ammonia species, hydronium, etc.), and polycations.

[0076] The additive mixture may contain one or more carboxylic acids. A carboxylic acid may be any of the classes of organic compounds, in which a carbon atom in the organic compound may be (i) bonded to an oxygen atom by a double bond, (ii) bonded to a hydroxyl group by a single bond, or (iii) a fourth bond of the carbon atom may be bonded to another carbon or hydrogen atom (for example, as in the case of formic acid). Examples of carboxylic acids may be or may contain citric acid, acetic acid, propionic acid, oxalic acid, phthalic acid, oleic acid, maleic acid, malic acid, sulfanilic acid, trithiocyanuric acid, stearic acid, acrylic acid, methacrylic acid, dibutylphthalic acid, fumaric acid, lactic acid, glycolic acid, tannic acid, lignocellulose, ethylenediaminetetraacetic acid, benzoic acid, aminobenzoic acid, periodic acid, etc. A carboxylic acid may be, for example, the conjugate acid of the corresponding carboxylate salt listed above, in which the anion is a carboxylate salt and the cation is a positively charged hydrogen ion (H+) moiety. The special additive mixture may also contain amino functional groups such as pyridine, carbamate, or any vitamin or protein.

[0077] An additive mixture may comprise one or more additives, each of which may be one or more of a hydrate, hydrated salt, carboxylate salt, carboxylate, or carboxylic acid. An additive mixture may comprise one or more of the following: fillers (e.g., silica, other carbon particles), oils (e.g., organic oils, silicon oil), metal oxides (e.g., zinc oxide, titanium oxide), peroxides or reaction products therefrom (e.g., hydrogen peroxide), sulfur-containing compounds (e.g., sulfur, benzenesulfenamide, thiocarbamate, dithiocarbamate), vulcanization accelerators (e.g., thiram, urea, thiourea, organic acids (e.g., stearic acid)), or any combination thereof. Other examples of components of an additive mixture can be found in "The Science and Technology of Rubber" (Mark, Erman, and Roland, Fourth Edition, Academic Press), the disclosure of which is incorporated herein by reference.

[0078] In operation 130 of Figure 1, the additive mixture may be added to the plasma carbon particles or plasma carbon black, for example, by adding a binder containing the additive mixture. For example, the additive mixture may be suspended or dissolved in water and / or in the form of an aqueous solution, and water, the additive mixture, and / or the aqueous solution may be added to (for example, in contact with) the plasma-generated carbon. The additive mixture may be added to the carbon particles in the feed container of the pelletizer after the carbon particles have been dried (for example, using a rotary kiln, vibrating fluidized bed (VFB) dryer, fluidized bed dryer, tray dryer, etc., or any combination thereof), as an undiluted spray, as a diluted spray (for example, diluted in a solvent), or any combination thereof.

[0079] In some cases, operation 130 may include adding a pelletizer solution to the plasma carbon particles. The pelletizer solution may be configured to bond the carbon particles to one or more other carbon particles, thereby forming a carbon pellet (e.g., plasma carbon black) containing the carbon particles (e.g., after pelletization). The additive mixture may include the pelletizer solution. For example, the pelletizer solution may be at least a part of the additive mixture. In some cases, the pelletizer solution may be added to the carbon particles after the additive mixture. The pelletizer solution may include, as non-limiting examples, water, lignosulfonates, sugars, molasses, polysorbate polymers (e.g., Tween® 80, Tween® 20, etc.), water-soluble binders such as polyethylene glycol, or any combination thereof. When the additives are primarily used to bond materials together for the mechanical integrity of the pellet, these may be examples of producing type A2, B2, or C2 plasma carbon black.

[0080] In some cases, the additive mixture may contain one or more sulfur-containing compounds. Examples of sulfur-containing compounds include, but are not limited to, organometallic sulfur compounds (e.g., compounds containing sulfur or sulfur-containing species bonded to one or more metal ions), metallic sulfur (e.g., compounds containing metal ions bonded to sulfur or sulfur-containing ions), polysulfides, sulfides, free sulfur, or any combination thereof. Sulfur-containing compounds may be present in proportions of at least about 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 weight percent or more of the total weight of the dried carbon pellet sample. Sulfur-containing compounds may be present in ratios of no more than approximately 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, and 0.01 weight percent of the total weight of the dried carbon pellet sample. Sulfur-containing compounds may be present in ratios within the range defined by any two of the aforementioned values. For example, sulfur-containing compounds may be present in ratios ranging from approximately 0.05 to approximately 0.8 weight percent. Weight percentages may refer to total weight percentages (e.g., weight percentages of the total composition including carbon particles). The weight percentage may be relative to the carbon particles (e.g., one or more hydrates, hydrated salts, carboxylate salts, carboxylates, or carboxylic acids, and the weight percentage of the carbon particles). For example, the additive mixture may contain 0.2 wt% sulfur, 0.3 wt% sodium acetate trihydrate, and the remaining weight (e.g., carbon black) may be 99.5%, or if 0.3 wt% binder is present, the remaining weight (e.g., carbon black) may be 99.2%. The amount of sulfur-containing compound may be similar to or substantially similar to the amount of hydrates, hydrated salts, carboxylate salts, carboxylates, or carboxylic acids contained in the additive mixture.The sulfur-containing compound may be in the form of one or more molecules, nanoparticles (e.g., particles with a size of a sphere or smaller than approximately 2 micrometers in volume), particles (e.g., particles with a size of up to approximately 10 micrometers, 50 micrometers, 100 micrometers, 150 micrometers, or larger), or any combination thereof.

[0081] The special binder materials used in plasma carbon black fillers types A3, B3, and C3 may include any member of the group of sulfur-containing organosilanes. Sulfur-containing organosilanes may contain polysulfide components or structures, such as bis(3-alkoxysilylalkyl) polysulfide, where the alkyl radical of the alkoxy group is selected from methyl and ethyl radicals, the alkyl radical of the silane moiety is selected from ethyl, propyl, and butyl radicals, and the polysulfide crosslinks contain (a) 2 to 6 sulfur atoms with an average of 2.1 to 2.8, or (b) 2 to 8 sulfur atoms with an average of 3.5 to 4.5. A typical example of such a coupling agent is bis-(3-triethoxysilylpropyl)-polysulfide, which has (a) 2 to 6 sulfur atoms with an average of 2.1 to 2.8 in its polysulfide crosslinks, or (b) 2 to 8 sulfur atoms with an average of 3.5 to 4.5 in its polysulfide crosslinks. Examples of coupling agents include bis(3-triethoxysilylpropyl)-tetrasulfide (TESPT), also known as Si69, and bis(3-triethoxysilylpropyl)-disulfide (TESPD), manufactured by Evonik. Additional sulfur-containing organosilane coupling agents may include 3-octanoylthio-1-propyltriethoxysilanes and mercapto-functional organosilanes, including so-called block mercaptan varieties such as Si363 silane produced by Evonik or Momentive's NXT silane. Specific examples of plasma carbon black fillers disclosed herein may utilize Si69 as a component of a special binder.

[0082] Some embodiments of the present disclosure may include tire rubber compositions in which precipitated silica may be additionally compounded. Passenger car tire treads may contain a considerable amount of precipitated silica, and the use of silica may be extended to other tire components such as sidewalls. Sulfur-containing organosilanes such as Si69 may function as silica-polymer coupling agents in tire rubber formulations containing precipitated silica to create silica-polymer bonds after mixing and curing (vulcanization) of the rubber, which can reduce tire rolling resistance and / or provide other tire performance improvements. An example of the plasma carbon black filler of the present disclosure incorporating Si69 as part of a special binder provides a unique means of delivering Si69 to a rubber formulation and may function synergistically with silica and silane coupling agents added to the rubber formulation. Si69 may also introduce carbon black-polymer coupling into the rubber compound.

[0083] In some examples where the carbon black filler is type B3, silica particles incorporated as trace amounts of filler components can function as carriers for special binder components. In some examples where the carbon black filler is type C3, furnace carbon black particles incorporated as trace amounts of filler components can function as carriers for special binder components.

[0084] Various embodiments of a tire rubber composition in which a plasma carbon black filler is compounded therein may include, but are not limited to, separate rubber components used in the construction of a tire, including a tread cap, tread base (also called subtread or undertread), sidewall, inner liner, body ply skim (or coat), belt skim (or coat), bead filler, or any combination thereof.

[0085] In some embodiments, when a plasma carbon black filler is compounded into a particular tire rubber composition, it may improve the thermal conductivity compared to a reference furnace carbon black filler. The increase in thermal conductivity of a tire rubber composition containing the plasma carbon black filler of this disclosure may be, for example, about 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 55%, 60%, or more, compared to a tire rubber composition that does not contain the plasma carbon black filler of this disclosure (e.g., contains only furnace carbon black). Alternatively, or in addition, the increase in the thermal conductivity of the tire rubber composition may be, for example, about 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, 1%, or less. The improvement in thermal conductivity from the plasma carbon black filler of this disclosure may be within the range defined by any two of the aforementioned percentage values. For example, the increase in thermal conductivity may be in the range of about 2% to 10%, 5% to 50%, 15% to 30%, 20% to 40%, or any other range. Such an improvement in thermal conductivity may be useful in promoting faster curing (vulcanization) of the tire components and improving heat transfer to counteract viscoelastic heat generation during tire use, as mentioned in the background section above.

[0086] In some embodiments, when plasma carbon black fillers are compounded into a particular tire rubber composition, they can improve filler dispersion compared to reference furnace carbon black fillers. This improved filler dispersion can, for example, improve the fatigue life (mechanical durability) of the tire rubber composition and result in greater wear resistance when the composition is used as a tread cap component.

[0087] In some embodiments, when a plasma carbon black filler is compounded into a particular tire rubber composition, it can reduce the viscoelastic loss tangent, known as tan delta (tanδ), compared to a reference furnace carbon black filler. Compared to a tire rubber composition that does not contain the plasma carbon black filler of the Disclosure (e.g., contains only furnace carbon black), the reduction in the viscoelastic loss tangent (tanδ) of a tire rubber composition containing the plasma carbon black filler of the Disclosure may be, for example, about 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 55%, 60%, or more. Alternatively, or in addition, the reduction in the viscoelastic loss loss tangent (tanδ) of the tire rubber composition may be, for example, about 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, 1%, or less. The improvement in tanδ from the plasma carbon black filler of this disclosure may be within the range defined by any two of the aforementioned percentage values. For example, the reduction in tanδ may be in the range of about 2% to 10%, 5% to 50%, 15% to 30%, 20% to 40%, or any other range. The reduced tanδ of the tire rubber composition may lead to lower rolling resistance and lower heat accumulation when the tire rubber composition is used as a component of a tire.

[0088] In the following Examples 1-9, standard techniques and / or equipment may be used to characterize the properties of the carbon black filler, which may include:

[0089] N2SA(m) via ASTM D6556 2 / g) and STSA(m 2N2SA is a test method used to measure the total surface area and external area of ​​carbon black based on multipoint nitrogen adsorption. N2SA measurement is based on the Brunauer-Emmett-Teller (BET) theory and includes the total surface area including micropores, i.e., pore diameters of less than 2 nm (20 Å). External area based on the statistical thickness method (STSA) can be defined as the specific surface area accessible to the rubber.

[0090] Structure (OAN) (mL / 100g) via ASTM D2414 - A test method used to calculate the structure of carbon black quantified using oil absorption (OAN). OAN is a measure of the number of primary particles fused together, more specifically, the amount of void volume within the aggregates of nanostructured aggregates. OAN is measured by dropping oil at a constant rate into a cylinder containing carbon black. The cylinder contains carbon black and two rotors moving at a constant speed. The torque required to rotate the rotors is maximized when the entire void volume between aggregates is filled. The curve is fitted to a quadratic curve, and a predetermined method is used to calculate the OAN value to give the formula OAN or structure value.

[0091] COAN (mL / 100g)-Compressed OAN or COAN via ASTM D3493 uses the same absorption method, however, the carbon black pellets are subjected to four extreme pressures (e.g., compression or crushing) in a piston before measurement to mimic crushing or shearing in rubber processing equipment.

[0092] To produce special grade plasma carbon black, the colloidal properties of furnace black (e.g., STSA or N2SA and OAN or COAN) and / or the in-rubber performance properties of furnace black can be matched (as discussed above), or plasma black with different colloidal and / or in-rubber performance properties can be produced and then mixed with precipitated silica or another carbon black (furnace carbon black or plasma carbon black) to produce a filler with suitable properties. For example, N660 and N234 (furnace or plasma) can be mixed to form N326 or N330 plasma carbon black. Additionally, the mixture can be mixed with activators such as organozinc, sulfenamide, or polysulfide organosilane or siloxane, or similar types of agents.

[0093] Various mixing techniques may be used to compound the plasma carbon black filler of this disclosure into rubber formulations, details of which are provided in the following sections for different tire rubber compositions used in Examples 1-9. Such mixing techniques may include using one or more of the following: a Farrel Tecnolab BR1600 Banbury mixer and tangential rotor with an internal volume of 1.57 L, a Reliable Rubber and Plastics Machinery Company lab-scale 2-roll mill, a Zwick / Roell 5kN load-frame long-stroke tensiometer, a Zwick / Roell digital durometer, an Alpha Premier RPA, an Alpha Premier Mooney viscometer, an Alpha View disperGRADER, an Alpha Pioneer density tester, a C-Therm Trident thermal conductive instrument, a suitable substitute(s), and / or any combination thereof.

[0094] The rubber compound into which the plasma carbon black filler of this disclosure may be compounded may include a mixture of an elastomer and a thermoplastic(or thermosetting)(or thermosetting plastic or thermosetting polymer).

[0095] The rubber compounding of tire rubber compositions can be carried out in an internal mixer (such as a Banbury type). Mixing can proceed in batch mixing stages, also called steps or passes, which may be unproductive. In the final mixing stage, also called the productive mixing stage, most of the curing / vulcanizing chemicals may be added. Other unproductive mixing stages may precede the final mixing stage, and these unproductive stages or passes are where particulate fillers, such as carbon black or precipitated silica, are dispersed and compounded into the rubber. Tire rubber formulations primarily containing carbon black fillers may be mixed in two or more stages or passes, with at least one unproductive mixing stage followed by at least one productive mixing stage. For compounds primarily containing precipitated silica as a filler, at least one additional unproductive mixing stage may be included, totaling at least three mixing stages or passes. Various other mixing schemes, e.g., additional unproductive mixing passes, tandem mixing, component masterbatch approaches, or any combination thereof may be used.

[0096] Examples 1–9, following detailed lab-scale mixing, illustrate and demonstrate the mixing of the plasma carbon black filler of this disclosure with rubber and other rubber compound components. Such lab-scale mixing provides a reasonable substitute for industrial-scale mixing, although equipment sizes may vary. Both operations may involve multiple mixing passes, a first mix (non-productive mix) carried out at a higher temperature, and subsequent mixes (productive mixes) carried out at lower temperatures as more reactive components are added. In some cases, industrial rubber mixing can be performed in a single mixing stage (one pass) by controlling the time and temperature while keeping below the onset of curing and adding the curing agent later in the mixing cycle. All or part of the mixing may be carried out using a two-roll mill. Various methods and sequences may be used to introduce components into the mixer. Various mixer types, including tangential and meshing types, may be used with various options for rotor design. Rubber compounds may also be mixed using special continuous mixing approaches, for example, by using a special twin-screw extruder.

[0097] After the mixing stage, the rubber compound may undergo further processing and / or molding using a two-roll mill, sheeter, calender, etc. For example, after the mixing stage, the rubber compound may be formed into sheets using a two-roll mill or sheeter, and then proceed to an offline batch, where the sheets are immersed in an aqueous solution and an anti-stick coating such as zinc stearate, calcium stearate, magnesium stearate, or related materials and combinations thereof is applied, followed by a cooling and drying stage, and then wiggling (wiggling) stacking of the rubber sheets onto pallets.

[0098] In embodiments, the disclosure includes the use of a plasma carbon black filler in a tire rubber composition for rubber articles that can be used as components of a vehicle tire. Figure 8 shows a schematic exemplary cross-sectional view of a tire 800 for a vehicle (not shown). This exemplary tire structure is representative and not limiting. The tire 800 has a rubber tread 810 having a molded tread pattern including a circumferential groove 815, a rubber subtread (tread base) 820, two or more belts 830 each having a plurality of reinforcing metal cords (wires) coated with rubber wire skim or coat (not shown), one or more body plies (e.g., carcass plies) 840 having a plurality of reinforcing cords coated with rubber body ply skim or coat (not shown), a rubber inner liner 850, two rubber sidewalls 860, and two bead regions 870 each having a rubber bead filler apex 872 and a bead bundle 875 each containing a plurality of metal cords coated with rubber bead filler (not shown). In some embodiments, the reinforcing metal cords of the bead bundle 875 are made of steel that can be coated with brass or other coatings. In some embodiments, the reinforcing metal cords of the belt 830 are made of steel that can be coated with brass or other coatings. The body ply 840 may include a pair of axially opposed end portions 845. Each axial end portion 845 of the body ply 840 may bend upward around its respective bead area to a position sufficient to secure each axial end portion 845. In some embodiments, such as some tires for passenger cars, the reinforcing cords of the body ply 840 may be made of woven cord material such as polyester, rayon, nylon, aramid, or similar suitable organic polymer compounds that can be coated with an adhesive or bonding coating. In some embodiments, such as some heavy truck and bus tires, the reinforcing cords of the body ply 840 may be made of steel that can be coated with brass or other coatings.The axial end portion 845 of the body ply 840 may engage with the axial outer surfaces of two flippers 880 and the axial inner surfaces of two chippers 890, which may contain a composition similar to that of the body ply 840. The example in Figure 8 is provided for illustrative purposes only, and the tire components may vary, including additional different components or fewer components, and it is assumed that the tire rubber compositions and methods of this disclosure are equally applicable to rubber articles, tire components, and tire constructions not shown.

[0099] Tires are complex structures, and seemingly minor details can strongly influence important performance characteristics such as road noise, air retention, fuel efficiency (MPG or MPGe), wear, fatigue, crack growth, premature oxidation or degradation, and tread life. Factors that can influence important quality parameters include, for example, tread shape, bead placement and shape, how the body ply and inner liner seal or not seal with each other, how the bead interacts with the tire rim, the thickness and composition of the polymer(s) coating the bead or body ply, and many other factors. How a tire is assembled and constructed, including material selection and manufacturing, can strongly influence its performance and lifespan.

[0100] Examples 1-9 below demonstrate the usefulness of plasma carbon black in tire rubber compositions for various rubber articles used in tire construction, including the tread, sub-tread, sidewall, inner liner, belt skim, body ply skim, and bead filler mentioned above.

[0101] The tire rubber compositions used in Examples 1-9 are representative and not intended to be limiting. Adjustments may be made to the type and amount of components in the tire rubber formulation to meet specific performance and / or processability requirements. Some components may also be shifted between or within different mixing stages, or their total amounts may be divided for separate additions in two or more different mixing stages. Adjustments to the mixing steps and mixing conditions at each step are also common if necessary to improve mixing quality and / or productivity. In addition, alternative suppliers of raw materials may offer grades that are substantially similar but not necessarily identical for use in tire rubber compositions. The weight fill amount of components in the rubber formulation / composition may be expressed in terms of 100 parts by weight (phr) of rubber.

[0102] Compression molding and curing of the rubber compound in a heated press may be performed to produce cured / vulcanized rubber test specimens for property testing. Uncured rubber compounds can also be tested for various properties.

[0103] For molding into tire components, tire rubber compositions can be molded using extrusion, calendering, and / or other rubber processing approaches. Various tire components can be combined to form an uncured (unvulcanized) tire, which can then be molded and cured into a vehicle tire. Uncured tire rubber compositions can be stored separately or in combination with other tire rubber compositions before the construction, molding, and curing of a composite tire. For example, after each of the tread (tread cap) and sub-tread (tread base) rubber compounds has been mixed, they can be extruded together (co-extruded) to form a combined tread cap and base, which can be stored in a continuous manner on a reel or cut to the length of the tire tread and stored in a reserved tray before being combined with other tire components in the tire construction process. Rubber compounds used to coat belt, ply, and bead reinforcing cords can be calendered or otherwise applied to the cords, and sheets or strips of such rubber-coated cords can be stored on a reel in an uncured state before the tire is constructed. The cord can be subjected to tension and cured under tension. The rubber compound can also be stored on a pallet in an uncured state after mixing but before molding operations such as extrusion and calendering. Tire construction can be carried out by assembling tire components to form an uncured (unvulcanized) tire using tire construction machines manufactured by the VMI Group and other companies. Methods for molding and curing the unvulcanized tire to form a finally cured (vulcanized) tire may include the use of clamshell molding or segmented tire molding (e.g., using a curing bladder inside the tire filled with high-pressure steam and a heated molding surface on the outside of the tire).

[0104] In the following Examples 1-9, standard techniques and / or equipment may be used to characterize the properties of the tire rubber composition, which may include:

[0105] Test apparatus for characterizing properties including 100% modulus of elasticity (M100), 300% modulus of elasticity (M300), tensile strength at break, and elongation at room temperature may comprise a lower fixture configured on a crosshead and held in a fixed position, and an upper fixture consisting of a load cell connected to a movable crosshead that moves with a constant strain. The test may conform to ASTM D412, with the ability to use rings or dumbbells.

[0106] A test apparatus for characterizing the Shore A hardness of rubber specimens may include a base housing with integrated electronics and a display, as well as a support table with adjustable specimen height. This apparatus may meet the requirements of ASTM D2240.

[0107] A test apparatus for measuring filler dispersion in a compound may utilize a sophisticated reflected light microscope to capture live images of multiple (e.g., five) different locations on a rubber sample. The images may be processed through image algorithms to suppress noise and irregularities on the surface, then filtered and thresholded to produce a black and white image. For example, Alpha Technologies' disperGRADER measures dispersion (%) and Z-value (%) using these functions in accordance with ASTM D7723.

[0108] A test apparatus for measuring the density of a cured rubber compound may be a semi-automatic densimeter that utilizes a hydrostatic method by comparing the weight of the sample in air and in an immersion solution. This process can be carried out in accordance with ASTM D297, g / cm³. 3 The density is measured. The weight of the sample in air, the weight in water, and the weight difference may be recorded and reported.

[0109] A test apparatus for measuring Mooney viscosity may include two heated platens and a cylindrical metal rotor. Mooney viscosity is defined as the shear torque resisting the rotation of a cylindrical metal rotor embedded in rubber having a cylindrical cavity. The test may be set to measure ML1+4(MU) and satisfy the setpoints specified by ASTM D1646.

[0110] A test apparatus for calculating the curing time of a rubber test specimen may be configured as a rotorless curing meter formed by two die cavities. For example, a rotorless curing meter, such as a Rubber Process Analyzer (RPA), eliminates the unheated rotor of a vibrating disk curing meter and can better distribute the temperature in the test specimen. The RPA measures torque, temperature, frequency, strain, pressure, and angle. The process may be set to meet setpoints specified by ASTM D5289, with ts2, t60, and t95 reported in minutes. A strain sweep, keeping the frequency and temperature constant, may be set up using the RPA to examine the dynamic properties before and after curing. The dynamic properties of the cured compound may be observed at specific temperatures, frequencies, and strains. For example, some tables below list properties, including storage modulus (G') and tan delta (tanδ), at specified temperatures, frequencies, and strains.

[0111] Test apparatus for measuring the thermal conductivity of cured rubber compounds may include the Modified Transient Plane Source (MTPS) method, which uses a single-sided sensor to directly measure the thermal conductivity and thermal permeability of the rubber. This process may be set up to comply with ASTM D7984, measuring the thermal conductivity in W / mK (watts per meter-kelvin) and Ws 1 / 2 / m 2 Thermal osmosis is measured in K ([watts / square root second] per [square meter - Kelvin]).

[0112] A test apparatus for measuring the electrical volume resistivity of a cured rubber compound may be configured with a four-point probe for measuring the sheet resistivity of semiconductors and a Keithley SourceMeter to provide measurement capabilities for a wide range of materials. This process may be configured to follow an ASTM F84 in-line four-point probe configuration, measuring electrical volume resistivity in ohms-cm. Electrical conductivity (siemens / cm) can be calculated as the reciprocal of the electrical volume resistivity measured in ohms-cm.

[0113] The test apparatus used to measure the DeMattia crack growth rate may include a test frame for mounting an adjustable fixed head with a grip for holding one end of the specimen(s) in a fixed position, and a reciprocating head for holding the other end of the specimen(s). Each specimen may be a molded strip with a centerline groove that can be penetrated before testing at a point equidistant from the side. With the specimen(s) firmly clamped in place, the reciprocating head cycles at a frequency of 5 Hz at a test temperature of 23°C. After the start of the test, the machine is stopped at periodic intervals to measure the length of the crack, thereby making it possible to calculate the crack growth rate in mm / min. This process may be set up to meet the setpoints specified by ASTM D813.

[0114] A test apparatus for evaluating the abrasion resistance of rubber materials by measuring the volume loss of a test specimen exposed to an abrasive medium may be configured with the abrasive / friction surface mounted on a rotating drum. The test specimen rotates while moving laterally across the rotating drum to ensure uniform contact between the test specimen and the abrasive medium. This process may be set up to comply with the specifications and requirements described in DIN 53516.

[0115] A test apparatus for evaluating the elasticity of rubber may be set up as a Schob-type pendulum with a spherical end mass at the end of the pendulum. The elastic (rebound) percentage is calculated from the ratio of the return energy from the spherical end mass to the applied energy when impacting the rubber test specimen under specified test conditions. The Schob-type pendulum is designed to provide an indicator of hysteretic energy loss. The rubber test specimen may be tested at temperatures from -20°C to 100°C by applying constant strain energy and strain rate. This process may be set up to comply with the specifications and requirements described in ASTM D7121. [Examples]

[0116] Exemplary rubber formulations demonstrate the usefulness of plasma carbon black fillers in various rubber articles used as components of tires, including treads, sub-treads, sidewalls, inner liners, body ply skim, belt skim, and bead fillers. The rubber chemicals / components in these exemplary tire rubber compositions are summarized in Table 4. As will be detailed later, various functionally comparable substitutions and alternative sources for these components may be used to achieve a desired balance of rubber properties and associated tire performance characteristics. The raw materials used herein, as well as sample components, mixing and preparation methods, and all other exemplary data are intended to be representative and not limiting. [Table 4-1] [Table 4-2] [Table 4-3] [Table 4-4]

[0117] Example 1: Tire sidewall The following examples demonstrate the usefulness of plasma carbon black when used in tire rubber compositions for use as a sidewall component of tires. The specific rubber formulations shown are representative and not limiting. The polyisoprene (e.g., natural rubber) (NR) to butadiene (e.g., butadiene rubber) (BR) (NR / BR) polymer ratio can vary from about 35 / 65 to about 65 / 35 in sidewall formulations and may include other elastomer polymers including epoxidized NR, various types of ethylene propylene diene monomer (EPDM), and lithium (anionic) BR. As environmental concerns grow and the desire to use more sustainable elastomers increases, the use of the largest possible percentage of natural rubber (NR), including up to 100%, may be increasingly emphasized. Various furnace carbon black grades, such as N550, N660, N650, and others, may be used. The fillers used may also include carbon fillers from the pyrolysis of recycled rubber materials, recycled rubber products such as end-of-life tires, biomass waste, and other sources. Various types of precipitated silica, with or without a variety of known sulfur-containing organosilanes and / or other coupling agents, can be used as fillers. Furnace carbon black, clay, graphene, precipitated silica, other inorganic particulate fillers, and carbon fillers recovered from the pyrolysis of end-of-life tires can be used at various levels of filler and in various combinations with the plasma carbon black filler of this disclosure. Other adjustments to the formulation can be made for various performance and processability reasons. Specifically, there are various options for the amount and type of curing / vulcanizing components, as well as for degradation inhibitors such as antioxidants, anti-ozone agents, and waxes. Processing aids such as oils and tackifying resins of various types and amounts may be used. The embodiments described herein relating to the use of plasma carbon black filler in tire rubber compositions used in sidewall components encompass a variety of reasonable sidewall formulations.

[0118] The following examples of tire sidewall compositions containing plasma carbon black fillers exhibit performance equivalent to reference carbon black from a furnace process in standard rubber tests (within approximately plus or minus 10%). Since furnace carbon black production generates several tons of CO2 per ton of carbon black produced, while plasma carbon black production generates less than 20% of that CO2, these examples demonstrate that plasma carbon black fillers in tire sidewall components can have a significant positive impact on tire sustainability without substantially impairing rubber properties. Compared to their respective furnace carbon black reference materials, some examples of plasma carbon black fillers may exhibit advantages in terms of improved filler dispersion and reduced hysteresis (tanδ).

[0119] In the tire sidewall composition example, plasma carbon black, when compounded into the rubber compound, yielded substantially higher thermal conductivity compared to comparative furnace carbon black, and the previously discussed predicted advantages to tire manufacturing and tire performance were surprisingly found.

[0120] The following is a list of exemplary sidewall compound components: [Table 5] [Table 6]

[0121] Summary of the mixing steps. First pass: Add polymers (natural rubber (NR) and butadiene rubber (BR)) and mix for 30 seconds, add carbon black and mix for 60 seconds, add naphthenic oil, phenolic resin, and stearic acid and mix for 30 seconds, and mix until a temperature drop of 125°C is reached, including two ram clean-out steps of 30 seconds each. Second pass: Add zinc oxide, sulfur, and MBTS to the first pass mix and mix until a temperature drop of 105°C is reached. [Table 7]

[0122] Detailed mixing steps. Banbury First Pass: Start temperature of 45°C and start RPM (revolutions per minute). Add polymer (e.g., SMR-L and diene 140ND) and mix for 30 seconds. While mixing continues, prepare a thickening oil by hand by pouring about 25% of carbon black (CB) into the oil. Add dry CB (the remaining about 75%) by pouring into the mixer throat and mix for 60 seconds. Add naphthenic oil (thickening oil containing about 25% of CB). Add zinc oxide, antioxidant DQ, stearic acid, and resin C595 and mix for 30 seconds. Ram clean and mix for 25 seconds. Ram clean and mix at 90 RPM until the temperature drops to 125°C. Milling First Pass: Set the mill water temperature to 80°F and start the mill gap gauge (also known as the mill roll gauge) at 1.2 mm. [Table 8]

[0123] Banbury second pass: Starting temperature 45°C and starting RPM 30. Adding ingredients: Add the non-productive mix (first pass compound), then add the anti-ozone agent PD-2, TBBS, and sulfur. Lower the ram and mix at 90 RPM until the temperature drops to 105°C. Milling second pass: Set the mill water temperature to 80°F. Start with a mill gap gauge of 1.2mm for initial banding and set the mill gap gauge to 0.8mm for pig roll mixing. Starting from one end, continuously angle cuts are made as the rubber rolls (also known as "pig rolls"), and once the rubber comes off the mill, the pig roll is fed back into the mill end-first. Eight such pig rolls are made, alternating the starting edges. For final sheet production, increase the mill gap gauge to 1.2mm.

[0124] Rubber properties. Using the BRNRW01 sidewall formulation, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples F2-F5) were compared with N550 furnace carbon black (Example F1), and the results are shown in Table 8. The colloidal properties of the plasma carbon black samples are within the same range as the N550 reference furnace carbon black. The examples containing plasma carbon black fillers exhibited rubber performance equivalent to the reference furnace black (within approximately plus or minus 10%), and several advantages were noted in terms of improved filler dispersion in the examples containing plasma carbon black fillers compared to the N550 reference. Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 9]

[0125] Using the BRNRW01 sidewall formulation, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples G2-G5) were compared with N762 furnace carbon black (Example G1), and the results are shown in Table 9. The colloidal properties of the plasma carbon black samples are within the same range as the N762 reference furnace carbon black. The examples containing plasma carbon black fillers exhibited rubber performance equivalent to the reference furnace black (within approximately plus or minus 10%), and several advantages were noted in terms of improved filler dispersion in the examples containing plasma carbon black fillers compared to the N762 reference. Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 10]

[0126] Using the BRNRW01 sidewall formulation, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples H2-H5) were compared with N660 furnace carbon black (Example H1), and the results are shown in Table 10. The colloidal properties of the plasma carbon black samples are within the same range as the N660 reference furnace carbon black. The examples containing plasma carbon black fillers exhibit rubber performance equivalent to the reference furnace black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 11]

[0127] Using the BRNRW01 sidewall formulation, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples I2-I5) were compared with N660 furnace carbon black (Example I1), and the results are shown in Table 11. The colloidal properties of the plasma carbon black samples are within the same range as the N660 reference furnace carbon black. The examples containing plasma carbon black fillers exhibited rubber performance equivalent to the reference furnace black (within approximately plus or minus 10%), and the advantages of the examples containing plasma carbon black fillers compared to the N660 reference are noteworthy in terms of improved filler dispersion and reduced viscoelastic loss tangent (tanδ). The loss tangent (tanδ) was reduced by 17% to 26% in the examples of sidewall rubber formulations containing plasma carbon black compared to the examples containing furnace carbon black N660. A reduced tanδ in the tire rubber composition can predict lower rolling resistance and lower viscoelastic heat accumulation when the tire rubber composition is used as a component of a tire or within a tire component. Improved filler dispersion can improve the fatigue life (mechanical durability) and wear resistance of the tire rubber composition.

[0128] A remarkable and surprising advantage of plasma carbon black filler over furnace carbon black in tire sidewall formulations is its increased (improved) thermal conductivity (k), which was 41% to 45% higher in plasma carbon black compared to N660 furnace carbon black in Example I1 in Examples I2 to I5. Such an improvement in thermal conductivity can facilitate faster curing (vulcanization) of tire components and improve heat transfer to counteract viscoelastic heat generation during tire use, as mentioned in the background section above. [Table 12]

[0129] Using the BRNRW01 sidewall formulation, the filler colloid properties were set to 30.3-40.2 m 2The rubber properties of A2 type plasma carbon black fillers were evaluated over a range of nitrogen surface area (N2SA) of 1 / g and over a range of OAN structure of 69.8–152.4 mL / 100g, and the results are shown in Tables 12 and 13 (Examples BD1–BD5 and BE1–BE5, respectively). Table 14 provides the rubber properties of the furnace carbon black reference material (Examples BF1–BF4). These examples allowed for the evaluation of the dependence of thermal conductivity (k) on the filler structure (oil absorption (OAN)), as shown in Figure 9. Notably, the plasma carbon black examples had k values ​​33%–47% higher than the corresponding furnace carbon black k values ​​for the same OAN, and the plasma carbon black examples showed a strong dependence of k on OAN compared to the k of furnace carbon black, which is almost independent of OAN. For example, the slope of the line (from linear regression) that fits the plasma carbon black data in Figure 9 is six times higher than the slope of the line that fits the furnace carbon black data.

[0130] Figure 10 shows the same k data plotted against the nitrogen surface area (N2SA) of carbon black. While there is no clear dependence of thermal conductivity (k) on filler surface area across the series of examples, the results highlight that a substantial increase in k for plasma carbon black compared to furnace carbon black is also observed when comparing fillers at a constant surface area. The same data provided in Tables 12–14 also show that a substantial thermal conductivity advantage is maintained when comparing plasma carbon black and furnace carbon black on a constant mechanical reinforcement basis, for example, using Shore A hardness, tensile stress at 100% strain (M100), or tensile stress at 300% strain (M300). [Table 13] [Table 14] [Table 15]

[0131] Example 2: Silica-containing tire sidewall Carbon black remains the primary filler for tire sidewalls. However, precipitated silica, combined with furnace carbon black grades such as N550, N660, and N650, and sulfur-containing organosilanes such as Si69 added as a silica-polymer coupling agent, is increasingly being utilized as a tire sidewall filler. Such formulations can provide advantages of reduced rolling resistance, less heat buildup, improved durability, and / or other tire performance compared to compositions containing carbon black filler alone. Some embodiments of this disclosure may involve incorporating plasma carbon black filler into sidewall formulations that additionally contain precipitated silica. Useful plasma carbon blacks may include types A3, B3, and / or C3, containing a variety of special binder additives, including the TESPT(Si69) silane coupling agent and / or other sulfur-containing organosilanes. Representative but non-limiting silica-containing sidewall formulations are shown in Table 15 below. Although the formulation is presented as a three-step mixing scheme, specifically, a two-step mixing scheme may be used for compounds with a low silica content (e.g., 15 phr), or other mixing schemes may be used where appropriate.

[0132] Embodiments incorporating plasma carbon black into silica-containing sidewall filler formulations may include cases where precipitated silica is the primary filler component and cases where carbon black is the primary filler component. It can be assumed that silica may be present at 0.5–99.5%, and carbon black at 0.5–99.5%. The present carbon black may be a mixture of plasma carbon black and furnace carbon black, with recovered carbon black present at up to 30–40%. Any combination of these fillers, as well as other additive fillers such as nanotubes and graphene, can be used. This is non-limiting in that small amounts of these filler components can cause significant performance differences. Additionally, small amounts of plasma carbon black can dramatically improve the environmental impact of the resulting products. Products with more plasma carbon black added to elastomer / carbon black composites will have a smaller CO2 footprint.

[0133] The following are the components of an exemplary sidewall compound containing silica. [Table 16]

[0134] Example 3: Tire inner liner The following examples demonstrate the usefulness of plasma carbon black when used in tire rubber compositions for use as inner liner components of tires. The specific rubber formulations shown are representative and not limiting. The bromobutyl rubber (BIIR) to polyisoprene (e.g., natural rubber) (NR) (BIIR / NR) polymer ratio can vary from 100 / 0 to about 70 / 30 in inner liner formulations, and other elastomer polymers can be used as trace polymer components, including various types of isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), ethylene-propylene-diene monomer (EPDM), and / or such. Various furnace carbon black grades such as N762, N772, N774, N660, N650, and others may be used. Various types of plate-like fillers, such as exfoliated and cleaved clay, graphene, and other options, can be included to improve gas barrier properties. Fillers may also include carbon fillers from the pyrolysis of recycled rubber materials, recycled rubber products such as end-of-life tires, biomass waste, and other sources. Diverse sulfur-containing organosilanes and / or precipitated silica, with or without other coupling agents, can be used as fillers. Furnace carbon black, clay, graphene, precipitated silica, other inorganic particulate fillers, and recovered carbon fillers from the pyrolysis of end-of-life tires, etc., can be used at various levels of filling and in various combinations with the plasma carbon black filler disclosed herein. Other adjustments to the formulations can be made for various performance and processability reasons. Specifically, there are various options for the amount and type of curing / vulcanizing components. Processing aids such as oils, tackifying resins, and homogenizers / resins (e.g., Promix400 from Flow Polymers), in various types and amounts, may be used. The embodiments described herein relating to the use of plasma carbon black fillers in tire rubber compositions used in inner liner components encompass a variety of reasonable inner liner formulations.

[0135] The following list summarizes the adjustments made to the BIIR inner liner and BIIR / NR inner liner formulations, and / or mixing schemes, during the research process toward the development of the tire rubber composition of this disclosure. Explored inner liner formulation adjustments include, for example, adding benzoic acid at 0.25 phr, adding n-cyclohexylthiophthalimide (CTP) at 0.25 phr, adding Retrocure G at 0.25 phr, adding MgO at 0.25 phr, reducing the sulfur content from 0.5 phr to 0.38 phr, moving the phenolic resin to the productive mixing stage (second pass), reducing the unproductive total mixing time, increasing the unproductive temperature drop to 125°C to 140°C and 150°C, adding Polyfil DL release clay at 60 phr, replacing Exxon Bromobutyl 2222 with Exxpro 3563, and adding 0.75 phr of amylphenol disulfide oligomer (Vultac 3) to the productive mixing stage.

[0136] The following examples of tire inner liner compositions containing plasma carbon black filler demonstrate performance equivalent to (within approximately plus or minus 10%) that of reference carbon black from a furnace process in standard rubber tests. While furnace carbon black production generates several tons of CO2 per ton of carbon black produced, plasma carbon black production generates less than 20% of that CO2. Therefore, these examples demonstrate that plasma carbon black filler in tire inner liner components can have a significant positive impact on tire sustainability without substantially impairing rubber properties.

[0137] In examples of tire inner liner compositions, plasma carbon black, when compounded into the rubber compound, yielded substantially higher (improved) thermal conductivity compared to comparative furnace carbon black, and the predicted advantages for tire manufacturing and tire performance discussed earlier were surprisingly found.

[0138] The components of an exemplary BII01 inner liner compound are listed below. [Table 17] [Table 18]

[0139] Summary of the mixing steps. First pass: Add the polymer and hydrocarbon resin blend (Exxon Bromobutyl 2222 and Proaid AC-740) and mix for 30 seconds. Add the carbon black and mix for 60 seconds. Add the naphthenic oil, phenolic resin, and stearic acid and mix for 30 seconds. Mix until a temperature drop of 125°C is reached, including two ram clean-out steps every 30 seconds. Second pass: Add the zinc oxide, sulfur, and MBTS to the first pass mix and mix until a temperature drop of 105°C is reached. [Table 19]

[0140] Detailed mixing steps. Banbury First Pass: Start temperature 45°C and start RPM 30. Add Proaid AC-740 and Exxon Bromobutyl 222 and mix for 30 seconds. While mixing continues, manually prepare the thickening oil by pouring about 25% of the carbon black (CB) into the oil. Add the dry CB (the remaining about 75%) by pouring it into the mixer throat and mix for 60 seconds. Add the naphthenic oil (thickening oil containing about 25% of the CB). Add the phenolic resin (SP1068) and stearic acid and mix for 30 seconds. Ram clean and mix for 25 seconds. Ram clean and mix at 90 RPM until the temperature drops to 125°C. Milling First Pass: Ensure the chiller unit is on and 45°F water is flowing through the rolls, and start the mill gap gauge (also known as the mill roll gauge) at 1.2 mm. [Table 20]

[0141] Banbury second pass: Starting temperature 45°C and starting RPM 30. Ingredients: Non-productive mix (first pass compound); add sulfur, MBTS, and zinc oxide. Lower the ram and mix at 90 RPM until the temperature drops to 105°C. Milling second pass: Cool the mill rolls through a chiller set to 45°F. Start the mill gap gauge at 1.2mm for initial banding and set the mill gap gauge to 0.8mm for pig roll mixing. Starting from one end, make continuous angled cuts as the rubber rolls (also known as "pig rolls") and once the rubber is out of the mill, feed the pig rolls back into the mill end-first. Make 10 such pig rolls, alternating the starting edges. For final sheet making, increase the mill gap gauge to 1.2mm.

[0142] Rubber properties. Using the BII01 inner liner formulation, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples J2-J5) were compared with N772 furnace carbon black (Example J1), and the results are shown in Table 19. The colloidal properties of the plasma carbon black samples are within the same range as the N772 reference furnace carbon black. The examples containing plasma carbon black fillers exhibit rubber performance equivalent to the reference furnace black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 21]

[0143] Using the BII01 inner liner formulation, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples K2-K5) were compared with N772 furnace carbon black (Example K1), and the results are shown in Table 20. The colloidal properties of the plasma carbon black samples are within the same range as the N772 reference furnace carbon black. The examples containing plasma carbon black fillers exhibit rubber performance equivalent to the reference furnace black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 22]

[0144] Using the BII01 inner liner formulation, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples L2-L5) were compared with N660 furnace carbon black (Example L1), and the results are shown in Table 21. The colloidal properties of the plasma carbon black samples are within the same range as the N660 reference furnace carbon black. The examples containing plasma carbon black fillers exhibit rubber performance equivalent to the reference furnace black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 23]

[0145] Using the BII01 inner liner formulation, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples M2-M5) were compared with N660 furnace carbon black (Example M1), and the results are shown in Table 22. The colloidal properties of the plasma carbon black samples are within the same range as the N660 reference furnace carbon black. The examples containing plasma carbon black fillers exhibit rubber performance equivalent to the reference furnace black (within approximately plus or minus 10%). Viscoelastic properties were not evaluated in these specific examples.

[0146] Regarding the thermal conductivity (k) characteristics of plasma carbon black, the remarkable and surprising advantages of plasma carbon black over furnace carbon black in tire inner liner compound BII01 were noted, which were 48% to 54% higher (improved) compared to N660 furnace carbon black. [Table 24]

[0147] BIIR inner liner containing clay. The release clay was compounded into the inner liner composition using the same formulation and mixing conditions as the BIIR inner liner above, except that 40 phr of Polyfil DL release clay was added together with dry carbon black in the first pass. Using the BII01 inner liner formulation with added clay, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples N2-N5) were compared to N762 furnace carbon black (Example N1), and the results are shown in Table 23. The colloidal properties of the plasma carbon black samples are within a similar range to the N762 reference furnace carbon black. The examples containing plasma carbon black fillers exhibit rubber performance equivalent to the reference furnace black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 25]

[0148] The components of an exemplary BINRI01 inner liner compound are listed below. [Table 26] [Table 27]

[0149] Summary of the mixing steps. First pass: Add polymers (Exxon Bromobutyl 2222 and SIR20) and hydrocarbon resin (Proaid AC-740) and mix for 30 seconds. Add carbon black and mix for 60 seconds. Add naphthenic oil, phenolic resin, and stearic acid and mix for 30 seconds. Mix until a temperature drop of 125°C is reached, including two ram clean-out steps every 30 seconds. Second pass: Add zinc oxide, sulfur, and MBTS to the first pass mix and mix until a temperature drop of 105°C is reached. [Table 28]

[0150] Detailed mixing steps. Banbury First Pass: Start temperature 45°C and start RPM 30. Add Proaid AC-740 and polymers (Exxon Bromobutyl 222 and SIR20) and mix for 30 seconds. While mixing continues, manually prepare the thickening oil by pouring about 25% of the carbon black (CB) into the oil. Add the dry CB (the remaining about 75%) by pouring it into the mixer throat and mix for 60 seconds. Add the naphthenic oil (thickening oil containing about 25% of the CB). Add the phenolic resin (SP1068) and stearic acid and mix for 30 seconds. Ram clean and mix for 25 seconds. Ram clean and mix at 90 RPM until the temperature drops to 125°C. Milling First Pass: Ensure the chiller unit is on and 45°F water is flowing through the rolls, and start the mill gap gauge (also known as the mill roll gauge) at 1.2 mm. [Table 29]

[0151] Banbury second pass: Start at a temperature of 45°C and 30 RPM. Add ingredients: non-productive mix (first pass compound); add sulfur, MBTS, and zinc oxide. Lower the ram and mix at 90 RPM until a drop temperature of 105°C is reached. Milling second pass: Cool the mill rolls through a chiller set to 45°F. Start the mill gap gauge at 1.2mm for initial banding and set the mill gap gauge to 0.8mm for pig roll mixing. Starting from one end, make continuous angled cuts as the rubber rolls (also known as "pig rolls"), and once the rubber is out of the mill, feed the pig rolls back into the mill end-first. Make 10 such pig rolls, alternating the starting edges, and increase the mill gap gauge to 1.2mm for the final sheet making.

[0152] Rubber properties. Using the BINRI01 inner liner formulation, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples O2-O5) were compared with N660 furnace carbon black (Example O1), and the results are shown in Table 27. The colloidal properties of the plasma carbon black samples are within the same range as the N660 reference furnace carbon black. The examples containing plasma carbon black fillers exhibit rubber performance equivalent to the reference furnace black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 30]

[0153] Using the BINRI01 inner liner formulation, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples P2-P5) were compared with N772 furnace carbon black (Example P1), and the results are shown in Table 28. The colloidal properties of the plasma carbon black samples are within the same range as the N772 reference furnace carbon black. The examples containing plasma carbon black fillers exhibit rubber performance equivalent to the reference furnace black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 31]

[0154] Using the BINRI01 inner liner formulation, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples Q2-Q5) were compared with N772 furnace carbon black (Example Q1), and the results are shown in Table 29. The colloidal properties of the plasma carbon black samples are within the same range as the N772 reference furnace carbon black. The examples containing plasma carbon black fillers exhibit rubber performance equivalent to the reference furnace black (within approximately plus or minus 10%). Thermal conductivity was not measured for these specific examples. [Table 32]

[0155] Using the BINRI01 inner liner formulation, the colloidal properties of the filler were set to 23.8-41.9 m 2 The rubber properties of A1, A2, and A3 type plasma carbon black fillers were evaluated, varying across a range of nitrogen surface area (N2SA) per g and OAN structure ranges of 59.9–108.2 mL / 100 g. The number of examples considered was 124, including examples nominally similar to Examples O2–O5, P2–P5, and Q2–Q5 in Tables 27–29 above. These examples allowed for the evaluation of the dependence of thermal conductivity (k) on filler structure (oil absorption (OAN)) compared to equivalent furnace carbon black grades N772 and N660, as shown in Figure 11. Notably, the plasma carbon black examples had k values ​​24%–41% higher than the corresponding furnace carbon black k values ​​for the same OAN, and the plasma carbon black examples showed a strong dependence of k on OAN compared to furnace carbon black k, which is almost independent of OAN. For example, the slope of the line (from linear regression) fitted to the plasma carbon black data in Figure 11 is almost four times higher than the slope of the line fitted to the furnace carbon black data. Similar results are noteworthy when k is plotted against the compressed oil absorption amount (COAN), as shown in the same figure.

[0156] BIIR / NR inner liners containing clay. The release clay was compounded into the inner liner composition using the same formulation and mixing conditions as the BIIR / NR inner liner above, except that 40 phr of Polyfil DL release clay was added with dry carbon black in the first pass to give a clay filler content of 17.95 wt% in the compound. Thermal conductivity was not measured for these specific examples. [Table 33]

[0157] The components of an exemplary CII01 inner liner compound are listed below. [Table 34] [Table 35]

[0158] Summary of the mixing steps. First pass: Add polymer (Exxon Chlorobutyl 1066), magnesium oxide, and hydrocarbon resin (Proaid AC-740) and mix for 30 seconds. Add carbon black and mix for 60 seconds. Add naphthenic oil, phenolic resin, stearic acid, and zinc oxide and mix for 30 seconds. Mix until a temperature drop of 125°C is reached, including two ram clean-out steps every 30 seconds. Second pass: Add sulfur and MBTS to the first pass mix and mix until a temperature drop of 105°C is reached. [Table 36]

[0159] Detailed mixing steps. Banbury First Pass: Start temperature 45°C and start RPM 30. Add Proaid AC-740, magnesium oxide, and Exxon Bromobutyl 2222 and mix for 30 seconds. While mixing continues, manually prepare the thickening oil by pouring about 25% of the carbon black (CB) into the oil. Add the dry CB (the remaining about 75%) by pouring it into the mixer throat and mix for 60 seconds. Add the naphthenic oil (thickening oil containing about 25% of the CB). Add the phenolic resin (SP1068), zinc oxide, and stearic acid and mix for 30 seconds. Ram clean and mix for 25 seconds. Ram clean and mix at 90 RPM until the temperature drops to 125°C. Milling First Pass: Ensure the chiller unit is on and 45°F water is flowing through the rolls, and start the mill gap gauge (also known as the mill roll gauge) at 1.2 mm. [Table 37]

[0160] Banbury second pass: Starting temperature 45°C and starting RPM 30. Ingredients: Non-productive mix (first pass compound); add sulfur and MBTS. Lower the ram and mix at 90 RPM until the temperature drops to 105°C. Milling second pass: Cool the mill rolls through a chiller set to 45°F. Start the mill gap gauge at 1.2mm for initial banding and set the mill gap gauge to 0.8mm for pig roll mixing. Starting from one end, make continuous angled cuts as the rubber rolls (also known as "pig rolls") and once the rubber is out of the mill, feed the pig rolls back into the mill end-first. Make 10 such pig rolls, alternating the starting edges. For final sheet making, increase the mill gap gauge to 1.2mm.

[0161] Rubber properties. Using the CII01 inner liner formulation, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples S2-S5) were compared with N772 furnace carbon black (Example S1), and the results are shown in Table 34. The colloidal properties of the plasma carbon black samples are within the same range as the N772 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 38]

[0162] Using the CII01 inner liner formulation, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples T2-T5) were compared with N660 furnace carbon black (Example T1), and the results are shown in Table 35. The colloidal properties of the plasma carbon black samples are within the same range as the N660 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 39]

[0163] Example 4: Body Price Kim The following examples demonstrate the usefulness of plasma carbon black when used in tire rubber compositions for use as a component of the tire body ply skim (also known as body ply coat). The specific rubber formulations shown are representative and not limiting. The NR / SBR polymer ratio can vary from 100 / 0 to about 60 / 40 in the body ply skim formulation, and emulsion SBR (ESBR) and / or various types of solution SBR (SSBR) can be used. Other elastomer polymers can be used as trace polymer components, including various types of IR, BR, and epoxidized NR. Various furnace carbon black grades such as N550, N660, N650, N330, and others can be used. The fillers used can also include carbon fillers from the pyrolysis of recycled rubber materials, recycled rubber products such as end-of-life tires, biomass waste, and other sources. Diverse sulfur-containing organosilanes and / or precipitated silica with or without other coupling agents can be used as fillers. Furnace carbon black, clay, graphene, precipitated silica, other inorganic particulate fillers, and carbon fillers recovered from the thermal decomposition of end-of-life tires can be used in various combinations with the plasma carbon black of this disclosure at various filler levels. Other adjustments to the formulation can be made for various performance and processability reasons. Specifically, there are various options for the amount and type of curing / vulcanizing components, and for anti-retardants such as antioxidants and anti-ozone agents. Processing aids such as oils and tackifying resins in various types and amounts can also be used. The embodiments described herein relate to the use of plasma carbon black in tire rubber compositions used as body ply skim components and encompass a variety of reasonable body ply and body ply skim formulations.

[0164] The following list summarizes the adjustments made to NR / SBR body price skim formulations and / or mixed schemes during the research process toward the development of the tire rubber composition of this disclosure. Explored adjustments to the body price skim formulations include, for example, the addition of Cure-Rite18 at 0.25 and 0.5 phr, the addition of DPTT at 0.25 and 0.5 phr, and Crystex. The process involves increasing CurePro from 2.2 phr to 2.5 phr while adding 0.2 phr of Cure-Rite18 and 0.2 phr of DPTT, decreasing MBTS and TBBS by 0.25 phr, then adding 0.5 phr of Cure-Rite18, decreasing MBTS and TBBS by 0.25 phr, then adding 0.5 phr of DPTT, moving the antioxidant DQ and anti-ozone agent PD-2 to the productive mixing stage for unproductive descent temperatures of 150°C and 165°C, adding 0.5 phr of benzofloxane to the unproductive mixing stage at a descent temperature of 150°C, moving the antioxidant DQ and anti-ozone agent PD-2 from the unproductive mixing stage to the productive mixing stage, adding 0.5 phr of benzofloxane to the unproductive mixing stage at a descent temperature of 150°C, and moving the antioxidant DQ and anti-ozone agent PD-2 from the unproductive mixing stage to the productive mixing stage. Adding 1 and 0.5 phr of benzofloxane to the first stage, adding 0.5 phr of benzofloxane to the non-productive mixing stage at a descent temperature of 165°C while moving the antioxidant DQ and anti-ozone agent PD-2 from the non-productive mixing stage to the productive mixing stage, increasing the descent temperature from 150°C to 165°C, respectively, increasing the amount of NR present in the mix from 70 phr to 85 and 100 phr while decreasing SBR from 30 phr to 15 and 0 phr, respectively, removing SP1068 from the mix at a descent temperature of 150°C, removing SP1068 from the mix at a descent temperature of 165°C, adding 0.1 phr, 0.25 phr, and 0.5 phr of CTP to the productive mixing stage, adding 0.2 phr of DPG to the productive mixing stage, adding 0.5 phr of pk-900 to the productive mixing stage, 2.Examples include replacing 2 phr of Crystex CurePro with 2 phr of Rubbermakers sulfur, adding Akrosorb 29460 at 1, 2, and 3 phr filling levels during the non-productive mixing stage, adding phr of carbon black for reinforcement, increasing sulfur in the low-temperature addition step, and adding sulfenamide or other curing agents.

[0165] The following examples of tire body plyskim compositions containing plasma carbon black exhibit comparable performance (within approximately plus or minus 10%) compared to reference carbon black from a furnace process in standard rubber tests. Since furnace carbon black production generates several tons of CO2 per ton of carbon black produced, while plasma carbon black production generates less than 20% of that CO2, these examples demonstrate that plasma carbon black fillers in tire body plyskim components can have a significant positive impact on tire sustainability without substantially impairing rubber properties. In some examples of plasma carbon black, a significant reduction in hysteresis (tan delta or tanδ) is noteworthy compared to the respective furnace carbon black reference.

[0166] In examples of tire body powder compositions, plasma carbon black, when compounded into the rubber compound, yielded substantially higher (improved) thermal conductivity compared to comparative furnace carbon black, and the previously discussed predicted advantages to tire manufacturing and tire performance were surprisingly found.

[0167] The following is a list of the ingredients of an exemplary NRESP01 Body Price Kim Compound. [Table 40] [Table 41]

[0168] Summary of the mixing steps. First pass: Add polymers (natural rubber (NR) and SBR) and mix for 60 seconds. Add half of the carbon black and mix for 60 seconds. Add the other half of the carbon black / plasticizer mix, phenol resin, antioxidant, and anti-ozone agent and mix for 60 seconds. Add stearic acid and zinc oxide and mix for 60 seconds. Mix until a temperature drop of 150°C is reached, including the clean-out step. Second pass: Add half of the first pass, MBTS, TBBS, Crystex CurePro, then the second half of the first pass and mix until a temperature drop of 105°C is reached. [Table 42]

[0169] Detailed mixing steps. Banbury First Pass: Start temperature 70°F and start RPM 40. Add polymers (SMR-L and ESBR1502) and mix for 60 seconds. While mixing continues, manually prepare the thickening oil by pouring about 25% of the carbon black (CB) into the oil. Add the dry CB (the remaining about 75%) by pouring it into the mixer throat and mix for 60 seconds. Add naphthenic oil (thickening oil containing about 25% of the CB), phenolic resin, antioxidant DQ, and PD-2 and mix for 60 seconds. Add stearic acid and zinc oxide and mix for 60 seconds. Ram clean and mix at 110 RPM until the temperature drops to 150°F. Milling First Pass: Set the mill water temperature to 140°F and start the mill gap gauge (also known as the mill roll gauge) at 1.2 mm. [Table 43]

[0170] Banbury second pass: Starting temperature 70°C and starting RPM 40. Adding ingredients: Add half of the non-productive mix (first pass compound), then MBTS, TBBS, and Crystex CurePro, then the second half of the non-productive mix. Lower the ram and mix at 60 RPM until the dropping temperature reaches 105°C. Milling second pass: Mill water temperature 140°F. Start mill gap gauge at 1.2mm for initial banding and set mill gap gauge to 0.8mm for pig roll mixing. Starting from one end, make continuous angled cuts as the rubber rolls (also known as "pig rolls"), and once the rubber is out of the mill, feed the pig roll back into the mill end-first. Make 10 such pig rolls, alternating the starting edges. For final sheet making, increase the mill gap gauge to 1.2mm.

[0171] Rubber properties. Using the NRESP01 body price skim formulation, the rubber properties of A1, A2, and A3 type plasma carbon black (tire rubber composition examples U2-U5) were compared with N550 furnace carbon black (Example U1), and the results are shown in Table 39. The colloidal properties of the plasma carbon black samples are within the same range as the N550 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within plus or minus approximately 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. In sample U5, which is a type A3 sample, the binders are sodium acetate, lignosulfonate, and sulfur. All components are present in concentrations of 0.2%-0.3%. The carbon black was carefully dried to preserve the hydrated state of the sodium acetate hydrate salt. [Table 44]

[0172] Using the NRESP01 body price skim formulation, the rubber properties of A1, A2, and A3 type plasma carbon blacks (tire rubber composition examples V2-V5) were compared with N660 furnace carbon black (Example V1), and the results are shown in Table 40. The colloidal properties of the plasma carbon black samples are within the same range as the N660 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 45]

[0173] Using the NRESP01 body price skim formulation, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples W2-W5) were compared with N660 furnace carbon black (Example W1), and the results are shown in Table 41. The colloidal properties of the plasma carbon black samples are within the same range as the N660 reference furnace carbon black. The examples containing plasma carbon black fillers exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 46]

[0174] Using the NRESP01 body price skim formulation, the rubber properties of A2, A3, B2, and B3 type plasma carbon black fillers (tire rubber composition examples AU2-AU5) were compared with N660 furnace carbon black (Example AU1), and the results are shown in Table 42. The B2 and B3 type plasma carbon black fillers contain silica in the binder, and the special additive for the B3 type plasma CB is Si69(TESPT) silane. The colloidal properties of the plasma carbon black samples are within a similar range to the N660 reference furnace carbon black. The examples containing plasma carbon black fillers exhibit rubber performance equivalent to the reference furnace carbon black (within plus or minus approximately 10%), and the advantages of the examples containing plasma carbon black fillers in terms of reduced viscoelastic loss tangent (tanδ) compared to the N660 reference are noteworthy. The reduced tanδ of the tire rubber composition can be predicted to result in lower rolling resistance and lower viscoelastic heat accumulation when the tire rubber composition is used as a component of a tire. Thermal conductivity was not evaluated for these specific examples. [Table 47]

[0175] Using NRESP01 body price skim formulations with three different carbon black filler amounts (phr) of 43, 50, and 57 parts per 100 parts of rubber, the rubber properties of A2 and A3 type plasma carbon black fillers (tire rubber composition examples BA2, BA3, BB2, BB3, BC2, and BC3) were compared with N660 furnace carbon black (examples BA1, BA2, and BA3), and the results are shown in Tables 43 to 45. The colloidal properties of the plasma carbon black samples are within a similar range to the N660 reference furnace carbon black. The examples containing plasma carbon black exhibited rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%), and the advantages of the examples containing plasma carbon black compared to the N660 reference are noteworthy in terms of reduced viscoelastic loss tangent (tanδ).

[0176] A remarkable and surprising advantage of plasma carbon black filler over furnace carbon black in tire body plyskim formulations is improved thermal conductivity (k), which was 27%–44% higher for plasma carbon black compared to N660 furnace carbon black. The data provided in Tables 43–45 and shown in Figures 12–14 also demonstrate that the substantial thermal conductivity advantage of plasma black is retained when examined on a constant mechanical reinforcement basis, for example, using Shore A hardness, tensile stress at 100% strain (M100), or tensile stress at 300% strain (M300). The highest filler amount of furnace carbon black (e.g., BC1), considered to be 57 phr, resulted in a thermal conductivity of 0.308 W / mK, which is still inferior to all thermal conductivity values ​​of plasma carbon black formulations, even at the lowest filler amount considered to be 43 phr. In other words, for the body price skim formulations in Tables 43-45 below, 43 phr plasma carbon black-filled rubber articles are more thermally conductive than 57 phr furnace carbon black-filled rubber articles. The values ​​of 0.364 W / mK (plasma carbon black) versus 0.308 W / mK (reference furnace carbon black) are equivalent to an 18% (improved) increase in thermal conductivity by filling with plasma carbon black at a fill amount of 43 phr instead of furnace carbon black at a higher fill amount of 57 phr. Generally, plasma carbon black-filled rubber articles can have a thermal conductivity of over approximately 0.33 W / mK for articles filled with 25% to 40% by weight of plasma carbon black. Corresponding furnace carbon black-filled rubber articles may not be more thermally conductive than semi-reinforced (SRF grade) furnace black at approximately 0.314 W / mK and N234 (tread grade) furnace black at a maximum of approximately 0.329 W / mK. [Table 48] [Table 49] [Table 50]

[0177] For example, compound modifications can be made to adjust the rubber properties as required for tire applications, in order to achieve a desirable balance of rubber properties and associated tire performance characteristics. In Table 46, Examples Mod1 to Mod4 represent such compound modifications to the detailed NRESP01 body price skim formulations above. The baseline example used the NRESP01 formulation without modification, as did the N660 control example (furnace carbon black reference). The plasma carbon black used in the baseline, Mod1, Mod2, Mod3, and Mod4 formulations is Monolith® commercial grade GB7260, which is a type A3 plasma carbon black. As shown in Table 47, the substantial advantage of higher (improved) thermal conductivity (k) of plasma carbon black versus furnace carbon black was maintained throughout these compound compound adjustments, with significant increases in k ranging from 42% to 57%. Figure 15, a corresponding stress-strain graph, further demonstrates that such formulation modifications can be used to match the stress-strain characteristics of furnace black. Notably, by increasing the amount of plasma carbon black in the formulation, the 300% modulus of elasticity (M300), along with various other properties, can be shifted to within 20% to 5%, or even to match the M300 of the furnace black counterpart. [Table 51] [Table 52]

[0178] NR / SBR body price skim containing Si69. Akrosorb 29460 was compounded into a body price skim composition using the same formulation and mixing conditions as the above NR / SBR formulation, except that Akrosorb 29460 was added in the first pass before stearic acid and zinc oxide, after spraying 0.5 phr of H2O into 400 g of CB, half of the carbon black oil mix, phenolic resin, antioxidant, and anti-ozone agent, and after the thickening naphthenic oil, phenolic resin, antioxidant, and anti-ozone agent step, and Akrosorb 29460 was added in the first pass, before stearic acid and zinc oxide, and after the thickening naphthenic oil, phenolic resin, antioxidant, and anti-ozone agent step, and mixed up to 130°C, stearic acid was added and mixed for 60 seconds at 60 RPM, zinc oxide was added and mixed for 60 seconds at 60 RPM, ram cleaning was performed, and the mixture was mixed until a temperature of 150°C was reached at 110 RPM. The results are shown in Table 48 below. Thermal conductivity was not evaluated for these specific examples. [Table 53]

[0179] Example 5: Tire tread base (sub-tread) The following examples demonstrate the usefulness of plasma carbon black when used in tire rubber compositions for use as a tread base component of tires. The tread base is also referred to as the subtread or undertread. The specific rubber formulations shown are representative and not limited to those described. In addition to formulations in which only the elastomer is NR, other elastomer polymers can be used as trace polymer components, including various types of IR, BR, SBR, and epoxidized NR. Various furnace carbon black grades such as N550, N660, N650, N330, and others may be used. Precipitated silica containing or not containing various sulfur-containing organosilanes and / or other coupling agents can be used as fillers. Fillers can also include carbon fillers from the pyrolysis of recycled rubber materials, recycled rubber products such as end-of-life tires, biomass waste, and other sources. Furnace carbon black, clay, graphene, precipitated silica, other inorganic particulate fillers, and carbon fillers recovered from the thermal decomposition of end-of-life tires can be used in various combinations with the plasma carbon black filler of this disclosure at various filler levels. Other adjustments to the formulation can be made for various performance and processability reasons. Specifically, there are various options for the amount and type of curing / vulcanizing components, and for degradation inhibitors such as antioxidants and anti-ozone agents. Processing aids such as oils and tackifying resins of various types and amounts may be used. The embodiments described herein relating to the use of plasma carbon black filler in tire rubber compositions used in tread base components encompass a variety of reasonable tread base formulations.

[0180] The following examples of tire tread base compositions containing plasma carbon black filler exhibit performance equivalent (within about plus or minus 10%) to reference carbon black from the furnace process in standard rubber tests. The production of furnace carbon black generates several tons of CO2 per ton of carbon black produced, while the production of plasma carbon black generates less than 20% of that CO2. These examples show that the plasma carbon black filler in tire tread base components can have a significant positive impact on tire sustainability without substantially impairing rubber properties.

[0181] In examples of tire tread base (sub-tread) compositions, plasma carbon black, when compounded into the rubber formulation, gives a substantially higher (improved) thermal conductivity compared to comparative furnace carbon black, and surprisingly, the predicted advantages for tire manufacturing and tire performance discussed above were discovered.

[0182] The components of an exemplary NR tread base (sub-tread) compound are listed below.

Table 54

Table 55

[0183] Overview of the mixing steps. First pass: Add polymer (natural rubber (NR)) and mix for 120 seconds. Add half of the carbon black and mix for 60 seconds. Add the second half of the carbon black, oil, wax, antioxidant and mix for 60 seconds. Add stearic acid and zinc oxide and mix for 60 seconds. Mix until a drop temperature of 150 °C is reached, including two ram clean-out steps every 30 seconds. Second pass: Add half of the first pass mix and mix for 15 seconds. Add the second half of the first pass mix and mix for 15 seconds. Add CBTS, sulfur, PK900, and CTP and mix until a drop temperature of 105 °C is reached. [Table 56]

[0184] Detailed mixing steps. Banbury first pass: Start temperature 70°C and start RPM 40. Add polymer (SMR-L) and mix for 120 seconds. Add half of dry carbon black (CB) by pouring into the mixer throat and mix for 60 seconds. Add the second half of dry CB, Akrowax 23, Akrosorb 9740, and PD-2 and mix for 60 seconds. Add stearic acid and zinc oxide and mix for 60 seconds. Ram clean and mix for 30 seconds. Ram clean and mix at 100 RPM until the temperature drops to 150°C. Milling first pass: Set the mill water temperature to 162°F and start the mill gap gauge (also known as the mill roll gauge) at 1.2 mm. [Table 57]

[0185] Banbury second pass: Starting temperature 70°C and starting RPM 40. Add half of the non-productive mix (first pass compound) and mix for 15 seconds. Add the second half of the non-productive mix and mix for 15 seconds. Add CBTS, sulfur, PK900, and CTP. Lower the ram and mix at 60 RPM until the temperature drops to 105°C. Milling second pass: Mill water temperature 160°F. Start the mill gap gauge at 1.2 mm for initial banding and set the mill gap gauge to 0.8 mm for pig roll mixing. Starting from one end, make continuous angled cuts as the rubber rolls (also known as "pig rolls") and once the rubber is out of the mill, feed the pig roll back into the mill end-first. Make 10 such pig rolls, alternating the starting edges, and increase the mill gap gauge to 1.2 mm for the final sheet making.

[0186] Rubber properties. Using an NRU02 tread base formulation containing 45 phr of carbon black, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples Y2-Y5) were compared with N550 furnace carbon black (Example Y1), and the results are shown in Table 52. The colloidal properties of the plasma carbon black samples are within the same range as the N550 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 58]

[0187] Using an NRU02 tread base formulation containing 45 phr of carbon black, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples Z2-Z5) were compared with N660 furnace carbon black (Example Z1), and the results are shown in Table 53. The colloidal properties of the plasma carbon black samples are within the same range as the N660 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 59]

[0188] Using an NRU02 tread base formulation containing 45 phr of carbon black, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples AA2-AA5) were compared with N660 furnace carbon black (Example AA1), and the results are shown in Table 54. The colloidal properties of the plasma carbon black samples are within the same range as the N660 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Viscoelastic properties were not evaluated in these specific examples. [Table 60]

[0189] Using an NRU02 tread base formulation containing 45 phr of carbon black, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples AB2-AB5) were compared with N762 furnace carbon black (Example AB1), and the results are shown in Table 55. The colloidal properties of the plasma carbon black samples are within the same range as the N762 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 61]

[0190] The components of an exemplary NR ASTM tread base (subtread) compound are listed below. [Table 62]

[0191] Overview of the mixing steps. Add polymer (natural rubber (NR)) and mix for 30 seconds. Add MBTS and mix for 30 seconds. Add stearic acid and mix for 60 seconds. Add half of zinc oxide and dry carbon black (CB) and mix for 90 seconds. Add the second half of dry CB and mix for 90 seconds. Add sulfur and mix for 60 seconds. Clean the ram and mix until the dropping temperature reaches 125°C.

Table 63

[0192] Detailed mixing steps. Banbury: Start temperature 45°C and start RPM 40. Add polymer (SMR-L) and mix for 30 seconds. Add MBTS and mix for 30 seconds. Add stearic acid and mix for 60 seconds. Add half of dry carbon black (CB) and zinc oxide and mix for 90 seconds. Add the second half of dry CB and mix for 90 seconds. Add sulfur and mix for 60 seconds. Clean the ram and mix at 70 RPM until the dropping temperature reaches 125°C. Milling: Set the water temperature of the mill to 165°F and start with a mill gap gauge (also known as a mill roll gauge) of 1.2 mm.

[0193] Rubber properties. Using an NRD01 ASTM D3192 natural rubber formulation containing 50 phr of carbon black, compare the rubber properties of plasma carbon black fillers of types A1, A2, and A3 (Examples AC2 - AC5 of tire rubber compositions) with N550 furnace carbon black (Example AC1), and show the results in Table 58. The colloidal properties of the plasma carbon black samples are in the same range as the N550 reference furnace carbon black. Examples containing plasma carbon black show rubber performance equivalent (within about plus or minus 10%) to the reference furnace carbon black. In these specific examples, viscoelastic properties and thermal conductivity were not evaluated.

Table 64

[0194] Using an NRD01 ASTM D3192 natural rubber compound containing 50 phr of carbon black, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples AD2-AD5) were compared to N660 furnace carbon black (Example AD1), and the results are shown in Table 59. The colloidal properties of the plasma carbon black samples are within the same range as the N660 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 65]

[0195] Example 6: Tire Tread The examples provide the usefulness of plasma carbon black when used in tire rubber compositions for use as a tread component of tires. The tread—the part of the tire that contacts the road surface—is also referred to as the tread cap to distinguish it from the tread base (subtread). The specific rubber formulations shown are representative and not limiting. The SBR / BR polymer ratio can vary from about 100 / 0 to about 20 / 80 in passenger tire formulations and may include other elastomer polymers, e.g., NR, IR, and lithium (anionic) BR. Two or more types of SBR can be used in combination, and there are many possible commercial options of ESBR and SSBR grades with diverse vinyl and styrene content. Functionalized SSBR and other functionalized elastomers may be used and are further detailed below. The NR / BR polymer ratio can vary from about 100 / 0 to about 20 / 80 in heavy-duty truck tire tread formulations and may include other elastomer polymers, including SBR, IR, and lithium (anionic) BR. Various furnace carbon black grades, such as N110, N134, N234, N220, N330, N339, N375, and others, can be used in tire treads. Fillers can also include carbon fillers from the pyrolysis of recycled rubber materials, recycled rubber products such as end-of-life tires, biomass waste, and other sources. Various types of precipitated silica, with or without a variety of known sulfur-containing organosilanes and / or other coupling agents, can be used as fillers. Furnace carbon black, clay, graphene, precipitated silica, other inorganic particulate fillers, and carbon fillers recovered from the pyrolysis of end-of-life tires can be used at various filler levels and in various combinations with the plasma carbon black disclosed. Other adjustments to the formulation can be made for various performance and processability reasons. Specifically, there are various options for the amount and type of curing / vulcanizing components, and for degradation inhibitors such as antioxidants and anti-ozone agents. Processing aids such as oils and tackifying resins of various types and amounts can be used.The embodiments described herein relating to the use of plasma carbon black fillers in tire rubber compositions used in tread components encompass a variety of reasonable tread formulations.

[0196] Functionalized solution SBR (functionalized SSBR) and other functionalized elastomers can be used, in particular, in tire tread formulations for passenger car tire treads. Functional groups can be incorporated into diene elastomers by coupling agents, polymerization initiators, polymerization terminaters, post-polymerization functionalization approaches, and incorporation of functionalized monomers. For coupling to carbon black, for example, functional groups containing C-Sn bonds or amination functional groups (e.g., aminobenzophenone) may be mentioned. For coupling to inorganic fillers such as silica, for example, silanol functional groups or polysiloxane functional groups, alkoxysilane groups, carboxyl groups, or polyether groups with silanol termini may be mentioned. Other examples of functionalized elastomers include epoxidized elastomers (e.g., SBR, BR, NR, or IR).

[0197] Representative grades of commercially available functionalized SSBRs and functionalized lithium BRs include, but are not limited to, Kumho Petrochemical Company (KKPC), H-series functionalized SSBRs (e.g., grades 5251H, 5270H); Asahi Kasei, Tufdene E-series functionalized SSBRs (e.g., E581, E680) and F-series functionalized SSBRs (e.g., F3440, F3420); LG Chem, F-series functionalized SSBRs (e.g., grades F3438, F1810, F4626E), M-series functionalized SSBRs (e.g., M3626, M1525), functionalized lithium BRs (e.g., F0010); and Arlanxeo, Buna FX-series functionalized SSBRs (e.g., grades FX3432A-2, FX5000). These grades, similar grades from other polymer suppliers, and all other known commercially available functionalized SSBRs, functionalized BRs, and other functionalized diene elastomers may be included in embodiments of the present disclosure.

[0198] Synergistic performance in tread formulations can be achieved between functionalized elastomers and plasma carbon black fillers, and a tread rubber composition can be envisioned in which such plasma carbon black fillers have, for example, (1) surface functional groups introduced to the particle surface through a particle manufacturing process, and / or (2) special functionalizing binders introduced during a pelletizing process. Functional surface groups on carbon black can be made to interact specifically with moieties in the polymer. For example, the functional group may be a polyol on the elastomer, and the group on the carbon black may be an acetonitrile group that can be reacted to form a urea-type moiety. Another possibility is an amine group that reacts with a carbonyl group, and these groups may be on either the carbon black or the elastomer. Carboxylic acid groups can also be added to the surface of carbon black particles(s) through oxidation via combinations of acids and peroxides such as nitric acid, Hammer reagent, modified Hammer reagent, sodium hypochlorite, sulfuric acid, and hydrogen peroxide. Another method for oxidizing the surface is through the use of ozone. Next, the oxygen groups on the surface of the carbon black can be reacted to form other reactive groups, such as unconjugated double bonds. Surface defects can also be created on the carbon black through the oxidation process, which can create reactivity that is beneficial for bonding to the elastomer, creating a tighter bond between the carbon black surface and the elastomer.

[0199] Other reactive groups that can be added include sulfones, quinones, and thioesters. These groups can be added via diazonium chemical reactions. Any group can be added, for example, via sequential addition of sodium thiosulfite, followed by an amino-functionalized thioester or sulfone.

[0200] Additionally, carbon oxide black can be treated with Si69 or several similar sulfidesiloxanes, which may be disulfides or tetrasulfides. Another term is organosilanes having a polysulfide moiety.

[0201] Hydrocarbon resins and natural resins may be rubber components used in tire treads to improve, for example, wet traction and / or other performance or processability characteristics. Examples of hydrocarbon resins include pure monomer resins, DCPD, C5, C9, and C5 / C9-based resins. Examples of natural resins include rosin-based resins and terpene-based resins. These hydrocarbon resins and natural resins can be hydrogenated to varying degrees. Examples of such resins used in tire rubber compositions are referred to, for example, in U.S. Patent No. 10,519,299, U.S. Patent No. 11,236,217, and the references cited herein, which are incorporated herein by reference.

[0202] Tire tread formulations whose primary filler type is furnace carbon black may utilize grades with smaller particle sizes (higher surface area), such as ASTM grades in the N100, N200, and N300 series, including N110, N134, N234, N220, N330, N339, N375, and others.

[0203] There may be furnace carbon black grades available commercially for use in tire tread compositions that have a lower surface area and a higher structure. Two such grades are STSA = 19m 2 ECORAX S204 from Orion with / g and OAN=138ml / 100g, and STSA=19m 2 This is ECORAX S206 from Orion, having a ratio of / g and OAN = 73 ml / 100g. The plasma carbon black fillers of this disclosure are considered to be equivalent to those commercially available grades used in tread rubber formulations, taking into account the range of surface area and structure available from thermal plasma processes.

[0204] Where examples of plasma carbon black fillers are not available for direct comparison with N100, N200, or N300 type carbon blacks, the plasma carbon black fillers are compared with N550, N660, and N772 grades, which are considered relevant furnace carbon black reference materials. Since SBR is a common type of diene elastomer used in passenger car tire treads, a basic SBR rubber compound (as specified in ASTM D3191) is used for carbon black comparisons. These results can also be used to demonstrate the usefulness of plasma carbon black fillers in any rubber compound in which SBR is the primary elastomer type. The usefulness of plasma carbon black as a tire tread filler is also demonstrated in various exemplary rubber compounds used in passenger car and heavy-duty truck (commercial heavy-duty vehicle) tire treads, as detailed below.

[0205] The following examples of tire tread compositions containing plasma carbon black fillers exhibit performance equivalent to (within approximately plus or minus 10%) that of reference carbon black from a furnace process in standard rubber tests. Since furnace carbon black production generates several tons of CO2 per ton of carbon black produced, while plasma carbon black production generates less than 20% of that CO2, these examples demonstrate that plasma carbon black fillers in tire tread components can have a significant positive impact on tire sustainability without substantially impairing rubber properties. Several advantages are noteworthy in terms of improved filler dispersion and reduced hysteresis (tan delta or tanδ) for certain examples of plasma carbon black fillers compared to their respective furnace carbon black references.

[0206] In the tire red composition examples, plasma carbon black, when compounded into the rubber compound, yielded substantially higher (improved) thermal conductivity compared to comparative furnace carbon black, and the predicted advantages for tire manufacturing and tire performance discussed earlier were surprisingly found.

[0207] SBR ASTM formulation. Consistent with ASTM 3191, except for the use of SBR1502 (uncolored antioxidant) instead of SBR1500 (colored antioxidant). These two grades of emulsion SBR are nominally identical, except for the antioxidant type. In some cases, a mixing scheme using two standard mixing passes was employed (as opposed to mixing TBBS with rubber in a two-roll mill as in the standard method), using a Banbury internal mixer with an increased mixing temperature drop in the first pass (unproductive), as indicated in the related matters below.

[0208] The components of an exemplary ESD01 tread compound are listed below. [Table 66]

[0209] Summary of mixing steps. Modified ASTM standard compound for testing carbon black in SBR by substituting SBR1500 with SBR1502. First pass: Add half of the SBR, zinc oxide, stearic acid, then the second half of the SBR and mix at 30 RPM for 30 seconds. Add carbon black and sulfur and mix at 30 RPM until the temperature drops to 100°C. Second pass: Mix in a 2-roll mill and add TBBS here. [Table 67]

[0210] Detailed mixing steps. Banbury: Starting temperature 15°C and starting RPM 30. Add half of the polymer (SBR1502), zinc oxide, stearic acid, then the second half of SBR1502 and mix for 15 seconds. Add carbon black and sulfur and mix for 30 seconds. Ram clean and mix for 25 seconds. Ram clean and mix at 30 RPM until the temperature drops to 100°C. Milling: Ensure the condenser is on and set to 45°F, and start the mill roll gauge at 1.2 mm. Pig Rolling: Mix TBBS into rolls. Set the mill gap gauge to 0.8 mm for pig roll mixing. Starting from one end, make continuous angled cuts as the rubber rolls (also known as "pig rolls"), and once the rubber is out of the mill, feed the pig roll back into the mill end-first. Make 10 such pig rolls, alternating the starting edges. In the final sheet fabrication, the mill gap gauge is increased to 1.2 mm.

[0211] Rubber properties. Using the ASTM ESBR tread compound (ESD01), the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples AE2-AE5) were compared with N550 furnace carbon black (Example AE1), and the results are shown in Table 62. The colloidal properties of the plasma carbon black samples are within the same range as the N550 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 68]

[0212] Using the ASTM ESBR tread compound (ESD01), the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples AF2-AF5) were compared with N660 furnace carbon black (Example AF1), and the results are shown in Table 63. The colloidal properties of the plasma carbon black samples are within the same range as the N660 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 69]

[0213] Using the ASTM ESBR tread compound (ESD01), the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples AG2-AG5) were compared with N660 furnace carbon black (Example AG1), and the results are shown in Table 64. The colloidal properties of the plasma carbon black samples are within the same range as the N660 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 70]

[0214] Using the ASTM ESBR tread compound (ESD01), the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples AH2-AH5) were compared with N772 furnace carbon black (Example AH1), and the results are shown in Table 65. The colloidal properties of the plasma carbon black samples are within the same range as the N772 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 71]

[0215] Using the ASTM ESBR tread compound (ESD01), the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples AI2-AI5) were compared with N772 furnace carbon black (Example AI1), and the results are shown in Table 66. The colloidal properties of the plasma carbon black samples are within the same range as the N772 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 72]

[0216] Using ASTM ESBR tread compound (ESD01), the colloidal properties of the filler were set to 24.2-43.0 m 2The rubber properties of A1, A2, and A3 type plasma carbon black fillers were evaluated, varying across a range of nitrogen surface area (N2SA) per g and an OAN structure range of 60.3–130.3 mL / 100 g. The number of examples considered was 141, including examples nominally similar to Examples AE2–AE5, AF2–AF5, AG2–AG5, AH2–AH5, and AI2–AI5 in Tables 62–66 above. These examples allowed for the evaluation of the dependence of thermal conductivity (k) on oil absorption (OAN) compared to equivalent furnace carbon black grades N772, N660, N550, N330, N326, N220, and N234. As shown in Figure 16, the plasma carbon black examples have k values ​​23% to 40% higher than the corresponding furnace carbon black k values ​​for the same OAN, and the plasma carbon black examples show a strong dependence of k on OAN compared to the k of furnace carbon black, which is almost independent of OAN. For example, the slope of the line (from linear regression) fitted to the plasma carbon black data in Figure 16 is almost four times higher than the slope of the line fitted to the furnace carbon black data. Similar results are noted when k is plotted against compressed oil absorption (COAN), which is also shown in Figure 16.

[0217] Figure 17 is a graph of thermal conductivity versus aggregate size quantified using dynamic light scattering (DLS), and also demonstrates a significant increase (improvement) in thermal conductivity (k) of plasma carbon black versus furnace carbon black. As shown in Figure 17, in the ASTM D3191 ESBR formulation (ESD01), a 24% increase in thermal conductivity of plasma carbon black compared to furnace carbon black at a constant Z-average aggregate size is noteworthy. Disk centrifugal photoprecipitation, another technique for measuring the aggregate size of carbon black fillers, may also be used.

[0218] Using the ESD01 ASTM ESBR tread compound, the rubber properties of A2, A3, B2, and B3 type plasma carbon black fillers (tire rubber composition examples AT2-AT5) were compared with N660 furnace carbon black (Example AT1), and the results are shown in Table 67. The B2 and B3 type plasma carbon black fillers contain silica in the binder, and the special additive for the B3 type plasma CB is Si69(TESPT) silane. The colloidal properties of the plasma carbon black samples are within the same range as the N660 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Thermal conductivity was not evaluated for these specific examples. [Table 73]

[0219] The mixing conditions in the following examples (Tables 68 to 71) were modified from the ASTM SBR standard as follows: the mixing stage was increased to a temperature drop of 150°C by increasing the mixer RPM to 72, and the productive mixing stage was carried out in the same manner as the ASTM SBR mix.

[0220] Using an ESD04 high-temperature drop SBR rubber compound containing 50 phr carbon black, the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples AJ2-AJ5) were compared with N660 furnace carbon black (Example AJ1), and the results are shown in Table 68. The colloidal properties of the plasma carbon black samples are within the same range as the N660 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). Viscoelastic properties and thermal conductivity were not evaluated in these specific examples. [Table 74]

[0221] The rubber properties of A2 type plasma carbon black fillers (tire rubber composition examples AQ1-AQ5) were compared using ESD04 high-temperature drop SBR rubber compounding containing 50 phr of carbon black, and the results are shown in Table 69. The colloidal properties of the plasma carbon black samples in Table 69 are within the same range as the N772, N660, N650, and N550 reference furnace carbon blacks in Table 71. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon blacks in Table 71 (within approximately plus or minus 10%). [Table 75]

[0222] The rubber properties of A2 type plasma carbon black fillers (tire rubber composition examples AR1-AR5) were compared using ESD04 high-temperature drop SBR rubber compound containing 50 phr carbon black, and the results are shown in Table 70. The colloidal properties of the plasma carbon black samples in Table 70 are within the same range as the N772, N660, N650, and N550 reference furnace carbon blacks in Table 71. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon blacks in Table 71 (within approximately plus or minus 10%). [Table 76]

[0223] Using ESD04 high-temperature drop SBR rubber compounding containing 50 phr carbon black, the rubber properties of A2 type plasma carbon black fillers from Tables 69 and 70 (Tire Rubber Composition Examples AQ1-AQ5 and AR1-AR5) were compared with furnace carbon blacks N772, N660, N650, and N550 (Tire Rubber Composition Examples AS1-AS4), and the results for furnace carbon black are shown in Table 71. The colloidal properties of the plasma carbon black samples in Tables 69 and 70 are within the same range as the reference furnace carbon blacks N772, N660, N650, and N550 in Table 71. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon blacks in Table 71 (within approximately plus or minus 10%). [Table 77]

[0224] Example 7: Silica passenger car tire tread In passenger car tires, precipitated silica can be used as a filler in the tread, including in combination with sulfur-containing organosilanes added as silica-polymer coupling agents. Organosilanes can be bis-(triethoxysilylpropyl)tetrasulfide (TESPT) (also known as Si69, manufactured by Evonik), bis-(triethoxysilylpropyl)disulfide (TESPD) (also known as Si75, manufactured by Evonik), silanes having mercaptan or blocked mercaptan groups, non-sulfur-containing silanes such as octyltriethoxysilane, any equivalent or close derivatives thereof, or any combination thereof. Exemplary commercially available silane coupling agents include Si69, primarily composed of TESPT, and Si75, primarily composed of TESPD, both manufactured by Evonik. Other companies offer grades of TESPT and TESPD supplied in liquid form or on solid carriers such as carbon black. Additional sulfur-containing organosilane coupling agents include 3-octanoylthio-1-propyltriethoxysilanes and mercapto-functional organosilanes, including so-called block mercaptan varieties such as Si363 silane produced by the NXT series of silanes from Evonik or Momentive.

[0225] In addition to various grades of precipitated silica, fumed silica, silica from so-called sustainable sources such as rice husk ash, and other types of silica can be used in tire compounds for various tire components, including the tread. Any silica filler from any source is included herein. Pre-treated silica, which is already incorporated into the silica filler by the manufacturer, may also be used, in contrast to organosilanes, which are added as separate raw materials during rubber mixing.

[0226] Silica and carbon black can be used together as fillers in tire treads and other tire components to achieve a desirable balance of tire performance characteristics. For example, tire tread formulations containing silica fillers and organosilanes reduce rolling resistance, improve wet traction, and / or provide other tire performance advantages compared to compositions containing furnace carbon black fillers alone. Plasma carbon black can be incorporated into silica-containing tread rubber formulations, including cases where precipitated silica is the primary filler component and cases where carbon black is the primary filler component. It can be assumed that silica can be present at 0.5–99.5%, and carbon black can also be present at 0.5–99.5%. The carbon black present may be plasma carbon black, or a mixture of both plasma carbon black and furnace carbon black. Additionally, recovered carbon black can be added at up to 30–40%, or any combination of these fillers, as well as other additive fillers such as nanotubes and graphene can be used. This is non-limiting in that small amounts of these components can cause a significant difference in performance. Additionally, small amounts of plasma carbon black can dramatically improve the environmental impact of the resulting products. Products with more plasma carbon black added to elastomer / carbon black composites will have a smaller CO2 emission footprint.

[0227] Examples of passenger car tire tread compounding include, but are not limited to, the compoundings shown in the table below. The compounding may include variations in the relative fill amounts of silica, plasma carbon black, and / or other components, as well as parameters.

[0228] The components of an example SSBRT01 silica tread compound are listed below. [Table 78] [Table 79] [Table 80]

[0229] Summary of mixing steps. First pass: Add polymers (natural rubber (NR) and SSBR) and mix for 60 seconds. Add half silica and carbon black / plasticizer mix and mix for 30 seconds. Add Si69 and mix for 30 seconds. Add the second half silica and mix for 30 seconds. Mix, including the clean-out step, maintain a batch temperature of 140°C for 120 seconds, and mix until the temperature drops to 150°C. Second pass: Add the unproductive mix from the first pass and mix for 30 seconds. Add the anti-ozone agent, zinc oxide, and stearic acid and mix for 30 seconds. Mix, including the clean-out step, until the temperature drops to 150°C. Third pass: Add the unproductive mix from the second pass and mix for 30 seconds. Add TBBS, TBZTD, DPG, and sulfur and mix until the temperature drops to 100°C. [Table 81]

[0230] Detailed mixing steps. Banbury First Pass: Starting temperature 40°C and starting RPM 30. Add polymers (Diene 140ND and Buna VSL4526-2HM) and mix at 120 RPM for 60 seconds. While mixing continues, manually prepare a thickening oil by pouring about half of the carbon black (CB) into the oil. Add half of Mansil 190G (precipitated silica). Add the remaining half of the dry CB. Add the TDAE oil (thickening oil containing about half of the CB) by pouring it into the mixer throat and mix at 60 RPM for 30 seconds. Add Si69 and mix for 30 seconds. Add the second half of Mansil 190G and mix for 30 seconds. Ram clean and mix at 150 RPM to 140°C, maintain 140°C by mixing at 90 RPM for 120 seconds, and mix at 130 RPM until the temperature drops to 150°C. Milling pass 1: Set the mill water temperature to 45°F and start with the mill gap gauge (also known as the mill roll gauge) at 1.2 mm. [Table 82]

[0231] Banbury second pass: Start at a temperature of 40°C and 30 RPM. Add the unproductive mix from the first pass and mix for 30 seconds. Add 6 PPD, zinc oxide, and stearic acid and mix for 30 seconds. Perform ram cleaning. Lower the ram and mix at 120 RPM until the temperature drops to 150°C. Milling second pass: Start with a mill water temperature of 45°F and a mill gap gauge of 1.2 mm for initial banding. [Table 83]

[0232] Banbury third pass: Temperature 40°C and starting RPM 30. Add the unproductive mix from the second pass and mix at 75 RPM for 30 seconds. Add TBBS, TBZTD, DPG, and sulfur and mix at 40 RPM for 30 seconds, then mix at 90 RPM until the temperature drops to 100°C. Milling third pass: Mill water temperature 45°F. Start with a mill gap gauge of 1.2 mm for initial banding and set the mill gap gauge to 0.8 mm for pig roll mixing. Starting from one end, make continuous angled cuts as the rubber rolls (also known as "pig rolls"), and once the rubber is out of the mill, feed the pig roll back into the mill with the end first. Make 10 such pig rolls, alternating the starting edges, and increase the mill gap gauge to 1.2 mm for the final sheet making.

[0233] Rubber properties. Using the SSBRT01 passenger car tire tread compound containing 60 phr of silica and 15 phr of carbon black (carbon black as a trace amount of filler), the rubber properties of A1 and A3 type plasma carbon black fillers (tire rubber composition examples AK2-AK4) were compared with N772 furnace carbon black (Example AK1), and the results are shown in Table 76. The colloidal properties of the plasma carbon black samples are within the same range as the N772 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within approximately plus or minus 10%). [Table 84]

[0234] Rubber samples containing plasma carbon black exhibit an increase (improvement) in thermal conductivity (k) compared to rubber samples containing furnace carbon black. The increase in k ranged from 5% to 9%, even when carbon black was included as a filler in only 15 phr of the SSBRT01 tread formulation compared to precipitated silica at 60 phr. Even with such low carbon black filler amounts, a substantially 3.1 to 7.5-fold (210% to 650%) improvement in electrical conductivity was observed (electrical conductivity is the reciprocal of the electrical volume resistivity reported in Table 76). Tire treads require sufficient conductivity to ensure that the vehicle is electrically grounded to the road. Since silica is not a conductive filler, carbon black can be added to silica-containing tread formulations to provide the necessary conductivity. The electrical conductivity results, including those in Table 76 above, demonstrate that the plasma carbon black formulations of this disclosure outperform furnace carbon black in this function.

[0235] The components of an example SSBRT02 silica tread compound are listed below. [Table 85] [Table 86] [Table 87]

[0236] Summary of mixing steps. First pass: Add polymers (natural rubber (NR) and SSBR) and mix for 60 seconds. Add half silica and carbon black / plasticizer mix and mix for 30 seconds. Add Si69 and mix for 30 seconds. Add the second half silica and mix for 30 seconds. Include a clean-out step. Mix and maintain a batch temperature of 140°C for 120 seconds, then mix until the temperature drops to 150°C. Second pass: Add the unproductive mix from the first pass and mix for 30 seconds. Add anti-ozone agent, zinc oxide, and stearic acid and mix for 30 seconds. Include a clean-out step. Mix until the temperature drops to 150°C. Third pass: Add the unproductive mix from the second pass and mix for 30 seconds. Add TBBS, TBZTD, DPG, and sulfur and mix until the temperature drops to 100°C. [Table 88]

[0237] Detailed mixing steps. Banbury First Pass: Starting temperature 40°C and starting RPM 30. Add polymers (diene 140ND and Buna VSL4526-2HM) and mix at 120 RPM for 60 seconds. While mixing continues, manually prepare a thickening oil by pouring about 25% of carbon black (CB) into the oil. Add half of Mansil 190G, add dry CB (the remaining about 75%), and pour into the mixer throat to add the TDAE oil (thickening oil containing about 25% of CB) and mix at 60 RPM for 30 seconds. Add Si69 and mix for 30 seconds. Add the second half of Mansil 190G and mix for 30 seconds. Ram clean and mix at 150 RPM to 140°C, maintain 140°C by mixing at 90 RPM for 120 seconds, and mix at 130 RPM until the temperature drops to 150°C. Milling pass 1: Set the mill water temperature to 45°F and start with the mill gap gauge (also known as the mill roll gauge) at 1.2 mm. [Table 89]

[0238] Banbury second pass: Start at a temperature of 40°C and 30 RPM. Add the unproductive mix from the first pass and mix for 30 seconds. Add 6 PPD, zinc oxide, and stearic acid and mix for 30 seconds. Perform ram cleaning. Lower the ram and mix at 120 RPM until the temperature drops to 150°C. Milling second pass: Start with a mill water temperature of 45°F and a mill gap gauge of 1.2 mm for initial banding. [Table 90]

[0239] Banbury third pass: Temperature 40°C and starting RPM 30. Add the unproductive mix from the second pass and mix at 75 RPM for 30 seconds. Add TBBS, TBZTD, DPG, and sulfur and mix at 40 RPM for 30 seconds, then mix at 90 RPM until the temperature drops to 100°C. Milling third pass: Mill water temperature 45°F. Start with a mill gap gauge of 1.2 mm for initial banding and set the mill gap gauge to 0.8 mm for pig roll mixing. Starting from one end, make continuous angled cuts as the rubber rolls (also known as "pig rolls"), and once the rubber is out of the mill, feed the pig roll back into the mill with the end first. Make 10 such pig rolls, alternating the starting edges, and increase the mill gap gauge to 1.2 mm for the final sheet making.

[0240] Rubber properties. Using the SSBRT02 passenger car tire tread formulation containing 15 phr of silica and 60 phr of carbon black (carbon black as the main filler), the rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples AL2-AL5) were compared with N772 furnace carbon black (Example AL1), and the results are shown in Table 81. The colloidal properties of the plasma carbon black samples are within the same range as the N772 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black (within plus or minus approximately 10%).

[0241] Regarding the thermal conductivity (k) properties of plasma carbon black, the remarkable and surprising advantages of plasma carbon black over furnace carbon black in the passenger car tire tread compound SSBRT02 were noted. This was 32% to 36% higher (improved) compared to N772 furnace carbon black. Although such N772 type carbon black is not commonly used as a primary filler in treads, the comparative advantages of plasma carbon black over furnace carbon black (thermal conductivity, sustainability, etc.) should be retained in carbon black tread grades. [Table 91]

[0242] Example 8: Large truck tire tread The components of an example NRBRT01 tread compound are listed below. [Table 92] [Table 93]

[0243] Summary of mixing steps. First pass: Add polymers (natural rubber (NR) and diene 140ND) and mix for 60 seconds. Add various grades of carbon black and mix for 60 seconds. Add carbon black / plasticizer mix, antioxidant, and anti-ozone agent and mix for 60 seconds. Add stearic acid and zinc oxide and mix for 15 seconds. Include a clean-out step. Mix until a temperature drop of 150°C is reached. Second pass: Add TBBS, CTP, and sulfur to the first pass mix and mix until a temperature drop of 105°C is reached. [Table 94]

[0244] Detailed mixing steps. Banbury First Pass: Start temperature 80°F and start RPM 40. Add polymers (SMR-L and diene 140ND) and mix for 60 seconds. While mixing continues, prepare thickening oil by hand by pouring about 25% of carbon black (CB) into the oil. Add dry CB (the remaining about 75%) by pouring into the mixer throat and mix for 60 seconds. Add naphthenic oil (thickening oil containing about 25% of N234CB), add TMQ and 6PPD and mix for 60 seconds. Add stearic acid and zinc oxide and mix for 15 seconds. Ram clean and mix at 80 RPM until the temperature drops to 150°F. Milling First Pass: Set the mill water temperature to 80°F and start the mill gap gauge (also known as the mill roll gauge) at 1.2 mm. [Table 95]

[0245] Banbury second pass: Temperature 80°F and starting RPM 40. Adding ingredients: Add the non-productive mix (first pass compound), then add TBBS, CTP, and sulfur. Lower the ram and mix at 60 RPM until the temperature drops to 105°F. Milling second pass: Mill water temperature 80°F. Start mill gap gauge at 1.2mm for initial banding and set mill gap gauge to 0.8mm for pig roll mixing. Starting from one end, continuously angle cuts are made as the rubber rolls (also known as "pig rolls"), and once the rubber is out of the mill, the pig roll is fed back into the mill end-first. Ten such pig rolls are made, alternating the starting edges. For final sheet making, increase mill gap gauge to 1.2mm.

[0246] Rubber Properties. The rubber properties of A2 and A3 type plasma carbon black fillers were compared using the NRBRT01 heavy truck tire tread formulation. The colloidal properties of the plasma carbon black samples were within the same range as the N660 reference furnace carbon black. A mixture of 15 phr of plasma carbon black and 45 phr of N234 furnace carbon black was used in tire rubber composition examples AM3 to AM5. Two furnace carbon black reference examples were used: NRBRT01 formulation containing 15 phr of N660 furnace carbon black and 45 phr of N234 furnace carbon black (Example AM1), and NRBRT01 formulation containing 57 phr of pure N234 furnace carbon black (Example AM2). The results are shown in Table 85. The examples containing plasma carbon black showed rubber performance equivalent to the reference furnace carbon black examples (within plus or minus approximately 10%). [Table 96]

[0247] The rubber properties of A2 and A3 type plasma carbon black fillers were compared using the NRBRT01 heavy truck tire tread formulation. The colloidal properties of the plasma carbon black samples were within the same range as the N660 reference furnace carbon black. A mixture of 15 phr of plasma carbon black and 45 phr of N134 furnace carbon black was used in tire rubber composition examples AN3 to AN5. Two furnace carbon black reference examples were used: an NRBRT01 formulation containing 15 phr of N660 furnace carbon black and 45 phr of N134 furnace carbon black (Example AN1), and an NRBRT01 formulation containing 57 phr of pure N134 furnace carbon black (Example AN2). The results are shown in Table 86. The examples containing plasma carbon black showed rubber performance equivalent to the reference furnace carbon black examples (within plus or minus approximately 10%). [Table 97]

[0248] Using the NRBRT01 heavy-duty truck tire tread formulation containing 65 phr of N772 type carbon black, the rubber properties of A2 and A3 type plasma carbon black fillers (tire rubber composition examples AO2-AO5) were compared with N772 furnace carbon black (Example AO1), and the results are shown in Table 87. The colloidal properties of the plasma carbon black samples are within the same range as the N772 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to the reference furnace carbon black examples (within approximately plus or minus 10%).

[0249] The remarkable and surprising advantages of plasma carbon black over furnace carbon black in the NRBRT01 heavy-duty truck tire tread formulation containing 65 phr carbon black in terms of thermal conductivity (k) were noted. This was 35% to 44% higher (improved) in the plasma carbon black tire rubber composition compared to the N772 reference furnace carbon black composition. Although N772 is not commonly used in tire tread compositions, fillers with colloidal properties similar to typical tread-grade furnace carbon black can be produced by a thermal plasma process, as shown in the following truck tire tread formulation examples (Table 88). [Table 98]

[0250] Using the NRBRT01 passenger car tire tread compound containing 50 phr of N234 type carbon black, the rubber properties of a type A2 plasma carbon black filler (tire rubber composition example AP2) were compared with N234 furnace carbon black (example AP1), and the results are shown in Table 88. The colloidal properties of the plasma carbon black samples are within the same range as those of the N234 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance equivalent to that of the reference furnace carbon black (within approximately plus or minus 10%).

[0251] Regarding the thermal conductivity (k) properties, the remarkable and surprising advantages of plasma carbon black filler over furnace carbon black in the NRBRT01 heavy truck tire tread formulation containing 50 phr carbon black were noted. This was significantly 62% higher (improved) in the plasma carbon black tire rubber composition compared to the N234 reference furnace carbon black. M234 is thermal plasma carbon black. [Table 99]

[0252] Example 9: Wire skim compound The following examples demonstrate the usefulness of plasma carbon black as a filler in tire rubber compositions for use as wire skim (also known as wire coat) compounds in the belt skim and bead filler components of tires. These tire rubber compositions can typically be used to coat reinforced steel cords coated with brass. Processes for incorporating the uncured rubber compound onto the steel cords may include, but are not limited to, calendering, pultrusion, and other wire coating operations. The specific rubber formulations shown are representative and not limited to. In addition to formulations where only the elastomer is NR, other elastomer polymers, including various types of IR, BR, SBR, and epoxidized NR, may be used as trace polymer components. Various furnace carbon black grades used include N326, N330, N550, and others. Precipitated silica containing or not containing a variety of known sulfur-containing organosilanes and / or other coupling agents can be used as fillers. Furnace carbon black, clay, graphene, precipitated silica, other inorganic particulate fillers, and carbon fillers recovered from the thermal decomposition of end-of-life tires can be used in various combinations with the plasma carbon black filler of this disclosure at various filler levels.

[0253] Various rubber components / additives may be included in the rubber formulation to promote adhesion between the steel cord and the wire skim rubber composition. Wire coating formulations may include reactive resins (also known as methylene acceptors) such as resocinol, resocinol-formaldehyde, phenol-formaldehyde, and cardanol, and related materials typically used in combination with methylene donors such as hexamethoxymethylmelamine (HMMM) or hexamethylenetetramine (HMT). Wire skim formulations may include metal adhesion promoters, including cobalt salts of organic acids, hydroxybenzoic acid, resocinol, complexes of organocalt and boron, and mixtures thereof. Cobalt naphthenate and cobalt boro-neodecanate are specific examples. In some cases, precipitated silica may be included, for example, to improve rubber-metal adhesion. The components mentioned above are intended as representative examples and not as limiting examples. Various steel wire pretreatments and coatings, as well as various components added to rubber formulations, to promote bonding between steel cords and rubber are discussed and cited in WJ Van Ooij, P.B. Harakuni, and G. Buytaert, Rubber Chem. Technol. 82:315-339 (2009), which are incorporated herein by reference. Additional materials used in wire coat formulations of tire belt skim (also known as belt coat) and bead filler components are described in U.S. Patent Publications 2019 / 0232718 and 2007 / 0010606, and U.S. Patents 9,023,928, 4,258,770, 5,126,501, and 4,594,381. Steel cords may also be coated with adhesive compositions such as resocinol-formaldehyde-latex (RFL) coatings.

[0254] Other formulation adjustments may be made for various performance and processability reasons. Specifically, there are various options for the amount and type of curing / vulcanizing components, and for degradation inhibitors such as antioxidants and anti-ozone agents. Processing aids such as oils and tackifying resins of various types and amounts may be used. The embodiments described herein relating to the use of plasma carbon black fillers in tire rubber compositions used in wire skim formulations encompass a variety of reasonable wire coat formulations.

[0255] Examples of suitable rubber formulations for wire skim compounds for bead fillers and belt skim components for tires are given on pages 78-80 and 110 of *The Rubber Formulary* by PACiullo and N. Hewitt (Noyes Publications, Norwich, NY, USA, 1999), which is incorporated herein by reference. Several representative formulations are also summarized in the table in JSDick, “Utilizing the RPA Variable Temperature Analysis for More Effective Tire Quality Assurance,” conference paper / proceeding, International Tire Exhibition & Conference (ITEC), Akron, Ohio, September 16-18, 2008.

[0256] The following examples of tire wire skim compositions containing plasma carbon black filler demonstrate performance equivalent to (within approximately plus or minus 10%) that of reference carbon black from a furnace process in standard rubber tests. Since furnace carbon black production generates several tons of CO2 per ton of carbon black produced, while plasma carbon black production generates less than 20% of that CO2, these examples demonstrate that plasma carbon black filler in tire wire skim compositions for belt skim and bead filler components can have a significant positive impact on tire sustainability without substantially impairing rubber properties.

[0257] In examples of tire wire skim compositions, plasma carbon black, when compounded into rubber formulations, yielded substantially higher (improved) thermal conductivity compared to comparable furnace carbon black fillers, and the previously discussed predicted advantages to tire manufacturing and tire performance were surprisingly found.

[0258] The components of an exemplary NRK01 wire skim compound are listed below. [Table 100] [Table 101]

[0259] Summary of mixing steps. First pass: Add polymer (natural rubber (NR)) and mix for 60 seconds. Add half of carbon black and mix for 60 seconds. Add the second half of carbon black and plasticizer mix, antioxidant, anti-ozone agent, and resocinol and mix for 60 seconds. Add stearic acid and zinc oxide and mix for 20 seconds. Include clean-out step. Mix until a temperature drop of 150°C is reached. Second pass: Add HMMM, TBBS, and Crystex CurePro to the first pass mix and mix until a temperature drop of 105°C is reached. [Table 102]

[0260] Detailed mixing steps. Banbury First Pass: Start temperature 80°F and start RPM 40. Add polymer (SMR-L) and mix for 60 seconds. While mixing continues, manually prepare thickening oil by pouring about 25% of carbon black (CB) into the oil. Add dry CB (the remaining about 75%) by pouring into the mixer throat and mix for 60 seconds. Add naphthenic oil (thickening oil containing about 25% of CB), add antioxidant DQ and resocinol and mix for 60 seconds. Add stearic acid and zinc oxide and mix for 20 seconds. Ram clean and mix at 100 RPM until the temperature drops to 150°F. Milling First Pass: Set the mill water temperature to 140°F and start the mill gap gauge (also known as the mill roll gauge) at 1.2 mm. [Table 103]

[0261] Banbury second pass: Start temperature 80°C and 40 RPM. Add ingredients: Add non-productive mix (first pass compound), then add HMMM, TBBS, and Crystex CurePro. Lower the ram and mix at 60 RPM until the temperature drops to 105°C. Milling second pass: Mill water temperature 140°F. Start mill gap gauge at 1.2mm for initial banding and set mill gap gauge to 0.8mm for pig roll mixing. Starting from one end, continuously angle cuts are made as the rubber rolls (also known as "pig rolls"), and once the rubber comes off the mill, the pig roll is fed back into the mill end-first. Ten such pig rolls are made, alternating the starting edges. For final sheet making, increase the mill gap gauge to 1.2mm.

[0262] Rubber properties. Using an NRK01 wire skim (also known as wire coat) formulation, the rubber properties of a Type A2 plasma carbon black filler (tire rubber composition example AV2) were compared with N326 furnace carbon black (example AV1), and the results are shown in Table 92. The colloidal properties of the plasma carbon black samples are within the same range as N326 reference furnace carbon black (a common grade of furnace carbon black used in steel belt skim and bead filler compounds). The examples containing the plasma carbon black filler exhibited rubber performance (within approximately plus or minus 10%) equivalent to the reference furnace carbon black, including the same curing adhesion, which predicts bonding performance similar to brass-coated steel cord.

[0263] Regarding the thermal conductivity (k) characteristics of tire rubber compositions, the remarkable and surprising advantages of plasma carbon black over furnace carbon black in tire wire skim formulation NRK01 were noted. This was 27% higher (improved) in the plasma carbon black tire rubber composition compared to the reference furnace carbon black N326. M326 is a thermal plasma carbon black sample. [Table 104]

[0264] The rubber properties of A1, A2, and A3 type plasma carbon black fillers (tire rubber composition examples AW2-AW5) were compared to N772 furnace carbon black (Example AW1) using an NRK01 wire skim formulation modified with 65 phr of carbon black compared to the original 55 phr, and the results are shown in Table 93. Since the NRK01 formulation originally used N326, a higher carbon black filler amount of 65 phr was used to account for the relative reinforcement difference between N772 and N326. The colloidal properties of the plasma carbon black samples are in a similar range to the N772 reference furnace carbon black. The examples containing plasma carbon black exhibit rubber performance (within plus or minus approximately 10%), including the same curing adhesion, which is equivalent to the reference furnace carbon black, and this predicts similar bonding performance to brass-coated steel cords.

[0265] Regarding the thermal conductivity (k) characteristics of tire rubber compositions, the remarkable and surprising advantages of plasma carbon black over furnace carbon black in tire wire skim formulation NRK01 were noted. This was 37% to 42% higher (improved) in the plasma carbon black tire rubber composition compared to the N772 reference furnace carbon black. [Table 105]

[0266] The rubber properties of A2 and A3 type plasma carbon black fillers were compared using NRK01 wire skim formulations. The colloidal properties of the plasma carbon black samples were in a similar range to those of the N772 reference furnace carbon black. A mixture of 27.5 phr of plasma carbon black and 27.5 phr of N234 furnace carbon black (a 50 / 50 mixture of plasma CB and furnace CB) was used in tire rubber composition examples AX3 to AX5. Two furnace carbon black reference examples were used: an NRK01 formulation containing 27.5 phr of N772 furnace carbon black and 27.5 phr of N234 furnace carbon black (Example AX1), and an NRK01 formulation containing 55 phr of N326 furnace carbon black (Example AX2) were used to form a 50 / 50 mixture in the formulation. The results are shown in Table 94. Examples containing plasma carbon black filler exhibit rubber performance (within approximately plus or minus 10%), including the same curing adhesion as reference furnace carbon black, which suggests similar bonding performance to brass-coated steel cords.

[0267] The remarkable and surprising advantages of plasma carbon black over furnace carbon black in tire wire skim formulation NRK01 regarding thermal conductivity (k) are noteworthy. Compared to the N772 / N234 reference material (Example AX1), the thermal conductivity was 15% to 22% higher (improved) in the plasma carbon black example. Compared to the N326 reference material (Example AX2), the thermal conductivity was 11% to 18% higher (improved) in the plasma carbon black example. Even when diluted 50% with a mixture of N234 furnace carbon black, plasma carbon black still provided a significant increase in the thermal conductivity (k) of the tire rubber composition compared to the full furnace carbon black reference example. [Table 106]

[0268] The components of an exemplary NRK03 wire skim compound are listed below. [Table 107] [Table 108]

[0269] Summary of mixing steps. First pass: Add polymer (natural rubber (NR)) and mix for 60 seconds. Add half carbon black and cobalt naphthenate and mix for 60 seconds. Add the second half carbon black / plasticizer mix, antioxidant, anti-ozone agent, and resocinol and mix for 60 seconds. Add stearic acid and zinc oxide and mix for 20 seconds. Include clean-out step. Mix until a temperature drop of 150°C is reached. Second pass: Add HMMM, TBBS, and Crystex CurePro to the first pass mix and mix until a temperature drop of 105°C is reached. [Table 109]

[0270] Detailed mixing steps. Banbury First Pass: Start temperature 80°F and start RPM 40. Add polymer (SMR-L) and mix for 60 seconds. While mixing continues, manually prepare thickening oil by pouring about 25% of carbon black (CB) into the oil. Add dry CB (the remaining about 75%) and cobalt naphthenate by pouring into the mixer throat and mix for 60 seconds. Add naphthenic oil (thickening oil containing about 25% of CB), add antioxidant DQ and resocinol and mix for 60 seconds. Add stearic acid and zinc oxide and mix for 20 seconds. Ram clean and mix at 100 RPM until the temperature drops to 150°F. Milling First Pass: Set the mill water temperature to 140°F and start the mill gap gauge (also known as the mill roll gauge) at 1.2 mm. [Table 110]

[0271] Banbury second pass: Start temperature 80°C and 40 RPM. Add ingredients: Add non-productive mix (first pass compound), then add HMMM, TBBS, and Crystex CurePro. Lower the ram and mix at 60 RPM until the temperature drops to 105°C. Milling second pass: Mill water temperature 140°F. Start mill gap gauge at 1.2mm for initial banding and set mill gap gauge to 0.8mm for pig roll mixing. Starting from one end, continuously angle cuts are made as the rubber rolls (also known as "pig rolls"), and once the rubber comes off the mill, the pig roll is fed back into the mill end-first. Ten such pig rolls are made, alternating the starting edges. For final sheet making, increase the mill gap gauge to 1.2mm.

[0272] Rubber properties. Using an NRK03 wire skim formulation modified with 65 phr of carbon black compared to the original 55 phr, the rubber properties of A2 and A3 type plasma carbon black fillers (tire rubber composition examples AY2-AY4) were compared with N772 furnace carbon black (Example AY1), and the results are shown in Table 98. Since the NRK03 formulation originally used N326, a higher carbon black filler amount of 65 phr was used to account for the relative reinforcement difference between N772 and N326. The colloidal properties of the plasma carbon black samples are in a similar range to the N772 reference furnace carbon black. The examples containing plasma carbon black fillers exhibit rubber performance (within plus or minus approximately 10%), including the same curing adhesion, which is equivalent to the reference furnace carbon black, and this predicts similar bonding performance to brass-coated steel cords.

[0273] Regarding the thermal conductivity (k) properties of tire rubber compositions, the remarkable and surprising advantages of plasma carbon black over furnace carbon black in tire wire skim formulation NRK03 were noted. This was significantly higher (improved) by 46% to 51% in the plasma carbon black tire rubber composition compared to the N772 reference furnace carbon black. [Table 111]

[0274] The rubber properties of A2 and A3 type plasma carbon black fillers were compared using an NRK03 wire skim formulation containing 1 phr of cobalt naphthenate. The colloidal properties of the plasma carbon black samples were in a similar range to those of the N772 reference furnace carbon black. A mixture of 27.5 phr of plasma carbon black and 27.5 phr of N234 furnace carbon black (a 50 / 50 mixture of plasma CB and furnace CB) was used in tire rubber composition examples AZ3 to AZ5. Two furnace carbon black reference examples: 27.5 phr of N772 furnace carbon black and 27.5 phr of N234 furnace carbon black (Example AZ1), and 55 phr of N326 furnace carbon black (Example AZ2) were used to form a 50 / 50 mixture in the formulation. The results are shown in Table 99. Examples containing plasma carbon black filler exhibit rubber performance (within approximately plus or minus 10%), including the same curing adhesion as reference furnace carbon black, which suggests similar bonding performance to brass-coated steel cords.

[0275] The remarkable and surprising advantages of plasma carbon black over furnace carbon black in the tire wire skim formulation NRK03 regarding thermal conductivity (k) are noteworthy. Compared to the N772 / N234 reference material (Example AZ1), the thermal conductivity was 11% to 16% higher (improved) in the plasma carbon black example. Compared to the N326 reference material (Example AZ2), the thermal conductivity was 7% to 13% higher (improved) in the plasma carbon black example. Even when diluted 50% with a mixture of N234 furnace carbon black, the plasma carbon black still provided a significant increase compared to the full furnace carbon black reference example. [Table 112]

[0276] The ongoing and anticipated evolution of raw materials used in tire rubber compositions, including several macro trends in rubber compounding, is included within the scope of this disclosure. Examples include efforts to replace conventional rubber components with less hazardous / toxic alternatives, including safer alternatives to resins up to the resocinol type, and the development of new stabilizers (antioxidants, anti-ozone agents, etc.) to replace 6PPD in tire compounding. The eventual elimination of the multifunctional stabilizer 6PPD from tire compounds may also lead to the inclusion of more saturated elastomers (EPDM, partially or fully hydrogenated SBR and BR, etc.) in tire rubber compounding. Sustainable raw materials such as vegetable oils, pyrolysis carbon from end-of-life tires and biomass raw materials, crushed rubber particles, natural resins, lignin, microcellulose, and nanocellulose are increasingly being used. Alternative sources of natural rubber, such as guayule and dandelion rubber, are being developed. This disclosure anticipates and incorporates all of these changing raw material sources and compositions. This disclosure also applies to non-pneumatic tire components (including, but not limited to, treads, sub-treads, and other components) having a tire rubber composition similar to those used in conventional pneumatic tires.

[0277] In any of the above embodiments, the elastomer latex slurry can be jet-milled together with the plasma carbon black slurry to pre-mix the rubber and carbon black. Instead of adding the elastomer and carbon black separately, this combination can be added in a single step. Particularly useful embodiments of this type of mixture are mixtures of natural rubber latex or emulsified styrene rubber latex with a carbon black slurry or dispersion. The carbon black dispersion may be an aqueous slurry, which may be pre-treated with a surfactant and then ultrasonically treated or mixed via high-shear or low-shear mixing. After mixing these two solutions, the rubber / carbon black mixture can be dried, for example, in a spray dryer or rotary kiln.

[0278] Any of the components or classes of components of the rubber articles described herein may be considered special binders. Special binders may be added to carbon black by spray during the pelletizing stage or after the carbon black has been pelletized (before or after the dryer), or they may be sprayed or added to carbon black while it is still soft before pelletizing.

[0279] Any of the following components or classes of components may be substituted for or thereby expanded upon by the components used in the exemplary formulations described in Examples 1-9 above.

[0280] Examples of elastomers used in the synthesis of rubber articles that can be used in tires include natural rubber (NR), diene copolymers including styrene-butadiene copolymers (e.g., styrene-butadiene rubber (SBR) with diverse microstructures), butadiene rubber (BR), isoprene rubber (IR), halo-isoprene rubber (e.g., chloroprene), halobutyl rubber (e.g., bromobutyl rubber (BIIR)), and related elastomer types. Ethylene-propylene-diene rubber (EPDM), and more saturated elastomers such as partially or fully hydrogenated SBR, BR, and IR can be incorporated into tire rubber formulations. Different elastomer types can be used in various combinations within rubber formulations. Natural rubber from various natural sources, including hevia, guayule, and dandelion rubber, can be used. Natural rubber can be chemically modified, or for example, epoxidized, hydrogenated, or deproteinized.

[0281] Functionalized SBR, BR, IR, and other functionalized elastomers can be used in tire rubber compositions. Functional groups can be incorporated into diene elastomers by coupling agents, polymerization initiators, polymerization terminaters, post-polymerization functionalization approaches, incorporation of functionalized monomers, and / or so. In non-limiting examples, functional groups containing C-Sn bonds or amination functional groups (e.g., aminobenzophenone) may be used for coupling to carbon black, and silanol functional groups, or polysiloxane functional groups, alkoxysilane groups, carboxylic acid groups, or polyether groups with silanol termini may be used for coupling to inorganic fillers such as silica. Other examples of functionalized elastomers include epoxidized elastomers (e.g., SBR, BR, NR, or IR). Representative grades of commercially available functionalized SSBRs and functionalized lithium BRs include, but are not limited to, Kumho Petrochemical Company (KKPC), H-series functionalized SSBRs (e.g., grades 5251H, 5270H); Asahi Kasei, Tufdene E-series functionalized SSBRs (e.g., E581, E680) and F-series functionalized SSBRs (e.g., F3440, F3420); LG Chem, F-series functionalized SSBRs (e.g., grades F3438, F1810, F4626E), M-series functionalized SSBRs (e.g., M3626, M1525), and functionalized lithium BRs (e.g., F0010); and Arlanxeo, Buna FX-series functionalized SSBRs (e.g., grades FX3432A-2, FX5000). These grades, similar grades from other polymer suppliers, and all other commercially available functionalized SSBRs, functionalized BRs, and other functionalized diene elastomers are included in embodiments of the present disclosure.

[0282] Various vulcanization accelerators available for compounding rubber articles can be classified by their chemical structure. Exemplary classifications include: 1. Thiazoles (mercapto), 2. Sulfenamides, 3. Guanidines, 4. Dithiocarbamates, 5. Thiurams, and 6. Special vulcanization accelerators. The raw materials for thiazoles are aniline, carbon disulfide, and sulfur. Examples of thiazole vulcanization accelerators, but not limited to, include 2-mercaptobenzothiazole (MBT), 2,2'-dibenzothiazole disulfide (MBTS), and zinc salts of 2-mercaptobenzothiazole or zinc-2-mercaptobenzothiazole (ZMBT). Sulfenamides can be produced by the reaction of 2-mercaptobenzothiazole with N-chloramine, or by the oxidation of suitable amine salts of 2-mercaptobenzothiazole. Examples of sulfenamide-type vulcanization accelerators include, but are not limited to, N-oxydiethylenebenzothiazole-2-sulfenamide (OBTS), N-cyclohexyl-2-benzothiazole sulfenamide (CBS or CBTS), N-tert-butyl-2-benzothiazole sulfenamide (BBTS), N-oxydiethylenethiocarbamyl-N-oxydiethylene sulfenamide (Cure-Rite18), 4-morpholinyl-2-benzothiazole disulfide (OMTS), and benzothiadyl 1,2-dicyclohexyl sulfenamide (DCBS). Examples of dithiocarbamate-type vulcanization accelerators, but not limited to them, include zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), zinc dibutyldithiocarbamate (ZDBC), zinc dibenzyldithiocarbamate (ZBED), N,N-di-n-butyldithiocarbamate / di-n-butylamine complex (ZDBCX), copper dimethyldithiocarbamate (CuDD), diethyldithiocarbamate tellurium (TDEC), and 2,2'-dithiodiethylammonium-bis-dibenzyldithiocarbamate (SAA-30).Examples of thiram-type vulcanization accelerators include, but are not limited to, tetramethylthiram monosulfide (TMTM), tetramethylthiram disulfide (TMTD), tetraethylthiram disulfide (TETD), a combination of tetramethylthiram disulfide / tetraethylthiram disulfide (TM / ETD), dipentamethylenethiram tetrahexasulfide (DPTT), and tetrabenzylthiram disulfide (TBzTD). Examples of guanidine-type vulcanization accelerators include guanidine and its derivatives, such as diphenylguanidine (DPG).

[0283] Retardants and anti-vulcanization agents may, but are not limited to, cyclohexylthiophthalimide (CTP). This is an organosulfur compound used in the manufacture of rubber articles to slow curing and stop (or inhibit) the occurrence of vulcanization reversal. Processing oils can be classified into three categories: paraffin, naphthenic, and aromatic. Sulfur and sulfur-donating molecules can be in the form of insoluble or soluble sulfur, nanoparticles, micron-sized particles, or particles larger than micron size, and may be known by brand names, such as Crystex and Rubbermakers.

[0284] The activator can be ZnO or other metal oxides. The metal oxide may be nanoparticles or high-surface-area particles, and may also be micron-sized or larger. ZnO activators can be prepared, for example, through French or American regulations.

[0285] Anti-degradation agents may include 1,2-dihydro-2,2,4-trimethylquinoline (TMQ), an antioxidant used in rubber compounds to protect rubber from oxidative degradation. Another anti-degradation agent (in particular, an anti-ozone agent) is 6PPD N 1 -(4-methylpentan-2-yl)-N 4-Phenylbenzene-1,4-diamine, which is being investigated because its corresponding 6PPD-quinone is cytotoxic to certain species of fish. Antioxidants can be assumed to be immobilized on the surface of either particles or polymers to prevent toxic molecules from becoming biologically available in rivers and streams. Other degradation inhibitors found in rubber formulations may be waxes. Microcrystalline waxes can migrate slowly to the rubber surface to form a surface barrier that protects the rubber from ozone and other degrading substances in the environment.

[0286] Adhesion promoters such as cobalt naphthenate, or other adhesion promoters that function similarly to cobalt naphthenate, can be used.

[0287] Other classes of materials include reinforcing tire components used in body plies. In passenger car tires, the reinforcing cords of the body ply may be made of woven cord materials such as polyester, rayon, nylon, aramid, or combinations thereof, or similar suitable organic polymer compounds that can be coated with an adhesive or binding coating such as resocinol-formaldehyde teflon (RFL). In heavy truck and bus tires, the reinforcing cords of the body ply may be made of steel that can be coated with brass or other coatings.

[0288] Another class of material for tire belts and beads is stainless steel wire, which can be coated with brass or other similar compositions. The brass coating may contain copper, but can be varied with other metallic elements.

[0289] Adhesion of the cord to the surrounding rubber matrix is ​​paramount, and altering the carbon black product, even between two suppliers of furnace black, can negatively impact the quality of such adhesion. Bonding between the rubber and the cord can be established through the formation of a copper sulfide interface phase. Adhesion may depend on the thickness of the sulfide layer and, therefore, the copper content in the brass coating. The example of steel cord illustrates the complexity of each component and building block used to manufacture the tire.

[0290] The cord can be activated for better adhesion. Adhesion activators, which may include polyepoxides, can improve the adhesion of the cord to the rubber compound after dipping it in an RFL dip. Treatment of the cord may involve treating it with an aqueous RFL emulsion containing resocinol formaldehyde resin and one or more elastomer latexes.

[0291] The curing agent and curing system may be incorporated into a rubber matrix, including, but not limited to, a rubber matrix for the tire wire and bead skim components. The curing system may be, or contain, a methylene acceptor and a methylene donor. The methylene acceptor may be mixed before or in the first pass, and the methylene donor may then be mixed in the next or second pass. These passes may be referred to as the non-productive (early) pass and the productive (later) pass.

[0292] The methylene acceptor can be, for example, any of resocinol, cardanol, phenolformaldehyde, 3,5-xylenol, alkylphenol, polyphenol, arylalkylphenol, hydroquinone, naphthalenediol, cresol, t-butylphenol, hydroxybenzene, and / or similar. Alternatively, novolac resins may be advantageous, either purchased or produced in situ from the reaction between phenol and formaldehyde, or any combination of phenolic resins, or any combination of two, three, or more phenolic resins in ratios of 10:90, 20:80, 30:70, 40:60, 50:50, or any other ratio. In addition to phenolic resins, epoxy resins can be used.

[0293] The methylene donor may be, for example, hexamethylenetetramine (HMT) or hexamethoxymethylmelamine (HMMM), or other such molecules that react with the methylene acceptor to form a cured crosslinked polymer resin within the final cured rubber article. When epoxy is used as the methylene acceptor, the methylene donor may be selected from aliphatic polyamines, alicyclic polyamines, and aromatic polyamines.

[0294] Methylene acceptors can be one type of resin. Other types of resins may be or may include non-reactive phenolic resins, petroleum resins, tackifying resins, processed resins, and other such resins. Hydrocarbon resins and natural resins are rubber components that can be used in tire rubber compositions. Examples of hydrocarbon resins include pure monomer resins, dicyclopentadiene (DCPD), C5, C9, and C5 / C9 based resins. Examples of natural resins include rosin-based resins and terpene-based resins. These hydrocarbon resins and natural resins can be hydrogenated to varying degrees.

[0295] Examples of compounding accelerators used in rubber compounds include diphenyl sulfide, xylyl mercaptan, phenylhydrazine, and pentachlorothiophenol. The filler level can be roughly estimated at 0.1–0.5 phr or 0.05–0.3 weight percent for natural rubber. Synthetic polymers may require more compounding accelerators, in which case levels of up to 1 weight percent can be observed.

[0296] The M100 or modulus of elasticity at 100% elongation of a rubber article can be predicted by the polymer, compound, and in the case of carbon black-filled rubber articles, by the surface area and structure of the carbon particles. For furnace carbon black and plasma carbon black with similar surface area (e.g., N2SA or STSA) and structure (e.g., OAN or COAN), the M100 value in the same tire rubber compound is typically within approximately ±0.2 MPa. However, while the filler behavior at the nanoscale may be similar in terms of reinforcement, thermal conductivity varies widely, and in many cases, plasma carbon black-filled rubber articles have a thermal conductivity that is 30% higher than their furnace carbon black-filled counterparts. The improved thermal conductivity in plasma carbon black-filled rubber articles can be 5%~10%~15%~20%~30%~40%, and even up to over 200%, which is a remarkable result.

[0297] Each tire compound / example disclosed herein is different but identical. For example, in the various examples presented within each of Examples 1-9, the total polymer filler amount ranged from 53.5 to 59.0 weight percent for all rubber compounds except the passenger car tread, which was 42.5 weight percent. Fillers (e.g., carbon black and precipitated silica) were filled in the range of 26.6 to 32.8 weight percent. Elemental sulfur was present at 0.3 to 2.3 weight percent, and vulcanization accelerators were filled at 0.4 to 2.0 weight percent. Many adjustments or modifications to the compound can be made to these exemplary tire rubber compositions to optimize performance or to suit specific goals of the compound (curing vs. softening vs. rolling resistance vs. hysteresis). It is assumed that these exemplary ranges may be extended to suit such purposes. In non-limiting examples, polymers may be present in amounts ranging from approximately 35% to 65% by weight, fillers in amounts ranging from approximately 22% to 38% by weight, elemental sulfur in amounts ranging from approximately 0% to 5% by weight, and vulcanization accelerators in amounts ranging from approximately 0% to 5% by weight.

[0298] The systems and methods of this disclosure are, for example, incorporated herein by reference in their entirety, International Patent Publication No. 2015 / 116807 ("SYSTEM FOR HIGH TEMPERATURE CHEMICAL PROCESSING"), International Patent Publication No. 2015 / 116797 ("INTEGRATION OF PLASMA AND HYDROGEN PROCESS WITH COMBINED CYCLE POWER PLANT AND STEAM REFORMERS"), International Patent Publication No. 2015 / 116798 ("USE OF FEEDSTOCK IN CARBON BLACK PLASMA PROCESS"), International Patent Publication No. 2015 / 116800 ("PLASMA GAS THROAT ASSEMBLY AND METHOD"), International Patent Publication No. 2015 / 116811 ("PLASMA REACTOR"), and International Patent Publication No. 2015 / 116943 ("PLASMA TORCH"). International Patent Publication No. 2016 / 126598 ("CARBON BLACK COMBUSTIBLE GAS SEPARATION"), International Patent Publication No. 2016 / 126599 ("CARBON BLACK GENERATING SYSTEM"), International Patent Publication No. 2016 / 126600 ("REGENERATIVE COOLING METHOD AND APPARATUS"), International Patent Publication No. 2017 / 019683 ("DC PLASMA TORCH ELECTRICAL POWER DESIGN METHOD AND APPARATUS"), International Patent Publication No. 2017 / 027385 ("METHOD OF MAKING CARBON BLACK"), International Patent Publication No. 2017 / 034980 ("HIGH TEMPERATURE HEAT INTEGRATION METHOD OF MAKING CARBON BLACK") "BLACK"), International Patent Publication No. 2017 / 044594 ("CIRCULAR FEW LAYER GRAPHENE"), International Patent Publication No. 2017 / 048621 ("CARBON BLACK FROM NATURAL GAS"), International Patent Publication No. 2017 / 190045 ("SECONDARY HEAT ADDITION")International Patent Publication No. 2017 / 190015 ("TORCH STINGER METHOD AND APPARATUS"), International Patent Publication No. 2018 / 165483 ("SYSTEMS AND METHODS OF MAKING CARBON PARTICLES WITH THERMAL TRANSFER GAS"), International Patent Publication No. 2018 / 195460 ("PARTICLE SYSTEMS AND METHODS"), International Patent Publication No. 2019 / 046322 ("PARTICLE SYSTEMS AND METHODS"), International Patent Publication No. 2019 / 046320 ("SYSTEMS AND METHODS FOR PARTICLE GENERATION"), International Patent Publication No. 2019 / 046324 ("PARTICLE SYSTEMS AND International Patent Publication No. 2019 / 084200 ("PARTICLE SYSTEMS AND METHODS"), International Patent Publication No. 2019 / 195461 ("SYSTEMS AND METHODS FOR PROCESSING"), International Patent Publication No. 2022 / 076306 ("SYSTEMS AND METHODS FOR PROCESSING"), International Patent Publication No. 2023 / 059520 ("SYSTEMS AND METHODS FOR ELECTRIC PROCESSING"), International Patent Publication No. 2023 / 137120 ("METHODS AND SYSTEMS FOR USING SILICON-CONTAINING ADDITIVES TO PRODUCE CARBON PARTICLES"), International Patent Publication No. 2023 / 235486 ("RECYCLED FEEDSTOCKS FOR CARBON AND HYDROGEN "PRODUCTION"), International Patent Publication No. 2024 / 086782 ("SYSTEMS AND METHOD FOR MODULATING REACTING FLOWS"), and International Patent Publication No. 2024 / 086831 ("METHODS AND ADDITIVES TO IMPROVE PERFORMANCE OF CARBONThe chemical processing and heating methods, chemical processing systems, reactors, and plasma torches described in "PARTICLES IN ELASTOMER COMPOSITES" may be combined with, or modified by, other systems and / or methods such as carbon particles.

[0299] Further variations and modifications of this disclosure will be obvious to those skilled in the art and are intended to be encompassed by the claims appended herein. Embodiments of this disclosure are shown and described herein, but such embodiments are provided only as examples. The scope of this disclosure is not intended to be limited by any particular embodiment provided herein. The descriptions and illustrations of embodiments herein are not intended to be construed as restrictive. Those skilled in the art will be able to conceive of countless variations, modifications, and substitutions without departing from this disclosure. It should be understood that no aspect of this disclosure is limited to any particular description, configuration, relative proportion, example, or result described herein, depending on a variety of conditions and variables. Various substitutes for the embodiments described herein may be used, and it should be understood that this disclosure also covers any such substitutes, modifications, variations, or equivalents. The following claims define the scope of the invention, and methods and structures within the scope of these claims and their equivalents are intended to be covered thereby.

Claims

1. A rubber article comprising at least 2% by weight of a plasma carbon black filler compounded therein, wherein the rubber article is of the type of inner liner, sidewall, subtread, bead skim, wire skim, tread, or body price skim.

2. The rubber article according to claim 1, comprising at least 10% by weight of natural rubber, butadiene rubber, halobutyl, butyl rubber, isoprene rubber, chloroprene rubber, EPDM, and / or synthetic elastomer.

3. The rubber article according to claim 1, comprising one or more of precipitated silica, recovered carbon, furnace carbon black, graphene, lignin, carbon nanotubes, and clay.

4. The rubber article according to claim 3, wherein the ratio of the plasma carbon black filler to the precipitated silica, the recovered carbon, the furnace carbon black, the graphene, the lignin, the carbon nanotubes, or the clay is in the range of 1:10 to 10:

1.

5. The rubber article according to claim 3, wherein the precipitated silica, the recovered carbon, or the furnace carbon black is present in a range of 15 phr to 60 phr.

6. The rubber article according to claim 1, wherein the rubber article contains a furnace carbon black filler and has improved thermal conductivity compared to a second rubber article of the same type that does not contain a plasma carbon black filler.

7. The rubber article according to claim 6, wherein the improved thermal conductivity is 0.33 W / mK or more.

8. The rubber article according to claim 6, wherein the improved thermal conductivity of the rubber article is at least 5% greater than the thermal conductivity of the second rubber article.

9. The rubber article according to claim 8, wherein the improved thermal conductivity of the rubber article exceeds the thermal conductivity of the second rubber article by at least 20%.

10. The rubber article according to claim 1, comprising at least 0.2% by weight of MBT or MBTS.

11. The rubber article according to claim 1, comprising sulfur in the range of approximately 0.05 to 5 weight percent.

12. The rubber article according to claim 1, wherein the rubber article contains a furnace carbon black filler and has improved diffusion compared to a second rubber article of the same type that does not contain a plasma carbon black filler.

13. The rubber article according to claim 1, wherein the rubber article has a reduced viscoelastic loss tangent (tanδ) compared to a second rubber article of the same type, and the second rubber article comprises (i) furnace carbon black in a weight percentage of no more than 20% of the plasma carbon black filler in the rubber article, and (ii) 0% by weight of the plasma carbon black filler.

14. The rubber article according to claim 13, wherein the reduced viscoelastic loss tangent (tanδ) is at least 2% lower than the viscoelastic loss tangent of the second rubber article.

15. Carbon particles produced by a thermal plasma process, wherein the carbon particles have characteristics including a spherical equivalent diameter of less than 1 micrometer, a lattice constant (Lc) greater than 3 nanometers (nm), and a deviation of less than 20% between the measured aggregate diameter and the calculated aggregate diameter, wherein the measured aggregate diameter is the Z-mean value measured by dynamic light scattering (DLS), and the calculated aggregate diameter (Da) is determined by the equation [Da = (2540 + (71 * OAN)) / STSA].

16. The carbon particles according to claim 15, wherein the carbon particles are pelletized and dried, and then contain silane added to the carbon particles.

17. The carbon particles according to claim 15, wherein the silicon content of the carbon particles is greater than 0.05% but less than 1%.

18. A rubber article comprising an elastomer composition, wherein the elastomer composition is a. A plasma carbon black filler compounded therein, wherein the plasma carbon black filler has an STSA and OAN of 15% or less of the comparative statistical thickness surface area (STSA) and comparative oil absorption amount (OAN) of a comparative furnace carbon black filler, respectively. b. A rubber article having a thermal conductivity at least 10% higher than the comparative thermal conductivity of the comparative elastomer composition containing the comparative furnace carbon black filler.

19. A rubber article comprising an elastomer composition, wherein the elastomer composition is a. It contains a compounded plasma carbon black filler, b. Each of the comparative elastomer compositions has a comparative 100% strain tensile stress (M100), comparative calculated average aggregate diameter (Da), or comparative Shore A hardness of M100, Da, or Shore A hardness within 15% of the comparative elastomer composition, wherein the comparative elastomer composition contains a furnace carbon black filler compounded therein. c. A rubber article having a thermal conductivity at least 10% higher than the comparative thermal conductivity of the comparative elastomer composition.

20. A tire comprising two sidewalls, two bead skims, and a tread, wherein each sidewall is configured to connect one of the two bead skims to the tread, and at least one of the two sidewalls, two bead regions, and the tread contains thermal plasma carbon black.

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