Method for processing recycled carbon, and the obtained pulverized recycled carbon and products containing it.

Abstract

Methods for processing recycled carbon are described. Methods utilizing media grinding to improve one or more properties of recycled carbon in products such as elastomer composites are described. The media grinding used may include media grinding that consumes a specific energy of 1 kWh / kg to 10 kWh / kg of dry-ground recycled carbon.

Description

Technical Field

[0001] The present invention relates to a method for treating reclaimed carbon (rC). The present invention further relates to ground reclaimed carbon useful for incorporation into products such as elastomers.

[0002] To avoid materials being discarded as waste and to avoid further depletion of natural resources, there is an increasing demand and effort for recycling materials.

[0003] End-of-life vehicle tires are often processed and reused in a wide range of end uses from sporting equipment to concrete. However, it is desirable to recycle tire components to obtain materials that can be combined with the originally used materials and reduce the amount of new materials required to manufacture new products.

[0004] In various industries, there is an increasing need for more sustainable materials and for reducing the carbon footprint. Therefore, the use of reclaimed carbon (rC) from used tires (or other sources) as an alternative to carbon black (CB) in rubber reinforcement applications can be a promising strategy. Tires and other rubbers contain various carbon blacks and other fillers in various forms, together with ceramic additives such as zinc oxide. As a result, the resulting rC has a different composition and microstructure from virgin carbon black. Reclaimed carbon suffers from low rubber reinforcement properties such as low tensile modulus, low tear strength, and / or low fatigue life when compared to CB having the same or nearly the same surface area and structure as measured by OAN. Therefore, there is a need in the art to develop processes by which rC and other similar particles that are not suitable as such for use as fillers in rubber reinforcement applications and other applications can be employed as suitable alternatives or suitable partial alternatives to virgin carbon black.

[0005] All patents and publications mentioned throughout this document are incorporated herein by reference in their entirety. [Overview of the project]

[0006] A key feature of this invention is to provide a method for improving recycled carbon for use in products.

[0007] A further feature of the present invention is that it provides the ability to utilize recycled carbon without interfering with the ability to manufacture industrially acceptable products such as elastomers.

[0008] A further feature of the present invention is to provide a method for making recycled carbon a more viable material for use as a reinforcing grade material or filler grade material in applications such as elastomers.

[0009] A further feature of the present invention is to provide a method for processing recycled carbon for use in polymer matrices or elastomer matrices while substantially maintaining most, if not all, of the product properties (e.g., undispersed areas, abrasion volume loss, M300 / M100, M300, M100).

[0010] A further feature of the present invention is to provide a method for "fine-tuning" recycled carbon to achieve or improve specific properties (e.g., undispersed areas, M300, M100, M300 / M100, or wear volume loss).

[0011] Furthermore, a feature of the present invention is to provide a method for processing recycled carbon, and as a result, particles combined with, for example, virgin carbon black, can have equivalent filler properties, such as acceptable dispersion, compared to using 100% virgin carbon black, although this is not limited to these examples.

[0012] A further feature of the present invention is the provision of pulverized recycled carbon and products containing it.

[0013] The present invention relates, in part, to a method for processing recycled carbon, as embodied and broadly described herein, in order to achieve these and other advantages and in accordance with the object of the present invention. The method comprises grinding wet recycled carbon to obtain pulverized recycled carbon, the grinding comprising, or at least comprising, using a medium grinding that consumes a specific energy of at least 1 kWh / kg, at least 1.25 kWh / kg, or at least 1.5 kWh / kg of the pulverized recycled carbon.

[0014] Furthermore, the present invention relates to a method for processing recycled carbon, the method comprising at least grinding wet recycled carbon to obtain pulverized recycled carbon, wherein the number of impacts per 1 kg of dry pulverized recycled carbon is at least 10 per 1 kg of dry pulverized recycled carbon during grinding. 13 Each medium collision, or during grinding, at least 2 × 10⁶ per kg of dry-ground recycled carbon. 13 To enable the occurrence of individual media collisions, or to ensure that the media grinding is performed during the grinding process, at least 5 × 10 per kg of dry-ground recycled carbon. 13 The system includes at least media crushing to enable the occurrence of individual media collisions.

[0015] The present invention further relates in part to pulverized recycled carbon, preferably produced by one of the methods of the present invention, having a D50 of 250-400 nm and a D90 of 350-1100 nm.

[0016] Furthermore, the present invention relates in part to pulverized recycled carbon produced by one of the methods of the present invention, and to products such as rubber products or elastomer products that contain or utilize the pulverized recycled carbon of the present invention.

[0017] As used herein, "char" refers to the solid material resulting from the thermal decomposition of rubber products.

[0018] As used herein, “dry-ground recycled carbon” refers to pyrolysis carbon that is substantially free of macroscopic contaminants, ground without the use of water, and optionally pelletized.

[0019] As used herein, "carbon black" means elemental carbon-containing carbon particles obtained by partial combustion or thermal decomposition of hydrocarbons, which are aggregated into aggregates and lumps.

[0020] As used herein, “recycled carbon” is a solid material resulting from the thermal decomposition of a rubber product containing, in any amount, carbon black (e.g., at least two different types of carbonaceous particulate fillers), but not limited to at least two different types of carbon black.

[0021] As used herein, “treated recycled carbon” means original recycled carbon that has been treated to remove at least one macroscopic contaminant, such as fabric or wire.

[0022] As used herein, "pyrolysis carbon" includes char, raw recycled carbon, treated recycled carbon, and dry-ground recycled carbon.

[0023] As used herein, “pulverized recycled carbon” or “pulverized rC” refers to pulverized pyrolysis carbon that is substantially free of macroscopic contaminants.

[0024] As used herein, “recycled carbon” refers to original recycled carbon that has been treated to remove macroscopic contaminants and optionally further ground. Therefore, treated recycled carbon, ground recycled carbon, dry-ground recycled carbon, and wet-ground recycled carbon all fall under the definition of recycled carbon.

[0025] As used herein, “wet-ground recycled carbon” is substantially free of macroscopic contaminants and is pyrolysis carbon ground in the presence of at least 50% by weight, preferably 65-99% by weight, of water based on the total weight of the material being ground.

[0026] This method may further include removing macroscopic contaminants from an initial slurry that may optionally contain up to 35% by weight of solids. Combining this may further include forming the initial slurry with water in combination with at least one auxiliary filler. The auxiliary fillers may be selected from the group consisting of carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, artificial polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, carbon black-coated particles, and mixtures of two or more of these.

[0027] The method may further include adding at least one additional filler selected from carbon black, silicon-treated carbon black, silica-coated carbon black, coated carbon black particles, and precipitated silica to the pulverized slurry to bring the solid content of the resulting wet-blended carbon mixture to 25-70% by weight. Addition may include adding an aqueous slurry containing at least one additional filler, adding additional water to the pulverized slurry, or both. The method may further include pelletizing the wet-blended carbon mixture to form pellets, spray-drying the wet-blended carbon mixture, and optionally drying the pellets.

[0028] The water may be a continuous flow of water, and the grinding slurry may be a continuous flow of grinding slurry. The combination may include metering and supplying pyrolysis carbon to the continuous flow of water. The combination may further include metering at least one auxiliary filler to the continuous flow of water. The auxiliary filler may be selected from the group consisting of carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, artificial polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, carbon black-coated particles, and mixtures of two or more of these. The method may further include metering at least one additional filler selected from carbon black, silicon-treated carbon black, silica-coated carbon black, carbon black-coated particles, and precipitated silica to the continuous flow of grinding slurry to make the solid content of the resulting wet-blended carbon mixture continuous flow 25-70% by weight or 1-35% by weight. Measuring may include measuring an aqueous slurry of additional fillers into a continuous flow of the pulverized slurry, measuring additional water into a continuous flow of the pulverized slurry, or both.

[0029] In any of these embodiments, the method may further include, for example, pelletizing the wet-blended carbon mixture to form pellets, or granulating the wet-blended carbon mixture by spray-drying the wet-blended carbon mixture. The pellets may be dried. The grinding slurry may be spray-dried, or its solid form may be granulated by another method. For example, the grinding slurry may be dehydrated to a predetermined moisture level and then pelletized.

[0030] In another embodiment, the present invention includes pellets produced using any combination or partial combination of the method steps described above.

[0031] In any of these embodiments, the particulate filler may further comprise one or more auxiliary fillers selected from carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, artificial polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, and carbon black-coated particles. The particulate filler may have a water content of 15-80% by weight, for example, 40-60% by weight.

[0032] The particulate filler may be in the form of pellets. The pellets may contain 15-80% water, for example 40-60% water, or 3% or less water, and / or substantially consist of particulate filler, optional water, and optional binder. The pellets may contain particulate filler according to any of these embodiments and at least one additional filler selected from carbon black, silicon-treated carbon black, silica-coated carbon black, carbon black-coated particles, and precipitated silica.

[0033] In another embodiment, the elastomer composite comprises a mixture of an elastomer and a particulate filler of 30-90 phr, for example, 30-70, 35-60, or 40-55 phr. The particulate filler comprises at least 10 wt% recycled carbon, for example, 10-100 wt%, 10-90 wt%, 15-80 wt%, 20-60 wt%, or 30-50 wt% recycled carbon, preferably 10-40 wt% or 20-40 wt% recycled carbon. The recycled carbon preferably has a D50 of 250-400 nm, more preferably 250-320 nm, and a D90 of 350-1100 nm, for example, 500-1100 nm. The particulate filler may further comprise one or more of the following: carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, artificial polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, and carbon black-coated particles. In certain preferred embodiments, the particulate filler preferably comprises carbon black.

[0034] In any of these embodiments, the elastomer may be selected from natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, polyisoprene rubber, ethylene-propylene copolymer, isobutylene-based rubber, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomer, fluoroelastomer, perfluoroelastomer, and blends thereof.

[0035] In any of these embodiments, the recycled carbon may be wet-ground recycled carbon. In any of these embodiments, the elastomer composite may be a vulcanized elastomer composite. The tire tread may comprise a vulcanized mixture of the elastomer composite and a vulcanizing agent package. Alternatively or additionally, the article may comprise a vulcanized mixture of the elastomer composite and a curing agent package. The article may be incorporated into a pneumatic tire, a non-pneumatic tire, or a solid tire. The article may be selected from tire treads, undertreads, inner liners, sidewalls, sidewall inserts, wire skims, and cushion gums for retreaded tires. Articles may be selected from hoses, linings, liners, seals, gaskets, vibration damping articles, track pads for trucks and truck propulsion vehicle equipment, engine mounts, seismic stabilizers, mining equipment screens, mining equipment linings, conveyor belts, chute liners, slurry pump liners, mud pump impellers, valve seats, valve bodies, piston hubs, piston rods, plungers, slurry mixing impellers and slurry pump impellers, grinding mill liners, cyclones and hydrocyclones, expansion joints, linings for dredging pumps and outboard motor pumps for marine equipment, shaft seals for marine, petroleum, aerospace, and other applications, propeller shafts, pipe linings, engine mounts, bushings, weatherstrips, windshield wipers, automotive parts, seals, gaskets, housings, wheel elements, and track elements.

[0036] In another embodiment, the elastomer composite comprises a mixture of elastomer and 30-90 phr of particulate filler. In a particular embodiment, the particulate filler comprises at least 10% by weight of recycled carbon. In any of these embodiments, the elastomer composite may be vulcanized, and / or the recycled carbon may be wet-ground recycled carbon.

[0037] Please understand that both the general description above and the detailed description below are merely illustrative and descriptive, and further illustrate the scope of the claimed invention.

[0038] The accompanying drawings incorporated herein and constituting part of this specification illustrate various features of the present invention and, together with the detailed description, serve to illustrate the principles of the present invention. [Brief explanation of the drawing]

[0039] [Figure 1] This graph shows a plot of volume-weighted frequency versus particle size in nanometers for samples taken at different residence times during the grinding process, and therefore indicates the change in particle size with respect to residence time in a mill containing the grinding medium. The "base sample" plot shows the particle size distribution in the slurry before grinding begins.

[0040] [Figure 2] The graph shows the amount of undispersed region in a cured elastomer composite with 50 phr filler as a function of rC concentration in the mixture / blend for different rC treatment methods, as indicated by the data labels. The data in the figure shows a control mixture without rC (black circles), a media-ground sample of the present invention (short dashed circles), and a blend of rC without media grinding (long dashed circles). The media grinding residence time is indicated on the data labels.

[0041] [Figure 3] This graph shows the wear volume loss of a compound containing 50 phr of filler as a function of rC concentration under various mixing methods. The data in the graph represent a control mixture without rC (black circles), a blend with media-ground rC (short dashed circles), and other rC mixing methods without media-ground rC (long dashed circles).

[0042] [Figure 4] This graph shows the strengthening index M300 / M100 as a function of rC concentration in a cured elastomer composite with 50 phr of filler. The data in the graph represent a control mixture without rC (black circles), a blend with media-ground rC (short dashed circles), and other rC mixing methods without media-ground rC (long dashed circles).

[0043] [Figure 5] This graph shows the tensile stress (M300) at 300% elongation of compounds containing 50 phr filler blended using various mixing methods, as a function of rC concentration. The data in the graph represent a control mixture without rC (black circles), blends with media-ground rC (short dashed circles), and other rC mixing methods without media-ground rC (long dashed circles).

[0044] [Figure 6] This graph shows the particle size distribution as a function of volume % for samples with different grinding times, and a control distribution is also shown.

[0045] [Figure 7] This graph shows the percentage of undispersed region as a function of particle size distribution (D90) for samples ground at different time intervals (in minutes, RT = residence time) and speeds.

[0046] [Figure 8] This graph shows the abrasion volume loss as a function of particle size distribution (D90) for samples ground at different time intervals (in minutes, RT = residence time) and speeds.

[0047] [Figure 9] This graph shows M100 as a function of particle size distribution (D90) for samples ground at different time intervals (in minutes, RT = residence time) and speeds.

[0048] [Figure 10] This graph shows the percentage of undispersed region as a function of filler content (weight %) for samples prepared with and without media grinding (black circles).

[0049] [Figure 11] This graph shows the wear volume loss (mm3) as a function of filler content (weight%) for samples prepared using media grinding (black circles) and samples prepared without media grinding (white circles).

[0050] The drawings are provided as simplified diagrams, not to scale, and do not necessarily show all possible embodiments or components that may exist. [Modes for carrying out the invention]

[0051] The present invention relates, in part, to a method for improving the condition of recycled carbon such that one or more properties of a product containing recycled carbon are maintained, or substantially maintained, compared to when 100% virgin carbon black is used in the same product.

[0052] The present invention further relates to a method for processing recycled carbon, the method comprising at least grinding wet recycled carbon to obtain pulverized recycled carbon, the grinding comprising at least dry grinding of recycled carbon at a rate of at least 1 kWh / kg, or at least 1.25 kWh / kg, or at least 1.5 kWh / kg per kg, for example, grinding a media that consumes a specific energy of 1 kWh / kg to 10 kWh / kg, or 1.25 kWh / kg to 3.5 kWh / kg, or 1.5 kWh / kg to 5 kWh / kg, or 1 kWh / kg to 3.1 kWh / kg, the media grinding being carried out using a grinding medium having a diameter of 2 mm or less.

[0053] Additionally or alternatively, the present invention further relates to a method for processing recycled carbon, the method comprising at least grinding wet recycled carbon to obtain pulverized recycled carbon, the grinding comprising at least media grinding, the media grinding wherein the number of collisions per kg of dry-pulverized recycled carbon during grinding is at least 10 per kg of dry-pulverized recycled carbon 13 Multiple media impacts, or at least 2 × 10⁶ per kg of dry-ground recycled carbon. 13 This process is carried out in such a way that it can result in multiple medium collisions, for example, 3 × 10⁶ per kg of dry-ground recycled carbon. 13 10 times 14 Multiple media impacts, or dry grinding recycled carbon, 4 x 10 per kg. 13 8 x 1013 circular media collisions, or 5×10 13 circles to 6×10 13 circular media collisions can be brought about during grinding.

[0054] Other aspects and options regarding the method of the present invention are further described herein.

[0055] In the present invention, unexpectedly, grinding rC using a media grinding technique (such as as described herein) can enhance or improve one or more specific rubber or elastomer properties (sometimes referred to herein as "rubber properties") compared to unground rC, or rC containing no media or media having a diameter greater than 2 mm. It has been discovered that in the present invention, by grinding rC using a media grinding technique, specific rubber properties can be enhanced or improved based on the time (residence time) that a unit element of slurry volume spends in the media mill. Furthermore, it has been discovered that certain rubber properties improve better at relatively short grinding times, other rubber properties improve at relatively long grinding times, and for all rubber properties, generally, the rubber properties do not improve further beyond a certain grinding time. Thus, there is a range of grinding times that is advantageous for achieving or improving specific properties and avoiding overgrinding of rC. As described herein, the media-grinded rC of the present invention and the method for forming the same were compared with N550 virgin carbon black (control). This type of carbon black has been shown in the past to be difficult to partially replace, even with ground rC, by rC.

[0056] Starting recycled carbon or rC (submitted for grinding), such as rC aggregates, are commercially available. Generally, rC aggregates result from the thermal decomposition of tires and / or other rubber materials containing filler or reinforcing materials such as carbon black. rC is primarily produced from carbon black used to reinforce rubber. rC may contain thermally decomposable components such as rubber components. rC may also be treated recycled carbon, in which case the raw recycled carbon has been treated to remove or substantially remove at least one macroscopic contaminant, such as fabric or wire. Recycled carbon is commercially available from suppliers such as Reoil Sp.z oo, Scandinavian Enviro Systems AB, Pyrum Innovations AG, or Bolder Industries, or CBp Cyprus Ltd.

[0057] rC may be treated to remove macroscopic contaminants. For example, wires and other macroscopic metallic contaminants can be removed using magnetic separation techniques known to those skilled in the art. Fibers and other non-magnetic macroscopic contaminants can be removed using filters or screens. rC may be treated before being mixed with water to form an initial slurry, and / or the initial slurry may be treated to remove macroscopic contaminants.

[0058] Alternatively or additionally, rC or pyrolysis carbon may be treated to remove ash, for example, by washing the pyrolysis carbon with acid or by using an ion exchanger. Exemplary methods are described in U.S. Patent No. 20150307714, Chinese Patent No. 101357758, and International Publication No. 2021 / 005124, all of which are incorporated herein by reference.

[0059] As an example, the starting recycled carbon particles (before grinding, as described herein) may have a mesh size 5 to 10 times smaller than the medium used. Other mesh sizes above or below this range may be used.

[0060] For grinding purposes, the recycled carbon in particulate form is wet-process recycled carbon.

[0061] Wet recycled carbon for grinding can be prepared by wetting recycled carbon with an aqueous solution such as water. Wetting of recycled carbon is generally performed before the recycled carbon is introduced into the mill. Wetting may be such that a mixture of recycled carbon and water, such as a slurry, is formed. The slurry may have at least 1% by weight of solids (e.g., at least 1% by weight of recycled carbon). The slurry may have about 1% to 35% or more of solids (based on the total weight of the slurry). The slurry may be in any range based on 1% to 30% by weight, 1% to 25% by weight, 1% to 20% by weight, 1% to 15% by weight, 1% to 10% by weight, 1% to 5% by weight, 5% to 35% by weight, 10% to 35% by weight, 15% to 35% by weight, 20% to 35% by weight, 25% to 35% by weight, or any range based on any two values ​​described herein.

[0062] The grinding includes at least one grinding step that utilizes media grinding using a grinding medium having a diameter of 2 mm or less. If more than one media grinding step is used, the type of media grinding with respect to the medium, the type of grinding or grinding time, or the number or size of the media may be the same or different.

[0063] The media grinding may be performed by agitated ball mill grinding, planetary ball mill grinding, or centrifugal ball mill grinding, or may include these methods.

[0064] One preferred method of grinding media is agitated ball mill grinding.

[0065] One option for the medium (which can be considered a crushing medium) is to use solid balls.

[0066] Solid balls can have an average size of, for example, approximately 0.25 mm to 2 mm. The average size may be 0.3 mm to 1.75 mm, or 0.4 mm to 1.5 mm, or 0.5 mm to 1 mm, or 0.6 mm to 1 mm, or 0.7 mm to 1 mm, or 0.8 mm to 1.5 mm.

[0067] As an option, the grinding medium may be such that the particle size of the starting recycled carbon is approximately 3 to 10 times smaller, or approximately 5 to 10 times smaller (e.g., 4 to 5 times smaller), than the size of the medium used (e.g., the average size of the medium used).

[0068] Solid balls may be metal balls, glass balls, ceramic balls, or polymer balls. Specific examples, but not limited to, include steel (e.g., chromium steel, or stainless steel such as 304SS and 316SS) or ceramics (e.g., agate, alumina, yttria-stabilized zirconia, zirconium silicate, zirconia-reinforced alumina, and tungsten carbide).

[0069] The grinding medium can be filled into the mill such that the volume fill is between 50% and 98% of the mill's volume. The volume fill may be less than 50% or more than 90% if necessary or desired. The volume fill may be 50% to 95%, or 60% to 90%, 70% to 90%, 80% to 90%, 50% to 80%, 50% to 70%, 50% to 60%, or any range based on any two values ​​described herein. The volume fill is based on the total volume (space) available for grinding in the mill.

[0070] The media grinding is operated such that the grinding consumes a specific energy of at least 1 kWh / kg, or at least 1.25 kWh / kg, or at least 1.5 kWh / kg per 1 kg of dry-ground recycled carbon, for example, 1 kWh / kg to 10 kWh / kg, or 1.25 kWh / kg to 3.5 kWh / kg, or 1.5 kWh / kg to 5 kWh / kg, or 1 kWh / kg to 3.1 kWh / kg, or 2.5 kWh / kg to 3.5 kWh / kg, or 4 kWh / kg to 5 kWh / kg, or any range based on any two values ​​described herein.

[0071] The specific energy used by the grinder can be used as a substitute for the degree of grinding. The amount of kWh consumed can be calculated per 1 kg of dry product (Formula: P m =t m * P / m p , where t m is the grinding time, P is the average mill specific energy, and m p (where is the batch dry weight), which can be calculated at various residence times. Similarly, the approximate number of media collisions can be calculated as follows:

number

[0072] The media grinding process can be characterized by the number of collisions per kilogram of dry-ground recycled carbon. The media grinding process used involves at least 10 collisions per kilogram of dry-ground recycled carbon during grinding. 13 During the impact or grinding of the medium, at least 2 × 10⁶ units per kg of dry-ground recycled carbon 13A collision of multiple media, for example, 10 13 particles / kg of media collisions ~10 14 particles / kg media collision, 3 × 10 13 particles / kg of media collisions ~10 14 A media collision of particles / kg, or 4 × 10 13 Media collisions of particles / kg ~8 × 10 13 A media collision of particles / kg, or 5 × 10⁻⁶ 13 Media collisions of particles / kg ~6 × 10 13 It can cause a media collision of units / kg.

[0073] In any of the methods of the present invention, the pulverization used may be such that the pulverized recycled carbon has a particle size distribution (PSD) and a D50 particle size with a value of 250 nm to 400 nm, preferably 250 nm to 320 nm. Similarly, or further, the PSD may have a D90 of 350 nm to 1100 nm, for example, 500 nm to 1100 nm, 600 nm to 1000 nm, 700 nm to 900 nm, or 800 nm to 1100 nm. The particle size distribution is measured by analytical centrifugation (disk centrifugation photoprecipitation) of the pulverized slurry, as described in Example 1. In this method, called PSD Method 1, an aqueous particle slurry (14 wt% solids) is diluted to 2000 ppm with DI water containing 600 ppm of Triton X100 surfactant. The diluted solution is then mixed for 5 minutes at 800 RPM using a DISPERMAT LC55 mixer equipped with a lightweight 30 mm diameter 18-tooth impeller. Next, the solution is stirred on a stirring plate using a magnetic stirring rod for 24 hours. Then, the sample solution is further diluted to 400 ppm using DI water containing 400 ppm Triton X100 surfactant and kept rotating in a 40 ml vial on rollers until measurement. Disk centrifuge (DC24000, CPS Instruments) measurement is performed at 5000 RPM. First, 24%, 22%, 20%, 18%, 16%, 14%, 12%, 10%, and 8% sucrose solutions in DI water are sequentially injected into the disk (1.6 ml each), followed by the injection of 1 ml of dodecane to seal the gradient. The gradient is given 1 hour to stabilize before measurement. In the disk centrifuge measurement, the sample density and refractive index are 1.86 g / cm³. 3 n = 1.84 + 0.846i. The result is 1.86 g / cm³. 3 This represents the equivalent sedimentation results for spherical particles with density and refractive index n = 1.84 + 0.846i. All measurements are stopped immediately after the signal reaches the baseline.

[0074] The grinding can be characterized by one or more properties achieved by the grinding of recycled carbon according to the present invention.

[0075] For example, grinding can result in a rubber sample having 20-60 phr (e.g., 20 phr, or 25 phr, or 30 phr, or 35 phr, or 40 phr, or 30-55 phr, or 40-50 phr) of ground recycled carbon, especially when prepared using techniques that combine wet pellets with an elastomer, resulting in up to 8% or up to 5%, or 1%-7%, or 1.5%-6%, or 1.75%-4% (disperser grader%) of undispersed region. Alternatively, a rubber sample having 20-80 phr of particulate filler, e.g., 30-70 phr, 40-60 phr, or 45-55 phr of particulate filler, where 10-40% by weight, e.g., 15-35% by weight, or 20-30% by weight, is ground recycled carbon, has up to 3% of undispersed region, e.g., 1%-3% of undispersed region. In one embodiment, the particulate filler is made of ground and recycled carbon and carbon black, for example, 35-110m 2 A blend of carbon black with a BET surface area of ​​1 / g, such as carbon black from the N300 or N500 series, such as N330 or N550 carbon black.

[0076] The Dispergrader (%) is calculated as follows: A hardened rubber sample is cut using a razor blade fixed to a manual cutting jig. The sample is placed on a Dispergrader instrument (Alpha Technologies) and imaged. The following settings are used: Filler volume fraction, 20%; Exposure time, 40 ms; Analytical color channel, Blue; Dispersion calculation threshold, 23 μm; Agglomeration fraction activation, 1; White area threshold, 0. The amount reported by Alpha Technologies as White Area % is interpreted as Undispersed Area.

[0077] As a further example, grinding is such that a rubber sample with 20–60 phr (e.g., 20 phr, 25 phr, 30 phr, 35 phr, or 40 phr) of ground recycled carbon results in a wear volume loss that is no more than 10% or less than 5% of a comparative rubber sample containing N550 carbon black instead of ground recycled carbon. The comparative rubber sample with N550 carbon black can be considered a "control sample," which has the same phr of N550 carbon black as used in the rubber sample with recycled carbon, and all other components are the same except that carbon black is used instead of recycled carbon. DIN wear is evaluated according to the standard ASTM D5963 rotation method. Alternatively or additionally, grinding may result in a wear volume loss of no more than 10% or no more than 5% of a comparative rubber sample having 100% N330 carbon black instead of the blend with ground recycled carbon, particularly when the rubber sample has 20-60 phr (e.g., 20 phr, 25 phr, 30 phr, 35 phr, or 40 phr) of filler containing a blend of 10%-40% by weight of N330 carbon black and ground recycled carbon, when prepared using techniques in which wet pellets are combined with elastomers. Alternatively, a rubber sample having particulate filler of 20-80 phr, for example, 30-70 phr, 40-60 phr, or 45-55 phr, wherein 10-40% by weight, for example, 25-40% by weight, 15-35% by weight, or 20-30% by weight is recycled carbon from a media grinding machine, is measured according to ASTM D5963 to 90-100 mm 3 For example, 91-95mm 3 It has wear loss. In one embodiment, the particulate filler is a medium-ground recycled carbon and carbon black, for example, 35-110m 2 A blend of carbon black with a BET surface area of ​​1 / g, such as carbon black from the N300 or N500 series, such as N330 or N550 carbon black.

[0078] As a further example, the grinding may be such that a rubber sample with 20–40 phr of ground recycled carbon results in an M300 / M100 ratio of a) not more than 10% or less than 5% of a comparative rubber sample (control sample) with N550 carbon black instead of ground recycled carbon, or b) 4.5–5. Tensile stress (including M300 or M100) is tested according to ASTM D412 Type C. Six dumbbells are used instead of five. M300 is the tensile stress at 300% elongation, and M100 is the tensile stress at 100% elongation.

[0079] As a further example, the grinding may result in a rubber sample with 20-40 phr of ground recycled carbon yielding M300 (MPa) or a maximum load (N) that is not more than 10% lower or more than 5% lower than a comparative rubber sample with N550 carbon black instead of ground recycled carbon.

[0080] The present invention further relates to pulverized recycled carbon produced by any method of the present invention. Pulverized recycled carbon may be characterized by one or more of the properties and / or features described herein.

[0081] As shown, in the present invention, it was unexpectedly discovered that a specific residence time for media grinding is more appropriate for specific rubber properties. To make this determination, the grinding material of the present invention was tested in an SBR composite as described in the Examples section. To further demonstrate that the media grinding material of the present invention contributes to the rubber properties, as shown in the Examples section, the media grinding material was compared with bulky (unground) rC and wet-mixed rC pellets (unground), and further compared with an N550 virgin carbon black sample.

[0082] In this invention, various relationships were discovered based on the phr of the media pulverization rC, preferably based on the pulverization time.

[0083] Regarding the rubber properties of the undispersed region (disperser grader%) of the filler in the elastomer composite, the undispersed region based on the medium grinding rC of a particular embodiment can be characterized based on Equation 2: Undispersed region (UA) ≤ 3.35 - (0.04 * phr rC). Phr rC is a media-ground rC according to the present invention and may be in the range of 10 phr to 50 phr, or 10 phr to 40 phr, 10 phr to 35 phr, 10 phr to 30 phr, 5 phr to 55 phr, or 7 phr to 20 phr. The media-ground rC may contain additional particulate fillers, such as carbon black, e.g., 35 to 110 m 2 Carbon black having a BET specific surface area of ​​1 / g, for example, carbon black from the N300 or N500 series, or for example, N330 or N550 carbon black, may be part of a blend. The total amount of filler may be 20-80 phr, for example, 30-70 phr, 40-60 phr, or 45-55 phr. The pulverized medium rC may be 10-40% by weight of the total filler, for example, 15-35% by weight or 20-30% by weight.

[0084] Abrasion volume loss (mm) in elastomer composites 3 Regarding the rubber properties, the wear volume loss based on the medium grinding rC of a particular embodiment can be characterized based on Equation 3: Wear Volume Loss (AVL) ≤ 100 + (0.1 * phr rC) (normalized to a control sample prepared by the same method except that N550 carbon black was used instead of pulverized rC). Phr rC is pulverized rC according to the present invention and may be in the range of 10 phr to 50 phr, or 10 phr to 40 phr, or 10 phr to 30 phr. Formula 3A: AVL ≤ 100 - (0.43 * phr rC) (normalized to N550 control) is achievable. Phr rC is media-ground rC according to the present invention and may be in amounts ranging from 10 phr to 50 phr, or in the range of 10 phr to 40 phr, 10 phr to 35 phr, 10 phr to 30 phr, 5 phr to 55 phr, or 7 phr to 20 phr. Media-ground rC may contain additional particulate fillers, such as carbon black, e.g., 35 to 110 m2 Carbon black having a BET specific surface area of ​​1 / g, for example, carbon black from the N300 or N500 series, or for example, N330 or N550 carbon black, may be part of a blend. The pulverized medium rC may be 10-40% by weight of the total filler, for example, 15-35% by weight or 20-30% by weight.

[0085] Regarding the rubber properties of strain stiffness (M300 / M100 index) in elastomer composites, for example, the strain stiffness (M300 / M100 index) based on the media grinding rC of a particular embodiment with a residence time of 2 minutes can be characterized based on Equation 4: M300 / M100 index ≥ 100 - (0.01 * phr rC)(normalized to N550 control). Phr rC is the media grinding rC according to the present invention, and may be in the range of 10 phr to 50 phr, or 10 phr to 40 phr, or 10 phr to 30 phr. Formula 4A: M300 / M100 exponent ≥ 100 + (0.38 * phr rC) (normalized to N550 control) is achievable. Phr rC is media-ground rC according to the present invention and may be in amounts ranging from 10 phr to 50 phr, or in the range of 10 phr to 40 phr, 10 phr to 35 phr, 10 phr to 30 phr, 5 phr to 55 phr, or 7 phr to 20 phr. Media-ground rC may contain additional particulate fillers, such as carbon black, e.g., 35 to 110 m 2 Carbon black having a BET specific surface area of ​​1 / g, for example, carbon black from the N300 or N500 series, or for example, N330 or N550 carbon black, may be part of a blend. The pulverized medium rC may be 10-40% by weight of the total filler, for example, 15-35% by weight or 20-30% by weight.

[0086] Regarding the rubber properties of high strain stiffness or tensile stress (M300) in elastomer composites, the high strain stiffness or tensile stress (M300) based on the media grinding rC of a particular embodiment can be characterized based on Equation 5: M300 ≥ 100 - (0.15 *phr rC) (normalized to N550 control). Phr rC is media-ground rC according to the present invention and may be in the range of 10 phr to 50 phr, or 10 phr to 40 phr, or 10 phr to 30 phr. Media-ground rC may contain additional particulate fillers, such as carbon black, e.g., 35 to 110 m 2 Carbon black having a BET specific surface area of ​​1 / g, for example, carbon black from the N300 or N500 series, for example, N330 or N550 carbon black, may be part of a blend. The pulverized medium rC may be 10-40% by weight of the total filler, for example, 15-35% by weight or 20-30% by weight. Formula 5A: M300≧100+(0.38 * phr rC)(normalized to N550 control) is achievable. In one embodiment, a method for processing granular carbon includes combining recycled carbon with water to form a mixture to form an initial slurry having 1 to 35% by weight of solids, and pulverizing the recycled carbon with a medium to form a medium-pulverized slurry of wet-pulverized recycled carbon and water.

[0087] The pyrolysis carbon can be combined with water to form an initial slurry having a solid filler content of 1 to 35% by weight, for example, 5 to 30% by weight, 7 to 25% by weight, 10 to 20% by weight, or 15 to 25% by weight. The filler content is preferably harmonized with the filler content requirements of downstream processes, including grinding and optional pelletizing.

[0088] The initial slurry may contain one or more auxiliary fillers, which may also benefit from being co-ground with pyrolysis carbon. Any particulate fillers that provide reinforcement or other beneficial properties to the rubber may be used. Exemplary auxiliary fillers include carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon (i.e., carbonaceous materials produced by the hydrothermal carbonization of lignin or other biomass, such as those described in, for example, U.S. Patent No. 1,0428218 or U.S. Patent No. 1,0035957, both of which are incorporated herein by reference), and artificial polysaccharides (such as those described in, for example, U.S. Patent Application Publication No. 2020 / 181370 and U.S. Patent Application Publication No. 2020 / 190270, both of which are incorporated herein by reference). Examples of carbon nanostructures (the entire content of which is incorporated herein by reference) include, but are not limited to, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, and carbon nanostructures such as those described in U.S. Patent Application Publication No. 2014 / 0093728 (the entire content of which is incorporated herein by reference), and carbon black coated particles (the entire content of which is incorporated herein by reference) such as those described in U.S. Patent No. 10519298. Preferably, macroscopic contaminants are removed from the pyrolysis carbon, either in a dry or slurry state, before combining the pyrolysis carbon with one or more auxiliary fillers. The auxiliary fillers may be combined with the pyrolysis carbon in a dry state, or may be added separately to water before, after, or simultaneously with the pyrolysis carbon to form an initial slurry. To avoid any segregation that may occur in the dry mixture of pyrolysis carbon and auxiliary fillers, the auxiliary fillers are preferably added directly to the water or initial slurry separately from the pyrolysis carbon. The ratio of pyrolysis carbon to auxiliary fillers in the initial slurry can be any range suitable for the desired end application and for grinding while maintaining an acceptable viscosity of the initial slurry.In one preferred embodiment, the auxiliary filler is virgin carbon black, for example, 35-110 mg. 2 Carbon black with a BET surface area of ​​1 / g, e.g., N300 or N500 series carbon black, e.g., N330 or N550 carbon black, and recycled carbon is used in amounts of 10-40% by weight of the total filler, e.g., 25-40% by weight, 15-35% by weight, or 20-30% by weight. In the continuous process, the auxiliary filler may be weighed continuously into the initial slurry or into a continuous flow of water, either as a powder or as an aqueous slurry of the auxiliary filler (or, if more than one auxiliary filler is used, as a slurry of more than one). Those skilled in the art will recognize that the appropriate packing amount for grinding depends on the properties of the auxiliary filler. For example, carbon nanotubes increase slurry viscosity at very low packing amounts, while higher packing amounts of precipitated silica may not dramatically increase viscosity.

[0089] Additional fillers may also be added to the pulverized slurry. Such additional fillers preferably do not require additional pulverization. Examples of additional fillers for addition to the pulverized slurry include, but are not limited to, carbon black, silica-coated carbon black, silica-treated carbon black, precipitated silica, carbon black-coated particles such as those described in U.S. Patent No. 10519298, and mixtures of two or more of these. Depending on the solid content of the pulverized slurry, it may also be desirable to add water along with the additional fillers to adjust the solid content of the resulting wet-blended carbon mixture. Alternatively or additionally, additional fillers may be added to the pulverized slurry as an aqueous slurry. In a continuous process, additional fillers may be continuously metered and supplied as a powder or aqueous slurry in the initial slurry or in a continuous flow of water. The total filler content may be such that the wet-blended carbon mixture can be easily formed into pellets or spray-dried. To form pellets, additional fillers and optional water added to the pulverized slurry may result in a solid content of 25–70% by weight, e.g., 30–65% by weight, 35–60% by weight, or 40–50% by weight, in the resulting wet-blended carbon mixture. In the case of spray drying, additional fillers and optional water added to the pulverized slurry may result in a solid content of 1–30% by weight, e.g., 1–10% by weight, 5–15% by weight, or 8–25% by weight, in the resulting wet-blended carbon mixture. In one preferred embodiment, the additional filler may be virgin carbon black, e.g., 35–110 m 2Carbon black having a BET surface area of ​​1 / g, such as N300 or N500 series carbon black, such as N330 or N550 carbon black, and recycled carbon is used in amounts of 10-40% of the total filler, for example, 25-40% by weight, 15-35% by weight, or 20-30% by weight. In the case of spray drying, it may be desirable to omit additional fillers. Those skilled in the art will know how to adjust the total filler load to prepare the desired pellets or the optimal load for spray drying in conventional equipment. The fillers added to the pulverized slurry may be the same as or different from any fillers added to the initial slurry.

[0090] Examples of carbon black for use in any of the embodiments of this specification include, but are not limited to, carbon blacks from the ASTM N100 series to N900 series, such as N100 series carbon black, N200 series carbon black, N300 series carbon black, such as N330 carbon black, N500 series carbon black, such as N550 carbon black, N600 series carbon black, N700 series carbon black, N800 series carbon black, or N900 series carbon black. Alternatively or additionally, such carbon blacks may have a viscosity of 35-110 m as measured by ASTM 6556. 2 The BET surface area may be 35-65 m² / g, for example. 2 / g, 65-90m 2 / g, or 90-110m 2The weight is / g. Trademarks Regal®, Black Pearls®, Spheron®, Sterling®, and Vulcan® available from Cabot Corporation, trademarks Raven®, Statex®, Furnex®, and Neotex® available from Birla Carbon (Columbian Chemicals), and carbon black sold under the CD and HV lines; trademarks Corax®, Durax®, Ecorax®, and Purex® available from Orion Engineered Carbons, as well as carbon blacks under the CK line and other lines, and other fillers suitable for use in rubber or tire applications may also be utilized in various embodiments. The carbon black may be chemically functionalized. Suitable chemically functionalized carbon blacks include those disclosed in International Publication No. 96 / 18688 and U.S. Patent Application Publication No. 2013 / 0165560, which are incorporated herein by reference.

[0091] Carbon black is at least about 15m 2 / g, for example, about 15m 2 / g ~ approx. 240m 2 / g, for example, about 35m 2 / g ~ approx. 230m2 / g, approx. 50m 2 / g~about 200m 2 / g, approx. 60m 2 / g ~ approx. 180m 2 / g, about 100m 2 / g~about 200m 2 It may have a statistical thickness surface area of ​​ / g (STSA, ASTM standard D6556).

[0092] Carbon black having any of the above surface areas may further have a structure indicated by the oil absorption capacity of compressed carbon black (COAN, ASTM D3493), approximately 50 to approximately 115 mL / 100g, for example, approximately 65 to approximately 75 mL / 100g, approximately 60 to approximately 95 mL / 100g, approximately 75 to approximately 85 mL / 100g, approximately 85 to approximately 95 mL / 100g, approximately 95 to approximately 105 mL / 100g, or approximately 105 to approximately 115 mL / 100g.

[0093] A mixture of any of these carbon blacks may be used.

[0094] The materials described herein as silicon-treated carbon black are not limited to coated or otherwise modified carbon black aggregates. They may also be different types of aggregates having two phases. One phase is carbon, still existing as graphite microcrystalline and / or amorphous carbon, while the second phase is silica, and possibly other silicon-containing species. Thus, the silicon-containing species phase of silicon-treated carbon black is an intrinsic part of the aggregate, distributed over at least a portion of it. Various silicon-treated blacks are available from Cabot Corporation under the name Ecoblack®, described in detail in U.S. Patent No. 6,028,137. It will be understood that multiphase aggregates differ significantly from the silica-coated carbon black described above, which consists of pre-formed single-phase carbon black aggregates with silicon-containing species deposited on their surface. Such carbon black may be surface-treated to arrange silica functional groups on the surface of the carbon black aggregate, for example, as described in U.S. Patents No. 6,929,783, 6,541,113 and 5,679,728.

[0095] Suitable precipitated silica for use in any of the embodiments herein includes both highly dispersible (HDS) granules and non-HDS precipitated silica. The precipitated silica may be chemically treated to include functional groups such as coupling agents that are bonded (adhered (e.g., chemically bonded)) or adsorbed (e.g., adsorbed) to the silica surface. Examples of suitable HDS grades include Perkasil® GT 3000GRAN silica from WR Grace & Co, Ultrasil® 7000 silica from Evonik Industries, Zeosil® 1165 MP and 1115 MP silica from Solvay SA, Hi-Sil® EZ 160G silica from PPG Industries, Inc., and Zeopol® 8741 or 8745 silica from Evonik Industries. Examples of suitable grades of conventional (non-HDS) precipitated silica include Perkasil® KS 408 silica from WR Grace & Co, Zeosil® 175GR silica from Solvay SA, Ultrasil® VN3 silica from Evonik Industries, and Hi-Sil® 243 silica from PPG Industries, Inc. Examples of suitable grades of hydrophobic precipitated silica include Agilon® 400, 454, or 458 silica from PPG Industries, Inc., and Coupsil® silica from Evonik Industries, such as Coupsil® 6109 silica.

[0096] Wet-blended carbon mixtures can be densified, for example, by granulation or pelletization. Any densification or pelletization method known to those skilled in the art can be used. For example, the method of Glaxner U.S. Patent No. 2,065,371 can be used. Generally, wet-blended carbon mixtures are formed into beads, which may then be optionally dried to reduce the water content to at most 1% to form blended carbon pellets. In addition to the water already present in the wet-blended carbon mixture, a wide variety of binder additives are known to be useful in the wet pelletization process to further improve the handling properties of the resulting pellets. Examples of such additives include, but are not limited to, hygroscopic organic liquids such as ethylene glycol, carbohydrates (e.g., sugars, molasses, soluble starch, sugars, lignin derivatives), rosin, sulfonates and sulfate anionic surfactants, fatty amine ethoxylate nonionic surfactants, sodium lignosulfonate, silane, sucrose, alkyl succinimide, alkylated succinate esters, and polyethylene oxide copolymer polydimethylsiloxane surfactants. Alternatively or additionally, the pellets do not need to be dried and may be used in a wet state, in which case a binder is not required. For example, wet pellets may have a water content of 15-80% by weight, for example, 40-60% by weight.

[0097] The resulting particulate filler may exist in the form of wet pellets or dry pellets, or in other forms (e.g., slurry before pelletizing or other drying methods), and may contain, on a dry basis, 2 to 100% by weight, for example, 5 to 98% by weight or 8 to 90% by weight, 10 to 60% by weight, 15 to 50% by weight, 10 to 100% by weight or 15 to 60% by weight, 10 to 90% by weight, 15 to 80% by weight, 20 to 60% by weight, or 30 to 50% by weight, or 20 to 50% by weight of recycled carbon, preferably wet-ground recycled carbon, and the remainder The additional and / or supplemental fillers are fillers other than recycled carbon, for example, one or more of the additional and / or supplemental fillers listed above, e.g., carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, artificial polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, and carbon black-coated particles. In certain preferred embodiments, the additional and / or auxiliary fillers are virgin carbon black, e.g., carbon black from the N300 or N500 series, e.g., N550 or N330 carbon black, and recycled carbon is present in the pellet in an amount of 10-40% by weight of the total fillers in the pellet, e.g., 25-40% by weight, 15-35% by weight, or 20-30% by weight. As described above, the pellets may contain a binder.

[0098] Alternatively or additionally, the wet-blended carbon mixture may be spray-dried using any spray-drying apparatus known to those skilled in the art. The resulting spray-dried particles may contain, on a dry basis, 2 to 100% by weight of recycled carbon, e.g., 5 to 98% by weight, 8 to 90% by weight, 10 to 60% by weight, 15 to 50% by weight, 10 to 100% by weight, 15 to 60% by weight, 10 to 90% by weight, 15 to 80% by weight, 20 to 60% by weight, 30 to 50% by weight, or 20 to 50% by weight of recycled carbon, preferably wet-ground recycled carbon, and further, 0 to 98% by weight, e.g., 2% to 95% by weight, 10% to 92% by weight, 40 to 90% by weight, or 50% to 80 or 85% by weight of carbon black, silica-coated carbon black, silica-treated carbon black, precipitated silica, or carbon black-coated particles. The material may contain additional fillers selected from the children and mixtures of two or more thereof, and may further contain one or more auxiliary fillers selected from carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, artificial polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, and carbon black-coated particles in amounts of 0 to 98% by weight, for example, 2% to 95% by weight, 10% to 92% by weight, 40 to 90% by weight, or 50% to 80 or 85% by weight. In certain preferred embodiments, the additional and / or auxiliary filler is virgin carbon black, e.g., N300 or N500 series carbon black, e.g., N550 or N330 carbon black, and recycled carbon is present in the spray-dried particles in an amount of 10-40% by weight, e.g., 25-40% by weight, 15-35% by weight, or 20-30% by weight.

[0099] Wet pellets, dry pellets, and / or spray-dried particles according to various embodiments of this specification can be combined with elastomers to form elastomer composites. The resulting elastomer composites may contain particulate fillers of 30 to 90 phr, for example, 30 to 70 phr, 35 to 60 phr, or 40 to 55 phr. The particulate fillers may contain 2 to 100% recycled carbon, for example, 5 to 98% by weight or 8 to 90% by weight, preferably 10 to 100% by weight, 10 to 90% by weight, 15 to 80% by weight, 20 to 60% by weight, or 30 to 50% by weight of recycled carbon. In certain preferred embodiments, the additional and / or supplemental fillers are carbon black, e.g., N300 or N500 series carbon black, e.g., N550 or N330 carbon black, and recycled carbon is present in the pellets in an amount of 10–40% by weight of the total fillers in the pellets, e.g., 25–40% by weight, 15–35% by weight, or 20–30% by weight. Both natural rubber and synthetic elastomers of any grade can be used. Blends of elastomers can also be used. For example, wet pellets, dry pellets and / or spray-dried particles may be combined with an elastomer to form a masterbatch, which may then be combined with additional elastomers of the same or different composition. Alternatively or additionally, two or more elastomers may be blended before mixing with the pellets. Alternatively or additionally, the elastomer composite may contain one or more fillers other than recycled carbon, and the fillers include any of the particulate fillers listed elsewhere in this specification and any other fillers known to those skilled in the art for use in elastomer composites. Such fillers may be included in the mixture or pellets together with pulverized recycled carbon, or, according to various embodiments herein, wet pellets, dry pellets, and / or spray-dried particles may be added separately to the elastomer.

[0100] Exemplary classes of elastomers include, but are not limited to, polymers such as rubber, 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dialkyl-1,3-butadiene (where alkyl may be methyl, ethyl, propyl, etc.), acrylonitrile, ethylene, and propylene (e.g., homopolymers, copolymers, and / or terpolymers). Elastomers may have a glass transition temperature (Tg) in the range of about -120°C to about 50°C, as measured by differential scanning calorimetry (DSC). Examples include, but are not limited to, styrene-butadiene rubber (SBR), natural rubber and their functionalized derivatives, such as epoxidized and chlorinated rubber, polybutadiene rubber, polyisoprene rubber, ethylene-propylene copolymer (e.g., EPDM), isobutylene rubber (e.g., butyl rubber), polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polyisoprene rubber, polysulfide rubber, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, and any of these oil-extracted derivatives. Any of the aforementioned blends and / or functionalized derivatives may also be used. Natural rubber may also be treated to chemically or enzymatically modify or reduce various non-rubber components.

[0101] Particularly suitable synthetic rubbers include copolymers of about 10 to about 70% by weight of styrene and about 90 to about 30% by weight of butadiene, for example, copolymers of 19 parts styrene and 81 parts butadiene, copolymers of 30 parts styrene and 70 parts butadiene, copolymers of 43 parts styrene and 57 parts butadiene, and copolymers of 50 parts styrene and 50 parts butadiene; polymers and copolymers of conjugated dienes such as polybutadiene, polyisoprene, and polychloroprene; and copolymers of these conjugated dienes with ethylenically active monomers copolymerizable with these, such as styrene, methylstyrene, chlorostyrene, acrylonitrile, 2-vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, allyl-substituted acrylates, vinyl ketones, methylisopropenyl ketone, methyl vinyl ether, α-methylene carboxylic acid, and their esters and amides (e.g., acrylic acid and dialkylacrylamide). Furthermore, copolymers of ethylene and propylene, as well as other high-alpha-olefins such as 1-butene and 1-pentene, are also suitable for use herein.

[0102] The elastomer composite may further contain additives to facilitate mixing, to promote vulcanization, or to impart specific properties to the vulcanized product of the elastomer composite. Numerous additives are well known to those skilled in the art and include, for example, adhesion promoters, antioxidants, ozone degradation inhibitors, coupling agents, curing agents, decomposition inhibitors, plasticizers, processing aids (e.g., liquid polymers, oils, etc.), oil extenders, waxes, resins, flame retardants, extender oils, lubricants, tackifiers, vulcanization activators such as zinc oxide and fatty acids, vulcanization accelerators, and mixtures thereof. Exemplary additives include, but are not limited to, zinc oxide and stearic acid. The general use and selection of such additives are well known to those skilled in the art.

[0103] Dry pellets and / or spray-dried pellets may be combined with elastomers as described above using any drying and mixing method known to those skilled in the art.

[0104] Alternatively or additionally, wet pellets can be combined with elastomers in accordance with one or more teachings from U.S. Patent Application Publication No. 20220332016, International Publication No. 2021247153, International Publication No. 2022125679, International Publication No. 2022125683, International Publication No. 2022125677, and International Publication No. 2022125675, all of which are incorporated herein by reference. For example, wet pellets and elastomers in solid form can be placed in a mixer and mixed under conditions of controlled temperature to remove at least some of the water in the pellets by evaporation. The elastomer may optionally be pre-kneaded before the introduction of the wet pellets. The wet filler may be added all at once or in aliquots.

[0105] Wet pellets can be combined with elastomers using any suitable mixer, such as a Banbury mixer or Brabender mixer, or other internal or closed mixer, or open mixer, or extruder, or continuous compounder, or kneading mixer, or a combination thereof. Other mixers include kneading-type closed mixers. Closed mixers commercially available from Farrel-Pomini, Harburg Freudenberger Maschinenbau GmbH (HF), Kobelco, or Pelmar Eng'r Ltd can be used. In addition to the option of using an internal circuit of steam, water, or other fluid in a rotor, an internal mixer may, additionally or alternatively, have a cooling or heating jacket in one or more areas or parts of the mixing chamber to control the temperature of the components being mixed therein. This may involve forming one or more heating / cooling zones in the wall or part of the wall of the mixer. The mixer may be a single-stage mixer or a multi-stage mixer (e.g., two or more stages). Examples of usable mixers and designs are described in European Patent No. 2423253(B1) and U.S. Patent No. 7,556,419, which are incorporated herein by reference.

[0106] Alternatively, the mixer may be a continuous mixer. For example, solid elastomers and wet fillers may be mechanically processed using one or more of the following: a continuous internal mixer, a twin-screw extruder, a single-screw extruder, or a roll mill, such as those described in U.S. Patent No. 9,855,686 (B2), the disclosure thereof is incorporated herein by reference. Suitable mixing and kneading equipment is well known to those skilled in the art and is commercially available, including, for example, the Unimix Continuous Mixer and MVX (Mixing, Venting, eXtruding) Machine from Farrel Pomini Corporation (Ansonia, Conn.), the FCM® Farrel Continuous Mixer, the Pomini Continuous Mixer, twin-rotor co-meshing extruder, twin-rotor counter-meshing extruder, continuous compounding extruder, the twin-screw grinding extruder from Kobe Steel, Ltd., and the Kobe Continuous Mixer. Alternative kneading equipment suitable for use with one or more embodiments disclosed herein is well known to those skilled in the art.

[0107] Mixing can be carried out using a mixer having at least one rotor, and the mixer may be one or more of a kneader, roll mill, screw extruder, twin-screw extruder, multi-screw extruder, continuous compounder, and / or twin-screw extruder. Mixing can be carried out using a mixer having at least one rotor, and the mixer may have a 2-blade rotor, a 4-blade rotor, a 6-blade rotor, an 8-blade rotor, and / or one or more screw rotors.

[0108] The mixing process for combining wet pellets with elastomer may be a single-stage or multi-stage process. In a multi-stage process, one or more mixers or mixer types may be used. In stages where a closed mixer is used, the filling percentage at each stage may be independently 72% or less, 70% or less, or 68% or less, or 66% or less, for example, about 30%-72%, 40%-70%, 45%-70%, 30%-60%, 50-72%, 50-70%, 50-68%, 60-72%, 60-70%, 60-68%, 65-72%, 65-70%, 65-68%, or 40-60%, or 50-60%. The mixer temperature may be controlled to control the temperature of the mixture, the amount of evaporated water, or both. For example, in a multi-stage process, the mixer temperature at each stage may be controlled to control the amount of water evaporated from the mixture in the first mixing stage and one or more subsequent stages. For example, the liquid content of the discharged composite material may be 10% to 99.9% (weight % vs. weight %), 10% to 95%, or 10% to 50% lower than the liquid content of the material introduced into the mixer. Alternatively or additionally, the rate of liquid release from the composite or mixture during mixing, for example by evaporation, can be measured as the time-averaged liquid release rate per kg of composite or mixture (e.g., total liquid removed / (release time × weight of composite)), and this rate may be 0.01 to 0.14 kg / (min·kg) or 0.01 to 0.07 kg / (min·kg), or other rates below or above this range.

[0109] Alternatively or additionally, mixing can provide a predetermined total specific energy (energy applied to a mixing system that drives one or more rotors per mass of composite material on a dry weight basis), for example, 1,000 kJ / kg composite material (or per kg of mixture present in the mixer) to 10,000 kJ / kg composite material (or per kg of mixture present in the mixer), for example, 2,000 kJ / kg to 5,000 kJ or 1,500 kJ / kg to 8,000 kJ / kg, 1,500 kJ / kg to 7,000 kJ / kg, 1,500 kJ / kg The specific energy can be controlled in one or more stages to allow values ​​such as g~6,000kJ / kg, 1,500kJ / kg~5,000kJ / kg, 1,500kJ / kg~3,000kJ / kg, 1,600kJ / kg~8,000kJ / kg, 1,600kJ / kg~7,000kJ / kg, 1,600kJ / kg~6,000kJ / kg, 1,600kJ / kg~5,000kJ / kg, 1,600kJ / kg~4,000kJ / kg, 1,600kJ / kg~3,000kJ / kg, or any other value in these ranges. Alternatively or additionally, the specific energy applied to the mixture can be divided to ensure that a predetermined amount of specific energy is applied before or after a portion of the filler, e.g., 75%, is added to the mixer. In other words, the filler does not need to be added all at once. The mixing time at each stage may be any appropriate time, for example, 1 to 40 minutes, 1 to 20 minutes, 1 to 15 minutes, 5 to 30 minutes, 5 to 20 minutes, 5 to 15 minutes, or 1 to 12 minutes, 1 to 10 minutes, 3 to 30 minutes, or other times. Alternatively or additionally, the dump discharge temperature at each stage may be 120°C to 180°C, 120°C to 190°C, 130°C to 180°C, for example, 140°C to 180°C, 150°C to 180°C, 130°C to 170°C, 140°C to 170°C, 150°C to 170°C, or other temperatures within or outside these ranges.

[0110] After any one or more mixing steps or stages, the resulting composite material may be subjected to one or more post-processing steps, for example, to mold or form the composite material and / or to enable improved handling. Post-processing can provide a composite material that can be dried, homogenized, extruded, calendered, crushed, granulated, cut, packaged, or sheeted. The composite material may be compounded and immediately vulcanized, or it may be held for a certain period before compounding. Suitable equipment for various post-processing steps includes, but is not limited to, one or more of the following: closed mixers, kneaders, roll mills, open mills, screw extruders, twin-screw extruders, multi-screw extruders, continuous compounders, and / or twin-screw discharge extruders equipped with roller dies (e.g., twin-screw sheeters) or fixed knives. Depending on the equipment or group of equipment used, it may be desirable to process the composite two or more times through the equipment, or through a series of similar or different equipment having the same or different operating settings (e.g., speed, temperature, energy input, etc.). Alternatively or additionally, the elastomer composite may be combined with added fillers, added elastomers, or both, before or as part of the vulcanization process. The additional fillers may be identical or different to the particulate fillers in the elastomer composite and may include any fillers known to those skilled in the art, including the fillers listed here as additional fillers and auxiliary fillers, and additional wet-ground recycled carbon. The added fillers and / or elastomers may increase or decrease the filler content of the vulcanized material relative to the elastomer composite.

[0111] To vulcanize elastomer composites, they are combined with a curing agent package containing a crosslinking agent, any necessary activators and accelerators, antioxidants, and any additional optional additives such as any of those listed above. When sulfur is used as a crosslinking agent, typical activators include zinc oxide and / or stearic acid, and typical accelerators include sulfenamides such as N-tert-butyl-2-benzothiazole sulfenamide (TBBS) and N-cyclohexyl-2-benzothiazole sulfonamide (CBS). Antioxidants include N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) and those described in International Publication No. 2012 / 037244. Other curing agents used in rubber processing include peroxides, urethane crosslinking agents, metal oxides, and acetoxysilane compounds. Further suitable components for sulfur-based and other crosslinking systems, as well as methods for mixing and vulcanizing elastomer composites, are well known to those skilled in the art. For example, typical procedures used in rubber compounding are described in Maurice Morton, Rubber Technology, 3rd Edition, Van Norstrand Reinhold Company, New York 1987, and 2nd Edition, Van Norstrand Reinhold Company, New York 1973.

[0112] Various rubber articles may incorporate vulcanized materials. For example, vulcanized materials may be incorporated into tires, such as pneumatic tires, non-pneumatic tires, or solid tires. For example, vulcanized materials may be incorporated into tire treads, tire carcasses, undertreads, inner liners, sidewalls, sidewall inserts, wire skims, or cushion gum for retreaded tires. Alternatively or additionally, vulcanized materials may be incorporated into hoses, linings, liners, seals, gaskets, vibration damping articles, trucks, track pads for truck propulsion vehicle systems, engine mounts, seismic stabilizers, mining equipment screens, mining equipment linings, conveyor belts, chute liners, slurry pump liners, mud pump impellers, valve seats, valve bodies, piston hubs, piston rods, plungers, slurry mixing impellers and slurry pump impellers, grinding mill liners, cyclones and hydrocyclones, expansion joints, linings for dredging pumps and outboard motor pumps for marine equipment, shaft seals for marine, petroleum, aerospace, and other applications, propeller shafts, or linings for pipes for transporting, for example, oil sands or tar sands. Alternatively or additionally, vulcanized materials may be incorporated into engine mounts, bushings, weatherstrips, windshield wipers, automotive parts, seals, gaskets, housings, and wheels or track elements.

[0113] The resulting vulcanized material may have fatigue properties equivalent to, or 10% or less less than, those of a vulcanized material produced by the same method and with the same composition, except that ASTM N550 carbon black is used instead of recycled carbon. Alternatively or additionally, the resulting vulcanized material may have fatigue properties equivalent to or exceeding 90% of those of a vulcanized material produced by the same method and using the same composition, except that recycled carbon is replaced with an equivalent amount of additional filler used in the vulcanized material produced according to the present invention.

[0114] The present invention includes the following aspects / embodiments / features in any order and / or any combination. 1. A method for processing recycled carbon, comprising grinding wet recycled carbon in a medium to obtain pulverized recycled carbon, wherein the medium grinding involves grinding 10 times per 1 kg of dry pulverized recycled carbon during the grinding process. 13 ~10 14 A method that brings about a medium collision. 2. A method for processing recycled carbon, comprising grinding wet recycled carbon through a medium to obtain pulverized recycled carbon, wherein the grinding involves grinding through a medium that consumes a specific energy of 1 kWh / kg to 10 kWh / kg compared to dry pulverized recycled carbon. 3. A method for processing recycled carbon, comprising grinding wet recycled carbon in a medium to obtain pulverized recycled carbon, wherein the medium grinding results in a volume-weighted particle size distribution of the pulverized recycled carbon measured by disk centrifugal photoprecipitation, where D50 is 250-400 nm, preferably 250-320 nm, and D90 is 350-1100 nm, for example 500-1100 nm. 4. The method according to any of the above or below embodiments / features / appearances, wherein the specific energy consumed during media grinding is 1 kWh / kg to 10 kWh / kg. 5. The method according to any of the above or below embodiments / features / appearances, wherein the specific energy consumed during media grinding is 1 kWh / kg to 3.5 kWh / kg. 6. The method according to any of the above or below embodiments / features / appearances, wherein the specific energy consumed during media grinding is 1.25 kWh / kg to 3.1 kWh / kg. 7. During the media grinding process, 10% of dry-ground recycled carbon is produced per 1 kg. 13 ~10 14 A method according to any of the above or below embodiments / features / appearances that results in a media collision. 8. During the media grinding process, 2 × 10⁶ units of dry-ground recycled carbon are produced per 1 kg. 13 ~10 14 The method of any of the above or below embodiments / features / appearances that results in individual media collisions. 9. During the media grinding process, dry grinding recycled carbon yields 3 × 10⁶ per 1 kg. 13 ~10 14The method of any of the above or below embodiments / features / appearances that results in individual media collisions. 10. The method according to any of the above or below embodiments / features / appearances, wherein the media grinding is agitated ball mill grinding, planetary ball mill grinding, or centrifugal ball mill grinding. 11. The method according to any of the above or below embodiments / features / appearances, wherein the media grinding is agitated ball mill grinding. 12. The method of any of the above or below embodiments / features / appearances, wherein the media being ground is solid balls having an average size of approximately 0.25 mm to 2 mm, for example, 0.25 to 1 mm, and a volume filling amount of 50% to 98% in the mill. 13. The method according to any of the above or below embodiments / features / appearances, wherein the volume-weighted particle size distribution of the media-pulverized recycled carbon, as measured by disk centrifugal photoprecipitation, has a D50 of 250-400 nm, preferably 250-320 nm, and a D90 of 350-1100 nm, for example, 500-1100 nm. 14. The method according to any of the above or below embodiments / features / appearances, wherein the grinding is such that the rubber sample having 20-60 phr of ground recycled carbon yields less than 10% or less than 5% of undispersed region (disperser grader%). 15. The method according to any of the above or below embodiments / features / appearances, wherein the pulverization is a rubber sample having 20-80 phr of particulate filler, e.g., 30-70 phr, 40-60 phr, or 45-55 phr of particulate filler, and 10-40% by weight, e.g., 15-35% by weight, or 20-30% by weight, of which the rubber sample has a maximum of 3% undispersed region, e.g., 1-3% undispersed region. 16. Grinding is performed on rubber samples with a grinding rC of 10-50 phr, for example, 10-40 phr, where UA ≤ 3.35 - (0.04 * The method according to any of the above or below embodiments / features / appearances, having an undistributed region UA ​​that satisfies phr rC). 17. The method of any above or below embodiment / feature / appearance, wherein the grinding results in a wear volume loss of 20-60 phr of a rubber sample having ground recycled carbon, which is not more than 10% higher or within 5% of a comparative rubber sample manufactured by the same method but containing N550 carbon black instead of ground recycled carbon. 18. A rubber sample having particulate filler of 20-80 phr, e.g., 30-70 phr, 40-60 phr, or 45-55 phr, wherein 10-40% by weight, e.g., 15-35% by weight, or 20-30% by weight, is recycled carbon from the grinding medium, and the rubber sample is measured according to ASTM D5963 to 90-100 mm 3 For example, 91-95mm 3 The method according to any of the above or below embodiments / features / appearances, having wear loss. 19. The particulate filler contains virgin carbon black, for example, 35-110 m 2 The method according to any of the above or below embodiments / features / appearances, wherein the carbon black having a BET surface area of ​​ / g is, for example, carbon black of the N300 or N500 series, for example, N330 or N550 carbon black, for example, N330 carbon black. 20. The method of any above or below embodiment / feature / appearance, wherein the grinding results in a rubber sample having 20-60 phr of ground recycled carbon, which is a) not less than 10% or less than 5% of a comparative rubber sample manufactured in the same manner but containing N550 carbon black instead of ground recycled carbon, or b) is 4.5-5. 21. The method according to any of the above or below embodiments / features / appearances, wherein the grinding results in a rubber sample having 20-60 phr of ground recycled carbon that is not more than 10% lower or not more than 5% lower than a comparative rubber sample manufactured by the same method but containing N550 carbon black instead of ground recycled carbon, with a maximum load (N) of M300 (MPa) or not more than 5% lower. 22. The method according to any one of the embodiments / features / appearances described above or below, wherein the particle size is measured according to the PSD method 1. 23. Grinded recycled carbon produced by any of the above or below embodiments / features / appearances described herein. 24. A particulate filler containing 10-40% by weight of recycled carbon, wherein the volume-weighted particle size distribution of the recycled carbon, as measured by disk centrifugal photoprecipitation, has a D50 of 250-400 nm, preferably 250-320 nm, and a D90 of 350-1100 nm, for example, 500-1100 nm. 25. Particulate fillers according to any of the above or below embodiments / features / appearances, comprising 15-35% by weight of recycled carbon, or 20-30% by weight of recycled carbon, or 25-35% by weight of recycled carbon. 26. Particulate fillers according to any above or below embodiments / features / appearances, further comprising one or more of the following: carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, artificial polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, and carbon black-coated particles. 27. Particulate fillers according to any of the above or below embodiments / features / aspects, further comprising carbon black having an OAN of 85-120 mL / 100g, for example, 90-117 mL / 100g, 95-115 mL / 100g, 100-113 mL / 100g, or 105-115 mL / 100g. 28. Particulate fillers according to any of the above or below embodiments / features / appearances, further comprising carbon black. 29. 35~11m 2 / g, for example, 35-65m 2 / g, 65-90m 2 / g, or 90-110m 2 A particulate filler according to any of the above or below embodiments / features / appearances, further comprising carbon black having a BET surface area of ​​1 / g. 30. Particulate fillers according to any of the above or below embodiments / features / aspects, further comprising carbon black of the N300 or N500 series, for example, N330 or N550 carbon black. 31. Particulate filler according to any of the above or below embodiments / features / appearances, wherein the particulate filler is in the form of pellets. 32. Particulate fillers according to any of the above or below embodiments / features / aspects, wherein the pellets substantially consist of particulate filler, optionally selected water, and optionally selected binder. 33. Particulate fillers of any of the above or below embodiments / features / appearances having a water content of 15-80%, for example, 40-60% by weight. 34. Particulate fillers of any of the above or below embodiments / features / aspects, wherein a rubber sample having 20-60 phr of pulverized recycled carbon results in less than 10% or less than 5% of undispersed region (disperser grader%). 35. A rubber sample having particulate fillers of 20-80 phr, for example, 30-70 phr, 40-60 phr, or 45-55 phr, having a maximum of 3% undispersed region, for example, 1-3% undispersed region, according to any of the above or below embodiments / features / aspects of particulate fillers. 36. A rubber sample containing recycled carbon of 10-50 phr, for example 10-40 phr, has a UA ≤ 3.35 - (0.04 * A particulate filler according to any of the above or below embodiments / features / appearances, having an undispersed region UA ​​satisfying phr rC). 37. Particulate fillers of any of the above or below embodiments / features / aspects that cause wear volume loss of a rubber sample having 20-60 phr of recycled carbon not more than 10% or less than 5% of a comparative rubber sample manufactured by the same method but having N550 carbon black instead of recycled carbon. 38. Rubber samples having particulate fillers of 20-80 phr, for example, 30-70 phr, 40-60 phr, or 45-55 phr, measured according to ASTM D5963, are 90-100 mm 3 For example, 91-95mm3 A particulate filler of any of the above or below embodiments / features / models having wear loss. 39. Particulate fillers of any of the above or below embodiments / features / aspects, wherein a rubber sample having 20-60 phr of recycled carbon results in an M300 / M100 ratio of a) not less than 10% or less than 5% of a comparative rubber sample manufactured by the same method but having N550 carbon black instead of recycled carbon, or b) 4.5-5. 40. A particulate filler of any of the above or below embodiments / features / models, wherein a rubber sample having 20-60 phr of recycled carbon yields a M300 (MPa) or maximum load (N) of a comparative rubber sample manufactured by the same method but having N550 carbon black instead of recycled carbon, at a rate not more than 10% lower or not more than 5% lower. 41. Particulate fillers of any of the above or below embodiments / features / models, the particle size of which is measured according to the PSD method 1. 42. A pellet comprising particulate filler according to any of the above or below embodiments / features / aspects, wherein the particulate filler further comprises at least one additional filler selected from carbon black, silicon-treated carbon black, silica-coated carbon black, carbon black-coated particles, and precipitated silica. 43. An elastomer composite comprising particulate filler according to any of the above or below embodiments / features / aspects and at least one elastomer, further optionally comprising one or more of the following: carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, artificial polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, and carbon black-coated particles. 44. Elastomer composites according to any of the above or below embodiments / features / models, wherein the elastomer composite is selected from natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, polyisoprene rubber, ethylene-propylene copolymer, isobutylene-based rubber, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, and blends thereof. 45. An elastomer composite according to any of the above or below embodiments / features / appearances, wherein the elastomer composite is a vulcanized elastomer composite. 46. ​​An elastomer composite according to any of the above or below embodiments / features / appearances having undispersed regions with a dispersion of 4% or less, for example, 3% or less of undispersed regions, or 1% to 3% of undispersed regions. 47. An elastomer composite according to any of the above or below embodiments / features / appearances, wherein the elastomer composite has 20 to 60 phr of particulate filler and less than 10% or less than 5% of undispersed regions (disperser grader%). 48. An elastomer composite according to any of the above or below embodiments / features / appearances, wherein the elastomer composite has particulate fillers of 20-80 phr, e.g., 30-70 phr, 40-60 phr, or 45-55 phr, and up to 3% undispersed region, e.g., 1-3% undispersed region (disperser grader %). 49. The elastomer composite has a medium grinding rC of 10-40 phr, for example, 10-40 phr, and UA ≤ 3.35 - (0.04 * An elastomer composite according to any of the above or below embodiments / features / models, having an undispersed region UA ​​that satisfies phr rC). 50. An elastomer composite according to any above or below embodiment / feature / appearance, wherein the elastomer composite has 20-60 phr of recycled carbon and has an abrasion volume loss that is not higher than 10% or within 5% of a comparative rubber sample having N550 carbon black instead of pulverized recycled carbon. 51. The elastomer composite contains particulate fillers of 20-80 phr, e.g., 30-70 phr, 40-60 phr, or 45-55 phr, and measures 90-100 mm according to ASTM D5963. 3 For example, 91-95mm 3 An elastomer composite according to any of the above or below embodiments / features / models having wear loss. 52. An elastomer composite according to any of the above or below embodiments / features / appearances, wherein the elastomer composite has an M300 / M100 ratio, wherein the elastomer composite is 20-60 phr of recycled carbon and a) not less than 10% or less than 5% of a comparative rubber sample having N550 carbon black instead of pulverized recycled carbon, or b) 4.5-5. 53. An elastomer composite having M300 (MPa) or a maximum load (N), having 20-60 phr of recycled carbon, and not less than 10% or less than 5% of a comparative rubber sample having N550 carbon black instead of pulverized recycled carbon. 54. A tire tread comprising a vulcanized product of a mixture comprising an elastomer composite according to any of the above or below embodiments / features / aspects and a curing agent package. 55. An article comprising a vulcanized product of a mixture comprising any of the above or below embodiments / features / models of an elastomer composite and a curing agent package. 56. Articles as described in any of the above or below embodiments / features / appearances, which are incorporated into a pneumatic tire, a non-pneumatic tire, or a solid tire. 57. Articles as described in any of the above or below embodiments / features / appearances, wherein the article is selected from tire treads, undertreads, inner liners, sidewalls, sidewall inserts, wire skims, and cushion gum for retreaded tires. 58. Articles in any above or below embodiments / features / models selected from hoses, linings, liners, seals, gaskets, vibration-damping articles, trucks, track pads for truck propulsion vehicle equipment, engine mounts, seismic stabilizers, mining equipment screens, mining equipment linings, conveyor belts, chute liners, slurry pump liners, mud pump impellers, valve seats, valve bodies, piston hubs, piston rods, plungers, slurry mixing impellers and slurry pump impellers, grinding mill liners, cyclones and hydrocyclones, expansion joints, linings for dredging pumps and outboard motor pumps for marine equipment, shaft seals for marine, petroleum, aerospace and other applications, propeller shafts, pipe linings, engine mounts, bushings, weatherstrips, windshield wipers, automotive parts, seals, gaskets, housings, wheel elements and track elements.

[0115] The present invention will be further illustrated by the following embodiments, which are intended to be essentially illustrative. [Examples]

[0116] Example 1 N550 and N330 CB pellets were jet-pulverized in a 4-inch (10.2 cm) Micron Master Jet Pulverizer SN 1634_Model 04-626 at a flow rate of approximately 2 kg / hr, an upper pressure of 80 psi (0.55 MPa), and a lower pressure of 40 psi (0.03 MPa) to obtain bulk material. rC was obtained in bulk form from a commercially available supplier, and the reported D50 was 2 μm. The measured PSD of this material is shown in Figures 1 and 6. All materials were dispersed in water at 14 wt% to form a slurry for pulverization. Wet pulverization was performed on a MiniCer media mill (Netzsch) using 0.5 mm YSZ beads at an 85% packing density and 4200 rpm in recirculation batch mode. "Residence time" was given by the formula "Residence time" = "Batch time". *The calculation is performed using "Mill Volume" / "Batch Volume," where "Batch Time" is the total execution time of the batch, "Mill Volume" is the volume of the grinding chamber minus the volume occupied by the medium, and "Batch Volume" is the total volume of the batch being ground.

[0117] A pulverized slurry containing 86% by weight of water was stirred on a hot plate set to 80°C until the moisture content reached 70% by weight. The batch was then pelletized in a pelletizer (Feeco Inc.) operated at 900 rpm by combining it with bulk N550 in a mass ratio of 4:6 to achieve a total moisture content of 50% by weight, thereby enabling pellet formation. Depending on the mixing method, the pellets were either dried in an 80°C oven or kept moist until mixing.

[0118] To characterize the particle size obtained in the slurry, a pulverized rC slurry (14 wt% solid) was diluted to 2000 ppm with DI water containing 600 ppm Triton X100 surfactant. The diluted solution was then mixed at 800 RPM for 5 minutes using a DISPERMAT LC55 mixer equipped with a lightweight 30 mm diameter 18-tooth impeller. The solution was then stirred for 24 hours using a magnetic stirring rod on a stirring plate. The sample solution was then further diluted to 400 ppm with DI water containing 400 ppm Triton X100 surfactant and kept rotating in a 40 ml vial on rollers until measurement.

[0119] Disk centrifuge (DC24000, CPS Instruments) measurements were performed at 5000 RPM. First, 24%, 22%, 20%, 18%, 16%, 14%, 12%, 10%, and 8% sucrose solutions in DI water were sequentially injected into the disk (1.6 ml each), followed by the injection of 1 ml of dodecane to seal the gradient. The gradient was given 1 hour to stabilize before measurement. In the disk centrifuge measurements, the held refractive index was 1.86 g / cm³. 3 n = 1.84 + 0.846i. The result was 1.86 g / cm³. 3This shows the equivalent sedimentation results for spherical particles with density and refractive index n = 1.84 + 0.846i. All measurements were stopped immediately after the signal reached the baseline.

[0120] The changes in particle size are shown in Figures 1 and 6. The particle distribution of the starting material had a D90 of 9 μm. After a residence time of 2.5 minutes, the D90 decreased to 3 μm and continued to decrease until it reached 0.34 μm after 40 minutes.

[0121] To determine what residence time is sufficient for the desired rubber properties, the pulverized material was tested in the SBR composite material. Details of each example, including the formulation and mixing protocols, are provided in Table 2 below.

[0122] [Table 2-1] [Table 2-2]

[0123] Table 2 shows the buffer solutions used in the experiment. In the experiment, the symbols / representations in Table 2 and Figures 2-5, along with the data results, have the following meanings. Dried N330 = N330 carbon black; rC is not present. Pelletize and dry before mixing. Wet N550 X min = N550, ground medium, where X indicates the grinding residence time - for example, "wet rC 20 min" means N550 medium ground for a residence time of 20 minutes and then co-pelletized with bulk N550 in a mass ratio of 4:6. Do not dry before mixing. Dried N550 = N550 carbon black; rC is not present. Pelletize and dry before mixing. Wet rC X minutes = rC, a medium ground according to the present invention, where X represents the grinding residence time. For example, "Wet rC 20 minutes" means that rC was ground for 20 minutes and then co-pelletized with bulk N550 in a mass ratio of 4:6. Do not dry before mixing. Dry rC blend = 4:6 parts by mass of rC and N550, co-pelletized and dried before mixing. Wet rC blend = 4:6 parts by mass of rC and N550, co-pelletized, not dried before mixing. Dry rC bulk blend = Non-pelletized rC and N550 mixed using a standard drying method. Dried rC = rC that has not been ground into a medium but has been pelletized and dried. Wet rC = rC that has not been ground into pellets but has not been dried. Dry rC bulk = rC that has not been crushed, pelletized, or mixed using conventional drying methods. For the "undried" samples, the degree of moisture content was such that the water content was 50% by weight.

[0124] In addition to the media-ground rC sample, the option of introducing rC as a bulky material, as well as the wet mixing of rC wet pellets and copellets, were evaluated. Figure 2 shows the dispersion quality in the resulting mixtures. The dry, bulky, and wet processes all produced rC mixes with worse dispersion than the control sample (long dashed circle), but the media-ground sample (short dashed circle) had dispersion comparable to the carbon black control sample (solid circle).

[0125] The experiment also demonstrated an improvement in rubber performance. Figure 3 shows the DIN wear volume loss. The media grinding material (short dashed circle) showed a volume loss comparable to the wet N550 2-minute control (solid circle), while other rC methods (long dashed circle) showed performance degradation compared to the control. The 40-minute residence time indicates degradation, likely due to deterioration of the rC structure, as seen in material softening, which can adversely affect DIN wear.

[0126] The slope of the tensile curve of the rubber compound, known as reinforcement, is important for wear performance. In Figure 4, the ratio of stresses at 300% and 100%, M300 / M100, was plotted to quantify reinforcement. As shown in the experiment, wet mixing resulted in N550 being more reinforced, comparable to dry-mixed N330. Reinforcement decreased when mixing was done using dry, wet, or cotton methods by increasing the rC content. However, the pulverized rC in the present invention did not show a decrease.

[0127] rC often exhibits inferior stiffness compared to CB mixtures. When rC was incorporated using bulky, dry, or wet methods, the expected decrease in stress at 300% elongation (M300) occurred, as shown in Figure 5. However, no decomposition was observed in the experiments conducted for this invention.

[0128] One optimal grinding time for strengthening and wear in these experiments was 20 minutes, but as shown in Figure 5, the optimal grinding time for low strain stiffness was 5 minutes. This may be due to the fracture of aggregates up to 5 minutes and the subsequent deterioration of the aggregate structure after 5 minutes.

[0129] Based on these observations, significantly higher rC content is possible by using media grinding to treat rC before manufacturing the composite. Compared to N550 compounds prepared by wet mixing, composites with up to 100% substitution may be possible with little to no degradation of properties.

[0130] Table 3 below summarizes some of the results achieved by the present invention and normalized against the “Wet N550 2 min” control described in the above examples. These normalized results were used to derive formulas describing the performance with and without the application of the present invention. [Table 3]

[0131] Rubber compounding: Rubber compositions were prepared using the formulations shown in Table 2. The SBR used was Kralex SBR 1502 styrene-butadiene rubber (Synthos). N550 was Spheron SO (Cabot Corp.). N330 was Vulcan 3 (Cabot Corp.). The jet-milled rC, not pelletized, was Carbon Green 6 (CBp Cyprus Ltd., Limassol, Cyprus), and in some examples, it was pelletized as shown in Table 2. Stearic acid, rubber grade (Akrochem Corp.); zinc oxide was RGT-M (Akrochem Corp.). Wax was AKROWAX (trademark) 5031 (Akrochem Corp.). Antioxidant was DQ (Akrochem Corp.). 6 PPD was Standard 6 PPD (Harwick Standard). Sulfur was Rubbermakers Sulfur (Akrochem Corp.). The BBTS was Accelerator BBTS (Akrochem Corp.). All compositions were mixed in a 1.6 L Banbury mixer equipped with two blade rotors. Dry mixed samples (pellet moisture < 1 wt%) were prepared in two steps as shown in Table 4. Wet mixed samples (pellet moisture > 1 wt%) were prepared in three steps as shown in Table 5. In any case, after each compounding step, the compound was sheeted on a two-roll mill operated at 50°C and approximately 22 rpm, followed by a 60-second banding process and passing through six times with a nip gap of approximately 5 mm, with a rest period of at least 3 hours before the next mixing step (or vulcanization after the final step). Curing was carried out in a heated press (150°C, 2500 lbs) for 40% of the time T90 + T90 as determined by a conventional rubber rheometer, where T90 is the time to reach 90% vulcanization. [Table 4] [Table 5]

[0132] Performance data for each vulcanized material was obtained using the following tests. Tensile stress at 100% elongation (M100) and 300% elongation (M300) were evaluated according to ASTM D412 (Test Method A, Die C) at 23°C, 50% relative humidity, and a crosshead speed of 500 mm / min. Tensile strain was measured using an extensometer. The M300 / M100 ratio is called the tensile stress ratio (or modulus ratio). For analysis of variance, cured rubber samples were cut using a razor blade fixed to a manual cutting jig. The samples were placed on a Dispergrader (Alpha Technologies) and imaged. The following settings were used: "Filler volume fraction", 20%; "Exposure time", 40 ms; "Analytical color channel", "Blue"; "Dispersion calculation threshold", 23 μm; "Activate aggregated fraction", 1; White area threshold, 0. The amount reported as "White area %" by the Alpha Technologies instrument was interpreted as "Undispersed area". DIN wear was evaluated according to the standard ASTM D5963 rotational method.

[0133] Example 2 N330 CB pellets (Cabot Corporation) were subjected to a jet mill to produce a bulky material as described in Example 1. rC pellets (Reoil-RCB, REOIL SP) were jet-milled. The resulting material had a D50 at 488 nm and a D90 at 3430 nm, as measured as described below. The jet-milled rC material was dispersed in water at 14% by weight to form a slurry for grinding. Wet grinding was performed on a Netzsch MiniCer wet media mill using 0.5 mm yttria-stabilized zirconia beads (YSZ, 3000 rpm or 4600 rpm) or 0.4-0.6 mm polystyrene beads (4600 rpm only), in a pass-through mode (single pass unless otherwise specified) with residence times and other settings as described in Table 6 below. The number of impacts was the same for polystyrene beads. However, the energy imparted during media grinding using PS beads is 0.5 times the energy imparted during media grinding using YSZ beads. [Table 6]

Table 7

[0134] To characterize the particle size obtained in the slurry, the milled rC slurry was diluted to 2000 ppm with DI water containing 600 ppm of Triton X100 surfactant. The diluted solution was then mixed at 800 RPM for 5 minutes by a DISPERMAT LC55 mixer equipped with a lightweight 30 mm diameter 18-tooth impeller. The solution was then stirred for 24 hours using a magnetic stir bar on a stirring plate. The sample solution was then further diluted to 400 ppm using DI water containing 400 ppm of Triton X100 surfactant and left rotating in a 40 ml vial on a roller until measurement.

[0135] Disk centrifuge (DC24000, CPS Instruments) measurements were performed at 5000 RPM. First, 24%, 22%, 20%, 18%, 16%, 14%, 12%, 10%, 8% sucrose solutions in DI water were sequentially injected into the disk (1.6 ml each), and then 1 ml of dodecane was injected to seal the gradient. The gradient was given 1 hour to stabilize before measurement. In the disk centrifuge measurement, the sample density and refractive index were set as 1.86 g / cm 3 and n = 1.84 + 0.846i. The results represent the equivalent sedimentation results of spherical particles having a density of 1.86 g / cm 3 and a refractive index of n = 1.84 + 0.846i. All measurements were stopped immediately after the signal reached the baseline. The D50 and D90 of various samples are shown in Table 7 below. 3 。

Table 8

[0136] A pulverized slurry containing 86 wt% water was centrifuged for 15 minutes using a Thermo Scientific Sorvall Legend XTR centrifuge to obtain a centrifugal cake that was approximately 70% solid. Each batch was then pelletized by combining appropriate amounts of centrifugal cake and slurry with bulk N330 carbon black in a rotating pin pelletizer operated at 900 rpm with walls heated to 50°C to form a blend containing 30 wt% rC and 70 wt% N330 carbon black. The pellets were dried in an oven at 80°C.

[0137] SBR composite materials were prepared using 50 phr (total) of rC and carbon black, following the mixing protocol in Table 4 and the vulcanization procedure described in Example 1, with the formulations listed in Table 8 (chemical substances described in Example 1). The samples were tested as described in Example 1. [Table 9]

[0138] As shown in Figure 7 (RT = Residence time (minutes)), even minimal grinding dramatically improved dispersion in the SBR compound, with several samples having grinding rC with a D90 of less than 1500 nm all showing an undispersed area of ​​less than 3% by weight. However, dispersion did not completely correlate with wear performance, with only grinding rC with a D90 of less than 1100 nm showing a wear of 95 mm during the wear test. 3 This resulted in a mass loss of less than 2.5 mPa (Figure 8; RT = residence time (minutes)). Furthermore, only pulverized rC with a D50 of 250-400 simultaneously yielded an M100 of at least 2.5 mPa, while pulverized rC with a lower D50 also yielded a lower modulus of elasticity (Figure 9, RT = residence time (minutes)).

[0139] Example 3 N330 CB pellets (Cabot Corporation) were subjected to a jet mill to produce a bulky material as described in Example 1. rC pellets (Reoil-RCB, REOIL SPZO.O.) were jet-milled and dispersed in water at 14% by weight to form a grinding slurry. Wet grinding was performed on a MiniCer media mill (Netzsch) using 0.5 mm YSZ beads at 85% packing density and 4600 rpm in recirculation batch mode with a residence time of 5 minutes. The particle sizes were characterized as described in Example 1. D50 was 271 microns and D90 was 412 microns.

[0140] A portion of the pulverized slurry containing 86% by weight water was centrifuged for 15 minutes using a Thermo Scientific Sorvall Legend XTR centrifuge to obtain a centrifugal cake. The centrifugal cake was then combined with the pulverized slurry to form a mixed slurry with the water content shown in Table 9. Each batch was then pelletized in a rotating pin pelletizer operated at 900 rpm with walls heated to 50°C by combining the mixed slurry with an appropriate amount of bulky N330 carbon black to achieve the rC and carbon black ratios shown in Table 9 below. Neat rC pellets were produced by drying the centrifugal cake at 80°C until a water content of 46% was reached. Bulky N330 was combined with water to achieve a solid fill content of approximately 58% by weight to form neat pellets. Depending on the mixing method, the pellets were either dried in an oven at 80°C or kept moist until rubber mixing. [Table 10]

[0141] SBR composite materials were prepared with 50 phr (total) of rC and carbon black using the formulations (chemicals described in Example 1) as listed in Table 8, along with the vulcanization procedure described in Example 1, and either the wet or dry mixing protocol described in Example 1. The rubber properties were measured using the method described in Example 1. As shown in Figure 10, grinding (black circles) dramatically improves filler dispersion compared to samples that were not ground in a media (white circles), particularly at 26% and 40% rC. However, at 100% rC, dry pellets show a dramatic decrease in dispersion quality, while elastomer composites produced using wet pellets still maintain good dispersion performance. This correlation is also observed in abrasion performance (Figure 11; media-ground sample - black circles; jet-mill ground sample - white circles).

[0142] Example 4 30% by weight of media pulverized and jet-pulverized rC and 70% Propel E6 carbon black STSA = 97m 2 Copellets from Cabot Corporation ( / g) were prepared together with jet-ground N330 carbon black pellets as described in Example 3. An SBR composite material containing 50 phr of filler was prepared as described in Example 3, except that 6 PPD was supplied from Westco, and characterized as described in Example 1. As shown in Table 10 below, by using medium-ground rC in combination with a carbon black with a higher surface area, such as Propel E6 carbon black, better or equivalent performance than that of N330 carbon black can be obtained (STSA = 76m). 2 ( / g). [Table 11]

[0143] While the present invention has been specifically shown and described with reference to its preferred embodiments, it will be understood by those skilled in the art that various modifications in form and detail can be made without departing from the scope of the invention as encompassed by the appended claims.

[0144] Where used herein, the terms "and / or" include any and all combinations of one or more of the enumerated items associated with them. Furthermore, all conjunctions used should be understood in the most comprehensive sense possible. Thus, the word "or" should be understood as having the logical definition of "or" rather than the logical definition of "exclusive OR," unless the context clearly requires otherwise. Additionally, the singular forms and the articles "a," "an," and "the" are intended to include the plural forms unless otherwise specified. It will be further understood that, where used herein, the terms "includes," "comprises," "including," and / or "comprising" indicate the presence of at least one of the described features, integers, processes, operations, elements, and components, but do not exclude the presence or addition of at least one other feature, integer, process, operation, element, component, or group thereof. Furthermore, if an element containing a component or subsystem is mentioned and / or indicated as being connected to or coupled to another element, it will be understood that it may be directly connected to or coupled to the other element, or that intervening elements may exist.

[0145] Unless otherwise specified, all terms used herein (including technical and scientific terms) have the same meaning as those commonly understood by those skilled in the art to which this invention pertains. Terms as defined in commonly used dictionaries should be interpreted as having the same meaning as their meaning in the context of the relevant art, and it will be further understood that they should not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0146] The applicants hereby specifically incorporate into this disclosure the entire contents of all cited references. Furthermore, where a quantity, concentration, or other value or parameter is given as a range, a preferred range, or a list of preferred upper and lower limits, this should be understood as specifically disclosing all ranges formed from any pair of any upper or preferred value and any lower or preferred value of any range, regardless of whether the range is disclosed separately. Where a numerical range is described herein, unless otherwise specified, the range is intended to include its endpoints, as well as all integers and fractions within that range. The range of the present invention is not intended to be limited to any specific values ​​enumerated when defining a range. For any range provided herein, the numerical range may be "about" these ranges, and vice versa, and where a range is provided using the term "about," these ranges may be exactly the numerical range provided. Any combination of embodiments, and / or components, and / or constituents, and / or properties described herein can be made herein and are considered part of the present invention.

[0147] Other embodiments of the present invention will be apparent to those skilled in the art from the discussion herein and the practice of the present invention disclosed herein. This specification and the examples, together with the true scope and spirit of the present invention as set forth by the following claims and equivalents, are intended to be illustrative only.

[0148] The above description of preferred embodiments of the present invention is presented for illustrative and explanatory purposes only. It is not intended to be exhaustive or to limit the invention to the exact forms disclosed. Modified and altered forms can be considered in light of the above art or obtained from the practice of the invention. The embodiments have been selected and described to illustrate the principles of the invention and their practical application, enabling those skilled in the art to utilize the invention in various embodiments and with various modifications suitable for specific intended uses. The scope of the invention is intended to be defined by the claims and equivalents appended herein.

Claims

1. A method for processing recycled carbon, comprising grinding wet recycled carbon in a medium to obtain pulverized recycled carbon, wherein the medium grinding involves 10 per 1 kg of dry pulverized recycled carbon during the grinding process. １３ ~10 １４ A method that brings about a medium collision.

2. A method for processing recycled carbon, comprising grinding wet recycled carbon through a medium to obtain pulverized recycled carbon, wherein the grinding includes grinding through a medium that consumes a specific energy of 1 kWh / kg to 10 kWh / kg of dry pulverized recycled carbon.

3. A method for processing recycled carbon, comprising grinding wet recycled carbon in a medium to obtain pulverized recycled carbon, wherein the medium grinding results in a volume-weighted particle size distribution of the pulverized recycled carbon measured by disk centrifugal photoprecipitation, where D50 is 250 to 400 nm, preferably 250 to 320 nm, and D90 is 350 to 1100 nm, for example, 500 to 1100 nm.

4. The method according to claim 1 or 3, wherein the specific energy consumed during the grinding of the media is 1 kWh / kg to 10 kWh / kg.

5. The method according to any one of claims 1 to 4, wherein the specific energy consumed during the grinding of the media is 1 kWh / kg to 3.5 kWh / kg.

6. The method according to any one of claims 1 to 5, wherein the specific energy is 1.25 kWh / kg to 3.1 kWh / kg.

7. The aforementioned media grinding process involves 10% of dry-ground recycled carbon per 1 kg during the grinding process. １３ ~10 １４ The method according to any one of claims 2 to 6, which brings about a media collision.

8. The aforementioned media grinding process involves 2 × 10 per kg of dry-ground recycled carbon during the grinding process. １３ ~10 １４ The method according to any one of claims 1 to 7, which brings about a media collision.

9. The aforementioned media grinding process involves 3 × 10 per kg of dry-ground recycled carbon during the grinding process. １３ ~10 １４ The method according to any one of claims 1 to 8, which brings about a media collision.

10. The method according to any one of claims 1 to 9, wherein the media grinding is performed by a stirred ball mill, a planetary ball mill, or a centrifugal ball mill.

11. The method according to any one of claims 1 to 10, wherein the media grinding is performed by stirring ball mill grinding.

12. The method according to any one of claims 1 to 11, wherein the media being ground is a solid ball having an average size of about 0.25 mm to 2 mm, for example, 0.25 to 1 mm, and a volume filling amount of 50% to 98% in the mill.

13. The method according to any one of claims 1 to 12, wherein the volume-weighted particle size distribution of the pulverized recycled carbon medium, as measured by disk centrifugal photoprecipitation, has a D50 of 250 to 400 nm, preferably 250 to 320 nm, and a D90 of 350 to 1100 nm, for example, 500 to 1100 nm.

14. The method according to any one of claims 1 to 13, wherein the grinding is such that the rubber sample having 20 to 60 phr of the ground recycled carbon results in an undispersed region (disperser grader %) of less than 10% or less than 5%.

15. The method according to any one of claims 1 to 14, wherein the pulverization is a rubber sample having 20 to 80 phr of particulate filler, for example 30 to 70 phr, 40 to 60 phr, or 45 to 55 phr of particulate filler, and 10 to 40% by weight, for example 15 to 35% by weight or 20 to 30% by weight of the rubber sample is recycled carbon from a pulverized medium, and the rubber sample has a maximum of 3% undispersed region, for example 1 to 3% undispersed region.

16. The pulverization is such that a rubber sample having a pulverized rC of 10 to 50 phr, for example 10 to 40 phr, has an undispersed region UA satisfying UA ≤ 3.35 - (0.04 ＊ phr rC), according to the method of any one of claims 1 to 15.

17. The method according to any one of claims 1 to 16, wherein the grinding is such that a rubber sample having 20 to 60 phr of the ground recycled carbon results in an abrasion volume loss that is not more than 10% or less than 5% of a comparative rubber sample produced by the same method but having N550 carbon black instead of the ground recycled carbon.

18. The aforementioned grinding is performed on a rubber sample having 20-80 phr of particulate filler, for example 30-70 phr, 40-60 phr, or 45-55 phr of particulate filler, wherein 10-40% by weight, for example 15-35% by weight or 20-30% by weight, is recycled carbon from the grinding medium, and the rubber sample is measured according to ASTM D5963 to be 90-100 mm. ３ For example, 91-95 mm ３ The method according to any one of claims 1 to 17, wherein the method has wear loss.

19. The particulate filler contains virgin carbon black, for example, 35 to 110 m ２ The method according to claim 18, wherein the carbon black having a BET surface area of ​​1 / g is, for example, carbon black of the N300 or N500 series, for example, N330 or N550 carbon black, for example, N330 carbon black.

20. The method according to any one of claims 1 to 19, wherein the grinding is such that a rubber sample having 20 to 60 phr of the ground recycled carbon results in an M300 / M100 ratio of a) not less than 10% or less than 5% of a comparative rubber sample produced by the same method but having N550 carbon black instead of the ground recycled carbon, or b) any of 4.5 to 5.

21. The method according to any one of claims 1 to 20, wherein the grinding is such that a rubber sample having 20 to 60 phr of the ground recycled carbon yields an M300 (MPa) or maximum load (N) that is not more than 10% lower or more than 5% lower than a comparative rubber sample produced by the same method but containing N550 carbon black instead of the ground recycled carbon.

22. The method according to any one of claims 1 to 21, wherein the particle size is measured according to the PSD method 1.

23. Crushed recycled carbon produced by the method described in any one of claims 1 to 22.

24. A particulate filler containing 10 to 40% by weight of recycled carbon, wherein the volume-weighted particle size distribution of the recycled carbon, as measured by disk centrifugal photoprecipitation, has a D50 of 250 to 400 nm, preferably 250 to 320 nm, and a D90 of 350 to 1100 nm, for example, 500 to 1100 nm.

25. The particulate filler according to claim 24, comprising 15 to 35% by weight of recycled carbon, or 20 to 30% by weight of recycled carbon, or 25 to 35% by weight of recycled carbon.

26. The particulate filler according to claim 24 or 25, further comprising one or more of the following: carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, artificial polysaccharide, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxide, metal carbonate, single-walled carbon nanotube, multi-walled carbon nanotube, carbon nanostructure, and carbon black-coated particles.

27. The particulate filler according to any one of claims 24 to 26, further comprising carbon black having an OAN of 85 to 120 mL / 100 g, for example, 90 to 117 mL / 100 g, 95 to 115 mL / 100 g, 100 to 113 mL / 100 g, or 105 to 115 mL / 100 g.

28. A particulate filler according to any one of claims 24 to 27, further comprising carbon black.

29. 35-11m ２ / g, for example, 35-65m ２ / g, 65-90m ２ / g, or 90-110m ２ The particulate filler according to any one of claims 24 to 28, further comprising carbon black having a BET surface area of ​​1 / g.

30. The particulate filler according to any one of claims 24 to 29, further comprising carbon black of the N300 or N500 series, for example, N330 or N550 carbon black.

31. The particulate filler according to any one of claims 24 to 30, wherein the particulate filler is in the form of pellets.

32. The particulate filler according to any one of claims 24 to 31, wherein the pellet substantially comprises the particulate filler, optionally water, and optionally a binder.

33. A particulate filler according to any one of claims 24 to 32, having a water content of 15 to 80%, for example, 40 to 60% by weight.

34. The particulate filler according to any one of claims 24 to 33, wherein a rubber sample having 20 to 60 phr of pulverized recycled carbon yields an undispersed region (disperser grader %) of less than 10% or less than 5%.

35. A particulate filler according to any one of claims 24 to 34, wherein a rubber sample having particulate filler in an amount of 20 to 80 phr, for example, 30 to 70 phr, 40 to 60 phr, or 45 to 55 phr, has a maximum of 3% undispersed region, for example, 1 to 3% undispersed region.

36. A rubber sample having the recycled carbon of 10 to 50 phr, for example 10 to 40 phr, has a UA ≤ 3.35 - (0.04 ＊ A particulate filler according to any one of claims 24 to 35, having an undispersed region UA ​​that satisfies phr rC.

37. A particulate filler according to any one of claims 24 to 36, wherein a rubber sample having 20 to 60 phr of recycled carbon results in a wear volume loss that is not more than 10% higher, or within 5%, of a comparative rubber sample manufactured by the same method but having N550 carbon black instead of recycled carbon.

38. A rubber sample having particulate filler of 20-80 phr, for example, 30-70 phr, 40-60 phr, or 45-55 phr, measured according to ASTM D5963, yields 90-100 mm ３ For example, 91-95 mm ３ A particulate filler according to any one of claims 24 to 37, having wear loss.

39. A particulate filler according to any one of claims 24 to 38, wherein a rubber sample having 20 to 60 phr of recycled carbon results in an M300 / M100 ratio of a comparative rubber sample manufactured by the same method but having N550 carbon black instead of recycled carbon, which is not less than 10% or less than 5%, or b) any of 4.5 to 5.

40. A particulate filler according to any one of claims 24 to 39, wherein a rubber sample having 20 to 60 phr of recycled carbon yields an M300 (MPa) or maximum load (N) that is not more than 10% lower or more than 5% lower than a comparative rubber sample manufactured by the same method but having N550 carbon black instead of recycled carbon.

41. A particulate filler according to any one of claims 24 to 40, wherein the particle size is measured according to the PSD method 1.

42. A pellet comprising a particulate filler according to any one of claims 24 to 41, wherein the particulate filler further comprises at least one additional filler selected from carbon black, silicon-treated carbon black, silica-coated carbon black, carbon black-coated particles, and precipitated silica.

43. An elastomer composite comprising particulate filler according to any one of claims 23 to 41, at least one elastomer, and optionally one or more of the following: carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, artificial polysaccharide, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxide, metal carbonate, single-walled carbon nanotube, multi-walled carbon nanotube, carbon nanostructure, and carbon black-coated particles.

44. The elastomer composite according to claim 43, wherein the elastomer composite is selected from natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, polyisoprene rubber, ethylene-propylene copolymer, isobutylene rubber, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomer, fluoroelastomer, perfluoroelastomer, and blends thereof.

45. The elastomer composite according to claim 43 or 44, wherein the elastomer composite is a vulcanized elastomer composite.

46. The elastomer composite according to any one of claims 43 to 45, having undispersed regions with a dispersion of 4% or less, for example, undispersed regions of 3% or less, or undispersed regions of 1% to 3%.

47. The elastomer composite according to any one of claims 43 to 46, wherein the elastomer composite has 20 to 60 phr of particulate filler and less than 10% or less than 5% of undispersed regions (disperser grader%).

48. The elastomer composite according to any one of claims 43 to 47, wherein the elastomer composite comprises 20 to 80 phr of particulate filler, for example, 30 to 70 phr, 40 to 60 phr, or 45 to 55 phr of particulate filler, and up to 3% of undispersed region, for example, 1 to 3% of undispersed region (disperser grader %).

49. The elastomer composite is 10 to 40 phr, for example, 10 to 40 phr of media pulverization rC, and UA ≤ 3.35 - (0.04 ＊ The elastomer composite according to any one of claims 43 to 48, having an undispersed region UA ​​that satisfies phr rC.

50. The elastomer composite according to any one of claims 43 to 49, wherein the elastomer composite has 20 to 60 phr of recycled carbon and has an abrasion volume loss that is not higher than 10% or within 5% of a comparative rubber sample having N550 carbon black instead of the pulverized recycled carbon.

51. The elastomer composite contains particulate fillers of 20-80 phr, for example, 30-70 phr, 40-60 phr, or 45-55 phr, and measures 90-100 mm according to ASTM D5963. ３ For example, 91-95 mm ３ An elastomer composite according to any one of claims 43 to 50, having wear loss.

52. The elastomer composite according to any one of claims 43 to 51, wherein the elastomer composite has an M300 / M100 ratio of 20 to 60 phr of recycled carbon and a) a comparative rubber sample having N550 carbon black instead of the pulverized recycled carbon, which is not less than 10% or less than 5%, or b) 4.5 to 5.

53. The elastomer composite according to any one of claims 43 to 52, wherein the elastomer composite has 20 to 60 phr of recycled carbon, and has an M300 (MPa) or maximum load (N) that is not less than 10% or less than 5% of a comparative rubber sample having N550 carbon black instead of the pulverized recycled carbon.

54. A tire tread comprising a vulcanized product of a mixture comprising an elastomer composite and a curing agent package according to any one of claims 43 to 53.

55. An article comprising a vulcanized product of a mixture comprising an elastomer composite and a curing agent package according to any one of claims 43 to 53.

56. An article according to any one of claims 43 to 53, which is incorporated into a pneumatic tire, a non-pneumatic tire, or a solid tire.

57. The article according to claim 55 or 56, wherein the article is selected from tire treads, undertreads, inner liners, sidewalls, sidewall inserts, wire skims, and cushion gum for retreaded tires.

58. The article according to claim 55, wherein the article is selected from hoses, linings, liners, seals, gaskets, vibration-damping articles, trucks, track pads for truck propulsion vehicle equipment, engine mounts, seismic stabilizers, mining equipment screens, mining equipment linings, conveyor belts, chute liners, slurry pump liners, mud pump impellers, valve seats, valve bodies, piston hubs, piston rods, plungers, slurry mixing impellers and slurry pump impellers, grinding mill liners, cyclones and hydrocyclones, expansion joints, linings for dredging pumps and outboard motor pumps for marine equipment, shaft seals for marine, petroleum, aerospace and other applications, propeller shafts, pipe linings, engine mounts, bushings, weatherstrips, windshield wipers, automotive parts, seals, gaskets, housings, wheel elements and track elements.

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