Processes for treating recovered carbon and resulting crushed recovered carbon and products containing it

Abstract

The invention relates to processes for treating recycled carbon. The invention further relates to processes using grinding media to improve one or more properties of recycled carbon in products, such as elastomeric composites. The grinding media used may include grinding media that expends a specific energy of 1 kWh / kg to 10 kWh / kg of dry-ground recycled carbon.

Description

Title of the invention: Methods for treating recovered carbon and resulting ground recovered carbon and products containing the same

[0001] CONTEXT OF THE INVENTION

[0002] The present invention relates to methods of processing recycled carbon (rC). The present invention further relates to ground recycled carbon useful for incorporation into products, such as elastomers.

[0003] There is increasing demand and effort in the field of recycling materials in order to prevent materials from being disposed of in landfills and avoid further depletion of natural resources.

[0004] End-of-life vehicle tires are frequently processed and reused in a wide range of end-use applications, from playground equipment to concrete. However, it is desirable to recycle tire components to obtain materials that can be combined with first-use materials to reduce the amount of new material needed to manufacture new products.

[0005] There is a growing need for more sustainable materials and a reduced carbon footprint in different industries. Thus, the use of recycled carbon (rC) from used tires (or other sources) as a substitute for carbon black (CB) in rubber reinforcement applications may be a promising strategy. Tires and other rubbers contain different carbon blacks and other fillers with diverse morphologies, as well as ceramic additives such as zinc oxide. Therefore, the resulting rC has a different composition and microstructure than virgin carbon black. Recycled carbon suffers from poor rubber reinforcement, such as low tensile modulus, low tear strength, and / or low fatigue life, compared to a CB with the same surface area and structure as measured by OAN.Accordingly, there is a need in the industry to develop processes that can utilize rC particles and other similar particles that are not suitable as such for use as filler in rubber reinforcement and other applications so as to make them a suitable replacement or partial replacement for virgin carbon black. SUMMARY OF THE INVENTION

[0006] A feature of the present invention is to provide methods for upgrading recycled carbon for use in products.

[0007] An additional feature of the present invention is to provide the ability to utilize recycled carbon without interfering with the ability to produce industrially acceptable products, such as elastomers.

[0008] Another feature of the present invention is to provide methods for making recycled carbon a more viable material for use as a reinforcement grade material or filler grade material in applications such as elastomers and the like.

[0009] Another additional feature of the present invention is to provide methods for processing recycled carbon for use in a polymer matrix or an elastomer matrix and maintaining substantially most, if not all, of the product properties (e.g., undispersed surface area, abrasion volume loss, M300 / M100, M300, M100).

[0010] Another feature of the present invention is to provide methods that "refine" recycled carbon to obtain or improve a certain property (such as undispersed surfaces, M300, M100, M300 / M100, or volume loss by abrasion).

[0011] Further, a feature of the present invention is to provide methods for processing recycled carbon, such that the particles in combination, for example, with virgin carbon black, can have comparable filler properties, such as, but not limited to, acceptable dispersion compared to using 100% virgin carbon black.

[0012] An additional feature of the present invention is to provide crushed recycled carbon and to provide products containing it.

[0013] To achieve these and other advantages, and in accordance with the objectives of the present invention, as embodied and broadly described herein, the present invention relates, in part, to a method of processing recycled carbon. The method comprises grinding wet recycled carbon to obtain ground recycled carbon and the grinding involves or at least includes the use of grinding media grinding that expends a specific energy of at least 1 kWh / kg or at least 1.25 kWh / kg, or at least 1.5 kWh / kg of dry ground recycled carbon.

[0014] Furthermore, the present invention relates to a method for processing recycled carbon, the method comprising at least grinding the wet recycled carbon to obtain ground recycled carbon, and the grinding comprising at least grinding body grinding such that the number of collisions per kg of dry ground recycled carbon of the recycled carbon can lead to at least 1013 grinding body collisions per kg of dry ground recycled carbon during grinding, or at least 2 X 1013 grinding body collisions per kg of dry ground recycled carbon during grinding, or well grinding by grinding media can result in at least 5 X 1013 collisions with the grinding media per kg of dry ground recycled carbon during grinding.

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

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

[0017] As used herein, "char residue" means a solid material resulting from the pyrolysis of rubber articles.

[0018] As used herein, "dry-milled recycled carbon" is pyrolysis carbon that is substantially free of macroscopic contaminants and has been milled without the use of water and optionally granulated.

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

[0020] As used herein, "recovered raw carbon" is a solid material resulting from the pyrolysis of rubber articles that contain at least two different types of carbonaceous particulate fillers, including, but not limited to, carbon black (e.g., at least two different types of carbon black), in any amount.

[0021] As used herein, "treated recycled carbon" means raw recycled carbon that has been treated to remove at least one macroscopic contaminant such as fabric or yarn.

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

[0023] As used herein, "ground recycled carbon" or "ground rC" is pyrolysis carbon that is substantially free of macroscopic contaminants and has been ground.

[0024] As used herein, "recycled carbon" is recovered raw carbon that has been processed to remove macroscopic contaminants and has optionally been further ground. Thus, processed recycled carbon, ground recycled carbon, dry ground recycled carbon, and wet ground recycled carbon all fall within the definition of recycled carbon.

[0025] As used herein, “wet-milled recycled carbon” is pyrolysis carbon that is substantially free of macroscopic contaminants and which has been ground in the presence of at least 50% by weight, preferably 65 to 99% by weight of water, relative to the total weight of the materials being ground.

[0026] The method may further comprise removing macroscopic contaminants from the initial suspension, which may optionally contain up to 35% by weight of solids. The combination may further comprise combining at least one additional filler material with water to form the liquid suspension. The additional filler material may be selected from the group consisting of carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, modified polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clays, nanoclays, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, carbon black-coated particles, and mixtures of two or more thereof.

[0027] The method may further comprise adding at least one additional filler material selected from carbon black, silicon-treated carbon black, silica-coated carbon black, carbon black-coated particles, and precipitated silica to the milled slurry to bring the solids content of the resulting wet-blended carbon mixture to 25 to 70% by weight. The addition may comprise adding an aqueous slurry comprising the one or more additional filler materials, adding additional water to the milled slurry, or both. The method may further comprise granulating the wet-blended carbon mixture to form pellets or spray drying the wet-blended carbon mixture and, optionally, drying the pellets.

[0028] The water may be a continuous stream of water, the milled slurry may be a continuous stream of the milled slurry, and the combination may include dosing pyrolysis carbon into the continuous stream of water. The combination may further include dosing at least one additional filler material into the continuous stream of water. The additional filler material may be selected from the group consisting of carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, modified polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clays, nanoclays, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, carbon black-coated particles, and mixtures of two or more thereof.The method may further comprise dosing at least one additional filler material selected from . carbon black, silicon-treated carbon black, silica-coated carbon black, carbon black-coated particles, and precipitated silica to the milled slurry to bring the solids content of the resulting continuous stream of wet-mixed carbon mixture to 25 to 70% by weight or 1 to 35% by weight. The dosing may include dosing an aqueous suspension of the additional filler material into the continuous stream of milled slurry, dosing additional water into the continuous stream of milled slurry, or both.

[0029] In any of these embodiments, the method may further comprise granulating the wet mixed carbon mixture, for example, by granulating the wet mixed carbon mixture to form pellets or spray drying the wet mixed carbon mixture. The pellets may be dried. The milled slurry may be spray dried or its solids may be otherwise granulated. For example, the milled slurry may be dehydrated to a predetermined moisture level and then granulated.

[0030] In another embodiment, the invention comprises granules produced using any combination or subcombination of the above process steps.

[0031] In any of these embodiments, the particulate filler material may further comprise one or more additional fillers selected from carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, modified polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clays, nanoclays, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, and carbon black-coated particles. The particulate filler material may have a moisture content of 15 to 80 wt.%, for example 40 to 60 wt.%.

[0032] The particulate filler material may be in the form of granules. The granules may comprise 15 to 80% water, for example 40 to 60% water, or may contain at most 3% water and / or may consist essentially of a particulate filler material, optionally water and an optional binder. A granule may contain a particulate filler material according to any of these embodiments and at least one additional filler material selected from carbon black, silicon-treated carbon black, silica-coated carbon black, carbon black-coated particles and precipitated silica.

[0033] In another embodiment, an elastomeric composite comprises a blend of an elastomer and 30 to 90 phr of particulate filler, for example 30 to 70, 35 to 60 or 40 to 55 phr. The particulate filler comprises at least 10 % by weight of recycled carbon, for example 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, preferably 10% by weight to 40% by weight or 20 to 40% by weight of recycled carbon. The recycled carbon preferably has a D50 of 250 to 400 nm, more preferably 250 to 320 nm, and a D90 of 350 to 1100 nm, for example 500 to 1100 nm. The particulate filler material may further comprise one or more of carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, modified polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clays, nanoclays, 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 material preferably comprises carbon black.

[0034] In any of these embodiments, the elastomer may be selected from natural rubbers, functionalized natural rubbers, styrene-butadiene rubbers, functionalized styrene-butadiene rubbers, polybutadiene rubbers, functionalized polybutadiene rubbers, polyisoprene rubbers, ethylene-propylene copolymers, isobutylene-based rubbers, polychloroprene rubbers, nitrile rubbers, hydrogenated nitrile rubbers, polysulfide rubbers, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, and mixtures thereof.

[0035] In any of these embodiments, the recycled carbon may be wet-milled recycled carbon. In any of these embodiments, the elastomeric composite may be a vulcanized elastomeric composite. A tire tread may comprise a vulcanizate of a blend of the elastomeric composite with a vulcanization preparation. Alternatively or additionally, an article may comprise a vulcanizate of a blend of the elastomeric composite with a vulcanization preparation. The article may be incorporated into pneumatic tires, non-pneumatic tires, or solid tires. The article may be selected from tire treads, undertreads, inner rubbers, sidewalls, sidewall inserts, a thin wire coating, and a toe rubber for retreaded tires.The item can be selected from flexible hoses, liners, intermediates, seals, gaskets, anti-vibration items, tracks, track pads for tracked vehicle equipment, engine mounts, seismic stabilizers, mining equipment guards, mining equipment liners, conveyor belts, chute liners, pump liners for . slurries, mud pump impellers, valve seats, valve bodies, piston hubs, piston rods, plungers, slurry mixing impellers and slurry pump impellers, mill linings, cyclones and hydrocyclones, expansion joints, linings for dredge pumps and outboard motor pumps for marine equipment, seals for marine, oilfield, aerospace and other applications, propeller shafts, pipe linings, engine mounts, bushings, weather stripping, windshield wipers, automotive components, gaskets, packings, housings, wheel components and track components.

[0036] In another embodiment, an elastomeric composite comprises a blend of an elastomer and 30 to 90 phr of particulate filler material. In some embodiments, the particulate filler material comprises at least 10% by weight of recycled carbon. In any of these embodiments, the elastomeric composite may be vulcanized and / or the recycled carbon may be wet-milled recycled carbon.

[0037] It is to be understood that the above general description and the following detailed description are given by way of example only and are intended to provide further explanation of the present invention as claimed.

[0038] The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate various features of the present invention and, together with the description, serve to explain the principles of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] [Fig. 1] [Fig. 1] is a graph showing the plot of volume-weighted frequency versus particle size in nm, for samples taken at different residence times during the grinding process, to represent the change in particle size as a function of residence time in the mill with the grinding media. The "base sample" plot describes the particle size distribution in the suspension before the start of grinding.

[0040] [Fig. 2] [Fig. 2] is a graph showing the amount of undispersed surface area in cured elastomeric composites containing 50 phr of filler as a function of rC concentration in blends / formulations for different rC processing methods, as indicated by the data labels. The data, in the figure, shows control blends without rC (solid circle), media-milled samples of the present invention (short dashed circles), and rC blends that were not media-milled (long dashed circles). The media-milling residence time is indicated on the data labels.

[0041] [Fig.3] [Fig.3] is a graph showing the volume loss by abrasion of compounds having 50 phr of filler material with different mixing processes as a function of the rC concentration. The data in the graph show control mixtures without rC (solid circle), mixtures with rC ground by grinding media (short dotted circle) and other rC mixing processes without grinding media (long dotted circles).

[0042] [Fig.4] [Fig.4] is a graph showing the reinforcement index M300 / M100 in cured elastomeric composites containing 50 phr of filler, as a function of rC concentration. The data in the graph show control mixes without rC (solid circle), mixes with rC ground by grinding media (short dotted circle) and other rC mixing processes without grinding media (long dotted circles).

[0043] [Fig.5]] [Fig.5] is a graph showing the volume loss by abrasion of compounds having 50 phr of filler material mixed by different mixing processes as a function of the rC concentration. The data in the graph show control mixtures without rC (solid circle), mixtures with rC ground by grinding media (short dotted circle) and other rC mixing processes without grinding media (long dotted circles).

[0044] [Fig.6] [Fig.6] is a graph showing the particle size distribution versus volume % for samples with different grinding times and a control distribution is also shown.

[0045] [Fig.7] [Fig.7] is a graph showing % undispersed surface area versus particle size distribution (D90) for samples ground at different times (in minutes, RT = residence time) and speeds.

[0046] [Fig.8] [Fig.8] is a graph showing volume loss by abrasion as a function of particle size distribution (D90) for samples ground at different times (in minutes, RT = residence time) and speeds.

[0047] [Fig.9] [Fig.9] is a graph representing M100 as a function of particle size distribution (D90) for samples ground at different times (in minutes, RT = residence time) and speeds.

[0048] [Fig. 10] [Fig. 10] is a graph of % undispersed surface area versus loading (wt%) for samples prepared with (solid circles) and without (open circles) media grinding.

[0049] [Fig. 11] [Fig. 11] is a graph showing volume loss by abrasion (mm3) as a function of filler material loading (wt%) for samples prepared with (solid circles) and without (open circles) grinding media.

[0050] The figures are not to scale and are provided as simplified views and do not necessarily represent all possible embodiments or components that may be present. DETAILED DESCRIPTION OF THE INVENTION

[0051] The present invention relates, in part, to methods for improving the condition of recycled carbon such that one or more properties of the product containing the recycled carbon are maintained or substantially maintained compared to using 100% virgin carbon black for 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 ground recycled carbon, and the grinding comprising at least grinding media grinding which expends a specific energy of at least 1 kWh / kg, or at least 1.25 kWh / kg, or at least 1.5 kWh / 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, when the grinding media grinding is carried out with a grinding media 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 the wet recycled carbon to obtain ground recycled carbon, and the grinding comprising at least grinding media grinding such that the number of collisions per kg of dry ground recycled carbon of the recycled carbon may result in at least 1013 grinding media collisions per kg of dry ground recycled carbon during grinding, or at least 2 X 1013 grinding media collisions per kg of dry ground recycled carbon during grinding, for example 3 X 1013 grinding media collisions per kg to 1014 grinding media collisions per kg, or 4 X 1013 grinding media collisions per kg to 8 X 1013 grinding media collisions per kg, or 5 X 1013 grinding media collisions per kg to 6 X 1013 collisions with the grinding body per kg of dry-ground recycled carbon during grinding.

[0054] Other aspects and options relating to the methods of the present invention are also described herein.

[0055] With the present invention, it has been unexpectedly discovered that grinding RC using grinding media grinding techniques (e.g., as described herein) relative to unground rC or rC without a grinding media or with a grinding media having a diameter greater than 2 mm, can enhance or improve one or more particular properties of the rubber or elastomer (referred to herein as "rubber properties"). With the present invention, it has been discovered that grinding rC using grinding media grinding techniques can improve certain rubber properties as a function of the time a unit volume element of suspension spends in the grinding media mill (residence time). Furthermore, certain rubber properties are better improved at shorter grinding times and other rubber properties at longer grinding times, and for all rubber properties, it has been found that, in general, rubber properties are not further improved beyond a certain grinding time and therefore there is a range of grinding times advantageous for obtaining or improving certain properties and avoiding excessive grinding of the rC. As described herein, the grinding media milled rC and the method for forming it of the present invention were compared with virgin carbon black N550 (as a control), since this type of carbon black, in the past, has proven difficult to replace, even partially, with rC, even milled rC.

[0056] Recycled carbon or starting rC (to be subjected to grinding), such as rC aggregates, is commercially available. Typically, rC aggregates are derived from the pyrolysis of tires and / or other rubber materials that contained filler materials or reinforcing materials, such as carbon black. rC consists primarily of carbon black that has been used to reinforce rubber. RC may contain components susceptible to pyrolysis, such as rubber components. rC may be treated recycled carbon, wherein the raw recycled carbon has been treated to remove or substantially remove at least one macroscopic contaminant such as fabric or yarn. Recycled carbon is commercially available from suppliers such as Reoil Sp. z oo z oo, Scandinavian Enviro Systems AB, Pyrum Innovations AG or Bolder Industries or CBp Cyprus Ltd.

[0057] The rC may be treated to remove macroscopic contaminants. For example, magnetic separation techniques known to those skilled in the art may be used to remove metal wires and other macroscopic metal contaminants. Filters or sieves may be used to remove fabrics and other non-magnetic macroscopic contaminants. The rC may be treated before being combined with water to form the initial suspension and / or the initial suspension may be treated to remove macroscopic contaminants.

[0058] Alternatively or additionally, the rC carbon or pyrolysis carbon may be treated to remove ash, for example by washing the pyrolysis carbon with an acid or using an ion exchanger. Exemplary methods are described in US20150307714, CN101357758 and WO2021 / 005124.

[0059] For example, the starting recycled carbon particles (before grinding as described herein) may have a sieve mesh size 5 to 10 times smaller than that of the grinding media used. Other sieve meshes above or below this range may be used.

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

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

[0062] The grinding comprises at least one grinding step that uses grinding media grinding with a grinding media having a diameter of less than or equal to 2 mm. If more than one grinding media grinding step is used, the type of grinding media grinding in terms of grinding media or grinding type or grinding time, or number or size of grinding media may be the same or different.

[0063] Grinding media grinding may be or include agitated ball grinding, planetary ball grinding, or centrifugal ball grinding.

[0064] A preferred grinding media milling is agitated ball milling.

[0065] The grinding body (which can be considered as a grinding body), possibly use a grinding body made of solid balls.

[0066] The solid grinding body, for example, may have an average size that is about 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] According to one option, the grinding body for grinding may have a size such that the particle size of the starting recycled carbon is about 3 times to about 10 times smaller or about 5 times to 10 times smaller (e.g., 4 times to 5 times smaller) than the size of the grinding body used (e.g., the average size of the grinding body used).

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

[0069] The grinding media may be loaded into the mill such that the volume loading is 50% to 98% in a mill. The volume loading may be less than 50% or greater than 90% if necessary or desired. The volume loading 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 two values ​​based on any two values ​​described herein. The volume loading is based on the total volume (space) available in the mill for grinding.

[0070] The grinding media grinding operates such that the grinding expends a specific energy of at least 1 kWh / kg, or at least 1.25 kWh / kg, or at least 1.5 kWh / 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 mill can be used as an indicator of the extent of grinding. The amount of kWh expended can be calculated per kg of dry product (P m = tm*Phn p, where tm is the grinding time, P is the average specific energy of the mill, and mp is the dry weight of the batch) at different residence times. Similarly, the approximate number of collisions with the grinding media can be calculated: ( , where vm is the maximum speed, nh is the number of balls, r _ &.......... ....... m mpdb dh is the diameter of the balls). For example, in the grinding apparatus used in Example 1, the relationship between specific energy, number of collisions and residence time is as follows: Table 1: Relationship between residence time, specific energy expended per kg of dry product and collisions with the grinding body per kg of dry product. [Tables 1] Residence time P mcm min kWh / kg number / kg 0.5 0.75 5.87E+12 1 1.51 1.17E+13 2 3.02 2.35E+13 5 7.54 5.67E+13 10 15.08 1.13E+14 20 30.17 2.27E+14 40 60.33 4.54E+14

[0072] Grinding by grinding media can be characterized by the number of collisions per kg of dry-ground recycled carbon. The grinding media used may result in at least 1013 grinding media collisions per kg of dry ground recycled carbon during grinding, or at least 2 x 1013 grinding media collisions per kg of dry ground recycled carbon during grinding, e.g. 1013 grinding media collisions per kg to 1014 grinding media collisions per kg, 3 x 1013 grinding media collisions per kg to 1014 grinding media collisions per kg, or 4 x 1013 grinding media collisions per kg to 8 x 1013 grinding media collisions per kg, or 5 x 1013 grinding media collisions per kg to 6 x 1013 grinding media collisions per kg of dry ground recycled carbon during grinding

[0073] For any of the methods of the present invention, the grinding used may be such that the ground recycled carbon has a particle size distribution (PSD) and a particle size of D50 that has a value of 250 nm to 400 nm, preferably 250 nm to 320 nm. Similarly, or in addition, the PSD may have a D90 of 350 nm to 1100 nm, for example 500 to 1100 nm, 600 to 1000 nm, 700 to 900 nm or 800 to 1100 nm. The particle size distribution is measured by analytical centrifugation (disc photosedimentometry) of the milled suspension as described in Example 1. In this method, referred to as PSD Method 1, a particulate aqueous suspension (14% by weight solids) is diluted to 2,000 ppm with DI water containing 600 ppm of Triton X100 surfactant. The diluted solution is then mixed by a DISPERMAT LC55 mixer equipped with a 30 mm diameter, 18-tooth lightweight impeller at 800 rpm for 5 minutes.Next, the solution is stirred using a magnetic stir bar on a stir plate for 24 hours. The sample solution is then diluted to 400 ppm using DI water containing 400 ppm Triton X100 surfactant and allowed to rotate in a 40 ml vial on a roller until measurement. Disk centrifuge measurements (DC24000, CPS Instruments) are performed at 5000 rpm. First, 24%, 22%, 20%, 18%, 16%, 14%, 12%, 10%, 8% sucrose solution in DI water are sequentially injected into the disk (1.6 ml for each), then 1 ml of dodecane is injected to seal the gradient. The gradient is allowed to stabilize for 1 hour before measurements. In disk centrifuge measurements, the mass . The volumetric mass and refractive index of the sample are set to 1.86 g / cm3 and n = 1.84 + 0.846i. The results represent the equivalent sedimentation result of a spherical particle with a density of 1.86 g / cm3 and a refractive index of n = 1.84 + 0.846i. All measurements are stopped immediately once the signal reaches the baseline.

[0074] The grinding may be characterized by one or more properties obtained by grinding the recycled carbon based on the present invention.

[0075] For example, the grinding is such that a rubber sample containing 20 to 60 phr (e.g., 20 phr, or 25 phr, or 30 phr, or 35 phr, or 40 phr or 30 to 55 phr or 40 to 50 phr) of the ground recycled carbon results in up to 8% or up to 5% undispersed surface area, or 1% to 7% or 1.5% to 6%, or 1.75% to 4% (% Dispergrader), particularly when prepared using techniques in which wet granules are combined with an elastomer. Alternatively, a rubber sample containing 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, of which 10 to 40% by weight is recycled carbon ground by grinding media, for example 15 to 35% by weight or 20 to 30% by weight, has up to 3% undispersed area, for example 1% to 3% undispersed area.In some embodiments, the particulate filler material is a mixture of recycled carbon ground by grinding media and carbon black, e.g., a carbon black having a BET specific surface area of ​​35 to 110 m2 / g, e.g., an N300 or N500 series carbon black, e.g., N330 or N550 carbon black.

[0076] The % Dispergrader is calculated as follows. The cured rubber sample is sectioned using a razor blade fixed in a hand cutting jig. The sample is mounted and imaged on a Dispergrader instrument (Alpha Technologies). The following parameters are used: “filler volume fraction”, 20%; “exposure time”, 40 ms; “color channel for analysis”, “blue”; “threshold for dispersion calculation”, 23 pm; Fraction of nodges to agglomerates, 1; white area threshold, 0. The amount indicated by the Alpha Technologies instrument as “White Area, %” is interpreted as “undispersed area”.

[0077] According to another example, the grinding is such that a rubber sample containing 20 to 60 phr (e.g., 20 phr, or 25 phr, or 30 phr, or 35 phr, or 40 phr) of the ground recycled carbon results in a volume loss by abrasion that is not more than 10% or at most 5% greater than a comparative rubber sample containing N550 carbon black instead of the ground recycled carbon. The comparative rubber sample containing N550 carbon black may be considered as a “control sample” and the control sample has the same pce of N550 carbon black as used for the rubber sample with recycled carbon and all other components are the same except for the use of carbon black instead of recycled carbon. DIN abrasion was evaluated according to the rotation method of ASTM D5963.Alternatively or additionally, the grinding is such that a rubber sample containing 20 to 60 phr (e.g. 20 phr, or 25 phr, or 30 phr, or 35 phr, or 40 phr) of filler material comprising a mixture of N330 carbon black and from 10 wt% to 40 wt% of the ground recycled carbon results in a volume loss by abrasion of not more than 10% or at most 5% greater than a comparative rubber sample containing 100% N330 carbon black instead of a mixture with the ground recycled carbon, particularly when prepared using techniques in which wet granules are combined with an elastomer.Alternatively, a rubber sample containing 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, of which 10 to 40 wt. % is recycled carbon ground by grinding media, for example, 25 to 40 wt. %, 15 to 35 wt. % or 20 to 30 wt. %, has an abrasion loss of 90 to 100 mm3, for example, 91 to 95 mm3, measured according to ASTM D5963. In some embodiments, the particulate filler material is a mixture of recycled carbon ground by grinding media and carbon black, e.g., a carbon black having a BET specific surface area of ​​35 to 110 m2 / g, e.g., an N300 or N500 series carbon black, e.g., N330 or N550 carbon black.

[0078] In another example, the grinding may be such that a rubber sample containing 20 to 40 phr of ground recycled carbon results in an M300 / M100 ratio that is either a) not more than 10% or at most 5% lower than a comparative rubber sample containing N550 carbon black (control sample) instead of the ground recycled carbon or b) 4.5 to 5. The tensile stress (comprising M300 or M100) is tested according to ASTM D412 Type C. 6 dumbbells are used instead of 5. M300 is the tensile stress at 300% elongation and M100 is the tensile stress at 100% elongation.

[0079] In another example, the grinding may be such that a rubber sample containing 20 to 40 phr of ground recycled carbon results in an M300 (MPa) or maximum load (N) that is not more than 10% lower or not more than 5% lower than a comparative rubber sample containing N550 carbon black instead of the ground recycled carbon.

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

[0081] As indicated, with the present invention, it has been unexpectedly discovered that certain residence times for grinding media grinding are more appropriate for certain rubber properties. To make this determination, the ground materials of the present invention were tested in SBR composites as described in the examples section. To further show that the material ground in the grinding media of the present invention contributed to the rubber properties, the material ground in the grinding media, as indicated in the examples section, was compared to flaky (unground) rC granules and wet (unground) blended rC granules and also compared to the virgin N550 carbon black samples.

[0082] With the present invention, various relationships have been discovered based on the pce of the rC ground by grinding media grinding and preferably based on the grinding time.

[0083] For the undispersed surface rubber property (% Dispergrader) of the filler in an elastomer composite, the undispersed surface area (according to the % Dispergrader) based on the rC milled by grinding medium grinding of some embodiments can be characterized based on equation 2: Undispersed Area (UA) < 3.35 - (0.04 * phr rC). The phr rC is a rC milled by grinding medium grinding according to the present invention and can be an amount ranging from 10 phr to 50 phr or from 10 phr to 40 phr, from 10 phr to 35 phr, from 10 phr to 30 phr, from 5 phr to 55 phr, from 7 phr to 20 phr. The rC ground by grinding media milling may be part of a mixture with an additional particulate filler material, e.g. carbon black, e.g. carbon black having a BET specific surface area of ​​35 to 110 m2 / g, e.g. N300 or N500 series carbon black, e.g. N330 or N550 carbon black.The total amount of filler material may be 20 to 80 phr, for example 30 to 70 phr, 40 to 60 phr, or 45 to 55 phr. The rC ground by grinding media grinding may be 10 to 40% by weight of the total filler material, for example 15 to 35% by weight or 20 to 30% by weight.

[0084] For the rubber property of abrasion volume loss (mm3) in an elastomeric composite, the abrasion volume loss based on the rC milled by grinding media of some embodiments can be characterized based on equation 3: Abrasion Volume Loss (AVL) < 100 + (0.1 * pce ​​rC) (normalized to a control sample produced in the same manner but with N550 carbon black in place of the rC ground by grinding media). The pce rC is a rC ground by grinding media according to the present invention and can be an amount ranging from 10 pce to 50 pce or from 10 pce to 40 pce, or from 10 pce to 30 pce. Equation 3A: AVL < 100 - (0.43 * pce ​​rC) (normalized to the N550 control) is achievable. The rC pce is a rC ground by grinding media grinding according to the present invention and may be an amount ranging from 10 pce to 50 pce or from 10 pce to 40 pce, from 10 pce to 35 pce, from 10 pce to 30 pce, from 5 pce to 55 pce, from 7 pce to 20 pce. The rC ground by grinding media grinding may be part of a mixture with an additional particulate filler material, e.g. carbon black, e.g. a carbon black having a BET specific surface area of ​​35 to 110 m2 / g, e.g. an N300 or N500 series carbon black, e.g. N330 or N550 carbon black.The rC ground by grinding media grinding may represent 10 to 40% by weight of the total feed material, for example 15 to 35% by weight or 20 to 30% by weight.

[0085] For the rubber property of deformation stiffness (M300 / M100 index) in an elastomeric composite, the deformation stiffness (M300 / M100 index) based on the rC ground by grinding media of some embodiments, for example with a residence time of 2 min, can be characterized based on equation 4: M300 / M100 index > 100 - (0.01 * phr rC) (normalized to the N550 control). The phr rC is a rC ground by grinding media according to the present invention and can be an amount ranging from 10 phr to 50 phr or from 10 phr to 40 phr, or from 10 phr to 30 phr. Equation 4A: M300 / M100 index > 100 (0.38 * pce ​​rC) (normalized to the N550 control) is achievable. The pce rC is an rC ground by grinding by grinding media according to the present invention and can be an amount ranging from 10 pce to 50 pce or from 10 pce to 40 pce, from 10 pce to 35 pce, from 10 pce to 30 pce, from 5 pce to 55 pce, from 7 pce to 20 pce.The rC milled by grinding media grinding may be part of a mixture with an additional particulate filler material, e.g. carbon black, e.g. a carbon black having a BET specific surface area of ​​35 to 110 m2 / g, e.g. a carbon black of the N300 or N500 series, e.g. carbon black N330 or N550. The rC milled by grinding media grinding may represent 10 to 40% by weight of the total filler material, e.g. 15 to 35% by weight or 20 to 30% by weight.

[0086] For the rubber property of high deformation stiffness or high tensile stress (M300) in an elastomer composite, the high deformation stiffness or high tensile stress (M300) based on the rC ground by grinding media of some embodiments can be characterized based on equation 5: M300 > 100 - (0.15 * pce ​​rC) (normalized to the control N550). The pce rC is a rC ground by grinding media according to the present invention and can be an amount ranging from 10 phr to 50 phr or from 10 phr to 40 phr, or from 10 phr to 30 phr. The rC ground by grinding media may be part of a mixture with an additional particulate filler, e.g., carbon black, e.g., a carbon black having a BET specific surface area of ​​35 to 110 m2 / g, e.g., an N300 or N500 series carbon black, e.g., carbon black N330 or N550. The rC ground by grinding media may be 10 to 40 wt.% of the total filler, e.g., 15 to 35 wt.% or 20 to 30 wt.%. Equation 5A: M300 > 100 (0.38 * phr rC) (normalized to the N550 control) is achievable.In one embodiment, a method of treating particulate carbon includes combining recycled carbon with water to form a mixture to form an initial slurry containing 1 to 35% by weight solids and media grinding the recycled carbon to form a ground slurry by media grinding of wet-milled recycled carbon and water.

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

[0088] The initial suspension may contain one or more additional fillers that may also benefit from co-grinding with the pyrolysis carbon. Any particulate filler that imparts reinforcement or other beneficial properties to the rubber may be used.Examples of additional filler materials include, but are not limited to, carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon (i.e., a carbonaceous material produced by hydrothermal carbonization) from lignin or other biomass, e.g., as described in US10428218 or US10035957, modified polysaccharides such as those described in US2020 / 181370 and US2020 / 190270, and graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clays, nanoclays, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures such as those described in US2014 / 0093728, and carbon black coated particles such as those described in US 10519298. .

[0089] Preferably, macroscopic contaminants are removed from the pyrolysis carbon, in a dry state or in a slurry state, before combining the pyrolysis carbon with the one or more additional filler materials. The one or more additional filler materials may be combined with the pyrolysis carbon. pyrolysis in the dry state or charged separately into water, before, after or at the same time as the pyrolysis carbon to form the initial slurry. In order to avoid any segregation that might occur in the dry mixtures of pyrolysis carbon and additional filler material, the additional filler material(s) are preferably charged directly into the water or the initial slurry separately from the pyrolysis carbon. The ratio of pyrolysis carbon and additional filler material in the initial slurry may be in any range suitable for the desired end-use application and to maintain an acceptable viscosity of the initial slurry so that it can be milled.In some preferred embodiments, the supplemental filler material is virgin carbon black, for example, a carbon black having a BET specific surface area of ​​35 to 110 m2 / g, for example, a carbon black of the N300 or N500 series, for example, carbon black N330 or N550, and the recycled carbon is used in an amount of 10 to 40% of the total filler material by weight, for example, 25 to 40% by weight, 15 to 35% by weight, or 20 to 30% by weight. In a continuous process, the supplemental filler material may be continuously dosed into the initial suspension or into the continuous stream of water in the form of powder or aqueous suspension of supplemental filler material (or more than one suspension if more than one supplemental filler material is used). It will be apparent to those skilled in the art that the suitable feedstock for milling will depend on the nature of the supplemental filler material.For example, carbon nanotubes will increase the viscosity of the suspension at very low rates, while higher rates of precipitated silica may not significantly increase the viscosity.

[0090] Additional filler material may also be added to the milled slurry. Such additional filler material preferably does not require additional grinding. Examples of additional filler materials to be added to the milled 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 US 10519298, and mixtures of two or more thereof. Depending on the solids loading of the milled slurry, it may also be desirable to add water with the additional filler material to adjust the solids loading of the resulting wet-blended carbon mixture. Alternatively or additionally, the additional filler material may be added to the milled slurry as an aqueous slurry.In a continuous process, the additional filler material may be continuously dosed into the initial suspension or into the continuous stream of water in the form of powder or aqueous suspension of additional filler material. The total filler material loading may be such that . The wet-mixed carbon mixture can be readily pelletized or spray-dried. To form pellets, the additional filler and optional water added to the milled slurry can bring the solids content of the resulting wet-mixed carbon mixture to 25 to 70 wt. %, for example, 30 to 65 wt. %, 35 to 60 wt. %, or 40 to 50 wt. %. For spray-drying, the additional filler and optional water added to the milled slurry can bring the solids content of the resulting wet-mixed carbon mixture to 1 to 30 wt. %, for example, 1 to 10 wt. %, 5 to 15 wt. %, or 8 to 25 wt. %.In some preferred embodiments, the additional filler material is virgin carbon black, e.g., a carbon black having a BET specific surface area of ​​35 to 110 m2 / g, e.g., an N300 or N500 series carbon black, e.g., N330 or N550 carbon black, and the recycled carbon is used in an amount of 10 to 40% of the total filler material, e.g., 25 to 40% by weight, 15 to 35% by weight, or 20 to 30% by weight. For spray drying, it may be desirable to omit the additional filler material. Those skilled in the art will know how to adjust the total filler material loading to prepare desirable granules or the optimum loading for spray drying in conventional apparatus. The filler material(s) added to the milled slurry may be the same as or different from any filler material added to the initial slurry.

[0091] Carbon black for use in any embodiment of the present invention includes, but is not limited to, ASTM N100 to N900 series carbon blacks, e.g., N100 series carbon blacks, N200 series carbon blacks, N300 series carbon blacks, e.g., N330 carbon black, N500 series carbon blacks, e.g., N550 carbon black, N600 series carbon blacks, N700 series carbon blacks, N800 series carbon blacks, or N900 series carbon blacks. Alternatively or additionally, these carbon blacks may have a BET specific surface area, as measured according to ASTM 6556, of 35 to 110 m2 / g, for example, 35 to 65 m2 / g, 65 to 90 m2 / g, or 90 to 110 m2 / g.Carbon blacks marketed under the Regai®, Black Pearls®, Spheron®, Sterling® and Vulcan® brands available from Cabot Corporation, the Raven®, Statex®, Fumex® and Neotex® brands and the CD and HV ranges available from Birla Carbon (Columbian Chemicals); and the Corax®, Durax®, Ecorax® and Purex® brands and the CK range and other carbon blacks available from Orion Engineered Carbons and other fillers suitable for use in rubber or tire applications. may also be exploited for use with various embodiments. The carbon blacks may be chemically functionalized. Suitable chemically functionalized carbon blacks include those described in WO 96 / 18688 and US2013 / 0165560.

[0092] The carbon black may have a statistical thickness specific surface area (STSA, ASTM D6556) of at least about 15 m2 / g, e.g., from about 15 m2 / g to about 240 m2 / g, e.g., from about 35 m2 / g to about 230 m2 / g, from about 50 m2 / g to about 200 m2 / g, from about 60 m2 / g to about 180 m2 / g, from about 100 m2 / g to about 200 m2 / g.

[0093] Carbon blacks having any of the above specific surface areas may further have a structure, as indicated by the Compressed Oil Adsorption Index for Carbon Black (COAN, ASTM D3493), of about 50 to about 115 ml / 100 g, for example, about 65 to about 75 ml / 100 g, about 60 to 95 ml / 100 g, about 75 to about 85 ml / 100 g, about 85 to about 95 ml / 100 g, about 95 to about 105 ml / 100 g, or about 105 to about 115 ml / 100 g.

[0094] Any mixtures of these carbon blacks may be used.

[0095] The materials described herein as silicon-treated carbon blacks are not limited to carbon black aggregates that have been coated or otherwise modified. They may also be a different type of aggregate having two phases. One phase consists of carbon, which will always be present as graphitic crystallite and / or amorphous carbon, while the second phase consists of silica (and possibly other silicon-containing species). Thus, the silicon-containing species phase of the silicon-treated carbon black is an intrinsic part of the aggregate; it is distributed throughout at least a portion of the aggregate. A variety of silicon-treated blacks are available from Cabot Corporation under the name Ecoblack™ and are further described in U.S. Patent No. 6,028,137.It will be appreciated that multi-phase aggregates are very different from the silica-coated carbon blacks discussed above, which consist of pre-formed single-phase carbon black aggregates having silicon-containing species deposited on their surface. Such carbon blacks may be surface-treated to place silica functionality on the surface of the carbon black aggregate as described, for example, in U.S. Patent Nos. 6,929,783, 6,541,113, and 5,679,728.

[0096] Precipitated silicas suitable for use in any embodiment of the present invention include both highly dispersible (HDS) granules and non-HDS precipitated silicas. The precipitated silica may have been chemically treated to include functional groups such as bonded (fixed (e.g., chemically attached) or adhered) coupling agents (e.g. adsorbed)) on the silica surface. Examples of suitable grades of HDS include Perkasil® GT 3000GRAN silica from WR Grâce & Co, Ultrasil® 7000 silica from Evonik Industries, Zeosil® 1165 MP and 1115 MP silicas 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 Grâce & 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® silicas from Evonik Industries, e.g., Coupsil® 6109 silica.

[0097] The wet-mixed carbon mixture may be densified, for example, granulated or pelletized. Any densification or pelletizing method known to those skilled in the art may be used. For example, the methods of U.S. Patent No. 2,065,371 to Glaxner may be used. Generally, the wet-milled carbon mixture is formed into beads, which may then optionally be dried to reduce the water content to at most 1% to form mixed carbon pellets. In addition to the water already present in the wet-mixed carbon mixture, a wide variety of binder additives are known to be useful in the wet-granulation process to further improve the handling characteristics of the resulting pellets.Such additives include, but are not limited to, hygroscopic organic liquids such as ethylene glycol, carbohydrates (e.g., sugar, molasses, soluble starches, saccharides, lignin derivatives), rosin, anionic sulfonate and sulfate surfactants, nonionic fatty amine ethoxylate surfactants, sodium lignosulfonates, silanes, sucrose, alkyl succinimides, alkyl succinic esters, and polyethylene-co-polydimethylsiloxane oxide surfactants. Alternatively or additionally, the granules need not be dried and may be used wet, in which case a binder may not be required. For example, wet pellets may have a moisture content of 15 to 80% by weight, for example 40 to 60% by weight.

[0098] The resulting particulate filler material, in the form of wet pellets or dry pellets or in another form (e.g., a suspension prior to granulation or another drying process), on a dry basis, may comprise 2 to 100% recycled carbon, 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, 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 recycled carbon milled by wet process, and the remainder being a filler material other than recycled carbon, for example, one or more of the additional and / or supplementary fillers listed above, for example, carbon black, silica-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, modified polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clays, nanoclays, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures and carbon black-coated particles.In some preferred embodiments, the additional and / or supplemental filler material is virgin carbon black, e.g., N300 or N500 series carbon black, e.g., N550 or N330 carbon black, and the recycled carbon is present in the pellet in an amount of 10-40%, e.g., 25-40%, 15-35%, or 20-30% by weight of the total filler material in the pellet. As noted above, the pellets may further contain a binder.

[0099] 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, in dry matter, may comprise 2 to 100% recycled carbon, 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, 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-milled recycled carbon, and 0 to 98%, for example 2% by weight to 95% by weight, for example 10% by weight to 92% by weight, 40 to 90% by weight, or 50% by weight to 80 or 85% by weight, an additional filler material selected from the carbon black, silica-coated carbon black, silica-treated carbon black, precipitated silica,carbon black coated particles and mixtures of at least two of them, and 0 to 98%, for example 2 wt% to 95 wt%, for example 10 wt% to 92 wt% 40 to 90 wt%, or 50 wt% to 80 or 85 wt%, of one or more additional fillers selected from carbon black, silica-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, modified polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clays, nanoclays, 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 supplemental filler material is virgin carbon black, , for example carbon black of the N300 or N500 series, for example carbon black N550 or N330, and the recycled carbon is present in the spray-dried particle in an amount of 10 to 40% by weight, for example 25 to 40%, 15 to 35% or 20 to 30% by weight.

[0100] The wet granules, dried granules and / or spray-dried particles according to the various embodiments of the present invention may be combined with an elastomer to form elastomeric composites. The resulting elastomeric composite may comprise 30 to 90 phr of particulate filler material, for example 30 to 70, 35 to 60 or 40 to 55 phr of particulate filler material. The particulate filler material may comprise 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 some preferred embodiments, the additional and / or supplemental filler material is virgin carbon black, e.g., N300 or N500 series carbon black, e.g., N550 or N330 carbon black, and the recycled carbon is present in the pellet in an amount of 10-40%, e.g., 25-40%, 15-35%, or 20-30% by weight, of the total filler material in the pellet. Any grade of natural rubber and a synthetic elastomer may be used. Blends of elastomers may also be used. For example, wet pellets, dried pellets, and / or spray-dried particles may be combined with an elastomer to form a masterbatch, which is then combined with an additional elastomer of the same or different composition. Alternatively or additionally, at least two elastomers may be blended prior to blending with the pellets.Alternatively or additionally, the elastomer composite may also contain one or more fillers in addition to the recycled carbon, including any of the particulate fillers listed elsewhere herein and any other fillers known to those skilled in the art for use in elastomer composites. Such fillers may be in a mixture or pellet with the ground recycled carbon or may be added to the elastomer separately from any of the wet pellets, dried pellets, and / or spray-dried particles according to the various embodiments of the present invention.

[0101] Examples of classes of elastomers include, but are not limited to, rubbers, rubbers, polymers (e.g., homopolymers, copolymers, and / or terpolymers) of 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dialkyl-1,3-butadiene, where alkyl may be methyl, ethyl, propyl, etc., acrylonitrile, ethylene, propylene, and the like. The elastomer may have a glass transition temperature (Tg), measured by calorimetry Differential Scanning Image (DSC), ranging from about -120°C to about 50°C. Examples include, but are not limited to, styrene-butadiene rubbers (SBR), natural rubbers and their functionalized derivatives such as epoxidized and chlorinated rubber, polybutadiene rubbers, polyisoprene rubbers, ethylene-propylene copolymers (e.g., EPDM), isobutylene-based rubbers (e.g., butyl rubber), polychloroprene rubbers, nitrile rubbers, hydrogenated nitrile rubbers, polyisoprene rubbers, polysulfide rubbers, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, and oil-extended derivatives of any of these. Blends and / or functionalized derivatives of any of the foregoing may also be used.Natural rubber can also be processed to chemically or enzymatically modify or reduce various non-rubber components.

[0102] Particularly suitable synthetic rubbers include: copolymers of about 10 to about 70 weight percent styrene and about 90 to about 30 weight percent butadiene such as a copolymer of 19 parts styrene and 81 parts butadiene, a copolymer of 30 parts styrene and 70 parts butadiene, a copolymer of 43 parts styrene and 57 parts butadiene and a copolymer of 50 parts styrene and 50 parts butadiene;polymers and copolymers of conjugated dienes such as polybutadiene, polyisoprene, polychloroprene and the like, and copolymers of such conjugated dienes with an ethylenic group-containing monomer copolymerizable therewith such as styrene, methylstyrene, chlorostyrene, acrylonitrile, 2-vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, allyl-substituted acrylates, vinyl ketone, methyl isopropenyl ketone, methyl vinyl ether, alpha-methylenecarboxylic acids and their esters and amides such as acrylic acid and dialkylacrylic acid amide. Copolymers of ethylene and other higher alpha-olefins such as propylene, 1-butene and 1-pentene are also suitable for use in the present invention. ;

[0103] The elastomeric composite may further comprise additives to facilitate mixing, promote vulcanization, or impart particular properties to a vulcanizate of the elastomeric composite. Many additives are well known to those skilled in the art and include, for example, adhesion promoters, antioxidants, antiozonants, coupling agents, curing agents, degradation inhibitors, plasticizers, processing aids (e.g., liquid polymers, oils, and the like), oily fillers, wax, resins, flame retardants, filler oils, lubricants, tackifiers, vulcanization activators such as zinc oxide, and acids fats, vulcanization accelerators and any mixture thereof. Examples of 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.

[0104] The dried granules and / or spray-dried granules may be combined with the elastomer as described above using any dry mixing method known to those skilled in the art.

[0105] Alternatively or additionally, the wet granules may be combined with an elastomer according to the teachings of one or more of US20220332016, WO2021247153, WO2022125679, WO2022125683, WO2022125677 and WO2022125675. For example, the wet granules and the elastomer in solid form may be charged into a mixer and mixed under conditions in which the temperatures are controlled to remove at least some of the water contained in the granules by evaporation. The elastomer is optionally pre-masticated before the introduction of the wet granules. The wet filler may be added all at once or in aliquots.

[0106] Any suitable mixer, such as a Banbury or Brabender mixer or other internal or closed mixer, or an open mixer, or an extruder or a continuous mixer or a kneader or a combination thereof, may be used to combine wet granules with an elastomer. Other mixers include a kneader-type internal mixer. Internal mixers marketed by Farrel-Pomini, Harburg Freudenberger Maschinenbau GmbH (HF), Kobelco or Pelmar Eng'r Ltd may be used. In addition to the possibility of using internal steam, water or other fluid circuits in the rotors, in addition or alternatively, the internal mixer may have cooling or heating jackets in a region or part or in several regions or parts of the mixing chamber to regulate the temperature of the components mixed therein.This may create one or more heating / cooling zones in a wall or wall portion of a mixer. The mixer may be a single-stage mixer or a multi-stage mixer (e.g., two or more stages). Examples of mixers and designs that may be used are described in European Patent No. 2423253B1 and US Patent No. 7,556,419.

[0107] Alternatively, the mixer may be a continuous mixer. For example, the solid elastomer and wet filler material may be mechanically worked using one or more continuous internal mixers, a twin-screw extruder, a single-screw extruder, or a roller mill, such as those described in U.S. Patent No. 9,855,686 B2. Suitable kneading and masticating devices are well known and commercially available, including, for example, a Unimix continuous mixer and an MVX (mix, vent, extrude) machine from Farrel Pomini Corporation, Ansonia, Connecticut, a Farrel FCM™ continuous mixer, a Pomini, Inc. long continuous mixer, a Pomini continuous mixer, meshing co-rotating twin-rotor extruders, non-mesh counter-rotating twin-rotor extruders, continuous mixing extruders, the biaxial grinding extruder produced by Kobe Steel, Ltd., and a Kobe continuous mixer. Other masticating apparatus suitable for use with one or more embodiments described herein will be known to those skilled in the art.

[0108] The mixing may be carried out with one or more mixers having at least one rotor and the mixer may be one or more of the following: a kneader, a rolling mill, a screw extruder, a twin-screw extruder, a multi-screw extruder, a continuous mixer and / or a twin-screw extruder. The mixing may be carried out with one or more mixers having at least one rotor and the mixer may have two-wing rotors, four-wing rotors, six-wing rotors, eight-wing rotors and / or one or more screw rotors.

[0109] The mixing process for combining wet granules with an elastomer may be a one-step (single-step) or multi-step (multi-step) process. In a multi-step process, one or more mixers or types of mixers may be used. For steps in which an internal mixer is used, the fill factor at each of these steps may independently be less than or equal to 72%, less than or equal to 70%, or less than or equal to 68%, or less than or equal to 66%, for example, about 30% to 72%, 40% to 70%, 45% to 70%, 30% to 60%, 50 to 72%, 50 to 70%, 50 to 68%, 60 to 72%, 60 to 70%, 60 to 68%, 65 to 72%, 65 to 70%, 65 to 68%, or 40 to 60% or 50 to 60% and the like. The temperature of the mixer may be controlled to regulate the temperature of the mixture, the amount of water evaporated, or both.For example, in a multi-stage process, the temperature of the mixer for each stage may be controlled to regulate the amount of water evaporated from the mixture in the first mixing stage and in one or more subsequent stages. For example, the liquid content of the discharged composite may be lower than the liquid content of the material charged to the mixer by a proportion of 10% to 99.9% (wt.% relative to wt.%), 10% to 95%, or 10% to 50%. Alternatively or additionally, the rate of release of liquid from the composite or mixture during mixing, e.g., by evaporation, may be measured as a time-averaged release rate of liquid per kg of composite or mixture (e.g., total liquid removed / (release time x composite weight), 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.

[0110] Alternatively or additionally, the mixing may be controlled in one or more stages to achieve a predetermined total specific energy (energy applied to a mixing system that drives one or more rotors per mass of composite on a dry weight basis), for example from 1,000 kJ / kg of composite (or per kg of mixture present in the mixer) to 10,000 kJ / kg of composite (or per kg of mixture present in the mixer), for example from 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 to 6,000 kJ / kg, 1,500 kJ / kg to 5,000 kJ / kg, 1,500 kJ / kg to 3,000 kJ / kg, 1 600 kJ / kg to 8,000 kJ / kg, 1,600 kJ / kg to 7,000 kJ / kg, 1,600 kJ / kg to 6,000 kJ / kg, 1,600 kJ / kg to 5,000 kJ / kg, 1,600 kJ / kg to 4,000 kJ / kg, 1,600 kJ / kg to 3,000 kJ / kg, or other values ​​within any of these ranges.Alternatively or additionally, the specific energy applied to the mixture may be divided to ensure that a certain amount of specific energy is applied before or after a portion, e.g., 75% of the filler material, has been added to the mixer. That is, it is not necessary to add the filler material all at once. The mixing times at each stage may be any suitable duration, e.g., 1 min to 40 min, 1 min to 20 min, 1 min to 15 min, 5 min to 30 min, 5 min to 20 min, 5 min to 15 min, or 1 min to 12 min, 1 min to 10 min, 3 min to 30 min, or other times. Alternatively or additionally, the drain discharge temperature for each stage may be 120°C to 180°C, 120°C to 190°C, 130°C to 180°C, e.g., 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.

[0111] After any one or more steps or stages of mixing, the resulting composite may be subjected to one or more post-processing steps, for example, to shape or form the composite and / or allow for improved handling. The post-processing may provide a composite that may be dried, homogenized, extruded, calendered, ground, granulated, cut, baled, or sheeted. The composite may be mixed and vulcanized immediately or may be held for a period of time prior to mixing. Suitable equipment for various post-processing steps includes, but is not limited to, one or more of an internal mixer, a kneader, a rolling mill, a roll mixer, a screw extruder, a twin-screw extruder, a multi-screw extruder, a continuous mixer, and / or a twin-screw discharge extruder equipped with a plate nozzle (e.g., a twin-screw rolling mill) or equipped with fixed knives.Depending on the device or devices used, it may be desirable to process the composite using the device more than once or using a series of similar devices. or different having the same or different operating parameters (e.g., speed, temperature, energy input, etc.). Alternatively or additionally, the elastomeric composite may be combined with an added filler, an added elastomer, or both, prior to or as part of the vulcanization process. The additional filler may be the same as or different from the particulate filler in the elastomeric composite and may include any filler known to those skilled in the art, including fillers listed as additional fillers in this instance and including additional wet-milled recycled carbon. The added filler and / or elastomer may increase or decrease the filler of the vulcanizate relative to the elastomeric composite.

[0112] To vulcanize the elastomeric composite material, it is combined with a vulcanization preparation comprising a crosslinking agent, any necessary activators and accelerators, an antioxidant, and additional optional additives such as one of those listed above. When sulfur is used as the 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 listed in WO2012 / 037244. Other curing agents used in rubber processing are peroxides, urethane crosslinkers, metal oxides, acetoxysilane compounds, etc.Additional components suitable for sulfur-based and other crosslinking systems and processes for blending and vulcanizing elastomeric composites are known to those skilled in the art. For example, typical procedures used for rubber formulation are described in Maurice Morton, Rubber Technology, 3rd Edition, Van Norstrand Reinhold Company, New York 1987, and 2nd Edition, Van Nordstrand Reinhold Company, New York 1973.

[0113] Various rubber articles may incorporate the vulcanizate. For example, the vulcanizate may be incorporated into a tire, e.g., pneumatic tires, non-pneumatic tires, or solid tires. For example, the vulcanizate may be incorporated into tire treads, tire casings, undertreads, inner rubbers, sidewalls, sidewall inserts, thin wire coating, and toe rubber for retreaded tires. Alternatively or additionally, the vulcanizate may be incorporated into hoses, liners, intermediates, seals, gaskets, anti-vibration articles, tracks, track pads for track-propelled vehicle equipment, engine mounts, seismic stabilizers, mining equipment guards, mining equipment liners, conveyor belts, chute liners, slurry pump liners, slurry pump impellers, valve seats, valve bodies, piston hubs, piston rods, plungers, slurry mixing impellers and slurry pump impellers, mill liners, cyclones and hydrocyclones, expansion joints, liners for dredge pumps and outboard motor pumps for marine equipment, seals for marine, oilfield, aerospace and other applications, propeller shafts, or liners for pipes used to transport, for example, oil sands or tar sands.Alternatively or additionally, the vulcanizate may be incorporated into engine mounts, bushings, weather stripping, windshield wipers, automotive components, gaskets, seals, housings, and wheel or track members.

[0114] The resulting vulcanizate may have fatigue properties, e.g., number of cycles to failure, equivalent to or not more than 10% lower than those of vulcanizates produced by the same process and with the same composition, but with ASTM N550 carbon black in place of the recycled carbon. Alternatively or additionally, the resulting vulcanizate may have fatigue properties equivalent to or greater than 90% of those of vulcanizates produced by the same process and with the same composition, except that the recycled carbon is replaced by an equal amount of additional filler material used in the vulcanizate produced according to the invention. 1. The present invention comprises the following aspects / embodiments / features in any order and / or in any combination: 1. A method for processing recycled carbon, said method comprising wet grinding media milling recycled carbon to obtain ground recycled carbon, wherein said grinding media milling results in 1013 to 1014 grinding media collisions per kg of dry ground recycled carbon, during said milling.2. A method for processing recycled carbon, said method comprising wet grinding media milling recycled carbon to obtain ground recycled carbon, wherein the milling comprises grinding media milling which expends a specific energy of 1 kWh / kg to 10 kWh / kg of dry ground recycled carbon. 3. A method of processing recycled carbon, said method comprising wet grinding of recycled carbon to obtain ground recycled carbon, wherein said grinding results in a volume-weighted particle size distribution of the ground recycled carbon, measured by disk centrifugal photosedimentometry with a D50 from 250 to 400 nm, preferably 250 to 320 nm, and a D90 of 350 to 1100 nm, for example 500 to 1100 nm. 4. A method according to any one of the preceding or following embodiments / features / aspects, wherein the specific energy expended during grinding by grinding media is from 1 kWh / kg to 10 kWh / kg. 5. A method according to any one of the preceding or following embodiments / features / aspects, wherein the specific energy expended during grinding by grinding media is from 1 kWh / kg to 3.5 kWh / kg. 6. A method according to any one of the preceding or following embodiments / features / aspects, wherein the specific energy is from 1.25 kWh / kg to 3.1 kWh / kg. 7. A method according to any one of the preceding or following embodiments / features / aspects, wherein said grinding by grinding media results in 1013 to 1014 collisions with the grinding media per kg of dry-ground recycled carbon, during said grinding. 8. A method according to any one of the preceding or following embodiments / features / aspects, wherein said grinding by grinding media results in 2 x 1013 to 1014 collisions with the grinding media per kg of dry-ground recycled carbon, during said grinding. 9. A method according to any one of the preceding or following embodiments / features / aspects, wherein said grinding by grinding media results in 3 x 1013 to 1014 collisions with the grinding media per kg of dry-ground recycled carbon, during said grinding. 10. A method according to any one of the preceding or following embodiments / features / aspects, wherein the grinding media grinding is agitated ball grinding, planetary ball grinding or centrifugal ball grinding.

[0115] 11. Method according to any one of the embodiments / characteristics / preceding or following aspects, wherein the grinding by grinding media is agitated ball grinding. 12. A method according to any one of the preceding or following embodiments / features / aspects, wherein the grinding media grinding uses a grinding media that is made of solid balls having an average size that is about 0.25 mm to 2 mm, for example 0.25 to 1 mm, and a volume loading of 50% to 98% in a mill.13. A method according to any one of the preceding or following embodiments / features / aspects, wherein a volume-weighted particle size distribution of the ground recycled carbon, measured by disc centrifugal photo sedimentometry 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. A method according to any one of the preceding or following embodiments / features / aspects, wherein the grinding is such that a rubber sample containing 20 to 60 phr of ground recycled carbon results in less than 10% or less than 5% undispersed surface area (% Dispergrader). 15. A method according to any one of the preceding or following embodiments / features / aspects, wherein the grinding is such that a rubber sample containing 20 to 80 phr of particulate filler material, for example, 30 to 70 phr, 40 to 60 phr, or 45 to 55 phr of particulate filler material, of which 10 to 40% by weight is recycled carbon ground by grinding media, for example, 15 to 35% by weight or 20 to 30% by weight, has up to 3% undispersed surface area, for example, 1 to 3% undispersed surface area. 16. A method according to any one of the preceding or following embodiments / features / aspects, wherein the grinding is such that a rubber sample containing 10 to 50 phr, for example 10 to 40 phr, of ground rC has an undispersed surface area UA satisfying UA < 3.35 - (0.04 * phr rC). 17. A method according to any one of the preceding or following embodiments / features / aspects, wherein the grinding is such that a rubber sample containing 20 to 60 phr of ground recycled carbon results in a volume loss by abrasion which is not more than 10% or at most 5% greater than a comparative rubber sample produced in the same manner but containing N550 carbon black instead of the ground recycled carbon. 18. A method according to any one of the preceding or following embodiments / features / aspects, wherein the grinding is such that a rubber sample containing 20 to 80 phr of particulate filler material, for example 30 to 70 phr, 40 to 60 phr, or 45 to 55 phr of particulate filler material, of which 10 to 40% by weight is recycled carbon ground by grinding media, for example 15 to 35% by weight or 20 to 30% by weight, has an abrasion loss of 90 to 100 mm3, for example, 91 to 95 mm3, measured according to ASTM D5963. 19. A method according to any one of the preceding or following embodiments / features / aspects, wherein the particulate filler material comprises virgin carbon black, for example a carbon black having a BET specific surface area of ​​35 to 110 m2 / g, for example an N300 or N500 series carbon black, for example N330 or N550 carbon black, for example N330 carbon black. 20. A method according to any one of the preceding or following embodiments / features / aspects, wherein the grinding is such that a rubber sample containing 20 to 60 pce of crushed recycled carbon results in an M300 / M100 ratio which is either a) not more than 10% lower or not more than 5% lower than a comparative rubber sample produced in the same way but containing N550 carbon black instead of crushed recycled carbon or b) 4.5 to 5. 21. A method according to any one of the preceding or following embodiments / features / aspects, wherein the grinding is such that a rubber sample containing 20 to 60 phr of ground recycled carbon results in an M300 (MPa) or maximum load (N) which is not more than 10% lower or not more than 5% lower than a comparative rubber sample produced in the same manner but containing N550 carbon black instead of the ground recycled carbon. 22. A method according to any one of the preceding or following embodiments / features / aspects, wherein the particle size is measured according to the PSD 1 method. 23. Ground recycled carbon produced by the method according to any one of the preceding or following embodiments / features / aspects.24. A particulate filler comprising 10 to 40% by weight of recycled carbon, wherein a volume-weighted particle size distribution of the recycled carbon measured by disk spin photosedimentometry 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. A particulate filler according to any one of the preceding or following embodiments / features / aspects, 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. A particulate filler according to any one of the preceding or following embodiments / features / aspects, further comprising one or more of carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, modified polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clays, nanoclays, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, and carbon black-coated particles. 27. A particulate filler according to any one of the preceding or following embodiments / features / aspects, 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 the preceding or following embodiments / features / aspects, further comprising carbon black. 29. A particulate filler according to any one of the preceding or following embodiments / features / aspects, further comprising a carbon black having a BET specific surface area of ​​35 to 110 m2 / g, for example 35 to 65 m2 / g, 65 to 90 m2 / g, or 90 to 110 m2 / g. 30. A particulate filler according to any one of the preceding or following embodiments / features / aspects, further comprising a carbon black of the N300 or N500 series, for example, carbon black N330 or N550. 31. A method according to any one of the preceding or following embodiments / features / aspects, wherein the particulate filler material is in the form of granules. 32. A particulate filler according to any one of the preceding or following embodiments / features / aspects, the granules consisting essentially of the particulate filler material, optional water and an optional binder. 33. A particulate filler according to any one of the preceding or following embodiments / features / aspects, the particulate filler material having a moisture content of 15 to 80%, for example 40 to 60% by weight. 34. Particulate filler according to any one of the preceding or following embodiments / features / aspects, a rubber sample containing 20 to 60 phr of ground recycled carbon resulting in less than 10% or less than 5% undispersed surface area (% Dispergrader). 35. A particulate filler according to any one of the preceding or following embodiments / features / aspects, a rubber sample containing 20 to 80 phr of the particulate filler material, for example, 30 to 70 phr, 40 to 60 phr or 45 to 55 phr of the particulate filler material, having up to 3% undispersed area, for example 1 to 3% undispersed area. 36. A particulate filler according to any one of the preceding or following embodiments / features / aspects, a rubber sample containing 10 to 50 phr, for example 10 to 40 phr, of recycled carbon having an undispersed surface area UA satisfying UA < 3.35 - (0.04 * phr rC). 37. A particulate filler according to any one of the preceding or following embodiments / features / aspects, a rubber sample containing 20 to 60 phr of recycled carbon resulting in a volume loss by abrasion which is not more than 10% or at most 5% greater than a comparative rubber sample produced in the same manner but containing N550 carbon black instead of the recycled carbon. 38. A particulate filler according to any one of the preceding or following embodiments / features / aspects, a rubber sample containing 20 to 80 phr of the particulate filler material, for example 30 to 70 phr, 40 to 60 phr, or 45 to 55 phr of the particulate filler material, having an abrasion loss of 90 to 100 mm3, for example, 91 to 95 mm3, measured according to ASTM D5963. 39. A particulate filler according to any one of the preceding or following embodiments / features / aspects, a rubber sample containing 20 to 60 phr of recycled carbon resulting in an M300 / M100 ratio which is either a) not more than 10% lower or not more than 5% lower than a comparative rubber sample produced in the same manner but containing N550 carbon black instead of the recycled carbon or b) 4.5 to 5. 40. A particulate filler according to any one of the preceding or following embodiments / features / aspects, a rubber sample containing 20 to 60 phr of recycled carbon resulting in an M300 (MPa) or maximum load (N) which is not more than 10% lower or not more than 5% lower than a comparative rubber sample produced in the same manner but containing N550 carbon black instead of the recycled carbon. 41. Particulate filler according to any one of the preceding or following embodiments / features / aspects, the particle size being measured according to the PSD 1 method. 42. A granule comprising the particulate filler material according to any one of the preceding or following embodiments / features / aspects, the particulate filler material further comprising at least one additional filler material selected from carbon black, silicon-treated carbon black, silica-coated carbon black, carbon black-coated particles and precipitated silica. 43. An elastomeric composite comprising the particulate filler material according to any one of the preceding or following embodiments / features / aspects and at least one elastomer, and optionally further comprising one or more of carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, modified polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clays, nanoclays, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures and carbon black-coated particles. 44. Elastomer composite according to any one of the preceding or following embodiments / features / aspects, the elastomer being chosen from natural rubbers, functionalized natural rubbers, styrene-butadiene rubbers, functionalized styrene-butadiene rubbers, polybutadiene rubbers, functionalized polybutadiene rubbers, polyisoprene rubbers, ethylene-propylene copolymers, isobutylene-based rubbers, polychloroprene rubbers, nitrile rubbers, hydrogenated nitrile rubbers, polysulfide rubbers, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, and mixtures thereof. 45. An elastomer composite according to any one of the preceding or following embodiments / features / aspects, the elastomer composite being a vulcanized elastomer composite. 46. ​​An elastomeric composite according to any one of the preceding or following embodiments / features / aspects, having a dispersion of less than or equal to 4% undispersed area, for example, less than or equal to 3% undispersed area or from 1% to 3% undispersed area. 47. An elastomeric composite according to any one of the preceding or following embodiments / features / aspects, the elastomeric composite containing 20 to 60 phr of particulate filler material and having less than 10% or less than 5% undispersed surface area (% Dispergrader). 48. An elastomeric composite according to any one of the preceding or following embodiments / features / aspects, the elastomeric composite containing 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% undispersed area, for example 1 to 3% undispersed area (% Dispergrader). 49. An elastomeric composite according to any one of the preceding or following embodiments / features / aspects, the elastomeric composite containing 10 to 40 phr, for example 10 to 40 phr, of an rC ground by grinding media and having an undispersed surface area UA satisfying UA < 3.35 - (0.04 * phr rC). 50. An elastomer composite according to any one of the preceding or following embodiments / features / aspects, the elastomer composite containing 20 to 60 phr of recycled carbon and exhibiting a volume loss by abrasion of not more than 10% or at most 5% greater than a comparative rubber sample containing N550 carbon black instead of the ground recycled carbon. 51. An elastomeric composite according to any one of the preceding or following embodiments / features / aspects, the elastomeric composite containing 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 having an abrasion loss of 90 to 100 mm3, for example, 91 to 95 mm3, measured according to ASTM D5963. 52. An elastomer composite according to any one of the preceding or following embodiments / features / aspects, the elastomer composite containing 20 to 60 phr of recycled carbon and having an M300 / M100 ratio which is either a) not more than 10% or at most 5% lower than a comparative rubber sample containing N550 carbon black instead of the ground recycled carbon or b) 4.5 to 5. 53. An elastomer composite according to any one of the preceding or following embodiments / features / aspects, the elastomer composite containing 20 to 60 phr of recycled carbon and having an M300 (MPa) or maximum load (N) that is not more than 10% lower or not more than 5% lower than a comparative rubber sample containing N550 carbon black instead of the ground recycled carbon 54. A tire tread comprising a vulcanizate of a mixture comprising the elastomeric composite according to any one of the preceding or following embodiments / features / aspects and a vulcanization preparation. 55. An article comprising a vulcanizate of a mixture comprising the elastomeric composite according to any one of the preceding or following embodiments / features / aspects and a vulcanization preparation. 56. An article according to any of the preceding or following embodiments / features / aspects, the article being incorporated into pneumatic tires, non-pneumatic tires or solid tires. 57. An article according to any one of the preceding or following embodiments / features / aspects, wherein the article is selected from treads, undertreads, inner rubbers, sidewalls, sidewall inserts, thin wire covering and toe rubber for retreaded tires. 58. An article according to any one of the preceding or following embodiments / features / aspects, the article being selected from flexible hoses, liners, intermediates, seals, gaskets, anti-vibration articles, tracks, track pads for track-propelled vehicle equipment, engine mounts, seismic stabilizers, mining equipment guards, mining equipment liners, conveyor belts, chute liners, slurry pump liners, slurry pump impellers, valve seats, valve bodies, piston hubs, piston rods, plungers, slurry mixing impellers and slurry pump impellers, mill liners, cyclones and hydrocyclones, expansion joints, liners for dredge pumps and outboard motor pumps for marine equipment,seals for marine, petroleum, aerospace and other applications, propeller shafts, pipe coverings, engine mounts, bushings, weather stripping, windshield wipers, automotive components, gaskets, seals, housings, wheel components and track components.

[0116] The present invention will become more clearly apparent from the following examples which are given by way of example only.

[0117] EXAMPLES - Example 1

[0118] CB N550 and N330 pellets were jet milled in a 4-inch (10.2 cm) Micron Master Jet Pulverizer SN 1634 Model 04-626 with a flow rate of approximately 2 kg / h and an upper pressure of 80 psi (0.55 MPa) and a lower pressure of 40 psi (0.03 MPa) to produce a flaky material. rC was obtained in flaky form from a commercial supplier, with a reported D50 of 2 µm. The measured PSD of this material is shown in [Fig.l] and [Fig.6]. All materials were dispersed in 14 wt% water to form a slurry for milling. Wet grinding was carried out in recirculating batch mode on a MiniCer grinding media mill (Netzsch) using 0.5 mm YSZ balls with a filling factor of 85% and at 4200 rpm.“Residence time” was calculated using the equation “residence time” = “batch duration” * “grinder volume” / “batch volume”, where “batch duration” is the total run time of a batch, “grinder volume” is the volume of the grinding chamber less the volume occupied by the grinding media, and “batch volume” is the total volume of the batch being ground.

[0119] The milled suspension, containing 86% by weight of water, was stirred on a hot plate set at 80°C until the moisture content reached 70% by weight. The batch was then granulated by combining it with flaky N550 in a proportion of 4:6 by weight in a granulator (Feeco Inc.) operating at 900 rpm so that the total water content became 50% by weight, allowing the formation of granules. The granules were either dried in an oven at 80°C or kept moist until blended, depending on the blending method.

[0120] In order to characterize the particle size obtained in the suspension, a suspension of ground rC (14% by weight of solid) was diluted to 2000 ppm with DI water containing 600 ppm of Triton X100 surfactant. The diluted solution was then mixed by a DISPERMAT LC55 mixer equipped with a 30 mm diameter 18-tooth light impeller at 800 rpm for 5 minutes. Then, the solution was stirred using a magnetic bar on a stir plate for 24 hours. The sample solution was then diluted to 400 ppm using DI water containing 400 ppm of Triton X100 surfactant and left to rotate in a 40 ml flask on a roller until measurement.

[0121] Disk centrifuge measurements (DC24000, CPS Instruments) were performed at 5000 rpm. First, 24%, 22%, 20%, 18%, 16%, 14%, 12%, 10%, 8% sucrose solution in DI water were sequentially injected into the disk (1.6 ml for each), and then 1 ml of dodecane was injected to seal the gradient. The gradient was left for 1 hour to stabilize before measurements. In particle size measurements, the sample density and refractive index were set to 1.86 g / cm3 and n = 1.84 + 0.846i. The results represent the equivalent sedimentation result of a spherical particle with a density of 1.86 g / cm3 and a refractive index of n = 1.84 + 0.846i. All measurements were stopped immediately once the signal reached the baseline.

[0122] The particle size changes are shown in [Fig.l] and [Fig.6]. The particle size distribution of the starting material indicated a D90 of 9 pm. After a residence time of 2.5 min, the D90 decreased to 3 pm and continued to decrease to 0.34 pm after 40 min.

[0123] In order to determine what residence time was sufficient to achieve suitable rubber properties, the ground materials were tested in an SBR composite. Details of each example, including the formulation and mixing protocol, are shown in Table 2 below.

[0124] [TABLE 2]: EEE Exe Exem Exem Ex Ex Ex Ex Ex Ex Ex Ex Ex X XXX compare foot and copy foot foot foot foot foot empty 5 tif 6 compact 6 compact 8 cc ifmp4 7 if 9 if 1 if 1 ooo 0 1 mmm PPP ar ar at at if if 1 2 3 NN r Mél rC sec mélan rC Mél N5 N5 N5 rC rC rC rC rC 5 3 C ang flocon ge de hu ang 50 rC rC rC rC 5 C ang flocon ge de hu ang 50 r e 50 de mi ne huC mi hu se mi hu hu hu mi mi 0 0 s of rC h mi mi of of of of of sse rC with wet flocon of 2 10 40 mmmmmmccmmm in in in in in in in in in in Step 1 Kralex S N330 5 0 rC, grand ules 5 0 Cogranu le nne rC5:N2, flo 50 rC, large oils, 50% H2O 50 Cogranu with rC:N 550 4:6, 50% H N550, 2 min, granulated, 50% H 20 35 N550, 2 min, granulated, 50% H 20 35 rC, 2 min, cogra nulated rC:N550 4:6, 50% H20 35 rC, 5 min, cogra nulated rC:N550 4:6, 50% H2O 35 rC, 10 m in, cogra nulated rC: N550 4: 6, 50% H2O 35 rC, 20 m in, cogra nulated rC: N550 4: 6, 50% H2O 35 rC, 40 m in, cogra 35 nulé rC: N550 4: 6, 50% H2O Stearic acid 2 2 2 2 2 2 Zinc oxide 3 3 3 3 3 3 Wax 1 1 1 1 1 1 Antioxidant DQ 1 ,5 1 ,5 1 ,5 1 ,5 1 ,5 1 ,5 Stangard 6PPD 3 3 3 3 3 2 2 2 2 2 2 2 2 2 2 Step 2 Sulfur 1 ,5 1 ,5 1 ,5 1 ,5 1 ,5 1 ,5 BBTS 1 ,5 1 ,5 1 ,5 1 ,5 1 ,5 1 ,5 Stearic acid 2 2 2 2 2 2 2 2 2 Zinc oxide R GT-M 3 3 3 3 3 3 3 3 3 3 Wax 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 E5 E5 Antioxidant DQ 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 E5 E5 Stangard 6PPD 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Step 3 Sulfur 1.5 1.5 1.5 1.5 1.5 1.5 1.5 E5 E5 BBTS 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 E5 E5 Compound Properties Concentration of rC, pce 0 0 5 0 20 50 20 50 20 0 0 0 14 14 14 14 14 Surface 1 2 1 13.8 23.2 16.1 21 12.0 3.4 2.0 1.7 2.8 2.4 1.8 2.0 1.5 not disp ,6 ,3 8 ,5 ersed: ,5 Dispergr ader (%) Constraint 1 1 1 11.6 8.7 11.0 8.2 10.7 12 13 13 12 13 12 12 12 te at 300 3 3 0 ,3 ,6 ,0 ,1 ,0 ,3 ,4 ,4 % def ,3 ,1 ,2 formation (mPa) Rate of 4 4 3 4.17 3.44 3.92 3.6 4.14 4.7 4.6 4.8 4.7 4.6 4.7 4.9 4.7 constraint ,2 ,6 ,8 7 1 4 3 0 8 9 5 6 te 300 % 2 8 5 / 100 % Loss of 1 1 1 146 177 154 168 154 138 137 136 140 138 138 130 138 volume 3 2 5 by abrasion 7 7 4 sion (mm3)

[0125] The formulations for the tests are shown in Table 2. In the tests, with the results shown in Table 2 and Figures 2 to 5, the symbols / formulations in the table and figures have the following meanings: N330 dry = N330 carbon black, no rC present; granulated and dried before mixing. Wet N550 X min = N550, ground by grinding media, X indicating the grinding residence time, e.g., “rC wet 20 min” means N550 ground by grinding media for a residence time of 20 minutes, then cogranulated with flaky N550 at a mass ratio of 4:6; not dried before mixing. N550 dry = N550 carbon black, no rC present; granulated and dried before mixing. rC wet X min = rC, ground by grinding media grinding according to the present invention, X indicating the grinding residence time, for example, “rC wet 20 min” means rC ground by grinding media milling for 20 minutes, then cogranulated with flaky N550 at a mass ratio of 4:6; not dried before mixing. Dry rC blend = 4:6 parts by mass of rC and N550, cogranulated and dried before mixing. Wet rC blend = 4:6 parts by mass of rC and N550, cogranulated and not dried before mixing. Dry rC flaky mix = rC and non-granulated N550 mixed dry according to the normal method. dry rC = rC which is not ground by grinding by grinding body but granulated and dried wet rC = rC which is not ground by grinding by grinding body but granulated and not dried Dry flaky rC = rC that is not ground by grinding media, not granulated and dry mixed according to the normal method. For the “undried” samples, the degree of wetting was such that the water content was 50% by weight.

[0126] In addition to the RC samples milled by grinding media milling, the possibility of introducing the RC as flaky material as well as the wet blending of wet RC granules and cogranules was evaluated. [Fig. 2] represents the dispersion quality in the resulting mixtures. The dry, flaky and wet processes all produced RC mixtures with poorer dispersion than the control samples (long dotted circles), while the samples milled by grinding media milling (short dotted circle) had comparable dispersion to the carbon black control samples (solid circle).

[0127] The tests also demonstrated an improvement in rubber performance. [Fig. 3] represents the volume loss by DIN abrasion. Materials ground by grinding media grinding (short dotted circles) showed a volume loss comparable to that of the 2 min wet N550 control (solid circle), while the other rC processes (long dotted circles) showed a degradation in performance compared to the control. A residence time of 40 minutes led to a degradation, probably due to a degradation of the rC structure, as indicated by softening of the material, which can negatively affect DIN abrasion.

[0128] The slope of the tensile curve of a rubber compound, called reinforcement, is important for abrasion performance. In [Fig.4], the stress ratio at 300 to 100%, M300 / M100, was plotted to quantify the reinforcement. As shown in the tests, the wet mix brought N550 to become more reinforcing, comparable to dry-blended N330. Increasing the rC content resulted in a decrease in reinforcement when blended using the dry, wet, or flaked processes. However, the rC milled by grinding media milling of the present invention did not show a decrease.

[0129] rC often results in lower stiffness than CB blends. rC incorporated using the flaky, dry, or wet processes produced the expected decrease in stress at 300% elongation (M300), as described in [Fig. 5]. But, in the tests conducted for the present invention, no degradation was observed.

[0130] While an optimal grinding time for reinforcement and abrasion for these tests was 20 minutes, the optimal grinding time for low deformation stiffness was 5 minutes, as shown in [Fig.5]. This may be due to the decomposition of agglomerates up to five minutes, and the subsequent degradation of the aggregate structure after five minutes.

[0131] Based on these observations, the use of grinding media milling to treat rC prior to producing composites allows for a considerably higher rC content to be achieved. Since there is little or no degradation in properties compared to N550 compounds prepared by wet blending, composites with a replacement rate of up to 100% may be possible.

[0132] Table 3 below presents a summary of some of the results obtained by the present invention, and normalized with respect to the “N550 wet 2 min” control, described in the example above. These normalized results were used to derive equations describing the performance with and without the application of the present invention. [Tables 3] Normalized control vs. N550 from the same mixing process Comparative example 7 Comparative example 8 Comparative example 9 Example 1 Example 2 Example 3 Example 4 Example 5 Wet RC Mixture Wet RC N550wet 2 min wet RC 2 min wet RC 5 min wet RC 10 min wet RC 20 min wet RC 40 min concentration in RC 50 20 0 14 14 14 14 Non-dispersed surface: Disperse (%) 643 357 100 84 72 54 60 45 Mod. 300 % (mPa) 67 87 100 98 105 100 101 101 Module 300 % / 100 % 78 88 100 100 99 102 105 101 Perte of volume (mm3) 121 111 100 101 100 100 94 100

[0133] Rubber Blending: Rubber composites were prepared using the formulation described in Table 2. The SBR used was Kralex SBR 1502 styrene-butadiene rubber (Synthos); the N550 was Spheron SO (Cabot Corp.); the N330 was Vulcan 3 (Cabot Corp.); the jet-milled ungranulated rC was Carbon Green 6 (CBp Cyprus Ltd., Limassol, Cyprus), in some cases granulated as shown in Table 2; stearic acid, rubber grade (Akrochem Corp.); zinc oxide was RGT-M (Akrochem Corp.); wax was AKR0WAXMT 5031 (Akrochem Corp.); antioxidant was DQ (Akrochem Corp.); 6PPD was Stangard 6PPD (Harwick Standard); sulfur was Rubbermakers Sulphur (Akrochem Corp); BBTS was Accelerator BBTS (Akrochem Corp.). All compositions were mixed in a 1.6 L Banbury mixer with two winged rotors.Dry-mixed samples (granule moisture < 1 wt%) were prepared in two steps as described in Table 4. Wet-mixed samples (granule moisture > 1 wt%) were prepared in three steps as described in Table 5. Regardless of the method used, after each formulation step, the compounds were sheeted on a 2-roll mill operating at 50 °C and approximately 22 rpm, followed by six passes through a nip of approximately 5 mm, with a rest time before the next mixing step (or curing, after the last step) of at least 3 hours. Curing was carried out in a heated press (160 °C, 2500 lb), for a time T90 + 40% of T90 as determined by a conventional rubber rheometer, where T90 is the time required to reach 90% vulcanization.

[0134] [TABLE 4]: Dry Mix Protocols - Step 1 Fill Factor, % 70 Rotor Speed, rpm 80 Starting Temperature, °C 80 Time (s) Description 0 Add Polymer 60 Add ¾ of the Filler 120 Add remaining filler 180 Scrape / sweep, add premixed chemicals 240 Scrape / sweep 300 Drain - adjust RPM to stay < 160°C Step 2 Fill Factor, % 65 Rotor Speed, rpm 60 Starting Temperature, °C 52 Time (s) Description 0 Add batch from previous step and hardeners 30 Scrape / sweep 90 Drain - Adjust RPM to stay < 150°C

[0135] [TABLE 5]: Wet Mix Protocols - Step 1 Fill Factor, % 70 Rotor Speed, rpm 100 Starting Temperature, °C 90 Time (s) Description 0 Add polymer and ¾ of the filler 150 Add remaining filler, mix to 1 50 °C time at 150 °C add 6PPD, reduce rpm to 80, mix to 155 °C time at 155 °C Scrape / Sweep, mix to 160 °C time at 160 °C Drain Step 2 Fill Factor, % 68 Rotor Speed, rpm 80 Starting Temperature, °C 52 Time (s) Description 0 Add compound from step 1 30 Add chemicals 90 Scrape / sweep 180 Drain - adjust speed to stay < 150 °C Step 3 Fill factor, % 65 Rotor speed, rpm 60 Starting temperature, °C 50 Time (s) Description 0 Add 1 / 2 masterbatch, hardeners and 1 / 2 masterbatch. 30 Scrape / sweep 90 Drain - Adjust rotor speed to stay < 150 °C

[0136] The following tests were used to obtain performance data on each of the vulcanizates. The tensile stress at 100% elongation (M100) and the tensile stress at 300% elongation (M300) were evaluated according to ASTM D412 (Test Method A, Type C) at 23°C, 50% relative humidity, and a cross-sectional speed of 500 mm / min. Extensometers were used to measure tensile strain. The M300 / M100 ratio is referred to as the tensile stress ratio (or reinforcement ratio). The cured rubber sample was sectioned using a razor blade secured in a hand-held cutting jig for dispersion analysis. The sample was mounted and imaged on a Dispergrader instrument (Alpha Technologies).The following parameters were used: “filler volume fraction”, 20%; “exposure time”, 40 ms; “color channel for analysis”, “blue”; “threshold for dispersion calculation”, 23 pm; nodge to agglomerate fraction, 1; white area threshold, 0. The amount indicated by the Alpha Technologies instrument as “White area, %” was interpreted as “undispersed area”. DIN abrasion was evaluated according to the rotation method of ASTM D5963. Example 2

[0137] CB N330 pellets (Cabot Corporation) were jet milled to produce a flaky material as described in Example 1. rC pellets (Reoil-RCB, REOIL SPZOO) were jet milled; the resulting material had a D50 of 488 nm and a D90 of 3430 nm, measured as described below. The Jet-milled RC material was dispersed in 14 wt% water to form a slurry for grinding. Wet grinding was performed in pass-through mode (single pass unless otherwise specified) on a Netzsch MiniCer wet grinding media mill using a 0.5 mm yttria-stabilized zirconia grinding media (YSZ, 3000 rpm or 4600 rpm) or 0.4-0.6 mm polystyrene beads (4600 rpm only) with residence time and other settings as shown in Table 6 below. The number of collisions is the same for polystyrene beads; however, the energy imparted during media grinding with PS beads is 0.5 times that imparted during media grinding with YSZ beads. [TableauxôA] Target Residence Time (min) Batch Duration (min) Flow Rate (cm3 / min) Pump Setting 0.1 0.58 690 298 0.2 1.16 345 149 0.5 2.90 138 60 1 5.80 69 30 2 11.59 34.5 15 4 22 52 (performed twice) 15 (performed twice)

[0138] [TableauxôB] 4,600 rpm (YSZ) 3,600 rpm (YSZ) min kWh / kg collisions per kg kWh / kg collisions per kg 0.1 0.15 1.1E+12 0.10 7.6E+11 0.2 0.30 2.3E+12 0.20 1.5E+12 0.5 0.75 5.7E+12 0.49 3.8E+12 1 1.51 1.1E+13 0.98 7.6E+12 2 3.02 2.3E+13 1.96 1.5E+13 4 6.03 4.5E+13 3.92 3E+13

[0139] In order to characterize the particle size obtained in the suspension, the milled rC suspension was diluted to 2000 ppm with DI water containing 600 ppm of Triton XI00 surfactant. The diluted solution was then mixed by a DISPERMAT LC55 mixer equipped with a 30 mm diameter 18-tooth light impeller at 800 rpm for 5 minutes. Then, the solution was stirred using a magnetic bar on a stir plate for 24 hours. The sample solution was was then diluted to 400 ppm using DI water containing 400 ppm Triton X100 surfactant and allowed to rotate in a 40 ml flask on a roller until measurement.

[0140] Disk centrifuge measurements (DC24000, CPS Instruments) were performed at 5000 rpm. First, 24%, 22%, 20%, 18%, 16%, 14%, 12%, 10%, 8% sucrose solution in DI water were sequentially injected into the disk (1.6 ml for each), and then 1 ml of dodecane was injected to seal the gradient. The gradient was allowed 1 hour to stabilize before measurements. In disk centrifuge measurements, the density and refractive index of the sample were set to 1.86 g / cm3 and n = 1.84 + 0.846i. The results represent the equivalent sedimentation result of a spherical particle with a density of 1.86 g / cm3 and a refractive index of n = 1.84 + 0.846i. All measurements were stopped immediately once the signal reached the baseline. The D50 and D90 for the different samples are shown in Table 7 below. [Paintings?] Grinding speed / ball composition Residence time (min) D50 (nm) D90 (nm) 4600 rpm (YSZ) 0.1 350 2016 0.2 313 1531 0.5 284 1194 1 272 858 2 242 500 4 223 379 3000 rpm (YSZ) 0.1 238 1156 0.2 334 1532 0.5 321 1273 1 320 921 2 287 757 4 247 432 4600 rpm (polystyrene) 0.1 378 2161 0.2 322 1631

[0141] The milled slurry, containing 86% by weight of water, was centrifuged using a Thermo Scientific Sorvall Legend XTR centrifuge for 15 minutes to obtain a spin cake containing approximately 70% solids. Each batch was then granulated by combining the appropriate amount of spin cake and slurry with flaky N330 carbon black in a rotating spindle granulator operating at 900 rpm with walls heated to 50°C to form a mixture with 30% rC and 70% N330 carbon black by weight. The granules were dried in an oven at 80°C.

[0142] SBR composites were prepared with 50 phr (total) of rC and carbon black according to the mixing protocol of Table 4 and the vulcanization procedure described in Example 1 with the formulation described in Table 8 below (chemicals as described in Example 1). The rubber properties were measured as described in Example 1. [Tables 8] Component Quantity (pce) SBR 100 Stearic acid 2 Zinc oxide 3 Wax 1 Antioxidant 1.5 6PPD 3 Sulfur 1.5 BBTS 1.5

[0143] As described in [Fig.7] (RT = residence time in minutes), even minimal grinding significantly improved dispersion in SBR compounds, with several samples, all with milled rC having a D90 below 1500 nm, exhibiting an undispersed surface area of ​​less than 3 wt%. However, dispersion is imperfectly correlated with abrasion performance, with only milled rC with a D90 less than or equal to 1100 nm delivering less than 95 mm3 of mass loss in an abrasion test ([Fig.8]; RT = residence time in minutes). more, only ground RC having a D50 of 250 to 400 simultaneously leading to an M100 of at least 2.5 MPa, while ground RC with a lower D50 also leading to lower moduli ([Fig.9], RT = residence time in minutes). Example 3

[0144] CB N330 granules (Cabot Corporation) were jet milled to produce a flaky material as described in Example 1. rC granules (Reoil-RCB, REOIL SPZ OO) were jet milled and dispersed in 14% by weight water to form a slurry for grinding. Wet grinding was carried out with a five-minute residence time in a recirculating batch mode on a MiniCer grinding media mill (Netzsch) using 0.5 mm YSZ balls with an 85% fill factor and at 4,600 rpm. Particle size was characterized as described in Example 1; D50 was 271 microns and D90 was 412 microns.

[0145] A portion of the milled slurry, containing 86% by weight of water, was centrifuged using a Thermo Scientific Sorvall Legend XTR centrifuge for 15 minutes to obtain a spin cake. The spin cake was then combined with the milled slurry to form a mixed slurry having a water content as shown in Table 9. The batch was then granulated by combining it and the mixed slurry with an appropriate amount of flaky N330 carbon black in a rotating spindle granulator operating at 900 rpm with walls heated to 50°C to achieve the proportions of rC and virgin carbon black in Table 9 below. Pure rC pellets were produced by drying the spin cake at 80°C until it reached a moisture content of 46%.Flaky N330 was combined with water to obtain a solids loading of approximately 58% by weight for the formation of neat granules. The granules were either dried in an oven at 80 °C or kept moist until blended with the rubber, depending on the blending method. [Tables 9] Proportion of rC in the final granule Proportion of water in the mixed rC suspension before mixing 26% by weight 18% 40% by weight 26% 100% by weight 46%

[0146] SBR composites were prepared with 50 phr (total) of rC and carbon black according to the wet-mix or dry-mix protocol described in Example 1, as well as the vulcanization procedure described in Example 1 using the formulation described in Table 8 (chemicals as described in Example 1). Rubber properties were measured as described in Example 1. As shown in [Fig. 10], milling (solid circles) significantly improves the dispersion of the filler material compared to samples that were not milled by media milling (open circles), especially at 26% and 40% rC. However, at 100% rC, dried granules show a sharp decrease in dispersion quality, while elastomeric composites produced with wet granules still maintain good dispersion performance. This correlation is also observed in the abrasion performance ([Fig. 1 1]; media milling samples - closed circles; jet milling samples - open circles). Example 4

[0147] Cogranules composed of 30 wt% media milled and jet milled rC and 70% Propel E6 carbon black (STSA = 97 m2 / g, Cabot Corporation), as well as jet milled N330 carbon black granules, were prepared as described in Example 3. SBR composites with 50 phr filler were prepared as described in Example 3, except that the 6PPD was from Westco, and characterized as described in Example 1. As described in Table 10 below, the use of a media milled rC in combination with a higher surface area carbon black such as Propel E6 carbon black results in performance better than or equivalent to that of an N330 carbon black (STSA = 76 m2 / g). [Tables 10] Charge Undispersed surface (%) Abrasion loss (mm3) M300 (MPa) M100 (MPa) N330 0.96 89 15 2.8 Cogranulated with rC ground by grinding media 0.47 82 15 3.1 Cogranulated with rC ground by jet 14.7 94 13 2.9

[0148] Although this invention has been particularly presented and described with reference to preferred embodiments thereof, it will be apparent to those skilled in the art that various modifications in form and detail may be made thereto without departing from the scope of the invention defined by the appended claims.

[0149] As used herein, the term "and / or" includes any and all combinations of one or more of the listed associated elements. Furthermore, all conjunctions used are to be understood in the most inclusive sense possible. Thus, the word "or" is to be understood as having the definition of a logical "or" rather than a logical "exclusive or" unless the context clearly requires otherwise. It will further be apparent that the terms: includes, comprises and / or including and / or comprising, when used in this specification, specify the presence of features, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other of the features, steps, operations, elements, components and / or groups thereof.Further, it will be apparent that where an element, including a component or subsystem, is referred to and / or represented as being linked or coupled to another element, it may be directly linked or coupled to the other element or intermediate elements may be present.

[0150] Unless otherwise indicated, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. It is further to be understood that terms, as defined in commonly used dictionaries, are to be interpreted as having a meaning that is consistent with their meaning in the context of the related art and are not to be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0151] Furthermore, where an amount, concentration, or other value or parameter is given as a range, preferred range, or list of preferable upper and preferable lower values, this is to be understood as specifically indicating all ranges formed from any pair of any upper preferred range limit or value and any lower preferred range limit or value, regardless of whether the ranges are described separately. Where a range of numerical values ​​is referred to herein, unless otherwise indicated, the range is intended to include its endpoints, as well as all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values ​​stated when defining a range.It is further understood that for any range provided herein, the numerical ranges may be "about" those ranges, and conversely, when a range is provided using "about" ranges, those ranges may be precisely the numerical ranges provided. Any combination of embodiments and / or elements and / or components and / or . properties mentioned herein can be realized herein and is considered part of the present invention.

[0152] Other embodiments of the present invention will become apparent to those skilled in the art from reading this specification and practicing the present invention described herein. It is to be understood that this specification and the examples are to be considered as given by way of example only, the true scope and spirit of the invention being indicated by the following claims and their equivalents.

[0153] The foregoing description of preferred embodiments of the present invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Modifications and variations are possible in light of the above teachings, or may be determined from practice of the invention. The embodiments have been selected and described in order to explain the principles of the invention and its practical application to enable those skilled in the art to use the invention in different embodiments and with different modifications suited to the particular use contemplated. The scope of the invention is intended to be defined by the appended claims and their equivalents.

Claims

Claims

1. A particulate filler comprising 10 to 40 wt% recycled carbon, wherein a volume-weighted particle size distribution of the recycled carbon measured by disk spin photosedimentometry 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.

2. A particulate filler according to claim 1, 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.

3. The particulate filler of claim 1 or 2, further comprising one or more of carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, modified polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clays, nanoclays, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, and carbon black-coated particles.

4. A particulate filler according to any one of claims 1 to 3, 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.

5. A particulate filler according to any one of claims 1 to 4, further comprising carbon black.

6. A particulate filler according to any one of claims 1 to 5, further comprising carbon black having a BET specific surface area of ​​35 to 110 m2 / g, for example 35-65 m2 / g, 65-90 m2 / g, or 90-110 m2 / g.

7. A particulate filler according to any one of claims 1 to 6, further comprising a carbon black of the N300 or N500 series, for example, carbon black N330 or N550.

8. A particulate filler according to any one of claims 1 to 7, the particulate filler material being in the form of granules.

9. A particulate filler according to claim 8, the granules consisting essentially of the particulate filler material, optional water and an optional binder.

10. A particulate filler according to any one of claims 1 to 9, the particulate filler material having a moisture content of 15 to 80%, for example 40 to 60% by weight.

11. A particulate filler according to any one of claims 1 to 10, wherein a rubber sample containing 20 to 60 phr of ground recycled carbon results in less than 10% or less than 5% undispersed surface area (% Dispergrader).

12. A particulate filler according to any one of claims 1 to 11, wherein a rubber sample containing 20 to 80 phr of particulate filler material, for example 30 to 70 phr, 40 to 60 phr, or 45 to 55 phr of particulate filler material, has up to 3% undispersed area, for example 1 to 3% undispersed area.

13. A particulate filler according to any one of claims 1 to 12, wherein a rubber sample containing 10 to 50 phr, for example 10 to 40 phr, of the recycled carbon has an undispersed surface area UA satisfying UA < 3.35 - (0.04 * phr rC).

14. A particulate filler according to any one of claims 1 to 13, wherein a rubber sample containing 20 to 60 phr of recycled carbon results in a volume loss by abrasion which is not more than 10% or at most 5% greater than a comparative rubber sample produced in the same manner but containing N550 carbon black instead of the recycled carbon.

15. A particulate filler according to any one of claims 1 to 14, wherein a rubber sample containing 20 to 80 phr of the particulate filler material, for example 30 to 70 phr, 40 to 60 phr, or 45 to 55 phr of particulate filler material, has an abrasion loss of 90 to 100 mm3, for example, 91 to 95 mm3, measured according to ASTM D5963.

16. A particulate filler according to any one of claims 1 to 15, wherein a rubber sample containing 20 to 60 phr of recycled carbon results in an M300 / M100 ratio which is either a) not more than 10% lower or is not more than 5% lower than a comparative rubber sample produced in the same manner but containing N550 carbon black instead of recycled carbon or b) from 4.5 to 5.

17. A particulate filler according to any one of claims 1 to 16, wherein a rubber sample containing 20 to 60 phr of recycled carbon results in an M300 (MPa) or maximum load (N) which is not more than 10% lower or not more than 5% lower than a comparative rubber sample produced in the same manner but containing N550 carbon black instead of the recycled carbon.

18. A particulate filler according to any one of claims 1 to 17, the particle size being measured according to the PSD 1 method.

19. A granule comprising the particulate filler material according to any one of claims 1 to 18, the particulate filler material further comprising at least one additional filler material selected from carbon black, silicon-treated carbon black, silica-coated carbon black, carbon black-coated particles and precipitated silica.

20. An elastomeric composite comprising the particulate filler material of any one of claims 1 to 18 and at least one elastomer, and optionally further comprising one or more of carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, modified polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clays, nanoclays, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, and carbon black-coated particles.

21. An elastomer composite according to claim 20, the elastomer being selected from natural rubbers, functionalized natural rubbers, styrene-butadiene rubbers, functionalized styrene-butadiene rubbers, polybutadiene rubbers, functionalized polybutadiene rubbers, polyisoprene rubbers, ethylene-propylene copolymers, isobutylene-based rubbers, polychloroprene rubbers, nitrile rubbers, hydrogenated nitrile rubbers, polysulfide rubbers, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, and mixtures thereof.

22. An elastomeric composite according to claim 20 or 21, the elastomeric composite being a vulcanized elastomeric composite.

23. An elastomeric composite according to any one of claims 20 to 22, having a dispersion of less than or equal to 4% undispersed area, for example, less than or equal to 3% undispersed area or from 1% to 3% undispersed area.

24. An elastomeric composite according to any one of claims 20 to 23, the elastomeric composite containing 20 to 60 phr of particulate filler material and having less than 10% or less than 5% undispersed surface area (% Dispergrader).

25. An elastomeric composite according to any one of claims 20 to 24, the elastomeric composite containing 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% undispersed area, for example 1 to 3% undispersed area (% Dispergrader).

26. An elastomeric composite according to any one of claims 20 to 25, the elastomeric composite containing 10 to 40 phr, for example 10 to 40 phr, of an rC ground by grinding by grinding media and having an undispersed surface UA satisfying UA < 3.35 - (0.04 * phr rC).

27. ​​An elastomeric composite according to any one of claims 20 to 26, the elastomeric composite containing 20 to 60 phr of recycled carbon and exhibiting a volume loss by abrasion of not more than 10% or at most 5% greater than a comparative rubber sample containing N550 carbon black instead of the ground recycled carbon.

28. An elastomeric composite according to any one of claims 20 to 27, the elastomeric composite containing 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 having an abrasion volume loss of 90 to 100 mm3, for example, 91 to 95 mm3, measured according to ASTM D5963.

29. An elastomeric composite according to any one of claims 20 to 28, the elastomeric composite containing 20 to 60 phr of recycled carbon and having an M300 / M100 ratio which is either a) not more than 10% or at most 5% lower than a sample of comparative rubber containing N550 carbon black instead of crushed recycled carbon or b) 4.5 to 5.

30. An elastomer composite according to any one of claims 20 to 29, the elastomer composite containing 20 to 60 phr of recycled carbon and having an M300 (MPa) or maximum load (N) which is not more than 10% lower or not more than 5% lower than a comparative rubber sample containing N550 carbon black instead of the ground recycled carbon.

31. A tire tread comprising a vulcanizate of a mixture comprising the elastomeric composite of any one of claims 20 to 30 and a vulcanization preparation.

32. An article comprising a vulcanizate of a mixture comprising the elastomeric composite of any one of claims 20 to 30 and a vulcanization preparation.

33. An article according to claim 55, the article being incorporated into pneumatic tires, non-pneumatic tires or solid tires.

34. An article according to claim 32 or 33, the article being selected from treads, undertreads, inner rubbers, sidewalls, sidewall inserts, a thin wire covering and a toe rubber for retreaded tires.

35. An article according to claim 32, the article being selected from flexible hoses, liners, intermediates, seals, gaskets, anti-vibration articles, tracks, track pads for track-propelled vehicle equipment, engine mounts, seismic stabilizers, mining equipment guards, mining equipment liners, conveyor belts, chute liners, slurry pump liners, slurry pump impellers, valve seats, valve bodies, piston hubs, piston rods, plungers, slurry mixing impellers and slurry pump impellers, mill liners, cyclones and hydrocyclones, expansion joints, liners for dredge pumps and outboard motor pumps for marine equipment, seals for marine, oilfield,aerospace and other, propeller shafts, pipe coverings, engine mounts, bushings, weather stripping, windshield wipers, automotive components, seals, gaskets, housings, wheel components and track components.

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