Method for treating recovered carbon and resulting ground recovered carbon and products containing same

Abstract

A method for treating recovered carbon is described. Methods of utilizing media milling to improve one or more properties of recovered carbon in a product, such as an elastomeric composite, are described. The media milling utilized may include media milling that consumes a specific energy of from 1 kWh / kg to 10 kWh / kg of the dry milled recovered carbon.

Description

Background Technology

[0001] This invention relates to a method for processing recycled carbon (rC). The invention also relates to milled recycled carbon that can be incorporated into products (e.g., elastomers).

[0002] There is a growing need and effort to recycle materials in order to prevent them from ending up in landfills and to avoid further depletion of natural resources.

[0003] End-of-life vehicle tires are often processed and reused in a wide range of end-use applications, from sports equipment to concrete. However, there is a desire to recycle tire components to obtain materials that can be combined with materials used for the first time, thereby reducing the amount of new material required to produce new products.

[0004] The demand for more sustainable materials and reduced carbon footprints is growing across various industries. Therefore, using 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 various types of carbon black and other fillers in various forms, as well as ceramic additives such as zinc oxide. Consequently, the resulting rC has a different composition and microstructure than unused carbon black. Compared to CB, which has the same or substantially the same surface area and structure (measured by OAN), recycled carbon suffers from lower rubber reinforcement, such as lower tensile modulus, lower tear strength, and / or lower fatigue life. Therefore, there is an industrial need to develop processes for rC and other similar particles that are unsuitable for use as fillers in rubber reinforcement and other applications, making them suitable alternatives or partial alternatives to unused carbon black.

[0005] All patents and publications mentioned in this article are incorporated herein by reference in their entirety. Summary of the Invention

[0006] One feature of the present invention is to provide a method for improving the use of recycled carbon in products.

[0007] Another feature of the invention is that it provides the ability to utilize recycled carbon without affecting the ability to produce industrially acceptable products (e.g., elastomers).

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

[0009] Another feature of the invention is to provide a method for treating recycled carbon in a polymer matrix or elastomer matrix and substantially retaining most (if not all) of the product properties (e.g., undispersed areas, wear volume loss, M300 / M100, M300, M100).

[0010] Another feature of the invention is that it provides a method for “fine-tuning” the recovered carbon to achieve or enhance certain properties (e.g., undispersed areas, M300, M100, M300 / M100, or wear volume loss).

[0011] Furthermore, a feature of the present invention is to provide a method for processing recycled carbon such that particles, for example, combined with unused carbon black, can have comparable filler properties, such as, but not limited to, acceptable dispersion compared to the use of 100% unused carbon black.

[0012] Another feature of the invention is that it provides milled, recycled carbon and provides products containing it.

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

[0014] Furthermore, the present invention relates to a method for processing recycled carbon, wherein the method comprises at least grinding wet recycled carbon to obtain ground recycled carbon, and wherein the grinding comprises at least media grinding such that the number of impacts per kg of dry-ground recycled carbon can result in at least 10 impacts per kg of dry-ground recycled carbon during the grinding process. 13 Secondary media collision, or at least 2 × 10⁻⁶ recovered carbon per kg of dry-milled material during grinding. 13 Secondary media collisions, or media grinding, can result in at least 5 × 10⁻⁶ recovered carbons per kg of dry-milled material during the grinding process. 13 Secondary medium collision.

[0015] The present invention also relates in part to milled and recycled carbon, which is preferably produced by one of the methods of the present invention and has a D50 of 250-400 nm and a D90 of 350-1100 nm.

[0016] Furthermore, this invention relates in part to milled and recycled carbon produced by one of the methods of this invention, and to products containing or utilizing the milled and recycled carbon of this invention, such as rubber products or elastomer products.

[0017] As used in this article, "char" refers to the solid material produced by the pyrolysis of rubber articles.

[0018] As used in this article, “dry-milled recycled carbon” refers to pyrolytic carbon that is essentially free of macroscopic contaminants and has been milled and optionally granulated without the use of water.

[0019] As used in this article, "carbon black" refers to carbon particles containing elemental carbon obtained by agglomerating into aggregates and clusters and through partial combustion or thermal decomposition of hydrocarbons.

[0020] As used herein, “raw recycled carbon” is a solid material produced by the pyrolysis of rubber articles that contains any amount of 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).

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

[0022] As used in this article, “pyrolytic carbon” includes carbon, raw recovered carbon, processed recovered carbon, and dry-milled recovered carbon.

[0023] As used in this article, “milled recycled carbon” or “milled rC” refers to pyrolytic carbon that is substantially free of macroscopic contaminants and has been milled.

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

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

[0026] The method may further include removing macroscopic contaminants from an initial slurry, which may optionally have up to 35% by weight of solids. The combination may further include combining at least one supplementary filler with water to form the initial slurry. The supplementary filler may be selected from carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, engineered polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, carbon black-coated particles, and mixtures of two or more of these.

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

[0028] The water can be a continuous flow, the milled slurry can be a continuous flow of milled slurry, and the combination can include metering the addition of pyrolytic carbon to the continuous flow of water. The combination can also include metering the addition of at least one supplementary filler to the continuous flow of water. The supplementary filler can be selected from carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, engineered polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, carbon black-coated particles, and mixtures of two or more of these. The method can also include metering the addition of at least one supplementary filler selected from carbon black, silicon-treated carbon black, silica-coated carbon black, carbon black-coated particles, and precipitated silica to the continuous flow of milled slurry, such that the resulting continuous flow of wet-blended carbon mixture has a solids content of 25-70% by weight or 1-35% by weight. Metering addition may include metering an aqueous slurry with additional filler into a continuous stream of milled slurry, metering additional water into a continuous stream of milled slurry, or both.

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

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

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

[0032] The granular filler may be in the form of granules. The granules may comprise 15-80% water, for example 40-60% water, or may comprise no more than 3% water and / or may consist substantially of granular filler, optional water, and optional binder. The granules may contain the granular filler according to any of these embodiments and at least one additional filler selected from carbon black, silicon-treated carbon black, silica-coated carbon black, carbon black-coated particles, and precipitated silica.

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

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

[0035] In any of these embodiments, the recycled carbon may be wet-milled recycled carbon. In any of these embodiments, the elastomeric compound may be a vulcanized elastomeric compound. The tire tread may include a vulcanized product of a mixture of the elastomeric compound and a curing package. Optionally or additionally, the article may include a vulcanized product of a mixture of the elastomeric compound and a curing package. The article may be incorporated into a pneumatic tire, a non-pneumatic tire, or a solid tire. The article may be selected from tire treads, bottom treads, liners, sidewalls, sidewall inserts, liner pads, and cushioning rubber for retreaded tires. Products can be selected from hoses, liners, gaskets, seals, washers, vibration damping products, tracks, track pads for tracked vehicles, engine mounts, seismic stabilizers, mining equipment screens, mining equipment liners, conveyor belts, chute liners, slurry pump liners, mud pump impellers, valve seats, valve bodies, piston hubs, piston rods, plungers, impellers for mixing slurries and slurry pump impellers, grinding mill liners, cyclone separators and hydrocyclones, expansion joints, linings for dredging pumps and outboard motor pumps for marine equipment, shaft seals for marine, oil, aerospace and other applications, propeller shafts, pipe liners, engine mounts, bushings, weatherstripping, windshield wipers, automotive parts, seals, washers, housings, wheel components, and track components.

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

[0037] It should be understood that the foregoing general description and the following detailed description are merely exemplary and explanatory, and are intended to provide further explanation of the claimed invention.

[0038] Various features of the invention are illustrated in conjunction with the accompanying drawings, which are incorporated in and constitute a part of this application, and together with the description, serve to explain the principles of the invention. Attached Figure Description

[0039] Figure 1This is a graph showing the volume-weighted frequency of samples collected at different residence times during the grinding process relative to particle size in nm, thus illustrating the change in particle size with residence time in a mill containing grinding media. The "Base Sample" graph depicts the particle size distribution in the slurry before grinding begins.

[0040] Figure 2 This is a graph showing the amount of undispersed region in a cured elastomer composite with 50 phr filler as a function of rC concentration in mixtures / blends with different rC treatment methods, as indicated by the data labels. The data in this graph show a control blend without rC (solid circles), a media-milled sample of the present invention (short dashed circles), and a blend without media milling of rC (long dashed circles). Media milling residence time is given in the data labels.

[0041] Figure 3 This is a graph showing the wear volume loss of a blend with 50 phr filler as a function of rC concentration under various mixing methods. The data in this graph provide a control blend without rC (solid circle), a blend with rC obtained through media milling (short dashed circle), and other rC mixing methods without media milling (long dashed circle).

[0042] Figure 4 This is a graph showing the reinforcing index M300 / M100 in a cured elastomer composite with 50 phr of filler as a function of rC concentration. The data in this graph provide a control blend without rC (solid circles), a blend with media-milled rC (short dashed circles), and other rC blending methods without media milling (long dashed circles).

[0043] Figure 5 This is a graph showing the tensile stress (M300) at 300% elongation as a function of rC concentration in blends of 50 phr fillers mixed using various blending methods. The data in this graph include a control blend without rC (solid circles), blends with media-milled rC (short dashed circles), and other rC blending methods without media milling (long dashed circles).

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

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

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

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

[0048] Figure 10 It is a graph showing the percentage of undispersed region in samples prepared by grinding with (solid circle) and without (hollow circle) media as a function of filler load (weight %).

[0049] Figure 11 This shows the wear volume loss (mm) of samples prepared by grinding with (solid circle) and without (hollow circle) media. 3 The graph shows the packing load as a function of the weight percentage.

[0050] The accompanying drawings are not drawn to scale and are provided as simplified views, and do not necessarily show all possible implementations or components that may exist. Detailed Implementation

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

[0052] The present invention also relates to a method for processing recycled carbon, wherein the method comprises at least grinding wet recycled carbon to obtain ground recycled carbon, and wherein the grinding comprises at least media grinding that consumes at least 1 kWh / kg, or at least 1.25 kWh / kg, or at least 1.5 kWh / kg of the specific energy of dry-ground recycled carbon, for example 1 kWh / kg-10 kWh / kg or 1.25 kWh / kg-3.5 kWh / kg or 1.5 kWh / kg-5 kWh / kg or 1 kWh / kg-3.1 kWh / kg, wherein the media grinding is carried out with grinding media having a diameter of 2 mm or less.

[0053] Alternatively or concurrently, the invention also relates to a method for processing recycled carbon, wherein the method comprises at least grinding wet recycled carbon to obtain ground recycled carbon, and wherein the grinding comprises at least media grinding such that the number of impacts per kg of dry-ground recycled carbon results in at least 10 impacts per kg of dry-ground recycled carbon during the grinding process. 13 Secondary media impact, or at least 2 × 10⁻⁶ recovered carbons per kg of dry-milled material during grinding. 13Secondary media collisions, for example, 3 × 10⁻⁶ kg of recovered carbon per kg of dry-milled material during grinding. 13 The secondary medium impacts each kg of dry-milled, recovered carbon 10 14 Secondary media collision, or 4 × 10⁻⁶ tons of recovered carbon per kg after dry milling. 13 The secondary medium impacts to produce 8 × 10⁸ tons of recovered carbon per kg of dry-milled material. 13 Secondary media collision, or 5 × 10⁻⁶ tons of recovered carbon per kg after dry milling 13 The secondary medium impacts to produce 6 × 10⁶ recovered carbons per kg of dry-milled material. 13 Secondary medium collision.

[0054] This document further describes other aspects and options related to the method of the present invention.

[0055] Using this invention, it has been unexpectedly discovered that grinding rC using media milling techniques (e.g., as described herein) can enhance or improve one or more certain rubber or elastomer properties (sometimes referred to herein as "rubber properties") compared to unground rC or rC without media or with media diameters greater than 2 mm. Through this invention, it has been found that grinding rC using media milling techniques can enhance or improve certain rubber properties based on the time spent (residence time) per unit element of slurry volume within the media mill. Furthermore, some rubber properties are better enhanced at lower milling times, while others are better enhanced at higher milling times. Moreover, for all rubber properties, it has been found that, generally, rubber properties do not improve further beyond a certain milling time, and therefore there exists a range of milling times that is advantageous for achieving or enhancing certain properties and avoiding over-grinding of rC. As described herein, the media-milled rC of this invention and its formation method are compared with unused N550 carbon black (as a control), because this type of carbon black has historically proven difficult to replace, even partially, with rC, or even ground rC.

[0056] The initial recycled carbon or rC (to be ground), such as rC aggregates, is commercially available. Typically, rC aggregates are produced by the pyrolysis of tires and / or other rubber materials containing filler or reinforcing materials such as carbon black. rC is primarily made from carbon black used to reinforce rubber. rC may contain pyrolyzable components, such as rubber components. rC can be treated recycled carbon, where the original 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, Scandinavian Enviro Systems AB, Pyrum Innovations AG, or Bolder Industries or CBp Cyprus Ltd.

[0057] rC can be treated to remove macroscopic contaminants. For example, magnetic separation techniques known to those skilled in the art can be used to remove wire and other macroscopic metallic contaminants. Filters or screens can be used to remove fabric and other non-magnetic macroscopic contaminants. rC can be treated before being combined with water to form an initial slurry, and / or the initial slurry can be treated to remove macroscopic contaminants.

[0058] Alternatively or additionally, rC or pyrolytic carbon can be treated to remove ash, for example, by washing the pyrolytic carbon with acid or by using an ion exchanger. Exemplary methods are described in US20150307714, CN101357758 and WO2021 / 005124, the entire contents of which are incorporated herein by reference.

[0059] As an example, the initial recycled carbon particles (before grinding as described herein) can have a mesh size that is 5 to 10 times smaller than the media used. Other mesh sizes, higher or lower than this range, can be used.

[0060] For grinding, the recovered carbon in granular form is wet recovered carbon.

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

[0062] The grinding includes at least one grinding step using grinding media with a diameter of 2 mm or smaller. If more than one grinding step is used, the type of grinding media, the number of media, or the size of the media may be the same or different, depending on the type of media, grinding method, or grinding time.

[0063] Media grinding can be or includes stirred ball milling, planetary ball milling, or centrifugal ball milling.

[0064] A preferred media grinding method is ball milling with stirring.

[0065] Alternatively, the medium (which can be considered an abrasive medium) is used as a solid sphere.

[0066] For example, a solid sphere may have an average size of approximately 0.25 mm to 2 mm. This 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] Alternatively, the grinding media can be of such size that the initial particle size of the recycled carbon is about 3 to about 10 times smaller or about 5 to 10 times smaller (e.g., 4 to 5 times smaller) than the size of the media used (e.g., the average size of the media used).

[0068] Solid spheres can be metal, glass, ceramic, or polymer. Specific examples include, but are not limited to, steel (e.g., chromium steel or stainless steel such as 304SS and 316SS) or ceramics (e.g., agate, alumina, yttrium-stabilized zirconium oxide, zirconium silicate, zirconium oxide-toughened alumina, and tungsten carbide).

[0069] Grinding media can be loaded into the mill to achieve a volumetric load of 50%–98%. If desired or necessary, the volumetric load can be lower than 50% or higher than 90%. The volumetric load can be 50%–95%, or 60%–90%, 70%–90%, 80%–90%, 50%–80%, 50%–70%, 50%–60%, or any range based on any two values ​​described herein. The volumetric load is based on the total volume (space) of the mill available for grinding.

[0070] The media milling operation results in a specific energy consumption of at least 1 kWh / kg of dry-milled recovered carbon, or at least 1.25 kWh / kg of dry-milled recovered carbon, or at least 1.5 kWh / kg of dry-milled recovered carbon, for example, 1 kWh / kg-10 kWh / kg or 1.25 kWh / kg-3.5 kWh / kg or 1.5 kWh / kg-5 kWh / kg or 1 kWh / kg-3.1 kWh / kg or 2.5 kWh / kg-3.5 kWh / kg or 4 kWh / kg-5 kWh / kg, or any range based on any two values ​​described herein.

[0071] The specific energy used in a mill can be used as a representative of the degree of grinding. The amount of kWh consumed per kg of dry product at different residence times can be calculated. ,in It refers to the grinding time. It is the average grinding specific energy, and (This refers to the dry weight of the batch). Similarly, the approximate number of collisions between media can be calculated: ( ,in It is cutting-edge speed. It is the number of beads. (This refers to the diameter of the bead). For example, in the grinding apparatus used in Example 1, the relationship between specific energy, number of collisions, and residence time is as follows:

[0072] Table 1: Relationship between residence time, specific energy consumed per kg of dry product, and media collision per kg of dry product

[0073]

[0074] Media milling can be characterized by the number of impacts per kg of dry-milled recovered carbon. The media milling used should result in at least 10 impacts per kg of dry-milled recovered carbon during the milling process. 13 Secondary media impact, or at least 2 × 10⁻⁶ recovered carbon per kg of dry-milled material during grinding. 13 Secondary media collisions, for example, during grinding, per kg of dry-milled recycled carbon 10 13 Secondary medium collision to 10 14 Secondary media collision, 3 × 10⁻⁶ tons of recovered carbon per kg after dry milling. 13 Secondary medium collision to 10 14 Secondary media collision, or 4 × 10⁻⁶ tons of recovered carbon per kg after dry milling. 13 Secondary medium collision to 8×10 13 Secondary media collision, or 5 × 10⁻⁶ tons of recovered carbon per kg after dry milling. 13 Secondary medium collision to 6×10 13 Secondary medium collision.

[0075] For any method of the present invention, the milling used can result in the milled, recovered carbon having a particle size distribution (PSD) and a D50 particle size of 250-400 nm, preferably 250-320 nm. Similarly, or additionally, the PSD can have a D90 of 350-1100 nm, for example 500-1100 nm, 600-1000 nm, 700-900 nm, or 800-1100 nm. As described in Example 1, the particle size distribution is measured by analytical centrifugation (disc centrifuge photoprecipitation method) of the milled slurry. In this method (referred to as PSD method 1), the aqueous granular slurry (14 wt% solids) is diluted to 2000 ppm with deionized water containing 600 ppm Triton X100 surfactant. The diluted solution was then mixed for 5 minutes at 800 RPM using a DISPERMAT LC55 mixer equipped with a lightweight 30 mm diameter 18-tooth impeller. The solution was then stirred on a stirring plate for 24 hours using a magnetic stir bar. The sample solution was then further diluted to 400 ppm using deionized water containing 400 ppm Triton X100 surfactant and spun on a roller in 40 ml vials until measurement. Measurements were performed using a disc centrifuge (DC24000, CPS Instruments) at 5000 RPM. First, 24%, 22%, 20%, 18%, 16%, 14%, 12%, 10%, and 8% sucrose solutions (in deionized water) were sequentially injected into the discs (1.6 ml each), followed by 1 ml of dodecane to seal the gradient. The gradient was allowed to stabilize for 1 hour before measurement. During disc centrifuge measurements, the sample density and refractive index were set to 1.86 g / cm³. 3 And n = 1.84 + 0.846i. The result indicates a density of 1.86 g / cm³. 3 The equivalent sedimentation result for spherical particles with a refractive index of n = 1.84 + 0.846i was also calculated. All measurements were stopped immediately after the signal reached the baseline.

[0076] The grinding process can be characterized by one or more properties achieved through grinding the recycled carbon based on the present invention.

[0077] For example, milling results in rubber samples with milled recycled carbon having a phr of 20-60 (e.g., 20 phr, or 25 phr, or 30 phr, or 35 phr, or 40 phr, or 30-55 phr, or 40-50 phr) producing up to 8% or up to 5% undispersed region, or 1%-7% or 1.5%-6% or 1.75%-4% (dispergrader)%, especially when prepared using a technique combining wet granules with an elastomer. Alternatively, rubber samples with granular fillers having a phr of 20-80 (e.g., 30-70 phr, 40-60 phr, or 45-55 phr) (where 10-40% by weight is media-milled recycled carbon, e.g., 15-35% by weight or 20-30% by weight) may have up to 3% undispersed region, e.g., 1%-3% undispersed region. In some embodiments, the granular filler is a blend of recycled carbon and carbon black that has been media-milled, for example, with a BET surface area of ​​35-110 m². 2 / g of carbon black, such as N300 or N500 series carbon black, such as N330 or N550 carbon black.

[0078] Dispersion percentage (%) was calculated as follows. The cured rubber sample was sliced ​​using a razor blade fixed in a manual cutting fixture. The sample was mounted on a dispersion instrument (Alpha Technologies) and imaged. The following settings were used: "Filler volume fraction", 20%; "Exposure time", 40 ms; "Color channel for analysis", "Blue"; "Threshold for dispersion calculation", 23 μm; nodule to aggregate fraction, 1; white area threshold, 0. The amount reported by Alpha Technologies as "white area, %" was interpreted as "undispersed area".

[0079] As a further example, grinding results in a rubber sample with 20-60 phr (e.g., 20 phr, 25 phr, 30 phr, 35 phr, or 40 phr) of ground recycled carbon, resulting in a wear volume loss no more than 10% greater or deviating by no more than 5% from a control rubber sample using N550 carbon black instead of ground recycled carbon. The control rubber sample with N550 carbon black can be considered a "control sample," and the control sample has the same N550 carbon black phr as the rubber sample with recycled carbon and all other components are identical, but uses carbon black instead of recycled carbon. DIN wear is evaluated according to the standard ASTM D5963 rotation method. Alternatively or additionally, grinding is performed such that rubber samples with 20-60 phr (e.g., 20 phr, 25 phr, 30 phr, 35 phr, or 40 phr) of filler (including a blend of N330 carbon black and 10-40 wt% of milled recycled carbon) result in a wear volume loss no more than 10% greater or deviating by no more than 5% from that of a control rubber sample with 100% N330 carbon black instead of a blend containing milled recycled carbon, particularly when prepared using techniques in which wet granules are combined with an elastomer. Alternatively, rubber samples with 20-80 phr of granular filler, such as 30-70 phr, 40-60 phr, or 45-55 phr of granular filler (where 10-40 wt% is media-milled recycled carbon, e.g., 25-40 wt%, 15-35 wt%, or 20-30 wt%), have a wear volume loss of 90-100 mm. 3 For example, 91-95mm 3 The wear loss, when measured according to ASTM D5963. In some embodiments, the granular filler is a blend of recycled carbon and carbon black, media-milled, for example, with a BET surface area of ​​35-110 m². 2 / g of carbon black, such as N300 or N500 series carbon black, such as N330 or N550 carbon black.

[0080] As a further example, grinding can produce an M300 / M100 ratio in a rubber sample with 20-40 phr of ground recycled carbon, such that: a) it is no more than 10% smaller or deviates from by no more than 5% compared to a control rubber sample using N550 carbon black (control sample) instead of ground recycled carbon, or b) 4.5-5. Tensile stress (including M300 or M100) is tested according to ASTM D412 Type C. Six dumbbells are used instead of five. M300 is the tensile stress at 300% elongation, and M100 is the tensile stress at 100% elongation.

[0081] As a further example, grinding can result in a rubber sample with 20-40 phr of ground recycled carbon producing an M300 (MPa) or maximum load (N) that is no more than 10% or 5% smaller than a control rubber sample with N550 carbon black instead of ground recycled carbon.

[0082] The present invention also relates to milled, recycled carbon produced by any of the methods of the present invention. The milled, recycled carbon can be characterized by any one or more of the properties and / or characteristics described herein.

[0083] As noted, using the present invention, it has been unexpectedly found that certain residence times in media milling are more suitable for certain rubber properties. To conduct this determination, the milled material of the present invention was tested in an SBR compound as described in the Examples section. To further demonstrate that the media-milled material of the present invention contributes to rubber properties, the media-milled material as shown in the Examples section was compared with fluffy (unmilled) rC and wet-mixed rC granules (unmilled), and also with unused N550 carbon black samples.

[0084] Using this invention, various relationships were discovered based on the phr of rC after media grinding, and preferably based on the grinding time.

[0085] For the rubber properties of the undispersed region (dispersion %) of the filler in the elastomer composite, the undispersed region (according to dispersion %) of rC after media milling in certain embodiments can be characterized based on Equation 2: Undispersed region (UA) ≤ 3.35 - (0.04) phr rC). phr rC is the media-milled rC according to the present invention, and can be in amounts ranging from 10 phr to 50 phr, or 10 phr to 40 phr, 10 phr to 35 phr, 10 phr to 30 phr, 5 phr to 55 phr, or 7 phr to 20 phr. The media-milled rC can be part of a blend with other granular fillers, such as carbon black, for example, BET with a surface area of ​​35-110 m². 2 / g of carbon black, such as N300 or N500 series carbon black, such as N330 or N550 carbon black. The total amount of filler can be 20-80 phr, such as 30-70 phr, 40-60 phr or 45-55 phr. The media-milled rC can be 10-40% by weight of the total filler, such as 15-35% by weight or 20-30% by weight.

[0086] For wear volume loss (mm) in elastomer composites 3The rubber properties of ) can be characterized based on the wear volume loss of rC after media abrasion in certain embodiments, which can be represented by Equation 3: Wear volume loss (AVL) ≤ 100 + (0.1 (phrrC) (normalized to a control sample produced in the same manner but using N550 carbon black instead of media-milled rC). phr rC is media-milled rC according to the present invention, and can be in the range of 10 phr-50 phr, 10 phr-40 phr, or 10 phr-30 phr. Equation 3A: AVL ≤ 100 - (0.43) The phr rC (normalized to N550 control) is achievable. The phr rC is the media-milled rC according to the invention, and can be in amounts ranging from 10 phr to 50 phr, or 10 phr to 40 phr, 10 phr to 35 phr, 10 phr to 30 phr, 5 phr to 55 phr, or 7 phr to 20 phr. The media-milled rC can be part of a blend with another granular filler, such as carbon black, for example, a BET filler with a surface area of ​​35-110 m². 2 / g of carbon black, such as N300 or N500 series carbon black, such as N330 or N550 carbon black. The media-milled rC can be 10-40% by weight of the total filler, for example, 15-35% by weight or 20-30% by weight.

[0087] For the rubber properties of strain stiffness (M300 / M100 index) in elastomeric composites, the strain stiffness (M300 / M100 index) based on media-milled rC (e.g., with a 2-minute residence time) in certain embodiments can be characterized based on Equation 4: M300 / M100 index ≥ 100 - (0.01 phr rC (normalized to N550 control). phr rC is the media-milled rC according to the present invention, and can be in the range of 10 phr-50 phr, 10 phr-40 phr, or 10 phr-30 phr. Equation 4A can be achieved: M300 / M100 exponent ≥ 100 + (0.38) phr rC (normalized to N550 control). phr rC is the media-milled rC according to the present invention, and can be in amounts ranging from 10 phr to 50 phr, or 10 phr to 40 phr, 10 phr to 35 phr, 10 phr to 30 phr, 5 phr to 55 phr, or 7 phr to 20 phr. The media-milled rC can be part of a blend with other granular fillers, such as carbon black, for example, BET with a surface area of ​​35-110 m². 2 / g of carbon black, such as N300 or N500 series carbon black, such as N330 or N550 carbon black. The media-milled rC can be 10-40% by weight of the total filler, for example, 15-35% by weight or 20-30% by weight.

[0088] For rubber properties with high strain stiffness or tensile stress (M300) in elastomer composites, the high strain stiffness or tensile stress (M300) of rC after media milling in certain embodiments can be characterized based on Equation 5: M300 ≥ 100 - (0.15) phr rC (normalized to N550 control). phr rC is the media-milled rC according to the present invention, and can be in the range of 10 phr-50 phr, 10 phr-40 phr, or 10 phr-30 phr. The media-milled rC can be part of a blend with other particulate fillers, such as carbon black, for example, BET with a surface area of ​​35-110 m². 2 / g of carbon black, such as N300 or N500 series carbon black, such as N330 or N550 carbon black. The rC after media milling can be 10-40% by weight of the total filler, for example, 15-35% by weight or 20-30% by weight. Equation 5A can be achieved: M300≥100+(0.38) (phr rC) (normalized to N550 control). In one embodiment, the method of processing granular carbon includes combining recovered carbon with water to form a mixture to form an initial slurry having 1-35% by weight solids, and media milling the recovered carbon to form a media-milled slurry of wet-milled recovered carbon and water.

[0089] Pyrolytic carbon can be combined with water to form an initial slurry with a solids loading of 1-35 wt%, for example 5-30 wt%, 7-25 wt%, 10-20 wt%, or 15-25 wt%. The loading is preferably coordinated with the loading requirements of downstream processes, including grinding and optional granulation.

[0090] The initial slurry may contain one or more supplementary fillers, which may also benefit from co-grinding with pyrolytic carbon. Any granular filler that provides reinforcement or other beneficial properties to the rubber can be used. Exemplary supplementary fillers include, but are not limited to, carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon (i.e., carbonaceous materials produced by hydrothermal carbonization of lignin or other biomass, such as those described in US10428218 or US10035957, the contents of which are incorporated herein by reference), engineered polysaccharides (such as those described in US2020 / 181370 and US2020 / 190270, the contents of which are incorporated herein by reference), and graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures (such as those described in US2014 / 0093728, the entire contents of which are incorporated herein by reference), and carbon black-coated particles (such as those described in US10519298, the entire contents of which are incorporated herein by reference). Preferably, macroscopic contaminants are removed from the pyrolytic carbon in its dry or slurry state before it is combined with one or more fillers. The filler may be combined with the dry pyrolytic carbon, or added separately to water before, after, or simultaneously with the pyrolytic carbon to form an initial slurry. To avoid any segregation that may occur in the dry mixture of pyrolytic carbon and filler, it is preferable to add the filler separately from the pyrolytic carbon directly to the water or initial slurry. The ratio of pyrolytic carbon to filler in the initial slurry can be any range suitable for the desired end-use application and maintains an acceptable viscosity of the initial slurry so that it can be ground. In some preferred embodiments, the filler is unused carbon black, for example, with a BET surface area of ​​35-110 m². 2 / g of carbon black, such as N300 or N500 series carbon black, such as N330 or N550 carbon black, and the amount of recycled carbon is 10-40% by weight of the total filler, for example 25-40% by weight, 15-35% by weight, or 20-30% by weight. In continuous processes, the supplementary filler can be continuously metered into the initial slurry or a continuous water flow as a powder or as an aqueous slurry (or more than one slurry if more than one supplementary filler is used). Those skilled in the art will recognize that the appropriate load for grinding will depend on the nature of the supplementary filler. For example, carbon nanotubes will increase the slurry viscosity at very low loads, while precipitated silica at higher loads may not significantly increase the viscosity.

[0091] Additional fillers can also be added to the milled slurry. Such additional fillers preferably do not require further milling. Exemplary additional fillers for addition 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 US10519298), and mixtures of two or more of these. Depending on the solids load of the milled slurry, water may also need to be added along with the additional filler to adjust the solids load of the resulting wet-blended carbon mixture. Alternatively or additionally, the additional filler can be added to the milled slurry as an aqueous slurry. In continuous processes, the additional filler can be continuously metered into the initial slurry or into a continuous flow of water, either as a powder or as an aqueous slurry of additional filler. The total filler load allows the wet-blended carbon mixture to be readily formed into granules or spray-dried. To form granules, additional fillers and optional water added to the milled slurry can result in a wet-blended carbon mixture with a solids content of 25-70% by weight, for example, 30-65% by weight, 35-60% by weight, or 40-50% by weight. For spray drying, additional fillers and optional water added to the milled slurry can result in a wet-blended carbon mixture with a solids content of 1-30% by weight, for example, 1-10% by weight, 5-15% by weight, or 8-25% by weight. In some preferred embodiments, the additional filler is unused carbon black, for example, with a BET surface area of ​​35-110 m². 2 / g of carbon black, such as N300 or N500 series carbon black, such as N330 or N550 carbon black, and the amount of recycled carbon is 10-40% of the total filler, for example 25-40% by weight, 15-35% by weight, or 20-30% by weight. For spray drying, it may be desirable to omit the additional filler. Those skilled in the art will recognize how to adjust the total filler load to prepare the desired pellets or the optimal load for spray drying in conventional equipment. The filler added to the milled slurry may be the same as or different from any filler added to the initial slurry.

[0092] Carbon blacks used in any of the embodiments described herein include, but are not limited to, ASTM N100-N900 series carbon blacks, such as N100 series carbon black, N200 series carbon black, N300 series carbon black (e.g., N330 carbon black), N500 series carbon black (e.g., N550 carbon black), N600 series carbon black, N700 series carbon black, N800 series carbon black, or N900 series carbon black. Alternatively or additionally, such carbon blacks may have a 35-110 μm, as measured by ASTM 6556. 2 / g BET surface area, for example, 35-65m² 2 / g、65-90m 2 / g or 90-110m2 / g. In addition, the following carbon blacks can be used in various embodiments: those sold under the trademarks Regal®, Black Pearls®, Spheron®, Sterling®, and Vulcan® from Cabot Corporation; those sold under the trademarks Raven®, Statex®, Furnex®, and Neotex®, as well as the CD and HV series, from BirlaCarbon (Columbian Chemicals); and those sold under the trademarks Corax®, Durax®, Ecorax®, and Purex®, as well as the CK series and other carbon blacks from Orion Engineered Carbons; and other fillers suitable for rubber or tire applications. The carbon black can be chemically functionalized. Suitable chemically functionalized carbon blacks include those disclosed in WO96 / 18688 and US2013 / 0165560, the disclosures of which are incorporated herein by reference.

[0093] The statistical thickness surface area (STSA, ASTM standard D6556) of carbon black can be at least about 15 m². 2 / g, for example, about 15m 2 / g to approximately 240m 2 / g, for example, about 35m 2 / g to approximately 230m 2 / g, approximately 50m 2 / g to approximately 200m 2 / g, approximately 60m 2 / g to approximately 180m 2 / g, approximately 100m 2 / g to approximately 200m 2 / g.

[0094] Carbon black having any of the above-mentioned surface areas may also have a structure given by the oil adsorption value (COAN, ASTM D3493) of compressed carbon black, which is 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.

[0095] Any mixture of these carbon blacks can be used.

[0096] The silicon-treated carbon black described herein is not limited to carbon black aggregates that have been coated or otherwise modified. It can also be aggregates of different kinds having two phases. One phase is carbon, which will still exist as graphitic microcrystals and / or amorphous carbon, while the second phase is silicon dioxide (and possibly other silicon-containing substances). Therefore, the silicon-containing phase of the silicon-treated carbon black is an inherent part of the aggregate; it is distributed in at least a portion of the aggregate. Various silicon-treated carbon blacks can be named... Purchased from Cabot Corporation and described in more detail in U.S. Patent No. 6,028,137. It should be understood that the multiphase aggregates are entirely different from the silica-coated carbon black described above, which consists of pre-formed single-phase carbon black aggregates having silicon-containing material deposited on its surface. Such carbon black can be surface-treated to place silica functionality on the surface of the carbon black aggregates, as described, for example, in U.S. Patent Nos. 6,929,783, 6,541,113, and 5,679,728.

[0097] Suitable precipitated silica for any of the embodiments described herein includes both highly dispersible (HDS) particles and non-HDS precipitated silica. The precipitated silica may have been chemically treated to include functional groups, such as coupling agents that are bonded (e.g., chemically linked) or attached (e.g., adsorbed) to the silica surface. Examples of suitable grades of HDS include Perkasil® GT 3000GRAN silica from WR Grace & Co, Ultrasil® 7000 silica from Evonik Industries, Zeosil® 1165 MP and 1115 MP silica from Solvay SA, Hi-Sil® EZ 160G silica from PPG Industries, Inc., and Zeopol® 8741 or 8745 silica from Evonik Industries. Examples of suitable grades of conventional (non-HDS) precipitated silica include Perkasil® KS 408 silica from WR Grace & Co, Zeosil® 175GR silica from Solvay SA, Ultrasil® VN3 silica from Evonik Industries, and Hi-Sil® 243 silica from PPG Industries, Inc. Examples of suitable grades of hydrophobic precipitated silica include Agilon® 400, 454, or 458 silica from PPG Industries, Inc., and Coupsil® silica from Evonik Industries, such as Coupsil® 6109 silica.

[0098] The wet-blended carbon mixture can be densified, for example, by granulation or pelletizing. Any densification or pelletizing method known to those skilled in the art can be employed. For example, the method of Glaxner's U.S. Patent No. 2,065,371 can be used. Typically, the wet-blended carbon mixture is formed into beads, which can then optionally be dried to reduce the water content to at most 1% to form the blended carbon pellets. In addition to the water already present in the wet-blended carbon mixture, a variety of binder additives are known to be used in the wet pelletizing process to further improve the processing properties of the resulting pellets. Such additives include, but are not limited to, hygroscopic organic liquids such as ethylene glycol, carbohydrates (e.g., sugars, molasses, soluble starches, sugars, lignin derivatives), rosin, sulfonate and sulfate anionic surfactants, fatty amine ethoxylated nonionic surfactants, sodium lignin sulfonate, silanes, sucrose, alkyl succinimides, alkylated succinates, and polyoxyethylene-co-polydimethylsiloxane surfactants. Alternatively or additionally, the pellets do not need to be dried and can be used wet, in which case a binder may not be necessary. For example, wet pellets may have a moisture content of 15-80% by weight, such as 40-60% by weight.

[0099] On a dry basis, the resulting granular filler, in wet or dry granule form or some other form (e.g., slurry prior to granulation or other drying methods), may contain 2-100% by weight, for example 5-98% by weight or 8-90% by weight, 10-60% by weight, 15-50% by weight, 10-100% by weight or 15-60% by weight, 10-90% by weight, 15-80% by weight, 20-60% by weight, or 30-50% by weight, or 20-50% by weight, of recovered carbon, preferably. The pellets are wet-milled recycled carbon, with the remainder being fillers different from the recycled carbon, such as one or more of the listed additional and / or supplementary fillers, including carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, engineered polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, and carbon black-coated particles. In some preferred embodiments, the additional and / or supplementary fillers are unused carbon black, such as N300 or N500 series carbon black, such as N550 or N330 carbon black, and the recycled carbon is present in the pellets in an amount of 10-40% by weight, for example 25-40% by weight, 15-35% by weight, or 20-30% by weight of the total filler in the pellets. As mentioned above, the pellets may also contain a binder.

[0100] Alternatively or additionally, the wet-blended carbon mixture can be spray-dried using any spray-drying equipment known to those skilled in the art. On a dry basis, the resulting spray-dried particles may contain: 2-100% recycled carbon, for example 5-98% or 8-90% by weight, 10-60% by weight, 15-50% by weight, 10-100% by weight, 15-60% by weight, 10-90% by weight, 15-80% by weight, 20-60% by weight, or 30-50% by weight, or 20-50% by weight, preferably wet-milled recycled carbon; and 0-98% for example 2%-95% by weight, for example 10%-92% by weight, 40-90% by weight, or 50%-80% or 85% by weight of additional filler (selected from carbon black, silica-coated carbon black, etc.). Silica-treated carbon black, precipitated silica, carbon black-coated particles, and mixtures of two or more of these); and 0-98%, for example 2%-95% by weight, for example 10%-92% by weight, 40-90% by weight, or 50%-80 or 85% by weight of one or more supplementary fillers (selected from carbon black, silica-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, engineered polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, and carbon black-coated particles). In some preferred embodiments, additional and / or supplementary filler is unused carbon black, such as N300 or N500 series carbon black, such as N550 or N330 carbon black, and recycled carbon is present in the spray-dried particles in an amount of 10-40% by weight, for example 25-40% by weight, 15-35% by weight, or 20-30% by weight.

[0101] Wet granules, dried granules, and / or spray-dried granules according to various embodiments herein can be combined with elastomers to form elastomer composites. The resulting elastomer composites may include 30-90 phr of granular filler, such as 30-70, 35-60, or 40-55 phr of granular filler. The granular filler may include 2-100% recycled carbon, such as 5-98% by weight or 8-90% by weight, preferably 10-100% by weight, 10-90% by weight, 15-80% by weight, 20-60% by weight, or 30-50% by weight of recycled carbon. In some preferred embodiments, additional and / or supplementary fillers are unused carbon black, such as N300 or N500 series carbon black, such as N550 or N330 carbon black, and the recycled carbon is present in the pellets in an amount of 10-40% by weight, for example 25-40% by weight, 15-35% by weight, or 20-30% by weight of the total filler in the pellets. Both natural rubber and synthetic elastomers of any grade can be used. Blends of elastomers can also be used. For example, wet pellets, dried pellets, and / or spray-dried granules can be combined with elastomers to form a masterbatch, which is then combined with another elastomer of the same or different composition. Optionally or additionally, two or more elastomers can be blended prior to mixing with the pellets. Optionally or additionally, the elastomer compound may also contain one or more fillers other than recycled carbon, including any granular fillers listed elsewhere herein and any other fillers known to those skilled in the art for use in elastomer compounds. Such fillers may be in the form of granules or mixtures containing ground and recycled carbon, or may be added separately to the elastomer from any of the wet granules, dried granules, and / or spray-dried particles according to various embodiments of this document.

[0102] Exemplary categories of elastomers include, but are not limited to: rubber; polymers (e.g., homopolymers, copolymers, and / or terpolymers) of 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dialkyl-1,3-butadiene (wherein the alkyl group may be methyl, ethyl, propyl, etc.), acrylonitrile, ethylene, propylene, etc. Elastomers may have a glass transition temperature (Tg) of about -120°C to about 50°C, as measured by differential scanning calorimetry (DSC). Examples include, but are not limited to, styrene-butadiene rubber (SBR), natural rubber and its functionalized derivatives such as epoxidized and chlorinated rubbers, polybutadiene rubber, polyisoprene rubber, ethylene-propylene copolymers (e.g., EPDM), isobutylene-based rubbers (e.g., butyl rubber), chloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polyisoprene rubber, polysulfide rubber, polyacrylate elastomers, fluorinated elastomers, perfluorinated elastomers, and oil-extended derivatives of any of these. Blends and / or functionalized derivatives of any of the aforementioned substances may also be used. Natural rubber may also be treated to chemically or enzymatically modify or reduce various non-rubber components.

[0103] Particularly suitable synthetic rubbers include: copolymers of about 10-70% by weight styrene and about 90-30% by weight butadiene, such as copolymers of 19 parts styrene and 81 parts butadiene, 30 parts styrene and 70 parts butadiene, 43 parts styrene and 57 parts butadiene, and 50 parts styrene and 50 parts butadiene; polymers and copolymers of conjugated dienes, such as polybutadiene, polyisoprene, polychloroprene, etc., and copolymers of such conjugated dienes with monomers containing olefinic groups that can be copolymerized therewith, such monomers containing olefinic groups as styrene, methylstyrene, chlorostyrene, acrylonitrile, 2-vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, allyl-substituted acrylates, vinyl ketones, methyl isopropenyl ketones, methyl vinyl ethers, etc. - Methylene carboxylic acids and their esters and amides, such as acrylic acid and dialkylacrylamides. Also applicable to this article are ethylene and other higher... Copolymers of olefins such as propylene, 1-butene and 1-pentene.

[0104] The elastomeric complex may further include additives to promote mixing, promote vulcanization, or impart specific properties to the vulcanization products of the elastomeric complex. Many additives are well known to those skilled in the art and include, for example, adhesion promoters, antioxidants, anti-ozone agents, coupling agents, curing agents, degradation inhibitors, plasticizers, processing aids (e.g., liquid polymers, oils, etc.), oil extenders, waxes, resins, flame retardants, extender oils, lubricants, tackifiers, vulcanization activators such as zinc oxide and fatty acids, vulcanization accelerators, and any mixtures thereof. Exemplary additives include, but are not limited to, zinc oxide and stearic acid. The general use and selection of such additives are well known to those skilled in the art.

[0105] The dried granules and / or spray-dried granules can be combined with the elastomer as described above using any dry mixing method known to those skilled in the art.

[0106] Optionally or additionally, wet pellets may be combined with elastomers in accordance with the teachings of one or more of US20220332016, WO2021247153, WO2022125679, WO2022125683, WO2022125677, and WO2022125675, the entire contents of which are incorporated herein by reference. For example, the wet pellets and the elastomer in solid form may be loaded into a mixer and mixed under temperature-controlled conditions to remove at least a portion of the water from the pellets by evaporation. Optionally, the elastomer may be pre-plasticized prior to the introduction of the wet pellets. The wet filler may be added all at once or in portions.

[0107] Any suitable mixer, such as a Banbury or Brabender mixer or other closed or enclosed mixer, or open mixer, or extruder or continuous compounding mill or kneading mixer or a combination thereof, can be used to combine wet pellets with elastomers. Other mixers include kneading-type closed mixers. Commercially available closed mixers from Farrel-Pomini, Harburg Freudenberger Maschinenbau GmbH (HF), Kobelco, or Pelmar Eng'r Ltd can be used. In addition to the option of using steam or water or other fluids in the internal loop of the rotor, the closed mixer may additionally or alternatively have a cooling or heating jacket in one or more areas or portions of the mixing chamber to control the temperature of the components being mixed therein. This can create one or more heating / cooling zones in the walls or a portion of the walls of the mixer. The mixer can be a single-stage mixer or a multi-stage mixer (e.g., two or more stages). Examples of mixers and designs that can be used are described in European Patent No. 2423253B1 and U.S. Patent No. 7,556,419, the disclosures of which are incorporated herein by reference.

[0108] Alternatively, the mixer can be a continuous mixer. For example, solid elastomers and wet fillers can be machined using one or more of a continuous closed mixer, a twin-screw extruder, a single-screw extruder, or a roller mill, such as those described in U.S. Patent No. 9,855,686B2, the disclosure of which is incorporated herein by reference. Suitable kneading and plasticizing apparatus are well known and commercially available, including, for example, the Unimix continuous mixer and MVX (mix, degas, extrude) machine from Farrel Pomini Corporation of Ansonia, Conn., the FCM™ Farrel continuous mixer, the long continuous mixer from Pomini, Inc., the Pomini continuous mixer, twin-rotor co-rotating meshing extruders, twin-rotor counter-rotating non-meshing extruders, continuous compounding extruders, twin-shaft milling extruders manufactured by Kobe Steel, Ltd., and Kobe continuous mixers. Alternative plasticizing apparatus suitable for use with one or more embodiments disclosed herein are familiar to those skilled in the art.

[0109] Mixing can be carried out using a mixer having at least one rotor, and the mixer can be one or more of the following: a kneader, a roller mill, a screw extruder, a twin-screw extruder, a multi-screw extruder, a continuous compounding mill, and / or a twin-screw extruder. Mixing can be carried out using a mixer having at least one rotor, and the mixer can have a two-wing rotor, a four-wing rotor, a six-wing rotor, an eight-wing rotor, and / or one or more screw rotors.

[0110] The mixing process of wet aggregates with elastomers can be a single-stage (one-stage) or multi-stage (multi-step) process. In a multi-stage process, one or more mixers or mixer types can be used. For stages using closed mixers, the fill factor at each such stage can independently not exceed 72%, 70%, 68%, or 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%, etc. The temperature of the mixer can be controlled to control the temperature of the mixture, the amount of water evaporated, or both. For example, in a multi-stage process, the temperature of the mixer at each stage can be controlled to control the amount of water evaporated from the mixture in the first mixing stage and one or more subsequent stages. For example, the liquid content of the discharged complex may be 10% to 99.9% (wt% vs. wt%), 10% to 95%, or 10% to 50% lower than the liquid content of the material loaded into the mixer. Alternatively or additionally, the rate at which liquid is released from the complex or mixture during mixing, for example by evaporation, can be measured as the time-averaged release rate of liquid per kg of the complex or mixture (e.g., total liquid removed / (release time)). The rate can be from 0.01 to 0.14 kg / (min) (complex weight), and the rate can be from 0.01 to 0.14 kg / (min). kg) or from 0.01 to 0.07 kg / (min) (kg) or other rates below or above that range.

[0111] Optionally or additionally, mixing can be controlled in one or more stages to allow a predetermined total specific energy (energy per mass of the compound applied to a mixing system driving one or more rotors, on a dry weight basis), for example from 1000 kJ / kg of the compound (or per kg of the mixture present in the mixer) to 10,000 kJ / kg of the compound (or per kg of the 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 7,000 kJ / kg, 1,500 kJ / kg to 8 ...8,000 kJ / kg, 1,500 kJ / kg to 8,000 kJ / kg, 1,500 kJ / kg to 8,000 kJ / kg, 1,500 kJ / kg to 8,000 kJ / kg, 1,500 kJ / kg to 8,000 kJ / kg, 1,500 kJ / kg to 8 00 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 any other values ​​within these ranges. Optionally or additionally, the specific energy applied to the mixture can be separated to ensure that a certain amount of specific energy is applied before or after a portion (e.g., 75%) of the filler is added to the mixer. That is, the filler does not need to be added all at once. The mixing time for each stage can be any suitable time, such as 1 to 40 minutes, 1 to 20 minutes, 1 to 15 minutes, 5 to 30 minutes, 5 to 20 minutes, 5 to 15 minutes, or 1 to 12 minutes, 1 to 10 minutes, 3 to 30 minutes, or other times. Optionally or additionally, the dump discharge temperature for each stage can be 120°C to 180°C, 120°C to 190°C, 130°C to 180°C, such as 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.

[0112] Following any one or more mixing steps or stages, the resulting compound may undergo one or more post-processing steps, such as shaping or forming the compound and / or allowing for improved treatment. Post-processing can provide a compound that can be dried, homogenized, extruded, calendered, ground, granulated, cut, packaged, or sheeted. The compound may be immediately compounded and vulcanized, or it may be held for a period of time prior to compounding. Suitable equipment for various post-processing steps includes, but is not limited to, closed mixers, kneaders, roller mills, open mills, screw extruders, twin-screw extruders, multi-screw extruders, continuous compounding mills, and / or one or more of the following: equipped with roller dies (e.g., twin-screw sheeters) or equipped with fixed blades: twin-screw discharge extruders. Depending on the one or more apparatuses used, it may be desirable to process the compound more than once or through a series of similar or different apparatuses with the same or different operating settings (e.g., speed, temperature, energy input, etc.). Optionally or additionally, before or as part of the vulcanization process, the elastomeric compound may be combined with added fillers, added elastomers, or both. The additional fillers may be the same as or different from the particulate fillers in the elastomeric compound and may include any fillers known to those skilled in the art, including those listed as additional and supplementary fillers in this case, and may include additional wet, milled, recycled carbon. The added fillers and / or elastomers may increase or decrease the filler loading of the vulcanized rubber relative to the elastomeric compound.

[0113] To vulcanize the elastomer composite, it is combined with a curing package comprising a crosslinking agent, any necessary activators and accelerators, antioxidants, and additional optional additives, such as any 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 sulfinamides such as N-tert-butyl-2-benzothiazole sulfinamide (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 crosslinking agents, metal oxides, acetoxysilane compounds, etc. Other suitable components for sulfur-based and other crosslinking systems, as well as methods for mixing and vulcanizing elastomer composites, are well known to those skilled in the art. For example, typical procedures for rubber compounding 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).

[0114] Various rubber products can incorporate the vulcanized product. For example, the vulcanized product can be incorporated into tires (e.g., pneumatic tires, non-pneumatic tires, or solid tires). For example, the vulcanized product can be incorporated into tire tread, tire carcass, bottom tread, liner, sidewall, sidewall insert, liner sheath, or cushioning rubber used in retreaded tires. Optionally or additionally, the vulcanized products can be incorporated into hoses, liners, gaskets, seals, washers, vibration damping products, tracks, track pads for tracked vehicles, engine mounts, seismic stabilizers, mining equipment screens, mining equipment liners, conveyor belts, chute liners, slurry pump liners, mud pump impellers, valve seats, valve bodies, piston hubs, piston rods, plungers, impellers for mixing slurries and slurry pump impellers, grinding mill liners, cyclone separators and hydrocyclones, expansion joints, linings for dredging pumps and outboard motor pumps for marine equipment, shaft seals for marine, oil, aerospace and other applications, propeller shafts, or linings for pipelines conveying, for example, oil sands or bituminous sands. Optionally or additionally, the vulcanized products can be incorporated into engine mounts, bushings, weatherstripping, windshield wipers, automotive parts, seals, washers, housings, and wheel or track components.

[0115] The resulting vulcanized product may have fatigue properties, for example, failure cycles, that are equivalent to or no more than 10% less than those of a vulcanized product produced by the same process and with the same composition (except that the recycled carbon is replaced with ASTM N550 carbon black). Alternatively or additionally, the fatigue properties of the resulting vulcanized product may be equal to or greater than 90% of those of a vulcanized product produced by the same process and with the same composition (except that the recycled carbon is replaced by an equal amount of the additional filler used in the vulcanized product produced according to the invention).

[0116] This invention includes the following aspects / implementations / features in any order and / or in any combination:

[0117] 1. A method for processing recovered carbon, the method comprising media milling wet recovered carbon to obtain milled recovered carbon, wherein the media milling results in 10 kg of dry-milled recovered carbon per kg of recovered carbon during the milling process. 13 -10 14 Secondary medium collision.

[0118] 2. A method for processing recovered carbon, the method comprising media milling wet recovered carbon to obtain milled recovered carbon, wherein the milling comprises media milling consuming a specific energy of 1 kWh / kg to 10 kWh / kg of dry-milled recovered carbon.

[0119] 3. A method for processing recovered carbon, the method comprising media milling wet recovered carbon to obtain milled recovered carbon, wherein the media milling results in a volume-weighted particle size distribution of the milled recovered carbon as measured by disc centrifuge photogravity determination, wherein D50 is 250-400 nm, preferably 250-320 nm, and D90 is 350-1100 nm, for example 500-1100 nm.

[0120] 4. The method according to any prior or subsequent embodiment / feature / aspect, wherein the specific energy consumed during media grinding is 1 kWh / kg to 10 kWh / kg.

[0121] 5. The method according to any prior or subsequent embodiment / feature / aspect, wherein the specific energy consumed during media grinding is 1 kWh / kg to 3.5 kWh / kg.

[0122] 6. The method according to any prior or subsequent implementation / feature / aspect, wherein the specific energy is 1.25 kWh / kg to 3.1 kWh / kg.

[0123] 7. A method according to any prior or subsequent embodiment / feature / aspect, wherein during the grinding process, the media grinding results in a yield of 10 kg of dry-milled, recovered carbon per kilogram.13 -10 14 Secondary medium collision.

[0124] 8. A method according to any prior or subsequent embodiment / feature / aspect, wherein during the grinding process, the media grinding results in 2 × 10⁻⁶ reclaimed carbon per kg of dry-milled material. 13 -10 14 Secondary medium collision.

[0125] 9. A method according to any prior or subsequent embodiment / feature / aspect, wherein during the grinding process, the media grinding results in 3 × 10⁻⁶ reclaimed carbon per kg of dry-milled carbon. 13 -10 14 Secondary medium collision.

[0126] 10. The method according to any prior or subsequent embodiment / feature / aspect, wherein the media grinding is a stirred ball mill, a planetary ball mill, or a centrifugal ball mill.

[0127] 11. The method according to any prior or subsequent embodiment / feature / aspect, wherein the media milling is a stirred ball milling.

[0128] 12. The method according to any prior or subsequent embodiment / feature / aspect, wherein the media used in the media grinding is a solid ball with an average size of about 0.25 mm to 2 mm, for example 0.25 to 1 mm, and the volumetric load in the mill is 50% to 98%.

[0129] 13. The method according to any prior or subsequent embodiment / feature / aspect, wherein the volume-weighted particle size distribution of the recovered carbon after media milling, as measured by disc centrifuge photogravure determination, has a D50 of 250-400 nm, preferably 250-320 nm, and a D90 of 350-1100 nm, for example 500-1100 nm.

[0130] 14. The method according to any prior or subsequent embodiment / feature / aspect, wherein the milling results in the milled recycled carbon rubber sample having 20-60 phr producing less than 10% or less than 5% of undispersed area (dispersion %).

[0131] 15. The method according to any prior or subsequent embodiment / feature / aspect, wherein the milling results in a rubber sample having granular filler of 20-80 phr, such as 30-70 phr, 40-60 phr, or 45-55 phr, with up to 3% undispersed region, for example, 1-3% undispersed region, wherein 10-40% by weight of the granular filler is recycled carbon milled by media, for example, 15-35% by weight or 20-30% by weight.

[0132] 16. The method according to any prior or subsequent embodiment / feature / aspect, wherein the milling results in a rubber sample with a milled rC of 10-50 phr, for example 10-40 phr, satisfying UA ≤ 3.35 - (0.04) The undispersed region UA ​​of phr rC).

[0133] 17. The method according to any prior or subsequent embodiment / feature / aspect, wherein the grinding results in a wear volume loss of the rubber sample with the ground recycled carbon having 20-60 phr that is no more than 10% greater or deviates by no more than 5% from that of a control rubber sample prepared in the same manner but with N550 carbon black instead of the ground recycled carbon.

[0134] 18. The method according to any prior or subsequent embodiment / feature / aspect, wherein the milling is such that, when measured according to ASTM D5963, a rubber sample having granular filler of 20-80 phr, such as 30-70 phr, 40-60 phr, or 45-55 phr, has a particle size of 90-100 mm. 3 For example, 91-95mm 3 The wear loss is due to the fact that 10-40% by weight, for example 15-35% by weight or 20-30% by weight of the granular filler is recycled carbon that has been media-milled.

[0135] 19. The method according to any prior or subsequent embodiment / feature / aspect, wherein the granular filler comprises unused carbon black, for example having a density of 35-110 μm. 2 Carbon black with a BET surface area of ​​ / g, such as N300 or N500 series carbon black, such as N330 or N550 carbon black, such as N330 carbon black.

[0136] 20. According to any prior or subsequent embodiment / feature / aspect of the method, wherein the milling results in the M300 / M100 ratio of the rubber sample with the milled recycled carbon having 20-60 phr being: a) not more than 10% smaller or deviating from a control rubber sample prepared in the same manner but with N550 carbon black instead of the milled recycled carbon by more than 5%; or, b) 4.5-5.

[0137] 21. The method according to any prior or subsequent embodiment / feature / aspect, wherein the milling results in the M300 (MPa) or maximum load (N) of the rubber sample with the milled recycled carbon having 20-60 phr being no more than 10% or 5% smaller than that of a control rubber sample prepared in the same manner but with N550 carbon black instead of the milled recycled carbon.

[0138] 22. According to any prior or subsequent implementation / feature / aspect of the method, wherein the granularity is measured according to PSD method 1.

[0139] 23. Milled, recycled carbon, prepared by means of any prior or subsequent embodiment / feature / aspect.

[0140] 24. A granular packing material comprising 10-40% by weight of recovered carbon, wherein the volume-weighted particle size distribution of the recovered carbon, as measured by optical sedimentation measurement using a disc centrifuge, has a D50 of 250-400 nm, preferably 250-320 nm, and a D90 of 350-1100 nm, for example 500-1100 nm.

[0141] 25. The granular filler according to any prior or subsequent embodiment / feature / aspect contains 15-35% by weight of recycled carbon or 20-30% by weight of recycled carbon or 25-35% by weight of recycled carbon.

[0142] 26. The particulate filler according to any prior or subsequent embodiment / feature / aspect further comprises one or more of the following: carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, engineered polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxide, metal carbonate, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, and carbon black-coated particles.

[0143] 27. The granular filler according to any prior or subsequent embodiment / feature / aspect further comprises carbon black having an OAN of 85-120 mL / 100g, for example, 90-117 mL / 100g, 95-115 mL / 100g, 100-113 mL / 100g, or 105-115 mL / 100g.

[0144] 28. The granular filler according to any prior or subsequent embodiment / feature / aspect further comprises carbon black.

[0145] 29. The granular filler according to any prior or subsequent embodiment / feature / aspect further comprises having a 35-110 μm... 2 / g for example 35-65m 2 / g、65-90m 2 / g or 90-110m 2 / g of BET surface area carbon black.

[0146] 30. The granular filler according to any prior or subsequent embodiment / feature / aspect further comprises N300 or N500 series carbon black, such as N330 or N550 carbon black.

[0147] 31. A granular filler according to any prior or subsequent embodiment / feature / aspect, wherein the granular filler is in the form of granules.

[0148] 32. The granular filler according to any prior or subsequent embodiment / feature / aspect, wherein the granules consist essentially of the granular filler, optional water, and optional binder.

[0149] 33. A granular filler according to any prior or subsequent embodiment / feature / aspect, wherein the granular filler has a moisture content of 15-80% by weight, for example 40-60% by weight.

[0150] 34. Particulate fillers according to any prior or subsequent embodiments / features / aspects, wherein a rubber sample having 20-60 phr of milled recycled carbon produces less than 10% or less than 5% of undispersed area (dispersion %).

[0151] 35. A granular filler according to any prior or subsequent embodiment / feature / aspect, wherein a rubber sample of the granular filler having 20-80 phr, such as 30-70 phr, 40-60 phr or 45-55 phr, has up to 3% undispersed area, for example, 1-3% undispersed area.

[0152] 36. Particulate fillers according to any prior or subsequent embodiment / feature / aspect, wherein the rubber sample having 10-50 phr, for example 10-40 phr, of the recycled carbon has a UA ≤ 3.35 - (0.04) The undispersed region UA ​​of phr rC).

[0153] 37. According to any prior or subsequent embodiment / feature / aspect of the granular filler, the wear volume loss caused by the rubber sample having 20-60 phr of the recycled carbon is no more than 10% greater than or deviates by no more than 5% from that of a control rubber sample prepared in the same manner but with N550 carbon black instead of the recycled carbon.

[0154] 38. Granular fillers according to any prior or subsequent embodiment / feature / aspect, wherein, when measured according to ASTM D5963, the rubber sample of the granular filler having 20-80 phr, such as 30-70 phr, 40-60 phr, or 45-55 phr, has a diameter of 90-100 mm. 3 For example, 91-95mm 3 Wear and tear.

[0155] 39. According to any prior or subsequent embodiment / feature / aspect of the granular filler, wherein the M300 / M100 ratio produced by the rubber sample having 20-60 phr of the recycled carbon is as follows: a) smaller than or deviating from by no more than 5% than a control rubber sample prepared in the same manner but with N550 carbon black instead of the recycled carbon; or b) 4.5-5.

[0156] 40. According to any prior or subsequent embodiment / feature / aspect of the granular filler, wherein the M300 (MPa) or maximum load (N) produced by the rubber sample having 20-60 phr of the recycled carbon is not more than 10% or 5% smaller than that of a control rubber sample prepared in the same manner but with N550 carbon black instead of the recycled carbon.

[0157] 41. Particulate fillers according to any prior or subsequent embodiments / features / aspects, wherein the particle size is measured according to PSD method 1.

[0158] 42. Granules comprising granular fillers according to any prior or subsequent embodiments / features / aspects, the granular fillers further comprising at least one filler selected from carbon black, silicon-treated carbon black, silica-coated carbon black, carbon black-coated particles, and precipitated silica.

[0159] 43. An elastomer composite comprising particulate filler according to any prior or subsequent embodiment / feature / aspect 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, engineered polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxide, metal carbonate, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, and carbon black-coated particles.

[0160] 44. An elastomer complex according to any prior or subsequent embodiment / feature / aspect, wherein the elastomer is selected from natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, polyisoprene rubber, ethylene-propylene copolymer, isobutylene-based rubber, chloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomers, fluorinated elastomers, perfluorinated elastomers, and blends thereof.

[0161] 45. An elastomeric compound according to any prior or subsequent embodiment / feature / aspect, wherein the elastomeric compound is a vulcanized elastomeric compound.

[0162] 46. ​​An elastomeric composite according to any prior or subsequent embodiment / feature / aspect, having a dispersion of no more than 4% undispersed area, for example, no more than 3% undispersed area or 1%-3% undispersed area.

[0163] 47. An elastomeric composite according to any prior or subsequent embodiment / feature / aspect, wherein the elastomeric composite has 20-60 phr of particulate filler and less than 10% or less than 5% of undispersed region (dispersion %).

[0164] 48. An elastomeric composite according to any prior or subsequent embodiment / feature / aspect, wherein the elastomeric composite has: 20-80 phr of particulate filler, for example, 30-70 phr, 40-60 phr or 45-55 phr of particulate filler; and up to 3% of undispersed region, for example, 1-3% of undispersed region (dispersion %).

[0165] 49. An elastomeric composite according to any prior or subsequent embodiment / feature / aspect, wherein said elastomeric composite has a media-milled rC of 10-40 phr, for example, 10-40 phr, and satisfies UA ≤ 3.35 - (0.04) The undispersed region UA ​​of phr rC).

[0166] 50. An elastomeric compound according to any prior or subsequent embodiment / feature / aspect, wherein the elastomeric compound has: 20-60 phr of the recycled carbon; and a wear volume loss not exceeding 10% or deviating from, that of, a control rubber sample using N550 carbon black instead of the milled recycled carbon.

[0167] 51. An elastomeric composite according to any prior or subsequent embodiment / feature / aspect, wherein the elastomeric composite has: 20-80 phr of particulate filler, for example, 30-70 phr, 40-60 phr, or 45-55 phr of particulate filler; and, when measured according to ASTM D5963, 90-100 mm 3 For example, 91-95mm 3 Wear and tear.

[0168] 52. An elastomeric composite according to any prior or subsequent embodiment / feature / aspect, wherein said elastomeric composite has:

[0169] The recovered carbon of 20-60 phr; and

[0170] The following are the M300 / M100 ratios:

[0171] a) The size of the comparative rubber sample using N550 carbon black instead of the milled, recycled carbon is not more than 10% smaller or the deviation from it is not more than 5% smaller, or

[0172] b) 4.5-5.

[0173] 53. An elastomeric compound according to any prior or subsequent embodiment / feature / aspect, wherein the elastomeric compound has: 20-60 phr of the recycled carbon; and an M300 (MPa) or maximum load (N) that is no more than 10% or no more than 5% smaller than that of a comparative rubber sample in which the milled recycled carbon is replaced with N550 carbon black.

[0174] 54. A tire tread comprising a vulcanized product containing a mixture of an elastomeric compound and a curing package according to any prior or subsequent embodiments / features / aspects.

[0175] 55. An article comprising a vulcanized product containing a mixture of an elastomeric compound and a curing package according to any prior or subsequent embodiments / features / aspects.

[0176] 56. Article of manufacture according to any prior or subsequent embodiment / feature / aspect, wherein said article is incorporated in a pneumatic tire, a non-pneumatic tire, or a solid tire.

[0177] 57. Articles of manufacture according to any prior or subsequent embodiments / features / aspects, wherein said articles are selected from tire treads, bottom treads, inner liners, sidewalls, sidewall inserts, liner wraps, and cushioning rubber for retreaded tires.

[0178] 58. Articles of manufacture according to any prior or subsequent embodiment / feature / aspect, wherein said articles are selected from hoses, liners, gaskets, seals, washers, vibration-damping articles, tracks, track pads for tracked vehicle equipment, engine mounts, seismic stabilizers, mining equipment screens, mining equipment liners, conveyor belts, chute liners, slurry pump liners, mud pump impellers, valve seats, valve bodies, piston hubs, piston rods, plungers, impellers for mixing slurries and slurry pump impellers, grinding mill liners, cyclone separators and hydrocyclones, expansion joints, linings for dredging pumps and outboard motor pumps for marine equipment, shaft seals for marine, oil, aerospace and other applications, propeller shafts, pipe liners, engine mounts, bushings, weatherstripping, windshield wipers, automotive parts, seals, washers, housings, wheel elements, and track elements.

[0179] The present invention will be further illustrated by the following embodiments, which are merely exemplary in nature.

[0180] Example

[0181] Example 1

[0182] N550 and N330 CB pellets were jet-milled in a 4-inch (10.2 cm) Micron Master Jet Pulverizer SN1634_Model 04-626 at a flow rate of approximately 2 kg / h and a top pressure of 80 psi (0.55 MPa) and a bottom pressure of 40 psi (0.03 MPa) to produce a fluffy material. rC was obtained from a commercial supplier in fluffy form with a reported D50 of 2 μm. The measured PSD of the material was at... Figure 1 and Figure 6 As given, all materials were dispersed in water at 14% by weight to form a slurry for grinding. Wet grinding was performed on a MiniCer media mill (Netzsch) using 0.5mm YSZ beads at 85% fill factor and 4200 rpm in a recirculating batch mode. The equation “residence time” = “batch time” was used. The "residence time" is calculated using the ratio of "mill volume" to "batch volume". The "batch time" is the total running time of the batch, the "mill volume" is the volume of the grinding chamber minus the volume occupied by the media, and the "batch volume" is the total volume of the batch being ground.

[0183] The ground slurry containing 86% by weight water is stirred on a hot plate set to 80°C until the moisture content reaches 70% by weight. This batch is then granulated by combining it with fluffy N550 in a 4:6 weight ratio in a granulator (Feeco Inc.) operating at 900 rpm, reducing the total water content to 50% by weight, thus allowing granule formation. Depending on the mixing method, the granules are dried in an oven at 80°C or kept moist until mixed.

[0184] To characterize the particle size obtained in the slurry, the milled rC slurry (14% wt% solids) was diluted to 2000 ppm with deionized water containing 600 ppm Triton X100 surfactant. The diluted solution was then mixed at 800 RPM for 5 minutes using a DISPERMAT LC55 mixer equipped with a lightweight 30 mm diameter 18-tooth impeller. The solution was then stirred on a stirring plate using a magnetic stir bar for 24 hours. The sample solution was then further diluted to 400 ppm with deionized water containing 400 ppm Triton X100 surfactant and spun on a roller in 40 ml vials until measurement.

[0185] Measurements were performed using a disc centrifuge (DC24000, CPS Instruments) at 5000 RPM. First, sucrose solutions of 24%, 22%, 20%, 18%, 16%, 14%, 12%, 10%, and 8% (in deionized water) were sequentially poured into the discs (1.6 ml each), followed by the addition of 1 ml of dodecane to seal the gradient. The gradient was allowed to stabilize for 1 hour before measurement. For particle size analysis, the sample density and refractive index were set to 1.86 g / cm³. 3 And n = 1.84 + 0.846i. The result indicates a density of 1.86 g / cm³. 3 The equivalent sedimentation result for spherical particles with a refractive index of n = 1.84 + 0.846i was also calculated. All measurements were stopped immediately after the signal reached the baseline.

[0186] The change in particle size is shown in Figure 1 and Figure 6 The initial material particle distribution had a D90 of 9 μm. After a residence time of 2.5 minutes, the D90 decreased to 3 μm and continued to decrease until it reached 0.34 μm at 40 minutes.

[0187] To determine the appropriate residence time for obtaining suitable rubber properties, the milled material was tested in the SBR compound. Details of each embodiment, including formulations and mixing schemes, are provided in Table 2 below.

[0188] Table 2

[0189]

[0190] The formulations used in the experiments are given in Table 2. The experimental data are listed in Table 2 and... Figure 2-5 In Chinese, the symbols / terms in tables and figures have the following meanings:

[0191] Dry N330 = N330 carbon black, rC is not present; it is granulated and dried before mixing.

[0192] Wet N550 X minutes = N550, ground with media, where X represents the grinding residence time - for example, "wet rC 20 minutes" means N550, ground with media, residence time of 20 minutes, and then co-granulated with fluffy N550 at a mass ratio of 4:6; not dried before mixing.

[0193] Dry N550 = N550 carbon black, rC is not present; it is granulated and dried before mixing.

[0194] Wet rC X minutes = rC, according to the present invention, after media grinding, where X represents the grinding residence time - for example, "wet rC 20 minutes" means that rC is media ground for 20 minutes and then co-granulated with fluffy N550 at a mass ratio of 4:6; not dried before mixing.

[0195] The dry rC blend consists of 4 parts by weight of rC and N550, co-granulated and dried before mixing.

[0196] The wet rC blend consists of 4 parts by weight of rC and N550, co-granulated and not dried before mixing.

[0197] Dry rC fluff blend = ungranulated rC and N550 mixed by normal drying method.

[0198] Dry rC = rC that has not been ground by media but has been granulated and dried.

[0199] Wet rC = rC that has not been ground by media but granulated and not dried

[0200] Dry rC fluff = rC that has not been ground in media, granulated, or mixed using normal drying methods.

[0201] For “undried” samples, the wetting amount results in a water content of 50% by weight.

[0202] In addition to media-milled rC samples, the options of introducing rC as a fluffy material and wet mixing of rC wet pellets and co-particles were also evaluated. Figure 2 The quality of dispersion in the resulting mixtures is shown. Dry, fluffy, and wet treatments all produced rC mixtures with poorer dispersion than the control sample (long dashed circle), while the media-milled sample (short dashed circle) had a dispersion comparable to the carbon black control sample (solid circle).

[0203] The experiment also showed improvements in rubber properties. Figure 3 The data shows the volumetric loss due to DIN wear. The material polished by the medium (short dashed circle) showed a volumetric loss comparable to the wet N550 2-minute control (solid circle), while other rC methods (long dashed circle) showed a performance degradation compared to the control. A residence time of 40 minutes showed degradation, likely due to rC structural degradation, as indicated by material softening, which can negatively impact DIN wear.

[0204] The slope of the tensile profile of a rubber compound (known as reinforcement) is important for its wear properties. Figure 4 In the diagram, the stress ratio M300 / M100 at 300% vs. 100% was plotted to quantify the enhancement. As shown in the experiments, wet mixing resulted in a significantly enhanced N550 compared to dry-mixed N330. Increasing the rC content when using dry, wet, or fluffing methods leads to a decrease in enhancement. However, the media-milled rC of the present invention did not show this decrease.

[0205] Compared to CB blends, rC often results in poorer stiffness. rC blends using the fluffing, dry, or wet methods produce the expected stress reduction at 300% elongation (M300), such as... Figure 5 As shown. However, no degradation was observed in the experiments conducted for this invention.

[0206] While the optimal grinding time for these experiments on reinforcement and wear is 20 minutes, the optimal grinding time for low strain stiffness is 5 minutes, such as... Figure 5 As shown. This is likely due to the aggregates breaking down within up to five minutes, followed by degradation of the aggregate structure after five minutes.

[0207] Based on these observations, treating rC with media milling prior to compound production makes it possible to achieve significantly higher rC contents. Since there is almost no or no reduction in performance compared to N550 blends prepared by wet mixing, compounds with up to 100% substitution are possible.

[0208] Table 3 below provides a summary of some results achieved through this invention, normalized to the "wet N550 2 minutes" control described in the above embodiments. These normalized results are used to derive equations describing the performance with and without the application of this invention.

[0209] Table 3

[0210]

[0211] rubber mixtureThe rubber compounds were prepared using the formulations given in Table 2. The SBR used was Kralex SBR 1502 styrene-butadiene rubber (Synthos); N550 was Spheron SO (Cabot Corp.); N330 was Vulcan 3 (Cabot Corp.); ungranulated, jet-milled rC was Carbon Green 6 (CBp Cyprus Ltd., Limassol, Cyprus), granulated in some cases as shown in Table 2; stearic acid, rubber grade (Akrochem Corp.); zinc oxide was RGT-M (Akrochem Corp.); and wax was AKROWAX. TM 5031 (Akrochem Corp.); antioxidant is DQ (Akrochem Corp.); 6PPD is Stangard 6PPD (Harwick Standard); sulfur is Rubbermakers Sulfur (Akrochem Corp.); BBTS is Accelerator BBTS (Akrochem Corp.). All compositions were mixed in a 1.6L Banbury mixer with two airfoil rotors. Dry-mixed samples (granular moisture <1 wt%) were prepared in two stages as described in Table 4. Wet-mixed samples (granular moisture >1 wt%) were prepared in three stages as described in Table 5. Regardless of the method used, after each mixing stage, the mixture was tableted on a two-roll mill operating at 50°C and approximately 22 rpm, then banded for 60 seconds and passed through six times with a roll gap of approximately 5 mm, and allowed to stand for at least 3 hours before the next mixing stage (or curing, after the last stage). Curing takes place in a heated press (150°C, 2500 lbs) for a duration of 40% of T90 as determined by a conventional rubber rheometer, where T90 is the time to achieve 90% vulcanization.

[0212] Table 4

[0213]

[0214] Table 5

[0215]

[0216] The following tests were used to obtain performance data for each vulcanization product. Tensile stress at 100% elongation (M100) and tensile stress at 300% elongation (M300) were evaluated using ASTM D412 (Test Method A, Type C) at 23°C, 50% relative humidity, and a crosshead speed of 500 mm / min. An elongation meter was used to measure tensile strain. The ratio of M300 / M100 is referred to as the tensile stress ratio (or reinforcement ratio). Cured rubber samples were sliced ​​using a razor blade fixed in a manual cutting fixture for dispersion analysis. The samples were mounted on a dispersion instrument (Alpha Technologies) and imaged. The following settings were used: “Filler Volume Fraction”, 20%; “Exposure Time”, 40 ms; “Color Channel for Analysis”, “Blue”; “Threshold for Dispersion Calculation”, 23 μm; Nodule to Aggregate Fraction, 1; White Area Threshold, 0. The amount reported as “White Area, %” by the Alpha Technologies instrument was interpreted as “Undispersed Area”. DIN wear was evaluated according to the standard ASTM D5963 rotation method.

[0217] Example 2

[0218] N330 CB pellets (Cabot Corporation) were jet-milled to produce a fluffy material as described in Example 1. rC pellets (Reoil-RCB, REOIL SP Z OO) were jet-milled; the resulting material had a D50 of 488 nm and a D90 of 3430 nm when measured as described below. The jet-milled rC material was dispersed in water at 14% by weight to form a slurry for grinding. Wet milling was performed on a Netzsch MiniCer wet media mill in a pass-through manner (single pass unless otherwise specified) using 0.5 mm yttrium-stabilized zirconia beads (YSZ, 3000 rpm or 4600 rpm) or 0.4–0.6 mm polystyrene beads (4600 rpm only), with residence times and other settings as shown in Table 6 below. The number of impacts with the polystyrene beads was the same; however, the energy imparted during media milling using PS beads was 0.5 times that imparted during media milling using YSZ beads.

[0219] Table 6A

[0220]

[0221] Table 6B

[0222]

[0223] To characterize the particle size obtained in the slurry, the milled rC slurry was diluted to 2000 ppm with deionized water containing 600 ppm Triton X100 surfactant. The diluted solution was then mixed at 800 RPM for 5 minutes using a DISPERMAT LC55 mixer equipped with a lightweight 30 mm diameter 18-tooth impeller. The solution was then stirred on a stirring plate using a magnetic stir bar for 24 hours. The sample solution was then further diluted to 400 ppm with deionized water containing 400 ppm Triton X100 surfactant and spun on a roller in 40 ml vials until measurement.

[0224] Measurements were performed using a disc centrifuge (DC24000, CPS Instruments) at 5000 RPM. First, sucrose solutions of 24%, 22%, 20%, 18%, 16%, 14%, 12%, 10%, and 8% (in deionized water) were sequentially poured into the discs (1.6 ml each), followed by the addition of 1 ml of dodecane to seal the gradient. The gradient was allowed to stabilize for 1 hour before measurement. During the disc centrifuge measurements, the sample density and refractive index were set to 1.86 g / cm³. 3 And n = 1.84 + 0.846i. The result indicates a density of 1.86 g / cm³. 3 The equivalent sedimentation results for spherical particles with a refractive index of n = 1.84 + 0.846i are also presented. All measurements were stopped immediately after the signal reached the baseline. The D50 and D90 values ​​for various samples are shown in Table 7 below.

[0225] Table 7

[0226]

[0227] Using a Thermo Scientific Sorvall Legend XTR centrifuge, a milled slurry containing 86% by weight of water was centrifuged for 15 minutes to obtain a centrifugal cake with approximately 70% solids. Each batch was then granulated by combining appropriate amounts of the centrifugal cake and slurry with fluffy N330 carbon black in a rotary pin granulator operated at 900 rpm with walls heated to 50°C, to form a blend with 30% rC and 70% N330 carbon black by weight. The granules were then dried in an oven at 80°C.

[0228] Using the mixing scheme in Table 4 and the vulcanization procedure described in Example 1, SBR composites were prepared with 50 phr (total) rC and carbon black using the formulations (chemicals as described in Example 1) shown in Table 8 below. Rubber properties were measured as described in Example 1.

[0229] Table 8

[0230]

[0231] like Figure 7 As shown (RT = residence time in minutes), even minimal milling significantly improved dispersion in the SBR blend, with several samples (all with milled rC having a D90 below 1500 nm) exhibiting less than 3% by weight of undispersed region. However, dispersion was not entirely correlated with wear performance; only milled rC with a D90 not greater than 1100 nm provided less than 95 mm during wear testing. 3 mass loss ( Figure 8 RT = residence time, in minutes. Furthermore, only milled rC with a D50 of 250-400 simultaneously provides an M100 of at least 2.5 MPa, while milled rC with a lower D50 also provides a lower modulus. Figure 9 RT = stay time, in minutes.

[0232] Example 3

[0233] N330 CB pellets (Cabot Corporation) were jet-milled to produce a fluffy material as described in Example 1. Reoil-RCB pellets (REOIL SP Z OO) were jet-milled and dispersed in water at 14% by weight to form a slurry for milling. Wet milling was performed on a MiniCer media mill (Netzsch) using 0.5 mm YSZ beads at 85% fill factor and 4600 rpm in a recirculating batch mode with a residence time of 5 minutes. Particle size was characterized as described in Example 1; D50 was 271 μm and D90 was 412 μm.

[0234] A portion of a milled slurry containing 86% by weight water was centrifuged for 15 minutes using a Thermo Scientific Sorvall Legend XTR centrifuge to obtain a centrifuged cake. The centrifuged cake was then combined with the milled slurry to form a mixed slurry with the water content shown in Table 9. The batch was then granulated by combining the mixed slurry with an appropriate amount of fluffy N330 carbon black in a rotary pin granulator operated at 900 rpm with walls heated to 50°C to achieve the rC and unused carbon black ratio shown in Table 9. Pure rC pellets were produced by drying the centrifuged cake at 80°C until it reached a moisture content of 46%. Fluffy N330 was combined with water to achieve a solids load of approximately 58% by weight for forming pure pellets. Depending on the mixing method, the pellets were dried in an oven at 80°C or kept moist until the rubber was mixed.

[0235] Table 9

[0236]

[0237] Using the wet or dry mixing scheme described in Example 1, along with the vulcanization procedure described in Example 1, and the formulations described in Table 8 (chemicals as described in Example 1), an SBR compound was prepared with 50 phr (total) rC and carbon black. Rubber properties were measured as described in Example 1. Figure 10 As shown, grinding (solid circles) significantly improved filler dispersion compared to unground samples (hollow circles), particularly at 26% and 40% rC. However, at 100% rC, dried granules exhibited a sharp decline in dispersion quality, while the elastomer composites produced from wet granules maintained good dispersibility. This correlation was also observed in wear properties (…). Figure 11 Samples ground by media are solid circles; samples ground by jet milling are hollow circles.

[0238] Example 4

[0239] As described in Example 3, 30% by weight of media-milled and jet-milled rC and 70% Propel E6 carbon black (STSA=97m) were prepared. 2 / g, Cabot Corporation), and a co-particle of spray-milled N330 carbon black granules. An SBR composite with 50 phr filler was prepared as described in Example 3, except that 6 PPD was sourced from Westco, and was characterized as described in Example 1. As shown in Table 10 below, the combination of media-milled rC with a high surface area carbon black such as Propel E6 carbon black yielded results superior to or equivalent to N330 carbon black (STSA=76m). 2 The performance of / g).

[0240] Table 10

[0241]

[0242] While the invention has been specifically shown and described with reference to preferred embodiments thereof, those skilled in the art will understand that various changes in form and detail may be made therein without departing from the scope of the invention as covered by the appended claims.

[0243] As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items. Furthermore, all conjunctions used should be understood in the most inclusive sense possible. Thus, the word “or” should be understood as having the definition of logical “or” rather than logical “exclusive OR”, unless the context explicitly states otherwise. Additionally, unless explicitly stated otherwise, the singular form and the articles “a,” “an,” and “the” are also intended to include the plural form. It will be further understood that, when used in this specification, the terms “comprising,” “including,” “containing,” and / or “containing” specify the presence of the stated features, integers, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. Furthermore, it should be understood that when an element comprising a component or subsystem is referred to and / or shown as connected or coupled to another element, it may be directly connected or coupled to the other element, or there may be intermediate elements present.

[0244] Unless otherwise defined, all terms used herein (including technical and scientific terms) shall have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It will be further understood that terms such as those defined in common dictionaries shall be interpreted as having the same meaning as their meaning in the context of the relevant field, and shall not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0245] The applicant specifically incorporates the entire contents of all cited references into this disclosure. Furthermore, when quantities, concentrations, or other values ​​or parameters are given as ranges (preferred intervals) or lists of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value and any lower or preferred value, regardless of whether the range is disclosed individually. Where numerical ranges are listed herein, unless otherwise stated, the range is intended to include its endpoints, as well as all integers and fractions within that range. When defining ranges, the scope of the invention is not intended to be limited to the specific values ​​listed. It should also be understood that for any range provided herein, the numerical range may be “about” or “around” these ranges, and vice versa; where ranges are provided using “about” or “around” ranges, these ranges may be precisely the numerical ranges provided. Any combination of embodiments and / or ingredients and / or components (components) and / or properties described herein may be carried out herein and considered part of the invention.

[0246] Other embodiments of the invention will become apparent to those skilled in the art in consideration of this specification and the practice of the invention disclosed herein. This specification and the embodiments are intended to be considered exemplary only, wherein the true scope and spirit of the invention are indicated by the appended claims and their equivalents.

[0247] The foregoing description of preferred embodiments of the 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 forms disclosed. Modifications and variations are possible in accordance with the foregoing teachings, or may be obtained from the practice of the invention. These embodiments were chosen and described to explain the principles of the invention and its practical application, enabling those skilled in the art to utilize the invention in various embodiments and to make various modifications according to the intended particular use. The scope of the invention is intended to be defined by the appended claims and their equivalents.

Claims

1. A method for processing recycled carbon, the method comprising media milling wet recycled carbon to obtain milled recycled carbon, wherein the media milling results in 10 13 -10 14 subsequent media collisions per kg of dry milled recycled carbon during the milling.

2. A method for processing recovered carbon, the method comprising media milling wet recovered carbon to obtain milled recovered carbon, wherein the milling comprises media milling consuming a specific energy of 1 kWh / kg to 10 kWh / kg of dry-milled recovered carbon.

3. A method for processing recovered carbon, the method comprising media milling wet recovered carbon to obtain milled recovered carbon, wherein the media milling results in a volume-weighted particle size distribution of the milled recovered carbon as measured by disc centrifuge photogravity determination, wherein D50 is 250-400 nm, preferably 250-320 nm, and D90 is 350-1100 nm, for example 500-1100 nm.

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

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

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

7. The method of any one of claims 2-6, wherein during the milling, the media milling results in 10 13 -10 14 subsequent media collisions.

8. The method of any one of claims 1-7, wherein during the milling, the media milling results in 2 x 10 13 -10 14 fewer media collisions per kg of recovered carbon dry milled.

9. The method of any one of claims 1-8, wherein during the milling, the media milling results in 3 x 10 13 -10 14 -10 14 -10 14 -10 14 -10 14 -10 14 -10 14 -10 14 -10 14 -10 14 -10 14 -10 14 -10 14 10. The method according to any one of claims 1-9, wherein the media grinding is a stirred ball mill, a planetary ball mill, or a centrifugal ball mill.

11. The method according to any one of claims 1-10, wherein the media milling is a stirred ball milling.

12. The method according to any one of claims 1-11, wherein the media used in the media grinding is a solid ball with an average size of about 0.25 mm to 2 mm, for example 0.25 to 1 mm, and the volumetric load in the mill is 50% to 98%.

13. The method according to any one of claims 1-12, wherein the volume-weighted particle size distribution of the recovered carbon after media milling, as measured by disc centrifuge photogravity determination, has a D50 of 250-400 nm, preferably 250-320 nm, and a D90 of 350-1100 nm, for example 500-1100 nm.

14. The method according to any one of claims 1-13, wherein the milling results in the milled rubber sample of recycled carbon having a dispersion of less than 10% or less than 5% of undispersed area (dispersion %).

15. The method according to any one of claims 1-14, wherein the milling results in a rubber sample having granular filler of 20-80 phr, for example 30-70 phr, 40-60 phr or 45-55 phr, with up to 3% undispersed region, for example 1-3% undispersed region, and 10-40% by weight of the granular filler is recycled carbon milled by media, for example 15-35% by weight or 20-30% by weight.

16. The method according to any one of claims 1-15, wherein the milling results in a milled rubber sample with an rC of 10-50 phr, for example 10-40 phr, satisfying UA ≤ 3.35 - (0.04) / 2. The undispersed region UA ​​of phr rC).

17. The method according to any one of claims 1-16, wherein the grinding results in a wear volume loss of the rubber sample with the ground recycled carbon having 20-60 phr that is no more than 10% greater or deviates by no more than 5% from that of a control rubber sample prepared in the same manner but with N550 carbon black instead of the ground recycled carbon.

18. The method according to any one of claims 1-17, wherein the milling process results in a rubber sample having granular filler of 20-80 phr, such as 30-70 phr, 40-60 phr, or 45-55 phr, when measured according to ASTM D5963, having a particle size of 90-100 mm. 3 For example, 91-95mm 3 The wear loss is due to the fact that 10-40% by weight, for example 15-35% by weight or 20-30% by weight of the granular filler is recycled carbon that has been media-milled.

19. The method of claim 18, wherein the granular filler comprises unused carbon black, for example having a density of 35-110 μm. 2 Carbon black with a BET surface area of ​​ / g, such as N300 or N500 series carbon black, such as N330 or N550 carbon black, such as N330 carbon black.

20. The method according to any one of claims 1-19, wherein the milling produces an M300 / M100 ratio of the milled recycled carbon rubber sample having 20-60 phr as follows: a) smaller than or deviating from by no more than 5% than a control rubber sample prepared in the same manner but using N550 carbon black instead of the milled recycled carbon; or b) 4.5-5.

21. The method according to any one of claims 1-20, wherein the milling results in the M300 (MPa) or maximum load (N) of the rubber sample with the milled recycled carbon having 20-60 phr being no more than 10% or 5% smaller than that of a control rubber sample prepared in the same manner but with N550 carbon black instead of the milled recycled carbon.

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

23. Milled and recycled carbon, prepared by any one of claims 1-22.

24. A granular packing material comprising 10-40% by weight of recovered carbon, wherein the volume-weighted particle size distribution of the recovered carbon, as measured by optical sedimentation measurement using a disc centrifuge, has a D50 of 250-400 nm, preferably 250-320 nm, and a D90 of 350-1100 nm, for example 500-1100 nm.

25. The granular filler according to claim 24, 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. The granular filler according to claim 24 or 25, further comprising one or more of the following: carbon black, silicon-treated carbon black, silica-coated carbon black, precipitated silica, hydrothermal carbon, engineered polysaccharides, graphene, graphene oxide, reduced graphene oxide, nanocellulose, lignin, clay, nanoclay, metal oxide, metal carbonate, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, and carbon black-coated particles.

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

28. The granular filler according to any one of claims 24-27, further comprising carbon black.

29. The granular filler according to any one of claims 24-28, further comprising a particle size of 35-110 μm. 2 / g for example 35-65m 2 / g、65-90m 2 / g or 90-110m 2 / g of BET surface area carbon black.

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

31. The granular filler according to any one of claims 24-30, wherein the granular filler is in the form of granules.

32. The granular filler according to any one of claims 24-31, wherein the granules consist substantially of the granular filler, optionally water, and optionally a binder.

33. The granular filler according to any one of claims 24-32, wherein the granular filler has a moisture content of 15-80% by weight, for example 40-60% by weight.

34. The granular filler according to any one of claims 24-33, wherein the rubber sample of milled recycled carbon having 20-60 phr produces less than 10% or less than 5% of undispersed area (dispersion %).

35. The granular filler according to any one of claims 24-34, wherein the rubber sample of the granular filler having 20-80 phr, for example 30-70 phr, 40-60 phr or 45-55 phr, has up to 3% undispersed region, for example 1-3% undispersed region.

36. The granular filler according to any one of claims 24-35, wherein the rubber sample having 10-50 phr, for example 10-40 phr, of the recycled carbon has a UA ≤ 3.35 - (0.04) The undispersed region UA ​​of phr rC).

37. The granular filler according to any one of claims 24-36, wherein the wear volume loss caused by the rubber sample having 20-60 phr of the recycled carbon is not more than 10% greater than or deviates from by 5% from that of a control rubber sample prepared in the same manner but using N550 carbon black instead of the recycled carbon.

38. The granular filler according to any one of claims 24-37, wherein, when measured according to ASTM D5963, the rubber sample of the granular filler having a phr of 20-80, for example 30-70, 40-60, or 45-55, phr has a diameter of 90-100 mm. 3 For example, 91-95mm 3 Wear and tear.

39. The granular filler according to any one of claims 24-38, wherein the M300 / M100 ratio produced by the rubber sample having 20-60 phr of the recycled carbon is: a) not more than 10% smaller or deviating from a control rubber sample prepared in the same manner but using N550 carbon black instead of the recycled carbon; or b) 4.5-5.

40. The granular filler according to any one of claims 24-39, wherein the M300 (MPa) or maximum load (N) produced by the rubber sample having 20-60 phr of the recycled carbon is not more than 10% or 5% smaller than that of a control rubber sample prepared in the same manner but using N550 carbon black instead of the recycled carbon.

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

42. Granules comprising granular filler according to any one of claims 24-41, said granular filler further comprising at least one filler selected from carbon black, silicon-treated carbon black, silica-coated carbon black, carbon black-coated particles, and precipitated silica.

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

44. The elastomer composite of claim 43, wherein the elastomer is selected from natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, polyisoprene rubber, ethylene-propylene copolymer, isobutylene-based rubber, chloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomers, fluorinated elastomers, perfluorinated elastomers, and blends thereof.

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

46. ​​The elastomeric composite according to any one of claims 43-45, wherein it has a dispersion of no more than 4% undispersed region, for example, no more than 3% undispersed region or 1%-3% undispersed region.

47. The elastomeric composite according to any one of claims 43-46, wherein, The elastomer composite has 20-60 phr of granular filler and less than 10% or less than 5% of undispersed regions (dispersion %).

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

49. The elastomeric composite according to any one of claims 43-48, wherein the elastomeric composite has a media-milled rC of 10-40 phr, for example, 10-40 phr, and satisfies UA ≤ 3.35 - (0.04) The undispersed region UA ​​of phr rC).

50. The elastomeric composite according to any one of claims 43-49, wherein the elastomeric composite comprises: 20-60 phr of the recycled carbon; and a wear volume loss not exceeding 10% or deviating from, that of, a control rubber sample in which the milled recycled carbon is replaced with N550 carbon black.

51. The elastomeric composite according to any one of claims 43-50, wherein, The elastomeric composite comprises: 20-80 phr of granular filler, for example, 30-70 phr, 40-60 phr, or 45-55 phr of granular filler; and, when measured according to ASTM D5963, 90-100 mm 3 For example, 91-95mm 3 Wear and tear.

52. The elastomeric composite according to any one of claims 43-51, wherein the elastomeric composite comprises: The recovered carbon of 20-60 phr; and The following are the M300 / M100 ratios: a) The size of the comparative rubber sample using N550 carbon black instead of the milled, recycled carbon is not more than 10% smaller or the deviation from it is not more than 5% smaller, or b) 4.5-5。 53. The elastomeric composite according to any one of claims 43-52, wherein the elastomeric composite comprises: 20-60 phr of the recycled carbon; and an M300 (MPa) or maximum load (N) that is not more than 10% or 5% smaller than that of a comparative rubber sample in which the milled recycled carbon is replaced with N550 carbon black.

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

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

56. The article of claim 43-53, wherein the article is incorporated in a pneumatic tire, a non-pneumatic tire, or a solid tire.

57. The article of claim 55 or 56, wherein the article is selected from tire tread, bottom tread, inner liner, sidewall, sidewall insert, liner sheath, and cushioning rubber for retreaded tires.

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

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