Elastomer compositions with improved properties

Abstract

The invention relates to an elastomer composition for a tyre bearing heavy loads based on at least one elastomer matrix, fillers including graphite and a reinforcing filler and a vulcanisation system, the composition being characterised in that: - the elastomer matrix comprises at least 50 phr of a diene elastomer chosen from the group consisting of isoprene elastomers, butadiene elastomers and mixtures of these diene elastomers; - the reinforcing filler predominantly comprises an acetylene black; - the graphite has a crystallite size Lc ranging from 80 to 500 nm, more preferentially from 90 to 400 nm, and more preferentially 100 to 300 nm; - the total content of fillers is less than or equal to 65 phr.

Description

[0001] Elastomeric compositions with improved properties

[0002] TECHNICAL FIELD

[0003] The field of the present invention is that of reinforced elastomeric compositions used for the manufacture of tires carrying heavy loads, such as those intended to equip a heavy goods vehicle, a civil engineering vehicle, a tractor, a bus, an airplane, etc.

[0004] TECHNOLOGICAL BACKGROUND

[0005] Tires intended for vehicles carrying heavy loads are provided with treads which, compared to the treads of tires for light vehicles, in particular passenger vehicles or vans, have greater thicknesses of rubber material, in particular to support the weight that these vehicles carry. Typically, the wearing part of the tread of a vehicle carrying heavy loads may have a thickness of at least 15 mm, that of a civil engineering vehicle at least 30 mm, or even up to 120 mm. These tires may in particular have an axial width greater than 37 inches.

[0006] During rolling, the elastomeric compositions, such as those of the tread, sidewalls, etc., of these tires are subjected to mechanical stresses and attacks resulting in particular from contact with the ground. In the case of a tire mounted on a vehicle carrying heavy loads, the mechanical stresses and attacks suffered are amplified by the effect of the weight carried by the tire.

[0007] For example, the tyres of mining vehicles are subjected to high stresses, both i) at the local level, i.e. when rolling over the macro-indenters represented by the stones which make up the tracks (crushed rock) and ii) at the global level by the passage of significant torque due to the slopes of the tracks to exit the mine shaft (slope of around 10%) and by U-turns for loading and unloading manoeuvres.

[0008] Furthermore, in the case of vehicles intended for mining or quarry use for transporting loads, access difficulties and performance requirements are leading vehicle manufacturers to increase their load capacity. As a result, the vehicles are becoming larger and larger, and therefore themselves increasingly heavy, and can carry an increasingly large load. The current masses of these vehicles can reach several hundred tonnes, and the same is true for the load to be transported; the total mass can reach up to 600 tonnes.

[0009] Tires on vehicles carrying heavy loads are therefore under increasing stress. They must have good wear properties, be able to transmit the necessary torque, and withstand stress, particularly from stones encountered on tracks. These high stresses are also encountered, in particular, on the treads of tires fitted to agricultural vehicles due to the stony soil of arable land.

[0010] The tires fitted to heavy construction site vehicles that travel on both stony and bituminous ground also experience the same attacks.

[0011] Due to the two aggravating factors of the weight carried by the tire and the aggressive nature of the rolling surface, the wear resistance and tear resistance of a tire for a civil engineering vehicle, an agricultural vehicle or a heavy goods vehicle proves crucial to minimize the impact of the attacks suffered in particular by the tread.

[0012] It is therefore important to have elastomeric compositions for vehicle tires, especially those carrying heavy loads, which contribute to wear resistance and resistance to aggression. Thus, these elastomeric compositions must be sufficiently rigid on the one hand and have good properties of deformation at break and tear resistance on the other hand.

[0013] To solve this problem, it is known to those skilled in the art, for example, to use a significant quantity of reinforcing fillers in order to obtain good rigidity of the elastomeric composition for this type of tire or to use increasingly fine reinforcing fillers.

[0014] However, the use of increasingly fine reinforcing fillers often requires increasing the level of plasticizers, such as oils or resins, in order to overcome the difficulties of implementation and processability of this type of reinforcing filler. However, the presence of plasticizers in elastomeric compositions causes a degradation of certain mechanical properties of the elastomeric compositions such as the properties of deformation at break.

[0015] Increasing the rate of reinforcing fillers also has a disadvantage. It leads to significant internal heating problems in the reinforcing belt, which can lead to tire degradation.

[0016] Indeed, the fact that tires for vehicles carrying heavy loads have, on the one hand, larger dimensions than tires for passenger vehicles and that, on the other hand, the elastomeric compositions are subjected to repeated and greater stresses and deformations given the load they carry, leads to heat generation. This heat generated when the tire is in motion is evacuated into the environment more or less quickly depending on the thermal conductivity values ​​of each tire composition. When the thermal conductivity of an elastomeric mixture is too low, the heat accumulates and leads to bakelization of the composition. The tire then loses its elastic properties, which is unfavorable for its use.

[0017] Thus, when manufacturers seek to improve the rigidity and / or resistance to attack of elastomeric compositions for tires carrying heavy loads, this improvement is often made to the detriment of other properties such as, for example, the hysteresis of the materials and therefore ultimately to the detriment of the temperature of the tire in operation.

[0018] Document WO2013 / 186150 proposes a solution for improving the thermal conductivity of elastomeric compositions. This document describes that the use of acetylene black in the presence of silica makes it possible to improve both thermal conductivity and hysteresis.

[0019] There is therefore still an unmet need for elastomeric compositions for tires carrying heavy loads, particularly of the civil engineering type, which better satisfy the compromise of properties of resistance to aggression, rigidity, deformation at break and thermal conductivity; or even advantageously improve this compromise compared to the compositions of the prior art.

[0020] The purpose of the present invention is to meet this need.

[0021] Continuing this research, the Inventors unexpectedly identified that for tires carrying heavy loads, particularly of the civil engineering type, the use of a specific graphite in an elastomeric composition comprising an acetylene black made it possible to obtain a good compromise of properties of resistance to aggression, rigidity, deformation at break and thermal conductivity, or even to improve this compromise of properties compared to the compositions of the prior art. Advantageously, the quantity of reinforcing fillers in the elastomeric composition can even be reduced; which is economically and environmentally more favorable given the scarcity of resources.

[0022] Thus, the subject of the invention is an elastomeric composition for a tire carrying heavy loads based on at least one elastomer matrix, fillers including graphite and a reinforcing filler and a vulcanization system, characterized in that: the elastomer matrix comprises at least 50 pce of a diene elastomer chosen from the group consisting of isoprene elastomers, butadiene elastomers and mixtures of these diene elastomers, the reinforcing filler mainly comprises an acetylene black, the graphite has a crystallite size Le comprised in a range from 80 to 500 nm, more preferably from 90 to 400 nm, more preferably from 100 to 300 nm, the total filler content is less than or equal to 65 pce.

[0023] Another subject of the invention relates to a heavy-duty tire which comprises at least one composition as described above. Preferably, the tire is a civil engineering tire or a heavy-duty tire.

[0024] DETAILED DESCRIPTION OF THE INVENTION

[0025] Definitions

[0026] The expression "composition based on" means a composition comprising the mixture and / or the in situ reaction product of the different constituents used, some of these constituents being able to react and / or being intended to react with each other, at least partially, during the different phases of manufacture of the composition; the composition can thus be in a totally or partially crosslinked state or in a non-crosslinked state.

[0027] By the expression "part by weight per hundred parts by weight of elastomer" (or pce), it is meant, within the meaning of the present invention, the part, by mass per hundred parts by mass of elastomer.

[0028] In this document, unless expressly stated otherwise, all percentages (%) indicated are percentages (%) by mass.

[0029] On the other hand, any interval of values ​​designated by the expression "between a and b" represents the domain of values ​​going from more than a to less than b (i.e., excluding the limits a and b) while any interval of values ​​designated by the expression "from a to b" means the domain of values ​​going from a to b (i.e., including the strict limits a and b).

[0030] When a “majority” compound is referred to, within the meaning of the present invention, this compound is the majority among the compounds of the same type in the composition, i.e. it is the one that represents the largest quantity by mass among the compounds of the same type. Thus, for example, a majority elastomer is the elastomer representing the largest mass relative to the total mass of the elastomers in the composition. In the same way, a so-called majority filler is the one representing the largest mass among the fillers in the composition. For example, in a system comprising a single elastomer, this is the majority within the meaning of the present invention; and in a system comprising two elastomers, the majority elastomer represents more than half of the mass of the elastomers. On the contrary, a “minority” compound is a compound that does not represent the largest mass fraction among the compounds of the same type.Preferably, by majority, we mean a compound present at more than 50% by weight, preferably more than 60%, 70%, 80%, 90% by weight, and more preferably the “majority” compound represents 100% by weight relative to the total weight of compounds of the same type.

[0031] The compounds mentioned in the description may be of fossil or bio-sourced origin. In the latter case, they may be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. Obviously, the compounds mentioned may also come from the recycling of materials already in use, that is to say, they may be, partially or totally, derived from a recycling process, or obtained from raw materials themselves derived from a recycling process. This includes in particular polymers, plasticizers, fillers, etc.

[0032] The term "heavy-duty vehicle tyre" means tyres, in particular those with radial carcass reinforcement, for vehicles carrying heavy loads, such as, for example, heavy goods vehicles, aircraft, metros, civil engineering machinery, tractors, trailers or road buses, fitted with wheels with rims having a nominal diameter greater than or equal to 19.5 inches. A heavy-duty vehicle is distinguished by the size of its axle(s) and in particular by the maximum permissible laden weight, which is greater than or equal to 3.5 tonnes. The term "tread" means the outer layer of the tyre which is in direct contact with the rolling surface.

[0033] "Acetylene black" or "acetylene-derived carbon black" or "acetylene carbon black" means any carbon black obtained by thermal decomposition of acetylene used as a raw material.

[0034] By “diene” elastomer (or indistinctly rubber), whether natural or synthetic, is meant, in a known manner, an elastomer consisting at least in part (i.e., a homopolymer or a copolymer) of diene monomer units (monomers bearing two carbon-carbon double bonds, conjugated or not). In the present application, diene elastomers are by definition non-thermoplastic. Preferably, when the diene elastomers are copolymers, they are random polymers. Diene elastomers can be classified into two categories: “essentially unsaturated” or “essentially saturated”.The term “essentially unsaturated” generally means a diene elastomer derived at least in part from conjugated diene monomers, having a content of units or patterns of diene origin (conjugated dienes) which is greater than 15% (mol %); thus, diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins such as EPDM do not fall within the preceding definition and may in particular be described as “essentially saturated” diene elastomers (low or very low content of patterns of diene origin, always less than 15 mol %). The diene elastomers which can be used in the context of the invention are essentially unsaturated diene elastomers. Butyl elastomers are therefore not usable in the context of the present invention since they are essentially saturated diene elastomers.

[0035] All glass transition temperature “Tg” values ​​are measured in a known manner by DSC (Differential Scanning Calorimetry) according to ASTM D3418 (2008).

[0036] Elastomeric matrix

[0037] As indicated above, the elastomeric composition of the invention comprises an elastomeric matrix.

[0038] By definition, the elastomer matrix refers to all the elastomers present in the composition. A polymer that does not have elastic properties like those of natural rubber will therefore not be considered as part of the elastomer matrix and its rate will not be taken into account in the calculation of the pce.

[0039] The elastomer matrix of the elastomeric composition of the invention comprises at least 50 pce of a diene elastomer chosen from the group consisting of isoprene elastomers, butadiene elastomers and mixtures of these diene elastomers. For example, the elastomer matrix may comprise an isoprene elastomer or a mixture of isoprene elastomers, a butadiene elastomer or a mixture of butadiene elastomers or even a mixture of isoprene and butadiene elastomers. These diene elastomers have a content of units or patterns of diene origin (conjugated dienes) which is greater than 15 mol%.Thus, the elastomer matrix of the composition of the present invention comprises at least 50 pce of a diene elastomer having a content of units or patterns of diene origin (conjugated dienes) which is greater than 15 mol%; this elastomer being chosen from the group consisting of isoprene elastomers, butadiene elastomers and mixtures of these diene elastomers. In addition to the aforementioned diene elastomers, the elastomer matrix may also comprise thermoplastic elastomers.

[0040] The term "isoprene elastomer" is understood to mean, in a known manner, a homopolymer or copolymer of isoprene. Isoprene copolymers comprise at least one isoprene monomer and at least one other monomer different from the isoprene monomer, the diene monomer content being greater than 15 mol%. Therefore, butyl rubber is excluded from the definition of isoprene elastomer. The other monomer may be ethylene, an olefin or a conjugated or unconjugated diene.

[0041] The term "butadiene elastomer" is understood to mean, in a known manner, a homopolymer or copolymer of butadiene. Butadiene copolymers comprise at least one butadiene monomer and another monomer different from the butadiene monomer; the levels of diene monomer being greater than 15 mol%. The other monomer may be ethylene, an olefin or a conjugated or unconjugated diene.

[0042] Suitable conjugated dienes are conjugated dienes having 4 to 12 carbon atoms, in particular 1,3-dienes, such as 1,3-butadiene and isoprene.

[0043] Suitable non-conjugated dienes are non-conjugated dienes with 6 to 12 carbon atoms, such as 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene.

[0044] Suitable olefins are vinylaromatic compounds having 8 to 20 carbon atoms and aliphatic α-monoolefins having 3 to 12 carbon atoms. Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methyl styrene, the commercial mixture "vinyl-toluene" and para-tert-butylstyrene. Suitable aliphatic α-monoolefins are, in particular, acylic aliphatic α-monoolefins having 3 to 18 carbon atoms.

[0045] More particularly, the isoprene elastomer may be chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), various isoprene copolymers and blends of these elastomers. Among the isoprene copolymers, mention will be made in particular of isoprene-styrene (SIR). Isobutene-isoprene copolymers (butyl rubber - IIR) are not part of the isoprene copolymers that can be used in the context of the invention because they are essentially saturated copolymers, having a content of diene origin units of less than 15% by mol.

[0046] This isoprene elastomer is preferably natural rubber or a synthetic cis-1,4 polyisoprene. Among these synthetic polyisoprenes, polyisoprenes having a rate (mol%) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%, are preferably used.

[0047] More particularly, the butadiene elastomer may be chosen from the group consisting of polybutadienes (BR), the various butadiene copolymers and the mixtures of these elastomers. Among the butadiene copolymers, mention will be made in particular of ethylene and butadiene copolymers (EBR), butadiene-styrene copolymers (SBR), isoprene-butadiene (BIR) or isoprene-butadiene-styrene (SBIR). For the sake of clarity, isoprene-butadiene and isoprene-butadiene-styrene elastomers are classified among the butadiene copolymers and not among the isoprene copolymers.

[0048] Suitable are polybutadienes and in particular those having a content (mol%) of -1,2 units of between 4% and 80% or those having a content (mol%) of cis-1,4 greater than 80%, polyisoprenes, butadiene-styrene copolymers and in particular those having a Tg (glass transition temperature (Tg, measured according to ASTM D3418-99)) of between 0°C and -90°C and more particularly between -10°C and -70°C, a styrene content of between 1% and 60% by weight and more particularly between 20% and 50%, a content (mol%) of -1,2 bonds of the butadiene part of between 4% and 75%, a content (mol%) of trans-1,4 bonds of between 10% and 80%, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5% and 90% by weight and a Tg of - 40°C to - 80°C, isoprene-styrene copolymers and in particular those having a styrene content of between 5% and 50% by weight and a Tg of between - 5 C and - 50°C.In the case of butadiene-styrene-isoprene copolymers, those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, an isoprene content of between 15% and 60% by weight and more particularly of between 20% and 50%, a butadiene content of between 5% and 50% by weight and more particularly of between 20% and 40%, a content (mol%) of -1,2 units in the butadiene part of between 4% and 85%, a content (mol%) of trans -1,4 units in the butadiene part of between 6% and 80%, a content (mol%) of -1,2 plus -3,4 units in the isoprene part of between 5% and 70% and a content (mol%) of trans -1,4 units in the isoprene part between 10% and 50%, and more generally any butadiene-styrene-isoprene copolymer having a Tg between - 5°C and - 70°C.

[0049] Advantageously, Diene Telastomer may be chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), isoprene-styrene copolymer (SIR), polybutadienes (BR), ethylene and butadiene copolymers (EBR), butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-butadiene-styrene copolymers (SB IR) and blends of these elastomers.

[0050] More advantageously still, Diene Telastomer can be chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), polybutadienes (BR), ethylene and butadiene copolymers (EBR), butadiene-styrene copolymers (SBR) and mixtures of these elastomers.

[0051] Even more advantageously, the diene elastomer may be an isoprene elastomer; even more preferably it is chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR) and mixtures of these elastomers.

[0052] The aforementioned diene elastomers can be modified, i.e. either coupled and / or star-shaped, or functionalized, or coupled and / or star-shaped and simultaneously functionalized.

[0053] Thus, the aforementioned diene elastomers, in particular when they are synthetic, can be coupled and / or star-shaped, for example by means of a silicon or tin atom which links the elastomer chains together.

[0054] The aforementioned diene elastomers may be simultaneously or alternatively functionalized and comprise at least one functional group. By functional group is meant a group comprising at least one heteroatom chosen from Si, N, S, O, P. Particularly suitable as functional groups are those comprising at least one function such as: silanol, an alkoxysilane, a primary, secondary or tertiary amine, cyclic or not, a thiol, an epoxide.

[0055] Particularly advantageously, the elastomeric composition of the invention may comprise from 60 to 100 phr, preferably from 70 to 100 phr, preferably from 80 to 100 phr, preferably from 90 to 100 phr, of a diene elastomer chosen from the group consisting of isoprene elastomers, butadiene elastomers and mixtures of these elastomers. According to one embodiment, the rubber composition may comprise from 60 to 99 phr, preferably 70 to 99 phr, for example from 80 to 98 phr, for example from 90 to 97 phr, of a diene elastomer chosen from the group consisting of isoprene elastomers, butadiene elastomers and mixtures of these elastomers; the remainder may be another different diene elastomer.

[0056] More particularly advantageously, the elastomeric composition of the invention may comprise from 60 to 100 phr, preferably from 70 to 100 phr, preferably from 80 to 100 phr, preferably from 90 to 100 phr, of an isoprene elastomer and mixtures of these elastomers. According to one embodiment, the rubber composition may comprise from 60 to 99 phr, preferably 70 to 99 phr, for example from 80 to 98 phr, for example from 90 to 97 phr, of an isoprene elastomer; the remainder may be another diene elastomer, preferably a butadiene elastomer as defined above.

[0057] Even more particularly advantageously, the elastomeric composition of the invention may comprise from 60 to 100 phr, preferably from 70 to 100 phr, preferably from 80 to 100 phr, preferably from 90 to 100 phr, of a diene elastomer chosen from the group consisting of natural rubber, synthetic polyisoprene and mixtures of these elastomers. According to one embodiment, the rubber composition may comprise from 60 to 99 phr, preferably 70 to 99 phr, for example from 80 to 98 phr, for example from 90 to 97 phr, of a diene elastomer chosen from the group consisting of natural rubber, synthetic polyisoprene and mixtures of these elastomers; the complement being able to be another diene elastomer, preferably a butadiene elastomer as defined above.

[0058] Charge

[0059] The elastomeric composition of the invention comprises fillers including a reinforcing filler and graphite.

[0060] By filler is meant here any type of filler, whether reinforcing or non-reinforcing or inert. As a reinforcing filler, it is known to those skilled in the art that it is carbon black or inorganic reinforcing fillers of the silica or alumina type. As a non-reinforcing or inert filler, it is known to those skilled in the art that it is graphite, clay, talc, mica, etc. In the context of the present invention, zinc oxide is not considered to be a non-reinforcing filler. It is an activator of the vulcanization system. The total level of fillers (i.e. the sum of the level of reinforcing fillers and non-reinforcing fillers) in the elastomeric composition of the present invention is less than or equal to 65 phr, preferably less than or equal to 60 phr, preferably less than or equal to 55 phr.More preferably, the total charge rate can be in a range from 20 to 65 pce, more preferably in a range from 25 to 60 pce, even more preferably from 25 to 55 pce. At this total charge rate, a good compromise of properties is obtained: resistance to aggression, rigidity, deformation at break and thermal conductivity.

[0061] Reinforcing charge

[0062] The elastomeric composition of the invention comprises a reinforcing filler, this reinforcing filler mainly comprising an acetylene black. In addition to acetylene black which is the predominant reinforcing filler, the elastomeric composition of the invention may optionally also comprise a second reinforcing filler such as silica and / or optionally a third reinforcing filler such as a carbon black different from acetylene carbon black, for example.

[0063] The total level of reinforcing filler, i.e. the level of acetylene black, the level of carbon black other than acetylene black if present and the level of silica when present, is less than or equal to 60 phr, more preferably less than or equal to 55 phr, more preferably less than or equal to 50 phr, more preferably less than or equal to 45 phr. This level of reinforcing filler is advantageously greater than or equal to 20 phr, more preferably greater than or equal to 25 phr, more preferably greater than or equal to 30 phr. Preferably, the level of reinforcing fillers in the elastomeric composition is within a range from 20 phr to 60 phr, more preferably from 25 phr to 55 phr, more preferably from 30 phr to 45 phr.

[0064] Acetylene black

[0065] Preferably, the acetylene black represents more than 55% by weight of the total weight of the reinforcing filler, more preferably still more than 60% by weight, more preferably still more than 80% by weight, more preferably still represents 100% by weight of the total weight of the reinforcing filler.

[0066] Thus, preferably the reinforcing filler content is less than or equal to 60 phr, more preferably less than or equal to 55 phr, more preferably less than or equal to 50 phr, more preferably less than or equal to 45 phr and the acetylene black represents more than 55% by weight of the total weight of the reinforcing filler, more preferably still more than 60% by weight, more preferably still more than 80% by weight, more preferably still represents 100% by weight of the total weight of the reinforcing filler.

[0067] Even more preferably, the level of reinforcing fillers in the elastomeric composition is within a range from 20 phr to 60 phr, more preferably from 25 phr to 55 phr, more preferably from 30 phr to 45 phr and the acetylene black represents more than 55% by weight of the total weight of the reinforcing filler, more preferably still more than 60% by weight, more preferably still more than 80% by weight, more preferably still represents 100% by weight of the total weight of the reinforcing filler.

[0068] The reinforcing fillers that can be used in the context of the present invention are described below.

[0069] The reinforcing filler mainly consists of acetylene black.

[0070] The acetylene black that can be used in the context of the present invention is a finely divided, amorphous carbon black, well known to those skilled in the art of tires.

[0071] It is generally obtained by thermal decomposition of a specific raw material which is acetylene.

[0072] The acetylene blacks usable in the context of the present invention may have a BET specific surface area, measured according to the ASTM D-3037 standard dated 1993, greater than or equal to 40 m 2 / g, preferably greater than or equal to 50 m 2 / g, preferably within a range of 55 to 160 m 2 / g, more preferably ranging from 60 to 150 m 2 / g.

[0073] The acetylene blacks usable in the present invention may preferably have an iodine absorption index measured according to standard ASTM D1510-21 greater than or equal to 65 m 2 / g, more preferably greater than or equal to 70 m 2 / g, more preferably still included in a range from 80 to 140 m 2 / g, more preferably still ranging from 85 to 130 m 2 / g.

[0074] The acetylene blacks usable in the present invention may preferably have an oil absorption index measured according to standard ASTM D1510-21 greater than or equal to 150 m 2 / g, more preferably greater than or equal to 155 m 2 / g, more preferably still included in a range from 160 to 260 m 2 / g, more preferably still ranging from 160 to 230 m 2 / g.

[0075] Acetylene blacks are well known to those skilled in the art and are commercially available from DENKA, ORION etc.

[0076] Carbon black other than carbon black derived from acetylene

[0077] According to one embodiment of the invention, the elastomeric composition may comprise, in addition to acetylene black, another carbon black different from acetylene black.

[0078] Carbon black other than acetylene black is a finely divided, amorphous carbon black well known to those skilled in the art of tires. It is generally obtained by thermal decomposition or incomplete combustion of hydrocarbons using the heat produced by the complete combustion of a fuel by air. The process for obtaining carbon black is the furnace process. Suitable carbon blacks other than acetylene black are all carbon blacks, in particular ASTM grade carbon black (carbon black classified according to ASTM D1765-17). Among these, we will particularly mention the reinforcing carbon blacks of the 100, 200, 300 series, or the 500, 600 or 700 series blacks (ASTM D-1765-2017 grades), such as for example blacks NI 15, N134, N234, N326, N330, N339, N347, N375, N550.These carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a support for some of the rubber additives used. The carbon blacks could, for example, already be incorporated into the diene elastomer, in particular isoprene, in the form of a masterbatch (see, for example, applications WO97 / 36724-A2 or WO99 / 16600-A1).

[0079] Carbon black other than acetylene black which may optionally be used in elastomeric compositions has little or no conductive properties. It therefore does not belong to the category of conductive carbon blacks. Carbon blacks are distinguished in particular from conductive carbon blacks by their structure, measurable by the oil absorption index evaluated according to the ASTM D2414-22 standard. Preferably, the carbon black other than acetylene black which can be used in the present invention has an oil absorption index measured according to the ASTM D2414-22 standard ("OAN index") in a range from 30 ml / 100g to 150 ml / 100g. Carbon blacks having conductive properties, also called conductive carbon black, have an oil absorption index measured according to the ASTM D2414-22 standard generally greater than 155 ml / 100g.

[0080] Preferably, the elastomeric composition of the invention contains less than 10 phr of carbon black other than acetylene black. More preferably, the elastomeric composition of the invention is free of carbon black other than acetylene black.

[0081] Silica

[0082] According to one embodiment of the invention, the elastomeric composition may comprise, in addition to acetylene black, a silica, in particular a precipitated silica, as a reinforcing filler and may further comprise an agent for coupling the silica to the diene elastomer of the elastomer matrix. In a known manner, the silicas may be characterized in particular by the presence of hydroxyl groups (-OH) on their surface.

[0083] The silica (SiCL) used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or pyrogenic silica having a BET specific surface area and a CTAB specific surface area both less than 450 m 2 / g, preferably within a range of 30 to 400 m 2 / g, especially from 60 to 300 m 2 / g.

[0084] Any type of precipitated silica may be used, in particular highly dispersible precipitated silicas (called "HDS" for "highly dispersible" or "highly dispersible silica"). These precipitated silicas, whether highly dispersible or not, are well known to those skilled in the art. Examples include the silicas described in applications WO03 / 016215-A1 and WO03 / 016387-A1. Among the commercial HDS silicas, it is possible to use in particular the silicas "Ultrasil ® 5000GR", "Ultrasil ® 7000GR" from the company Evonik, the silicas "Zeosil ® 1085GR", "Zeosil® 1115 MP", "Zeosil® 1165MP", "Zeosil® Premium 200MP", "Zeosil® HRS 1200 MP" from the company Solvay.As non-HDS silica, the following commercial silicas can be used: silicas “Ultrasil ® VN2GR”, “Ultrasil ® VN3GR” from Evonik, silica “Zeosil® 175GR” from Solvay, silicas “Hi-Sil EZ120G(-D)”, “Hi-Sil EZ160G(-D)”, “Hi-Sil EZ200G(-D)”, “Hi-Sil 243LD”, “Hi-Sil 210”, “Hi-Sil HDP 320G” from PPG.

[0085] The physical state in which the reinforcing inorganic filler is presented is indifferent, whether in the form of powder, microbeads, granules, or even beads or any other suitable densified form. Of course, the term reinforcing inorganic filler also means mixtures of different reinforcing inorganic fillers, in particular silicas as described above.

[0086] The rate of silica used is always lower than the rate of black used, since silica is a minority reinforcing inorganic filler in the elastomeric composition. Preferably, the silica represents 45% by weight or less of the total weight of the reinforcing filler, more preferably represents 40% by weight or less, more preferably represents 20% by weight or less of the total weight of the reinforcing filler.

[0087] The BET specific surface area of ​​silica is determined by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society" (Vol. 60, page 309, February 1938), and more precisely according to a method adapted from the NF ISO 5794-1 standard, annex E of June 2010 [multipoint volumetric method (5 points) - gas: nitrogen - vacuum degassing: one hour at 160°C - relative pressure range p / po: 0.05 to 0.17],

[0088] For inorganic fillers such as silica, for example, the CTAB specific surface area values ​​were determined according to standard NF ISO 5794-1, annex G of June 2010. The process is based on the adsorption of CTAB (N-hexadecyl-N,N,N-trimethylammonium bromide) on the "external" surface of the reinforcing filler.

[0089] To couple the silica to the diene elastomer, it is possible to use, in a well-known manner, an at least bifunctional coupling agent (or bonding agent) intended to ensure a sufficient connection, of a chemical and / or physical nature, between the silica (surface of its particles) and the diene elastomer. In particular, at least bifunctional organosilanes or polyorganosiloxanes are used. By "bifunctional", we mean a compound having a first functional group capable of interacting with the inorganic filler and a second functional group capable of interacting with the diene elastomer. For example, such a bifunctional compound may comprise a first functional group comprising a silicon atom, said first functional group being capable of interacting with the hydroxyl groups of an inorganic filler and a second functional group comprising a sulfur atom, said second functional group being capable of interacting with the diene elastomer.

[0090] Preferably, the organosilanes are chosen from the group consisting of polysulfurized organosilanes (symmetrical or asymmetrical) such as bis(3-triethoxysilylpropyl) tetrasulfide, abbreviated TESPT, marketed under the name “Si69” by the company Evonik or bis-(triethoxysilylpropyl) disulfide, abbreviated TESPD, marketed under the name “Si75” by the company Evonik, polyorganosiloxanes, mercaptosilanes, blocked mercaptosilanes, such as S-(3-(triethoxysilyl)propyl) octanethioate marketed by the company Momentive under the name “NXT Silane”. More preferably, the organosilane is a polysulfurized organosilane.

[0091] Typically the coupling agent content represents from 0.5% to 15% by weight relative to the amount of reinforcing inorganic filler. This content is easily adjusted by a person skilled in the art according to the silica content used in the elastomeric composition of the invention. The elastomeric compositions of the invention may also contain silica-covering agents when such a filler is used, making it possible to improve their processability in the raw state.These coating agents are well known (see for example patent applications WO2006 / 125533-A1, WO2007 / 017060-A1 and WO2007 / 003408-A1), examples of which are hydrolyzable silanes such as hydroxysilanes (see for example WO2009 / 062733-A2), alkylalkoxysilanes, polyols (for example diols or triols), polyethers (for example polyethylene glycols), primary, secondary or tertiary amines, hydroxylated or hydrolyzable polyorganosiloxanes (for example α,β-dihydroxy-poly-organosilanes (see for example EP0784072-A1).

[0092] When present, the silica content in the elastomeric composition usable in the context of the invention is preferably within a range from 5 to 20 pce, more preferably from 7 to 15 pce.

[0093] Graphite

[0094] The composition of the invention comprises at least one graphite. The elastomeric composition of the invention may contain a single graphite as described below or a mixture of several graphites as described below.

[0095] Graphite is generally understood to mean a set of stacked graphene planes, graphene being an atomic-thick sheet in which the carbon atoms are arranged in a predominantly hexagonal lattice. Unlike the aforementioned carbon blacks, graphite therefore has a crystalline structure.

[0096] Graphite can be natural or synthetic. When graphite is synthetic, it can be obtained through a complex process of cooking petroleum coke at very high temperatures.

[0097] Graphite is not considered a reinforcing filler and is therefore not included in the calculation of reinforcing fillers. Graphite is a filler and is therefore included in the calculation of the total filler rate.

[0098] The graphite usable in the context of the present invention has a crystallite size noted Le comprised in a range from 80 to 500 nm, more preferably from 90 to 400 nm, more preferably from 100 to 300 nm. The measurement of the crystallite size is described in paragraph 1 of the methods and measurements section.

[0099] The graphite usable in the context of the present invention may have a BET specific surface area in a range from 10 to 50 m 2 / g; preferably ranging from 15 to 40 m 2 / g, more preferably still ranging from 20 to 30 m 2 / g. The measurement of the BET specific surface area is described in paragraph 2 of the methods and measurements section.

[0100] The graphite usable in the context of the present invention may have a particle size distribution D90 comprised in a range from 50 to 150 pm, more preferably from 60 to 140 pm, even more preferably from 70 to 130 pm. The D90 corresponds to the 90th percentile of the mass distribution of particle size, that is to say that 90% by mass of the particles have a size less than the D90 and 10% by mass of the particles have a size greater than the D90. It is expressed in pm. The measurement of the D90 is described in paragraph 3 of the methods and measurements section.

[0101] Preferably, the graphite usable in the context of the present invention is an expanded graphite.

[0102] Preferably, the level of graphite in the elastomeric composition of the present invention is within a range from 1 to 12 pce, more preferably from 1 to 11 pce.

[0103] Preferably, the mass ratio of graphite relative to acetylene black in the elastomeric composition is within a range from 0.05 to 0.5, preferably from 0.06 to 0.4.

[0104] The graphites that can be used in the context of the present invention are commercially available from suppliers such as Imerys for example.

[0105] Surprisingly, the inventors have identified that the use of the aforementioned graphite in an elastomeric composition for tires carrying heavy loads, particularly of the civil engineering type, makes it possible to obtain a good compromise of properties of resistance to aggression, rigidity, deformation at break and thermal conductivity, or even to improve this compromise of properties compared to the compositions of the prior art. Advantageously, the quantity of reinforcing fillers in the elastomeric composition can even be reduced.

[0106] Vulcanization system

[0107] The elastomeric composition of the invention comprises a vulcanization system known to those skilled in the art in the field of elastomeric compositions for tires.

[0108] Sulfur can be supplied in any form, including molecular sulfur, or a sulfur-donating agent.

[0109] At least one vulcanization accelerator is also preferably present, and, optionally, also preferably, various known vulcanization activators may be used such as zinc oxide, stearic acid or equivalent compound such as stearic acid salts and transition metal salts, guanidine derivatives (in particular diphenylguanidine), or even known vulcanization retarders. Note that zinc oxide is considered a vulcanization activator and not a filler. It is therefore not taken into account in the calculation of the total filler content.

[0110] Sulphur is used at a preferential rate ranging from 0.5 to 10 pce, in particular from 1 to 5 pce.

[0111] The vulcanization accelerator is used at a preferential rate in the range of 0.5 to 10 pce, more preferably in the range of 0.5 to 5.0 pce.

[0112] Any compound capable of acting as an accelerator for the vulcanization of diene elastomers in the presence of sulfur may be used as an accelerator, in particular accelerators of the thiazole type and their derivatives, accelerators of the sulfenamide, thiuram, dithiocarbamate, dithiophosphate, thiourea and xanthate types. Examples of such accelerators include, but are not limited to, the following compounds: 2-mercaptobenzothiazyl disulfide (abbreviated as "MBTS"), N-cyclohexyl-2-benzothiazyl sulfenamide ("CBS"), N,N-dicyclohexyl-2-benzothiazyl sulfenamide ("DCBS"), N-tert-butyl-2-benzothiazyl sulfenamide ("TBBS"), N-tert-butyl-2-benzothiazyl sulfenimide ("TB SI"), tetrabenzylthiuram disulfide ("TBZTD"), zinc dibenzyldithiocarbamate ("ZBEC") and mixtures of these compounds.

[0113] Plasticizers

[0114] The elastomeric composition of the invention may optionally comprise at least one plasticizer.

[0115] In a manner known to those skilled in the art of elastomeric compositions for tires, this plasticizer is preferably chosen from high glass transition temperature (Tg) hydrocarbon resins, low Tg hydrocarbon resins, plasticizing oils and mixtures thereof. Preferably, the plasticizer is chosen from high Tg hydrocarbon resins, plasticizing oils and mixtures thereof.

[0116] A high Tg hydrocarbon resin is by definition a solid at room temperature and pressure (20°C, 1 atm), while a plasticizing oil is liquid at room temperature and a low Tg hydrocarbon resin is viscous at room temperature.

[0117] The total level of plasticizer in the elastomeric composition of the invention may be within a range from 0 to 10 pce, more preferably from 0 to 5 pce.

[0118] Preferably, if the elastomeric composition comprises a plasticizer, the plasticizer is a hydrocarbon resin having a Tg greater than 20°C.

[0119] Preferably, if the elastomeric composition comprises a plasticizer, preferably a hydrocarbon resin having a Tg greater than 20°C, the level of plasticizer is within a range from 1 to 10 pce, preferably from 1 to 5 pce.

[0120] Preferably, the elastomeric composition is free of plasticizer.

[0121] Hydrocarbon resins, also called hydrocarbon plasticizing resins, are polymers well known to those skilled in the art, essentially based on carbon and hydrogen but which may contain other types of atoms, for example oxygen, which can be used in particular as plasticizing agents or tackifying agents in polymer matrices. They are by nature at least partially miscible (i.e., compatible) at the rates used with the polymer compositions for which they are intended, so as to act as true diluting agents. They have been described for example in the work entitled "Hydrocarbon Resins" by R. Mildenberg, M. Zander and G. Collin (New York, VCH, 1997, ISBN 3-527-28617-9) of which chapter 5 is devoted to their applications, in particular in pneumatic rubber (5.5. "Rubber Tires and Mechanical Goods").As is known, these hydrocarbon resins can also be called thermoplastic resins in the sense that they soften upon heating and can thus be molded. Hydrocarbon resins can be aliphatic, or aromatic or of the aliphatic / aromatic type, that is to say based on aliphatic and / or aromatic monomers. They can be natural or synthetic, based on petroleum or not (if this is the case, also known as petroleum resins).

[0122] Plasticizers are commercially available from suppliers such as Arizona, Kraton, Exxon, etc.

[0123] Other additives

[0124] The elastomeric compositions in accordance with the invention may also comprise all or part of the usual additives and processing agents, known to those skilled in the art and usually used in elastomeric compositions for tires, such as fillers (reinforcing or non-reinforcing / other than those mentioned above), pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, antioxidants, anti-fatigue agents, reinforcing resins (as described for example in application WO 02 / 10269).

[0125] Manufacture of elastomeric compositions

[0126] The elastomeric compositions in accordance with the invention can be manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art:

[0127] - a first phase of working or thermomechanical mixing (so-called "non-productive" phase), which can be carried out in a single thermomechanical step during which all the necessary constituents are introduced into a suitable mixer such as a conventional internal mixer (for example of the 'Banbury' type), in particular the elastomer matrix, the fillers (in particular acetylene black and graphite), any other various additives, with the exception of the crosslinking system. The incorporation of the filler into the elastomer can be carried out in one or more stages by thermomechanical mixing.In the case where the filler is already incorporated in whole or in part into the elastomer in the form of a masterbatch as described for example in applications WO 97 / 36724 or WO 99 / 16600, it is the masterbatch which is directly mixed and where appropriate the other elastomers or fillers present in the composition which are not in the form of a masterbatch are incorporated, as well as any other various additives other than the crosslinking system.

[0128] The non-productive phase can be carried out at high temperature, up to a maximum temperature in the range from 110°C to 200°C, preferably in the range from 130°C to 185°C, for a duration generally in the range from 2 to 10 minutes.

[0129] - a second phase of mechanical work (so-called "productive" phase), which is carried out in an external mixer such as a roller mixer, after cooling the mixture obtained during the first non-productive phase to a lower temperature, typically below 120°C, for example in a range from 40°C to 100°C. The crosslinking system is then incorporated, and everything is then mixed for a few minutes, for example in a range from 5 to 15 min.

[0130] The final composition thus obtained is then calendered, for example, in the form of a sheet or plate, in particular for characterization in the laboratory, or extruded in the form of an elastomeric semi-finished product (or profile) usable for the manufacture of a tire.

[0131] The composition can be either in the raw state (before crosslinking or vulcanization), or in the cooked state (after crosslinking or vulcanization), can be a semi-finished product which can be used in a tire.

[0132] The crosslinking of the composition can be carried out in a manner known to those skilled in the art, for example at a temperature in the range from 100°C to 200°C, under pressure.

[0133] Pneumatic

[0134] The present invention also relates to a tire comprising an elastomeric composition of the invention as described above.

[0135] Given the improved compromise of properties within the framework of the present invention, the tire is a tire for vehicles carrying heavy loads, advantageously chosen from the group consisting of heavy-duty tires, civil engineering tires, mining tires, aircraft tires, bus tires, metro tires and agricultural tires.

[0136] The elastomeric composition of the invention can be used in any type of position of these different tires.

[0137] The tire according to the invention has better resistance to attacks, better rigidity, better deformation at break and better thermal conductivity. It therefore has better endurance and, given its good thermal conductivity, can roll faster in safety.

[0138] METHODS AND MEASURES:

[0139] 1- Measurement of the size of crystallites by X-ray diffraction

[0140] The crystallite size Le is determined from the full width at half maximum of the peaks (commonly called FWHM) obtained by analysis of X-ray diffraction patterns.

[0141] The contribution to the broadening of the diffraction peak is mainly related to the size of the crystallites, the presence of irregularities in the atomic stacking, point, linear or plane defects and finally to an instrumental part. For the graphite powder, only the size of the crystallites is considered significant and will be measured using the Scherrer formula:

[0142] [Math 1] with K the form factor (0.89), A the wavelength of Cu Ka (1.541874Â) and 9 the angle of the plane diffraction peak (002) (in rad).

[0143] The preparation and acquisition follow the method described in the AFNOR standards NF EN 13925-1, NF EN 13925-2, NF EN 13925-3 published in 2003.

[0144] Data are collected using a Malvern PANalytical Empyrean diffractometer coupled with a PIXcel3D-Medipix3 detector. The diffractometer has the following characteristics, as shown in Table 1:

[0145] [Table 2]

[0146] Table 1: Instrument data and measurement parameters

[0147] Data were analyzed using PANalytical X'Pert HighScore Plus software.

[0148] 2- Measurement of the BET specific surface area of ​​graphite

[0149] The method is based on recording the absorption isotherm of liquid nitrogen in the range p / pO = 0.04-0.26 at 77 K. Following the procedure proposed by Brunauer, Emmet and Teller (Adsorption of Gases in Multimolecular Layers, J. Am. Chem. Soc, 1938, 60, 309-319), the monolayer capacity can be determined. Based on the cross-section of the nitrogen molecule, the monolayer capacity and the weight of the sample, the specific surface area can then be calculated.

[0150] 3 -Measurement of graphite particle size The mass distribution of graphite particle size can be measured by laser granulometry, on a mastersizer 3000 type device from Malveme. The measurement is carried out in liquid form, diluted in alcohol after a preliminary treatment of 1 min of ultrasound to ensure the dispersion of the particles. The measurement is carried out in accordance with the ISO- 13320-1 standard dated 2009 and makes it possible to determine in particular the D90, that is to say the average diameter below which 90% by mass of the total population of particles is present.

[0151] 4-Thermal conductivity:

[0152] The thermal conductivity of a material is a physical quantity that characterizes the ability of a material to allow heat transfer by conduction. It represents the quantity of heat transferred per unit of surface area and time, under a temperature gradient of 1 degree Kelvin and per meter. It is expressed in W.m'hK' 1 . Thus a thermal conductivity of 1 Wm -1 .K -1 represents the amount of heat that propagates through a material by thermal conduction, across a surface of 1 m 2 , over a distance of 1 m.

[0153] Thermal conductivity is measured at room temperature (23°C) on a Hotdisk TPS 2500 thermal analyzer with a type 5501 probe, according to ISO 22007-2: 2015. The measuring specimen (consisting of the cooked composition to be analyzed) is circular in shape (diameter 5 cm, thickness 5 mm) and the measurement is carried out in the direction of the thickness.

[0154] The results are given in base 100, with the arbitrary value 100 being assigned to the control to calculate and compare the thermal conductivity of the different samples tested. The value in base 100 for the sample to be tested is calculated according to the operation: (thermal conductivity value of the sample to be tested / thermal conductivity value of the control) x 100. In this way, a result below 100 will indicate a decrease in thermal conductivity and therefore a decrease in heat transfer by conduction. Conversely, a result above 100 will indicate an increase in thermal conductivity and therefore an improvement in heat transfer by conduction.

[0155] 5- Tensile tests:

[0156] These tensile tests are used to determine the properties at break. Unless otherwise indicated, they are based on the French standard NF T46-002 of September 1988.

[0157] A treatment of the tensile recordings allows the modulus curve to be plotted as a function of elongation. The breaking stresses (in MPa) and the elongations at break (in %) are recorded.

[0158] All these traction measurements are carried out at a temperature of 60°C ± 2°C, and under normal hygrometry conditions (50 ± 5% relative humidity) according to the French standard NF T40-101 (December 1979).

[0159] Thus, the energy to cause rupture (fracture energy) of the specimen can be determined, which is the product of the breaking stress and the elongation at rupture (fracture energy = breaking stress * elongation at rupture). The results are given on a base of 100; the arbitrary value 100 is assigned to the control for the breaking stress, the elongation at rupture and the breaking energy respectively. A result below 100 for the breaking stress, the elongation at rupture or the breaking energy indicates a decrease in the value concerned, which corresponds to a decrease in the breaking strain property and conversely, a result above 100 indicates an increase in this value, which corresponds to an improvement in the breaking strain.

[0160] 6-Mechanical resistance in the presence of crack initiation

[0161] Measurement of mechanical resistance in the presence of crack initiation (tearability): The force and tear deformation are measured on a specimen stretched at 375 mm / min to cause the specimen to rupture. The tensile specimen consists of a parallelepiped-shaped rubber plate, 2.5 mm thick, 84 mm long and 10 mm wide. Three very fine notches 3 mm long are made using a razor blade, halfway along and aligned in the width direction of the specimen, before starting the test. The force (N / mm) to be exerted to obtain rupture is determined and the elongation at rupture is measured. The Energy to cause rupture (Tear Energy) of the specimen can be determined, which is the product of the force and the elongation at rupture. The test was conducted in air at a temperature of 100°C.The results are given on a base of 100, with the arbitrary value 100 being assigned to the control to calculate and compare the fracture energy of the different samples tested. High values ​​reflect good cohesion of the rubber composition although showing crack initiations, which corresponds to an improvement in the tear resistance performance.

[0162] 7-Dynamic properties:

[0163] The dynamic property tan(ô)max is measured on a viscoanalyzer (Metravib VA4000), according to the ASTM D 5992-96 standard. The response of a sample of vulcanized composition (cylindrical specimen 4 mm thick and 400 mm2 in cross-section) is recorded, subjected to sinusoidal stress in alternating simple shear, at a frequency of 10 Hz and a temperature of 100°C7 according to the ASTM D 1349-99 standard. A strain amplitude sweep is carried out from 0.1 to 50% (forward cycle), then from 50% to 0.1% (return cycle). The result used is the complex dynamic shear modulus G*. On the return cycle, the value of G* at 35% strain is recorded.

[0164] The results are given in base 100, with the arbitrary value 100 being assigned to the control to calculate and compare the complex modulus G*35% of the different samples tested. The value in base 100 for the sample to be tested is calculated according to the operation: (value of the complex modulus G*35% of the sample to be tested / value of the complex modulus G*35% of the control) x 100. In this way, a result lower than 100 will indicate a decrease in the complex modulus G*35% and therefore a decrease in the stiffness of the composition. Conversely, a result higher than 100 will indicate an increase in the complex modulus G*35% and therefore an improvement in the stiffness of the composition.

[0165] 8- Microstructure of diene elastomers:

[0166] The microstructure of elastomers is characterized by the near infrared spectroscopy (NIR) technique.

[0167] Near infrared spectroscopy (NIR) is used to quantitatively determine the mass content of styrene in the elastomer as well as its microstructure (relative distribution of 1,2-, 1,4-trans and 1,4-cis butadiene units). The principle of the method is based on the Beer-Lambert law generalized to a multicomponent system. Since the method is indirect, it uses a multivariate calibration [Vilmin, F.; Dussap, C.; Coste, N. Applied Spectroscopy 2006, 60, 619-29] carried out using standard elastomers of composition determined by NMR 13 C. The styrene content and microstructure are then calculated from the NIR spectrum of an elastomer film approximately 730 pm thick. The spectrum acquisition is carried out in transmission mode between 4000 and 6200 cm' 1 with a resolution of 2 cm' 1 , using a Bruker Tensor 37 Fourier transform near-infrared spectrometer equipped with a Peltier-cooled InGaAs detector.

[0168] EXAMPLES

[0169] Test No. 1:

[0170] The purpose of this test is to demonstrate that the elastomeric compositions of the invention present a better compromise of properties - resistance to aggression, rigidity, deformation at break and thermal conductivity - compared to a composition of the prior art.

[0171] For this, 4 elastomeric compositions are prepared, particularly intended for the manufacture of tires carrying heavy loads, in particular for a civil engineering tire:

[0172] T0 is a control composition not including graphite and which presents a good compromise of properties - resistance to aggression, rigidity, deformation at break and thermal conductivity; it represents the state of the prior art;

[0173] Tl is a control composition comprising graphite;

[0174] C1 and C2 are compositions according to the invention comprising a specific graph.

[0175] Table 2 gives the formulation of the different compositions, the rates being expressed in pce (parts by weight per hundred parts by weight of elastomers).

[0176] [Table 2]

[0177] (1) Natural rubber

[0178] (2) Acetylene black with a BET specific surface area of ​​74 m 2 / g measured according to ASTM D-3037 dated 1993, an iodine absorption index = 92 mg / g measured according to ASTM D1510-21, an oil absorption index (OAN) measured according to D2414-22 equal to 160 ml / 100g. This type of acetylene black can be sold by under the reference "Denka Black".

[0179] (3) Natural graphite of 150 mesh (in English “150 mesh graphite”), having a specific surface area BET = 0.5 m 2 / g, a D9o=15O pm and a Lc=493 nm. This graphite is marketed by Imerys under the reference “Timrex 80*150”. The BET specific surface area, the D90 and the crystallite size Le are measured according to the methods described above. (4) Expanded graphite with a BET specific surface area = 25 m 2 / g, a Ü9o= 105 pm and a

[0180] Lc=157 nm. This graphite is marketed by Imerys under the reference “Timex C-Term 001”. The BET specific surface area, D90 and crystallite size Le are measured according to the methods described above.

[0181] (5) Nl,3-dimethylbutyl-N-phenyl-para-phenylenediamine marketed by Flexys under the reference “Santoflex 6-PPD”

[0182] (6) Stearin marketed by the company Uniquema under the name “Pristerene 4931) (7) N-cyclohexyl-2-benzothiazyl-sulfenamide marketed by Flexys under the reference “Santocure CBS”

[0183] (8) diphenylguanidine marketed by Flexys under the reference “Perkacit”

[0184] (9) Silica “Zeozil 1165 MP” type HDS marketed by the company Solvay, CTAB specific surface area equal to 160 m 2 / g and a BET specific surface area equal to 165 m 2 / g.

[0185] (10) Coupling agent Bis[3-(triethoxysilyl)propyl] tetrasulfide silane (TESPT) marketed by Evonik under the reference “Si69”

[0186] (11) Polyethylene glycol marketed by Dow Corning under the reference “carbowax 8000”

[0187] The elastomeric compositions to be tested are prepared as follows: the natural rubber, then the reinforcing filler, the graphite, and then the various other ingredients except for the sulfur and the vulcanization accelerator are introduced into an internal mixer, filled to 70% and with an initial tank temperature of approximately 60°C. Thermomechanical work (non-productive phase) is then carried out in one or two stages (total mixing time equal to approximately 3 to 6 min, until a maximum "fall" temperature of approximately 160-165°C is reached). The elastomeric compositions are prepared as indicated above. The silica, the coupling agent and the PEG are added during the non-productive phase of the manufacturing process. The resulting mixture is recovered, cooled and then sulfur and vulcanization accelerator are added to an external mixer (homo-finisher) at 40°C, mixing everything (productive phase) for 4 to 10 minutes.

[0188] The compositions are then shaped for measurements of their physical or mechanical properties (for example in the form of test pieces) and if necessary cooked (or vulcanized) for measurements of the cured properties.

[0189] The properties measured after cooking at 120°C for 300 min are reported in Table 3.

[0190] [Table 3] Compared to the TO elastomeric composition, the use of a 150 mesh natural graphite improves thermal conductivity and elongation at break but at the expense of rigidity, breaking energy and tearing energy (and therefore resistance to aggression).

[0191] The use of a graphite having a crystallite size of 157 nm (elastomeric composition according to the invention C1) surprisingly makes it possible to obtain the same thermal conductivity and the same elongation at break as those of the control composition T1. On the other hand, it provides properties of breaking energy, tearing energy and rigidity which are significantly higher than those of the control composition T1 and comparable to those of the control composition T0. These effects are obtained with a graphite content which is significantly lower than the graphite content used in the elastomeric composition T1.

[0192] Advantageously, the compromise of properties - resistance to aggression, rigidity, deformation at break and thermal conductivity - is always improved even when the graphite content is increased without increasing the filler content. The elastomeric composition according to the invention C2 generally has better properties compared to the control compositions T0 and TL

[0193] Test #2:

[0194] The purpose of this test is to demonstrate that the elastomeric compositions of the invention have a better compromise of properties - resistance to aggression, rigidity, deformation at break and thermal conductivity - compared to a composition of the prior art. These compositions do not include silica.

[0195] For this, 4 elastomeric compositions are prepared, particularly intended for the manufacture of tires for heavy goods vehicle tires:

[0196] T2 is a control composition not including graphite and which presents a good compromise of properties - resistance to aggression, rigidity, deformation at break and thermal conductivity;

[0197] T3 is a control composition comprising graphite;

[0198] C3 and C4 are compositions according to the invention comprising a specific graph.

[0199] Table 4 gives the formulation of the different compositions, the rates being expressed in pce (parts by weight per hundred parts by weight of elastomers).

[0200] [Table 4]

[0201] Ingredients (1) to (8) are the same as those in the compositions of Table 2.

[0202] The compositions are then shaped for measurements of their physical or mechanical properties (for example in the form of 4 mm test pieces, etc.) and if necessary cooked (or vulcanized) for measurements of the cured properties.

[0203] The properties measured after cooking at 120°C for 300 min are reported in Table 5.

[0204] [Table 5] As with the previous compositions, the elastomeric compositions according to the invention C3 and C4 comprise the best compromise of properties - resistance to aggression, rigidity, deformation at break and thermal conductivity - compared to the control compositions T3 and T4.

Claims

Claims 1. Elastomeric composition for a tire carrying heavy loads based on at least one elastomer matrix, fillers including graphite and a reinforcing filler and a vulcanization system, characterized in that: the elastomer matrix comprises at least 50 pce of a diene elastomer chosen from the group consisting of isoprene elastomers, butadiene elastomers and mixtures of these diene elastomers, the reinforcing filler mainly comprises an acetylene black, the graphite has a crystallite size Le in a range from 80 to 500 nm, more preferably from 90 to 400 nm, more preferably from 100 to 300 nm, the total filler content is less than or equal to 65 pce.

2. Elastomeric composition according to claim 1, in which the total rate of fillers is less than or equal to 60 pce, preferably less than or equal to 55 pce.

3. Elastomeric composition according to claim 1, in which the total rate of fillers is within a range from 20 to 65 phr, more preferably within a range from 25 to 60 phr, more preferably still from 25 to 55 phr.

4. Elastomeric composition according to any one of the preceding claims, in which the graphite has a BET specific surface area in a range from 10 to 50 m 2 / g, preferably ranging from 15 to 40 m 2 / g, more preferably still ranging from 20 to 30 m 2 / g.

5. Elastomeric composition according to any one of the preceding claims, in which the graphite has a particle size distribution D90 comprised in a range from 50 to 150 pm, more preferably from 60 to 140 pm, even more preferably from 70 to 130 pm.

6. Elastomeric composition according to any one of the preceding claims, in which the graphite is an expanded graphite.

7. Elastomeric composition according to any one of the preceding claims, in which the reinforcing filler further comprises at least one precipitated silica and the composition further comprises an agent for coupling the silica to the diene elastomer of the elastomeric matrix.

8. Elastomeric composition according to claim 7, in which the silica content is within a range from 5 to 20 phr, more preferably from 7 to 15 phr and the coupling agent content represents from 0.5% to 15% by weight relative to the quantity of silica.

9. Elastomeric composition according to any one of the preceding claims, in which the graphite content is within a range from 1 to 12 pce, more preferably from 2 to 11 pce.

10. Elastomeric composition according to any one of the preceding claims, in which the level of diene elastomer is within a range from 60 to 100 pce, preferably from 70 to 100 pce, preferably from 80 to 100 pce, preferably from 90 to 100 pce.

11. Elastomeric composition according to any one of the preceding claims, in which the diene elastomer is selected from the group consisting of natural rubber, synthetic polyisoprene, isoprene-styrene copolymers, polybutadienes, ethylene-butadiene copolymers, butadiene-styrene copolymers, isoprene-butadiene copolymers, isoprene-butadiene-styrene copolymers and mixtures of these diene elastomers, preferably selected from the group consisting of natural rubber, synthetic polyisoprene, polybutadienes, ethylene-butadiene copolymers, butadiene-styrene copolymers and mixtures of these diene elastomers, more preferably still is selected from the group consisting of natural rubber, synthetic polyisoprene and the mixture of these diene elastomers.

12. Elastomeric composition according to any one of the preceding claims, in which the level of reinforcing fillers is less than or equal to 60 phr, more preferably less than or equal to 55 phr, more preferably less than or equal to 50 phr, more preferably less than or equal to 45 phr.

13. An elastomeric composition according to any one of the preceding claims, wherein the acetylene black has an oil absorption index measured according to ASTM D1510-21 of greater than or equal to 150 m. 2 / g, more preferably greater than or equal to 155 m 2 / g, more preferably still included in a range from 160 to 260 m 2 / g, more preferably still ranging from 160 to 230 m 2 / g.

14. Heavy-duty tire comprising at least one composition according to any one of claims 1 to 13, preferably the tire is a civil engineering tire or a heavy-duty tire.

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