Rubber composition and rubber article incorporating it.

Abstract

The invention relates to a rubber composition based on at least one EPM copolymer or one EPDM terpolymer, and a rubber article incorporating it, such as a seal or a pipe (10) eg for an air, water or cooling circuit equipping a fuel cell.The composition comprises:- a filler comprising a carbon black and a lamellar inorganic filler,- a processing aid system,- a plasticizer system, and- a crosslinking system comprising a peroxide,wherein the composition comprises, in mass fractions: 28-32% of the carbon black, which is selected from ASTM N600 or N700 series blacks, and those having a specific surface area of ​​15-25 m² / g, an iodine adsorption index of 16-24 mg / g and a DBP absorption index of 90-110 mL / 100 g, 10-20% of the lamellar inorganic filler, 1.0-6.0% of the processing aid system, which comprises a carbon black covering agent, and 10-22% of the plasticizer system. Fig. 2.

Description

Title of the invention: Rubber composition and rubber article incorporating it. Technical field

[0001] The invention relates to a rubber composition based on at least one ethylene-propylene copolymer (EPM) or one ethylene-propylene-diene terpolymer (EPDM), and a rubber article, such as a hose or a seal, incorporating this composition. The invention applies in particular to a single-layer or multi-layer hose for conveying a fluid under pressure, the fluid being able to be a liquid, a gas, a mixture of gases or a supercritical fluid. The invention applies in particular to such a hose for a humidified air, ultrapure water or coolant circuit equipping a fuel cell (e.g. a proton exchange membrane "PEMFC", such as a hydrogen fuel cell), for example for an electric motor vehicle "FCEV" (for fuel cell electric vehicle which can be of the passenger, heavy goods vehicle, agricultural or civil engineering type), railway, aquatic, air or space, or to such a hose for an industrial installation. Prior art

[0002] In a known manner, a hose for a cooling circuit of a motor vehicle thermal engine may be single-layer or multi-layer depending on the pressure of the fluid conveyed, and may in the multi-layer case be reinforced by a reinforcement, for example textile (which surmounts an internal rubber layer and which is surmounted by an external rubber layer exposed to the air surrounding the hose). The rubber of the hose in contact with which the coolant (usually glycolated water) circulates is generally based on at least one ethylene-propylene-diene terpolymer (EPDM), due to the reduced physicochemical affinity of EPDM with the water-ethylene glycol mixture which makes it possible to prevent the rubber from swelling and to give it satisfactory impermeability to this coolant.

[0003] The rubber hoses used in a cooling circuit equipping a hydrogen fuel cell of an electric motor vehicle "FCEV" also transfer a coolant of the glycolated water type, with consequently the same double necessity, for the single or internal layer of the hose, to have satisfactory resistance to swelling and impermeability in contact with this liquid. However, the rubber compositions of the single or internal layer of hoses for the cooling, ultrapure water and humidified air circuits connected to a hydrogen fuel cell, must also meet other cumulative requirements, including those set out below.

[0004] A first requirement to be met by these compositions is that they must generate a minimized release of ions into the circulating aqueous fluid, the reduced initial ionic conductivity of which must remain low (even after prolonged contact with this fluid), in order to avoid short circuits. However, a disadvantage of the usual compositions based on an EPDM is that they are often likely to release into the fluid a high quantity of metal ions originating from some of the additives used in addition to the EPDM.

[0005] A second requirement to be met by these compositions is that they must also participate in the electrical insulation of the hydrogen fuel cell, the materials used must therefore be highly resistive by having a maximized volume electrical resistivity, ideally equal to or greater than 1.0.108 Ohm.cm. However, a disadvantage of the usual compositions based on an EPDM is that they have volume resistivities that are sometimes insufficient, located in an intermediate zone called "percolation", i.e. between 104 and 108 Ohm.cm.

[0006] Document EP 1 291 466 B1 discloses a rubber composition for a hose equipping in particular a fuel cell, the composition being presented as generating minimized contamination for the transported fluid and maximized volume resistivity. The composition comprises (A) at least one rubber selected from an EPM, an EPDM and a silicone rubber, (B) 1-10 phr of a peroxide as the sole crosslinking agent and (C) 20-130 phr of a filler of laminar crystalline structure, with phr designating parts by weight per 100 parts of (A). The composition of Example 7 comprises (mass fractions) 29.48% of an EPDM, 1.24% of a peroxide crosslinking system, 29.48% of an “Asahi No. 52” carbon black, 22.11% of kaolinite and 17.69% of a paraffinic plasticizer, for a volume resistivity of the composition measured at 2.1011 Ohm.cm and an electrical conductivity of pure water of 14.4 pS / cm after 168 hours of heat treatment applied to a 50 g sheet of the rubber composition, immersed in 250 mL of pure water at 100°C.

[0007] A disadvantage of the compositions presented in EP 1 291 466 B1 is that they do not include the slightest additive to aid their implementation, which penalizes their ability to be extruded, in particular, and thus does not make them usable for constituting pipes under satisfactory conditions.

[0008] Another disadvantage of the compositions presented in EP 1 291 466 B1 is that the electrical conductivity measurements described in this relatively old document do not satisfy the conditions adopted in recent years to ensure the reliability of conductivity measurements after aging. Indeed, this document does not disclose the dimensions of the samples tested (the length, width and thickness of the rubber sheets are unknown), which does not allow us to know the ratio of exposed rubber surface area / volume of water, which is decisive in an aging test of a sample in contact with a fluid. Statement of the invention

[0009] An aim of the present invention is to provide a rubber composition which can be used in particular in a pipe conveying humidified air, an aqueous cooling liquid or ultrapure water in connection with a fuel cell, which in particular overcomes the aforementioned drawbacks, while having satisfactory processability in the crosslinkable state and also satisfactory properties in the crosslinked state, including minimized ion release in an aqueous medium and maximized electrical resistivity.

[0010] This aim is achieved in that the Applicant has just discovered, in an unexpected manner in view of the aforementioned prior art, that if specific mass fractions of a semi-reinforcing carbon black, a lamellar inorganic filler, a processing aid system including a covering agent for said carbon black and a plasticizing system are used in a rubber composition based on a peroxide-crosslinkable EPM or EPDM, then it is possible to obtain the single layer of a single-layer pipe or at least one internal layer of a multi-layer pipe having satisfactory processability in the crosslinkable state and physicochemical and mechanical properties which are also satisfactory in the crosslinked state, with in particular a minimization of the release of ions by the rubber composition towards the fluid conveyed in contact with it while giving this composition a sufficiently high volume resistivity,thus making this composition particularly well suited to constituting a single-layer pipe or at least an internal layer of a multi-layer pipe conveying humidified air, an aqueous cooling liquid or ultrapure water, in connection with a fuel cell.

[0011] A rubber composition according to the invention is based on at least one elastomer chosen from ethylene-propylene copolymers (EPM) and ethylene-propylene-diene terpolymers (EPDM), and the composition comprises: - a filler comprising a carbon black and a lamellar inorganic filler, - a processing aid system, - a plasticizing system, and - a crosslinking system comprising a peroxide, and, according to the invention, the composition comprises (in mass fractions): 28-32% of the carbon black, which is chosen from ASTM N600 or N700 series carbon blacks, and carbon blacks with a BET specific surface area of ​​15-25 m2 / g, an iodine adsorption index of 16-24 mg / g according to ASTM D1510, and a dibutyl phthalate (DBP) absorption index of 90-110 mL / 100 g according to ASTM 2414-90, 10-20% of the lamellar inorganic loading, 1.0-6.0% of the processing aid system, which comprises a carbon black covering agent capable of binding to acidic functional groups of said carbon black, and 10-22% of the plasticizer system.

[0012] It should be noted that this implementation assistance system thus defined contributes to optimizing: - the suitability of the composition for implementation in combination with this plasticizing system, and - crosslinking the composition, by covering the acid functions of said carbon black so as to minimize the absorption of peroxide by this carbon black.

[0013] It will also be noted that the mixed filler according to the invention, comprising the aforementioned quantities of carbon black and of the lamellar inorganic filler, contributes significantly to the joint achievement of a minimized release of ionic species by the composition into the aqueous fluid in contact with it, and of a volume resistivity which is on the contrary very high for said composition.

[0014] By the expression "based on", it is meant in the present description that the composition or ingredient considered comprises predominantly by weight the constituent concerned, i.e. according to a mass fraction greater than 50%, preferably greater than 75% and possibly up to 100%.

[0015] As elastomer(s) usable in a composition according to the invention, one or more EPDMs are advantageously used, the or each EPDM being modified or not, preferably not extended with oil and having: - mass rates of units derived from ethylene of 47-71%, of a non-conjugated diene (such as ethylidene norbornene: ENB) of 3-7%, and preferably - a Mooney viscosity ML(l+4) at 125°C between 65 and 90.

[0016] Preferably, said at least one EPDM, not extended with oil, has: - mass rates of units derived from ethylene of 50-68%, of a non-conjugated diene (such as ENB) of 4.0-6.0%, and preferably - a Mooney viscosity ML(l+4) at 125°C between 70 and 85. For example, a blend of two non-oil-extended EPDMs can be used, one of which has a mass rate of ethylene units of 47-53% and a Mooney viscosity ML(l+4) at 125°C of between 65 and 75, and the other of which has a rate mass of units from ethylene of 65-71% and a Mooney viscosity ML(l+4) at 125°C between 80 and 90.

[0017] Also preferably, the composition comprises said at least one EPDM elastomer in a mass fraction of 25-40% (eg 30-35%), preferably comprising a mixture of a first EPDM and a second EPDM with mass contents of units derived from ethylene of 48-52% and 66-70%, respectively, with eg the respective mass fractions of the first EPDM and the second EPDM in the mixture being 40-60% and 60-40%.

[0018] It will be noted that these compositions according to the invention based on at least one EPM or EPDM thus have a high resistivity in particular thanks to said lamellar inorganic filler, despite the use of a high quantity of carbon black which is known to penalize this resistivity (by increasing the electrical conductivity). This high resistivity makes it possible in particular to minimize the electrochemical degradation of the internal layer of the pipe in contact with the fluid that it carries, when this fluid is a cooling liquid, for example of the glycolated water type, without penalizing the resistance of the pipe to its external environment.

[0019] By "filler" is meant in the present description several individual fillers of reinforcing or non-reinforcing grades for the elastomer concerned, which are dispersed homogeneously in the composition and by "lamellar inorganic filler" is meant a mineral filler (sometimes called "white filler" or "clear filler") having a lamellar structure, as opposed to organic fillers such as carbon blacks and non-lamellar inorganic fillers such as silicas.

[0020] Preferably, said carbon black (i.e. ASTM N600 or N700 series, or having a BET surface area of ​​15-25 m2 / g, an iodine adsorption index of 16-24 mg / g and a DBP absorption index of 90-110 mL / 100 g), is present in the composition in a mass fraction of 28.5-31.5%, or even 29.0-31.0%.

[0021] Even more preferably, the carbon black according to the invention belongs to the ASTM N600 series (and can then correspond to or be similar to ASTM N650 or N660 grade blacks), or it has a BET specific surface area of ​​17-23 m2 / g, an iodine adsorption index of 18-22 mg / g according to ASTM D1510, and a DBP absorption index of 95-105 mL / 100 g according to ASTM 2414-90.

[0022] By "lamellar inorganic filler" is meant here an inorganic filler which has a form factor greater than 10, preferably greater than 20, it being specified that by "form factor" ("aspect ratio" in English), is meant in a known manner the ratio of the largest average dimension (usually width or length) to the smallest average dimension (usually thickness) characterizing lamellae of the inorganic filler. This average ratio can be measured by scanning electron microscopy (SEM).

[0023] Advantageously, the lamellar inorganic filler can be chosen from phyllosilicates and talcs.

[0024] By "phyllosilicate" is meant, in a known manner, a subgroup of the silicate group, the phyllosilicates being constructed by stacking tetrahedral layers ("T") where the tetrahedra share three vertices out of four (the "basal" oxygens), the fourth vertex (the "apical" oxygen) being connected to an octahedral layer ("O") occupied by different cations. Suitable phyllosilicates include, for example, smectites, kaolinite and kaolins, micas, vermiculites and montmorillonites.

[0025] In a known manner, we mean: - by “kaolinite”, a phyllosilicate mineral species composed of hydrated aluminum silicate, of formula Al2Si2O5(OH)4; - by “mica”, a mineral group within phyllosilicates mainly based on aluminium and potassium silicate; and - by “talc”, a mineral species essentially composed of doubly hydroxylated magnesium silicate of formula Mg3Si4Oi0(OH)2.

[0026] Preferably, the lamellar inorganic filler of the composition according to the invention comprises a kaolin, a mica or a talc which is present in the composition in a mass fraction of 12-18%, more preferably 13-17% and for example 14-16%.

[0027] Even more preferably, the lamellar inorganic filler comprises a kaolin, for example calcined, according to a mass fraction in the composition of 12-18%, for example 13-17%, or even 14-16%. The kaolin, preferably calcined at more than 600°C, may in particular have mass fractions of SiO2, Al2O3 and Fe2O3 of 50-65%, 30-45% and 0.5-1.5% respectively, and an average grain size d50 of 1-2 pm.

[0028] According to a preferred embodiment of the invention, the filler of the composition according to the invention comprises in combination: - a carbon black of N600 series, or having a BET specific surface area of ​​17-23 m2 / g, an iodine adsorption index of 18-22 mg / g and a DBP absorption index of 95-105 mL / 100 g, and - a kaolin, a mica or a talc (preferably a kaolin, for example calcined as described above) as a lamellar inorganic filler.

[0029] According to another characteristic of the invention, the filler of said composition may advantageously be free of - non-lamellar inorganic filler, then being free of silica and calcium carbonate, in particular, and - lamellar inorganic filler provided with silane groups.

[0030] As a covering agent capable of binding to acid functional groups of carbon black (of the N600 or N700 series or having a BET specific surface area of ​​15-25 m2 / g, an iodine adsorption index of 16-24 mg / g and a DBP absorption index of 90-110 mL / 100 g), mention may be made of a polyethylene glycol preferably having a number-average molecular mass Mn inclusively of between 3000 and 5000 g / mol, for example 3500-4500 g / mol.

[0031] According to another characteristic of the invention, said implementation assistance system may further comprise at least one lubricating agent, for example chosen from compounds based on fatty acid esters and for example aliphatic fatty acid esters having from 14 to 22 carbon atoms.

[0032] It will be noted that said lubricating agent can advantageously perform an external lubricant function for the rubber composition, thereby ensuring external lubrication of the interface with the processing equipment (e.g. reduced adhesion with the metal surfaces with which the composition is in contact during its processing, including the surface of the extruder).

[0033] Preferably, the composition according to the invention comprises the processing aid system in a mass fraction of 1.5-4.0%, which processing aid system may then comprise said at least one lubricating agent in addition to said covering agent.

[0034] More preferably, the implementation aid system consists of said at least one lubricating agent and said covering agent, and may then be present in the composition in a mass fraction of 2.0-3.5%.

[0035] Generally speaking, the implementation aid system may be free of any agent for activating the crosslinking system (the composition then advantageously being free of zinc oxide and stearic acid).

[0036] As a plasticizing system that can be used according to the invention, a plasticizing oil and / or a plasticizing resin can be used, it being specified that the plasticizing system is preferably present in the composition in a mass fraction of 12-20% (more preferably 14-18%), and can advantageously comprise a high viscosity oil (with a kinematic viscosity at 100°C, measured according to standard ASTM D 445, of at least 30 mm2 / s).

[0037] As a variant of this high viscosity oil, at least one oil chosen from mineral oils (e.g. paraffinic, naphthenic and / or aromatic), oils derived from biomass (including modified or unmodified vegetable oils), and mixtures thereof may be used.

[0038] It will be noted that the implementation aid system as defined above, together with the aforementioned filler and plasticizing system, makes it possible to give the crosslinkable composition according to the invention a Mooney viscosity ML(l+4) at 100° C reduced while opposing its premature crosslinking (grinding), thus making the composition of the invention suitable for being implemented by extrusion, due to a satisfactory visual appearance with an absence of holes, cracks and shrinkage of the extrudate.

[0039] According to another characteristic of the invention, the composition may comprise the crosslinking system in a mass fraction of 2.5-4.0% (preferably 3.0-3.5%), which comprises an organic peroxide and a crosslinking co-agent, eg triallyl cyanurate (TAC) or triallyl isocyanurate (TAIC).

[0040] It will be noted that this co-agent makes it possible to significantly improve the crosslinking by the peroxide and therefore the mechanical and physical properties of the composition, in comparison with a control composition crosslinked without co-agent added to the same organic peroxide.

[0041] A composition according to the invention may further comprise an antioxidant system comprising at least one antioxidant, preferably heterocyclic aromatic (e.g. based on polymerized 2,2,4-trimethyl-1,2-dihydroquinoline).

[0042] According to another characteristic of the invention, the composition can advantageously have, in the crosslinked state, a volume resistivity, measured according to standard IEC 62631 3, which is equal to or greater than 1.0.108 Ohm.cm, preferably equal to or greater than 1.0.109 Ohm.cm.

[0043] It will be noted that this very high volume resistivity of the rubber composition according to the invention makes it possible to contribute effectively to the electrical insulation of the fuel cell, at least one of the humidified air, water and cooling circuits of which is equipped with a pipe incorporating this composition.

[0044] According to another characteristic of the invention which can be combined with the previous one, after aging by immersion of samples consisting of the crosslinked composition in a volume of an aqueous liquid chosen from ultrapure water and water-ethylene glycol mixtures, for 2 to 4 weeks at 80°C, with a ratio of the surface area of ​​the plate / volume of the aqueous liquid imposed at 30 mm2 / mL and the samples cut with a punch of dimensions 40 x 60 mm in a plate of thickness 2.0 ± 0.2 mm, the aqueous liquid can advantageously have a final ionic conductivity Cf less than or equal to its initial ionic conductivity Ci (before said immersion) increased by 10 pS / cm: Cf - Ci < 10 pS / cm, and preferably Cf - Ci < 8 pS / cm when the aqueous liquid is ultrapure water.

[0045] It will be noted that this minimal difference in ionic conductivity for the aqueous liquid before and after said aging carried out according to this well-defined and reproducible protocol, demonstrates a minimization of the release of ions by the composition of rubber to the aqueous liquid carried in contact with it, which helps to avoid short circuits in the fuel cell installation.

[0046] According to another general aspect of the invention, a rubber article according to the invention is chosen from pipes for transferring a liquid, gaseous or supercritical fluid under pressure and sealing joints, the article comprising or consisting of a rubber composition extruded in the crosslinkable state and then crosslinked, as defined by any one of the characteristics above.

[0047] Preferably, the article is a pipe for a circuit connected to a fuel cell carrying humidified air, a water-ethylene glycol coolant or ultrapure water, and the pipe is then: - single layer, consisting of said rubber composition, or - multi-layer, comprising a radially inner layer consisting of said rubber composition, at least one reinforcing layer overlying it, and a radially outer covering layer.

[0048] Even more preferably, the pipe is configured to convey ultrapure water or a water-ethylene glycol coolant, and it is such that: - the rubber composition has in the crosslinked state a volume resistivity, measured according to standard IEC 62631 3, which is equal to or greater than 1.0.108 Ohm.cm, preferably equal to or greater than 1.0.109 Ohm.cm, and - after aging by immersion of samples consisting of the crosslinked rubber composition in a volume of an aqueous liquid chosen from ultrapure water and water-ethylene glycol mixtures, for 2 to 4 weeks at 80°C, with a surface area ratio of each sample / volume of aqueous liquid imposed at 30 mm2 / mL and the samples cut with a 40 x 60 mm die from a plate with a thickness of 2.0 ± 0.2 mm, said aqueous liquid has a final ionic conductivity Cf less than or equal to its initial ionic conductivity Ci (before said immersion) increased by 10 pS / cm: Cf - Ci < 10 pS / cm, and preferably Cf - Ci < 8 pS / cm when the aqueous liquid is ultrapure water.

[0049] According to yet another general aspect of the invention, said crosslinkable rubber composition can be prepared by implementing a process essentially comprising the following successive steps: (a) introduction of the ingredients of the composition, with the exception of the crosslinking system, into an internal mixer; b) one-stage thermomechanical work in this internal mixer, until reaching a maximum "drop" temperature, for example 20-130°C; c) recovery and then cooling of the mixture thus obtained; then d) addition of the crosslinking system to the peroxide in an external mixer (e.g. cylinder mixer) at a temperature of 95-105°C, with mechanical work in this external mixer of the crosslinkable composition thus obtained.

[0050] Alternatively, the crosslinking system may be introduced during step b), or during a second introduction into the internal mixer following cooling of the precursor mixture resulting from the first step. Brief description of the drawings

[0051] Other characteristics, advantages and details of the invention will emerge from reading the following description of exemplary embodiments of the invention, given for illustrative purposes in relation to the attached drawings, among which: Fig.l

[0052] [Fig.l] is a schematic side and perspective view of a single-layer pipe according to the invention. Fig. 2

[0053] [Fig.2] is a schematic side and perspective view with partial cutaways of a multilayer pipe according to an example of the invention. Fig. 3

[0054] [Fig.3] is a schematic side and perspective view with partial cutaways of a multilayer pipe according to another example of the invention. Fig. 4

[0055] [Fig.4] is a schematic side and perspective view with partial cutaways of a multilayer pipe according to another example of the invention. Fig. 5

[0056] [Fig.5] is a schematic side and perspective view with partial cutaways of a multilayer pipe according to another example of the invention. Fig. 6

[0057] [Fig.6] is a schematic view of a fuel cell installation in which at least one of the humidified air, cooling and water circuits connected thereto comprises a single-layer or multi-layer pipe according to the invention. Examples of embodiments of the invention

[0058] The single-layer pipe 1 of [Fig. 1] is for example capable of conveying a fluid at a pressure of at most 3. 105 Pa and a temperature of at most 120° C, and it can be assembled with two connectors, for example thermoplastic. This pipe 1 is made of a composition according to the invention as defined above.

[0059] The multilayer pipe 10 of [Fig. 2] is for example capable of conveying a fluid at a pressure which may be equal to or greater than 3.105 Pa, and it comprises a radially internal tube 11, a reinforcing layer 12 and a covering layer radially external 13, it being specified that at least the tube 11 is made of a composition according to the invention as defined above.

[0060] The reinforcing layer 12 may comprise, without limitation, a knit, braid or cover based on multifilament yarns made from one or more textile material(s), for example from a polyamide (e.g. aramid), polyester (e.g. PET) or rayon (the term "yarn" usually designating both a yarn based on a multitude of elementary filaments of small diameter which are twisted together, and a twist obtained by twisting several yarns).

[0061] The multilayer pipe 20 of [Fig. 3] differs from that of [Fig. 2], in that the internal tube 21 is surmounted by an intermediate layer 22 itself surmounted by a reinforcing layer 23 covered by a covering layer 24, it being specified that at least the tube 21 is made of a composition according to the invention.

[0062] The multilayer pipe 30 of [Fig.4] differs from that of [Fig.3], in that the internal tube 31 is surmounted by an internal reinforcing layer 32 itself surmounted by an intermediate layer 33 covered by an external reinforcing layer 34 then by a covering layer 35, it being specified that at least the tube 31 is made of a composition according to the invention.

[0063] The multilayer pipe 40 of [Fig. 5] differs from that of [Fig. 3], in that the internal tube 41 is surmounted by a barrier layer 42 of plastic material forming an interfold, then by an intermediate layer 43 covered with a reinforcing layer 44, itself surmounted by a covering layer 45, with at least the tube 41 which is made of a composition according to the invention.

[0064] It will be noted that a multilayer pipe according to the invention could comprise an arrangement of layers differing from those illustrated in Figures 2-5, both in the number of its layers and in their respective functions.

[0065] The fuel cell installation illustrated in [Fig. 6] without limitation essentially comprises, around and in connection with a fuel cell 50, such as a hydrogen cell for example of the “PEMFC” type: - a closed cooling loop 60 carrying a cooling liquid comprising for example a water-ethylene glycol mixture, which notably comprises a condenser 61 equipped with a fan 61a, a regulation valve 62 and a non-return valve 63; - an air loop 70, 70' conveying air which comprises, downstream of a filter 71 and a compressor 72, a humidifier 73 bringing (portion 70) the humidified air into the stack 50, and extracting it from the latter (portion 70') to air / water separators 81 and 82 respectively located upstream and downstream of a condenser 74 equipped with a fan 74a receiving the air outlet from the upstream air / water separator 81, the air outlet from the downstream air / water separator 82 leading to an air outlet from the installation via a control valve 75; - a water loop 80, 80' extending (portion 80) from the respective water outlets of the upstream 81 and downstream 82 separators to a water tank 83, provided with the water outlet of the installation and a line 80' for supplying the humidifier 73 with water; - a hydrogen loop 90, 90' comprising a portion 90 extending from a hydrogen tank 91 to the stack 50 via a filter 92, with a recirculation 93 of the hydrogen leaving the stack 50 to the filter 92 and to a portion 90' of hydrogen outlet of the installation via a control valve 94; and - an electrical circuit 100 comprising a power unit 101 connected to the cell 50.

[0066] It will be noted that pipes according to the invention could be incorporated into at least one of the cooling, air and water circuits equipping a fuel cell, but with the or each circuit incorporating these pipes which could have characteristics different from those of [Fig.6].

[0067] Preparation of a rubber composition II according to the invention and of “control” compositions C1, C2 and C3 not in accordance with the invention:

[0068] Each of the rubber compositions II and C1-C3 was prepared essentially by carrying out the following process.

[0069] The ingredients of each composition, with the exception of the crosslinking system, were introduced into a Banbury® type internal mixer. One-stage thermomechanical work was then carried out (mixing time: 30 s to 2 min.), until a maximum "drop" temperature of approximately 125°C was reached. The resulting mixture was collected, cooled, and then the crosslinking system was added to an external roller mixer at 100°C, mixing everything for about 2 min. in a mechanical working step.

[0070] Each crosslinkable rubber composition thus obtained was shaped in the form of cylindrical test pieces for measuring properties in the uncrosslinked state (Mooney viscosity ML(l+4) at 100°C according to ISO 289-1, and roasting time t5 without premature crosslinking at 135°C according to ISO 289-2), and in the form of dumbbell-type test pieces for measuring physical and mechanical properties in the crosslinked state after curing the test pieces at 180°C.

[0071] In particular, the following were measured on the dumbbell-type test pieces respectively made up of crosslinked compositions II and C1-C3: - the hardness in DIDC points (International Rubber Hardness Degrees), according to the ISO 48:2010 standard, - the breaking stress Cr and the elongation at break Ar, in uniaxial tension according to standard ISO 37:2017, and - the volume electrical resistivity at 1000 V according to standard IEC 62631 3.

[0072] Measurements of the ionic conductivity of ultrapure water (initial ionic conductivity Ci less than 1.0 pS / cm) were also carried out, after aging by immersion of samples consisting of each crosslinked composition II and C1-C3 in a volume of this ultrapure water, for 2 to 4 weeks at 80°C, with a plate surface area / aqueous liquid volume ratio imposed at 30 mm2 / mL (the volume of water being adjusted in the bottles to maintain this ratio) and the samples which were cut with a punch of dimensions 40 x 60 mm in a plate of thickness 2.0 ± 0.2 mm, by measuring the difference AC = Cf - Ci between the final ionic conductivity Cf and the initial ionic conductivity Ci of the ultrapure water, respectively after and before said immersion.

[0073] For this purpose, a “Mettler Toledo - Five Easy F30” conductivity meter with a “Mettler Toledo - INLAB 720” conductivity cell (measuring range of 0.01-500 pS / cm, after initial calibration of the conductivity meter), and 250 mL flasks fitted with GL45 caps (the flasks being rinsed each time with ultrapure water and dried with Joseph paper) were used. For each test, three samples from the same plate were used, the thickness of which was measured by a 5-point method (leading to a considered average thickness).

[0074] Each bottle was filled with 175 mL of ultrapure water, to obtain the plate surface area / water volume ratio equal to 30 mm2 / mL, then a first conductivity measurement Ci was carried out on the water alone in each bottle. The first plate of each crosslinked composition (previously rinsed) was then introduced into a first bottle, which was recapped and then shaken for a few seconds. The first conductivity measurement was then carried out immediately after immersion, then a second sample of the same crosslinked composition was inserted into another bottle, and so on for all compositions II and C1-C3 tested.

[0075] The aforementioned aging was carried out for 2 to 4 weeks, with the bottles containing the immersed samples tested being placed in an oven at 80°C following each final conductivity measurement Cf, it being specified that before each measurement following aging, each bottle was removed from the oven to be placed for 4 hours at 23°C in a cooling enclosure.

[0076] The following table 1 details the respective formulations of compositions II and C1-C3 (in pce: parts by weight per 100 parts of EPDM elastomers), [Tables 1] II Cl C2 C3 EPDM 1*50 30 50 30 EPDM 2*50 70 50 70 Carbon black ASTM N600 series*95 110 75 75 Calcined Kaolin * 45 29 50 50 Plasticizing Oil * 50 54 35 35 Coating Agent: PEG 4000 2.8 2.8 2.8 2.8 Lubricating Agent * 4.6 4.6 4.6 4.6 Quinoline Antioxidant 1.2 1.2 1.2 1.2 TAC Co-Agent 0.7 0.7 0.7 0.7 Organic Bis-Peroxide 9.4 9.4 9.4 9.4 TOTAL (parts by weight) 308.7 311.7 278.7 278.7

[0077] The ingredients identified in Table 1 by the sign * had the following characteristics: - EPDM 1: mass content of units derived from ethylene of 50%, units derived from ethylidene norbornene of 5.0%, and Mooney viscosity ML(l+4) at 125°C of 70. - EPDM 2: mass content of units derived from ethylene of 68%, units derived from ethylidene norbornene of 4.9%, and Mooney viscosity ML(l+4) at 125°C of 85. - Carbon black with a BET specific surface area according to ASTM D 6556 of approximately 20 m2 / g, an iodine adsorption index according to ASTM D 1510 of approximately 20 mg / g, and a DBP absorption index according to ASTM 2414-90 of approximately 100 mL / 100 g. - Calcined kaolin comprising mass fractions of SiO2, Al2O3, and Fe2O3 of 55-60%, 35-40% and 0.5-1.0% respectively, and an average grain size d50 of between 1.0 and 1.5 pm. - Plasticizing oil: oil with a kinematic viscosity at 100°C, measured according to ASTM D 445, of between 30 and 40 mm2 / s. - Lubricating agent: mixture of aliphatic fatty acid esters.

[0078] Table 2 below gives the mass fractions (in %) of the ingredients of Table 1 in each composition II and C1-C3.

[0079] [Tables2] II Cl C2 C3 EPDM 1 * 16.20 9.62 17.94 10.76 EPDM 2 * 16.20 22.46 17.94 25.12 Carbon black ASTM N600 series * 30.77 35.29 26.91 26.91 Calcined kaolin * 14.58 9.30 17.94 17.94 Plasticizing oil * 16.20 17.32 12.56 12.56 Coating agent: PEG 4000 0.91 0.90 1.00 1.00 Lubricating agent * 1.49 1.48 1.65 1.65 Quinoline antioxidant 0.39 0.38 0.43 0.43 TAC co-agent 0.22 0.23 0.25 0.25 Organic bis-peroxide 3.04 3.02 3.38 3.38 TOTAL (%) 100.00 100.00 100.00 100.00

[0080] Table 3 below presents the essential rheological properties of the compositions obtained II and C1-C3, comprising for each of them: - the Mooney viscosity ML(l+4) at 100°C, measured according to ISO 289-1; - the initial curing time t5 without premature crosslinking, according to ISO 289-2; and - the suitability for extrusion in the form of a pipe (“extrudability”, including the behavior and appearance of the extrudate made from the crosslinkable composition). [Tables 3] II Cl C2 C3 ML(l+4) at 100°C 72.0 73.6 81.0 82.0 Roasting time t5 (min.) at 135°C 14.8 22.4 14.4 13.4 Extrusion capacity good good poor poor “good” indicated a satisfactory appearance (smooth), an absence of holes, cracks or fissures and no shrinkage of the extrudate. “bad” indicated an unsatisfactory appearance, with holes, cracks or fissures, and significant shrinkage of the extrudate.

[0081] Table 4 below shows the physical and mechanical properties of the obtained crosslinked compositions II and C1-C3, measured as indicated above on dumbbell-type test pieces. [Tables 4] II Cl C2 C3 Volume electrical resistivity (Ohm.cm) 1.0.109 2.4.105 4.7.108 1.3.108 Difference in ionic conductivity of pure water after 2 weeks AC = Cf - Ci (pS / cm) 7.2 5.1 6.2 8.2 IRHD hardness (points) 65 65 65 69 Stress at break Cr (MPa) 11.2 12.5 11.9 12.8 Elongation at break Ar (%) 444 400 398 399

[0082] The properties obtained in Tables 3 and 4 show that composition II according to the invention has, compared to control compositions C1-C3: - in the crosslinkable state: improved processability, as shown by the minimum Mooney viscosity ML(l+4) for a similar curing time t5 and the appearance satisfactory visual appearance of the extrudate with an absence of holes, cracks and shrinkage following extrusion, and - in the crosslinked state: physicochemical and mechanical properties are also improved, including in particular: a maximum volume resistivity (approximately 1.0.109 Ohm.cm) combined with a reduced release of ions towards the fluid in contact with it, and improved fracture properties for similar hardness (see significantly improved elongation-to-break for similar stress-to-break).

[0083] These overall improved properties are due in particular to the specific mass fractions in the composition according to the invention: - said carbon black (between 28% and 32%, unlike the mass fractions of 35.29% and 26.91% used in compositions C1-C3), and - other ingredients, including in particular the mass fractions of the elastomer matrix, the lamellar inorganic filler, the processing aid system (comprising the covering agent and the lubricating agent) and the plasticizing system.

[0084] These improved properties make the compositions according to the invention particularly well suited for constituting in particular: - a single-layer pipe or at least one inner layer of a multi-layer pipe carrying humidified air, an aqueous cooling liquid or ultrapure water, in connection with a fuel cell, and even - all or part of a seal, for example for the bodywork of a motor vehicle or for a building.

Claims

Claims

1. Rubber composition in particular usable in a pipe (1, 10, 20, 30, 40) of humidified air, aqueous cooling liquid or ultrapure water connected to a fuel cell (50), the composition being based on at least one elastomer chosen from ethylene-propylene copolymers (EPM) and ethylene-propylene-diene terpolymers (EPDM), and comprising: - a filler comprising a carbon black and a lamellar inorganic filler, - an implementation aid system, - a plasticizing system, and - a crosslinking system comprising a peroxide, in which the composition comprises, in mass fractions: 28-32% of the carbon black, which is chosen from carbon blacks of ASTM N600 or N700 series, and carbon blacks having a BET specific surface area of ​​15-25 m2 / g, an index iodine adsorption index of 16-24 mg / g according to ASTM D1510, and a DBP absorption index of 90-110 mL / 100 g according to ASTM 2414-90,10-20% of the lamellar inorganic filler, 1.0-6.0% of the processing aid system, which comprises a carbon black covering agent capable of binding to acidic functional groups of said carbon black, and 10-22% of the plasticizer system.,

2. A rubber composition according to claim 1, wherein the composition comprises said at least one elastomer which is an EPDM in a mass fraction of 25-40%, the composition preferably comprising a mixture of a first EPDM and a second EPDM at mass levels of units derived from ethylene of 48-52% and 66-70%, respectively, and for example wherein the mass fraction of the first EPDM and the second EPDM in said mixture are respectively 40-60% and 60-40%.

3. A rubber composition according to any preceding claim, wherein said coating agent comprises a polyethylene glycol, which preferably has a mass molecular weight Mn number average inclusively between 3000 and 5000 g / mol.

4. Rubber composition according to one of the preceding claims, in which said processing aid system further comprises at least one lubricating agent, for example chosen from compounds based on fatty acid esters and for example aliphatic fatty acid esters having from 14 to 22 carbon atoms.

5. Composition according to one of the preceding claims, in which the composition comprises the processing aid system in a mass fraction of 1.5-4.0%, which is preferably free of crosslinking system activating agent, the composition being for example free of zinc oxide and stearic acid.

6. A rubber composition according to any preceding claim, wherein the lamellar inorganic filler is selected from phyllosilicates and talcs, and preferably wherein the lamellar inorganic filler comprises a kaolin, a mica or a talc which is present in the composition in a mass fraction of 12-18%.

7. A rubber composition according to claim 6, wherein the lamellar inorganic filler is calcined kaolin, and / or said carbon black is of N600 series or has said BET specific surface area of ​​17-23 m2 / g, said iodine adsorption index of 18-22 mg / g and said DBP absorption index of 95-105 mL / 100 g.

8. Rubber composition according to one of the preceding claims, in which the filler is free of: - non-lamellar inorganic filler, being free of silica and calcium carbonate, and - lamellar inorganic filler provided with silane groups.

9. A rubber composition according to any preceding claim, wherein the composition comprises the plasticizing system in a mass fraction of 12-20%, which preferably comprises an oil having a kinematic viscosity at 100°C, measured according to ASTM D 445, of at least 30 mm2 / s.

10. A rubber composition according to any preceding claim, wherein the composition comprises the crosslinking system in a mass fraction of 2.5-4.0%, which comprises an organic peroxide and a co-crosslinking agent, for example triallyl cyanurate (TAC) or triallyl isocyanurate (TAIC).

11. Rubber composition according to one of the preceding claims, in which the composition has in the crosslinked state a volume resistivity, measured according to standard IEC 62631 3, which is equal to or greater than 1.0.108 Ohm.cm, preferably equal to or greater than 1.0.109 Ohm.cm.

12. Rubber composition according to one of the preceding claims, wherein, after aging for 2 to 4 weeks at a temperature of 80°C by immersing samples consisting of said composition in a volume of an aqueous liquid chosen from ultrapure water and water-ethylene glycol mixtures, with a plate surface area / aqueous liquid volume ratio imposed at 30 mm2 / mL and the samples which are cut with a die cutter of dimensions 40 x 60 mm from a plate of thickness 2.0 ± 0.2 mm, the aqueous liquid has a final ionic conductivity Cf less than or equal to its initial ionic conductivity Ci before said immersion, increased by 10 pS / cm: Cf - Ci < 10 pS / cm, and preferably Cf - Ci < 8 pS / cm when the aqueous liquid is ultrapure water.

13. Rubber article chosen from pipes (1, 10, 20, 30, 40) for transferring a liquid, gaseous or supercritical fluid under pressure and sealing joints, in which the article comprises or is made of a rubber composition according to one of the preceding claims, extruded in the crosslinkable state and then crosslinked.

14. Article according to claim 13, wherein the article is a pipe (1, 10, 20, 30, 40) for a circuit (60, 70, 80) connected to a fuel cell (50) carrying humidified air, a water-ethylene glycol coolant or ultrapure water, and wherein the pipe (1, 10, 20, 30, 40) is: - single-layer, being made of said rubber composition, or - multi-layer, comprising a radially inner layer (11) made of said rubber composition, at least one reinforcing layer (12) overlying it, and a radially outer covering layer (13).

15. Article according to claim 14, wherein the pipe (1, 10, 20, 30, 40) is configured to convey an aqueous liquid consisting of ultrapure water or a water-ethylene glycol coolant, the rubber composition having in the crosslinked state a volume resistivity, measured according to standard IEC 62631 3, which is equal to or greater than 1.0.108 Ohm.cm, preferably equal to or greater than 1.0.109 Ohm.cm, and after aging by immersion of samples consisting of said composition in a volume of aqueous liquid for 2 to 4 weeks at a temperature of 80°C, with a surface area ratio of each sample / volume of aqueous liquid imposed at 30 mm2 / mL and the samples which are cut with a punch of dimensions 40 x 60 mm in a plate of thickness 2.0 ± 0.2 mm, the aqueous liquid having a final ionic conductivity Cf less than or equal to its initial ionic conductivity Ci before said immersion, increased by 10 pS / cm: Cf - Ci < 10 pS / cm, and preferably Cf - Ci < 8 pS / cm when the aqueous liquid is ultrapure water.

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