FAST AND LOW TEMPERATURE COATING COMPOSITION FOR THE MANUFACTURE OF COMPOSITE PRESSURE TANKS FOR THE ON-BOARD STORAGE OF GASY HYDROGEN.

Abstract

The invention relates to a composition (C) comprising (A) 70 to 95 parts by mass of an epoxy resin of viscosity less than or equal to 20 Pa.s, preferably between 1 and 20, more preferably between 1 and 10, at a temperature between 20°C and 25°C, and (B) 5 to 30 parts by mass of a hardener dispersed in the resin, per 100 parts by mass of resin present in the composition, and in that the hardener is an ionic liquid containing a phosphonium cation of formula P(R1R2R3R4)+ in which R1, R2, R3 and R4, identical or different, represent a hydrogen atom, an alkyl radical having 1 to 18 carbon atoms, an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted, and - an acetate anion of formula (R5CO2)- in which R5 represents a hydrogen atom, an alkyl radical having 1 to 18 carbon atoms, an aryl radical having 6 to 20 atoms of carbon, said alkyl and aryl radicals possibly being substituted, or - a phosphinate anion of formula [[(CH3)3CCH2CH(CH3)CH2]2P(O)O]-.Another object of the invention is the use of a composition (C) for the manufacture of a hydrogen tank, in particular a pressurized tank of types II, III, IV and V, comprising a composite material, for the on-board storage of gaseous hydrogen. Figure for the abstract: None.

Description

Title of the invention: FAST-COOKED, LOW-TEMPERATURE COMPOSITION FOR THE MANUFACTURE OF COMPOSITE MATERIAL PRESSURE TANKS FOR THE ON-BOARD STORAGE OF GASY HYDROGEN. Technical field of the invention

[0001] The present invention relates to the field of manufacturing pressurized tanks comprising a composite material, of types II, III, IV, and V, for the storage of gaseous hydrogen and any other gas of interest under pressure, for fixed, transportable, and mobile applications, such as hydrogen storage infrastructure, hydrogen transport for refueling, hydrogen rail vehicles, buses, trucks, aircraft, boats and other hydrogen vehicles, and hydrogen cars. Technical background

[0002] Today, on-board storage systems for gaseous hydrogen in pressurized tanks for mobility applications exist, but only a few manufacturers market a few thousand or tens of thousands of approved tanks per year. With the emergence of the market for low-carbon mobility and pressurized storage, there is no supply chain (transformation of raw materials and components into a finished product delivered to the end customer) ready for mass production (millions of units per year) at a moderate cost. For example, the compact, reliable, safe, and economical storage of gaseous hydrogen at 700 bar is a major challenge for the widespread commercialization of fuel cell electric vehicles (FCEVs) and other fuel cell applications.While some lightweight FECVs with a range of over 500 km have appeared since 2015, economically affordable onboard hydrogen storage remains a major obstacle, and the number of tanks manufactured remains low. Much of the effort in hydrogen storage programs is focused on developing cost-effective hydrogen storage technologies with improved energy density (gravimetric capacity close to 6%, meaning that 6% of the storage system's mass is hydrogen).

[0003] Hydrogen tanks for automotive, bus, truck, train, airplane, and boat applications are already available, but they do not yet meet all the requirements. Manufacturers' expectations regarding the mass production of hydrogen-powered systems. This is true not only for the manufacture of H2 tanks but also for the deployment and use of fuel cell mobility devices.

[0004] Although the manufacturing cost of Type II, III, IV, and V pressure tanks incorporating a composite material for on-board storage of gaseous hydrogen represents approximately 10% to 30% of the storage system cost, mass production capacity is a major challenge for automotive integrators. The polymerization step (also called curing or baking) of the composite material matrix, which provides pressure resistance, is the main step currently limiting the tank manufacturing speed. The composite material matrix for pressure tanks is generally an epoxy matrix.

[0005] In order to be able to produce several million vehicles per year, the polymerization time of the matrices of the composite materials used for type II, III, IV and V tanks must be considerably reduced.

[0006] Today, with epoxy matrices, the polymerization (or hardening) process time for a 700 bar pressure tank is about 12 to 16 hours, which is too long for mass production such as that required for the automotive industry.

[0007] The wet filament winding process is, in general, the most used by manufacturers for the production of pressure vessels of types II, III, IV and V.

[0008] Thus, there is a real need for a new epoxy resin-based composition specific to the wet filament winding process for the manufacture of pressure tanks of types II, III, IV and V, comprising a composite material, in particular for on-board storage of gaseous hydrogen, which is capable of meeting the constraints of mass production and which is industrially interesting.

[0009] In particular, there is a real need for an epoxy resin-based composition such as described above which makes it possible to substantially reduce the duration of the polymerization step of the matrix of the composite material in order to minimize the manufacturing cycle time of a tank.

[0010] Moreover, in certain cases, particularly when the tank is fitted with an internal lining or polyethylene bladder, polymerization at temperatures less than or equal to 170°C may be desired by manufacturers.

[0011] There is therefore a real need for an epoxy resin-based composition such as the one described above that allows manufacturers to easily adapt the temperature of The polymerization step depends on the nature of the bladder (or liner) when there is one. Thus, the polymerization step can be carried out optimally at any temperature and even at low temperature, i.e. at maximum temperatures less than or equal to 170°C, for example at maximum temperatures ranging from 60°C to 170°C, from 60°C to 150°C, from 60°C to 130°C, from 60°C to 110°C, from 60°C to 105°C.

[0012] The low temperature allows the use of a wider choice of materials for the bladder (also called internal lining or liner in English), and also allows for more latitude in controlling the exothermicity of cooking, particularly when the thickness of composite material is significant, for example a thickness of 2 to 5 cm.

[0013] To achieve this, the present invention proposes a new epoxy resin-based composition for the composite material which takes into account the technical and regulatory constraints related to composite pressure tanks of types II, III, IV and V, for the storage of on-board hydrogen. Summary of the invention

[0014] The present invention relates to a composition (C) characterized in that it comprises

[0015] (A) 70 to 95 parts by mass of an epoxy resin with a viscosity of less than or equal to 20 Pa.s, preferably between 1 and 20 Pa.s, more preferably between 1 and 10 Pa.s, at a temperature between 20°C and 25°C, and

[0016] (B) 5 to 30 parts by mass of a hardener dispersed in the resin,

[0017] for 100 parts by mass of resin present in the composition,

[0018] and in that the hardener is an ionic liquid containing a phosphonium cation of formula P(RiR2R3R4)+ in which Rb R2, R3 and R4, identical or different, represent a hydrogen atom, an alkyl radical having 1 to 18 carbon atoms, an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted, and

[0019] - an acetate anion of formula (R5CO2) in which R5 represents an atom of hydrogen, an alkyl radical having 1 to 18 carbon atoms, an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted, or

[0020] - a phosphinate anion of formula (PO2R6R7) in which R6 and R7 are identical or different, represent a hydrogen atom, an alkyl radical having 2 to 16 carbon atoms, an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals possibly being substituted.

[0021] Tanks comprising a composite material operating under pressure are categorized:

[0022] - Type II tanks, known as coiled tanks, are metallic and reinforced by a winding circumferential fiber on the cylindrical part only, generally with carbon or glass (composite reinforcement),

[0023] - Type III tanks have a metallic casing (also called an internal lining (or bladder or liner in English), a gas barrier, and a composite reinforcement over the entire external surface,

[0024] - type IV tanks, which differ from type III by a polymer liner, and

[0025] - Type V tanks, which differ from Type IV by the absence of the liner in polymer.

[0026] For example, a type IV pressure vessel made of composite material consists of an internal lining of polymer material, also called a bladder or liner, most often thermoplastic, with metal connectors, called bosses, at one or both ends. The bosses connect the vessel to the storage system. The liner provides hydrogen tightness. This assembly is covered with a structural composite material, providing structure under internal pressure, usually comprising a thermosetting matrix, most often an epoxy resin, and reinforcement most often based on long fibers, for example, carbon or glass.

[0027] The present invention therefore aims to support the development of on-board storage systems for gaseous hydrogen (CGH2 compressed gaseous hydrogen, CPV Composite Pressure Vessel) in improved pressurized tanks, in order to anticipate the future massive deployment of the aforementioned technologies, in particular by focusing on the composition of the composite material of the tank, and more specifically on the resin and its polymerization reaction which strongly impacts manufacturing rates over periods exceeding 10 hours in general.

[0028] The composition of the invention is particularly advantageous because it has a rapid polymerization compared to the epoxy matrix-based compositions used today, notably thanks to the use of phosphorus ionic liquids as a hardener. Indeed, the polymerization time of the epoxy matrix in a composition according to the invention is less than 12 hours, less than 10 hours, in particular less than or equal to 8 hours, in particular less than or equal to 6 hours, more particularly less than or equal to 4 hours, and even more particularly less than or equal to 2 hours.

[0029] The composition of the invention is also particularly advantageous because the polymerization step can be carried out optimally at any temperature and even at low temperatures, that is to say at maximum temperatures less than or equal to 170°C, for example at maximum temperatures ranging from 60°C to 170°C, from 60°C to 150°C, from 60°C to 130°C, from 60°C to 110°C, from 60°C to 105°C, thanks to the use of ionic liquids (B) as hardeners.

[0030] As previously stated, the composition according to the invention takes into account the technical and regulatory constraints related to composite tanks operating under pressure, for example at a pressure between 200 and 900 bar, for the storage of onboard hydrogen. This new composition is specific to the wet filament winding process, which is generally the most widely used by manufacturers.

[0031] Another object of the invention is the use of a composition (C) according to the invention for wet-impregnating a bundle of fibers (F), the fibers (F) being selected from

[0032] - organic fibers selected from polyethylene fibers, poly(p - phenylene-2,6-benzobisoxazole) or PBO, aramid, polyamide, flax, polyester or other organic fiber;

[0033] - inorganic fibers selected from glass, carbon, and carbide fibers silicon, basalt, or other inorganic fiber.

[0034] The impregnation of the fibers can be carried out by immersion in a bath, by contact, by injection or by spraying. These impregnation techniques are well known to those skilled in the art.

[0035] Another object of the invention is a method for manufacturing parts comprising a composite material operating under pressure, for example at a pressure between 200 and 900 bar, by wet filament winding, comprising at least one step of impregnating a bundle of fibers (F) selected from

[0036] - organic fibers selected from polyethylene fibers, poly(p - phenylene-2,6-benzobisoxazole) or PBO, aramid, polyamide, flax, polyester or other organic fiber;

[0037] - inorganic fibers selected from glass, carbon, and carbide fibers silicon, basalt, or other inorganic fiber,

[0038] by a composition (C) according to the invention.

[0039] More specifically, the process for manufacturing parts comprising a composite material operating under pressure comprises at least the following steps:

[0040] i) impregnation of a bundle of fibers (F) selected from

[0041] - organic fibers selected from polyethylene fibers, poly(p - phenylene-2,6-benzobisoxazole) or PBO, aramid, polyamide, flax, polyester or other organic fiber;

[0042] - inorganic fibers selected from glass, carbon, and carbide fibers silicon, basalt, or other inorganic fiber.

[0043] of a composition (C) according to the invention;

[0044] ii) winding of the impregnated fibers around a bladder or a mandrel;

[0045] iii) polymerization of composition (C) at a temperature less than or equal to 170°C.

[0046] This process can also be used for the manufacture of parts comprising a composite material which do not require operation under pressure within the meaning of the invention.

[0047] The composite part can be a pressure vessel of types II, III, IV, and V for the on-board storage of gaseous hydrogen. Preferably, the part is a type IV vessel.

[0048] Impregnation can be achieved by immersion in a bath containing a composition (C) according to the invention, in contact with a composition (C) according to the invention, by injection or by spraying of a composition (C) according to the invention.

[0049] Polymerization can be carried out at maximum temperatures less than or equal to 170°C, for example at maximum temperatures ranging from 60°C to 170°C, from 60°C to 150°C, from 60°C to 130°C, from 60°C to 110°C, from 60°C to 105°C. The manufacturer will choose the temperature according to their manufacturing constraints.

[0050] Said fiber bundle (F) is impregnated with composition (C), with a mass percentage of (F) between 40 and 70% and a mass percentage of (C) between 30 and 60%.

[0051] The fiber bundle can be in the form of strands, ribbons, a sheet or aggregate of loose non-woven fibers, or in woven form.

[0052] The composition (C) according to the invention can be used for the manufacture of pressure tanks of types II, III, IV, and V, comprising a composite material, for the on-board storage of gaseous hydrogen, in particular for both fixed and mobile applications, such as hydrogen storage infrastructure, hydrogen transport for refueling, hydrogen rail vehicles, buses, trucks, aircraft, boats and other hydrogen vehicles, and hydrogen cars.

[0053] The invention therefore relates to the use of a composition (C) according to the invention, for the manufacture of a hydrogen tank, in particular a pressure tank, of types II, III, IV and V, made of composite material, for the on-board storage of gaseous hydrogen.

[0054] In the context of the present invention, a part or tank is said to operate under pressure when the nominal operating pressure is on the order of several hundred bars, for example at a nominal operating pressure ranging from 200 to 900 bars. Detailed description of the invention

[0055] The present invention relates to a composition (C) characterized in that it comprises

[0056] (A) 70 to 95 parts by mass of an epoxy resin with a viscosity of less than or equal to 20 Pa.s, preferably between 1 and 20 Pa.s, more preferably between 1 and 10 Pa.s, at a temperature between 20°C and 25°C, and

[0057] (B) 5 to 30 parts by mass of a hardener dispersed in the resin,

[0058] for 100 parts by mass of resin present in the composition,

[0059] and in that the hardener is an ionic liquid containing a phosphonium cation of formula P(RiR2R3R4)+ in which RB R2, R3 and R4, identical or different, represent a hydrogen atom, an alkyl radical having 1 to 18 carbon atoms, an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted, and

[0060] - an acetate anion of formula (R5CO2) in which R5 represents an atom of hydrogen, an alkyl radical having 1 to 18 carbon atoms, an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted, or

[0061] - a phosphinate anion of formula (PO2R6R7) in which R6 and R7 are identical or different, represent a hydrogen atom, an alkyl radical having 2 to 16 carbon atoms, an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals possibly being substituted.

[0062] For the purposes of this invention, an "alkyl" radical is a linear, branched, or cyclic, saturated carbon radical, optionally substituted, generally comprising from 1 to 18 carbon atoms, for example, from 1 to 14 carbon atoms, for example, from 1 to 10 carbon atoms. Examples of saturated linear or branched alkyl radicals include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and their branched isomers. Examples of cyclic alkyl radicals include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicylco[2,l,l]hexyl, and bicyclo[2,2,l]heptyl.

[0063] In the specific case of a phosphinate anion, the "alkyl" radical is a linear, branched or cyclic, saturated, possibly substituted carbon radical, generally comprising from 2 to 16 carbon atoms, for example from 4 to 16 carbon atoms.

[0064] The term "aryl" designates a mono- or poly-cyclic aromatic substituent generally comprising 6 to 20 carbon atoms, for example, 6 to 10 carbon atoms. Examples include phenyl, benzyl, naphthyl, and phenanthrenyl groups.

[0065] Alkyl and aryl radicals may optionally be substituted by one or more hydroxyl groups (-OH), one or more alkoxy groups (-O-alkyl); one or several aryloxy (-O-aryl) groups; one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms; with alkyl and aryl as defined within the scope of the present invention.

[0066] In the phosphonium cation, R2, R3 and R4, whether identical or different, represent

[0067] - a hydrogen atom,

[0068] - an alkyl radical selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and their branched isomers,

[0069] - an aryl radical selected from phenyl, benzyl,

[0070] said alkyl and aryl radicals being optionally substituted.

[0071] The phosphonium cation can be chosen from [(C6Hi3)3(Ci4H29)P]+, [(C4H9)3(Ci4H29 )P]+, [(C4H9)3(C2H5)P]+, [(C8H17)4P]+, [(C4H9)3(CH3)Ph [(iso-C4H9)3(CH3)P]L [(H)4P]+, [(CH3)4P]+, [(Ph)4P]+, [(Ph)3(CH3)P]+, [(C6H13)3(C14H29)P]+, [(CH2OH)4P]+.

[0072] More particularly, the phosphonium cation can be chosen from [(C6Hi3)3(Ci4H29 )P]+, [(C4H9)3(C14H29)P]+, [(C4H9)3(C2H5)P]+, [(C8H17)4P]+, [(C4H9)3(CH3)P]+, [(iso-C4H9) 3(CH3)P]+, [(C6H13)3(C14H29)P]+.

[0073] According to a first embodiment of the invention, in the composition, the ionic liquid contains a phosphinate anion of formula (PO2R6R7) in which R6 and R7, identical or different, represent a hydrogen atom, an alkyl radical having 2 to 16 carbon atoms, an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted, and a phosphonium cation as defined above.

[0074] In this first embodiment, the phosphinate anion of formula (PO2R6R7) in which R6 and R7, identical or different, represent

[0075] - a hydrogen atom,

[0076] - an alkyl radical selected from butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and their branched isomers,

[0077] - an aryl radical selected from phenyl, benzyl,

[0078] said alkyl and aryl radicals being optionally substituted.

[0079] The phosphinate anion can be chosen from (PO2H2), (PO2(C7H3O)2), [[(CH3)3CCH2] CH(CH3)CH2]2P(O)O], (PO2Ph2).

[0080] The ionic liquid may contain a phosphinate anion of formula [[(CH3)3 CCH2CH(CH3)CH2]2P(O)O] and a phosphonium cation as defined above.

[0081] In this first embodiment, the ionic liquid can be trihexyl(tetradecyl)phosphonium bis-2,4,4-(trimethylpentyl)phosphinate or CYPHOS® IL104 from Cytec Industries Inc.

[0082] In this first embodiment, when the ionic liquid contains a phosphinate anion as described above, the composition comprises 5 to 20 parts by mass of ionic liquid(s), for 100 parts by mass of epoxy resin present in the composition.

[0083] In all variants and embodiments of the invention, the composition (C) can be polymerized under the action of temperature according to the desired application and characteristics. Those skilled in the art will know how to choose and adapt these conditions.

[0084] According to a second embodiment of the invention, the composition comprises an ionic liquid which contains an acetate anion of formula (R5CO2) in which R5 represents a hydrogen atom, an alkyl radical having 1 to 18 carbon atoms, an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted, and a phosphonium cation as defined above.

[0085] In this second embodiment, in the acetate anion, R5 represents

[0086] - a hydrogen atom,

[0087] - an alkyl radical selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and their branched isomers, and their branched isomers,

[0088] - an aryl radical selected from phenyl, benzyl,

[0089] said alkyl and aryl radicals being optionally substituted.

[0090] The acetate anion can be chosen from ((CH3)CO2), ((C5Hn)CO2), ((CH3CH2CH(CH3 )CH2CH2)CO2), ((C7H15)CO2), ((CH3CH2CH2CH2CH(CH3)CH2CH2)CO2), ((CH3)3 CCH2CH(CH3)CH2CH2CH2)CO2), (CH3CH(CH3)CH2CH2CH2CH(CH3)CH2)CO2), ((C 9h19)CO2).

[0091] In this second embodiment, when the ionic liquid contains an acetate anion as described above, the composition comprises 5 to 20 parts by mass of ionic liquid, for 100 parts by mass of epoxy resin present in the composition.

[0092] In this other embodiment, the ionic liquid can be trihexyl(tetradecyl)phosphonium decanoate or CYPHOS® IL 103 from Strem Chemicals Inc.

[0093] The epoxy resin (A) present in the composition may be, for example, of the bisphenol type, such as bisphenol A, bisphenol B, bisphenol F, bisphenol S, ortho-, meta-, paracresol novolac.

[0094] The epoxy resin (A) may be the Araldite® LY 566 bisphenol A type resin, marketed by the Huntsman company.

[0095] The epoxy resin (A) has a viscosity less than or equal to 20 Pa.s, preferably between 1 and 20 Pa.s, more preferably between 1 and 10 Pa.s, at a temperature between 20°C and 25°C.

[0096] Viscosity is measured at a temperature between 20°C and 25°C, using a The ARES rheometer, from TA® Instruments, uses a planar-on-planar geometry with 25 mm (upper geometry) and 40 mm (lower geometry) aluminum discs. The compound is deposited hot (60°C) onto the discs and then cooled to a temperature between 20°C and 25°C to perform the viscosity measurement. The Dynamic Frequency Sweep (DFS) test (strain controlled) of 1-100 rad / s is performed with a strain of approximately 10%. The viscosity measurement is taken at a frequency of 6 rad / s.

[0097] The composition according to the invention can be prepared by mixing components (A) and (B) as shown in the examples. In particular, the process consists of mixing an epoxy resin (A) and an ionic liquid (B) as defined above, until a homogeneous composition is obtained, at a temperature that prevents the initiation of polymerization of (A).

[0098] The composition can be prepared in a simple (glass) reactor equipped with a stirring paddle and under air. The temperature can be controlled by a heating plate and a silicone oil bath.

[0099] Continuous mixing is a process of continuously dosing ingredients directly into the mixing zone and, consequently, generating a continuous flow of mixed product at the mixer outlet. This principle ensures perfect control of the point at which the ingredients meet and therefore a unique distribution quality for the mixed product. The resulting product is thus in the form of a homogeneous mixture. Any continuous mixer known to those skilled in the art can be used to manufacture the composition.

[0100] Without wishing to be bound by theory, the inventors have observed that the use of ionic liquids as described above as hardeners in a composition according to the invention allows polymerization via a catalytic rather than an addition mechanism. The ionic liquids make it possible to reduce the amount of polymerizing agent or hardener required for the complete polymerization of the epoxy matrix (i.e., 20-50 parts per 100 parts of resin or phr, for standard amine systems). Indeed, the ionic liquid, under the influence of temperature, will allow the opening of the oxirane ring by the nucleophilic attack of the anion on the α-carbon of this group.

[0101] This so-called activation reaction leads to the formation of alkoxide, a reactive functional group with respect to the other epoxide motifs. A second step, called propagation, consists of the homopolymerization of the alkoxide motifs formed on the oxirane rings.

[0102] Under suitable temperature conditions, this reaction continues until complete crosslinking of the epoxy matrix (conversion > 95%).

[0103] It should be noted that, thanks to the use of ionic liquids as described above, composition (C) has a rapid polymerization compared with the epoxy matrix-based compositions used today. Indeed, the polymerization time of the epoxy matrix in a composition (C) according to the invention is less than 12 hours, less than 10 hours in particular less than or equal to 8 hours, in particular less than or equal to 6 hours, more particularly less than or equal to 4 hours, and even more particularly less than or equal to 2 hours.

[0104] Another object of the invention is the use of a composition (C) according to the invention for wet-impregnating a bundle of fibers (F), the fibers (F) being selected from

[0105] - organic fibers selected from polyethylene fibers, poly(p - phenylene-2,6-benzobisoxazole) or PBO, aramid, polyamide, flax, polyester or other organic fiber;

[0106] - inorganic fibers selected from glass, carbon, carbide fibers silicon, basalt, or other inorganic fiber.

[0107] The fiber bundle (F) may be in the form of strands, ribbons, a sheet or aggregate of loose non-woven fibers, or in woven form.

[0108] The reinforcing fiber bundle preferably comprises 1000 to 70000 filaments having a diameter of 3 to 100 pm.

[0109] Preferably, the fibers (F) are carbon fibers. For example, TORAYCA T720 carbon fibers from Toray® may be used.

[0110] Another object of the invention is a method for manufacturing parts comprising a composite material operating under pressure, implemented by wet filament winding, comprising at least one step of impregnating a bundle of fibers (F) selected from

[0111] - organic fibers selected from polyethylene fibers, poly(p - phenylene-2,6-benzobisoxazole) or PBO, aramid, polyamide, flax, polyester or other organic fiber;

[0112] - inorganic fibers selected from glass, carbon, carbide fibers silicon, basalt, or other inorganic fiber.

[0113] by a composition (C) according to the invention.

[0114] More specifically, the process for manufacturing parts comprising a composite material operating under pressure comprises at least the following steps:

[0115] i) impregnation of a bundle of fibers (F) selected from

[0116] - organic fibers selected from polyethylene fibers, poly(p - phenylene-2,6-benzobisoxazole) or PBO, aramid, polyamide, flax, polyester or other organic fiber;

[0117] - inorganic fibers selected from glass, carbon, carbide fibers silicon, basalt, or other inorganic fiber,

[0118] of a composition (C) according to the invention;

[0119] ii) winding of the impregnated fibres around a bladder or a mandrel;

[0120] iii) polymerization of composition (C) at a temperature less than or equal to 170°C.

[0121] As already indicated, the process of the invention also allows the manufacture of parts comprising a composite material not requiring operation under pressure within the meaning of the invention.

[0122] The component comprising a composite material may be a pressure vessel of types II, III, IV, and V for the on-board storage of gaseous hydrogen. Preferably, the component is a type IV vessel.

[0123] Implementation by wet filament winding is a process well known to those skilled in the art. In this process, the fibers (F) are continuously fed from a roll and pass through a bath containing a composition (C) before being wound around a bladder or mandrel.

[0124] Said fiber bundle (F) is impregnated with composition (C), with a mass percentage of (F) between 40 and 70% and a mass percentage of (C) between 30 and 60%.

[0125] The fiber bundle (F) may be in the form of strands, ribbons, a sheet or aggregate of loose non-woven fibers, or in woven form.

[0126] In step i), the impregnation of the moving fiber bundle (F) by the composition (C) is carried out continuously in a bath containing said composition (C) according to the invention, at a temperature ranging from 10 to 80°C, for example from 10 to 50°C.

[0127] The duration of this impregnation can range from a few seconds to a few minutes, for example, from 10 seconds to 5 minutes.

[0128] The impregnation bath contains the composition (C) according to the invention.

[0129] After step (i), the impregnated fibres are wound onto a mandrel, at a temperature less than or equal to 30°C, for example between 20 and 30°C.

[0130] In step (i), the impregnation of the fiber bundle (F) by the composition (C) can be done by techniques well known to those skilled in the art, such as those mentioned above.

[0131] Said fiber bundle (F) is impregnated with composition (C), with a mass percentage of (F) between 40 and 70% and that of (C) between 30 and 60%.

[0132] The implementation by wet filament winding is particularly suitable for the manufacture of parts comprising a composite material operating at a nominal operating pressure as defined above, such as, for example, storage tanks operating under pressure.

[0133] The step of winding the impregnated fibers ii) is carried out continuously around a rotating mandrel. The winding is performed around a polymer liner for type IV tanks, or around a metal mandrel for type II and III tanks, or around a soluble or removable mandrel for the re- V-type servos.

[0134] The fiber deposition system is achieved by guiding the fibers which move back and forth and laterally during the rotation of the liner or mandrel, so that these fibers are wound and / or deposited uniformly.

[0135] Two fiber deposition methods can be used in the manufacture of a cylindrical or spherical part. Circumferential winding, which allows the fiber layer to be deposited with an orientation of 90° to the liner axis, and helical winding, which allows the fiber layer to be deposited with an orientation other than 90°. These two techniques are well known to those skilled in the art and are described, for example, in Hojjati et al., Composites Engineering, Vol. 5, Pages 51-59, 1995; De Carvalho et al., Composites Manufacturing, Vol. 6, Pages 79-84, 1995; Koussios et al., Journal of Materials Design and Applications, Vol. 219, Pages 25-35, 2005; Zu et al., Interfacial Interactions in Composites and Other Applications, Vol. 41, Pages 1312-1320, 2010.

[0136] At the end of the winding deposition phase, during step iii), polymerization can take place at maximum temperatures less than or equal to 170°C, for example at maximum temperatures ranging from 60°C to 170°C, from 60°C to 150°C, from 60°C to 130°C, from 60°C to 110°C, from 60°C to 105°C. The manufacturer will choose the temperature according to its manufacturing constraints.

[0137] This step iii) generally takes place in an oven or tunnel furnace. Heating is maintained until complete polymerization of the epoxy matrix of composition (C) (conversion >95%).

[0138] Implementation by filament winding can also be carried out on a polymer bladder or liner, in particular a polyethylene or polyamide bladder or liner.

[0139] The liner is the internal lining of the tank. It has two main functions: to ensure the watertightness of the structure and to act as a mandrel. Indeed, its rotation allows the fibers, previously impregnated with composition (C), to be deposited directly onto its outer surface.

[0140] According to one embodiment, the liner is made of polyethylene.

[0141] According to another embodiment, the liner is made of polyamide.

[0142] According to another embodiment, the liner is metallic, such as aluminum or stainless steel.

[0143] The composition (C) according to the invention undergoes rapid (only a few hours) and low-temperature curing, as previously stated, during the manufacture of composite pressure tanks of types II, III, IV, and V for the onboard storage of gaseous hydrogen. The rapid curing and the possibility of low-temperature curing of the composition are essentially due to the use of the liquid ionic (B) as a hardener.

[0144] Composition (C) includes an epoxy resin (A) because this type of thermosetting polymer is most commonly used for the manufacture of pressure tanks for on-board hydrogen storage.

[0145] The composition (C) according to the invention can therefore be used for the manufacture of pressure tanks of types II, III, IV and V, made of composite material, for the on-board storage of gaseous hydrogen, in particular for both fixed and mobile applications, such as hydrogen storage infrastructure, hydrogen transport for refueling, hydrogen rail vehicles, buses, trucks, aircraft, boats and other hydrogen vehicles, and hydrogen cars.

[0146] The invention therefore relates to the use of a composition (C) according to the invention, for the manufacture of a hydrogen tank, in particular a pressure tank, of types II, III, IV and V, made of composite material, for the on-board storage of gaseous hydrogen.

[0147] The tanks thus obtained can be approved according to the criteria of the regulations currently in force (such as EC79 or R134). EXAMPLES

[0148] Protocol for preparing a composition according to the invention

[0149] Araldite® LY 566 epoxy resin, marketed by Huntsman, and of the bisphenol A type, has a viscosity of 10 Pa.s at 20°C. Araldite® LY 566 epoxy resin is liquid at room temperature (20°C - 25°C).

[0150] The resin is introduced into a thermostatically controlled reactor, and then CYPHOS® IL 104 (trihexyl(tetradecyl)phosphonium bis-2,4,4-(trimethylpentyl)phosphinate or [R4PA]), marketed by Cytec Industries Inc., or CYPHOS® IL 103 (trihexyl(tetradecyl)phosphonium decanoate), marketed by Strem Chemicals, is added at a ratio of 10 parts by weight (pp or phr in English) (10 parts Cyphos® IL 103 to 100 parts of LY 556 resin). The mixture is stirred for approximately 20 minutes at 40°C.

[0151] Once homogenized, a composition according to the invention is obtained and can be used for impregnating reinforcing fibers. During this step, the composition is continuously diffused onto a strand of TORAYCA T720 carbon fiber from Toray® at a temperature between 10 and 50°C. This temperature should be adjusted by a person skilled in the art.

[0152] The wick impregnated with the composition (resin + ionic liquid) can then be wound onto the liner. Cooking cycle

[0153] The proposed curing cycles for the polymerization of a composition such as that prepared above are 5 hours with a polymerization step lasting:

[0154] 2h at 80 °C then 3h at 130 °C, or 2h at 80 °C then 3h at 105 °C for the ionic liquid CYPHOS® IL 104;

[0155] Ih at 50 °C, then Ih at 70 °C, then 3h at 105 °C or at 130 °C CYPHOS® IL 103.

[0156] In summary, the compositions according to the invention can be used for preparing tanks for 1 to 2 days for wet filament winding applications, particularly for Type IV hydrogen tanks. These compositions address the issue of curing times by offering polymerization times on thick composites (> 30 mm) of less than 5 hours. Furthermore, these compositions can be used with both polyethylene (PE) and polyamide (PE) liners, the two main polymer materials used in the manufacture of Type IV hydrogen tanks. Finally, these compositions make it possible to replace amine hardeners, which are problematic from a health perspective.

Claims

Demands

1. Composition (C) characterized in that it comprises (A) 70 to 95 parts by mass of an epoxy resin of viscosity less than or equal to 20 Pa.s, preferably between 1 and 20 Pa.s, more preferably between 1 and 10 Pa.(s), at a temperature between 20°C and 25°C, and (B) 5 to 30 parts by mass of a hardener dispersed in the resin, per 100 parts by mass of resin present in the composition, and in that the hardener is an ionic liquid containing a phosphonium cation of formula P(RiR2R3R4)+ in which R2, R3, and R4, identical or different, represent a hydrogen atom, an alkyl radical having 1 to 18 carbon atoms, an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted, and - an acetate anion of formula (R5CO2) in which R5 represents a hydrogen atom, an alkyl radical having 1 to 18 carbon atoms, an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted, the viscosity being measured at a temperature between 20°C and 25°C, using an ARES Rheometer device from TA® instruments.

2. Composition according to claim 1, characterized in that in the phosphonium cation Rh R2, R3 and R4, identical or different, represent - a hydrogen atom, - an alkyl radical selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and their branched isomers, - an aryl radical selected from phenyl, benzyl, said alkyl and aryl radicals being optionally substituted.

3. Composition according to claim 1 or 2, characterized in that the phosphonium cation is selected from [(C6H3)3(Ci4H29)P]+, [(C4H9)3(C14H29)P]\ [(C4H9)3(C2H5)P]+, [(C8H17)4P]\ [(C4H9)3(CH3)P]+, [(iso-C4H9)3(CH3)P]\ [(H)4P]\ [(CH3)4P]\ [(Ph)4P]h [(Ph)3(CH3)P]+, [(C6H13)3(C14H29)P]\ [(CH2OH)4P]h

4. A composition according to any one of claims 1 to 3, characterized in that the ionic liquid contains an acetate anion of formula (R5CO2), in which R5 represents - a hydrogen atony, - an alkyl radical selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and their branched isomers, - an aryl radical selected from phenyl, benzyl, said alkyl and aryl radicals being optionally substituted.

5. Composition according to claim 4, characterized in that the acetate anion is selected from ((CH3)CO2), ((C5Hn)CO2), ((CH3CH2CH(CH3 )CH2CH2)CO2), ((C7H15)CO2), ((CH3CH2CH2CH2CH(CH3)CH2CH2)CO 2), ((CH3)3CCH2CH(CH3)CH2CH2CH2)CO2), (CH3CH(CH3)CH2CH2CH 2CH(CH3)CH2)CO2), ((C9H19)CO2).

6. Composition according to any one of claims 1 to 5, characterized in that it comprises 5 to 20 parts by mass of ionic liquid, for 100 parts by mass of epoxy resin present in the composition.

7. Use of a composition (C) according to any one of claims 1 to 6, or of a composition comprising: (A) 70 to 95 parts by mass of an epoxy resin of viscosity less than or equal to 20 Pa.s, preferably between 1 and 20 Pa.s, more preferably between 1 and 10 Pa.(s), at a temperature between 20°C and 25°C, and (B) 5 to 30 parts by mass of a hardener dispersed in the resin, per 100 parts by mass of resin present in the composition, and in that the hardener is an ionic liquid containing a phosphonium cation of formula P(RiR2R3R4)+ in which R2, R3, and R4 are as defined in claim 1 or 2, and - a phosphinate anion of formula (PO2R6R7) in which R6 and R7, identical or different, represent - a hydrogen atom, - an alkyl radical selected from butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and their branched isomers, - an aryl radical selected from phenyl, benzyl, said alkyl and aryl radicals being optionally substituted a hydrogen atom, an alkyl radical having 2 to 16 carbon atoms, an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals possibly being substituted,. to impregnate a bundle of fibers (F) by wet process, the fibers (F) being chosen from - organic fibers chosen from polyethylene, poly(p-phenylene-2,6-benzobisoxazole) or PBO, aramid, polyamide, flax, polyester fibers; - inorganic fibers chosen from glass, carbon, silicon carbide, basalt fibers.

8. Use according to claim 7, characterized in that when the composition used comprises a hardener which is an ionic liquid containing a phosphinate anion, said phosphinate anion is of formula [[(CH3)3CCH2CH(CH3)CH2]2P(O)O].

9. A method for manufacturing parts comprising a composite material operating under pressure, characterized in that it comprises at least the following steps: i) impregnation of a bundle of fibers (F) selected from - organic fibers selected from polyethylene, poly(p-phenylene-2,6-benzobisoxazole) or PBO, aramid, polyamide, flax, polyester fibers; - inorganic fibers selected from glass, carbon, silicon carbide, basalt fibers, of a composition (C) according to any one of claims 1 to 6, or of a composition as defined in one of claims 7 or 8; ii) winding of the impregnated fibers around a bladder or mandrel; iii) polymerization of the composition (C) at a temperature less than or equal to 170°C.

10. A method according to claim 10, characterized in that said fiber bundle (F) is impregnated with the composition (C) according to any one of claims 1 to 6, or with the composition as defined in any one of claims 7 or 8, with a mass percentage of (F) between 40 and 70% and with a mass percentage of (C) between 30 and 60%.

11. Use of a composition (C) according to any one of claims 1 to 6, for the manufacture of a hydrogen tank, in particular a pressurized tank, of types II, III, IV and V, comprising a composite material, for the on-board storage of hydrogen gas.