Thermoplastic composite materials

Abstract

A thermoplastic composite material suitable for the manufacture of articles, in particular pressure vessels, for the storage and transportation of gasses. The vessel is particularly adapted for the storage and transportation of compressed gasses in vehicles.

Description

CYT 2024 / 008 1 THERMOPLASTIC COMPOSITE MATERIALS Cross-reference to related patent application

[0001] This application claims priorities filed on 2024 September 12 in the United States of America with Nr 63 / 694034, and on 2024 October 25 in Europe with Nr 24208990.2, the whole content of each of these applications being incorporated herein by reference for all purposes. Technical Field

[0002] The invention relates to a thermoplastic composite materials provided with excellent mechanical properties, interfacial adhesion, and low hydrogen permeation. This combination of properties makes these materials suitable for the manufacture of articles adapted for the storage and transportation of gases, in particular hydrogen. The invention further relates to the articles, such as pressure vessels, comprising the thermoplastic composite material. Background Art

[0003] To achieve levels of decarbonisation required to meet the Intergovernmental Panel on Climate Change target of preventing global warming greater than 1.5 °C above pre-industrial levels, strong global action to reduce carbon emissions is being undertaken. Hydrogen, in particular the so-called “green hydrogen”, that is hydrogen produced using clean energy sources, as an energy carrier has been identified as suitable for meeting these climate objectives. A key challenge to enabling the use of hydrogen, particularly in weight-critical aerospace and automotive environments, is storing it with high volumetric and gravimetric density.

[0004] Despite its popularity, the storage of hydrogen as a gas is challenging as it is the lightest element and must be held at very high pressure (i.e., 350– 700 bar) to achieve practical densities. The storage or transportation of large volumes of highly compressed hydrogen requires a shift from the use of metal containers or piping to lighter materials, such as polymeric materials. The same holds true for storage or transportation of liquidCYT 2024 / 008 2 hydrogen or cryo-compressed hydrogen. Vessels comprising composite materials is an area of significant interest due to the potential for high strength, low weight, and corrosion resistance offered by these materials.

[0005] Composite materials typically consist of a polymer matrix (a continuous phase) and a dispersed phase of continuous fibers that provide reinforcement. For hydrogen storage tanks, these materials must satisfy several key properties: - Mechanical Strength and Durability: The tank must withstand high pressures required for hydrogen storage (often in the range of 350-700 bar) without failure over its operational life. - Lightweight: To maximize the efficiency of hydrogen storage, especially for mobile applications like vehicles, the tanks must be as light as possible without compromising safety or performance. - Thermal Stability: During the filling and release of hydrogen, the tank will experience changes in temperature. The materials must maintain their integrity and performance characteristics over a wide range of temperatures, from - 65°C to 100°C for large tanks for compressed hydrogen. - Permeability: the composite material need minimal hydrogen permeation to prevent leaks, which could pose safety risks and reduce the efficiency of storage. - Durability and permeability for storing and transporting liquid hydrogen: the tank must withstand large temperature cycles from room temperature down to - 252.8°C for liquid hydrogen and down to - 233°C for cryo-compressed hydrogen.

[0006] Pressure vessels characterized by high gas barrier properties have been used for storing various gasses such as oxygen, carbon dioxide, nitrogen, argon, LPG (liquefied petroleum gas), methane, hydrogen, over a long period of time. Pressure vessels comprising a non-structural inner layer, or liner, surrounded with a structural fiber reinforced composite material for containing the fluid or gas under pressure are known. The liner acts as a barrier between the fluid or gas and the fiber reinforced composite material, thus preventing leaks and / or other degradations of the structureCYT 2024 / 008 3 of the fiber reinforced composite material.

[0007] Composite materials typically include structural reinforcing fibers embedded in a polymer matrix. Composite materials have been employed in a wide variety of applications. For example, continuous fiber composites have been used to form fiber reinforced composite tapes, ribbons, rods, prepregs, laminates, and profiles useful as lightweight structural reinforcements as well as protective casings. Composite materials comprising a thermoplastic polymer matrix are known to offer a number of benefits over thermosetting based materials. For example, thermoplastic prepregs can be more rapidly fabricated into articles. Another advantage is that thermoplastic articles may be recycled.

[0008] The need still exists to develop articles for the transport and storage of hydrogen and gasses in general, in particular pressure vessels, which combine high performance qualities in terms of impermeability to the stored gas, mechanical properties, at both low and high temperature, and high thermal degradation temperature, for ease of processing. An additional advantage for the application would be the non-flammability of the pressure vessel.

[0009] The objective of the invention is thus providing articles, such as pressure vessels, having very low permeability to gasses, such as hydrogen, and good mechanical resistance over a wide range of temperatures without requiring the use of structural layers made of metal or other non- thermoplastic polymeric materials. The objective is achieved by the thermoplastic composite material of the invention. The inventors have found that a good compromise between permeability to hydrogen, good mechanical properties and increased interfacial adhesion can be obtained by a vessel comprising a thermoplastic composite material as defined in the appended claims. Summary of invention

[0010] A first object of the invention is a thermoplastic composite material as defined in claims 1 to 8, which comprises continuous reinforcing fibers and a polymer matrix, said polymer matrix comprising a poly(arylene sulfide)CYT 2024 / 008 4 polymer; a poly(aryl ether sulfone) polymer; and optionally a poly(amide imide) polymer.

[0011] The continuous reinforcing fibers are advantageously carbon fibers.

[0012] A second object of the invention is a multilayer structure comprising the thermoplastic composite materials. The multilayer structure is suitable for use in a large number of demanding applications. Non-limiting examples are the use in articles for storing or transporting a fluid (gas or liquid) comprising at least one layer made of the thermoplastic composite material of the invention. The article may be a vessel, preferably a pressure vessel, that is a vessel for the storage of a gas under pressure, or a vessel for storing liquids or cryo-compressed gasses.

[0013] A further object of the invention is a compressed gas in a vessel comprising at least one layer made of the thermoplastic composite material of the invention. The compressed gas may be in direct contact with the layer made of the thermoplastic composite material of the invention. Still another object of the invention is a liquid in a vessel comprising at least one layer made of the thermoplastic composite material of the invention. The liquid or cryo-compressed gas may be in direct contact with the layer made of the thermoplastic composite material. Further objects of the invention are a method for making the composite material as well as the article. Description of invention

[0014] In the present application: - any description, even though described in relation to a specific embodiment, is applicable to and interchangeable with other embodiments of the present disclosure; - where an element or component is said to be included in and / or selected from a list of recited elements or components, it should be understood that in related embodiments explicitly contemplated here, the element or component can also be any one of the individual recited elements or components, or can also be selected from a group consisting of any two or more of the explicitly listed elements or components; any element orCYT 2024 / 008 5 component recited in a list of elements or components may be omitted from such list; - any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited ranges as well as the endpoints of the range and equivalents; - the indeterminate article “a” in an expression like “a poly(arylene sulfide) polymer”, is intended to mean “one or more”, or “at least one” unless indicated otherwise; and - the use of brackets “( )” before and after names of compounds, symbols or numbers, has the mere purpose of better distinguishing that name, symbol or number from the rest of the text; thus, said parentheses could also be omitted.

[0015] A first object of the invention is a thermoplastic composite material which comprises continuous reinforcing fibers and a polymer matrix, said polymer matrix comprising: - a poly(arylene sulfide) polymer; - 1.0 to 25.0 wt%, with respect to the weight of the polymer matrix, of a poly(aryl ether sulfone) polymer which is a polymer of which at least 80.0 mol % of the recurring units are recurring units (RPAES) of formula (K):as defined in detail hereafter; and - 0.0 to 10.0 wt%, with respect to the weight of the polymer matrix, of a poly(amide imide) polymer, with the proviso that when in formula (K) T is a sulfone group [-S(=O)2-] the amount of poly(aryl ether sulfone) polymer in the polymer matrix is at most 17.5 wt%.CYT 2024 / 008 6

[0016] The polymer matrix comprises at least 50.0 wt%, generally at least 55.0 wt%, of the poly(arylene sulfide) polymer, with respect to the total weight of the polymer matrix.

[0017] The poly(arylene sulfide) polymer

[0018] The poly(arylene sulfide) polymer typically contains at least 80.0 mol% of a recurring unit (RPAS) having at least one aromatic ring bonded to a sulfur atom. The amount of recurring unit (RPAS) is typically at least 85.0 mol%, at least 90.0 mol%, at least 95.0 mol%, at least 97.0 mol%, at least 98.0 mol%, at least 99.0 mol% or at least 99.9 mol%. As used herein, mol% is relative to the total number of recurring units in the poly(arylene sulfide) polymer, unless explicitly noted otherwise.

[0019] Recurring unit (RPAS) is represented by a formula selected from the following group of formulae:- R is, at each instance, independently selected from the group consisting of a C1-C12 alkyl group, a C7-C24 alkylaryl group, a C7-C24 aralkyl group, a C6-C24 arylene group, and a C6-C18 aryloxy group;CYT 2024 / 008 7 -T is selected from the group consisting of a bond, –CO-, -SO2-, -O-, - C(CH3)2, phenyl and -CH2-; - i is, at each instance, independently 0 or an integer from 1 to 4.

[0020] For the sake of clarity, when i is zero, the corresponding aromatic rings are unsubstituted.

[0021] The poly(arylene sulfide) polymer can be amorphous or semi-crystalline.

[0022] Preferably, the poly(arylene sulfide) polymer has a melt flow rate of at most 700 g / 10 min, more preferably of at most 500 g / 10 min. Preferably, the poly(arylene sulfide) has a melt flow rate of at least 1 g / 10 min, more preferably of at least 5 g / 10 min. The melt flow rate of any poly(arylene sulfide) polymer refers to the value measured at 5 kg and 315.6°C, according to ASTM D1238, procedure B.

[0023] Preferably, the poly(arylene sulfide) polymer is poly(phenylene sulfide) (hereinafter referred to as “PPS”). The expression “poly(phenylene sulfide)” or PPS, is used to refer to a poly(arylene sulfide) polymer where the recurring unit (RPAS) is represented by formula (1). More preferably, recurring unit (RPAS) is represented by formula (4):

[0024] Most preferably the recurring unit (RPAS) is represented by formula (4) in which i = 0.

[0025] The PPS may be acid washed or not acid washed. In some embodiments, the PPS is acetic acid washed PPS.

[0026] In a preferred embodiment, the PPS polymer is such that at least 90.0 mol% of the recurring units are recurring units of formula (4) in which i= 0. The PPS polymer may consist essentially of recurring units of formula (4) in which i = 0.

[0027] Suitable PPS is commercially available under the trade name Ryton® PPS from Solvay Specialty Polymers USA, LLC.

[0028] The PPS advantageously has a melt flow rate (at 5 kg and 315.6°C) of 10 to 200 g / 10 min, for example from 30 to 150 g / 10 min.

[0029] The poly(aryl ether sulfone) polymerCYT 2024 / 008 8

[0030] The polymer matrix in the thermoplastic composite of the present invention further comprises at least one poly(aryl ether sulfone) polymer.

[0031] For the purpose of the present invention, a “poly(aryl ether sulfone) polymer” denotes any polymer of which at least 80.0 mol % of the recurring units are recurring units (RPAES) of formula (K), the mol% being based on the total number of moles of recurring units in the polymer:where R, at each location, is independently selected from the group consisting of a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate; h, for each R, is independently zero or an integer ranging from 1 to 4, and T is selected from the group consisting of a bond, a sulfone group [-S(=O)2-] and a group –C(Rj)(Rk)-, where Rjand Rk, equal to or different from each other, are selected from a hydrogen, a halogen, an alkyl, an alkenyl, an alkynyl, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate.

[0032] T may be a sulfone group [-S(=O)2-]. T is preferably selected from the group consisting of a bond and a group –C(Rj)(Rk)-, where Rjand Rk, equal to or different from each other, are selected from a hydrogen, a halogen, an alkyl, an alkenyl, an alkynyl, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate. T is more preferably a bond or a group –C(Rj)(Rk)- in which Rj and Rk are alkyl groups. More preferably T is a bond or a group – C(Rj)(Rk)- in which Rjand Rkare methyl groups.CYT 2024 / 008 9

[0033] At least 85.0 mol% (based on the total number of moles of recurring units in the polymer), at least 90.0 mol%, at least 95.0 mol%, at least 99.0 mol% or all of the recurring units in the poly(aryl ether sulfone) polymer are recurring units (RPAES).

[0034] The poly(aryl ether sulfone) polymer may be selected from the group consisting of polysulfone (PSU), polyphenylsulfone (PPSU), or polyethersulfone (PES). The poly(aryl ether sulfone) polymer is preferably selected from the group consisting of polysulfone (PSU) and polyphenylsulfone (PPSU), more preferably it is polysulfone (PSU).

[0035] For the purpose of the present invention, a polysulfone (PSU) denotes any polymer comprising at least 80 mol% recurring units (RPSU) of formula (L), the mol% being based on the total number of moles in the polymer:

[0036] At least 85.0 mol%, at least 90.0 mol%, at least 95.0 mol%, at least 99.0 mol% or all of the recurring units in the PSU are recurring units (RPSU) of formula (L).

[0037] Advantageously, the polysulfone polymer comprises at least 80.0 mol% of recurring units which are recurring units (RPSU) of formula (L’):(the mol% being based on the total number of moles of recurring units in the polymer).

[0038] At least 85 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol% or all of the recurring units in the PSU are recurring units (RPSU) of formula (L’).

[0039] For the avoidance of doubt, formula (L)and (L’) correspond to formula (K) when T= –C(Rj)(Rk)- and both Rj and Rk are methyl groups.CYT 2024 / 008 10

[0040] The PSU polymer of the present invention can be a homopolymer or a copolymer. If the PSU polymer is a copolymer, it can be a random, alternate or block copolymer.

[0041] PSU is available as Udel® PSU from Solvay Specialty Polymers USA, L.L.C.

[0042] Alternatively, the poly(aryl ether sulfone) polymer can be a polyphenylsulfone polymer (PPSU).

[0043] As used herein, a polyphenylsulfone (PPSU) denotes any polymer comprising at least 80.0 mol% recurring units (RPPSU) of formula (M), the mol % being based on the total number of moles of recurring units in the polymer:.

[0044] According to an embodiment of the present disclosure, at least 85.0 mol% (based on the total number of moles of recurring units in the polymer), at at least 90.0 mol %, at least 95.0 mol %, at least 99.0 mol % or all of the recurring units in the PPSU are recurring units (RPPSU) of formula (M).

[0045] For the avoidance of doubt, formula (M) corresponds to formula (K) when T is a carbon-carbon bond.

[0046] The PPSU polymer of the present invention can be a homopolymer or a copolymer. If the PPSU polymer is a copolymer, it can be a random, alternating, or block copolymer.

[0047] PPSU can be prepared by known methods and is notably available as RADEL®PPSU from Solvay Specialty Polymers USA, L.L.C.

[0048] As used herein, a polyethersulfone (PES) denotes any polymer comprising at least 80.0 mol % recurring units (RPES) of formula (O), the mol% being based on the total number of moles of recurring units in the polymer:CYT 2024 / 008 11

[0049] At least 85.0 mol% (based on the total number of moles of recurring units in the polymer), at least 90.0 mol%, at least 95.0 mol%, at least 99.0 mol% or all of the recurring units in the PES are recurring units (RPES) of formula (O).

[0050] For the avoidance of doubt, formula (O) corresponds to formula (K) when T= [-S(=O)2-].

[0051] PES can be prepared by known methods and is notably available as VERADEL®PESU from Solvay Specialty Polymers USA, LLC.

[0052] The Polyamide-Imide (PAI) Polymer

[0053] The presently disclosed polymer matrix may optionally comprise a polyamide-imide (PAI) polymer. The PAI polymer of the present disclosure can comprise recurring units having at least 50.0 mol% of the recurring units comprising an aromatic ring and one or more of an amic acid group or an imide group [referred to as recurring units (RPAI) herein]. The PAI polymer can also comprise more than 90.0 mol% of recurring units (RPAI). The polymer solution can comprise one or more than one PAI polymer.

[0054] The acid number (mg of KOH / g polymer) of the PAI polymer may be 100 or more and even 120 or more. It may be up to the theoretical acid number for a resin that comprises only amic acid units. In certain embodiments, it may be up to 170 mg KOH / g polymer. The acid number may be determined by titration, such as a potentiometric titration method according to ASTM D664. In particular it may be determined by the potentiometric titration method described by ASTM D664, where N-methylpyrrolidone (NMP) is the solvent, and titrants are potassium hydroxide and tributylammonium chloride.

[0055] The recurring units (RPAI) are chosen from the group consisting of:CYT 2024 / 008 12wherein the symbol → in each formula denotes isomerism so that, in any recurring unit within the aromatic polyamic acid structure, the groups to which the arrows point may exist as shown or in an interchanged position. In formulae (RPAI-A) to (RPAI-E) Ar is an aromatic tetravalent group, which may comprise one or more than one aromatic ring, and which are preferably selected from the group consisting of:with X being selected from the group consisting of –O-, -C(O)-, -S-, -SO2-, -CH2-, -C(CF3)2-, -(CF2)n- with n= 1,2,3,4 or 5; R is an aromatic divalent group, which may comprise one or more than one aromatic ring, andCYT 2024 / 008 13 which are preferably selected from the group consisting of: ,with Y being selected from the group consisting of –O-, -C(O)-, -S-, -SO2-, or 5,

[0056] Alternatively, or in addition, the recurring units (RPAI) are chosen from the group consisting of units (i), (ii), and (iii) as follows:and / or the corresponding imide-group containing recurring unit:(i-b),CYT 2024 / 008 14 wherein the attachment of the two amide groups to the aromatic ring as shown in (i-a) will be understood to represent the 1,3 and the 1,4 polyamide-amic acid configurations;(ii-a), and / or the corresponding imide-group containing recurring unit:(ii-b), wherein the attachment of the two amide groups to the aromatic ring as shown in (ii-a) will be understood to represent the 1,3 and the 1,4 polyamide-amic acid configurations; andand / or the corresponding imide-group containing recurring unit:(iii-b),CYT 2024 / 008 15 wherein the attachment of the two amide groups to the aromatic ring as shown in (iii-a) will be understood to represent the 1,3 and the 1,4 polyamide-amic acid configurations.

[0057] The recurring units (RPAI) can be recurring units (i) or a mixture of the recurring units (ii) and (iii).

[0058] The amount of recurring units comprising an amic group can be determined by any suitable technique, such as spectroscopic techniques or titration techniques which are known to those of ordinary skill in the art.

[0059] When recurring units (RPAI) are selected from those of formulae (RPAI-A), (RPAI-B), (RPAI-C), (RPAI-D), (RPAI-E), as detailed above, the molar percentage of recurring units (RPAI) comprising at least one amic acid group may be expressed as follows: where [(RPAI-A) units], [(RPAI-B) units], [(RPAI-C)units], [(RPAI-D) units], and [(RPAI-E) units] denote, respectively molar concentration of the different recurring units (RPAI) as above described.

[0060] When recurring units (RPAI) are selected from those of formulae (RPAI-A), and (RPAI-C), as detailed above, the molar percentage of recurring units (RPAI) comprising at least one amic acid group may be expressed as follows: [(RPAI-A) units] [(RPA -A) units] + [(R -C) units]IPAI

[0061] The recurring units (RPAI) can have at least 50.0 mol%, even at least 60.0 mol%, still at least 70.0 mol% of recurring units (RPAI) comprise at least one amic acid group. Alternatively, or in addition, 70.0 to 95.0 mol%, even 75.0 to 90.0 mol% of recurring units (RPAI) comprise at least one amic acid group.

[0062] The PAI polymer can be manufactured by a process which includes the polycondensation reaction between at least an aromatic polycarboxylic acid halide monomer and at least an aromatic diamine.

[0063] The number average molecular weight (Mn) of the PAI polymer can be at least 1000, preferably at least 1500, more preferably at least 2000. The number average molecular weight (Mn) of the PAI polymer can be 20000CYT 2024 / 008 16 or less, preferably 15000 or less. The molecular weight of the PAI polymer (Mw and Mn) may be and is usually determined using gel permeation chromatography (GPC) using a polystyrene standard.

[0064] Non-limiting examples of suitable Polymers (PAI) are available under the trade name Torlon® PAI from Solvay Specialty Polymers USA, LLC.

[0065] The polymer matrix

[0066] The polymer matrix comprises: - a poly(arylene sulfide) polymer; - 1.0 to 25.0 wt% of a poly(aryl ether sulfone) polymer as defined above; and - 0.0 to 10.0 wt% of a poly(amide imide) polymer, with the proviso that when in formula (K) T is a sulfone group [-S(=O)2-] the amount of poly(aryl ether sulfone) polymer in the polymer matrix is at most 17.5 wt%.

[0067] The percentage by weight of the poly(arylene sulfide) polymer, of the poly(aryl ether sulfone) polymer, of the poly(amide imide) polymer, and of further components of the polymer matrix add up to 100.0 wt%.

[0068] The amount of poly(aryl ether sulfone) polymer may be at least 1.5 wt%, at least 2.0 wt%, even at least 2.5 wt% with respect to the weight of the polymer matrix.

[0069] When T in formula (K) is different from a sulfone group, the amount of poly(aryl ether sulfone) polymer may be at most 22.5 wt%, at most 20.0 wt%, at most 17.5 wt%, at most 15.0 wt%, even at most 12.5 wt% with respect to the weight of the polymer matrix.

[0070] When T in formula (K) is a sulfone group, the amount of poly(aryl ether sulfone) polymer is at most 15.0 wt%, at most 14.0 wt%, even at most 12.5 wt% with respect to the weight of the polymer matrix.

[0071] The poly(aryl ether sulfone) may advantageously be polysulfone(PSU).

[0072] The presence of the poly(amide imide) polymer in the polymer matrix is optional.

[0073] When the poly(amide imide) polymer is present, the polymer matrix contains at least 0.5 wt%, at least 1.0 wt% even at least 1.5 wt%. The poly(amide imide) polymer is generally at most 8.5 wt%, even at most 7.5 wt%.CYT 2024 / 008 17

[0074] The polymer matrix may comprise one or more additives commonly employed in the formulation of poly(arylene sulfide) polymers. Non-limiting examples of suitable additives are antioxidants (e.g. ultraviolet light stabilizers and heat stabilizers), processing aids, nucleating agents, lubricants, flame retardants, smoke-suppressing agents, anti-static agents, anti-blocking agents, colorants, and pigments.

[0075] Processing aids aim to reduce the viscosity and melt flow rate to improve impregnation of the fibers (discussed in detail below). Desirable processing aids include organic substances having a molecular weight of from 100 g / mol to 1,000 g / mol, including, but not limited to, a paraffin, an olefin, an olefin oligomer, an alkoxylated acyclic carboxylic acid, an alkoxylated acyclic carboxylic acid, amide, an acyclic carboxylic acid, an acyclic carboxylic acid ester, an acyclic carboxylic acid alkali metal salt, an acyclic carboxylic acid amide, an alkoxylated acyclic alcohol, an acyclic alcohol, an alkoxylated alkyl phenol, an alkyl phenol, and any combination of two or more thereof. Particularly desirable combinations of processing aids include, but are not limited to, paraffin and a sterically hindered phenolic stabilizer. In some embodiments, the concentration of the processing aid is from 0.05 wt% to 1.00 wt%, from 0.05 wt% to 0.50 wt% or from 0.10 wt% to 0.50 wt%. For clarity, in embodiments including a combination of processing aids, the concentration of each processing aid or the total concentration of all processing aids is within the previously described ranges.

[0076] The polymer matrix may be free of additional components or processing aids. In such embodiments, the total concentration of the additional components, processing aids, or both in the polymer matrix is no more than 1 wt%, no more than 0.5 wt%, no more than 0.1 wt%, no more than 0.05 wt%, or no more than 0.01 wt%, no more than 0.005 wt% or no more than 0.001 wt%.

[0077] The total amount of additives may be 20.0 wt% or less, even 10.0 wt% or less with respect to the total weight of the polymer matrix. When present the amount of one or more additives is at least 1.0 wt%, even at least 2.0 wt%, relative to the total weight of the polymer matrix.CYT 2024 / 008 18

[0078] The poly(arylene sulfide) polymer typically represents the balance to 100 wt% in the polymer matrix. The poly(arylene sulfide) polymer is generally at least 50.0 wt% of the polymer matrix, even at least 55.0 wt%, typically at least 60.0 wt%, or even at least 70.0 wt% relative to the total weight of the polymer matrix.

[0079] The poly(arylene sulfide) polymer is preferably PPS.

[0080] Advantageous results in terms of flexural strength, short beam shear strength, transverse cracking resistance, and reduced hydrogen permeation were obtained when the polymer matrix had one of the following compositions: - a polymer matrix composition 1 (PM1) comprising: PPS, preferably 75.0 to 98.0 wt% of PPS, more preferably 85.0 to 98.0 wt%; and 2.0 to 25.0 wt%, preferably 2.0 to 15.0 wt% of PSU; - a polymer matrix composition 2 (PM2) comprising: PPS, preferably 75.0 to 98.0 wt% of PPS, more preferably 85.0 to 98.0 wt%; and 2.0 to 25.0 wt%, preferably 2.0 to 15.0 wt% of PPSU; - a polymer matrix composition 3 (PM3) comprising: PPS, preferably 70.0 to 85.0 wt% of PPS, 2.5 to 20.0 wt% of PSU and 0.5 to 10.0 wt% of a poly(amide imide) polymer; - a polymer matrix composition 4 (PM4) comprising: PPS, preferably 70.0 to 85.0 wt% of PPS, 2.5 to 20.0 wt% of PPSU and 0.5 to 10.0 wt% of a poly(amide imide) polymer.

[0081] The thermoplastic composite material

[0082] The thermoplastic composite material comprises continuous reinforcing fibers impregnated with the polymer matrix as detailed above. As used herein, the expression “continuous reinforcing fiber” refers to a fiber having a length of at least 5 mm. The length of the fiber corresponds to the longest dimension of the fiber.

[0083] The continuous reinforcing fiber may have a length, in the longest dimension, of at least 1 cm, at least 25 cm or at least 50 cm. The length of the continuous reinforcing fiber is dependent on the shape and size of the finished part.

[0084] The expression “continuous fiber” is used herein also to refer to a yarn. A yarn is a continuous strand of one or more fibers, one or more filaments, orCYT 2024 / 008 19 material in a form suitable for use in the production of textiles, sewing, crocheting, knitting, weaving, stitching, etc. Yarns include, for example, (1) a plurality of filaments laid or bundled together without applied or intentional twist, sometimes referred to as a zero-twist yarn or a non-twisted yarn; (2) a plurality of filaments laid or bundled together and are either interlaced, have false-twist, or are textured in some manner; (3) a plurality of filaments laid or bundled together with a degree of twist, sometimes referred to as a twisted yarn; (4) a single filament with or without twist, sometimes referred to a monofilament or monofilament yarn.

[0085] The continuous reinforcing fiber is selected from the group consisting of glass fiber, carbon fibers, aluminum fiber, metallic fibers, ceramic fiber, titanium fiber, magnesium fiber, boron carbide fibers, rock wool fiber, steel fiber, aramid fiber and natural fiber (e.g. cotton, linen and wood). Preferably, the continuous reinforcing fiber is selected from the group consisting of glass fiber, carbon fiber, aramid fiber, and ceramic fiber. Advantageously, the continuous reinforcing fiber is carbon fiber. As used herein, the term “carbon fiber” is intended to include graphitized, partially graphitized, and ungraphitized carbon reinforcing fibers, as well as mixtures thereof. The carbon fibers can be obtained by heat treatment and pyrolysis of different polymer precursors such as, for example, rayon, polyacrylonitrile (PAN), aromatic polyamide or phenolic resin; carbon fibers may also be obtained from pitchy materials. The term “graphite fiber” is intended to denote carbon fibers obtained by high temperature pyrolysis (over 2000°C) of carbon fibers, wherein the carbon atoms place in a way similar to the graphite structure. The carbon fibers may be chosen from the group consisting of PAN-based carbon fibers, pitch based carbon fibers, graphite fibers, and mixtures thereof.

[0086] The carbon fibers may be sized or unsized. Suitable unsized carbon fibers are commercially available from Mitsubishi under the trade name Grafil® G34-70012K were used. They are supplied in the form of a tow comprising 12,000 individual fibers. The individual fiber diameter is ca.7 μm.

[0087] The thermoplastic composite material may include one or more additional continuous reinforcing fibers, each distinct in compositions and as described above.CYT 2024 / 008 20

[0088] Overall, the continuous reinforcing fibers constitute at least 5.0% of the total volume of the thermoplastic composite material. Typically the continuous reinforcing fibers represent at least 10.0%, even at least 15.0%, even at least 20.0%, at least 25.0%, even at least 30.0% of the total volume of the thermoplastic composite material. The continuous reinforcing fibers are no more than 80.0%, no more than 75.0%, even no more than 70.0% of the total volume of the thermoplastic composite material. The continuous reinforcing fibers may conveniently represent from 20.0% to 75.0%, from 25.0% to 70.0%, from 25.0% to 65.0% and even from 30.0% to 60.0% of the total volume of the thermoplastic composite material. The polymer matrix represents the remainder of the volume of the thermoplastic composite material.

[0089] The continuous reinforcing fibers in the thermoplastic composite material are generally aligned along a single direction. Generally aligned fibers are oriented such that at least 70%, at least 80%, at least 90% or at least 95% of the fibers have a direction that is within 30 degrees, within 25 degrees, within 20 degrees, within 15 degrees, or within 10 degrees along the direction of the other fibers.

[0090] The continuous reinforcing fibers in the thermoplastic composite material may be arranged at an angle the ones with respect to the others. The continuous reinforcing fibers might be arranged as a woven fabric or a layered fabric or any combination of one or more.

[0091] The thermoplastic composite material can be fabricated by methods well known in the art. In general, the method of fabrication includes a step of impregnation of the continuous reinforcing fibers with the polymer matrix, and subsequent cooling or drying to form the thermoplastic composite material.

[0092] Impregnation of the continuous reinforcing fibers with the polymer matrix may take place, for instance, by means of a melt impregnation process, which includes contacting the continuous reinforcing fibers with a melt of the polymer matrix. Subsequent to melt impregnation, the impregnated continuous reinforcing fibers are cooled to form a solid composite.

[0093] Impregnation of the continuous reinforcing fibers with the polymer matrix may take place by means of a film infusion (double belt process).CYT 2024 / 008 21

[0094] Impregnation may take place by means of a solution process or, preferably, a slurry process. In a solution process, a solution is formed by dissolving the polymer in a liquid medium. The solution is coated onto a surface of the continuous reinforcing fibers, for example, by passing the fibers through a bath of the solution. Subsequently, the coated fibers are then heated and consolidated. In a slurry process, the continuous fibers are impregnated with particles of the polymer, for example, by passing the fibers through a suspension of the particles or a fluidized bed of the particles. Subsequently, the fibers containing the polymer particles are heated and consolidated.

[0095] The thermoplastic composite material has a thickness which is usually between 100 microns and 500 microns. The thickness is adapted to provide multilayer structures which can be easily shaped to provide an article, such as a vessel or a pipe.

[0096] The multilayer structure

[0097] An object of the invention is a multilayer structure comprising the thermoplastic composite material.

[0098] The multilayer structure comprises two, three, four, five, six, seven, eight, nine, ten, 50, 80, 100 or even more layers consisting of the thermoplastic composite material, such as 200 or 300 layers.

[0099] The multilayer structure may additionally comprise one or more layers that are free of continuous reinforcing fibers. The additional layers may or may not comprise a poly(arylene sulfide) polymer. Preferably, the additional layers are not made of metallic strips of material.

[0100] The inventive multilayer structure is characterized by high thermal resistance, good hydrogen barrier, which is maintained after thermal cycling over a very wide temperature range, low transverse cracking, excellent interfacial strength and non-flammability. These features make the multilayer structure particularly well adapted for a wide range of demanding applications.

[0101] The article

[0102] A further object of the invention is an article comprising at least one layer consisting of the thermoplastic composite material which comprises continuous reinforcing fibers and a polymer matrix, said polymer matrix comprising:CYT 2024 / 008 22 - a poly(arylene sulfide) polymer; - 1.0 to 25.0 wt%, with respect to the weight of the polymer matrix, of a poly(aryl ether sulfone) polymer which is a polymer of which at least 80.0 mol % of the recurring units are recurring units (RPAES) of formula (K):as defined above; and - 0.0 to 10.0 wt% with respect to the weight of the polymer matrix of a poly(amide imide) polymer.

[0103] When T in formula (K) is a sulfone group [-S(=O)2-] the polymer matrix may conveniently comprise at most 17.5 wt%, even at most 15.0 wt% of the poly(aryl ether sulfone) polymer.

[0104] In formula (K), T may advantageously be selected from the group consisting of a bond or a group –C(Rj)(Rk)- in which Rj and Rk are alkyl groups, preferably methyl groups.

[0105] The presently disclosed composite materials can be desirably incorporated into articles for use in a wide variety of application settings, such as automotive components, battery housings, aerospace components, oil and gas drilling components, components for Smart Devices, medical housings or components for medical devices, components of Urban Air Mobility devices, and an electronic device.

[0106] With respect to automotive applications, the inventive composites can be integrated into automotive components including, but not limited to, pans (e.g. oil pans), panels (e.g. exterior body panels, including but not limited to quarter panels, trunk, hood; and interior body panels, including but not limited to, door panels and dash panels), side-panels, mirrors, bumpers, bars (e.g., torsion bars and sway bars), rods, suspensions components (e.g., suspension rods, leaf springs, suspension arms), turbo charger components (e.g. housings, volutes, compressor wheels and impellers) and housings for battery components.CYT 2024 / 008 23

[0107] The thermoplastic composites described herein can also be desirably integrated into aerospace components, oil and gas drilling components (e.g. downhole drilling tubes, chemical injection tubes, undersea umbilicals and hydraulic control lines), mobile electronic device components, articles for geothermal applications as well as in the carbon capture utilization and storage.

[0108] The thermoplastic composite material of the present invention, thanks to its excellence in both flexural strength and reduced hydrogen permeability, is suitable for use as a component in an article for the storage or transportation of compressed gas, in particular hydrogen. The inventive composite material may be also used in the storage and transportation of liquids, in particular hydrogen, as well as storage and transportation of cryo-compressed hydrogen. Notable non-limiting examples of articles are hoses, pipes, tubes, joints, tanks, reservoirs, vessels or, in general, piping systems.

[0109] The hose for compressed hydrogen is used as a hose for charging a fuel- cell vehicle or the like with hydrogen from a hydrogen station. Since the hose for compressed hydrogen is subject to repeated temperature changes (heat cycles) from -40°C or lower to 90°C or higher due to charging and discharging of high-pressure hydrogen, it is required to have high heat cycle resistance, pressure cycle resistance as well as flexibility.

[0110] The hose for high-pressure hydrogen is a hose comprising or consisting of the multilayer structure as above defined.

[0111] The vessel

[0112] The term “vessel” is used herein to refer to a hollow container or any system for the transportation of a fluid, in particular a pressurized gas. The vessel of the invention can be a hollow container for containing a gas, preferably a pressurized gas.

[0113] The vessel may consist of one or, preferably, more than one layer consisting of the thermoplastic material of the invention. Notable examples of vessels of this type are the so-called Type V, or liner-less vessels, that is vessels that do not have an internal liner so the composite material acts as both the gas barrier and load bearing structure.CYT 2024 / 008 24

[0114] Type V vessels may be manufactured using filament winding, a technique that winds tensioned bands of fibres around a rotating mandrel or even by means of automated fiber placing techniques.

[0115] Alternatively, the vessel of the invention may be a Type IV vessel, that is a vessel comprising an internal barrier layer, or liner, and one or more than one layers consisting of the thermoplastic composite material of the invention. The liner forms the interior surface of the vessel, in contact with the gas. When more layers of the thermoplastic composite material are present they typically have the same composition. However, the volume % of fibers and the nature of the fibers used may vary from one layer to the next, typically from the inner to the outer surface of the vessel or between the hoop and helicoidal layers.

[0116] The vessel comprises a hollow body and at least one boss. A boss is known by a person skilled in the art and it refers to the opening in which a closure is attached which allows flow of gas or fluid in and out the vessel. A boss is usually made of metal. The boss could alternatively be made of a polymeric material, for instance a PPS.

[0117] The hollow body may have any shape suitable for the storage of a gas, in particular of a gas under pressure.

[0118] In certain conventional embodiments, the vessel has a cylindrical shape and a boss is placed at the end. Often, a vessel has two bosses at each end of the cylindrical shape.

[0119] The shape of the hollow body is determined by the desired use. It is usually but not exclusively cylindrical; it typically has a diameter of between 10.0 cm and 1.00 m. The hollow body could also have a conical or even an irregular shape.

[0120] The length of a hollow body also depends on the end use and may for example be between 50.0 cm and up to lengths as large as 10.0 m. These higher lengths are usually employed for gas transport. As an example, for vessels in trucks the length is usually between 1.0 m and 3.0 m.

[0121] The vessel of the invention may have an internal volume between 3.5 dm3and 10.0 m3, even from 5.0 dm3to 5.0 m3. The internal volume of the vessel may be at least 10.0 dm3, even at least 15.0 dm3. The internalCYT 2024 / 008 25 volume may be up to 0.5 m3, even up to 1.0 m3, up to 5.0 m3, even up to 10.0 m3.

[0122] The vessel may be prepared according to any method known in the art.

[0123] The vessel of the invention is characterized by a good hydrogen barrier and mechanical properties.

[0124] The vessel according to the invention exhibits a nominal pressure of at least 2.5 MPa, typically at least 20.0 MPa, even at least 30.0 MPa. The nominal pressure may be up to 70.0 MPa, 100 MPa, even 150.00 MPa and more. Advantageously, the vessel of the invention has a nominal pressure of 20.0 to 70.0 MPa.

[0125] A burst pressure of at least 157.5 MPa may be reached for the storage of hydrogen gas with a vessel according to the invention. Vessels for the storage of compressed hydrogen typically require nominal pressures of 35.0 MPa or 70.0 MPa. Burst pressures, measured according to ECE R134, are typically up to 78.8 MPa and 157.5 MPa, respectively.

[0126] A further object of the invention is a compressed gas in a vessel of the first object, wherein Layer (BL) is in contact with the compressed gas. The gas is advantageously selected from the group consisting of hydrogen, oxygen, nitrogen, argon, helium, methane, propane, compressed natural gas, CO2and ammonia.

[0127] The gas is typically at a pressure of at least 5.0 MPa, preferably at least 10.0 MPa. Depending on the gas, the pressure may be up to 150.0 MPa.

[0128] A further object of the invention is a vehicle comprising the vessel, the compressed gas contained in the vessel or the liquid or cryo-compressed gas contained in the vessel.

[0129] The vehicle may be a car, a truck, a train, a ship, an urban mobility vehicle, an airplane, a helicopter or any other vehicle that could be powered using the conversion of a gas into energy by any means.

[0130] Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

[0131] The embodiments above are intended to be illustrative and not limiting. Additional embodiments are within the inventive concepts. In addition,CYT 2024 / 008 26 although the present invention is described with reference to particular embodiments, those skilled in the art will recognize that changes can be made in form and detail without departing from the spirit and scope of the invention.

[0132] EXAMPLES

[0133] MATERIALS

[0134] PPS1 is Ryton® M2000 SFP, a poly(phenylene sulfide) polymer powder commercially available from Solvay Specialty Polymers USA, LLC

[0135] PSU1 is Udel® P-1850 a polysulfone polymer commercially available from Solvay Specialty Polymers USA, LLC.

[0136] PAI1 is Torlon® AI-30 a polyamideimide polymer commercially available from Solvay Specialty Polymers USA, LLC

[0137] Carbon fiber: Grafil® G34-700 PAN-based fiber, unsized 12 K, commercially available from Mitsubishi.

[0121] General procedure for preparation of composite material

[0122] A slurry-based impregnation process was employed to create unidirectional carbon fiber tapes impregnated with the compositions provided in Table 1 below. Table 1 Ex.1 Ex.2 Ex.3 C. Ex 1 PPS1 (wt%) 96.0 85.0 81.0 100.0 PSU1 (wt%) 4.0 15.0 15.0 - PAI1 (wt%) - - 4.0 -

[0123] Unsized carbon fibers commercially available from Mitsubishi under the trade name Grafil®G34-700 were used. They were supplied in the form of a tow comprising 12,000 individual fibers. The individual fiber diameter was 7 μm. A sufficient number of tows were used to make a 76-mm wide unidirectional tape. The dry web of collimated, continuous fibers were passed through an aqueous bath containing water, the polymer particlesCYT 2024 / 008 27 of Example 1-3 or Comparative Example 1, and a surfactant (Rhodasurf® Bc729, supplied by Syensqo).

[0124] At the start of the run, the aqueous bath initially contained 896 g of polymer dispersed in 29 kg of water with 2.7 g of surfactant added to help with polymer dispersion. A secondary slurry recharge was created with 2470 g of polymer dispersed in 14 kg of water and 7.43 g of surfactant to help with dispersion. The recharge was used to resupply the slurry bath with the polymer and water that the carbon fiber web dragged out of the bath during production while also maintaining the bath level and slurry concentration necessary for the target fiber volume fraction (Vf) of 0.60. The fiber volume fraction was maintained via weight checks on the tape.

[0125] The line was allowed to equilibrate for 1.5 hours prior to collecting the prepreg tape. After passing through the aqueous bath, the web of collimated fibers were passed underneath a series of infrared lamps which facilitated evaporation of the water and consolidation of the polymer. The tape was then passed through a die heated to 340 °C, then through a heated calendar maintained at 120 °C, and then a series of cooling rolls before being wound onto a cardboard core. The line speed was set at 1.0 m / min. The prepreg tape had a nominal fiber volume fraction of 0.60 (60 vol%), which resulted in a final polymer content of 32 wt %, and a fiber areal weight of 150 g / m2.

[0126] Laminate Preparation and characterization

[0127] Composite laminates were prepared on a Rucks KV 275.11 Upstroke Press equipped with 600 mm x 600 mm, a maximum platen temperature of 450 °C, and a maximum press force of 1000 kN. The prepreg tape was cut and welded to proper ply dimensions according to the mold being used to press the laminates. The plies were stacked based on desired thickness and layup of the laminate. The edges of the ply stack were taped with Kapton® to maintain fiber alignment and the dried for 2 h at 80°C in a desiccant oven. The dried ply stack was sandwiched between Kapton® sheets coated with Zyvax® Composite Shield Release and placed in a steel window frame mold of 7” x 11” and placed into the press. TheCYT 2024 / 008 28 prepared mold was then heated according to the procedure displayed in Table 2. Table 2 Temp (°C) Pressure Dwell time (min) (kPa) Step 1 340 2413 12-15 Step 2 120 2413 15-18 Step 3 120 0 -

[0128] Samples were cut from the resulting laminates and tested according to the ASTM standards displayed in Table 3. For 0° and 90° flexural tests, a three point loading system for center loading was used to test flexural properties in polymer matrix composites with a standard dimension of 4 mm in thickness and 13 mm in width. A center load was applied to induce three-point bending at a rate of 1 mm / min. For 0° short-beam shear tests, the test sample was placed on a standard fixture with the fibers parallel to the loading direction. A load was applied to induce flex at a rate of 1 mm / min. The results all of which are given in Table 3.

[0129] For transverse crack observations, [0 / 90] layup of laminates were cut at a 45° bias and examined using optical microscopy. Specifically, the cut laminates were mounted and set in a two-component epoxy resin (such as Epoxicure 2™ from Buehler). After curing, the puck was progressively abraded and polished using first sandpaper then a diamond slurry on a felt pad. The sandpapers have grits of 280 / P320 to 1200 / P4000, and the series of diamond slurries (Glennel® Diamond Suspension from Electron Microscopy Sciences) have particle sizes sequentially of 3.0 μm, 1.0 μm, and eventually 0.1 μm. The polished samples were then imaged using an optical microscope under magnification levels of 100-300x to look for transverse cracks.

[0130] The results of which are given in Table 3.CYT 2024 / 008 29 Table 3 Ex.1 Ex.2 Ex.3 C. Ex.1 Tape fiber areal 150 150 150 150 weight (g / m²) Tape fiber volume 0.60 0.60 0.60 0.60 fraction 90° Flexural ASTM 135 ± 4 129 ± 4 92 ± 4 94 ± 5 strength (MPa) D7264 0° Short beam ASTM 99 ± 1 97 ± 3 92 ± 2 89 ± 2 shear strength D2344 (MPa) Transverse N N N Y cracks

[0131] The laminates of Examples 1 to 3 showed no transverse cracks differently from the laminate of Comp. Example 1.90° flexural strength and 0° short beam shear strength of the inventive laminates were also better compared to those of the laminate of Comparative Example 1.

[0138] H2Permeation coefficient determination

[0139] Samples for hydrogen permeation testing were prepared have been prepared following the press consolidation conditions described above. Lay up: [0,+45,90,-45]2s. Samples of 90 x 90 mm were cut and mounted on a cell so as to form a barrier between two chambers. An epoxy glue was put around the sheets to minimize side permeation. The cell was conditioned at 55 °C to determine H2 permeation according to the H2 tank standard R 134

[0140] was mounted on a cell so as to form a barrier between two chambers. One chamber contained the test gas (H2) and the other chamber was purged with a sweep gas (synthetic air). The feed side was pressurized with H2and during the measurement, the concentration of H2in the sweep gas flow was measured, typically with an electrochemical H2 sensor. Permeation coefficient (P) is calculated according to the equation 1 (Eq. 1):CYT 2024 / 008 30 P = (C·D·d / A·pp).(T°·p / T·p°) [Eq.1] wherein: P = permeation coefficient (Ncm3·mm / m2·day·bar) C = penetrant concentration (ppm) D = sweep gas flow rate (mL / min) d = sample thickness (mm) A = testing area in contact with the gas (m2) pp = penetrant partial pressure (bar) T = ambient temperature (K) p = ambient pressure (bar) T° = standard temperature (273.15 K) p° = standard pressure (1.013 bar)

[0141] Further normalization is done to standard temperature and pressure, i.e. 273.15 K and 1.013 bar.

[0142] Plate samples were tested under the following conditions: - Condition 0: as such, no thermal treatment (@ 55°C); - Condition 1: after 5 thermal cycles as follows 30 minutes at - 65 °C and 30 minutes at 100 °C; - Condition 2: after 5 thermal cycles as in Condition 1 followed by 5 cycles in liquid nitrogen (30 minutes in liquid nitrogen and 30 minutes at room temperature), - Condition 3: after 5 thermal cycles 5 thermal cycles as in Condition 1 followed by 50 cycles in liquid nitrogen (30 minutes in liquid nitrogen and 30 minutes at room temperature).

[0143] The results (hydrogen permeation coefficient at 55 °C), N.cm3(STP).mm / m2.day.bar are shown in Table 4.CYT 2024 / 008 31 Table 4 Condition 0 Condition 1 Condition 2 Condition 3 (N cm3(STP) (N cm3(STP) (N cm3(STP) (N cm3(STP) mm / m2d bar) mm / m2d bar) mm / m2d bar) mm / m2d bar) Ex.1 15 15 17 17 Ex.2 28 25 n / a n / a C. Ex.1 14 34 n / a n / a

[0144] The inventive materials show markedly lower hydrogen gas permeation after thermal cycling, making them great candidates for pressurized hydrogen tanks, i.e. tanks type 4 (with a polymeric liner), tanks type 4.5 (with a PPS liner) and even tanks type 5 (full composite, no liner). Furthermore inventive materials show low hydrogen gas permeation after thermal cycling and subsequent cycling in liquid nitrogen, making them also great candidates for liquid H2 and cryo-compressed hydrogen tanks i.e. tanks type 4 (with a polymeric liner), tanks type 4.5 (with a PPS liner) and even tanks type 5 (full composite, no liner)

[0145] The good performance in terms of H2 permeation, lack of transverse cracking and good flexural strength of the inventive materials make them very good candidates for the preparation of both liquid and and cryo- compressed hydrogen tanks.

Claims

CYT 2024 / 008 32 Claims 1. A thermoplastic composite material which comprises continuous reinforcing fibers and a polymer matrix, said polymer matrix comprising: - a poly(arylene sulfide) polymer; - 1.0 to 25.0 wt%, with respect to the weight of the polymer matrix, of a poly(aryl ether sulfone) polymer which is a polymer of which at least 80.0 mol % of the recurring units are recurring units (RPAES) of formula (K):wherein R, at each location, is independently selected from the group consisting of a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate; h, for each R, is independently zero or an integer ranging from 1 to 4; and T is selected from the group consisting of a bond, a sulfone group [-S(=O)2-], and a group –C(Rj)(Rk)-, where Rj and Rk, equal to or different from each other, are selected from a hydrogen, a halogen, an alkyl, an alkenyl, an alkynyl, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate; and - 0.0 to 10.0 wt% with respect to the weight of the polymer matrix of a poly(amide imide) polymer, with the proviso that when in formula (K) T is a sulfone group [-S(=O)2-] the amount of poly(aryl ether sulfone) polymer in the polymer matrix is at most 17.5 wt%.

2. The thermoplastic composite material of claim 1 or 2 which comprises at least at least 50.0 wt% of the poly(arylene sulfide) polymer with respect to the weight of the polymer matrix.CYT 2024 / 008 33 3. The thermoplastic composite material of any one of the preceding claims which comprises 85.0 to 98.0 wt% of the poly(arylene sulfide) polymer; and 2.0 to 15.0 wt% of a poly(aryl ether sulfone) polymer.

4. The thermoplastic composite material of any one of the preceding claims wherein the poly(arylene sulfide) polymer is a polymer that contains at least 80.0 mol% of a recurring unit (RPAS) represented by formula (4):in which R is, at each instance, independently selected from the group consisting of a C1-C12 alkyl group, a C7-C24 alkylaryl group, a C7-C24 aralkyl group, a C6-C24 arylene group, and a C6-C18 aryloxy group; and i is 0 or an integer between 1 to 4, preferably i is 0.

5. The thermoplastic composite material of any one of the preceding claims in which the poly(aryl ether sulfone) polymer is selected from the group consisting of polymers of formula (K) wherein T is selected from the group consisting of a bond and a group –C(Rj)(Rk)-, where Rj and Rk, equal to or different from each other, are selected from a hydrogen, a halogen, an alkyl, an alkenyl, an alkynyl, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate; preferably T is a bond or a group – C(Rj)(Rk)- in which Rjand Rkare alkyl groups, more preferably methyl groups.

6. The thermoplastic composite material of any one of the preceding claims which contains 0.5 to 10.0 wt% of a poly(amide imide) polymer with respect to the weight of the polymer matrix.

7. The thermoplastic composite material of any one of the preceding claims in which the continuous reinforcing fibers have a length of at least 5 mm.

8. The thermoplastic composite material of any one of the preceding claims in which the continuous reinforcing fibers are selected from the group consisting of glass fibers, carbon fibers, aramid fibers, and ceramic fibers; preferably carbon fibers.

9. A multilayer structure comprising the thermoplastic composite material of any one of the preceding claims..CYT 2024 / 008 34 10. An article comprising a thermoplastic composite material which comprises continuous reinforcing fibers and a polymer matrix, said polymer matrix comprising: - a poly(arylene sulfide) polymer; - 1.0 to 25.0 wt%, with respect to the weight of the polymer matrix, of a poly(aryl ether sulfone) polymer which is a polymer of which at least 80.0 mol % of the recurring units are recurring units (RPAES) of formula (K):wherein R, at each location, is independently selected from the group consisting of a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate; h, for each R, is independently zero or an integer ranging from 1 to 4; and T is selected from the group consisting of a bond, a sulfone group [-S(=O)2-], and a group –C(Rj)(Rk)-, where Rjand Rk, equal to or different from each other, are selected from a hydrogen, a halogen, an alkyl, an alkenyl, an alkynyl, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate; and - 0.0 to 10.0 wt% with respect to the weight of the polymer matrix of a poly(amide imide) polymer.

11. The article of claim 10 wherein when in formula (K) T is a sulfone group [-S(=O)2-] the amount of poly(aryl ether sulfone) polymer in the polymer matrix is at most 17.5 wt%.

12. The article of claim 10 or 11 which is an automotive component, battery housing, aerospace component, oil and gas drilling component, component for Smart Devices, medical housing or component for medical device, component of Urban Air Mobility device, electronic device or an article for the storage or transportation of compressed gas.CYT 2024 / 008 35 13. The article of any one of claims 10 to 12 which is in the shape of a hollow body which has one or more of the following: - a diameter of 10.0 cm to 1.0 m; - a length of 50.0 cm to 10.0 m; - an internal volume of 3.5 dm3to 5.0 m3.

14. A liquid, compressed or cryo-compressed gas, preferably selected from the group consisting of hydrogen, oxygen, nitrogen, argon, helium, methane, propane, natural gas, CO2, ammonia, contained in the article of claim 13.

15. A vehicle comprising the article of claim 13 or the liquid, compressed or cryo- compressed gas of claim 14. .

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