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    • 专利摘要:
    The present invention relates to a multilayer structure, intended for the transport, distribution or storage of hydrogen, comprising, from the inside to the outside, at least one waterproofing layer and at least one composite reinforcing layer, said innermost composite reinforcing layer being welded to said outermost adjacent sealing layer, said sealing layers consisting of a composition predominantly comprising at least one thermoplastic polymer P1i (i = 1 to n, n being the number of sealing layers) semi-crystalline whose Tf, as measured according to ISO 11357-3: 2013, is less than 280 ° C, in particular less than 265 ° C, said at least one thermoplastic polymer of each layer d 'sealing may be the same or different, and at least one of said composite reinforcement layers consisting of a fibrous material in the form of continuous fibers impregnated with a composition mainly comprising at least one poly thermoplastic mother P2j, (j = 1 to m, m being the number of reinforcing layers) in particular semi-crystalline, said thermoplastic polymer P2j having a Tg, as measured according to ISO 11357-3: 2013, greater than the maximum temperature use of said structure (Tu), in particular Tg ≥ Tu + 20 ° C.
    公开号:FR3099409A1
    申请号:FR1908669
    申请日:2019-07-30
    公开日:2021-02-05
    发明作者:Gilles Hochstetter；Patrick Dang；Thibaut SAVART
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] This patent application concerns composite multilayer structures for the transport, distribution or storage of hydrogen and their manufacturing process.
    [0002] One of the goals sought in the automotive field is to offer less and less polluting vehicles. Thus, electric or hybrid vehicles comprising a battery aim to gradually replace thermal vehicles, such as gasoline or diesel vehicles. However, it turns out that the battery is a relatively complex component of the vehicle. Depending on where the battery is located in the vehicle, it may need to be protected from impact and the external environment, which may be extreme temperatures and varying humidity. It is also necessary to avoid any risk of flames.
    [0003] In addition, it is important that its operating temperature does not exceed 55°C so as not to damage the battery cells and preserve its lifespan. Conversely, for example in winter, it may be necessary to raise the temperature of the battery in order to optimize its operation.
    [0004] In addition, the electric vehicle still suffers today from several problems, namely the autonomy of the battery, the use in these batteries of rare earths whose resources are not inexhaustible as well as a problem of electricity production in different countries to be able to recharge the batteries.
    [0005] Hydrogen therefore represents an alternative to the electric battery since hydrogen can be transformed into electricity by means of a fuel cell and thus power electric vehicles.
    [0006] Nevertheless, the storage of hydrogen is technically difficult and expensive due to its very low molar mass and its very low liquefaction temperature, especially when it comes to mobile storage. However, to be effective, storage must be carried out in small volumes, which requires maintaining the hydrogen under high pressure, given the temperatures at which the vehicles are used. This is the case, in particular, of fuel cell hybrid road vehicles for which the aim is to have a range of around 600 to 700 km, or even less for essentially urban uses in addition to an electric base on batteries.
    [0007] Hydrogen tanks generally consist of a metal envelope (liner) which must prevent the permeation of hydrogen. This first casing must itself be protected by a second casing (in general made of composite materials) intended to withstand the internal pressure of the reservoir (for example, 700 bars) and resistant to possible shocks or sources of heat. The valve system must also be safe.
    [0008] According to the Memento on hydrogen of the French association for hydrogen and the fuel cell (AFHYPAC) Sheet 4.2, revision December 2016, the storage and distribution of pressurized hydrogen has been standard practice for many years. years, with bottles or assemblies of cylindrical bottles, in steel, inflated to 20 or 25 MPa (types I and II). The disadvantage of this storage mode is the size – only 14 kg/m3 at 20 MPa and at ordinary temperature (21°C) against 100 kg/ m3 for methane – and above all the weight which results from the use low stress steels to avoid hydrogen embrittlement problems. The situation changed radically with the appearance of the technology of so-called type III or IV composite tanks. Their basic principle is to separate the two essential functions of sealing and mechanical strength to manage them independently of each other. In this type of tank, a resin bladder (thermosetting or thermoplastic) also called liner (or sealing sheath) is associated with a reinforcing structure made up of fibers (glass, aramid, carbon) also called sheath or reinforcing layer which allow to work at much higher pressures while reducing the mass and avoiding the risk of explosive rupture in the event of severe external attacks. This is how 70 MPa (700bars) has practically become the current standard.
    [0009] In type IV tanks, the liner and the reinforcement layer are made of different materials, which has the disadvantage of presenting a lack of adhesion between the liner and the reinforcement layer, which poses problems of collapse of the liner when simultaneously, on the one hand, there is an accumulation of gas at the interface between the liner and the composite and, on the other hand, a drop in the internal pressure of the tank.
    [0010] This problem has given rise to the development of type V tanks, which are based on the use of the same polymer for the liner and for the matrix of the composite in order to guarantee excellent and lasting adhesion between the liner and the composite.
    [0011] In the case of the transport or distribution of hydrogen by means of rigid or flexible pipes, it is also preferable that the hydrogen be in a small volume and therefore under high pressure, to ensure a sufficient flow. Thus, as for the storage, transport or distribution of hydrogen, it is interesting to use composite pipes (pipes) made up of a sealing sheath (ensuring watertightness and chemical resistance), reinforced with an outer layer made of composite material, which is manufactured by filament winding, from unidirectional tapes (UD) deposited in successive layers on the liner. When you want to make this pipe flexible, it is interesting to roll up the UD tape with one or more orientation angles relative to the axis of the pipe so that the composite reinforcement can withstand the deformations of the composite pipe. when using it. The composite reinforcement allows the pipe to resist the internal pressure of the pipe generated by the transported fluid.
    [0012] As with storage tanks, the sealing sheath must resist collapse, especially during production stoppages leading to a sudden drop in pressure. This risk of collapse exists when the sheath is not adherent to the composite reinforcement and gas may then be present between the sealing sheath and the composite reinforcement. To avoid this phenomenon, one solution is to put an internal reinforcement in the pressure duct called a carcass: this reinforcement, often metallic, is perforated to be flexible and is therefore not sealed against the transported fluid. It adds weight, a degree of complexity and overhead to the hose. Also, to reduce the weight, or even eliminate the internal carcass of the composite pipes, it is necessary that the composite reinforcement adheres to the sealing sheath, as in the case of type V storage tanks.
    [0013] Furthermore, the sealing sheath must be able to be extruded continuously, possibly on the support of an internal carcass, as indicated above. This sealing sheath must be sufficiently chemically stable so that its mechanical characteristics and its sealing do not degrade in a prohibitive manner during the life of the tank or hose.
    [0014] In the case of a flexible pipe comprising an internal metal carcass, the sealing sheath must also resist the effect of the creep of the material constituting it, following the stresses generated on the sealing sheath by the internal pressure of the pipe. Creep occurs in the joints (space or gap) between the metal armor (for example of self-stapled or T zeta geometry) on which the sheath rests when the pipe is pressurized by the transported effluent, creating growths of material which generate stress concentrations and are therefore preferred rupture zones of the sealing sheath: the material constituting the sealing sheath must therefore also withstand these stress concentrations.
    [0015] For example, Airborne has developed different flexible pipes, without internal carcass and comprising a sealing sheath adherent to the composite reinforcement, including:
    [0016] a PA 11 liner with a PA11 FC composite (JIP completed in 2011) or a PA12 liner with PA12 FC composite or even a PVDF liner with a PVDF FC composite. However, all these structures have the disadvantage that the matrix of the composite reinforcement has a glass transition temperature, Tg, lower than the temperature of use of the pipe, Tu, or, in the case of pipes based on PA11 or PA12, a Tg of 50°C in the dry state for an operating temperature of the pipe, Tu, of 60 to 80°C and in the case of PVDF, a Tg of -40°C, for an operating temperature in continues above 100°C and often close to 130°C. In the particular case of PVDF, the rigidity (modulus) of the matrix remains high beyond its Tg until another transition is reached, the alpha transition towards 100°C, beyond which its behavior becomes purely rubbery. Thus, in all the industrial and commercial cases of composite pipe with a TP matrix that we have just mentioned, the matrix of the composite reinforcement is in a completely rubbery state, at the temperature Tu of use of the composite pipe.
    [0017] To remedy this problem and have a composite reinforcement whose matrix has a Tg greater than the maximum temperature of use, so as not to be in a rubbery state at the temperature of use, in this case 130° C, Kutting & Total, then Vitrex and Magma, have developed a solution consisting of a PEEK sealing sheath (liner) reinforced with a PEEK matrix composite as well. The Tg of PEEK is 140°C and therefore meets the requirement of great rigidity thanks to the fact that this Tg is higher than the maximum temperature of use. The disadvantage is that, consequently, the sealing sheath (liner) is also very rigid, which can limit its resistance to fatigue and which is a major drawback for the production of flexible pipes. In addition, the implementation temperature of this type of sealing sheath is very high (typically 380-400°C) and in the case of the usual transformation process which is the extrusion of tubes, this poses great difficulties. in terms of tooling and process control.
    [0018] In addition, Ticona (Celanese) is in partnership with Airborne, offering a composite pipe comprising a PPS FC reinforcement and a PPS sealing sheath.
    [0019] For Tu > 90°C, this structure poses the same problem for the matrix of the composite as the solution based on PVDF (i.e. Tg < Tu ), but which also presents the problem of the temperature of transformation (typically 350°C versus 250°C, for PPS and PVDF, respectively).
    [0020] For Tu <90°C, PPS is suitable for the composite matrix but the problem of the extrusion temperature of the sealing sheath (liner) remains, as well as that of its high rigidity, which limits the flexibility of the composite pipe.
    [0021] The case of hydrogen tanks poses a similar technical problem because its rapid filling with hydrogen causes an increase in the temperature of the tank due to the compression of the hydrogen, in particular at approximately 110°C, which requires a oversizing of the composite, in the case where the matrix of the composite has a Tg lower than this temperature.
    [0022] Thus, it remains to optimize on the one hand, the composite matrix so as to optimize its mechanical resistance at high temperature and on the other hand the material composing the sealing sheath, so as to optimize its implementation temperature, without degrading the adhesion of the composite reinforcement to the sealing sheath. Thus, the possible modification of the composition of the material making up the sealing sheath, which will be made to ensure miscibility or less partial with the matrix of the composite, must not result in a significant increase in the manufacturing temperature (extrusion- blowing, injection, rotational molding, etc. of this liner, compared to what is practiced today with polyamides and PVDF.
    [0023] These problems are solved by the provision of a multilayer structure of the present invention which is a fully bonded composite pipe or tank, "bi-material", and composed of a composite reinforcement of high resistance, it that is to say comprising a high Tg matrix, deposited in particular by filament winding on a liner previously extruded at relatively low temperature. The adhesion between the composite and the liner is very good.
    [0024] Throughout this description, the terms "liner", "sealing sheath" and "pressure sheath" have the same meaning.
    [0025] The present invention therefore relates to a multilayer structure, intended for the transport or storage of hydrogen, comprising, from the inside outwards, at least a sealing layer and at least one composite reinforcement layer,
    [0026] said innermost composite reinforcement layer being welded to said outermost adjacent sealing layer,
    [0027] said sealing layers being made of a composition mainly comprising at least one semi-crystalline thermoplastic polymer P1i (i=1 to n, n being the number of sealing layers) whose Tm, as measured according to ISO 11357- 3: 2013, is less than 280° C., in particular less than 265° C.,
    [0028] said at least one thermoplastic polymer of each sealing layer possibly being identical or different, and at least one of said composite reinforcement layers consisting of a fibrous material in the form of continuous fibers impregnated with a composition mainly comprising at least a thermoplastic polymer P2j, (j=1 to m, m being the number of reinforcing layers) in particular semi-crystalline, said thermoplastic polymer P2j having a Tg, as measured according to ISO 11357-3: 2013, greater than the temperature maximum use of said structure (Tu), in particular Tg ≥ Tu + 20°C, in particular Tg ≥ Tu + 30°C.
    [0029] The inventors have therefore unexpectedly found that the use of a different polymer for the composite matrix and the liner and in particular:
    [0030] a matrix of the composite reinforcement composed of a polymer having a Tg significantly higher than the maximum operating temperature of the tank or the pipe, Tu, (Tg > Tu+20°C, in particular Tg ≥ Tu + 30°C, typically) so as to remain in its vitreous domain and have a high rigidity, thus allowing the composite to have a high mechanical resistance,
    [0031] the semi-crystalline polymer making up the liner having a low melting temperature, Tm, allowing transformation by extrusion, extrusion blow molding, rotational molding, injection or by winding a film of pure resin, as the case may be, at a moderate and usual temperature for the skilled in the art, in relation to the Tm of this polymer which is lower than 280°C, preferably lower than 265°C. The low Tf semi-crystalline polymers known to date also have a low Tg, which will, in most cases, be lower than the maximum temperature of use. Consequently, the polymer making up the liner will work in its rubbery domain and will therefore be very flexible and therefore very resistant to fatigue. Its semi-crystalline character will ensure good resistance to chemical attacks and to abrasion and creep,
    [0032] and the two aforementioned polymers (the one making up the matrix of the composite and the one making up the liner) are sufficiently miscible with each other to ensure the weldability of the composite on the liner and consequently excellent adhesion between the liner and the composite. The durability of the adhesion will be guaranteed by the durability of the material constituting the mixture at the interface of the two materials, in other words in the welded joint. The miscibility of the two polymers is reflected, preferably by a single Tg, or failing that, by a characteristic signature of a partially homogeneous mixture, for example by the presence of two Tgs of intermediate values to the Tg of the two pure polymers.
    [0033] By “multilayer structure” is meant for example a reservoir, a pipe or tube, comprising or consisting of several layers, in particular of two layers.
    [0034] The sealing layer or layers are the innermost layers compared to the composite reinforcement layers which are the outermost layers.
    [0035] The sealing layer is in contact with the hydrogen even if an inner and therefore the innermost layer, non-sealed metal, formed by a profiled metal strip wound helically such as a strip stapled to form said carcass, is present and on which the sealing layer or layers are coated by extrusion.
    [0036] When several sealing layers are present, only the innermost layer of the sealing layers is in direct contact with the hydrogen.
    [0037] When only a sealing layer and a composite reinforcement layer are present, thus leading to a two-layer multilayer structure, then these two layers are welded and therefore adhere to each other, in direct contact with each other. the other.
    [0038] When several layers of sealing are present and/or several layers of composite reinforcement, then the outermost layer of said sealing layers, and therefore opposite the layer in contact with the hydrogen, is welded to the layer the innermost of said composite reinforcement, and therefore adhere to each other, in direct contact with each other.
    [0039] The other layers of composite reinforcement are also welded together.
    [0040] The other sealing layers are also welded together.
    [0041] With regard to the sealing layer(s) and the thermoplastic polymer P1i
    [0042] One or more sealing layers may be present.
    [0043] Each of said layers consists of a composition mainly comprising at least one thermoplastic polymer P1i, i corresponding to the number of layers present. i is comprised from 1 to 10, in particular from 1 to 5, in particular from 1 to 3, preferentially i=1.
    [0044] The term “predominantly” means that said at least one polymer is present at more than 50% by weight relative to the total weight of the composition.
    [0045] Advantageously, said at least one majority polymer is present at more than 60% by weight, in particular at more than 70% by weight, particularly at more than 80% by weight, more particularly greater than or equal to 90% by weight 90% by weight, relative to the total weight of the composition.
    [0046] Said composition can also comprise impact modifiers and/or additives.
    [0047] Additives may be selected from antioxidant, heat stabilizer, UV absorber, light stabilizer, lubricant, inorganic filler, flame retardant, nucleating agent, plasticizer, colorant, black carbon and carbon nanofillers.
    [0048] Advantageously, said composition consists of said thermoplastic polymer P1i mainly, from 0 to 5% by weight of impact modifier, from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100% (based on a max of P2i by 90%.
    [0049] Said at least one majority polymer of each layer can be identical or different.
    [0050] In one embodiment, a single majority polymer is present at least in the sealing layer welded to the composite reinforcement layer.
    [0051] P1i thermoplastic polymer
    [0052] The term thermoplastic, or thermoplastic polymer, is understood to mean a material that is generally solid at room temperature, semi-crystalline, and which softens during an increase in temperature, in particular after passing its glass transition temperature (Tg), and which may exhibit a direct fusion on passing its so-called melting temperature (Tf), and which becomes solid again when the temperature drops below its crystallization temperature.
    [0053] Tg, Tc and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2:2013 and 11357-3:2013 respectively.
    [0054] The number-average molecular mass Mn of said thermoplastic polymer is preferably in a range extending from 10,000 to 40,000, preferably from 12,000 to 30,000. These Mn values may correspond to inherent viscosities greater than or equal to 0.8 as determined in the m-cresol according to the ISO 307:2007 standard but changing the solvent (use of m-cresol instead of sulfuric acid and the temperature being 20°C).
    [0055] Examples of suitable semi-crystalline thermoplastic polymers in the present invention include:
    [0056] polyamides, including copolymers, for example polyamide-polyether copolymers, polyesters, and PVDF and a PVDF/PEI blend in which PVDF is predominant.
    [0057] More particularly preferred among the semi-crystalline polymers are the polyamides and their semi-crystalline copolymers.
    [0058] The nomenclature used to define polyamides is described in standard ISO 1874-1:2011 "Plastics - Polyamide (PA) materials for molding and extrusion - Part 1: Designation", in particular on page 3 (tables 1 and 2) and is well known to those skilled in the art.
    [0059] The polyamide can be a homopolyamide or a copolyamide or a mixture thereof.
    [0060] Advantageously, said thermoplastic polymer is a long-chain aliphatic polyamide, that is to say a polyamide having an average number of carbon atoms per nitrogen atom greater than 8.5, preferably greater than 9.
    [0061] In particular, the long-chain aliphatic polyamide is chosen from:
    [0062] polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1010 (PA1010), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or a mixture of these or a copolyamide of these, in particular PA11 and PA12.
    [0063] Advantageously, said thermoplastic polymer is a long-chain semi-aromatic polyamide, that is to say a polyamide having an average number of carbon atoms per nitrogen atom greater than 8.5, preferably greater than 9 and a melting temperature between 240°C to less than 280°C.
    [0064] In particular, the long-chain semi-aromatic polyamide is chosen from polyamide 11/5T or 11/6T or 11/10T. Obviously in this case, the rate of 11 must be chosen so that the Tm of said polymers is less than 280°C, preferably less than 265°C.
    [0065] Advantageously, each sealing layer consists of a composition comprising the same type of polymer, in particular a polyamide.
    [0066] Advantageously, said composition comprising said polymer P1i is black in color and capable of absorbing radiation suitable for welding.
    [0067] There are various methods for welding thermoplastic polymer elements. Thus, it can be used heating blades with or without contact, ultrasound, infrared, application of vibrations, rotation of one element to be welded against another or even laser welding.
    [0068] The welding of thermoplastic polymer elements, in particular by laser welding, requires that the two elements to be welded have different properties with respect to radiation, in particular laser: one of the elements must be transparent to radiation, in particular laser, and the other must absorb radiation, in particular laser radiation. The radiation, in particular laser radiation, thus passes through the transparent element and then reaches the absorbing element, where it is converted into heat. This makes it possible to melt the contact zone between the two elements and therefore to produce the weld.
    [0069] In some applications, it is desirable for the two parts to be welded to be black in color, thus including the part transparent to laser radiation.
    [0070] In order to make them absorbent, it is known to add various additives to them, including for example carbon black, which gives the polymer a black color and makes it possible to absorb radiation suitable for welding.
    [0071] In one embodiment, the welding is carried out by a system chosen from among lasers, infrared (IR) heating, LED heating, induction heating or by μwaves or high-frequency (HF) heating.
    [0072] In the case where the welding is carried out by laser welding, then the composition P1i comprises non-agglomerated or non-aggregated carbonaceous fillers.
    [0073] In the case where the welding is carried out by induction, then the composition P1i comprises metallic particles.
    [0074] Advantageously, the welding is carried out by a laser system.
    [0075] Regarding the composite reinforcement layer and the thermoplastic polymer P2j
    [0076] One or more layers of composite reinforcement may be present.
    [0077] Each of said layers consists of a composition mainly comprising at least one thermoplastic polymer P2j, j corresponding to the number of layers present.
    [0078] j is comprised from 1 to 10, in particular from 1 to 5, in particular from 1 to 3, preferably j=1.
    [0079] The term “predominantly” means that said at least one polymer is present at more than 50% by weight relative to the total weight of the composition.
    [0080] Advantageously, said at least one majority polymer is present at more than 60% by weight, in particular at more than 70% by weight, particularly at more than 80% by weight, more particularly greater than or equal to 90% by weight, relative to the weight composition total,
    [0081] Said composition can also comprise impact modifiers and/or additives.
    [0082] The additives can be chosen from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a nucleating agent, a plasticizer and a colorant.
    [0083] Advantageously, said composition consists of said thermoplastic polymer P2j mainly, from 0 to 5% by weight of impact modifier, from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100% (based on a max of P2d by 90%.
    [0084] Said at least one majority polymer of each layer can be identical or different.
    [0085] In one embodiment, a single majority polymer is present at least in the composite reinforcement layer welded to the sealing layer.
    [0086] In one embodiment, each reinforcement layer comprises the same type of polymer, in particular a polyamide.
    [0087] P2j Thermoplastic Polymer
    [0088] Thermoplastic or thermoplastic polymer is understood to mean a material which is generally solid at room temperature, which may be semi-crystalline or amorphous, in particular semi-crystalline and which softens when the temperature rises, in particular after passing from its temperature of glass transition (Tg) and flows at a higher temperature when it is amorphous, or which can present a frank melting on passing its so-called melting temperature (Tf) when it is semi-crystalline, and which becomes solid again when 'a decrease in temperature below its crystallization temperature, Tc, (for a semi-crystalline) and below its glass transition temperature (for an amorphous).
    [0089] Tg, Tc and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2:2013 and 11357-3:2013 respectively.
    [0090] The polymer P2j of the composition of at least one of said composite reinforcement layers is such that its Tg is greater than the maximum operating temperature (Tu) of said structure and in particular, the Tg ≥ Tu + 20°C, in particular Tg ≥ Tu + 30°C.
    [0091] In one embodiment, the polymer P2j has a Tg≥Tu+20°C, in particular Tg≥Tu+30°C, regardless of the position of said reinforcing layer.
    [0092] In another embodiment, said reinforcing layer consisting of a composition comprising the polymer P2j exhibiting a Tg ≥ Tu + 20°C, in particular Tg ≥ Tu + 30°C, is the layer welded to said sealing layer.
    [0093] In one embodiment, the polymer P2j of the composition of at least one of said composite reinforcement layers is such that its Tg is greater than the maximum operating temperature (Tu) of said structure Tg ≥ Tu + 20°C and said reinforcing layer consisting of a composition comprising the polymer P2j is the layer welded to said sealing layer.
    [0094] In one embodiment, the polymer P2j of the composition of at least one of said composite reinforcement layers is such that its Tg is greater than the maximum operating temperature (Tu) of said structure Tg ≥ Tu + 30°C and said reinforcing layer consisting of a composition comprising the polymer P2j is the layer welded to said sealing layer.
    [0095] In another embodiment, said reinforcing layer consisting of a composition comprising the polymer P2j has a Tg ≥ Tu + 20°C, in particular Tg ≥ Tu + 30°C, is the outermost reinforcing layer of the structure . The number-average molecular mass Mn of said thermoplastic polymer is preferably in a range extending from 10,000 to 40,000, preferably from 12,000 to 30,000. These Mn values may correspond to inherent viscosities greater than or equal to 0.8 as determined in the m-cresol according to the ISO 307:2007 standard but changing the solvent (use of m-cresol instead of sulfuric acid and the temperature being 20°C).
    [0096] Examples of suitable semi-crystalline thermoplastic polymers in the present invention include:
    [0097] polyamides, in particular comprising an aromatic and/or cycloaliphatic structure, including copolymers, for example polyamide-polyether copolymers, polyesters,
    [0098] polyaryletherketones (PAEK),
    [0099] polyetherether ketones (PEEK),
    [0100] polyetherketone ketones (PEKK),
    [0101] polyetherketoneetherketone ketones (PEKEKK),
    [0102] polyimides, in particular polyetherimides (PEI) or polyamide-imides,
    [0103] polylsulphones (PSU) in particular polyarylsulphones such as polyphenyl sulphones (PPSU),
    [0104] polyethersulfones (PES).
    [0105] semi-crystalline polymers are more particularly preferred, and in particular polyamides and their semi-crystalline copolymers.
    [0106] The nomenclature used to define polyamides is described in standard ISO 1874-1:2011 "Plastics - Polyamide (PA) materials for molding and extrusion - Part 1: Designation", in particular on page 3 (tables 1 and 2) and is well known to those skilled in the art.
    [0107] The polyamide can be a homopolyamide or a copolyamide or a mixture thereof.
    [0108] Advantageously, the semi-crystalline polyamides are semi-aromatic polyamides, in particular a semi-aromatic polyamide of formula X/YAr, as described in EP1505099, in particular a semi-aromatic polyamide of formula A/XT in which A is chosen from a unit obtained from an amino acid, a unit obtained from a lactam and a unit corresponding to the formula (diamine in Ca).(diacid in Cb), with a representing the number of carbon atoms of the diamine and b representing the number of carbon atoms of the diacid, a and b each being between 4 and 36, advantageously between 9 and 18, the unit (diamine in Ca) being chosen from aliphatic diamines, linear or branched, diamines cycloaliphatics and alkylaromatic diamines and the unit (Cb diacid) being chosen from aliphatic, linear or branched diacids, cycloaliphatic diacids and aromatic diacids;
    [0109] XT denotes a unit obtained from the polycondensation of a Cx diamine and terephthalic acid, with x representing the number of carbon atoms of the Cx diamine, x being between 5 and 36, advantageously between 9 and 18, in particular a polyamide of formula A/5T, A/6T, A/9T, A/10T or A/11T, A being as defined above, in particular a polyamide chosen from a PA MPMDT/6T, a PA11/10T, PA 5T/10T, PA 11/BACT, PA 11/6T/10T, PA MXDT/10T, PA MPMDT/10T, PA BACT/10T, PA BACT/6T, PA BACT /10T/6T, one PA 11/BACT/6T, PA 11/MPMDT/6T, PA 11/MPMDT/10T, PA 11/BACT/10T, one PA 11/MXDT/10T, one 11/5T/10T.
    [0110] T corresponds to terephthalic acid, MXD corresponds to m-xylylene diamine, MPMD corresponds to methylpentamethylene diamine and BAC corresponds to bis(aminomethyl)cyclohexane. The said semi-aromatic polyamides defined above have in particular a Tg greater than or equal to 80°C.
    [0111] Advantageously, each composite reinforcement layer consists of a composition comprising the same type of polymer, in particular a polyamide.
    [0112] Advantageously, said composition comprising said polymer P2j is transparent to radiation suitable for welding.
    [0113] Thermoplastic polymers are generally transparent for the needs of welding, in particular laser. The carbon nanofillers make it possible to impart a black color to a layer of a composition comprising a thermoplastic polymer, while retaining the transparency to laser radiation of said layer.
    [0114] Advantageously, the carbon nanofillers are non-agglomerated or non-aggregated.
    [0115] Advantageously, the carbon nanofillers are incorporated into the composition in an amount of 100 ppm to 500 ppm, and preferably of 100 ppm to 250 ppm.
    [0116] Advantageously, the carbon nanofillers are chosen from carbon nanotubes (CNTs), carbon nanofibers, graphene, nanometric carbon black and mixtures thereof.
    [0117] Advantageously, the carbon nanofillers are devoid of nanometric carbon black.
    [0118] In one embodiment, the welding is carried out by a system chosen from laser, IR heating or induction heating.
    [0119] Advantageously, the welding is carried out by a laser system.
    [0120] Advantageously, the laser radiation is infrared laser radiation, and preferably has a wavelength between 700 nm and 1200 nm and preferably between 800 nm and 1100 nm.
    [0121] Regarding the structure
    [0122] Said multilayer structure therefore comprises at least one sealing layer and at least one composite reinforcement layer which are welded.
    [0123] In one embodiment, in said multilayer structure, each polymer P1i of each sealing layer is partially or totally miscible with each polymer P1i of the adjacent layer(s), each polymer P2j of each reinforcing layer is partially or totally totally miscible with each polymer P2j of the adjacent layer(s), and each polymer P2j is partially or totally miscible with each polymer P1i when they are adjacent, and the polymer P21 is partially or totally miscible with the polymer P11 which is is adjacent,
    [0124] the total or partial miscibility of said polymers being defined by the difference in glass transition temperature of the two resins, in the mixture, relative to the difference in glass transition temperature of the two resins, before mixing, and the miscibility being total when the said difference is equal to 0, and the miscibility being partial, when said difference is different from 0.
    [0125] When the miscibility of said polymers is partial, said difference is said miscibility is all the greater as said difference is small.
    [0126] Advantageously, when the miscibility of said polymers is partial, said difference is less than 30%, preferably less than 20%, in absolute value.
    [0127] In one embodiment, the glass transition temperature or temperatures of the mixture, depending on whether the miscibility is total or partial, which must be between the glass transition temperatures of said polymers before mixing and different from them, by at least 5 °C, preferably at least 10°C.
    [0128] The expression "totally miscible" means that when, for example, two polymers P1 1 and P1 2 having respectively a Tg1 1 and a Tg1 2, are present respectively in two sealing layers or two adjacent reinforcing layers, then the mixture of the two polymers has only one Tg1 1 1 2 whose value is between Tg1 1 and one Tg1 2.
    [0129] This value Tg1 1 1 2 is then higher than Tg1 1 by at least 5°C, in particular by at least 10°C and lower than Tg1 2 by at least 5°C, in particular by at least 10° vs.
    [0130] The expression "partially miscible" means that when, for example, two polymers P11and P12respectively presenting a Tg11and a Tg12, are present respectively in two sealing layers or two adjacent reinforcement layers, then the mixture of the two polymers has two Tg: Tg’11and Tg'12, with Tg11< Tg’11< Tg’12< Tg12.
    [0131] These Tg'1 1 and Tg'1 2 values are then higher than Tg1 1 by at least 5°C, in particular by at least 10°C and lower than Tg1 2 by at least 5°C, in particular d at least 10°C.
    [0132] Advantageously, said welded sealing and reinforcing layers consist of compositions which respectively comprise different polymers.
    [0133] Nevertheless, said different polymers may be of the same type.
    [0134] Thus, if one of the two welded composite waterproofing and reinforcement layers consists of a composition comprising an aliphatic polyamide, then the other layer consists of a composition comprising a polyamide which is not aliphatic and which is for example a semi-aromatic polyamide so as to have a high tg polymer as the matrix of the composite reinforcement.
    [0135] Said multilayer structure can include up to 10 layers of waterproofing and up to 10 layers of composite reinforcement.
    [0136] It is quite obvious that said multilayer structure is not necessarily symmetrical and that it can therefore comprise more sealing layers than composite layers or vice versa.
    [0137] Advantageously, said multilayer structure comprises one, two, three, four, five, six, seven, eight, nine or ten sealing layers and one, two, three, four, five, six, seven, eight, nine or ten of composite reinforcement.
    [0138] Advantageously, said multilayer structure comprises one, two, three, four or five layers of sealing and one, two, three, four or five layers of composite reinforcement.
    [0139] Advantageously, said multilayer structure comprises one, two or three layers of sealing and one two or three layers of composite reinforcement.
    [0140] Advantageously, they consist of compositions which respectively comprise different polymers.
    [0141] Advantageously, they consist of compositions which respectively comprise polyamides corresponding to the polyamides P1i and P2j.
    [0142] Advantageously, they consist of compositions which respectively comprise different polyamides.
    [0143] In one embodiment, said multilayer structure comprises a single sealing layer and several reinforcing layers, said sealing layer being welded to said adjacent reinforcing layer.
    [0144] In another embodiment, said multilayer structure comprises a single reinforcing layer and several sealing layers, said reinforcing layer being welded to said adjacent sealing layer.
    [0145] In an advantageous embodiment, said multilayer structure comprises a single sealing layer and a single composite reinforcement layer which are welded.
    [0146] All combinations of these two layers are therefore within the scope of the invention, provided that at least said innermost composite reinforcement layer is welded to said outermost adjacent sealing layer, the other layers being welded between them or not.
    [0147] Advantageously, in said multilayer structure, each sealing layer consists of a composition comprising the same type of polymer P1i, in particular a polyamide.
    [0148] By the expression same type of polymer, it is necessary to understand for example a polyamide which can be an identical or different polyamide depending on the layers.
    [0149] Advantageously, said polymer P1i is a polyamide and said polymer P2j is a polyamide.
    [0150] Advantageously, the polyamide P1i is identical for all the sealing layers.
    [0151] Advantageously, said polymer P1i is a long-chain aliphatic polyamide, in particular PA1010, PA 1012, PA 1212, PA11, PA12, in particular PA 11 or PA12.
    [0152] Advantageously, the polyamide P1i is a long-chain semi-aromatic polyamide, in particular PA 11/5T, PA 11/6T or PA 11/10T. Obviously in this case, the rate of 11 must be chosen judiciously so that the Tm of said polymers is less than 280°C, preferably 265°C.
    [0153] Advantageously, in said multilayer structure, each reinforcing layer consists of a composition comprising the same type of polymer P2j, in particular a polyamide.
    [0154] Advantageously, the polyamide P2j is identical for all the reinforcing layers.
    [0155] Advantageously, said polymer P2j is a semi-aromatic polyamide, in particular chosen from PA MPMDT/6T, PA 11/10T, PA 11/BACT, PA 5T/10T, PA 11/6T/10T, PA MXDT/10T, one PA MPMDT/10T, one PA BACT/10T, one PA BACT/6T, PA BACT/10T/6T, one PA 11/BACT/6T, PA 11/MPMDT/6T, PA 11/MPMDT/10T , PA 11/BACT/10T, a PA 11/MXDT/10T and a PA 5T/10T.
    [0156] Advantageously, in said multilayer structure, each sealing layer consists of a composition comprising the same type of polymer P1i, in particular a polyamide, and each reinforcing layer consists of a composition comprising the same type of polymer P2j, particular a polyamide, provided that the polyamides P1i and P2j are different, that is to say that if the sealing layer or layers is or consist of compositions comprising a long-chain aliphatic polyamide then the layer or layers sealing is or are made up of compositions comprising a semi-aromatic polyamide.
    [0157] Advantageously, said polymer P1i is a long-chain aliphatic polyamide, in particular PA1010, PA 1012, PA 1212, PA11, PA12, in particular PA 11 or PA12 and said polymer P2j is a semi-aromatic polyamide, in particular chosen from a PA MPMDT /6T, PA PA11/10T, PA 11/BACT, PA 5T/10T, PA 11/6T/10T, PA MXDT/10T, PA MPMDT/10T, PA BACT/10T, PA BACT /6T, PA BACT/10T/6T, one PA 11/BACT/6T, PA 11/MPMDT/6T, PA 11/MPMDT/10T, PA 11/ BACT/10T, one PA 11/MXDT/10T and one PA 5T /10T.
    [0158] Advantageously, said multilayer structure consists of a single reinforcing layer and a single sealing layer in which said polymer P1i is a long-chain aliphatic polyamide, in particular PA1010, PA 1012, PA 1212, PA11, PA12, in particular PA 11 or PA12 and said polymer P2j is a semi-aromatic polyamide, in particular chosen from a PA MPMDT/6T, a PA PA11/10T, a PA 11/BACT, a PA 11/6T/10T, a PA MXDT/ 10T, one PA MPMDT/10T, one PA BACT/10T, one PA BACT/6T, PA BACT/10T/6T, one PA 11/BACT/6T, PA 11/MPMDT/6T, PA 11/MPMDT/10T, PA 11/ BACT/10T, one PA 11/MXDT/10T.
    [0159] According to one embodiment, said multilayer structure is a reservoir.
    [0160] According to another embodiment, said multilayer structure is a flexible pipe.
    [0161] Advantageously, the maximum operating temperature Tu of said multilayer structure is greater than 50° C., in particular greater than 100° C.
    [0162] In one embodiment, said multilayer structure defined above has a resistance to decompression and an ability to dry.
    [0163] Indeed, in the case of the storage or transport of hydrogen, the hydrogen can diffuse through the sealing layer(s), from the inside of the tube or the tank towards the interface between the last layer of sealing and the first layer of composite reinforcement, due to the permeability of the sealing layer(s) to transported or stored hydrogen. The accumulation of hydrogen at this location can generate a pressure which will lead to buckling (collapse) of the sealing layer(s), when the internal pressure in the tube or in the tank is lower than the pressure at the interface with the composite reinforcement, which may occur in particular when the pumping or transport of hydrogen is stopped or when the storage tank is empty. The same applies during proof tests on tanks under internal water pressure: this water is likely to migrate by permeation, at the interface between the composite reinforcement and the last layer of waterproofing and will subsequently be very difficult to eliminate, leading to long and costly drying cycles of said storage tanks, in particular under vacuum.
    [0164] In another embodiment, said multilayer structure defined above further comprises a metal carcass located inside the sealing layer.
    [0165] This metal carcass is not sealed and corresponds to the innermost layer.
    [0166] Advantageously, said multilayer structure further comprises at least one outer layer, in particular metal, said layer being the outermost layer of said multilayer structure.
    [0167] Said outer layer is a second reinforcement layer but metallic and not composite.
    [0168] There may also be on the structure a polymeric protective layer (outermost layer) which has in particular an anti-abrasion role or which makes it possible to put an inscription on the structure.
    [0169] Regarding the fibrous material
    [0170] As regards the fibers forming said fibrous material, these are in particular fibers of mineral, organic or plant origin.
    [0171] Advantageously, said fibrous material can be sized or not sized.
    [0172] Said fibrous material may therefore comprise up to 0.1% by weight of a material of organic nature (thermosetting or thermoplastic resin type) called size.
    [0173] Among the fibers of mineral origin, mention may be made of carbon fibers, glass fibers, basalt or basalt-based fibers, silica fibers, or silicon carbide fibers for example. Among the fibers of organic origin, mention may be made of fibers based on thermoplastic or thermosetting polymer, such as semi-aromatic polyamide fibers, aramid fibers or polyolefin fibers for example. Preferably, they are based on an amorphous thermoplastic polymer and have a glass transition temperature Tg higher than the Tg of the polymer or mixture of thermoplastic polymer constituting the pre-impregnation matrix when the latter is amorphous, or higher than the Tm polymer or mixture of thermoplastic polymer constituting the pre-impregnation matrix when the latter is semi-crystalline. Advantageously, they are based on a semi-crystalline thermoplastic polymer and have a melting point Tf higher than the Tg of the polymer or thermoplastic polymer mixture constituting the pre-impregnation matrix when the latter is amorphous, or higher than the Tm polymer or mixture of thermoplastic polymer constituting the pre-impregnation matrix when the latter is semi-crystalline. Thus, there is no risk of melting for the organic fibers forming the fibrous material during impregnation by the thermoplastic matrix of the final composite. Among the fibers of plant origin, mention may be made of natural fibers based on flax, hemp, lignin, bamboo, silk, in particular spider silk, sisal, and other cellulosic fibers, in particular viscose. These fibers of vegetable origin can be used pure, treated or coated with a coating layer, in order to facilitate adhesion and impregnation of the thermoplastic polymer matrix.
    [0174] The fibrous material can also be a fabric, braided or woven with fibers.
    [0175] It can also match fibers with holding threads.
    [0176] These building fibers can be used alone or in mixtures. Thus, organic fibers can be mixed with mineral fibers to be pre-impregnated with thermoplastic polymer powder and form the pre-impregnated fibrous material.
    [0177] Organic fiber rovings can have several grammages. They may also have several geometries. The fibers making up the fibrous material may also be in the form of a mixture of these reinforcing fibers of different geometries. The fibers are continuous fibers.
    [0178] Preferably, the fibrous material consists of continuous carbon or glass fibers or their mixture, in particular carbon fibers. It is used in the form of a wick or several wicks.
    [0179] According to another aspect, the present invention relates to a method of manufacturing a multilayer structure as defined above, characterized in that it comprises a step of welding the reinforcing layer as defined above to the layer sealing as defined above.
    [0180] Advantageously, the welding step is carried out by a system chosen from among the laser, infrared heating (IR), heating by LED, heating by induction or by µwaves or high frequency heating (HF).
    [0181] Advantageously, said method comprises a step of extruding said pressure layer onto a metal carcass and a step of welding the reinforcing layer to the sealing layer.
    [0182] EXAMPLES
    [0183] In all the examples, the reservoirs are obtained by rotational molding of the liner at a temperature adapted to the nature of the thermoplastic resin used, but in all cases below 280° C.
    [0184] In the case of epoxy, a wet filament winding process is then used which consists of winding fibers around the liner, which fibers are pre-impregnated in a bath of liquid epoxy. The reservoir is then polymerized in an oven for 2 hours.
    [0185] In all other cases, a fibrous material previously impregnated with the thermoplastic resin (tape) is then used. This tape is deposited by filament winding using a robot comprising a 1500W power laser heater at a speed of 12m/min and there is no polymerization step.
    [0186] Example1 (counterexample):
    [0187] Type IV hydrogen storage tank, composed of an epoxy composite reinforcement (Tg 80°C) T700SC31E carbon fiber (produced by Toray) and a PA6 sealing layer. : no miscibility between the 2 resins (see table 1) which prevents any welding between the fibrous reinforcement and the sealing layer.
    [0188] Example 2 (counterexample):
    [0189] Type IV hydrogen storage tank, composed of an epoxy composite reinforcement (Tg 80°C) T700SC31E carbon fiber (produced by Toray) and an HDPE sealing layer. : no miscibility between the 2 resins (see table 1) which prevents any welding between the fibrous reinforcement and the sealing layer.
    [0190] Example 3: Hydrogen storage tank of type between IV and V, composed of a BACT/10T carbon fiber T700SC31E composite reinforcement (produced by Toray) and a PA6 sealing layer: good partial miscibility between the 2 resins (see table I) which allows good welding between the fibrous reinforcement and the sealing layer.
    [0191] The BACT/10T type composition chosen has a melting temperature, Tm, of 283°C, a crystallization temperature, Tc, of 250°C and a glass transition temperature of 164°C.
    [0192] Tg, Tc and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2:2013 and 11357-3:2013 respectively.
    [0193] Example 4: Type IV and V hydrogen storage tank, composed of a BACT/10T carbon fiber T700SC31E composite reinforcement (produced by Toray) and a PA66 sealing layer: good partial miscibility between the 2 resins (see table I) which allows good welding between the fibrous reinforcement and the sealing layer. The BACT/10T type composition chosen has a melting temperature, Tm, of 283°C, a crystallization temperature, Tc, of 250°C and a glass transition temperature of 164°C. Tg, Tc and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2:2013 and 11357-3:2013 respectively.
    [0194] The higher melting point of the PA66 liner (268.8°C) compared to the PA6 liner (220°C) of example 3, facilitates the implementation of the tape and the manufacture of the tank.
    [0195] Example 5: Hydrogen storage tank of type between IV and V, composed of a composite reinforcement 11/BACT/10T carbon fiber CT24-5.0/270-T140 (produced by SGL Carbon) and a layer of sealing in PA11: good partial miscibility between the 2 resins (see table 1) which leads to a good weld between the fibrous reinforcement and the sealing layer. The type 11/BACT/10T composition chosen has a melting temperature, Tm, of 280°C, a crystallization temperature, Tc, of 220°C and a glass transition temperature of 160°C. Tg, Tc and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2:2013 and 11357-3:2013 respectively.
    [0196] Example 6: Hydrogen storage tank of type between IV and V, composed of a composite reinforcement 11/BACT/10T carbon fiber CT24-5.0/270-T140 (produced by SGL Carbon) and a layer of sealing in PA11/10T: good partial miscibility between the 2 resins (see table 1) which leads to a good weld between the fibrous reinforcement and the sealing layer.
    [0197] The type 11/BACT/10T composition chosen has a melting temperature, Tm, of 280°C, a crystallization temperature, Tc, of 220°C and a glass transition temperature of 160°C. Tg, Tc and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2:2013 and 11357-3:2013 respectively.
    [0198] The 11/10T composition used for the liner leads to a Tf of 255°C.
    [0199] The fact of using an 11/10T liner whose melting point is 255°C, close to that of the 11/BACT/10T resin used as the composite matrix, facilitates the implementation of the tank.
    [0200] Example 7: Hydrogen storage tank of type between IV and V, composed of a composite reinforcement 11/BACT carbon fiber CT24-5.0/270-T140 (produced by SGL Carbon) and a sealing layer in PA11: good partial miscibility between the 2 resins (see table 1) which leads to good welding between the fibrous reinforcement and the sealing layer. The type 11/BACT composition chosen has a melting temperature, Tm, of 278°C, a crystallization temperature, Tc, of 210°C and a glass transition temperature of 157°C. Tg, Tc and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2:2013 and 11357-3:2013 respectively.
    [0201] The fact of using a polymer of the 11/BACT type which crystallizes slowly, makes it possible to lower the temperatures of implementation of the tape compared to the 11/BACT/10T of the previous example and facilitates the use of a liner in PA11.
    [0202] Example 8: Hydrogen storage tank of type between IV and V, composed of a composite reinforcement 11/BACT carbon fiber CT24-5.0/270-T140 (produced by SGL Carbon) and a sealing layer in PA11/10T: good partial miscibility between the 2 resins (see table 1) which leads to good welding between the fibrous reinforcement and the sealing layer.
    [0203] The type 11/BACT composition chosen has a melting temperature, Tm, of 278°C, a crystallization temperature, Tc, of 210°C and a glass transition temperature of 157°C. Tg, Tc and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2:2013 and 11357-3:2013 respectively.
    [0204] The 11/10T composition used for the liner leads to a Tf of 255°C.
    [0205] The fact of using a liner in 11/10T whose melting point is 255°C, close to 11/BACT which constitutes the reinforcing resin of the composite, facilitates the implementation of the tank.
    [0206] In all the examples in Table 1 below, to assess the miscibility of the resins, the mixtures were made from powders with a particle size of approximately 150 μm on micro-DSM with a recirculation time of 1 minute after merger. All the mixtures were made at 300°C, except for the epoxy-polyethylene mixture which was made at 220°C.
    [0207] At the end of the mixing, the mixture is injected into a mold to make a specimen which will be characterized in DMA.
    [0208] Resin type Mixed (50/50 by weight) Tg of each pure resin (Tg P1 and Tg P2) Tg of each resin in the mixture (Tg P'1 and Tg P'2) *** Ratio of the difference between the Tgs of the resin in the mixture and the Tgs of each pure resin (Tg P'2-Tg P'1)/ (Tg P'2-Tg P'1) (%) Example 1 Epoxy Epoxy + PA6 80 80 100 PA6 50 50 Example 2 Epoxy Epoxy + HDPE 130 130 100 HDPE -100 -100 Example 3 BACT/10T BACT/10T + PA6 178 109 12 PA6 50 94 Example 4 BACT/10T BACT/10T + PA66 178 110 12 PA66 60 96 Example 5 11/BACT/10T 11/BACT/10T + PA11 168 115 21 PA11 50 90 Example 6 11/BACT/10T 11/BACT/10T + 11/10T 168 134 14 11/10T 80 122 Example 7 11/BACT 11/BACT + PA11 168 120 30 PA11 50 85 Example 8 11/BACT 11/BACT + 11/10T 168 130 10 11/10T 80 121
    [0209] ***Tg measurements are made by DMTA according to ISO 4664-1
    [0210] Miscibility test results:
    [0211] - column 4: glass transition temperature of each resin before mixing
    [0212] - column 5: glass transition temperature of the resins in the mixture
    [0213] - column 6: ratio between the differences in glass transition temperature of the resins in the mixture and before the mixture.
    [0214] 100% indicates immiscibility of the resins,
    [0215] <80% indicates low miscibility,
    [0216] < 30% indicates good albeit partial miscibility,
    [0217] 0 indicates complete miscibility.
    权利要求:
    Claims (24)
    [0001]
    Multilayer structure, intended for the transport, distribution or storage of hydrogen, comprising, from the inside outwards, at least a sealing layer and at least one composite reinforcement layer,said innermost composite reinforcement layer being welded to said outermost adjacent sealing layer,said sealing layers being made of a composition mainly comprising at least one semi-crystalline thermoplastic polymer P1i (i=1 to n, n being the number of sealing layers) whose Tm, as measured according to ISO 11357- 3: 2013, is less than 280° C., in particular less than 265° C.,said at least one thermoplastic polymer of each sealing layer possibly being identical or different, and at least one of said composite reinforcement layers consisting of a fibrous material in the form of continuous fibers impregnated with a composition mainly comprising at least a thermoplastic polymer P2j, (j=1 to m, m being the number of reinforcing layers) in particular semi-crystalline, said thermoplastic polymer P2j having a Tg, as measured according to ISO 11357-3: 2013, greater than the temperature maximum use of said structure (Tu), in particular Tg ≥ Tu + 20°C, in particular Tg ≥ Tu + 30°C.
    [0002]
    Multilayer structure according to Claim 1, in which each polymer P1i of each sealing layer is partially or totally miscible with each polymer P1i of the adjacent layer(s), each polymer P2j of each reinforcing layer is partially or totally miscible with each polymer P2j of the adjacent layer(s), and the polymer P21 is partially or totally miscible with the polymer P11 which is adjacent to it, the total or partial miscibility of said polymers being defined by the difference in glass transition temperature of the two resins, in the mixture, relative to the difference in glass transition temperature of the two resins, before mixing, and the miscibility being total when the said difference is equal to 0, and the miscibility being partial, when said difference is different from 0.
    [0003]
    Multilayer structure according to Claim 1 or 2, characterized in that the maximum operating temperature Tu is greater than 50°C, in particular greater than 100°C.
    [0004]
    Multilayer structure according to one of Claims 1 to 3, characterized in that each sealing layer comprises the same type of polymer, in particular a polyamide.
    [0005]
    Multilayer structure according to one of Claims 1 to 3, characterized in that each reinforcing layer comprises the same type of polymer, in particular a polyamide.
    [0006]
    Multilayer structure according to one of Claims 4 or 5, characterized in that each sealing layer comprises the same type of polymer, in particular a polyamide, and each reinforcing layer comprises the same type of polymer, in particular a polyamide.
    [0007]
    Multilayer structure according to one of Claims 1 to 6, characterized in that it has a single sealing layer and a single reinforcing layer.
    [0008]
    Multilayer structure according to one of Claims 1 to 7, characterized in that the said structure is a tank or a flexible pipe.
    [0009]
    Multilayer structure according to one of Claims 1 to 8, characterized in that the said composition comprising the said polymers P1 and P2 also comprises additives, such as carbon blacks, carbon nanotubes (CNTs) or graphenes enabling them to absorb radiation suitable for welding.
    [0010]
    Multilayer structure according to one of Claims 1 to 9, characterized in that the said composition comprising the said polymer P2j is transparent to radiation suitable for welding.
    [0011]
    Multilayer structure according to Claim 9 or 10, characterized in that the welding is carried out by a system chosen from laser, infrared heating (IR), heating by LED, heating by induction or by µwaves or high-frequency heating. (HF).
    [0012]
    Multilayer structure according to one of Claims 1 to 11, characterized in that the said polymer P1i is a polyamide.
    [0013]
    Multilayer structure according to one of Claims 1 to 11, characterized in that the said polymer P2j is a polyamide.
    [0014]
    Multilayer structure according to one of Claims 12 or 13, characterized in that the said polymer P1i and the said polymer P2j are polyamides.
    [0015]
    Multilayer structure according to Claim 12 or 14, characterized in that the said polymer P1i is a long-chain aliphatic polyamide, in particular PA1010, PA 1012, PA 1212, PA11, PA12, in particular PA 11 or PA12 or semi-aromatic, in particular PA11/5T, PA11/6T and PA11/10T.
    [0016]
    Multilayer structure according to Claim 13 or 14, characterized in that the said polymer P2j is a semi-aromatic polyamide, in particular chosen from a PA MPMDT/6T, a PA 11/10T, a PA 11/BACT, a PA 5T/10T PA 11/6T/10T, PA MXDT/10T, PA MPMDT/10T, PA BACT/10T, PA BACT/6T, PA BACT/10T/6T, PA 11/BACT/6T, PA 11/ MPMDT/6T, PA 11/MPMDT/10T, PA 11/BACT/10T, one PA 11/MXDT/10T, one PA11/5T/10T.
    [0017]
    Multilayer structure according to one of Claims 14 to 16, characterized in that the said polymer P1i is a long-chain aliphatic polyamide, in particular PA1010, PA 1012, PA 1212, PA11, PA12, or semi-aromatic, in particular PA 11 /5T, or PA 11/6T or PA 11/10T, in particular PA 11 or PA12 and said polymer P2j is a semi-aromatic polyamide, in particular chosen from a PA MPMDT/6T, a PA PA11/10T, a PA 11/ BACT, one PA 5T/10T, one PA 11/6T/10T, one PA MXDT/10T, one PA MPMDT/10T, one PA BACT/10T, one PA BACT/6T, PA BACT/10T/6T, one PA 11 /BACT/6T, PA 11/MPMDT/6T, PA 11/MPMDT/10T, PA 11/BACT/10T, one PA 11/MXDT/10T, one PA11/5T/10T.
    [0018]
    Multilayer structure according to one of Claims 1 to 17, characterized in that it has a resistance to decompression and an ability to dry.
    [0019]
    Multilayer structure according to one of Claims 1 to 18, characterized in that the said structure further comprises a metal carcass located inside the sealing layer.
    [0020]
    Multilayer structure according to one of Claims 1 to 19, characterized in that the said structure also comprises at least one outer layer, in particular of metal, the said layer being the outermost layer of the said multilayer structure.
    [0021]
    Multilayer structure according to one of Claims 1 to 20, characterized in that the fibrous material is chosen from among glass fibers and carbon or basalt or basalt-based fibers.
    [0022]
    Method of manufacturing a multilayer structure as defined in one of Claims 1 to 21, characterized in that it comprises a step of welding the reinforcing layer as defined in Claim 1 to the sealing layer as defined in claim 1.
    [0023]
    Process according to Claim 22, characterized in that the welding step is carried out by a system chosen from among lasers, infrared (IR) heating, LED heating, induction heating or microwave heating or high frequencies (HF).
    [0024]
    Method according to claim 22 or 23, characterized in that it comprises a step of extruding said pressure layer on a metal carcass and a step of welding the reinforcing layer onto the sealing layer.
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    EP3663081B1|2021-05-26|Multilayer tubular structure intended for transporting an air-conditioning fluid
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    同族专利:
    公开号 | 公开日
    WO2021019181A1|2021-02-04|
    CN114174066A|2022-03-11|
    FR3099409B1|2021-10-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2003074258A1|2002-03-04|2003-09-12|Solvay |Assembly method and a plastic composite tube|
    EP1505099A2|2003-08-05|2005-02-09|Arkema|Flexible semi-aromatic polyamides with low humidity uptake|
    EP2851190A1|2013-09-24|2015-03-25|Hanil Tube Corporation|Hydrogen transfer tube|
    EP3309438A1|2015-06-09|2018-04-18|The Yokohama Rubber Co., Ltd.|Hydrogen-dispensing hose|
    FR3049952A1|2016-04-08|2017-10-13|Arkema France|POLYAMIDE COMPOSITION FOR PIPES CONTAINING PETROLEUM OR GAS|
    FR3059072A1|2016-11-18|2018-05-25|Technip France|FLEXIBLE FLUID TRANSPORT DRIVE, ASSOCIATED INSTALLATION AND METHOD|
    FR3106646A1|2020-01-28|2021-07-30|Arkema France|MULTI-LAYER STRUCTURE FOR TRANSPORT OR STORAGE OF HYDROGEN|
    FR3106647B1|2020-01-28|2021-12-31|Arkema France|MULTILAYER STRUCTURE FOR TRANSPORT OR STORAGE OF HYDROGEN|
    法律状态:
    2020-06-11| PLFP| Fee payment|Year of fee payment: 2 |
    2021-02-05| PLSC| Publication of the preliminary search report|Effective date: 20210205 |
    2021-06-11| PLFP| Fee payment|Year of fee payment: 3 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1908669A|FR3099409B1|2019-07-30|2019-07-30|MULTI-LAYER STRUCTURE FOR TRANSPORT OR STORAGE OF HYDROGEN|
    FR1908669|2019-07-30|FR1908669A| FR3099409B1|2019-07-30|2019-07-30|MULTI-LAYER STRUCTURE FOR TRANSPORT OR STORAGE OF HYDROGEN|
    CN202080055439.8A| CN114174066A|2019-07-30|2020-07-28|Multilayer structure for transporting or storing hydrogen|
    PCT/FR2020/051386| WO2021019181A1|2019-07-30|2020-07-28|Multilayer structure for transporting or storing hydrogen|
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