Multilayer structure and container constructed therefrom

Abstract

A hollow composite container is provided having a wall comprised of a multilayer structure comprising a thermoplastic layer, a fibrous layer, and a layer comprising both a plurality of filaments and a thermoset polymer. The container is manufactured in part by a rotational molding process and is characterized by strong bonding between the layers of the multilayer structure. The container can be used to store and deliver powders, liquids, gases and cryogenic substances, in particular hazardous substances.

Description

Technical Field

[0001] The present disclosure relates to a multilayer structure comprising a thermoplastic layer, a fiber layer, and a layer comprising both a plurality of filaments and a thermosetting polymer. The present disclosure also relates to containers incorporating the multilayer structure and to containers manufactured using a rotational molding process. The containers can be used to store and transport materials, particularly, but not exclusively, hazardous liquids, gases, and powders, as well as cryogenic materials. Background Art

[0002] Storage tanks are widely used to transport both hazardous and non-hazardous materials such as liquids, gases and powders. For the transport of hazardous materials, storage tanks must comply with several local and international regulations.

[0003] Tanks used to transport hazardous materials are typically constructed of metal, which imparts structural strength, and may be lined with an elastomeric lining to protect the metal from the corrosive nature of the tank contents.

[0004] However, lined metal tanks have a number of disadvantages, including their excessive weight, which increases transportation costs, and the potential for the lining material to degrade over time due to contact with the tank contents or to separate from the inner wall of the metal tank, necessitating repair or replacement of the liner.

[0005] International Patent Application Publication No. WO 2007 / 093006 discloses an article having a composite construction and a method for making the same. The article comprises a fiber material and a thermoplastic. The fiber material may include glass fiber or carbon fiber. Suitable thermoplastics include polyethylene, polypropylene, polyvinylidene fluoride, and ethylene chlorotrifluoroethylene. The article may also comprise a thermosetting polymer selected from polyesters, vinyl esters, epoxy resins, and polyurethanes. The article may be formed by rotational molding. However, the present disclosure is general in nature and, in particular, does not address details of how the composite article is manufactured, details of the various components and their relationships, and properties of the composite article.

[0006] Therefore, there remains a need to provide alternative structures for manufacturing transport containers for hazardous materials.

[0007] The reference to any prior art in this specification is not an acknowledgement or implication that this prior art forms part of the common general knowledge in any jurisdiction, nor does it mean that this prior art could be reasonably understood by a person skilled in the art to be related to and / or combined with other prior art. Summary of the Invention

[0008] In one aspect, the present disclosure provides a hollow composite container, wherein a wall of the hollow composite container comprises a multilayer structure comprising:

[0009] an inner layer comprising one or more thermoplastic polymers;

[0010] an outer layer comprising a plurality of filaments and one or more thermosetting polymers, the plurality of filaments being selected from one or more of the following: carbon filaments, glass filaments, aramid filaments, and basalt filaments; and

[0011] a middle layer disposed between the inner layer and the outer layer, the middle layer comprising one or more fiber materials;

[0012] wherein the one or more fiber materials are at least partially infiltrated with both the one or more thermoplastic polymers and the one or more thermosetting polymers.

[0013] In an embodiment, the one or more thermoplastic polymers of the inner layer include one or more of: ethylene homopolymers, ethylene copolymers, propylene homopolymers, propylene copolymers, fluoropolymers, polyvinyl chloride, polyvinylidene chloride, polyaryletherketones (e.g., polyetheretherketones), and polyamides.

[0014] In an embodiment, the one or more thermosetting polymers of the outer layer comprise one or more of the following: vinyl esters, bismaleimides, polyesters, polyacrylates, epoxies, and polyurethanes.

[0015] In an embodiment, the one or more fiber materials of the intermediate layer comprise one or more woven textile materials.

[0016] In an embodiment, the one or more woven textile materials comprise one or more of: a woven material, a knitted material, and a braided material.

[0017] In an embodiment, the one or more woven textile materials comprise plied yarns.

[0018] In embodiments, the spacing between at least some yarns of the fiber material of the intermediate layer is from about 0.01 microns to about 5000 microns, or from about 0.1 microns to about 5000 microns, or between about 1 micron and about 5000 microns, or between about 10 microns and about 5000 microns.

[0019] In an embodiment, the one or more fiber materials of the intermediate layer include one or more of ceramic fibers and polymer fibers.

[0020] The one or more ceramic fibers may comprise one or more of: glass fibers, carbon fibers, and basalt fibers, or precursors thereof.

[0021] The one or more polymeric fibers may comprise one or both synthetic polymers and natural polymers.

[0022] The one or more polymeric fibers may comprise one or more of polyamides and polyolefins. Suitable polyolefins include polyethylene and polypropylene.

[0023] In embodiments, the plurality of filaments of the outer layer have a filament diameter of about 0.1 micrometer to about 500 micrometers, or about 0.1 micrometer to about 100 micrometers, or about 0.1 micrometer to about 50 micrometers, or about 1 micrometer to about 20 micrometers.

[0024] In embodiments, the plurality of filaments of the outer layer are in the form of one or more of: wound filaments, textile segments comprising a plurality of yarns, braided yarns, and chopped fibers.

[0025] In an embodiment, the inner layer of the multilayer structure has a thickness of about 0.1 mm to about 50 mm, the middle layer has a thickness of about 0.1 mm to about 5 mm, and the outer layer has a thickness of about 0.1 mm to about 1000 mm.

[0026] In an embodiment, a thermoplastic polymer is embedded in the interstices between the yarns of said fiber material of said intermediate layer.

[0027] In an embodiment, a thermoplastic polymer is embedded within the structure of the individual yarns of said fiber material of said intermediate layer.

[0028] In an embodiment, tendrils of the fibrous material of the intermediate layer extend from the surface of the yarn into the inner layer.

[0029] In an embodiment, the bonding strength between the thermoplastic polymer and the fiber layer is greater than the cohesive strength of the thermoplastic polymer.

[0030] In embodiments, the thermoplastic polymer is embedded in the fiber layer to such an extent that the multilayer structure fails in shear due to cohesive failure of the thermoplastic polymer.

[0031] In an embodiment, the maximum lap shear strength of the multilayer structure is proportional to the tensile strength of the thermoplastic polymer.

[0032] In an embodiment, the maximum lap shear strength of the multilayer structure is equal to the tensile strength of the thermoplastic polymer multiplied by 0.58.

[0033] In embodiments, the lap shear strength of the multilayer structure is greater than about 3 MPa, or greater than about 4 MPa, or greater than about 5 MPa, or greater than about 6 MPa, or greater than about 7 MPa, or greater than about 8 MPa, or greater than about 9 MPa, or greater than about 10 MPa.

[0034] In an embodiment, the single pressure average permeability of the fiber layer is less than 10-11m2.

[0035] In an embodiment, the single pressure average permeability of the fiber layer is less than about 9*10-12m2, or less than about 8*10-12m2, or less than about 7*10-12m2, or less than about 6*10-12m2, or less than about 5*10-12m2, or less than about 4*10-12m2.

[0036] In an embodiment, the thermoplastic polymer does not fully penetrate through the thickness of the fibrous layer. That is, at least a portion of the surface of the fibrous layer is not fully penetrated by the thermoplastic polymer. Preferably, substantially all of the surface of the fibrous layer is not fully penetrated by the thermoplastic polymer.

[0037] In embodiments, the hollow composite container is not limited by shape. In some embodiments, the hollow composite container has a generally spherical, cylindrical, or spherocylinder shape.

[0038] In another aspect, the present disclosure provides a method of manufacturing a hollow composite container, the method comprising the steps of:

[0039] a) applying one or more fiber materials to the inner surface of the hollow mold;

[0040] b) heating and rotating the hollow mold in the presence of one or more thermoplastic polymers within the hollow mold such that the thermoplastic polymers melt and at least partially penetrate the fibrous material;

[0041] c) cooling the mold to solidify the thermoplastic polymer;

[0042] d) demoulding the hollow thermoplastic polymer / fiber material composite container from the mold; and one or more steps of steps e) to g);

[0043] e) applying a plurality of filaments to the exterior of the hollow thermoplastic polymer / fiber material composite vessel, the plurality of filaments being selected from one or more of the following: carbon filaments, glass filaments, aramid filaments, and basalt filaments, wherein prior to application, the plurality of filaments are at least partially wetted with one or more thermosetting polymers;

[0044] f) applying a plurality of filaments to the exterior of the hollow thermoplastic polymer / fiber material composite vessel, followed by application of one or more thermosetting polymers, the plurality of filaments being selected from one or more of the following: carbon filaments, glass filaments, aramid filaments, and basalt filaments;

[0045] g) applying one or more thermosetting polymers to the exterior of the hollow thermoplastic polymer / fiber material composite container, followed by applying a plurality of filaments selected from one or more of the following: carbon filaments, glass filaments, aramid filaments, and basalt filaments.

[0046] In embodiments, the method further comprises curing the one or more thermosetting polymers.

[0047] In an embodiment, the mold is rotated in two directions simultaneously.

[0048] In embodiments, the hollow composite container has a generally spherical, cylindrical, or spherocylinder shape.

[0049] In an embodiment, the fiber material may be fixed to the inner surface of the mold by, for example, mechanical means or adhesive means or by applying pressure.

[0050] It should be understood that the method aspects of the present disclosure may include any one or more embodiments of the hollow composite container aspects.

[0051] Advantages of the presently disclosed hollow composite containers include one or more of the following:

[0052] The wall of the container exhibits high shear strength due to the strong coupling between the middle layer and the inner and outer layers;

[0053] The inner layer provides a barrier layer for containing hazardous materials;

[0054] • The use of a rotational moulding process enables seamless integration of the inner thermoplastic polymer layer with the fibre layer.

[0055] Unless expressly stated otherwise, any embodiment herein should be considered applicable to any other embodiment mutatis mutandis.

[0056] The present disclosure is not to be limited in scope by the specific embodiments described herein, which are intended for illustrative purposes only. Functionally equivalent products, compositions, and processes, as described herein, are clearly within the scope of the present disclosure.

[0057] Further aspects of the disclosure and further embodiments of the aspects described in the preceding paragraphs will become apparent from the following description, which is given by way of example and with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] Figure 1 (a) is a schematic diagram of a generally spherical hollow composite container, and Figure 1 (b) is an exploded view of a multi-layer wall structure according to an embodiment of the present disclosure.

[0059] Figure 2 is a graphic representation of the penetration of a thermoplastic polymer into the spaces between the yarns of a woven fiber material.

[0060] Figure 3 is a graphic representation of the structure of a yarn of a woven fiber material infiltrated with a thermoplastic polymer.

[0061] Figure 4 is a graphic representation of the interaction of a thermoplastic polymer with fibrils protruding from the yarns of a woven fiber material.

[0062] Figure 5 (a) and (b) are micrographs of the interface between the polyethylene layer and the woven fiber layer, indicating areas where the polyethylene has penetrated into the spaces between the yarns of the fiber layer.

[0063] Figure 6 is a photograph of polyethylene adhesion resulting from a lap joint test showing fibers from the woven fiber layer attached to the failed surface.

[0064] Figure 7 is a photograph of a woven fiber layer resulting from a lap joint test showing polyethylene-rich locations.

[0065] Figure 8 is a micrograph of the interface between a thermoplastic polymer layer and a layer of woven fiber material, the micrograph highlighting the fiber tendrils of the fiber layer embedded in the thermoplastic polymer layer.

[0066] Figure 9 is a photograph of a failure surface resulting from a lap joint test of a multilayer structure having a nonwoven fiber layer, the photograph showing the fiber layers being white in color to be located on both failure surfaces. DETAILED DESCRIPTION

[0067] It should be understood that the disclosure described and defined in this specification extends to all alternative combinations of two or more of the individual features mentioned or evident from the text or drawings. All of these different combinations constitute various alternative aspects of the disclosure.

[0068] definition

[0069] For the purpose of interpreting this specification, terms used in the singular will also include the plural form, and vice versa.

[0070] As used herein, the term "comprise" and variations of the term such as "comprising," "comprises," and "comprised" are not intended to exclude additional additives, components, integers, or steps unless the context requires otherwise.

[0071] As used herein, "about" when referring to a measurable value such as an amount, duration, etc., is intended to encompass variations of ±20% or ±10%, in some instances ±5%, in some instances ±1%, and in some instances ±0.1% relative to the specified value, as such variations are suitable for performing the disclosed methods.

[0072] Range: Throughout this disclosure, various aspects of the present disclosure may be presented in range format. It should be understood that descriptions in range format are merely for convenience and brevity and should not be construed as fixed limitations on the scope of the present disclosure. Thus, descriptions of ranges should be considered to have specifically disclosed all possible subranges as well as individual numerical values ​​within the ranges. For example, descriptions of ranges such as 1 to 6 should be considered to have specifically disclosed subranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., as well as individual numbers within the ranges, such as 1, 2, 2.7, 3, 4, 5, 5.3, and 6. This applies regardless of the width of the range.

[0073] The present disclosure provides a hollow composite container comprising three layers: an inner layer comprising one or more thermoplastic polymers, a middle layer comprising one or more fiber materials, and an outer layer comprising a plurality of filaments and one or more thermosetting polymers. The inventors have discovered that certain fiber material architectures can provide multilayer structures with advantageous properties.

[0074] Inner layer - thermoplastic polymer

[0075] The thermoplastic polymer used to construct the inner layer is preferably resistant to various substances and conditions, for example, resistant to one or more of high pH, ​​low pH, oxidizing agents, reducing agents, solvents, high pressure gases, cryogenic substances, penetration, and abrasion.

[0076] The thermoplastic polymer may comprise one or more of an ethylene homopolymer, an ethylene copolymer, a propylene homopolymer, a propylene copolymer, a fluoropolymer, polyvinyl chloride, polyvinylidene chloride, a polyaryletherketone (eg, polyetheretherketone), and a polyamide.

[0077] The ethylene homopolymer may be a high density ethylene homopolymer or a low density ethylene homopolymer. The ethylene copolymer may be a copolymer of ethylene and one or more α-olefins or one or more cycloolefins. The propylene homopolymer may be a polypropylene. The propylene copolymer may be a copolymer of propylene and one or more α-olefins.

[0078] Suitable fluoropolymers include one or more of polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, perfluoroalkoxyalkanes, fluorinated ethylene-propylene, ethylene tetrafluoroethylene, ethylene chlorotrifluoroethylene, polyethylene tetrafluoroethylene, and polyethylene chlorotrifluoroethylene.

[0079] In embodiments, the inner layer has a thickness of about 0.1 mm to about 50 mm, or about 0.2 mm to about 50 mm, or about 0.5 mm to about 50 mm, or about 1 mm to about 50 mm, or about 2 mm to about 50 mm, or about 0.1 mm to about 40 mm, or about 0.2 mm to about 30 mm, or about 0.1 mm to about 20 mm, or about 0.1 mm to about 10 mm, or about 0.1 mm to about 5 mm, or about 0.5 mm to about 40 mm, or about 0.1 mm to about 30 mm, or about 1 mm to about 40 mm, or about 1 mm to about 30 mm, or about 1 mm to about 20 mm, or about 1 mm to about 10 mm, or about 2 mm to about 30 mm.

[0080] Middle layer - fiber material

[0081] In an embodiment, the one or more fiber materials of the intermediate layer comprise one or more woven textile materials.

[0082] In an embodiment, the one or more woven textile materials comprise one or more of: a woven material, a knitted material, and a braided material.

[0083] In an embodiment, the one or more woven textile materials comprise plied yarns.

[0084] In embodiments, the spacing between at least some of the yarns of the fiber material of the intermediate layer is from about 0.01 microns to about 5000 microns, or from about 0.1 microns to about 5000 microns, or between about 1 micron and about 5000 microns, or between about 10 microns and about 5000 microns, or between about 0.01 microns and about 1000 microns, or between about 0.1 microns and about 1000 microns, or between about 1 micron and about 1000 microns, or between about 10 microns and about 1000 microns.

[0085] In an embodiment, the one or more fiber materials of the intermediate layer include one or more of ceramic fibers and polymer fibers.

[0086] The one or more ceramic fibers may comprise one or more of: glass fibers, carbon fibers, and basalt fibers, or precursors thereof.

[0087] The one or more polymeric fibers may comprise one or both synthetic polymers and natural polymers.

[0088] The one or more polymeric fibers may comprise one or more of polyamides and polyolefins. Suitable polyolefins include polyethylene and polypropylene.

[0089] In an embodiment, the thickness of the intermediate layer is from about 0.1 mm to about 5 mm, or from about 0.2 mm to about 5 mm, or from about 0.3 mm to about 5 mm, or from about 0.4 mm to about 5 mm, or from about 0.5 mm to about 5 mm, or from about 0.1 mm to about 4 mm, or from about 0.1 mm to about 3 mm, or from about 0.1 mm to about 2 mm, or from about 0.2 mm to about 3 mm, or from about 0.3 mm to about 3 mm.

[0090] Outer layer - filament

[0091] The plurality of filaments include one or more of the following: carbon filaments, glass filaments, aramid filaments, and basalt filaments.

[0092] In embodiments, the plurality of filaments in the outer layer have a filament diameter of about 0.1 micrometer to about 500 micrometers, or about 0.1 micrometer to about 100 micrometers, or about 0.1 micrometer to about 50 micrometers, or about 1 micrometer to about 20 micrometers.

[0093] In embodiments, the plurality of filaments in the outer layer are in the form of one or more of: wound filaments, textile segments comprising a plurality of yarns, braided yarns, and chopped fibers.

[0094] Outer layer - thermosetting polymer

[0095] Thermosetting polymers are used as binding polymers for the plurality of filaments in the outer layer.The one or more thermosetting polymers in the outer layer may comprise one or more of the following: polyesters, polyacrylates, epoxies, vinyl esters, bismaleimides, and polyurethanes.

[0096] In an embodiment, the thermosetting polymer comprises epoxy vinyl ester.

[0097] In an embodiment, the outer layer comprising a plurality of filaments and one or more thermosetting polymers has a thickness of about 0.1 mm to about 200 mm, or about 0.5 mm to about 200 mm, or about 1 mm to about 200 mm, or about 2 mm to about 200 mm, or about 5 mm to about 200 mm, or about 10 mm to about 200 mm, or about 0.1 mm to about 100 mm, or about 0.1 mm to about 50 mm, or about 0.5 mm to about 100 mm, or about 0.5 mm to about 50 mm, or about 1 mm to about 50 mm, or about 1 mm to about 40 mm, or about 1 mm to about 30 mm, or about 1 mm to about 20 mm, or about 2 mm to about 50 mm, or about 2 mm to about 40 mm, or about 2 mm to about 30 mm, or about 2 mm to about 20 mm.

[0098] In embodiments, the total thickness of the walls of the hollow composite containers disclosed herein is from about 0.5 mm to about 250 mm, or from about 1 mm to about 200 mm, or from about 2 mm to about 200 mm, or from about 5 mm to about 200 mm, or from about 5 mm to about 150 mm, or from about 5 mm to about 100 mm, or from about 10 mm to about 150 mm, or from about 10 mm to about 100 mm, or from about 10 mm to about 50 mm.

[0099] Method for preparing hollow composite material container

[0100] One method of making the hollow composite container of the present disclosure utilizes, in part, rotational molding.

[0101] In an exemplary embodiment of manufacturing a generally spherocylindrical hollow composite container, a multi-segment mold may be used. The multi-segment mold may take the form of a hollow cylindrical center segment and two hemispherical outer segments that, when assembled, form the hollow spherocylindrical mold.

[0102] In the first step, the inner surface of the mold segment is coated with a fiber layer. The fiber layer can be attached to the inner surface of the mold segment by a variety of means, including mechanical attachment. The fiber layer can be laid down by hand, or the process can be automated.

[0103] After covering the inner surfaces of the mold segment surfaces with the fiber layers, the mold segments are assembled.

[0104] The thermoplastic polymer, for example in the form of a powder or pellets, is introduced into the mold through a suitable orifice, and the orifice is closed.

[0105] The mold is then heated and rotated in two directions. As the mold is heated, the thermoplastic polymer melts and coats the fiber layer on the inner surface of the mold. As the thermoplastic melts, it penetrates the fiber layer to at least some extent.

[0106] The mold is heated to a temperature sufficient to melt the thermoplastic polymer. It should be understood that the temperature will depend on the melting point of the thermoplastic polymer.

[0107] After a certain period of time, the mold is cooled, causing the thermoplastic polymer to solidify.

[0108] The mold is then opened and the hollow thermoplastic polymer / fibrous material container is demoulded.

[0109] Then, the hollow composite container of the present disclosure is completed in one or a combination of the following ways.

[0110] A plurality of filaments are applied to the exterior of a hollow thermoplastic polymer / fiber material composite container, the plurality of filaments being selected from one or more of the following: carbon filaments, glass filaments, aramid filaments, and basalt filaments, wherein prior to application, the plurality of filaments are at least partially wetted with one or more thermosetting polymers.

[0111] A plurality of filaments selected from one or more of the following: carbon filaments, glass filaments, aramid filaments, and basalt filaments are applied to the exterior of the hollow thermoplastic polymer / fiber material composite vessel followed by application of one or more thermoset polymers.

[0112] One or more thermoset polymers are applied to the exterior of the hollow thermoplastic polymer / fiber material composite vessel, followed by application of a plurality of filaments selected from one or more of the following: carbon filaments, glass filaments, aramid filaments, and basalt filaments.

[0113] The plurality of filaments may be in the form of yarn and / or in the form of a preformed sheet.

[0114] The thermosetting polymer is then cured. Depending on the nature of the thermosetting polymer, curing may be carried out at elevated temperatures.

[0115] Multi-layer structure

[0116] The multi-layer wall structure of the hollow composite container of the present disclosure has advantageous mechanical properties.Since one application of the presently disclosed hollow composite container is the transport and storage of hazardous liquids, it is desirable that the wall structure have mechanical properties that mitigate the risk of structural failure.

[0117] The multilayer structure of the hollow composite container of the present disclosure can be characterized in part by the interaction of the thermoplastic polymer layers and the fiber layers.

[0118] Figure 1 (a) is a schematic diagram of a generally spherical cylindrical hollow composite container 1 having a multi-layer wall structure 2 according to an embodiment of the present disclosure.

[0119] Figure 1(b) is an exploded view of a multi-layer wall structure according to an embodiment of the present disclosure, showing an inner thermoplastic polymer layer 3, an intermediate woven fiber layer 4, and an outer layer 5 comprising a plurality of filaments and one or more thermosetting polymers. Vertical arrows 6 depict the penetration of the thermoplastic polymer partially through the thickness of the woven fiber layer.

[0120] Figure 2 、 3 Figures 4 and 5 show three mechanisms by which the thermoplastic polymer layers and the fiber layers of a multilayer structure interact and can independently contribute to the mechanical strength of the multilayer structure.

[0121] Figure 2 、 3 4 and 4 show the form of a wound yarn framework according to one embodiment of the present disclosure.

[0122] like Figure 2 The first mechanism shown is characterized by gaps in the fiber layer structure into which thermoplastic can flow during manufacturing. Figure 2 Two intertwined yarns 1 and 2 are shown. These yarns are typically composed of two or more smaller fiber bundles that are twisted together, creating regular gaps 3 when placed against adjacent yarns. The yarns themselves have difficulty filling these gaps due to constraints within the fabric, even when placed under pressure. However, during melt processing, thermoplastic can flow into these gaps and, when solidified within the gaps, create mechanical interlocking and anchoring.

[0123] This is Figure 5 (a) and (b), which show micrographs of failure modes resulting from lap joint testing of a multilayer structure according to the present disclosure comprising a woven fiber layer and a polyethylene thermoplastic polymer layer. Areas of thermoplastic polymer that have penetrated into the interstices between the yarns of the fiber layer are evident, as highlighted by the black ovals.

[0124] Figure 3 The second mechanism, shown in , is characterized by the penetration of the thermoplastic polymer into the structure of the yarn itself, which then creates a mechanical lock upon solidification. Both the fabric and the fabric yarn are permeable, and the thermoplastic polymer can flow into the yarn during melt processing. Figure 3 Two intertwined yarns 1 and 2 are shown. The yarns are porous, schematically shown as 4. The thermoplastic polymer solidifies within the structure of the yarns, creating a mechanical interlock.

[0125] This is Figure 6 and 7This is demonstrated in the Figures 1 and 2, which show the surfaces of the polyethylene layer and the woven fiber layer after the lap joint test, respectively. Broken fibers remain on the surface of the thermoplastic polymer adherend, and thermoplastic-rich areas and streaks are visible on the fiber layer side adherend.

[0126] Figure 4 The third mechanism, shown in Figure 1, is based on tendrils extending from the yarn into the thermoplastic polymer layer and extending inward within the thermoplastic-infiltrated yarn, thereby promoting shear transfer in and around the yarn. Two intertwined yarns are shown as 1 and 2. Tendrils 3 are shown extending from the bulked yarn surface and can interact with the thermoplastic polymer 5 that has infiltrated around the tendrils.

[0127] This is Figure 8 This is demonstrated in a micrograph of which the black oval highlights the yarn tendrils from the woven fiber layer embedded in the polyethylene thermoplastic polymer layer.

[0128] Fabric processing techniques, including stretch-break treatments, can damage the yarn, causing it to fray. These broken and / or frayed fibers can extend outward from the yarn and penetrate deeper into the thermoplastic polymer layer than the yarn would if it were undamaged. Broken and / or frayed fibers can also extend inward within the yarn infiltrated with the thermoplastic polymer. After melt forming and after the thermoplastic polymer cools, the broken and / or frayed yarns can become mechanically interlocked and anchored.

[0129] Another characteristic feature of the multilayer structure disclosed herein is that, after the first two layers (i.e., the inner layer of thermoplastic polymer and the middle layer of fibers) are formed, the fiber layer forms a surface for applying an outer layer comprising a plurality of filaments and a thermosetting polymer. The thermosetting polymer advantageously penetrates the fibers of the fiber layer, and after the thermosetting polymer is cured, the fibers create a strong bond between the plurality of filaments and the thermosetting polymer and the fiber layer.

[0130] In some preferred embodiments, the fiber layer has a fiber architecture that facilitates forming a multilayer structure with desired mechanical properties. For example, a woven architecture comprising multiple yarns of ceramic fibers or polymer fibers can improve the shear strength of the multilayer structure.

[0131] In some preferred embodiments, the permeability of the fiber layer to thermoplastic polymer infiltration is an important parameter for controlling the shear strength of the presently disclosed multilayer structure. If the permeability is too high, this may result in a reduction in shear strength. Therefore, a relatively low permeability is desirable.

[0132] Lap shear testing studies indicate that the primary failure mode of the disclosed multilayer structures is within the thermoplastic layer. This is advantageous because the shear strength of the multilayer structure can depend on the tensile strength of the thermoplastic. Therefore, the shear strength of the multilayer structure can be controlled by varying the properties of the thermoplastic.

[0133] The average lap shear strength of the presently disclosed multilayer structures may be greater than about 3 MPa, or greater than about 4 MPa, or greater than about 5 MPa, or greater than about 6 MPa, or greater than about 7 MPa, or greater than about 8 MPa, or greater than about 9 MPa, or greater than about 10 MPa. Specific embodiments

[0135] A hollow composite container, wherein the wall of the hollow composite container comprises a multilayer structure, the multilayer structure comprising:

[0136] an inner layer comprising one or more thermoplastic polymers selected from one or more of the following: ethylene homopolymers, ethylene copolymers, propylene homopolymers, propylene copolymers, fluoropolymers, polyvinyl chloride, polyvinylidene chloride, polyaryletherketones (e.g., polyetheretherketone), and polyamides;

[0137] an outer layer comprising a plurality of filaments and one or more thermosetting polymers, the plurality of filaments being selected from one or more of the following: carbon filaments, glass filaments, aramid filaments, and basalt filaments; and

[0138] a middle layer disposed between the inner layer and the outer layer, the middle layer comprising one or more fiber materials in the form of a woven textile material;

[0139] wherein the one or more woven fabric materials are at least partially infiltrated with both the one or more thermoplastic polymers and the one or more thermosetting polymers.

[0140] A hollow composite container, wherein the wall of the hollow composite container comprises a multilayer structure, the multilayer structure comprising:

[0141] an inner layer comprising one or more thermoplastic polymers selected from one or more of the following: ethylene homopolymers, ethylene copolymers, propylene homopolymers, propylene copolymers, fluoropolymers, polyvinyl chloride, polyvinylidene chloride, polyaryletherketones (e.g., polyetheretherketone), and polyamides;

[0142] an outer layer comprising a plurality of filaments selected from one or more of the group consisting of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of the group consisting of polyesters, polyacrylates, epoxies, vinyl esters, bismaleimides, and polyurethanes; and

[0143] a middle layer disposed between the inner layer and the outer layer, the middle layer comprising one or more fiber materials in the form of a woven textile material;

[0144] wherein the one or more woven fabric materials are at least partially infiltrated with both the one or more thermoplastic polymers and the one or more thermosetting polymers.

[0145] A hollow composite container, wherein the wall of the hollow composite container comprises a multilayer structure, the multilayer structure comprising:

[0146] an inner layer comprising one or more thermoplastic polymers selected from one or more of the following: ethylene homopolymers, ethylene copolymers, propylene homopolymers, propylene copolymers, fluoropolymers, polyvinyl chloride, polyvinylidene chloride, polyaryletherketones (e.g., polyetheretherketone), and polyamides;

[0147] an outer layer comprising a plurality of filaments selected from one or more of the group consisting of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of the group consisting of polyesters, polyacrylates, epoxies, vinyl esters, bismaleimides, and polyurethanes; and

[0148] a middle layer disposed between the inner layer and the outer layer, the middle layer comprising one or more fiber materials in the form of a woven textile material;

[0149] wherein the one or more woven fabric materials are at least partially infiltrated with both the one or more thermoplastic polymers and the one or more thermosetting polymers, and

[0150] The inner layer of the multilayer structure has a thickness of about 0.1 mm to about 50 mm, the middle layer has a thickness of about 0.1 mm to about 5 mm, and the outer layer has a thickness of about 2 mm to about 500 mm.

[0151] A hollow composite container, wherein the wall of the hollow composite container comprises a multilayer structure, the multilayer structure comprising:

[0152] an inner layer comprising one or more thermoplastic polymers selected from one or more of the following: ethylene homopolymers, ethylene copolymers, propylene homopolymers, propylene copolymers, fluoropolymers, polyvinyl chloride, polyvinylidene chloride, polyaryletherketones (e.g., polyetheretherketone), and polyamides;

[0153] an outer layer comprising a plurality of filaments selected from one or more of the group consisting of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of the group consisting of polyesters, polyacrylates, epoxies, vinyl esters, bismaleimides, and polyurethanes; and

[0154] a middle layer disposed between the inner layer and the outer layer, the middle layer comprising one or more fiber materials in the form of a woven textile material;

[0155] wherein said one or more woven fabric materials are at least partially infiltrated with both said one or more thermoplastic polymers and said one or more thermosetting polymers;

[0156] wherein the inner layer of the multilayer structure has a thickness of about 0.1 mm to about 10 mm, the middle layer has a thickness of about 0.1 mm to about 5 mm, and the outer layer has a thickness of about 2 mm to about 500 mm; and

[0157] The multilayer structure has a lap shear strength greater than about 5 MPa.

[0158] A hollow composite container, wherein the wall of the hollow composite container comprises a multilayer structure, the multilayer structure comprising:

[0159] an inner layer comprising one or more thermoplastic polymers selected from one or more of the following: ethylene homopolymers, ethylene copolymers, propylene homopolymers, propylene copolymers, fluoropolymers, polyvinyl chloride, polyvinylidene chloride, polyaryletherketones (e.g., polyetheretherketone), and polyamides;

[0160] an outer layer comprising a plurality of filaments selected from one or more of the group consisting of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of the group consisting of polyesters, polyacrylates, epoxies, vinyl esters, bismaleimides, and polyurethanes; and

[0161] a middle layer disposed between the inner layer and the outer layer, the middle layer comprising one or more fiber materials in the form of a woven textile material;

[0162] wherein said one or more woven fabric materials are at least partially infiltrated with both said one or more thermoplastic polymers and said one or more thermosetting polymers;

[0163] The inner layer of the multilayer structure has a thickness of about 0.1 mm to about 10 mm, the middle layer has a thickness of about 0.2 mm to about 3 mm, and the outer layer has a thickness of about 2 mm to about 500 mm.

[0164] In an embodiment, the multi-layer structure has a lap shear strength greater than about 5 MPa.

[0165] In any of the embodiments disclosed herein, the multilayer structure has a lap shear strength greater than about 6 MPa, or greater than about 7 MPa, or greater than about 8 MPa, or greater than about 9 MPa, or greater than about 10 MPa.

[0166] Purpose of Containers

[0167] The hollow composite containers disclosed herein are widely used in the storage and transport of materials where both structural strength and chemical sealing are desired, for example, in the storage and transport of corrosive chemicals (such as strong acids and bases, hydrogen peroxide, etc.), as well as for the storage and transport of high-pressure gases and cryogenic substances.

[0168] Examples

[0169] Example 1: Fabrication of hollow composite containers

[0170] A three-part mold comprising a generally cylindrically shaped middle section and two generally hemispherically shaped end sections is lined on its inner surface with a fiber layer of a woven textile (an example of a woven fabric material).

[0171] The mold segments are then assembled to produce a hollow spherical mold.

[0172] The mold is transferred to a rotary molding unit, and a specific mass of thermoplastic polymer powder (polyethylene) is added to the internal cavity of the mold. The mold is then rotated and heated to a temperature sufficient to melt the thermoplastic polymer and cover the surface of the inner surface of the inner surface mold of the fiber layer. After a certain period of time, heating is stopped, and as the mold and its contents cool, the thermoplastic polymer solidifies to provide a smooth, continuous, solid thermoplastic layer on the surface of the inner surface of the inner surface mold of the fiber layer.

[0173] The mould is then opened and the hollow container having a wall defined by two layers is demoulded. The inner layer comprises coagulated thermoplastic polyethylene and the outer layer comprises a fibrous material.

[0174] The fiber layer of the hollow container thus prepared is then treated with an epoxy vinyl ester thermosetting polymer and the polymer is allowed to harden. A layer consisting of carbon fiber filaments and epoxy vinyl ester is then applied to the exterior of the container and the thermosetting polymer is allowed to harden.

[0175] Example 2

[0176] The procedure of Example 1 was followed except that a nonwoven fiber layer (an example of a nonwoven fabric material) was substituted for the woven fiber layer.

[0177] Example 3: Mechanical Testing

[0178] A number of containers were prepared according to Examples 1 and 2 comprising an inner polyethylene layer, a middle fiber layer, and an outer layer comprising a plurality of filaments and a thermoset polymer.

[0179] The thickness of the inner polyethylene layer was about 10 mm, and the thickness of the outer layer comprising the plurality of filaments and the thermosetting polymer was about 10 mm.

[0180] The total thickness of the multilayer structure was approximately 20 mm.

[0181] Panels of the container's wall are cut and removed for testing. The panels are typically 200mm in length and 20mm in width.

[0182] The panel was prepared for the lap shear test by cutting two grooves, each 5 mm, from the centerline, one groove on the outer layer of carbon fiber and the other on the inner polyethylene layer. The first groove was cut through the carbon fiber layer and the middle layer of fiber material until the polyethylene layer was visible. The panel was flipped over and the grooves were cut through the polyethylene layer until the middle layer of fiber material became visible.

[0183] The lap shear strength of the grooved panels was measured using a general purpose tensile testing apparatus according to BS EN 13121-3:2008, section D.8.

[0184] The multi-layer structure formed by the method of Example 2 produced a lap shear strength between about 1.5 MPa and about 2.8 MPa.

[0185] In contrast, the multilayer structure formed by the method of Example 1 produced a lap shear strength between about 9.4 MPa and about 11.5 MPa.

[0186] The lap shear strength of the multilayer structure of Example 1 indicates cohesive failure of the polyethylene (see e.g. Figure 5 and 6 ), while the much lower lap shear strength of the multilayer structure of Example 2 indicates that the shear failure is far below the cohesive strength of polyethylene. Figure 9, which shows the fiber layer in white color to be located on two failure surfaces, which indicates that shear failure has occurred within the fiber layer.

[0187] Therefore, there are significant advantages in utilizing woven fiber layers which, when infiltrated with thermoplastic polymers such as polyethylene, result in multilayer structures having significantly higher lap shear strength.

[0188] Example 4 - Permeability Study

[0189] The single pressure permeability (K) of the four fiber layers was determined by flowing a fluid of known viscosity through fiber layers of known thickness and measuring the pressure drop.

[0190] The studies were carried out in the device using the method described in DE 10 2013 102 486. The permeability was calculated using Darcy's law based on the following formula:

[0191]

[0192] in

[0193] ●K is the permeability of the fiber layer, expressed in m 2 Unit

[0194] ●Q is the flow rate of the fluid through the fiber layer, in cubic meters per second

[0195] ●Δp is the pressure drop across the fiber layer, in Pa

[0196] ●A is the area of ​​the measurement location, in m 2 Unit

[0197] ●V is the kinematic viscosity of the fluid, in square meters per second

[0198] ●ΔL is the length of the fluid flowing into the fiber layer, in meters.

[0199] It should be noted that the distance traveled by the fluid through the fiber layer is equal to the time over which the measurement is taken multiplied by the flow rate.

[0200] The measurements were performed in triplicate and the average values ​​of the results are collected in the table below.

[0201] fiber layer <![CDATA[Single - pressure average permeability (m 2 )]]> Permeability normalized to nonwoven fibers Non-woven fabrics (as in Example 2) <![CDATA[1.04*10 -11 ]]> 1.00 Woven ceramic fibers (as in Example 1) <![CDATA[2.64*10 -12 ]]> 0.25 Woven polymer fibers (as in Example 1) <![CDATA[1.83*10 -12 ]]> 0.18 Woven ceramic fibers (as in Example 1) <![CDATA[4.10*10 -13 ]]> 0.04

[0202] The average permeability of the woven fiber layer is significantly lower than that of the non-woven fiber layer. This indicates that higher resistance to penetration of molten thermoplastic polymer into the fiber layer during the manufacture of the multilayer structure is beneficial for producing a multilayer structure with higher lap shear strength.

Claims

1. A hollow composite container, wherein the wall of the hollow composite container comprises a multilayer structure, the multilayer structure comprising: an inner layer comprising one or more thermoplastic polymers; an outer layer comprising a plurality of filaments and one or more thermosetting polymers, the plurality of filaments being selected from one or more of the following: carbon filaments, glass filaments, aramid filaments, and basalt filaments; as well as a middle layer disposed between the inner layer and the outer layer, the middle layer comprising one or more fiber materials; wherein the one or more fiber materials are at least partially infiltrated with both the one or more thermoplastic polymers and the one or more thermosetting polymers.

2. The hollow composite container of claim 1 , wherein the one or more thermoplastic polymers of the inner layer comprise one or more of the following: ethylene homopolymers, ethylene copolymers, propylene homopolymers, propylene copolymers, fluoropolymers, polyvinyl chloride, polyvinylidene chloride, polyaryletherketones, and polyamides.

3. A hollow composite container according to claim 1 or claim 2, wherein the one or more thermoplastic polymers comprises polyethylene.

4. The hollow composite container of claim 1 or claim 2, wherein the one or more thermoplastic polymers comprises ethylene tetrafluoroethylene.

5. The hollow composite container of claim 1 or claim 2, wherein the one or more thermoplastic polymers comprises ethylene chlorotrifluoroethylene.

6. The hollow composite container according to any one of claims 1 to 5, wherein the one or more thermosetting polymers of the outer layer comprise one or more of the following: polyesters, polyacrylates, epoxies, vinyl esters, bismaleimides, and polyurethanes.

7. The hollow composite container according to any one of claims 1 to 6, wherein the one or more fibrous materials of the intermediate layer comprise one or more woven fabric materials.

8. The hollow composite container of claim 7, wherein the one or more woven fabric materials comprise one or more of the following: a woven material, a knitted material, and a braided material.

9. A hollow composite container according to claim 7 or claim 8, wherein the one or more woven fabric materials comprises plied yarns.

10. A hollow composite container according to claim 9, wherein the spacing between at least some of the yarns of the fiber material of the intermediate layer is from about 0.01 microns to about 5000 microns, or from about 0.1 microns to about 5000 microns, or between about 1 micron and about 5000 microns, or between about 10 microns and about 5000 microns.

11. The hollow composite container according to any one of claims 1 to 10, wherein the one or more fiber materials of the intermediate layer comprise one or more of ceramic fibers and polymer fibers.

12. The hollow composite vessel of claim 11, wherein the one or more ceramic fibers comprise one or more of: glass fibers, carbon fibers, and basalt fibers, or precursors thereof.

13. The hollow composite container of claim 11, wherein the one or more polymeric fibers comprise one or both of a synthetic polymer and a natural polymer.

14. The hollow composite container of claim 11, wherein the one or more polymeric fibers comprise one or more of a polyamide and a polyolefin.

15. The hollow composite container according to any one of claims 1 to 14, wherein the plurality of filaments in the outer layer have a filament diameter of about 0.1 micron to about 500 microns, or about 0.1 micron to about 100 microns, or about 0.1 micron to about 50 microns, or about 1 micron to about 20 microns.

16. The hollow composite container according to any one of claims 1 to 15, wherein the plurality of filaments of the outer layer are in the form of one or more of the following: wound filaments, textile segments comprising a plurality of yarns, braided yarns, and chopped fibers.

17. The hollow composite container according to any one of claims 1 to 16, wherein the thickness of the inner layer of the multilayer structure is about 0.1 mm to about 50 mm, the thickness of the middle layer is about 0.1 mm to about 5 mm, and the thickness of the outer layer is about 0.1 mm to about 1000 mm.

18. The hollow composite container of any one of claims 1 to 17, wherein the inner layer of the multi-layer structure has a thickness of about 0.2 mm to about 30 mm.

19. The hollow composite container of any one of claims 1 to 18, wherein the intermediate layer has a thickness of about 0.2 mm to about 3 mm.

20. The hollow composite container of any one of claims 1 to 19, wherein the outer layer has a thickness of about 2 mm to about 30 mm.

21. The hollow composite container of any one of claims 1 to 20, wherein the total thickness of the wall of the hollow composite container is from about 5 mm to about 1000 mm.

22. A hollow composite container according to any one of claims 1 to 21 wherein a thermoplastic polymer is embedded in the interstices between the yarns of the fibrous material.

23. A hollow composite container according to any one of claims 1 to 22, wherein a thermoplastic polymer is embedded within the structure of the individual yarns of the fibrous material.

24. A hollow composite vessel according to any one of claims 1 to 23, wherein tendrils of the fibrous material of the intermediate layer extend from the surface of the yarn into the inner layer.

25. The hollow composite container according to any one of claims 1 to 24, wherein the bonding strength between the thermoplastic polymer and the fiber layer is greater than the cohesive strength of the thermoplastic polymer.

26. The hollow composite container of any one of claims 1 to 25, wherein the thermoplastic polymer is embedded in the fiber layers to such an extent that the multilayer structure fails in shear due to cohesive failure of the thermoplastic polymer.

27. The hollow composite container of any one of claims 1 to 26, wherein the maximum lap shear strength of the multilayer structure is proportional to the tensile strength of the thermoplastic polymer.

28. The hollow composite container of any one of claims 1 to 27, wherein the maximum lap shear strength of the multilayer structure is substantially equal to the tensile strength of the thermoplastic polymer multiplied by 0.

58.

29. The hollow composite container of any one of claims 1 to 28, wherein the lap shear strength of the multilayer structure is greater than about 5 MPa.

30. The hollow composite container of any one of claims 1 to 29, wherein the lap shear strength of the multilayer structure is greater than about 6 MPa.

31. The hollow composite container of any one of claims 1 to 30, wherein the lap shear strength of the multilayer structure is greater than about 7 MPa.

32. The hollow composite container of any one of claims 1 to 31, wherein the lap shear strength of the multilayer structure is greater than about 8 MPa.

33. The hollow composite container of any one of claims 1 to 32, wherein the lap shear strength of the multilayer structure is greater than about 9 MPa.

34. The hollow composite container of any one of claims 1 to 33, wherein the lap shear strength of the multilayer structure is greater than about 10 MPa.

35. The hollow composite container according to any one of claims 1 to 34, wherein the single pressure average permeability of the fiber layer is less than about 10 -11 m 2 .

36. The hollow composite container according to any one of claims 1 to 35, wherein the single pressure average permeability of the fiber layer is less than about 9*10 -12 m 2 , or less than about 8*10 -12 m 2 , or less than about 7*10 -12 m 2 , or less than about 6*10 -12 m 2 , or less than about 5*10 -12 m 2 , or less than about 4*10 -12 m 2 .

37. The hollow composite container of any one of claims 1 to 36, wherein the hollow composite container has a generally spherical, cylindrical, or spherocylindrical shape.

38. A method of manufacturing a hollow composite container, the method comprising the steps of: a) applying one or more fiber materials to the inner surface of the hollow mold; b) heating and rotating the hollow mold in the presence of one or more thermoplastic polymers within the hollow mold such that the thermoplastic polymers melt and at least partially penetrate the fibrous material; c) cooling the mold to solidify the thermoplastic polymer; d) demoulding the hollow thermoplastic polymer / fiber material composite container from the mold; and one or more steps of steps e) to g); e) applying a plurality of filaments to the exterior of the hollow thermoplastic polymer / fiber material composite vessel, the plurality of filaments being selected from one or more of the following: carbon filaments, glass filaments, aramid filaments, and basalt filaments, wherein prior to application, the plurality of filaments are at least partially wetted with one or more thermosetting polymers; f) applying a plurality of filaments to the exterior of the hollow thermoplastic polymer / fiber material composite vessel, followed by application of one or more thermosetting polymers, the plurality of filaments being selected from one or more of the following: carbon filaments, glass filaments, aramid filaments, and basalt filaments; g) applying one or more thermosetting polymers to the exterior of the hollow thermoplastic polymer / fiber material composite container, followed by applying a plurality of filaments selected from one or more of the following: carbon filaments, glass filaments, aramid filaments, and basalt filaments.

39. The method of claim 38, further comprising curing the one or more thermosetting polymers.

40. A method according to claim 38 or claim 39, wherein the mould is rotated in two directions simultaneously.

41. The method of any one of claims 38 to 40, wherein the hollow composite container has a generally spherical, cylindrical, or spherocylindrical shape.

42. A method according to any one of claims 38 to 41 , wherein the fibrous material is fixed to the inner surface of the mould by mechanical means or adhesive means or by the application of pressure.

43. The method of any one of claims 38 to 42, wherein the one or more thermoplastic polymers comprise one or more of: ethylene homopolymers, ethylene copolymers, propylene homopolymers, propylene copolymers, fluoropolymers, polyvinyl chloride, polyvinylidene chloride, polyaryletherketones, and polyamides.

44. The method of any one of claims 38 to 43, wherein the one or more thermoplastic polymers comprises polyethylene.

45. The method of any one of claims 38 to 43, wherein the one or more thermoplastic polymers comprises ethylene tetrafluoroethylene.

46. ​​The method of any one of claims 38 to 43, wherein the one or more thermoplastic polymers comprises ethylene chlorotrifluoroethylene.

47. The method of any one of claims 38 to 46, wherein the one or more thermosetting polymers comprise one or more of the following: polyesters, polyacrylates, epoxies, vinyl esters, bismaleimides, and polyurethanes.

48. The method of any one of claims 38 to 47, wherein the one or more fiber materials comprise one or more woven fabric materials.

49. The method of claim 48, wherein the one or more woven fabric materials comprise one or more of: a woven material, a knitted material, and a braided material.

50. A method according to claim 48 or claim 49, wherein the one or more woven fabric materials comprise plied yarns.

51. The method of any one of claims 38 to 50, wherein the one or more fiber materials comprise one or more of ceramic fibers and polymer fibers.

52. The method of claim 51, wherein the one or more ceramic fibers comprise one or more of: glass fibers, carbon fibers, and basalt fibers, or precursors thereof.

53. The method of claim 51, wherein the one or more polymeric fibers comprise one or both of a synthetic polymer and a natural polymer.

54. The method of claim 51, wherein the one or more polymeric fibers comprise one or more of a polyamide and a polyolefin.

55. The method of any one of claims 38 to 54, wherein the plurality of filaments have a filament diameter of about 0.1 micron to about 500 microns, or about 0.1 micron to about 100 microns, or about 0.1 micron to about 50 microns, or about 1 micron to about 20 microns.

56. The method of any one of claims 38 to 55, wherein the plurality of filaments is in the form of one or more of: wound filaments, a textile segment comprising a plurality of yarns, a braided yarn, and chopped fibers.

57. The hollow composite container of claim 1, wherein a wall of the hollow composite container comprises a multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of the following: ethylene homopolymers, ethylene copolymers, propylene homopolymers, propylene copolymers, fluoropolymers, polyvinyl chloride, polyvinylidene chloride, polyaryletherketones, and polyamides; an outer layer comprising a plurality of filaments and one or more thermosetting polymers, the plurality of filaments being selected from one or more of the following: carbon filaments, glass filaments, aramid filaments, and basalt filaments; as well as a middle layer disposed between the inner layer and the outer layer, the middle layer comprising one or more fiber materials in the form of a woven textile material; wherein the one or more woven fabric materials are at least partially infiltrated with both the one or more thermoplastic polymers and the one or more thermosetting polymers.

58. The hollow composite container of claim 1, wherein a wall of the hollow composite container comprises a multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of the following: ethylene homopolymers, ethylene copolymers, propylene homopolymers, propylene copolymers, fluoropolymers, polyvinyl chloride, polyvinylidene chloride, polyaryletherketones, and polyamides; an outer layer comprising a plurality of filaments selected from one or more of the group consisting of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of the group consisting of polyesters, polyacrylates, epoxies, vinyl esters, bismaleimides, and polyurethanes; as well as a middle layer disposed between the inner layer and the outer layer, the middle layer comprising one or more fiber materials in the form of a woven textile material; wherein the one or more woven fabric materials are at least partially infiltrated with both the one or more thermoplastic polymers and the one or more thermosetting polymers.

59. The hollow composite container of claim 1, wherein a wall of the hollow composite container comprises a multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of the following: ethylene homopolymers, ethylene copolymers, propylene homopolymers, propylene copolymers, fluoropolymers, polyvinyl chloride, polyvinylidene chloride, polyaryletherketones, and polyamides; an outer layer comprising a plurality of filaments selected from one or more of the group consisting of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of the group consisting of polyesters, polyacrylates, epoxy and vinyl esters, bismaleimides, and polyurethanes; and a middle layer disposed between the inner layer and the outer layer, the middle layer comprising one or more fiber materials in the form of a woven textile material; wherein the one or more woven fabric materials are at least partially infiltrated with both the one or more thermoplastic polymers and the one or more thermosetting polymers; and The inner layer of the multilayer structure has a thickness of about 0.1 mm to about 50 mm, the middle layer has a thickness of about 0.1 mm to about 5 mm, and the outer layer has a thickness of about 2 mm to about 500 mm.

60. The hollow composite container of claim 1, wherein a wall of the hollow composite container comprises a multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of the following: ethylene homopolymers, ethylene copolymers, propylene homopolymers, propylene copolymers, fluoropolymers, polyvinyl chloride, polyvinylidene chloride, polyaryletherketones, and polyamides; an outer layer comprising a plurality of filaments selected from one or more of the group consisting of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of the group consisting of polyesters, polyacrylates, epoxies, vinyl esters, bismaleimides, and polyurethanes; as well as a middle layer disposed between the inner layer and the outer layer, the middle layer comprising one or more fiber materials in the form of a woven textile material; wherein said one or more woven fabric materials are at least partially infiltrated with both said one or more thermoplastic polymers and said one or more thermosetting polymers; wherein the inner layer of the multilayer structure has a thickness of about 0.1 mm to about 50 mm, the middle layer has a thickness of about 0.1 mm to about 5 mm, and the outer layer has a thickness of about 2 mm to about 500 mm; and The multilayer structure has a lap shear strength greater than about 5 MPa.

61. The hollow composite container of claim 1 , wherein a wall of the hollow composite container comprises a multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of the following: ethylene homopolymers, ethylene copolymers, propylene homopolymers, propylene copolymers, fluoropolymers, polyvinyl chloride, polyvinylidene chloride, polyaryletherketones, and polyamides; an outer layer comprising a plurality of filaments selected from one or more of the group consisting of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of the group consisting of polyesters, polyacrylates, epoxies, vinyl esters, bismaleimides, and polyurethanes; as well as a middle layer disposed between the inner layer and the outer layer, the middle layer comprising one or more fiber materials in the form of a woven textile material; wherein said one or more woven fabric materials are at least partially infiltrated with both said one or more thermoplastic polymers and said one or more thermosetting polymers; wherein the inner layer of the multilayer structure has a thickness of about 0.1 mm to about 50 mm, the middle layer has a thickness of about 0.1 mm to about 5 mm, and the outer layer has a thickness of about 2 mm to about 500 mm; and The average permeability of the fiber layer is less than about 10 -11 m 2 .

62. The hollow composite container of claim 1, wherein a wall of the hollow composite container comprises a multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of the following: ethylene homopolymers, ethylene copolymers, propylene homopolymers, propylene copolymers, fluoropolymers, polyvinyl chloride, polyvinylidene chloride, polyaryletherketones, and polyamides; an outer layer comprising a plurality of filaments selected from one or more of the group consisting of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of the group consisting of polyesters, polyacrylates, epoxies, vinyl esters, bismaleimides, and polyurethanes; as well as a middle layer disposed between the inner layer and the outer layer, the middle layer comprising one or more fiber materials in the form of a woven textile material; wherein said one or more woven fabric materials are at least partially infiltrated with both said one or more thermoplastic polymers and said one or more thermosetting polymers; wherein the inner layer of the multilayer structure has a thickness of about 0.1 mm to about 50 mm, the middle layer has a thickness of about 0.1 mm to about 5 mm, and the outer layer has a thickness of about 2 mm to about 500 mm; and The maximum overlap shear strength of the multilayer structure is proportional to the tensile strength of the thermoplastic polymer.

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