Multilayer structures and containers constructed therefrom

Abstract

A hollow composite container is provided having a wall constructed from a multilayer structure including a thermoplastic layer, a fibrous layer, and a layer including both a plurality of filaments and a thermosetting polymer. The container is manufactured in part by a rotational molding process and is characterized by strong bonds between the layers of the multilayer structure. The container can be used for the storage and transport of powders, liquids, gases, and cryogenic materials, particularly hazardous materials.

Description

[Technical Field]

[0001] The present disclosure relates to multi-layer structures including a thermoplastic layer, a fibrous layer, and a layer including both a plurality of filaments and a thermosetting polymer. The disclosure also relates to containers incorporating the multi-layer structures and the manufacture of containers utilizing a rotational molding process. The containers may find use in the storage and transport of substances, particularly, but not exclusively, hazardous liquids, gases, and powders, as well as cryogenic materials. [Background technology]

[0002] Tanks are widely used for the transportation of substances such as liquids, gases, powders, etc., both hazardous and non-hazardous. For the transportation of hazardous substances, tanks must meet many local and international regulations.

[0003] Tanks for transporting hazardous materials are generally constructed from metal to provide structural strength and may be lined with a resilient liner to protect the metal from the corrosive properties of the tank contents.

[0004] However, lined metal tanks have many disadvantages, including the excessive weight of the tank, which increases transportation costs, and the possibility that the liner material may deteriorate over time due to contact with the tank contents or become detached from the interior wall of the metal tank, requiring repair or replacement of the liner.

[0005] International Patent Application Publication No. WO 2007 / 093006 discloses composite structural articles and methods for their manufacture. The articles include a fibrous material and a thermoplastic material. The fibrous material may include glass fiber or carbon fiber. Suitable thermoplastic materials include polyethylene, polypropylene, polyvinylidene fluoride, and ethylene chlorotrifluoroethylene. The articles may also include a thermosetting polymer selected from polyester, vinyl ester, epoxy, and polyurethane. The articles may be formed via rotational molding. However, this disclosure is general in nature and does not specifically address details of how the composite articles are manufactured, details of the different components and their relationships, or the performance of the composite articles.

[0006] Therefore, there remains a need to provide alternative structures for use in the manufacture of shipping containers for hazardous materials.

[0007] The reference to any prior art herein is not an admission or suggestion that this prior art forms part of the common general knowledge in any jurisdiction, or that this prior art would be understood by, considered relevant, and / or could reasonably be expected to be combined with other pieces of prior art by a person skilled in the 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 multi-layer structure, the multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers; an outer layer comprising a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers; an intermediate layer disposed between the inner layer and the outer layer, the intermediate layer comprising one or more fibrous materials; The one or more fibrous materials are at least partially infiltrated with both one or more thermoplastic polymers and one or more thermosetting polymers.

[0009] In embodiments, the one or more thermoplastic polymers of the inner layer include one or more of an ethylene homopolymer, an ethylene copolymer, a propylene homopolymer, a propylene copolymer, a fluoropolymer, a polyvinyl chloride, a polyvinylidene chloride, a polyaryletherketone (e.g., a polyetheretherketone), and a polyamide.

[0010] In embodiments, the one or more thermosetting polymers of the outer layer include one or more of vinyl esters, bismaleimides, polyesters, polyacrylates, epoxies, and polyurethanes.

[0011] In an embodiment, the one or more fibrous materials of the intermediate layer comprise one or more textured woven materials.

[0012] In embodiments, the one or more textured textile materials include one or more of a woven material, a knit material, and a braided material.

[0013] In an embodiment, one or more of the textured woven materials comprises plied yarns.

[0014] In embodiments, the spacing between at least some of the yarns of the fibrous material of the intermediate layer is from about 0.01 micrometers to about 5000 micrometers, or from about 0.1 micrometers to about 5000 micrometers, or from about 1 micrometer to about 5000 micrometers, or from about 10 micrometers to about 5000 micrometers.

[0015] In an embodiment, the one or more fibrous materials of the intermediate layer include one or more of ceramic fibers and polymeric fibers.

[0016] The one or more ceramic fibers may include one or more of glass fibers, carbon fibers, and basalt fibers, or precursors thereof.

[0017] The one or more polymeric fibers may include one or both of a synthetic polymer and a natural polymer.

[0018] The one or more polymeric fibers may comprise one or more of a polyamide and a polyolefin. Suitable polyolefins include polyethylene and polypropylene.

[0019] In embodiments, the plurality of filaments in the outer layer have a filament diameter of from about 0.1 micrometers to about 500 micrometers, or from about 0.1 micrometers to about 100 micrometers, or from about 0.1 micrometers to about 50 micrometers, or from about 1 micrometer to about 20 micrometers.

[0020] In embodiments, the plurality of filaments of the outer layer are in the form of one or more of wound filaments, a fabric section comprising a plurality of threads, braided yarns, and chopped fibers.

[0021] In an embodiment, the thickness of the inner layer of the multi-layer 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.

[0022] In an embodiment, the thermoplastic polymer is embedded in the interstices between the yarns of the fibrous material of the intermediate layer.

[0023] In an embodiment, the thermoplastic polymer is embedded within the structure of the individual threads of the fibrous material of the intermediate layer.

[0024] In an embodiment, the tendrils of fibrous material of the middle layer extend from the surface of the yarn into the inner layer.

[0025] In embodiments, the strength of the bond between the thermoplastic polymer and the fibrous layer is greater than the cohesive strength of the thermoplastic polymer.

[0026] In embodiments, the thermoplastic polymer is embedded in the fibrous layer to the extent that shear failure of the multi-layer structure occurs via cohesive failure of the thermoplastic polymer.

[0027] In embodiments, the multi-layer structure has a maximum lap shear strength that is proportional to the tensile strength of the thermoplastic polymer.

[0028] In an embodiment, the multilayer structure has a maximum lap shear strength equal to the tensile strength of the thermoplastic polymer multiplied by 0.58.

[0029] 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.

[0030] In an embodiment, the fibrous layer comprises 10 -11 m 2 has a single pressure average permeability of less than

[0031] In an embodiment, the fibrous layer is about 9×10 -12 m 2 Less than or about 8 x 10 -12 m 2 Less than or about 7 x 10 -12 m 2 Less than or about 6 x 10 -12 m 2 Less than or about 5 x 10 -12 m 2 Less than or about 4 x 10 -12 m 2 has a single pressure average permeability of less than

[0032] In embodiments, the thermoplastic polymer is not completely infiltrated through the thickness of the fibrous layer, i.e., at least a portion of the surface of the fibrous layer is not completely penetrated by the thermoplastic polymer. Preferably, substantially all of the surface of the fibrous layer is not completely penetrated by the thermoplastic polymer.

[0033] In embodiments, the hollow composite vessel is not limited by shape. In some embodiments, the hollow composite vessel is generally spherical, cylindrical, or spherocylindrical in shape.

[0034] In another aspect, the present disclosure provides a method of manufacturing a hollow composite container, comprising the steps of: a) applying one or more fibrous materials to the interior surface of a hollow mold; b) heating and rotating the hollow mold in the presence of another thermoplastic polymer located within the hollow mold such that the thermoplastic polymer melts and at least partially infiltrates the fibrous material; c) cooling the mold so that the thermoplastic polymer solidifies; d) removing the hollow thermoplastic polymer / fibrous material composite container from the mold; and one or more of steps e) to g), wherein steps e) to g) include: e) applying a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments to the exterior of the hollow thermoplastic polymer / fibrous material composite container, wherein prior to applying, the plurality of filaments are at least partially wetted with one or more thermosetting polymers; f) applying a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments to the exterior of the hollow thermoplastic polymer / fibrous material composite container, followed by applying one or more thermosetting polymers; g) applying one or more thermosetting polymers to the exterior of the hollow thermoplastic polymer / fibrous material composite container, followed by applying a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments.

[0035] In an embodiment, the method further comprises curing the one or more thermosetting polymers.

[0036] In an embodiment, the mold is rotated about two directions simultaneously.

[0037] In embodiments, the hollow composite vessel is generally of a spherical, cylindrical, or spherocylindrical shape.

[0038] In embodiments, the fibrous material may be secured to the interior surface of the mold, for example, via mechanical or adhesive means, or via the application of pressure.

[0039] It will be understood that the method aspects of the present disclosure can include any one or more of the embodiments of the hollow composite vessel aspects.

[0040] Advantages of the hollow composite container of the present disclosure include one or more of the following: The container wall exhibits high shear strength due to the strong bond between the middle layer and the inner and outer layers. The inner layer provides a barrier layer for containment of harmful substances. The use of a rotational molding process allows for seamless integration of the inner thermoplastic polymer layer with the fibrous layer.

[0041] Any embodiment herein shall apply mutatis mutandis to any other embodiment unless specifically stated otherwise.

[0042] The present disclosure is not to be limited in scope by the specific embodiments described herein, which are intended for purposes of exemplification only. Functionally equivalent products, compositions, and processes are clearly within the scope of the present disclosure as described herein.

[0043] Further aspects of the disclosure, and further embodiments of the aspects described in the previous paragraphs, will become apparent from the following description, given by way of example and with reference to the accompanying drawings. [Brief explanation of the drawings]

[0044] [Figure 1] FIG. 1(a) is a schematic diagram of a generally spherical-cylindrical hollow composite container according to an embodiment of the present disclosure, and FIG. 1(b) is an exploded view of its multi-layer wall structure. [Figure 2] FIG. 1 illustrates a thermoplastic polymer infiltrating the spaces between the yarns of a woven fibrous material. [Figure 3] FIG. 1 illustrates a thermoplastic polymer infiltrating the structure of the yarns of a woven fibrous material. [Figure 4] FIG. 1 illustrates a thermoplastic polymer interacting with fibrils protruding from yarns of a woven fibrous material. [Figure 5] 5(a) and (b) are photomicrographs of the interface between the polyethylene layer and the woven fibrous layer, showing areas of polyethylene infiltration into the spaces between the yarns of the fibrous layer. [Figure 6] 1 is a photograph of bonded polyethylene from a lap joint test showing fibers from the woven fibrous layer attached to the fracture surface. [Figure 7] 1 is a photograph of a woven fibrous layer from a lap joint test showing areas of high polyethylene concentration. [Figure 8] 1 is a photomicrograph of the interface between a thermoplastic polymer layer and a woven fibrous material layer, highlighting the fiber tendrils of the fibrous layer embedded within the thermoplastic polymer layer. [Figure 9] Photograph of the fracture surface from a lap joint test of a multi-layer structure with a non-woven fibrous layer, showing the white fibrous layer on both fracture surfaces. DETAILED DESCRIPTION OF THE INVENTION

[0045] It will be understood that the disclosure described and defined herein extends to all alternative combinations of two or more of the individual features mentioned or apparent from the text or drawings, all of which different combinations constitute various alternative aspects of the disclosure.

[0046] definition For purposes of interpreting this specification, terms used in the singular will also include the plural and vice versa.

[0047] As used herein, unless the context requires otherwise, the term "comprise" and variations of the term such as "comprising," "comprises," and "comprised" are not intended to exclude further additives, ingredients, integers, or steps.

[0048] As used herein, when referring to measurable values such as amounts, temporal durations, etc., "about" is meant to encompass variations of ±20% or ±10%, in some instances ±5%, in some instances ±1%, and in some instances ±0.1% from the particular value, as such variations are appropriate for carrying out the disclosed methods.

[0049] Ranges: Throughout this disclosure, various aspects of the present disclosure may be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosure. Accordingly, the description of a range should be considered to have specifically disclosed all possible subranges as well as individual numerical values within that range. For example, a description of a range 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 that range, e.g., 1, 2, 2.7, 3, 4, 5, 5.3, and 6. This applies regardless of the breadth of the range.

[0050] 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 fibrous materials, and an outer layer comprising a plurality of filaments and one or more thermosetting polymers. The inventors have discovered that certain fibrous material architectures can provide multilayered structures with advantageous properties.

[0051] Inner layer - thermoplastic polymer Thermoplastic polymers for use in the construction of the inner layer preferably have resistance to a variety of substances and conditions, such as resistance to one or more of high pH, low pH, oxidizing agents, reducing agents, solvents, propellants, cryogenic substances, permeation, and abrasion.

[0052] The thermoplastic polymer may include one or more of ethylene homopolymer, ethylene copolymer, propylene homopolymer, propylene copolymer, fluoropolymer, polyvinyl chloride, polyvinylidene chloride, polyaryletherketone (e.g., polyetheretherketone), and polyamide.

[0053] The ethylene homopolymer can be a high density ethylene homopolymer or a low density ethylene homopolymer. The ethylene copolymer can be a copolymer of ethylene with one or more alpha olefins or one or more cyclic olefins. The propylene homopolymer can be polypropylene. The propylene copolymer can be a copolymer of propylene and one or more alpha olefins.

[0054] 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.

[0055] In an embodiment, the thickness of the inner layer is 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.

[0056] Middle layer - fibrous material In an embodiment, the one or more fibrous materials of the intermediate layer comprise one or more textured woven materials.

[0057] In embodiments, the one or more textured textile materials include one or more of a woven material, a knit material, and a braided material.

[0058] In an embodiment, one or more of the textured woven materials comprises plied yarns.

[0059] In embodiments, the spacing between at least some of the yarns of the fibrous material of the intermediate layer is from about 0.01 micrometers to about 5000 micrometers, or from about 0.1 micrometers to about 5000 micrometers, or from about 1 micrometer to about 5000 micrometers, or from about 10 micrometers to about 5000 micrometers, or from about 0.01 micrometers to about 1000 micrometers, or from about 0.1 micrometers to about 1000 micrometers, or from about 1 micrometers to about 1000 micrometers, or from about 10 micrometers to about 1000 micrometers.

[0060] In an embodiment, the one or more fibrous materials of the intermediate layer include one or more of ceramic fibers and polymeric fibers.

[0061] The one or more ceramic fibers may include one or more of glass fibers, carbon fibers, and basalt fibers, or precursors thereof.

[0062] The one or more polymeric fibers may include one or both of a synthetic polymer and a natural polymer.

[0063] The one or more polymeric fibers may comprise one or more of a polyamide and a polyolefin. Suitable polyolefins include polyethylene and polypropylene.

[0064] 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.

[0065] Outer layer - filament The plurality of filaments is comprised of one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments.

[0066] In embodiments, the plurality of filaments in the outer layer have a filament diameter of from about 0.1 micrometers to about 500 micrometers, or from about 0.1 micrometers to about 100 micrometers, or from about 0.1 micrometers to about 50 micrometers, or from about 1 micrometer to about 20 micrometers.

[0067] In embodiments, the plurality of filaments of the outer layer are in the form of one or more of wound filaments, a fabric section comprising multiple threads, braided yarns, and chopped fibers.

[0068] Outer layer - thermosetting polymer The thermosetting polymer acts as a binder polymer for the filaments in the outer layer. The one or more thermosetting polymers in the outer layer can include one or more of polyester, polyacrylate, epoxy, vinyl ester, bismaleimide, and polyurethane.

[0069] In embodiments, the thermosetting polymer comprises an epoxy vinyl ester.

[0070] In embodiments, the thickness of the outer layer comprising a plurality of filaments and one or more thermosetting polymers is from about 0.1 mm to about 200 mm, or from about 0.5 mm to about 200 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 10 mm to about 200 mm, or from about 0.1 mm to about 100 mm, or from about 0.1 mm to about 50 mm, or from about 0.5 mm to about 100 mm, or from about 0.5 mm to about 50 mm, or from about 1 mm to about 50 mm, or from about 1 mm to about 40 mm, or from about 1 mm to about 30 mm, or from about 1 mm to about 20 mm, or from about 2 mm to about 50 mm, or from about 2 mm to about 40 mm, or from about 2 mm to about 30 mm, or from about 2 mm to about 20 mm.

[0071] In an embodiment, the total wall thickness of the hollow composite container 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.

[0072] Method for preparing hollow composite containers One method for preparing the hollow composite containers of the present disclosure utilizes, in part, rotational molding.

[0073] Generally, in an exemplary embodiment for the manufacture of a spherical-cylindrical hollow composite container, a multi-section mold may be utilized, which may take the form of a hollow cylindrical center section and two hemispherical outer sections, which when assembled form the hollow spherical-cylindrical mold.

[0074] In a first step, the interior surfaces of the mold sections are coated with a fibrous layer. The fibrous layer can be attached to the interior surfaces of the mold sections by a number of means, including mechanical attachment. The fibrous layer can be applied by hand, or the process can be automated.

[0075] After coating the interior surfaces of the mold section surfaces with a fibrous layer, the mold sections are assembled.

[0076] For example, a thermoplastic polymer in the form of a powder or pellets is introduced into the mold through a suitable orifice and the orifice is closed.

[0077] The mold is then heated and rotated in two directions. As the mold heats, the thermoplastic polymer melts and coats the fibrous layer on the inner surface of the mold. As the thermoplastic resin melts, it infiltrates the fibrous layer, at least to some extent.

[0078] The mold is heated to a temperature sufficient to melt the thermoplastic polymer, it being understood that the temperature will depend on the melting point of the thermoplastic polymer.

[0079] After a period of time, the mold is cooled and the thermoplastic polymer solidifies.

[0080] The mold is then opened and the hollow thermoplastic polymer / fibrous material container is removed.

[0081] The hollow composite container of the present disclosure is then completed in one or a combination of the following ways:

[0082] A plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments are applied to the exterior of the hollow thermoplastic polymer / fibrous material composite container, and prior to application, the plurality of filaments are at least partially wetted with one or more thermosetting polymers.

[0083] A plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments are applied to the exterior of a hollow thermoplastic polymer / fibrous material composite vessel, followed by application of one or more thermosetting polymers.

[0084] One or more thermosetting polymers are applied to the exterior of the hollow thermoplastic polymer / fibrous material composite container, followed by application of a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments.

[0085] The plurality of filaments may be in the form of a yarn and / or in the form of a pre-fabricated sheet.

[0086] The thermosetting polymer is then cured. Depending on the nature of the thermosetting polymer, curing may be carried out at elevated temperatures.

[0087] multilayer structure The multi-layer wall structure of the hollow composite container of the present disclosure has advantageous mechanical properties. Because one application of the hollow composite container of the present disclosure is the transport and storage of hazardous liquids, it is desirable that the wall structure have mechanical properties that reduce the risk of structural failure.

[0088] The multi-layered structure of the hollow composite container of the present disclosure may be characterized, in part, by the interaction of the thermoplastic polymer layer and the fibrous layer.

[0089] FIG. 1(a) is a schematic diagram of a generally spherical-cylindrical hollow composite container 1 having a multilayered wall structure 2 according to one embodiment of the present disclosure.

[0090] 1(b) is an exploded view of a multilayered wall structure according to an embodiment of the present disclosure illustrating an inner thermoplastic polymer layer 3, an intermediate woven fibrous layer 4, and an outer layer 5 comprising a plurality of filaments and one or more thermosetting polymers. Vertical arrows 6 depict infiltration of the thermoplastic polymer partially through the thickness of the woven fibrous layer.

[0091] 2, 3, and 4 illustrate three mechanisms of interaction between the thermoplastic polymer layer and the fibrous layer of a multilayer structure, which may independently contribute to the mechanical strength of the multilayer structure.

[0092] 2, 3, and 4 illustrate the configuration of a twisted yarn architecture according to one embodiment of the present disclosure.

[0093] The first mechanism, illustrated in Figure 2, is characterized by gaps within the fibrous layer architecture into which the thermoplastic resin can flow during fabrication. Figure 2 shows two intertwined yarns 1 and 2. The yarns are typically composed of two or more smaller fiber bundles twisted together, forming regular gaps 3 when laid against adjacent yarns. Due to constraints within the woven fabric, these gaps are difficult for the yarns to fill by themselves, even when placed under compression. However, during melt processing, the thermoplastic resin can flow into these gaps, creating mechanical interlocks and bonds once solidified within the gaps.

[0094] This is clearly illustrated in Figures 5(a) and (b), which show photomicrographs of the failure mode resulting from lap joint testing of a multi-layer structure according to the present disclosure, including a woven fibrous layer and a polyethylene thermoplastic polymer layer. There are clearly areas of thermoplastic polymer that have infiltrated the interstitial spaces within the fibrous layer yarns, as highlighted by the black ovals.

[0095] The second mechanism, illustrated in Figure 3, is characterized by the penetration of the thermoplastic polymer into the structure of the yarn itself, followed by mechanical interlocking upon solidification. Both the woven fabric and the woven yarns are permeable, allowing the thermoplastic polymer to flow into the yarns during melt processing. Figure 3 shows two intertwined yarns, 1 and 2. The yarns are porous and are depicted diagrammatically as 4. The thermoplastic polymer solidifies within the yarn structure, forming a mechanical interlock.

[0096] This is clearly shown in Figures 6 and 7, which show the surfaces of the polyethylene layer and the woven fibrous layer, respectively, after lap joint testing. Broken fibers remain on the surface of the thermoplastic polymer adhesive, and thermoplastic-rich areas and streaks are visible on the fibrous layer adhesive.

[0097] The third mechanism, illustrated in Figure 4, is based on tendrils from the yarn that extend into the thermoplastic polymer layer and extend inward within the thermoplastic-permeated yarn, contributing to shear transfer within and around the yarn. Two entangled yarns are illustrated as 1 and 2. Tendril 3 is illustrated extending from the bulk yarn surface and can interact with thermoplastic polymer 5 infiltrating around the tendril.

[0098] This is clearly shown in the micrograph of Figure 8, which highlights dark, oval-shaped thread tendrils from the woven fibrous layer embedded in the polyethylene thermoplastic polymer layer.

[0099] Woven fabric processing techniques, including stretch-breaking, damage yarns and result in abrasion. These broken and / or abraded fibers can extend outward from the yarn further than an undamaged yarn would, and can even extend into the thermoplastic polymer layer. Broken and / or abraded fibers can also extend inward within the yarn through which the thermoplastic polymer penetrates. After melt formation and upon cooling of the thermoplastic polymer, the broken and / or abraded yarns form mechanical interlocks and bonds.

[0100] A further feature that characterizes the multilayer structure of the present disclosure is that after the formation of the first two layers, i.e., the inner thermoplastic polymer layer and the middle fibrous layer, the fibrous layer forms a surface for application of an outer layer comprising a plurality of filaments and a thermosetting polymer, which advantageously penetrates the fibers of the fibrous layer and, after curing of the thermosetting polymer, provides a strong bond between the plurality of filaments and the thermosetting polymer and the fibrous layer.

[0101] In some preferred embodiments, the fibrous layer has a fiber architecture that is advantageous in forming a multilayered structure with desirable mechanical properties. For example, a woven architecture comprising multiple strands of ceramic or polymeric fibers may improve the shear strength of the multilayered structure.

[0102] In some preferred embodiments, the permeability of the fibrous layer to thermoplastic polymer infiltration is an important parameter in controlling the shear strength of the multilayer structure of the present disclosure. If the permeability is too high, this can result in a reduction in shear strength. Therefore, a relatively low permeability is desirable.

[0103] Lap shear testing studies have revealed that the primary failure mode for the multi-layered structures of the present disclosure is within the thermoplastic layers. This is advantageous because the shear strength of the multi-layered structure can depend on the tensile strength of the thermoplastic resin. Therefore, the shear strength of the multi-layered structure can be controlled by varying the properties of the thermoplastic resin.

[0104] The average lap shear strength for multilayer structures of the present disclosure can 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.

[0105] Specific Embodiments 1. A hollow composite container, wherein a wall of the hollow composite container comprises a multi-layer structure, the multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of ethylene homopolymer, ethylene copolymer, propylene homopolymer, propylene copolymer, fluoropolymer, polyvinyl chloride, polyvinylidene chloride, polyaryletherketone (e.g., polyetheretherketone), and polyamide; an outer layer comprising a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers; an intermediate layer disposed between the inner layer and the outer layer, the intermediate layer comprising one or more fibrous materials in the form of a textured woven material; A hollow composite container, wherein the one or more engineered woven materials are at least partially infiltrated with both one or more thermoplastic polymers and one or more thermosetting polymers.

[0106] 1. A hollow composite container, wherein a wall of the hollow composite container comprises a multi-layer structure, the multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of ethylene homopolymer, ethylene copolymer, propylene homopolymer, propylene copolymer, fluoropolymer, polyvinyl chloride, polyvinylidene chloride, polyaryletherketone (e.g., polyetheretherketone), and polyamide; an outer layer comprising a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of polyester, polyacrylate, epoxy, vinyl ester, bismaleimide, and polyurethane; an intermediate layer disposed between the inner layer and the outer layer, the intermediate layer comprising one or more fibrous materials in the form of a textured woven material; A hollow composite container, wherein one or more engineered woven materials are at least partially infiltrated with both one or more thermoplastic polymers and one or more thermosetting polymers.

[0107] 1. A hollow composite container, wherein a wall of the hollow composite container comprises a multi-layer structure, the multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of ethylene homopolymer, ethylene copolymer, propylene homopolymer, propylene copolymer, fluoropolymer, polyvinyl chloride, polyvinylidene chloride, polyaryletherketone (e.g., polyetheretherketone), and polyamide; an outer layer comprising a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of polyester, polyacrylate, epoxy, vinyl ester, bismaleimide, and polyurethane; an intermediate layer disposed between the inner layer and the outer layer, the intermediate layer comprising one or more fibrous materials in the form of a textured woven material; the one or more textured woven materials are at least partially infiltrated with both one or more thermoplastic polymers and one or more thermosetting polymers; A hollow composite container having a multilayer structure in which the inner layer 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.

[0108] 1. A hollow composite container, wherein a wall of the hollow composite container comprises a multi-layer structure, the multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of ethylene homopolymer, ethylene copolymer, propylene homopolymer, propylene copolymer, fluoropolymer, polyvinyl chloride, polyvinylidene chloride, polyaryletherketone (e.g., polyetheretherketone), and polyamide; an outer layer comprising a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of polyester, polyacrylate, epoxy, vinyl ester, bismaleimide, and polyurethane; an intermediate layer disposed between the inner layer and the outer layer, the intermediate layer comprising one or more fibrous materials in the form of a textured woven material; the one or more textured woven materials are at least partially infiltrated with both one or more thermoplastic polymers and one or more thermosetting polymers; The thickness of the inner layer of the multilayer structure is about 0.1 mm to about 10 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 2 mm to about 500 mm; A hollow composite container having a multilayer structure with a lap shear strength greater than about 5 MPa.

[0109] 1. A hollow composite container, wherein a wall of the hollow composite container comprises a multi-layer structure, the multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of ethylene homopolymer, ethylene copolymer, propylene homopolymer, propylene copolymer, fluoropolymer, polyvinyl chloride, polyvinylidene chloride, polyaryletherketone (e.g., polyetheretherketone), and polyamide; an outer layer comprising a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of polyester, polyacrylate, epoxy, vinyl ester, bismaleimide, and polyurethane; an intermediate layer disposed between the inner layer and the outer layer, the intermediate layer comprising one or more fibrous materials in the form of a textured woven material; the one or more textured woven materials are at least partially infiltrated with both one or more thermoplastic polymers and one or more thermosetting polymers; A hollow composite container having a multilayer structure in which the inner layer 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.

[0110] In an embodiment, the lap shear strength of the multi-layer structure is greater than about 5 MPa.

[0111] In any one of the embodiments disclosed herein, the lap shear strength of the multi-layer structure is 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.

[0112] Use of containers The hollow composite containers of the present disclosure find wide application in the storage and transport of materials where both structural strength and chemical containment are desirable, for example, in the storage and transport of corrosive chemicals such as strong acids and bases, hydrogen peroxide, and the like, and also in the storage and transport of high-pressure gases and cryogenic materials. [Example]

[0113] Example 1: Fabrication of hollow composite container A three-part mold, including a generally cylindrical central section and two generally hemispherical end sections, was lined on its inner surface with a fibrous layer of woven fabric (an example of a processed woven material).

[0114] The mold sections were then assembled to provide a hollow spherical cylindrical mold.

[0115] The mold was transferred to a rotational molding unit, and a specific mass of thermoplastic polymer powder (polyethylene) was added to the mold's internal cavity. The mold was then rotated and heated to a temperature sufficient to melt the thermoplastic polymer and coat the surface of the fibrous layer lining the mold's internal surface. After a certain period of time, heating was discontinued, and as the mold and its contents cooled, the thermoplastic polymer solidified to provide a smooth, continuous layer of solid thermoplastic resin on the surface of the fibrous layer lining the mold's internal surface.

[0116] The mold was then opened to reveal a hollow container having a wall defined by two layers: an inner layer comprising solidified thermoplastic polyethylene and an outer layer comprising a fibrous material.

[0117] The fibrous layer of the hollow container so produced was then treated with an epoxy vinyl ester thermosetting polymer and the polymer was allowed to cure. A layer of carbon fiber filaments and epoxy vinyl ester was then applied to the outside of the container and the thermosetting polymer was allowed to cure.

[0118] Example 2 The method of Example 1 was followed except that the woven fibrous layer was replaced with a non-woven fibrous layer (an example of an untextured woven material).

[0119] Example 3: Mechanical testing A number of containers were prepared according to Examples 1 and 2, including an inner polyethylene layer, a middle fibrous layer, and an outer layer comprising a plurality of filaments and a thermosetting polymer.

[0120] The inner polyethylene layer was approximately 10 mm thick, and the outer layer, comprising a plurality of filaments and a thermosetting polymer, was approximately 10 mm thick.

[0121] The total thickness of the multilayer structure was approximately 20 mm.

[0122] A panel of the container wall was cut and removed for testing, typically measuring 200 mm in length and 20 mm in width.

[0123] The panels were prepared for lap shear testing by cutting two slots, each 5 mm from the centerline, one on the outer carbon fiber layer and the other on the inner polyethylene layer. The first slot was cut through the carbon fiber layer and the fibrous interlayer until the polyethylene layer was visible. The panel was inverted, and a slot was cut through the polyethylene layer until the fibrous interlayer was visible.

[0124] The lap shear strength of the slotted panels was measured using a universal tensile testing apparatus according to BS EN13121-3:2008 section D.8.

[0125] The multilayered structure formed by the method of Example 2 provided a lap shear strength of between about 1.5 MPa and about 2.8 MPa.

[0126] In contrast, the multilayered structure formed by the method of Example 1 provided a lap shear strength of between about 9.4 MPa and about 11.5 MPa.

[0127] The lap shear strength of the multilayered structure of Example 1 showed cohesive failure of the polyethylene (see, e.g., Figures 5 and 6), while the much lower lap shear strength of the multilayered structure of Example 2 showed shear failure well below the cohesive strength of the polyethylene. See Figure 9, which shows that the white fibrous layer is on both failure surfaces, indicating that the shear failure occurred within the fibrous layer.

[0128] Therefore, there are clear advantages to utilizing a woven fibrous layer that, when infiltrated with a thermoplastic polymer such as polyethylene, produces a multi-layer structure with significantly higher lap shear strength.

[0129] Example 4 - Permeability Test The single pressure permeability (K) of the four fibrous layers was determined by flowing a fluid of known viscosity through a fibrous layer of known thickness and measuring the pressure drop.

[0130] Testing was carried out using the equipment and methods described in DE 102013102486. The transmittance was calculated using Darcy's law based on the following formula:

number

[0131] During the ceremony, ·K is the fibrous layer permeability (m 2 ) Q is the flow rate of fluid through the fibrous layer (m 3 / s). ·Δp is the pressure drop across the fibrous layer (Pa). A is the area of the measurement site (m 2 ) ·v is the kinematic viscosity of the fluid (m 2 / s). ΔL is the length of fluid flow into the fibrous layer (m).

[0132] Note that the distance traveled by a fluid through the fibrous layer is equal to the time the measurement is taken multiplied by the flow rate.

[0133] Measurements were performed in triplicate and the average results are tabulated below. [Table 1]

[0134] The single pressure average permeability of the woven fibrous layer was significantly lower than that of the non-woven fibrous layer, suggesting that a higher resistance to permeation of molten thermoplastic polymer into the fibrous layer during multilayer construction is advantageous in providing a multilayered structure with higher lap shear strength.

Claims

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

2. 10. The hollow composite container of claim 1, wherein the one or more thermoplastic polymers of the inner layer comprise one or more of an ethylene homopolymer, an ethylene copolymer, a propylene homopolymer, a propylene copolymer, a fluoropolymer, a polyvinyl chloride, a polyvinylidene chloride, a polyaryletherketone, and a polyamide.

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

4. 3. The hollow composite container according to claim 1 or 2, wherein the one or more thermoplastic polymers comprise ethylene tetrafluoroethylene.

5. 3. The hollow composite container according to claim 1 or 2, wherein the one or more thermoplastic polymers comprise ethylene chlorotrifluoroethylene.

6. 6. The hollow composite container according to claim 1, wherein the one or more thermosetting polymers of the outer layer include one or more of polyester, polyacrylate, epoxy, vinyl ester, bismaleimide, and polyurethane.

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 textured woven materials.

8. 8. The hollow composite container of claim 7, wherein the one or more engineered textile materials comprise one or more of a woven material, a knit material, and a braided material.

9. 9. The hollow composite container of claim 7 or 8, wherein the one or more textured woven materials comprise plied yarns.

10. 10. The hollow composite container of claim 9, wherein the spacing between at least some of the yarns of the fibrous material of the intermediate layer is from about 0.01 micrometers to about 5000 micrometers, or from about 0.1 micrometers to about 5000 micrometers, or from about 1 micrometer to about 5000 micrometers, or from about 10 micrometers to about 5000 micrometers.

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

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

14. 12. 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. 15. The hollow composite container according to any one of claims 1 to 14, wherein the plurality of filaments of the outer layer have a filament diameter of from about 0.1 micrometers to about 500 micrometers, or from about 0.1 micrometers to about 100 micrometers, or from about 0.1 micrometers to about 50 micrometers, or from about 1 micrometer to about 20 micrometers.

16. 16. The hollow composite container of claim 1, wherein the plurality of filaments of the outer layer are in the form of one or more of wound filaments, a fabric section comprising a plurality of threads, braided yarn, 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 from about 0.1 mm to about 50 mm, the thickness of the intermediate layer is from about 0.1 mm to about 5 mm, and the thickness of the outer layer is from about 0.1 mm to about 1000 mm.

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

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

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

21. 21. The hollow composite container according to any one of claims 1 to 20, wherein the total thickness of the walls 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 threads of said fibrous material.

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

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

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

26. 26. The hollow composite container of any one of claims 1 to 25, wherein the thermoplastic polymer is embedded in the fibrous layer to the extent that shear failure of the multilayer structure occurs via cohesive failure of the thermoplastic polymer.

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

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

58.

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

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

35. The fibrous layer is about 10 －１１ m ２ 35. The hollow composite container according to any one of claims 1 to 34, having a single pressure average permeability of less than 1000 MPa.

36. The fibrous layer is about 9*10 －１２ m ２ Less than or about 8*10 －１２ m ２ Less than or about 7*10 －１２ m ２ Less than or about 6*10 －１２ m ２ Less than or about 5*10 －１２ m ２ Less than or about 4*10 －１２ m ２ 36. The hollow composite container according to any one of claims 1 to 35, having a single pressure average permeability of less than 1000 MPa.

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

38. 1. A method for manufacturing a hollow composite container, said method comprising the steps of: a) applying one or more fibrous materials to the interior surface of a hollow mold; b) heating and rotating the hollow mold in the presence of another thermoplastic polymer located within the hollow mold, causing the thermoplastic polymer to melt and at least partially infiltrate the fibrous material; c) cooling the mold to solidify the thermoplastic polymer; d) removing the hollow thermoplastic polymer / fibrous material composite container from said mold; and further comprising one or more of the following steps e) to g): The steps e) to g) are e) applying a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments to the exterior of the hollow thermoplastic polymer / fibrous material composite container, 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 selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments to the exterior of the hollow thermoplastic polymer / fibrous material composite container, followed by applying one or more thermosetting polymers; g) applying one or more thermosetting polymers to the exterior of the hollow thermoplastic polymer / fibrous material composite container, followed by applying a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments; That's the method.

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

40. 40. The method of claim 38 or 39, wherein the mold is rotated in two directions simultaneously.

41. The method according to any one of claims 38 to 40, wherein the hollow composite container is of 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 or adhesive means or by application of pressure.

43. 43. The method of any one of claims 38 to 42, wherein the one or more thermoplastic polymers 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, and a polyamide.

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

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

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

47. 47. The method of any one of claims 38 to 46, wherein the one or more thermosetting polymers comprise one or more of polyester, polyacrylate, epoxy, vinyl ester, bismaleimide, and polyurethane.

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

49. 49. The method of claim 48, wherein the one or more textured textile materials comprise one or more of a woven material, a knit material, and a braided material.

50. 50. The method of claim 48 or 49, wherein the one or more textured woven materials comprise plied yarns.

51. 51. The method of any one of claims 38 to 50, wherein the one or more fibrous materials comprise one or more of the following: ceramic fibers and polymeric fibers.

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

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

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

56. 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 fabric section comprising multiple threads, braided yarn, and chopped fibers.

57. 1. A hollow composite container, wherein a wall of the hollow composite container comprises a multi-layer structure, the multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of ethylene homopolymer, ethylene copolymer, propylene homopolymer, propylene copolymer, fluoropolymer, polyvinyl chloride, polyvinylidene chloride, polyaryletherketone, and polyamide; an outer layer comprising a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers; an intermediate layer disposed between the inner layer and the outer layer, the intermediate layer comprising one or more fibrous materials in the form of a textured woven material; 10. The hollow composite container of claim 1, wherein the one or more engineered woven materials are at least partially infiltrated with both the one or more thermoplastic polymers and the one or more thermosetting polymers.

58. 1. A hollow composite container, wherein a wall of the hollow composite container comprises a multi-layer structure, the multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of ethylene homopolymer, ethylene copolymer, propylene homopolymer, propylene copolymer, fluoropolymer, polyvinyl chloride, polyvinylidene chloride, polyaryletherketone, and polyamide; an outer layer comprising a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of polyester, polyacrylate, epoxy, vinyl ester, bismaleimide, and polyurethane; an intermediate layer disposed between the inner layer and the outer layer, the intermediate layer comprising one or more fibrous materials in the form of a textured woven material; 10. The hollow composite container of claim 1, wherein the one or more engineered woven materials are at least partially infiltrated with both the one or more thermoplastic polymers and the one or more thermosetting polymers.

59. 1. A hollow composite container, wherein a wall of the hollow composite container comprises a multi-layer structure, the multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of ethylene homopolymer, ethylene copolymer, propylene homopolymer, propylene copolymer, fluoropolymer, polyvinyl chloride, polyvinylidene chloride, polyaryletherketone, and polyamide; an outer layer comprising a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of polyester, polyacrylate, epoxy, vinyl ester, bismaleimide, and polyurethane; an intermediate layer disposed between the inner layer and the outer layer, the intermediate layer comprising one or more fibrous materials in the form of a textured woven material; the one or more textured woven materials are at least partially infiltrated with both the one or more thermoplastic polymers and the one or more thermoset polymers; 2. The hollow composite container according to claim 1, wherein the thickness of the inner layer of the multilayer structure is from about 0.1 mm to about 50 mm, the thickness of the intermediate layer is from about 0.1 mm to about 5 mm, and the thickness of the outer layer is from about 2 mm to about 500 mm.

60. 1. A hollow composite container, wherein a wall of the hollow composite container comprises a multi-layer structure, the multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of ethylene homopolymer, ethylene copolymer, propylene homopolymer, propylene copolymer, fluoropolymer, polyvinyl chloride, polyvinylidene chloride, polyaryletherketone, and polyamide; an outer layer comprising a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of polyester, polyacrylate, epoxy, vinyl ester, bismaleimide, and polyurethane; an intermediate layer disposed between the inner layer and the outer layer, the intermediate layer comprising one or more fibrous materials in the form of a textured woven material; the one or more textured woven materials are at least partially infiltrated with both the one or more thermoplastic polymers and the one or more thermoset polymers; the thickness of the inner layer of the multi-layer structure is from about 0.1 mm to about 50 mm, the thickness of the middle layer is from about 0.1 mm to about 5 mm, and the thickness of the outer layer is from about 2 mm to about 500 mm; 10. The hollow composite container of claim 1, wherein the multi-layer structure has a lap shear strength greater than about 5 MPa.

61. 1. A hollow composite container, wherein a wall of the hollow composite container comprises a multi-layer structure, the multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of ethylene homopolymer, ethylene copolymer, propylene homopolymer, propylene copolymer, fluoropolymer, polyvinyl chloride, polyvinylidene chloride, polyaryletherketone, and polyamide; an outer layer comprising a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of polyester, polyacrylate, epoxy, vinyl ester, bismaleimide, and polyurethane; an intermediate layer disposed between the inner layer and the outer layer, the intermediate layer comprising one or more fibrous materials in the form of a textured woven material; the one or more textured woven materials are at least partially infiltrated with both the one or more thermoplastic polymers and the one or more thermoset polymers; the thickness of the inner layer of the multi-layer structure is from about 0.1 mm to about 50 mm, the thickness of the middle layer is from about 0.1 mm to about 5 mm, and the thickness of the outer layer is from about 2 mm to about 500 mm; The fibrous layer is about 10 －１１ m ２ 10. The hollow composite container of claim 1, having a single pressure average permeability of less than 1000 MPa.

62. 1. A hollow composite container, wherein a wall of the hollow composite container comprises a multi-layer structure, the multi-layer structure comprising: an inner layer comprising one or more thermoplastic polymers selected from one or more of ethylene homopolymer, ethylene copolymer, propylene homopolymer, propylene copolymer, fluoropolymer, polyvinyl chloride, polyvinylidene chloride, polyaryletherketone, and polyamide; an outer layer comprising a plurality of filaments selected from one or more of carbon filaments, glass filaments, aramid filaments, and basalt filaments, and one or more thermosetting polymers selected from one or more of polyester, polyacrylate, epoxy, vinyl ester, bismaleimide, and polyurethane; an intermediate layer disposed between the inner layer and the outer layer, the intermediate layer comprising one or more fibrous materials in the form of a textured woven material; the one or more textured woven materials are at least partially infiltrated with both the one or more thermoplastic polymers and the one or more thermoset polymers; the thickness of the inner layer of the multi-layer structure is from about 0.1 mm to about 50 mm, the thickness of the middle layer is from about 0.1 mm to about 5 mm, and the thickness of the outer layer is from about 2 mm to about 500 mm; 10. The hollow composite container of claim 1, wherein said multi-layer structure has a maximum lap shear strength proportional to the tensile strength of said thermoplastic polymer.

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