Structural shell

Abstract

This invention provides a recyclable structural shell containing basalt fiber-reinforced material. [Solution] The present invention provides a structural shell comprising a basalt fiber-reinforced material, wherein the basalt fiber-reinforced material comprises a polymer material, and the polymer material can be at least partially thermally decomposed at a temperature of 200 to 600°C.

Description

[Technical Field]

[0001] The present invention relates to a recyclable structural shell (or structural shell) for the hull, structural grid and / or deck or wind turbine blade of a marine vessel (or ship), a method for manufacturing a structural shell, and a method for disassembling a structural shell.

[0002] Yacht hulls are typically constructed from fiber-reinforced plastics, usually fiberglass and / or carbon fiber. Such fiber-reinforced plastics are strong, lightweight, and easy to mold into shapes such as decks, hulls, and bulkheads. Contrary to the green image of yachts, much of the yachting industry remains stagnant when it comes to sustainability. The two biggest threats are: (i) the use of toxic plastics and fiberglass, and (ii) the lack of real solutions when the boat shell reaches the end of its lifespan.

[0003] While environmentally friendly solutions using sustainable materials are on the right track, they only enable downcycling that inevitably leads the final product to landfills when it reaches the end of its lifespan. One reason for this is that glass and carbon fibers with desirable physical and mechanical properties are used, and their porous nature allows them to absorb some of the resin, forming a strong bond with the resin. This results in strong, lightweight composites (or composite materials) that can be used in ship hulls, etc., but currently, glass and / or carbon fibers are basically "single-use," meaning they cannot be recycled when they reach the end of their lifespan. Furthermore, in such applications, glass and / or carbon fibers are commonly used to reinforce thermosetting plastics. Therefore, when ship hulls, etc., reach the end of their lifespan, there are few disposal options other than landfills, especially for impregnated glass and / or carbon fibers. Downcycling of some materials may be possible.

[0004] For example, new "green" composites using flax (hemp) are being developed. However, because these fibers tend to absorb the resin used in the composite, material separation after the end of life is impossible, and the material can only be downcycled.

[0005] Basalt fibers have been studied as an alternative "green" fiber for applications such as yachts, but typically only vinyl esters, polyesters, or (green) epoxy resins have been used. Since all of these resins are thermosetting plastics, they change from liquid to hard during the manufacturing process and cannot revert back to a liquid state. Therefore, recovering, reusing, and / or recycling basalt fibers is not easy. As a result, many composites end up as "single-use" materials and are likely to end up in landfills.

[0006] KR20090079109A discloses a method for manufacturing a boat composite containing basalt fibers, and a boat manufactured using the same. However, this composite provides a high-strength thermosetting resin by using a polyester-containing resin and a curing agent containing methyl ketone peroxide. Therefore, as mentioned above, basalt fibers cannot be easily recovered, and the composite can generally only be downcycled at best when it reaches the end of its lifespan. Furthermore, there is no mention of recycling the composite.

[0007] CN109370186A relates to a method for manufacturing a low-temperature resistant and environmentally friendly glass fiber reinforced plastic septic tank. CN111098528A relates to a system for manufacturing fully impregnated thermoplastic prepregs. US2019 / 330432A relates to a two-component hybrid matrix system consisting of polyurethane and polymethacrylate for the manufacture of short fiber reinforced semi-finished products. US2020 / 047427A relates to a process for manufacturing thermoplastic polymer composite parts and the objects obtained by such process. WO2020 / 088173A1 relates to a porous composite material capable of generating an electric arc in a microwave electric field, a method for preparing the same, and the use of the same. JPH11335929A relates to highly conductive carbon fibers and the manufacture of the same. JP 2003012857A relates to a method and apparatus for processing fiber-reinforced plastic waste.

[0008] Therefore, there is a need to provide structural shells that can be substantially recycled when they reach the end of their lifespan, not only when used in marine vessels but also in non-marine sectors. In particular, there is a need to provide structural shells that include fiber-reinforced resin, where both the fibers and the resin can be recovered and recycled or downcycled without significant degradation of their physical and mechanical properties, preferably with substantially no degradation of their physical and / or mechanical properties.

[0009] A further object of this disclosure is to provide such a substantially recyclable structural shell having high flexural strength per unit area.

[0010] The present invention aims to address at least some of the problems related to the prior art, or at least to provide a commercially acceptable alternative solution thereto. [Modes for carrying out the invention]

[0011] The present invention provides, according to the claims appended herein, a structural shell, a hull for an offshore vessel, a structural grid for an offshore vessel, a deck for an offshore vessel, an offshore vessel, a wind turbine blade, skis and / or ski poles, a method for manufacturing a structural shell, and a method for disassembling a structural shell.

[0012] Specifically, in one embodiment, the present invention provides a structural shell comprising a basalt fiber-reinforced material, the basalt fiber-reinforced material comprising a polymer material, the polymer material being capable of at least partially thermally cracking at a temperature of 200 to 600°C.

[0013] Each aspect or embodiment defined herein may be combined with any other aspect or embodiment unless otherwise expressly indicated. In particular, features indicated as preferred or advantageous may be combined with other features indicated as preferred or advantageous.

[0014] As used herein, the term “structural shell” may include layered sheets or layers of material having a thickness significantly smaller than the main surface area. Therefore, a structural shell may be a thin-walled body. A structural shell may be designed to withstand external loads, such as fluid pressure, aerodynamic loads, and / or impacts, applied to the main surface area of ​​the material. In particular, a structural shell may be the hull and / or deck of a marine vessel, the blades of a wind turbine, skis and / or ski poles, the fuselage of an aircraft, the body of a land vehicle, and the like. A structural shell may be supported by a frame.

[0015] As used herein, the term "basalt fiber" may encompass materials made from extremely fine fibers of basalt, which is composed of the minerals plagioclase, pyroxene, and olivine. Basalt fibers can be produced, for example, by a method that includes melting bulk basalt, homogenizing the basalt, and extracting the fibers by extruding the molten basalt. Preferably, highly acidic (silica content of 46% or more) and low iron basalt is used for the production of basalt fibers. Typically, the bulk basalt is crushed and washed before melting. Basalt fibers typically have a filament diameter between 10 and 20 μm.

[0016] As used herein, the term “fiber-reinforced material” may encompass fiber-reinforced composite materials. Basalt fiber-reinforced materials include polymer materials. Typically, the composite material therefore includes a polymer matrix reinforced with basalt fibers.

[0017] Polymer materials can decompose at least partially thermally at temperatures of 200–600°C. As used herein, the term “thermally decompose” may encompass, for example, the pyrolysis of polymer materials by depolymerization and / or removal of crosslinks. Without wishing to be bound by theory, it is understood that polymers in polymer materials depolymerize at least partially due to homolytic fitting of carbon-carbon bonds in the polymer backbone during thermal cracking. In other words, in some embodiments, for example, polymer materials can depolymerize and / or decrosslink at temperatures of 200–600°C.

[0018] Preferably, the polymer material is a thermoplastic material. The thermoplastic material may be a thermoplastic plastic or a material exhibiting the properties of a thermoplastic plastic. As used herein, the term “thermoplastic resin” may encompass materials that soften when heated and harden when cooled, as defined in the art.

[0019] Preferably, the polymer material of the present invention comprises polymethacrylate, and more preferably poly(methyl methacrylate). A commercially available polymethacrylate particularly suitable for use in the present invention is Elium®, manufactured by Arkema. The polymer material may also comprise other (thermoplastic) polymers, such as other polyacrylates, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamides, polyesters and polyurethanes, polyetheretherketones, liquid crystalline polymers, polysulfones and polyphenylene sulfides, provided that the polymer material can be at least partially thermally decomposed at temperatures of 200 to 600°C.

[0020] The inventors have surprisingly discovered that by using basalt fibers to reinforce a material containing a polymer material, the polymer material can be at least partially thermally decomposed at temperatures of 200-600°C, thereby producing a structural shell with high flexural strength per unit area for use in the hulls of marine vessels and the like, the basalt fibers are recoverable at the end of their lifespan, and the physical and / or mechanical properties of the basalt fibers do not deteriorate substantially, preferably not at all. The polymer material and / or the resin used in the manufacture of the polymer material are also recoverable by heating. While we do not wish to be bound by theory, this is thought to be because basalt fibers have a melting point of about 1500°C or higher. Therefore, the obtained at least partially thermally decomposed polymer material and / or basalt fibers can be recovered independently of the heated structural shell. While we do not wish to be bound by theory, this is also thought to be because basalt fibers substantially, preferably do not absorb resin. Therefore, the basalt fiber reinforced material can be heated to at least partially thermally decompose the polymer material, thereby forming a liquid from which the basalt fibers can be recovered. Furthermore, it is believed that the bonds formed between the polymer material and the basalt fibers are broken when the polymer material is at least partially thermally decomposed, thereby allowing the basalt fibers to be separated from the at least partially thermally decomposed polymer material with substantially no polymer material residue remaining on the basalt fibers. Thus, the recovered basalt fibers can be recovered with substantially, or preferably not at all, degradation of their physical and / or mechanical properties. This makes it possible for the basalt fibers to be fully recycled for use, for example, in further structural shells. Preferably, the at least partially thermally decomposed polymer material is liquid at 20°C, i.e., room temperature. This property may allow for easier separation of the basalt fibers from the at least partially thermally decomposed polymer material. For example, this property may allow for easier separation of the basalt fibers from the at least partially thermally decomposed polymer material once the heating process is complete and the at least partially thermally decomposed polymer material has cooled.This is particularly easily achieved when the polymer material contains polymethacrylate, and is even more particularly achieved when the polymer material contains Elium® from Arkema.

[0021] As a result, when the lifespan expires, it is possible to manufacture a structural shell in which the starting materials of the resin and basalt fibers can be recovered in a state where they can be reused, for example, in another structural shell or the like. That is, it is surprising that the structural shell of the present invention can have sufficient strength for commercial use while being recyclable. It is possible to manufacture a composite material that does not substantially absorb the resin so that the fibers can be recycled, and it would not be expected that such a composite material would have sufficient, preferably desirable flexural strength for use in a structural shell such as a boat hull for marine vessels. However, it will be understood that the structural shell described herein can also have any suitable use other than in the marine field. For example, the structural shell described herein can be used in any of the following non-limiting list of uses: wind-powered, manual, electric, and combustion-propelled boats (e.g., dinghies, kayaks, powerboats, sailboats, motorboats, etc.); skis; ski poles; construction poles (e.g., scaffolds); spinnaker poles and / or bouse splits (e.g., components of railways, trams, subways (noses, side panels, etc.), wind turbine blades, furniture (chairs, tables, closets, etc.), automotive structures and body parts, radar / antenna covers, residential building materials (walls, roofs, floors, etc.), flagpoles, window frames, doors, suitcases, flight simulators, etc.).

[0022] Preferably, the basalt fibers are completely encapsulated (or enclosed; encapsulate) by the polymer material. However, typically, it is possible to see fiber print-through on the surface of the basalt fiber reinforcement. Such a structural shell has a high flexural strength per unit area and may be suitable for use in the hull and / or deck of a marine vessel, the blade of a wind turbine, skis, ski poles, the fuselage of an aircraft, the body of a land vehicle, etc.

[0023] Preferably, the basalt fiber reinforcement material contains substantially no voids. Particularly preferably, the basalt fiber reinforcement material contains less than 1% by volume of voids (or cavities, or void spaces; void), more preferably less than 0.5% by volume of voids, and most preferably contains substantially no voids. Such a material can exhibit high bending strength and be less likely to delaminate during bending or flexing.

[0024] The weight ratio of the basalt fiber to the polymer material in the structural shell is preferably 80:20 to 40:60, more preferably 75:25 to 50:50, and even more preferably 70:30 to 55:45. Such ratios provide an optimal balance of cost, weight, and strength per unit area of the structural shell by reducing the amount of resin required.

[0025] Preferably, the basalt fibers are dispersed in the polymer material in a regular arrangement, and preferably, the fiber-reinforced material comprises multiple layers of substantially parallel basalt fibers, where the average direction of the substantially parallel basalt fibers differs in adjacent layers. More preferably, the average direction of the substantially parallel basalt fibers in each layer is about 45° or about 90° with respect to the average direction of the substantially parallel basalt fibers in adjacent layers. Most preferably, the layers of substantially parallel basalt fibers are arranged in a quaternary direction, preferably with relative directions of -45°, 90°, 0-90°, and 0°; in a triaxial direction, preferably with relative directions of -45°, 90°, and 45°; in a biaxial direction, preferably with relative directions of 0° and 90°; or in a uniaxial direction. Such arrangement of basalt fibers in the polymer material can provide a quasi-isotropic composite material exhibiting substantially equal mechanical properties in all planar directions. Such arrangement of basalt fibers within a polymer material can also provide a structural shell with desirable high flexural strength and abrasion resistance per unit area. In particular, during the production of the basalt fiber-reinforced material of the present invention, the inventors selected several weaves (or fabrics) of basalt fibers based on weight ratio and fiber orientation. Specifically, three types of fiber orientations were created: (i) UNI (unidirectional or one-directional fiber yarn), (ii) BI (biaxial or 90° bidirectional fiber yarn), and (iii) TRI (triaxial or 45-90° tridirectional fiber yarn). In some embodiments, these weaves of basalt fibers can be layered on top of each other to form a layered structure that can exhibit quasi-isotropic properties, i.e., substantially equal mechanical properties in all planar directions. The load of each weave on each other can also be varied depending on the required properties and / or the purpose of the composite material to be obtained. However, it will be understood that the present invention is not limited to a particular type of basalt fiber weave, and any conventional weave used in the art may be used in the basalt fiber-reinforced material described herein. The typical load of basalt fibers in weaving is 100-1200 g / m 2 Preferably, 200-700 g / m² for use in ship hulls, etc. 2 That's fine.

[0026] In some embodiments, the structural shell further comprises a core, preferably a polymer core. The polymer core typically comprises polyester, preferably poly(ethylene terephthalate) (PET), and preferably PET foam. As used herein, the term “PET foam” may encompass materials containing PET, and PET may contain a plurality of gas-filled voids. However, in the structural shells described herein, the voids may be substantially filled with polymer material, preferably completely filled with polymer material. The polymer core may form a layer within the structural shell. Typically, such a layer may be located in the center of the structural shell. For example, the polymer core may form a layer sandwiched between two or more layers of basalt fiber-reinforced material, or a layer completely surrounded by basalt fiber-reinforced material. Advantageously, when the structural shell further comprises a polymer core, the thickness of the structural shell can be increased without increasing the weight per unit area of ​​the structural shell as much as when the structural shell does not contain a polymer core. It will be understood that the inclusion of a polymer core may reduce the tensile strength per unit area. However, such structural shells are particularly preferred when used, for example, on the decks of marine vessels, where such loss of tensile strength can be compensated for by an increase in flexural strength. In some embodiments, other materials may be used for the polymer core instead of the PET core, such as PVC or balsa. However, PVC cores are not very preferred in this invention because they cannot be recycled. The polymer core may have any thickness depending on the specific application in the structural shell. However, typically, the polymer core may have a thickness of 1 mm to 300 mm, preferably 1 mm to 100 mm, more preferably 5 to 50 mm, and even more preferably 10 to 30 mm.

[0027] As an alternative to PET cores, polymer cores may contain the same polymer material as basalt-fiber-reinforced materials. In other words, cores may be formed from polymer material that does not contain basalt fibers. Such cores may be recovered simultaneously with the polymer material of basalt-fiber-reinforced materials.

[0028] As an alternative to the polymer core, the structural shell may include a core containing, for example, aluminum (melting point: approximately 650°C), rock wool, or balsa wood.

[0029] Preferably, the polymer material can at least partially melt at a temperature of 150-300°C, preferably 200-250°C, and / or at least partially decompose at a temperature lower than the temperature at which it can at least partially decompose. This is particularly preferable when the structural shell consists of a polymer core. Furthermore, the polymer material can at least partially decompose at a temperature of 300-500°C, more preferably 350-400°C. In addition to the advantages mentioned above, this is also particularly preferable when the structural shell contains a polymer core. Having such properties makes it possible to recover the polymer core more easily, for example, when disassembling the structural shell. This is especially easier when the melting temperature of the polymer core is, for example, 200-300°C. This is because, when heated, the polymer material can melt at a lower temperature than the polymer core, making it easier to separate and recover the polymer core from the heated structural shell. In particular, the solid polymer core can be removed more easily from the liquid polymer material. This could also reduce the possibility of cross-contamination between the polymer core and the at least partially thermally decomposed polymer material when heated to higher temperatures, and allow the at least partially thermally decomposed polymer material to be recycled. This may be because the polymer core can be removed from the heated structural shell before the structural shell is heated to the point where the polymer material is at least partially thermally decomposed (therefore, melting of the polymer core and mixing of the molten polymer core with the melted and / or at least partially thermally decomposed polymer material are avoided). In this case, the polymer core, the at least partially thermally decomposed polymer material and basalt fibers can each be recovered separately.

[0030] The polymer material is described as being at least partially melted and / or at least partially thermally decomposed at the above temperature. Typically, the polymer material can be substantially melted or thermally decomposed at the above temperature, and more typically, can be completely melted or thermally decomposed at the above temperature.

[0031] In some embodiments, the structural shell may further include a gel coat, typically on its outer surface. Typically, the gel coat contains an unsaturated polyester resin and / or a vinyl ester. Preferably, the gel coat contains a pigment. The use of a gel coat can advantageously provide a high-quality finish to the visible surface of the basalt fiber-reinforced material. Typically, the gel coat provides a colored, glossy surface that improves the aesthetic appearance of the structural shell, such as the surface of a boat hull. The use of a gel coat can substantially reduce the number of labor hours required to manufacture the final structural shell for use in, for example, a marine vessel hull. This is because the use of a gel coat may eliminate the need to paint and / or polish the basalt fiber-reinforced material. The gel coat typically has a thickness of 1 mm to 3 mm.

[0032] Preferably, the structural shell exhibits a flexural strength of 600–800 MPa before aging. This is typically measured using a three-point bending setup. Aging of the structural shell may include, for example, seawater aging.

[0033] In a preferred embodiment, a structural shell is provided comprising a basalt fiber-reinforced material, the basalt fiber-reinforced material comprising basalt fibers, a polymer material, and optionally a curing agent, wherein the polymer material can decompose at least partially thermally at a temperature of 200-600°C, and the polymer material comprises polymethacrylate.

[0034] In a further embodiment, the present invention provides a structural shell comprising a basalt fiber-reinforced polymer material, the polymer material being at least partially thermally decomposed at temperatures of 200 to 600°C.

[0035] The advantages and preferred features of the first embodiment also apply to this embodiment.

[0036] In a further embodiment, the present invention provides a structural shell comprising a basalt fiber-reinforced thermoplastic material.

[0037] The advantages and preferred features of the first embodiment also apply to this embodiment.

[0038] In a further embodiment, the present invention provides a basalt fiber-reinforced material comprising a polymer material which can be at least partially thermally decomposed at a temperature of 200 to 600°C. The basalt fiber-reinforced material may be used for structural shells.

[0039] The advantages and preferred features of the first embodiment apply equally to this embodiment.

[0040] In a further embodiment, the present invention provides a hull for an offshore vessel, including a structural shell as described herein.

[0041] The advantages and preferred features of the first embodiment also apply to this embodiment.

[0042] In a further embodiment, the present invention provides a structural grid for offshore vessels, including the structural shell described herein.

[0043] The advantages and preferred features of the first embodiment also apply to this embodiment.

[0044] In a further embodiment, the present invention provides a deck for an offshore vessel, including a structural shell as described herein.

[0045] The advantages and preferred features of the first embodiment also apply to this embodiment.

[0046] In a further embodiment, the present invention provides an offshore vessel comprising at least one hull and / or at least one structural grid and / or at least one deck, wherein the at least one hull and / or at least one structural grid and / or at least one deck is as described above.

[0047] The advantages and preferred features of the first embodiment also apply to this embodiment.

[0048] At least one deck may be attached to the hull and / or at least partially formed by the hull. The marine vessel may include powered vessels (e.g., those powered by mechanically or electrically powered engines), sailing vessels (e.g., yachts or dinghies), rowboats, and the like.

[0049] At least one hull may include at least a portion of a structural shell. The hull may be for bearing the hydraulic load when the ocean vessel is afloat and may form at least portion of the bottom and sides of the ocean vessel. The composite material may extend over at least 90% or all of the hull's surface area.

[0050] At least one hull may include a structural shell in a monolithic structure. As a result, by selecting an appropriate thickness, at least one hull can have relatively high strength and impact resistance per unit area. Such an arrangement is particularly suitable when the offshore vessel includes a powerboat and therefore the hull is repeatedly subjected to high-force impacts from waves when traveling at high speeds.

[0051] Alternatively, at least one hull may include a sandwich structure (e.g., having PET layers) structural shell, which may have lower weight per unit area and lower strength per unit area than a monolithic structure. Such an arrangement may be suitable when the ocean vessel includes sailboats or rowboats and therefore travels at relatively low speeds with relatively small impact forces on the hull.

[0052] At least one deck may include a structural shell in the sandwich structure. As a result, at least one deck may have lower strength per unit area than at least one hull. However, at least one deck may have lower weight per unit area than at least one hull in order to reduce the overall weight of the offshore vessel.

[0053] At least one structural grid may be used to provide general support and structure within the internal structure of a marine vessel, such as within the hull.

[0054] In certain embodiments, the offshore vessel may be a rigid inflatable boat comprising a rigid hull and tubes around at least a portion of the upper edge of the rigid hull. The rigid hull is preferably a monolithic structure and may include a structural shell. The tubes may have any cross-section, such as circular, semicircular, square, or triangular. The tubes may be hollow or filled with, for example, foam and / or rubber and / or plastic. For example, the tubes may be D-collars.

[0055] In a further embodiment, the present invention provides a wind turbine blade including a structural shell as described herein.

[0056] The advantages and preferred features of the first embodiment also apply to this embodiment.

[0057] In a further embodiment, the present invention provides a ski or ski pole comprising a structural shell as described herein.

[0058] The advantages and preferred features of the first embodiment also apply to this embodiment.

[0059] In a further embodiment, the present invention provides a ballistic panel comprising a structural shell as described herein. Advantageously, the ballistic panel may pass ballistic tests NIJ-STD-0108.01 Level III and NIJ-STD-0108.01 Level IIIA.

[0060] The advantages and preferred features of the first embodiment also apply to this embodiment.

[0061] Preferably, the ballistic panels have a weight ratio of polymer material to basalt fibers of 0.35 to 0.45, preferably 0.39 to 0.44. A weight ratio of polymer material to basalt fibers of about 0.41 to about 0.43 has been found to be particularly effective. Such ratios can improve the ballistic performance of the panels.

[0062] Ballistic panels may be used, for example, in body armor (e.g., helmets or bulletproof vests), vehicles, aircraft, or structures (e.g., buildings).

[0063] In further embodiments, the present invention provides body armor, helmets, bulletproof vests, vehicles, aircraft, structures, or buildings, including the ballistic panels described herein.

[0064] The advantages and preferred features of the first embodiment also apply to this embodiment.

[0065] In a further embodiment, the present invention provides a method for manufacturing a structural shell, hull, deck, structural grid, offshore vessel, wind turbine blade, ski or ski pole, or ballistic panel as described herein, the method is To provide a mold Introducing basalt fibers into a mold; Forming structural shells, hulls, decks, structural grids, marine vessels, wind turbine blades, skis or ski poles, or bulletproof panels by bringing basalt fibers into contact with a mixture containing resin and a hardening agent at a relative pressure of -0.65 bar or less; and This includes recovering structural shells, hulls, decks, structural grids, marine vessels, wind turbine blades, skis or ski poles, or bulletproof panels from molds.

[0066] The advantages and preferred features of the first embodiment also apply to this embodiment.

[0067] Typically, the general term for such methods of manufacturing structural shells, etc., can be understood as "vacuum injection." Vacuum injection methods are known in the art.

[0068] As used herein, the term “mold” may encompass a hollow container or shell used to shape a resin during curing into basalt fiber-reinforced materials. Molds may be suitable for molding resin into shapes such as the hulls and / or decks of marine vessels, wind turbine blades, aircraft fuselages, and land vehicle bodies.

[0069] Basalt fibers may be introduced into the mold in a regular arrangement, preferably such that the resulting fiber-reinforced material contains multiple layers of substantially parallel basalt fibers, where the average direction of the substantially parallel basalt fibers differs in adjacent layers. More preferably, the basalt fibers are introduced into the mold such that the average direction of the substantially parallel basalt fibers in each layer is about 45° or about 90° with respect to the average direction of the substantially parallel basalt fibers in adjacent layers. Most preferably, the basalt fibers are introduced into the mold such that the layers of substantially parallel basalt fibers are arranged in four axial directions, preferably with relative directions of basalt fibers at -45°, 90°, 0-90°, and 0°; three axial directions, preferably with relative directions of basalt fibers at -45°, 90°, and 45°; two axial directions, preferably with relative directions of basalt fibers at 0° and 90°; or unidirectionally. Such an arrangement of basalt fibers within a polymer material can provide a quasi-isotropic composite material exhibiting substantially equal mechanical properties in all planar directions. Such an arrangement of basalt fibers within a polymer material can also provide a structural shell with desirablely high flexural strength and abrasion resistance per unit area.

[0070] While we do not wish to be bound by theory, it is believed that the negative relative pressure applied during the contact step may allow the resin to completely encapsulate the basalt fibers, while simultaneously eliminating substantially all gas voids from the basalt fiber-reinforced material. Thus, a structural shell substantially free of gas voids can be provided in the basalt fiber-reinforced material. Such a structural shell may exhibit desirable high flexural strength and / or impact resistance and / or reduced likelihood of delamination during flexing or bending per unit area.

[0071] This method may, advantageously, include one or more of the following: To improve the flow of resin during injection, apply ultrasound during the contact step; Hand layup of composite elements; Pultrusion; Prepreg process; Resin transfer molding, and Vacuum-assisted resin transfer molding.

[0072] As used herein, the term “resin” may encompass fluids containing monomers and / or polymers that, when mixed with a curing agent, can polymerize and / or crosslink to provide a solid polymer material. As used herein, the term “curing agent” may encompass substances that cure the resin, for example, by polymerization and / or crosslinking, or in other ways.

[0073] Preferably, the resin comprises a methacrylate monomer, more preferably a methyl methacrylate (or methyl methacrylate) monomer, and even more preferably 50 to 85% by weight of a methyl methacrylate monomer and / or 10 to 50% by weight of an acrylic polymer.

[0074] Preferably, the curing agent comprises an organic peroxide, preferably benzoyl peroxide. A commercially available organic peroxide particularly suitable for use in the present invention is Perkadox® GB-50X from Nouryon. Other organic peroxides and / or Perkadox® curing agents may also be used. Examples include di(2,4-dichlorobenzoyl) peroxide, di(4-methylbenzoyl) peroxide, di(tert-butylperoxyisopropyl)benzene and / or dicumyl peroxide, or mixtures thereof with or without benzoyl peroxide. Other commercially available organic peroxides particularly suitable for use in the present invention are Elium® 191XO / SA (polymerization time longer than approximately 3 hours) and Elium® 158XO / SA (polymerization time shorter than approximately 1 hour) from Arkema. These are three-component all-liquid systems comprising two resins and a curing agent (MEKP-type Butanox M50).

[0075] Preferably, the mixture contains a curing agent in an amount of 0.5 to 30 phr, more preferably 1 to 15 phr, even more preferably 1.5 to 4 phr, and even more preferably 2.5 to 4 phr (wherein "phr" means per 100 parts by weight as used herein). This is typically the amount required to provide satisfactory curing of the resin in order to obtain the basalt fiber reinforced material described herein.

[0076] Typically, basalt fibers and the mixture are brought into contact at a relative pressure of -0.65 to -1.15 bar. Preferably, the basalt fibers and the mixture are brought into contact at a relative pressure of -0.7 to -1.15 bar, more preferably -0.85 to -1.15 bar, even more preferably -0.9 to -1.1 bar, and still more preferably -0.95 to -1.05 bar. Relative pressures above 0.65 bar, or -0.85 bar for some materials, typically do not eliminate substantially all gas voids from the basalt fiber-reinforced material and / or do not allow for the formation of a strong bond between the polymer material and the basalt fibers. In general, the lower the relative pressure, the denser the resulting basalt fiber-reinforced material will be, and the stronger the bond formed between the basalt fibers and the polymer material. This low pressure is particularly important when the structural shell contains a polymer core. While we do not wish to be bound by theory, this is to ensure that the resin can be effectively drawn through all, preferably all, voids in the foam of the polymer core. However, relative pressures below -1.15 bar can deform the mold and / or basalt fiber reinforced material. Furthermore, such low relative pressures can damage the vacuum bag. In some structural shell designs, relative pressures below -1.05 bar can deform the mold and / or basalt fiber reinforced material.

[0077] Typically, basalt fibers and a mixture are brought into contact at a temperature of 10–40°C, preferably 14–30°C. Within this temperature range, significant cost reductions in the manufacturing process are possible, as at least more complex equipment is not required.

[0078] Typically, basalt fibers and a mixture are brought into contact at a humidity of 30-70%, preferably 40-50%.

[0079] Preferably, the basalt fibers and the mixture are brought into contact under pressure for 5 minutes to 12 hours, preferably 1 to 6 hours, more preferably 90 minutes to 3 hours. The basalt fibers are brought into contact with the mixture under pressure for a time suitable for providing a solid structural shell. This may allow the structural shell to harden completely before removal from the mold. If the contact temperature is high, the contact time should be shortened. Once the structural shell is removed from the mold, it can be brought into contact at a temperature of 50 to 150°C for typically 1 to 10 hours. This may be a “post-curing” step.

[0080] Contacting basalt fibers with a mixture containing resin and curing agent typically involves introducing the resin and curing agent into a bag containing a mold. Typically, the resin and curing agent are exposed to atmospheric pressure to bring them into the (reduced pressure) bag. Alternatively, the resin and curing agent are exposed to a positive pressure of +0.1 to +15 bar, preferably +0.2 to +0.6 bar, to bring them into the bag.

[0081] In a further embodiment, the method further includes forming a gel coat in the mold before introducing the basalt fibers into the mold.

[0082] In further embodiments, the method further includes introducing a polymer core into a mold before contacting the basalt fibers with the mixture. Typically, the polymer core is introduced into the mold between two or more basalt fibers, preferably so as to form a layer separating two or more layers of basalt fibers. The polymer core may be introduced into the mold and surrounded by the basalt fibers. Alternatively, the polymer core may be sandwiched between layers of basalt fibers.

[0083] In some embodiments, the mixture further comprises a rheological modifier and / or a mold release agent. The rheological modifier may improve the flow of the resin into the mold, and the mold release agent may help to facilitate the removal of the structural shell, etc., from the mold. Examples of such additives include Cirex® 388 and Chemtrend® R&B.

[0084] Furthermore, the manufacturing method of structural shells, etc., described herein may be safer than that of the prior art. This is because the reaction of the resins and curing agents used herein generates less heat than that of the prior art for manufacturing hulls, etc., for marine vessels, especially when the resins and curing agents used are as described above. Therefore, since the manufactured structural shells, etc., can be heated to lower temperatures, this method can reduce the risk of fire during the vacuum injection process.

[0085] In a further embodiment, the present invention provides a method for dismantling a structural shell, hull, deck, structural grid offshore vessel, wind turbine blade, ski or ski pole, or bulletproof panel (or other object) as described herein, the method comprising: To provide structural shells, hulls, decks, structural grids, marine vessels, wind turbine blades, skis or ski poles, bulletproof panels (or other objects as described herein); Heating a structural shell, hull, deck, structural grid, marine vessel, wind turbine blade, ski or ski pole, or ballistic panel (or other object as described herein) to a temperature of 200–600°C to at least partially thermally decompose the polymer material; To separate polymer materials that have been at least partially thermally decomposed from basalt fibers; and To recover basalt fibers and / or at least partially thermally decomposed polymer materials.

[0086] The advantages and preferred features of the first embodiment also apply to this embodiment.

[0087] Preferably, heating is carried out in an inert atmosphere, preferably in the substantial absence of oxygen. While we do not wish to be bound by theory, such conditions are thought to reduce the possibility of the polymer material and / or polymer core burning and / or being damaged in any way during the process of decomposing the structural shell. Preferably, heating is carried out at a temperature of 250–500°C, more preferably 300–500°C, and even more preferably 350–400°C.

[0088] Preferably, heating is carried out at a pressure of at least 10 bar. Such high pressure can promote pyrolysis such that the material can be recycled into fuel, monomer, or other valuable materials by pyrolysis and catalytic decomposition processes.

[0089] The recovered basalt fibers are preferably suitable for reuse and / or recycling. For example, the recovered basalt fibers are suitable for reuse in the structural shell according to the present invention or for other applications. We do not wish to be bound by theory, but this is because the basalt fibers may not absorb substantial amounts of resin, if any, during manufacturing, and therefore the basalt fibers can be recovered in substantially the same condition as before they were used in the structural shell. For example, the recovered basalt fibers may not show substantial degradation in their physical and / or mechanical properties. The details of this reason are as described above.

[0090] The recovered, at least partially thermally decomposed polymer material may also be suitable for reuse and / or recycling or downcycling. For example, the recovered, at least partially thermally decomposed polymer material may be suitable for reuse in the structural shell according to the present invention, or for use in other applications. Although we do not wish to be bound by theory, the recovered, at least partially thermally decomposed polymer material may be recovered in a form suitable for remixing with a curing agent and remolding to form a new product. For example, the recovered, at least partially thermally decomposed polymer material may not show substantially degradation in its physical and / or mechanical properties compared to the resin used to manufacture the structural shell, etc.

[0091] In some embodiments, the structural shell includes a polymer core, and the method further includes recovering the polymer core. Preferably, the polymer core is recovered before heating to a temperature of 200-600°C, and the method is Heating a structural shell, hull, deck, marine vessel, wind turbine blade or skis and / or ski poles (or other objects as specified herein) to a temperature of 150-300°C to at least partially melt the polymer material; To separate the polymer core from at least partially molten polymer material; and Including the recovery of the polymer core.

[0092] The recovered polymer core may also be suitable for reuse and / or recycling or downcycling. For example, the recovered polymer core may be suitable for reuse in the structural shell according to the present invention, or for use in other applications. While we do not wish to be bound by theory, this is because the recovered polymer core may not show substantially degradation in its physical and / or mechanical properties. This is because, at this low temperature, the polymer core preferably remains solid. The advantages of this are as described above.

[0093] In some embodiments, the structural shell includes a gel coat, and the method further includes removing the gel coat at least partially mechanically and / or by combustion before heating. For example, the gel coat can be removed at least partially mechanically by sanding. By removing the gel coat at least partially, the possibility of the recovered product being contaminated by any remaining gel coat can be reduced.

[0094] In a further embodiment, the present invention provides a method for dismantling a structural shell, hull, deck, structural grid offshore vessel, wind turbine blade, ski or ski pole, or bulletproof panel (or other object) as described herein, the method comprising: To provide structural shells, hulls, decks, structural grids, marine vessels, wind turbine blades, skis or ski poles, or bulletproof panels (or other objects as described herein); Combining a structural shell, hull, deck, structural grid, marine vessel, wind turbine blade, ski or ski pole (or other object as described herein) with a solvent to at least partially melt a polymer material; and To recover basalt fibers and / or polymer materials and / or solvents.

[0095] The advantages and preferred features of the first embodiment also apply to this embodiment.

[0096] Basalt fibers can be recovered without substantially, typically entirely, degrading their physical and / or mechanical properties. The solvent must be capable of at least partially dissolving the polymer material. Suitable solvents are known in the art. Particularly preferred solvents are those containing acetone. Typically, substantially all of the polymer material is dissolved in the solvent. The polymer material may be recovered, for example, by evaporating the solvent. The solvent may also be recovered, for example, by condensing the evaporated solvent.

[0097] Furthermore, the structural shell of the present invention may be recycled using mechanical methods such as compounding with other polymers and / or forming sheets by hot pressing. [Brief explanation of the drawing]

[0098] Next, the present invention will be described in reference to the following non-limiting drawings:

[0099] [Figure 1] Figure 1 is a schematic diagram of an offshore vessel including a structural shell according to the present invention. [Figure 2] Figure 2 is a schematic diagram of the cross-section XY of Figure 1. [Figure 3] Figure 3 is a flowchart of the method for manufacturing a structural shell according to the present invention. [Figure 4] Figure 4 is a flowchart showing a method for disassembling a structural shell according to the present invention. [Figure 5] Figure 5 is a flowchart showing a method for disassembling a structural shell according to the present invention. [Figure 6] Figure 6 is a schematic diagram of an exploded view of the basalt fiber layer structure of the structural shell according to the present invention.

[0100] Referring to Figure 1, a schematic diagram (generally indicated as 1) of an offshore vessel according to the present invention having a hull 2 ​​and a deck 3 is shown. Figure 2 is a cross-sectional view along the line XY in Figure 1. A structural shell (generally indicated as 4) is shown, which includes a polymer core 5 oriented with a polymer material 6 reinforced with basalt fibers 7. The basalt fiber reinforced material 6 is coated with a gel coat 8.

[0101] Referring to Figure 3, a flowchart (generally shown in 9) of a method for manufacturing a structural shell, hull, structural grid, deck, offshore vessel, wind turbine blade or ski and / or ski pole according to the present invention is shown. The method comprises 10 providing a mold, 11 introducing basalt fibers into the mold, 12 contacting the basalt fibers with a mixture containing a resin and a curing agent at a relative pressure of -0.65 bar or less to form a structural shell, hull, deck, offshore vessel, wind turbine blade or ski and / or ski pole, and 13 recovering the structural shell, hull, structural grid, deck, offshore vessel, wind turbine blade or ski and / or ski pole from the mold. Optionally, the method further comprises 15 forming a gel coat in the mold before introducing the basalt fibers into the mold. Optionally, the method further comprises 16 introducing a polymer core into the mold before contacting the basalt fibers with the mixture.

[0102] Referring to Figure 4, a flowchart (generally shown in 17) of a method for disassembling a structural shell, hull, structural grid, deck, offshore vessel, wind turbine blade or ski and / or ski pole according to the present invention is shown. The method comprises 18 providing a structural shell, structural grid, hull, deck, offshore vessel, wind turbine blade or ski and / or ski pole, 19 heating the structural shell, hull, structural grid, deck, offshore vessel, wind turbine blade or ski and / or ski pole to a temperature of 200-600°C to at least partially thermally decompose the polymer material, 20 separating the at least partially thermally decomposed polymer material from the basalt fibers, and 21 recovering the basalt fibers and / or the at least partially thermally decomposed polymer material. Optionally, the structural shell includes a polymer core, and the method further comprises 22 recovering the polymer core. Optionally, the structural shell includes a gel coat, and the method further comprises 23 at least partially mechanically removing the gel coat before heating and / or removing the gel coat by combustion.

[0103] Referring to Figure 5, a flowchart (generally shown in 30) illustrates a method for disassembling a structural shell, hull, structural grid, deck, offshore vessel, wind turbine blade, or ski and / or ski pole according to the present invention. The method comprises 31 providing a structural shell, hull, deck, structural grid, offshore vessel, wind turbine blade, ski and / or ski pole (or other object as described herein), 32 contacting the structural shell, hull, deck, structural grid, offshore vessel, wind turbine blade, ski or ski pole (or other object as described herein) with a solvent to at least partially dissolve the polymer material, and 33 recovering the basalt fibers and / or polymer material.

[0104] Referring to Figure 6, an exploded schematic diagram of the basalt fiber layer structure (generally shown as 24) of the structural shell according to the present invention is shown. Multiple layers of substantially parallel basalt fibers 7 are shown, and the average direction of the substantially parallel basalt fibers 7 in each layer is about 45° or about 90° with respect to the average direction of the substantially parallel basalt fibers 7 in adjacent layers.

[0105] Next, the present invention will be described in relation to the following non-limiting embodiments.

[0106] Example 1 The basalt fiber-reinforced material described herein was manufactured according to the method described herein. The material had a monolithic structure; that is, the material consisted of a single piece of basalt fiber-reinforced material. The manufactured material was a 1m x 1m panel.

[0107] Step 1. The basalt fiber fabric (layers) was laid up in the following three layers: Layer 1: 600TRI(600g / m 2 (Triaxial fabric) Layer 2: 550UNI(550g / m 2 (Unidirectional weave) Layer 3: 600TRI(600g / m 2 (Triaxial fabric)

[0108] Step 2: A wooden table was wrapped like an envelope, ensuring a complete vacuum around it. The layered structure from Step 1 was introduced into the envelope. The resin wrap was sealed with tack tape to completely seal the bag. The layered structure from Step 1 was inside this "envelope" and ready to be injected. Peel ply was added on top of the layers (to easily separate the vacuum bag from the composite and improve the final finish), and mesh was added on top of that to allow the resin to flow more smoothly. Spiral tubes were placed at one end of the vacuum table (the end of each part of the envelope) to help the resin flow more smoothly across the width of the panel.

[0109] A vacuum pump was attached to a vacuum container (to capture resin overflow). A relative pressure of -1.0 bar was applied to check the airtightness of the bag. When the relative pressure reached -1.0 bar, the valve was closed and the vacuum pump was stopped to perform a so-called drop test (to measure air leakage).

[0110] After completing the above steps, 3000g of Arkema's Elium® and 85g of benzoyl peroxide curing agent (Nurion's Percadox® GB-50X) were mixed in a bucket. After mixing, the bucket containing the Elium® / Percadox® GB-50X resin was connected to a vacuum bag, and the vacuum pump was started again. This created a negative relative pressure throughout the panel, causing the resin to flow.

[0111] This step was performed at room temperature.

[0112] Step 3. The resin was held under reduced pressure for approximately 90 minutes. The composite was then left overnight in a vacuum bag, and the vacuum bag was removed the following morning to recover the basalt fiber reinforcement.

[0113] The monolithic basalt fiber-reinforced material could be recycled using the method described herein.

[0114] Example 2 A monolithic basalt fiber reinforced material was manufactured as described in Example 1. However, the layer structure in Step 1 was different. In this example, the basalt fiber fabric (layer) was laminated with the following four layers:

[0115] Layer 1: 550UNI (550 g / m 2 unidirectional fabric) Layer 2: 300BI (300 g / m 2 biaxial fabric) Layer 3: 300BI (300 g / m 2 biaxial fabric) Layer 4: 550UNI (550 g / m 2 unidirectional fabric, oriented 90° from Layer 1)

[0116] The monolithic basalt fiber reinforced material could be recycled by the method described herein.

[0117] Example 3 A sandwich-structured basalt fiber reinforced material was manufactured as described in Example 1. However, the layer structure in Step 1 was different. In this example, the basalt fiber fabric (layer) was laminated with the following four layers, and there was a PET foam core in the center:

[0118] Layer 1: 550UNI (550 g / m 2 unidirectional fabric) Layer 2: 300BI (300 g / m 2 biaxial fabric) Layer 3: PET foam core (thickness: 20 mm) Layer 4: 300BI (300 g / m 2 biaxial fabric) Layer 5: 550UNI (550 g / m 2 unidirectional fabric)

[0119] The sandwich-structured material was a panel of 1 m × 0.10 m. The sandwich-structured basalt fiber reinforced material could be recycled by the method described herein.

[0120] If a PET core is present, it is important that the resin flows through the injection holes of the PET core, creating a strong bond at both ends of the sandwich.

[0121] Example 4 Panels containing the basalt fiber-reinforced material described herein were prepared according to the following method steps:

[0122] 1. Before starting work: Prepare a laminating room with a room temperature of 18-24°C. Maximum humidity: 45%. 2. Degrease and clean the lamination table; 3. Apply release wax to the lamination table; 4. Apply the first layer of Peel Ply and seal both ends with aerosol adhesive; 5. Mark the layer setup with masking tape; 6. Laminate the textile fabric according to Table 1; 7. Cover the laminate with peel ply and bond the edges with aerosol adhesive; 8. Place the tacky tape on the flat surface of the laminating table; 9. Add the mesh flow media and keep the surface flat with masking tape; Attach three 10.10mm spirals and position them with masking tape. Place one suction point on the fabric, one suction point in the middle of the lamination, and one suction point at the end on the mesh flow media; 11. Install a vacuum point at the center of the spiral; 12. Set up the vacuum pack on the tacky tape. If there are gaps in the table, wrap the laminated table around them; 13. Attach a 10mm IV hose to the vacuum point and seal the connection with tacky tape; 14. Perform a vacuum test before administering intravenous fluids. Pressure: -0.80 / -1.00 bar. Drop rate: 0.5 bar / 20 minutes; 15. Mix 2.7% Percadox GB50 with Elium (10kg Elium = 270g Percadox GB50); 16. Degas the elium / Parcadox mixture for 7-10 minutes; 17. Place the bucket of degassed resin mixture under the lamination table and level it; 18. Place the IV hose into the plastic bucket (finally, secure it to a rigid rod with tape to keep it in place); 19. Slowly open valve #2, allowing all the resin to enter the tube, making sure no air gets in. Close the valve before the resin enters the fibers; 20. Open valve #1 and begin intravenous fluid administration; 21. Once the resin has flowed 3 cm behind vacuum point #2, open valve point #2 25% to 50%, and fully open it when the resin is visible on the panel; 22. Once the catalyst has started working and the panel temperature has reached 35°C, close vacuum point #1. 23. Maintain a vacuum until the resin is completely cured; 24. Wait until the panel temperature drops to room temperature; 25. Demold.

[0123] [Table 1]

[0124] Therefore, the total area of ​​the fabric and panels is 32m². 2 That was the case.

[0125] Three different pressures—-0.80, -0.85, and -0.90 bar—were used to manufacture the three panels with the 32-layer structure shown in Table 1. The total weight of each component in each panel is shown in Table 2.

[0126] [Table 2]

[0127] This indicates that the more negative pressure is applied, the lower the resin-to-fiber ratio within the panel becomes.

[0128] Furthermore, panels with approximately half the area were created using the same method. The layer configuration is shown in Table 3.

[0129] [Table 3]

[0130] Therefore, the total area of ​​the fabric and panels is 17.28 m². 2 That was the case.

[0131] Three panels with the 32-layer structure shown in Table 3 were manufactured using the same three pressures: -0.80, -0.85, and -0.90 bar. The total weight of each component in each panel is shown in Table 4.

[0132] [Table 4]

[0133] The panels were subjected to armor protection ballistic resistance testing (NIJ-STD-0108.01 Level III and IIIA) and passed.

[0134] Example 5 Panels containing the basalt fiber-reinforced material described herein were prepared according to the following method steps:

[0135] 1. Before starting work: Prepare the laminating room at a room temperature of 18-24°C. Maximum humidity: 45%. 2. Degrease and clean the lamination table; 3. Apply release wax to the lamination table; 4. Apply the first layer of Peel Ply and seal both ends with aerosol adhesive; 5. Mark the layer setup with masking tape; 6. Laminate the textile fabric according to Table 5; 7. Cover the laminate with peel ply and bond the edges with aerosol adhesive; 8. Place the tacky tape on the flat surface of the laminating table; 9. Add the mesh flow media and keep the surface flat with masking tape; Attach three 10.10mm spirals and position them with masking tape. Place one suction point on the fabric, one suction point in the middle of the lamination process, and one suction point at the end on the mesh flow media; 11. Install a vacuum point at the center of the spiral; 12. Install a pressure gauge; 13. Set up the vacuum pack on the tacky tape. If there are gaps in the table, wrap the laminated table; 14. Attach a 10mm IV hose to the vacuum point and seal the connection with tacky tape; 15. Perform a vacuum test before injection. Pressure -1.00 bar. Drop tolerance 0.5 bar / 20 minutes; 16. Mix 2.7% Percadox GB50 with Elium (10kg Elium = 270g Percadox GB50); 17. Degas the elium / Parcadox mixture for 7-10 minutes; 18. Place the bucket of degassed resin mixture under the lamination table and level it; 19. Place the IV hose into the plastic bucket (finally secure the hose to a rigid rod with tape to keep it in place); 20. Open valve #1 and begin injection; 21. Once the resin has flowed 3 cm behind vacuum point #2, open valve point #2; 22. Once fully injected, close vacuum point #2; 23. Once the catalyst has started working and the panel temperature has risen to 35°C, close vacuum point #1. 24. Maintain a vacuum until the resin is completely cured; 25. Wait until the panel temperature drops to room temperature; 26. Demold.

[0136] [Table 5]

[0137] Therefore, the total area of ​​the fabric and panels is 32m². 2 The total weight of the panel was 24.83 kg, consisting of 17.60 kg of fiber, 7.04 kg of resin, and 0.19 kg of Percadox.

[0138] Panels having a quasi-isotropic laminate were also manufactured according to the above procedure, with a layer structure as shown in Table 6.

[0139] [Table 6]

[0140] The panel area is 43m². 2 So, UNI is 22m 2 BI is 21m 2 The total weight of the panel was 25.96 kg, consisting of 18.40 kg of fiber (12.10 kg of UNI and 6.30 kg of BI), 7.36 kg of resin, and 0.20 kg of Percadox.

[0141] Smaller panels with the same layer structure are also manufactured using the procedure described above, and the layer structure is defined in Tables 7 and 8.

[0142] [Table 7]

[0143] Therefore, the total area of ​​the fabric and panels is 25.92 m². 2 The total weight of the panel was 18.90 kg, consisting of 14.26 kg of fiber and 4.64 kg of resin. Therefore, the ratio of resin to fiber was 32.54%, and the thickness of the panel was 12.12 mm.

[0144] [Table 8]

[0145] Therefore, the total area of ​​the fabric and panels is 34.83 m². 2 And UNI is 17.82m 2 BI is 17.01m 2 The total weight of the panel was 20.70 kg, consisting of 14.90 kg of fiber and 5.80 kg of resin. The ratio of resin to fiber was 38.93%, and the panel thickness was 13.20 mm.

[0146] The above panels were subjected to armor protection ballistic resistance testing (NIJ-STD-0108.01 Level III and IIIA) and passed.

[0147] The detailed description provided herein is for illustrative and illustrative purposes only and is not intended to limit the scope of the appended claims. Many of the modifications in the currently preferred embodiments illustrated herein will be obvious to those skilled in the art and will remain within the scope of the appended claims and their equivalents.

Claims

1. A structural shell comprising a basalt fiber-reinforced material, wherein the basalt fiber-reinforced material comprises a polymer material, and the polymer material is at least partially thermally decomposed at a temperature of 200 to 600°C.

2. The structural shell according to claim 1, wherein the polymer material is a thermoplastic material.

3. The structural shell according to claim 1 or 2, wherein the polymer material comprises polymethacrylate.

4. The structural shell according to any one of claims 1 to 3, wherein the polymer material comprises polymethyl methacrylate.

5. The structural shell according to any one of claims 1 to 4, wherein the polymer material can be at least partially melted at a temperature of 150 to 300°C, preferably 200 to 250°C, and / or the polymer material can be at least partially melted at a temperature lower than the temperature at which it can be at least partially thermally decomposed.

6. The structural shell according to any one of claims 1 to 5, wherein the polymer material can be at least partially thermally decomposed at a temperature of 300 to 500°C, preferably 350 to 400°C.

7. The structural shell according to any one of claims 1 to 6, wherein the at least partially thermally decomposed polymer material is liquid at 20°C.

8. The structural shell according to any one of claims 1 to 7, wherein the weight ratio of the basalt fibers to the polymer material is 80:20 to 40:60, preferably 75:25 to 50:50, more preferably 70:30 to 55:45, and most preferably about 60:

40.

9. A structural shell according to any one of claims 1 to 8, wherein basalt fibers are dispersed in the polymer material in a regular arrangement, and preferably the basalt fiber-reinforced material comprises a plurality of substantially parallel basalt fibers, the average direction of the substantially parallel basalt fibers differs in adjacent layers.

10. The structural shell according to claim 9, wherein the average direction of the substantially parallel basalt fibers in each layer is at about 45° or about 90° with respect to the average direction of the substantially parallel basalt fibers in an adjacent layer.

11. The structural shell according to claim 9 or 10, wherein the substantially parallel layers of basalt fibers are arranged in four axial directions, preferably in the relative directions of the basalt fibers of -45°, 90°, 0-90°, and 0°; in three axial directions, preferably in the relative directions of the basalt fibers of -45°, 90°, and 45°; in two axial directions, preferably in the relative directions of the basalt fibers of 0° and 90°; or in one direction.

12. The structural shell according to any one of claims 1 to 11, wherein the basalt fiber-reinforced material has a thickness of 0.5 to 3.0 mm, preferably 1.0 to 2.0 mm.

13. A structural shell according to any one of claims 1 to 12, further comprising a polymer core.

14. The structural shell according to claim 13, wherein the polymer core comprises polyester.

15. The structural shell according to claim 14, wherein the polyester comprises PET, preferably the PET comprises PET foam.

16. The structural shell according to any one of claims 13 to 15, wherein the polymer core has a melting temperature of 200 to 300°C, preferably 230 to 270°C.

17. A structural shell according to any one of claims 1 to 16, further comprising a gel coat.

18. The structural shell according to claim 17, wherein the gel coat comprises an unsaturated polyester resin and / or a vinyl ester.

19. The structural shell according to claim 17 or 18, wherein the gel coat contains a pigment.

20. The structural shell according to any one of claims 1 to 19, wherein the structural shell exhibits a bending strength of 600 to 800 MPa before aging.

21. A hull for an offshore vessel, comprising a structural shell according to any one of claims 1 to 20.

22. A structural grid for an offshore vessel, comprising a structural shell according to any one of claims 1 to 20.

23. A deck for an offshore vessel, comprising a structural shell according to any one of claims 1 to 20, preferably a structural shell according to any one of claims 13 to 16.

24. An offshore vessel comprising at least one hull and / or at least one structural grid and / or at least one deck according to claim 21 and / or claim 22 and / or claim 23.

25. A wind turbine blade comprising a structural shell according to any one of claims 1 to 20.

26. A ski or ski pole comprising a structural shell according to any one of claims 1 to 20.

27. A ballistic panel comprising a structural shell according to any one of claims 1 to 20.

28. The ballistic panel according to claim 27, wherein the weight ratio of the polymer material to the basalt fibers is 0.35 to 0.45, preferably 0.39 to 0.

44.

29. A structural shell according to any one of claims 1 to 20, a hull according to claim 21, a deck according to claim 22, a structural grid according to claim 23, an ocean vessel according to claim 24, a wind turbine blade according to claim 25, a ski or ski pole according to claim 26, or a method for manufacturing a bulletproof panel according to claim 27 or claim 28, wherein the manufacturing method is To provide a mold, Introducing basalt fibers into the aforementioned mold, The basalt fibers and a mixture containing resin and a hardening agent are brought into contact at a relative pressure of -0.65 bar or less to form structural shells, hulls, structural grids, decks, marine vessels, wind turbine blades, skis and / or ski poles, or bulletproof panels, and A manufacturing method comprising recovering the structural shell, hull, structural grid, deck, offshore vessel, wind turbine blade, skis and / or ski poles, or ballistic panels from the mold.

30. The manufacturing method according to claim 29, wherein the resin comprises a methacrylate monomer, preferably a methyl methacrylate monomer, more preferably 50 to 85% by weight of a methyl methacrylate monomer and / or 10 to 50% by weight of an acrylic polymer.

31. The method according to claim 29 or 30, wherein the curing agent comprises an organic peroxide, preferably benzoyl peroxide.

32. The method according to any one of claims 29 to 31, wherein the mixture contains the curing agent in an amount of 0.5 to 30 phr, preferably 1 to 15 phr, more preferably 1.5 to 4 phr, and even more preferably 2.5 to 4 phr.

33. The method according to any one of claims 29 to 32, wherein the basalt fibers and the mixture are brought into contact at a relative pressure of -0.7 to -1.15 bar, preferably -0.9 to -1.1 bar, and more preferably -0.95 to -1.05 bar.

34. The method according to any one of claims 29 to 33, wherein the basalt fibers and the mixture are brought into contact at a temperature of 10 to 40°C, preferably 14 to 30°C.

35. The method according to any one of claims 29 to 34, comprising bringing the basalt fibers and the mixture into contact at a humidity of 30 to 70%, preferably 40 to 50%.

36. The method according to any one of claims 29 to 35, wherein the basalt fibers and the mixture are brought into contact under the pressure for 5 minutes to 12 hours, preferably 1 hour to 6 hours, more preferably 90 minutes to 3 hours.

37. The method according to any one of claims 29 to 36, further comprising forming a gel coat in the mold before introducing the basalt fibers into the mold.

38. The method according to any one of claims 29 to 37, further comprising introducing a polymer core into the mold before contacting the basalt fibers with the mixture.

39. The method according to claim 38, wherein the polymer core is introduced into the mold between two or more basalt fibers, and preferably the polymer core is introduced into the mold to form a layer that separates two or more layers of basalt fibers.

40. A method for disassembling a structural shell according to any one of claims 1 to 20, a hull according to claim 21, a deck according to claim 22, a structural grid according to claim 23, an ocean vessel according to claim 24, a wind turbine blade according to claim 25, a ski or ski pole according to claim 26, or a ballistic panel according to claim 27 or claim 28, wherein the method is To provide the aforementioned structural shell, hull, structural grid, deck, offshore vessel, wind turbine blade, ski or ski pole, or bulletproof panel, Heating the structural shell, hull, structural grid, deck, offshore vessel, wind turbine blade, ski or ski pole, or bulletproof panel to a temperature of 200 to 600°C to at least partially thermally decompose the polymer material. Separating the polymer material, which has been at least partially thermally decomposed, from the basalt fibers, and A method comprising recovering basalt fibers and / or at least partially thermally decomposed polymer material.

41. The method according to claim 40, wherein the heating is carried out in an inert atmosphere, preferably in the substantially absence of oxygen.

42. The method according to claim 40 or 41, wherein the heating is carried out at a temperature of 250 to 500°C, preferably 300 to 500°C, and more preferably 350 to 400°C.

43. The method according to any one of claims 40 to 42, wherein the heating is carried out at a pressure of at least 10 bar.

44. The method according to any one of claims 40 to 43, wherein the structural shell comprises a polymer core, and the method further comprises recovering the polymer core.

45. Before heating to a temperature of 200-600°C, The structural shell, hull, structural grid, deck, offshore vessel, wind turbine blade, ski or ski pole, or bulletproof panel is heated to a temperature of 150 to 300°C to at least partially melt the polymer material. Separating the polymer core from the at least partially molten polymer material, and The method according to claim 44, further comprising recovering the polymer core.

46. The method according to any one of claims 40 to 45, wherein the structural shell comprises a gel coat, and the method further comprises at least partially mechanically removing the gel coat before heating and / or removal of the gel coat by combustion.

47. A method for disassembling a structural shell according to any one of claims 1 to 20, a hull according to claim 21, a deck according to claim 22, a structural grid according to claim 23, an ocean vessel according to claim 24, a wind turbine blade according to claim 25, a ski or ski pole according to claim 26, or a ballistic panel according to claim 27 or claim 28, wherein the method is To provide the aforementioned structural shell, hull, deck, structural grid, marine vessel, wind turbine blade, ski or ski pole, or bulletproof panel, The process involves bringing the structural shell, hull, deck, structural grid, marine vessel, wind turbine blade, ski or ski pole, or bulletproof panel into contact with a solvent to at least partially dissolve the polymer material, and The method comprising recovering basalt fibers and / or polymer materials.

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