Fiber-reinforced thermoplastic composite articles containing recycled polymer fibers

Abstract

Thermoplastic composite articles are described that include recycled polymer fibers in one or more of a core layer and a skin layer. In a particular arrangement, the thermoplastic composite article may include a porous core layer that includes a web of an open cell structure that includes a random intersection of a plurality of reinforcing fibers and a plurality of recycled polymer fibers held together by a thermoplastic material, and a skin layer disposed on a first surface of the porous core layer. The thermoplastic material may include virgin thermoplastic material and recycled thermoplastic material, as appropriate. Exterior and interior components manufactured using the thermoplastic composite article are also described.

Description

[Technical Field]

[0001] Priority application This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 419,634, filed October 26, 2022, and U.S. Provisional Application No. 63 / 522,043, filed June 20, 2023, the entire disclosures of each of which are incorporated herein by reference. Fiber-reinforced thermoplastic composite articles are described that include recycled polymer fibers. In some configurations, the composite articles include a plurality of reinforcing fibers, some of which may be recycled polymer fibers. Optionally, recycled thermoplastic materials may also be present. [Background technology]

[0002] Composite articles often include a variety of materials that impart desired properties to the article, and the exact materials selected may vary depending on the intended use of the composite article. Summary of the Invention

[0003] Certain aspects and features are described with respect to composite articles that may include recycled polymeric fibers in one or more layers of the composite article. In some embodiments, the recycled polymeric fibers may be present in one or more of the core layer, skin layers, or both. Optionally, the composite article may also include recycled thermoplastic materials, alone or in combination with recycled polymeric fibers and / or biomaterials. In an aspect, a thermoplastic composite article includes a porous core layer including an open-cell structured web including a random intersection of a plurality of reinforcing fibers and a plurality of recycled polymer fibers held together by a thermoplastic material, and a skin layer disposed on a first surface of the porous core layer. In certain embodiments, the recycled polymer fibers are selected from the group consisting of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled copolyamide fibers, recycled high-density polyethylene fibers, and combinations thereof. In other embodiments, the thermoplastic material of the porous core layer comprises virgin thermoplastic material, recycled thermoplastic material, or both, wherein the virgin thermoplastic material or recycled thermoplastic material is independently at least one of polyethylene, polypropylene, polystyrene, polyimide, polyetherimide, acrylonitrile styrene, butadiene, polyethylene terephthalate, polybutylene terephthalate, polybutylene tetrachlorate, polyvinyl chloride, polyphenylene ether, polycarbonate, polyestercarbonate, polyester, acrylonitrile-butyl acrylate-styrene polymer, amorphous nylon, polyarylene ether ketone, polyphenylene sulfide, polyarylsulfone, polyethersulfone, poly(1,4 phenylene) compound, silicone, and mixtures thereof. In some embodiments, the plurality of reinforcing fibers of the porous core layer are selected from the group consisting of glass fibers, carbon fibers, graphite fibers, synthetic organic fibers, inorganic fibers, natural fibers, mineral fibers, metal fibers, metallized inorganic fibers, metallized synthetic fibers, ceramic fibers, biofibers, rice husk fibers, kenaf fibers, and combinations thereof.

[0004] In certain embodiments, the skin layer is selected from the group consisting of a fabric, a film, a scrim, a flim, a porous nonwoven material, a porous knitted material, a decorative layer, and combinations thereof. In other embodiments, the plurality of reinforcing fibers is present in an amount of 20% to 80% by weight, based on the weight of the porous core layer. In some examples, the plurality of recycled polymer fibers is present in an amount of 20% to 80% by weight, based on the weight of the porous core layer. In other embodiments, the plurality of recycled polymer fibers comprises monomer units that are different from the monomer units of the plurality of reinforcing fibers. In some examples, the plurality of recycled polymer fibers and the plurality of reinforcing fibers each comprise a similar average diameter and average length. In some configurations, the thermoplastic composite article is assembled and arranged as a vehicle panel, a vehicle underbody panel, an exterior vehicle part, an interior vehicle part, an automobile headliner, a recreational vehicle panel, or a recreational vehicle part.

[0005] In other embodiments, the skin layers comprise a plurality of recycled polymer fibers. In certain embodiments, the plurality of recycled polymer fibers in the porous core layer and the plurality of recycled polymer fibers in the skin layers are independently selected from the group consisting of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled copolyamide fibers, recycled high-density polyethylene fibers, and combinations thereof. In other embodiments, the plurality of recycled polymer fibers in the porous core layer and the plurality of recycled polymer fibers in the skin layers comprise different monomer units.

[0006] In additional embodiments, the thermoplastic material of the porous core layer is selected from the group consisting of virgin polyethylene, virgin polypropylene, virgin polystyrene, virgin polyimide, virgin polyetherimide, virgin acrylonitrile styrene, virgin butadiene, virgin polyethylene terephthalate, virgin polybutylene terephthalate, virgin polybutylene tetrachlorate, virgin polyvinyl chloride, virgin polyphenylene ether, virgin polycarbonate, virgin polyestercarbonate, virgin polyester, virgin acrylonitrile-butyl acrylate-styrene polymer, virgin amorphous nylon, virgin polyarylene ether ketone, virgin polyphenylene sulfide, virgin polyarylsulfone, virgin polyethersulfone, virgin poly(1,4 The polymerizable composition may comprise at least one of recycled poly(1,4 phenylene) compounds, recycled polyethylene, recycled polypropylene, recycled polystyrene, recycled polyimide, recycled polyetherimide, recycled acrylonitrile styrene, recycled butadiene, recycled polyethylene terephthalate, recycled polybutylene terephthalate, recycled polybutylene tetrachlorate, recycled polyvinyl chloride, recycled polyphenylene ether, recycled polycarbonate, recycled polyester carbonate, recycled polyester, recycled acrylonitrile-butyl acrylate-styrene polymer, recycled amorphous nylon, recycled polyarylene ether ketone, recycled polyphenylene sulfide, recycled polyarylsulfone, recycled polyethersulfone, recycled poly(1,4 phenylene) compounds, recycled silicone, and mixtures thereof.

[0007] In some configurations, the plurality of reinforcing fibers of the porous core layer are selected from the group consisting of glass fibers, carbon fibers, graphite fibers, synthetic organic fibers, inorganic fibers, natural fibers, mineral fibers, metal fibers, metallized inorganic fibers, metallized synthetic fibers, ceramic fibers, and combinations thereof. In other configurations, the skin layer is selected from the group consisting of a fabric, a film, a scrim, a flim, a porous nonwoven material, a porous knitted material, a decorative layer, and combinations thereof. In other examples, the plurality of reinforcing fibers and the plurality of recycled polymer fibers in the porous core layer are independently present in an amount of 20% to 80% by weight, based on the weight of the porous core layer. In some examples, the plurality of recycled polymer fibers in the skin layers comprise monomer units that are different from the monomer units of the plurality of reinforcing fibers in the porous core layer. In some cases, the thermoplastic material of the porous core layer comprises a virgin polyolefin material or a recycled polyolefin material or both, the plurality of reinforcing fibers of the porous core layer comprise glass fibers, and the plurality of recycled polymer fibers of the porous core layer are selected from the group consisting of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled copolyamide fibers, recycled high-density polyethylene fibers, and combinations thereof.

[0008] In another configuration, the thermoplastic material of the porous core layer comprises virgin polyolefin material or recycled polyolefin material or both, the plurality of reinforcing fibers of the porous core layer comprise glass fibers, and the plurality of recycled polymer fibers of the skin layers are selected from the group consisting of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled copolyamide fibers, recycled high-density polyethylene fibers, and combinations thereof. In another aspect, a thermoplastic composite article includes a porous core layer comprising an open-cell structured web including a random intersection of a plurality of reinforcing fibers held together by a thermoplastic material, and a skin layer disposed on a first surface of the porous core layer and including a plurality of recycled polymer fibers. In some embodiments, the plurality of recycled polymer fibers in the skin layers are selected from the group consisting of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled copolyamide fibers, recycled high-density polyethylene fibers, and combinations thereof. In other embodiments, the plurality of reinforcing fibers in the porous core layer and the plurality of recycled polymer fibers in the skin layers contain a common monomer unit. In some examples, the thermoplastic material of the porous core layer comprises a virgin thermoplastic material, a recycled thermoplastic material, or both, and the virgin thermoplastic material or the recycled thermoplastic material is independently at least one of polyethylene, polypropylene, polystyrene, polyimide, polyetherimide, acrylonitrile styrene, butadiene, polyethylene terephthalate, polybutylene terephthalate, polybutylene tetrachlorate, polyvinyl chloride, polyphenylene ether, polycarbonate, polyester carbonate, polyester, acrylonitrile-butyl acrylate-styrene polymer, amorphous nylon, polyarylene ether ketone, polyphenylene sulfide, polyarylsulfone, polyethersulfone, poly(1,4 phenylene) compounds, silicone, and mixtures thereof.

[0009] In certain embodiments, the plurality of reinforcing fibers of the porous core layer are selected from the group consisting of glass fibers, carbon fibers, graphite fibers, synthetic organic fibers, inorganic fibers, natural fibers, mineral fibers, metal fibers, metallized inorganic fibers, metallized synthetic fibers, ceramic fibers, and combinations thereof. In some embodiments, the skin layer is selected from the group consisting of a fabric, a film, a scrim, a flim, a porous nonwoven material, a porous knitted material, a decorative layer, and combinations thereof. In a specific example, the plurality of reinforcing fibers are present in an amount of 20% to 80% by weight based on the weight of the porous core layer.

[0010] In certain configurations, the plurality of recycled polymer fibers in the skin layers include monomer units that are different from monomer units of the plurality of reinforcing fibers in the porous core layer. In other embodiments, the thermoplastic composite article is assembled and arranged as a vehicle panel, a vehicle underbody panel, an exterior vehicle part, an interior vehicle part, an automobile headliner, a recreational vehicle panel, or a recreational vehicle part. In some embodiments, the plurality of thermoplastic materials of the porous core layer comprise virgin polyolefin materials or recycled polyolefin materials or both, the plurality of reinforcing fibers of the porous core layer comprise glass fibers, and the recycled polymer fibers of the skin layers are selected from the group consisting of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled copolyamide fibers, recycled high-density polyethylene fibers, and combinations thereof.

[0011] In an additional aspect, a method for making a thermoplastic composite article includes adding a plurality of reinforcing fibers, a plurality of recycled polymer fibers, and a thermoplastic material to an agitated aqueous foam solution to form a dispersed mixture. The method may also include depositing the dispersed mixture of the plurality of reinforcing fibers, the recycled polymer fibers, and the thermoplastic material onto a forming support element. The method may also include draining liquid from the deposited dispersed mixture to form a web. The method may also include heating the web at or above the softening temperature of the thermoplastic material; and compressing the heated web to a predetermined thickness. The method may also include disposing a skin layer on the compressed web to provide the thermoplastic composite article. In certain embodiments, the skin layer comprises a plurality of recycled polymeric fibers, hi other embodiments, the thermoplastic material comprises a blend of virgin and recycled thermoplastic materials.

[0012] In another aspect, a method for making a thermoplastic composite article includes adding a plurality of reinforcing fibers and a thermoplastic material to an agitated aqueous foam solution to form a dispersed mixture. The method may also include depositing the dispersed mixture of the plurality of reinforcing fibers and the thermoplastic material onto a forming support element. The method may also include draining liquid from the deposited dispersed mixture to form a web. The method may also include heating the web at or above the softening temperature of the thermoplastic material; and compressing the heated web to a predetermined thickness. The method may also include disposing a skin layer comprising a plurality of recycled polymeric fibers on the compressed web to provide the thermoplastic composite article. In some embodiments, the thermoplastic material comprises a blend of virgin and recycled thermoplastic materials. Additional aspects, embodiments, configurations, examples, features, and elements are described in further detail below. Certain specific figures will be described with reference to the accompanying figures. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a diagram of a core layer comprising thermoplastic material and recycled polymer fibers, according to certain embodiments. [Figure 2] FIG. 1 is a diagram of a fiber-reinforced thermoplastic composite article including a core layer comprising thermoplastic material and recycled polymer fibers in combination with skin layers, according to certain embodiments. [Figure 3] FIG. 1 is a diagram of a fiber-reinforced thermoplastic composite article including a core layer comprising thermoplastic material and recycled polymer fibers in combination with two skin layers, according to certain embodiments. [Figure 4] FIG. 1 is a diagram of a fiber-reinforced thermoplastic composite article including a core layer comprising a thermoplastic material and recycled polymer fibers in combination with a decorative layer, according to certain embodiments. [Figure 5] FIG. 1 is a diagram of a fiber-reinforced thermoplastic composite article including a core layer including a thermoplastic material and non-recycled polymer fibers in combination with skin layers including recycled polymer fibers, according to certain embodiments. [Figure 6] FIG. 1 is a diagram of a fiber-reinforced thermoplastic composite article including a core layer comprising a thermoplastic material and non-recycled polymer fibers in combination with a skin layer comprising recycled polymer fibers and another skin layer, according to certain embodiments. [Figure 7] FIG. 1 is a diagram of a fiber-reinforced thermoplastic composite article comprising a core layer comprising thermoplastic material and non-recycled polymer fibers in combination with skin layers and decorative layers comprising recycled polymer fibers, according to certain embodiments. [Figure 8] FIG. 1 is a diagram of a core layer comprising a thermoplastic material and recycled polymer fibers combined with a core layer comprising a thermoplastic material and non-recycled polymer fibers, according to certain embodiments. [Figure 9] FIG. 1 is a diagram of a core layer comprising thermoplastic material and recycled polymeric fibers combined with a core layer comprising thermoplastic material and non-recycled polymeric fibers in combination with skin layers, according to certain embodiments. [Figure 10] FIG. 1 is a diagram of a core layer comprising thermoplastic material and recycled polymeric fibers combined with a core layer comprising thermoplastic material and non-recycled polymeric fibers in combination with skin layers, according to certain embodiments. [Figure 11] FIG. 1 is a diagram of a core layer comprising thermoplastic material and recycled polymer fibers combined with two skin layers, with the core layer comprising thermoplastic material and non-recycled polymer fibers, according to certain embodiments. [Figure 12] FIG. 1 is a diagram of a core layer comprising a thermoplastic material and recycled polymer fibers combined with a decorative layer, according to certain embodiments, to a core layer comprising a thermoplastic material and non-recycled polymer fibers. [Figure 13] FIG. 1 is a diagram of a core layer comprising a thermoplastic material and recycled polymer fibers bonded via a skin layer to a core layer comprising a thermoplastic material and non-recycled polymer fibers, according to certain embodiments. [Figure 14] FIG. 1 is a diagram of a headliner according to certain embodiments. [Figure 15] 1 is a diagram of an underbody shield according to certain embodiments. [Figure 16]FIG. 1 is a diagram of an interior trim according to certain embodiments. [Figure 17] 1 is a diagram of a ceiling panel according to certain embodiments. [Figure 18] FIG. 1 is a diagram of a cubicle panel according to certain embodiments. [Figure 19] FIG. 1 is a diagram of a structural panel according to certain embodiments. [Figure 20] FIG. 10 is another view of a structural panel, according to certain embodiments. [Figure 21] 1 is a diagram of a wall panel in accordance with certain embodiments. [Figure 22] FIG. 1 is a diagram of a siding panel in accordance with certain embodiments. [Figure 23] 1 is a diagram of a roofing panel according to certain embodiments. [Figure 24] FIG. 1 is a diagram of a roofing shingle according to certain embodiments. [Figure 25] 1 is a diagram of an interior panel of a recreational vehicle according to certain embodiments. [Figure 26] 1 is a diagram of an exterior panel of a recreational vehicle according to certain embodiments. [Figure 27] FIG. 1 is a diagram of an interior trim according to certain embodiments. [Figure 28] 1 is a diagram of a vehicle in accordance with certain embodiments. [Figure 29] 1 is a diagram of a recreational vehicle in accordance with certain embodiments. [Figure 30] 1 is an illustration of an airplane in accordance with certain embodiments. [Figure 31] FIG. 1 is a diagram of a spacecraft in accordance with certain embodiments. [Figure 32] The results of testing specific formulations in Examples 1-3 are shown. [Figure 33] The results of testing specific formulations in Examples 1-3 are shown. [Figure 34] The results of testing specific formulations in Examples 1-3 are shown. [Figure 35] The results of testing specific formulations in Examples 1-3 are shown. [Figure 36] The results of testing specific formulations in Examples 1-3 are shown. [Figure 37] The results of testing specific formulations in Examples 1-3 are shown. [Figure 38] The results of testing specific formulations in Examples 1-3 are shown. [Figure 39] The results of testing specific formulations in Examples 1-3 are shown. [Figure 40] The results of testing specific formulations in Examples 1-3 are shown. [Figure 41] The results of testing specific formulations in Examples 1-3 are shown. [Figure 42] The results of testing specific formulations in Examples 1-3 are shown. [Figure 43] The results of testing specific formulations in Examples 1-3 are shown. [Figure 44] 1 shows the results of testing specific formulations in Example 4. [Figure 45] 1 shows the results of testing specific formulations in Example 4. [Figure 46] 1 shows the results of testing specific formulations in Example 4. [Figure 47] 1 shows the results of testing specific formulations in Example 4. [Figure 48] 1 shows the results of testing specific formulations in Example 5. [Figure 49] 1 shows the results of testing specific formulations in Example 5. [Figure 50] 1 shows the results of testing specific formulations in Example 5. [Figure 51] 1 shows the results of testing specific formulations in Example 5. [Figure 52] 1 shows the results of testing specific formulations in Example 6. [Figure 53] 1 shows the results of testing specific formulations in Example 6. [Figure 54] 1 shows the results of testing specific formulations in Example 6. [Figure 55]1 shows the results of testing specific formulations in Example 6. [Figure 56] 1 shows the results of testing specific formulations in Example 7. [Figure 57] 1 shows the results of testing specific formulations in Example 7. [Figure 58] 1 shows the results of testing specific formulations in Example 7. [Figure 59] 1 shows the results of testing specific formulations in Example 7. [Figure 60] 1 shows the results of testing specific formulations in Example 7. [Figure 61] 1 shows the results of testing specific formulations in Example 7. [Figure 62] 1 shows the results of testing specific formulations in Example 7. [Figure 63] 1 shows the results of testing specific formulations in Example 7. [Figure 64] 1 shows the results of testing specific formulations in Example 8. [Figure 65] 1 shows the results of testing specific formulations in Example 8. [Figure 66] 1 shows the results of testing specific formulations in Example 8. [Figure 67] 1 shows the results of testing specific formulations in Example 8. [Figure 68] 1 shows the results of testing specific formulations in Example 8. [Figure 69] 1 shows the results of testing specific formulations in Example 8. [Figure 70] 1 shows the results of testing specific formulations in Example 8. [Figure 71] 1 shows the results of testing specific formulations in Example 8. [Figure 72] 1 shows the results of testing specific formulations in Example 9. [Figure 73] 1 shows the results of testing specific formulations in Example 9. [Figure 74] 1 shows the results of testing specific formulations in Example 9. [Figure 75]1 shows the results of testing specific formulations in Example 9. [Figure 76] 1 shows the results of testing specific formulations in Example 9. [Figure 77] 1 shows the results of testing specific formulations in Example 9. [Figure 78] 1 shows the results of testing specific formulations in Example 9. [Figure 79] 1 shows the results of testing specific formulations in Example 9. [Figure 80] 1 shows the results of testing specific formulations in Example 9. [Figure 81] 1 shows the results of testing specific formulations in Example 10. [Figure 82] 1 shows the results of testing specific formulations in Example 10. [Figure 83] 1 shows the results of testing specific formulations in Example 10. [Figure 84] 1 shows the results of testing specific formulations in Example 10. [Figure 85] 1 shows the results of testing specific formulations in Example 10. [Figure 86] 1 shows the results of testing specific formulations in Example 10. [Figure 87] 1 shows the results of testing specific formulations in Example 11. [Figure 88] 1 shows the results of testing specific formulations in Example 11. [Figure 89] 1 shows the results of testing specific formulations in Example 11. [Figure 90] 1 shows the results of testing specific formulations in Example 11. [Figure 91] 1 shows the results of testing specific formulations in Example 11. [Figure 92] 1 shows the results of testing specific formulations in Example 11. [Figure 93] 1 shows the results of testing specific formulations in Example 11. [Figure 94] 1 shows the results of testing specific formulations in Example 11. [Figure 95] 1 shows the results of testing specific formulations in Example 11. [Figure 96] 1 shows the results of testing specific formulations in Example 11. [Figure 97] 1 shows the results of testing specific formulations in Example 11. [Figure 98] 1 shows the results of testing specific formulations in Example 11. [Figure 99] 1 shows the results of testing specific formulations in Example 11. [Figure 100] 1 shows the results of testing specific formulations in Example 11. [Figure 101] 1 shows the results of testing specific formulations in Example 11. [Figure 102] 1 shows the results of testing specific formulations in Example 11. DETAILED DESCRIPTION OF THE INVENTION

[0014] Given the benefit of this disclosure, those skilled in the art will recognize that the dimensions, sizes, shading, arrangements, and other features in the figures are provided for illustrative purposes only and are not intended to limit the technology to any one configuration, size, or arrangement. Various components and features of fiber-reinforced thermoplastic composite articles containing recycled polymer fibers in one, two, three, or more different components or layers are discussed. As used herein, "recycled polymer fibers" refers to fibers that include material that has been pre-polymerized, subjected to one or more chemical or physical processes, and then formed into polymer fibers by placing the pre-polymerized material into a suitable form to produce the fibers. In some embodiments, recycled polymer fibers may be produced from non-fibrous materials that have been converted into a suitable form to enable the production of polymer fibers. In other embodiments, recycled polymer fibers may be produced from fibrous materials that have an inappropriate size, diameter, or properties for use in the thermoplastic composite articles described herein. For example, very short fibers, less than 2 mm in length, may be inappropriate for providing suitable mechanical properties in the fiber-reinforced thermoplastic composite articles described herein. Short fibers may be subjected to chemical and / or physical treatments to convert the short fibers into a suitable form, enabling the production of recycled polymer fibers having the appropriate length and / or size. In some cases, the converted material can be regenerated into polymer fibers by forcing the fibers through holes in a die or other device to provide continuous polymer filaments. For example, the converted material can be melt-spun, solution-spun, wet-spun, gel-spun, liquid crystal-spun, dispersion-spun, reaction-spun, electrospun, or other techniques to provide polymer filaments. The polymer filaments can then be cut and sized to provide suitable fiber lengths and diameters for use in the fiber-reinforced thermoplastic composite articles described herein. Exemplary recycled polymer fiber sizes and dimensions are discussed below.

[0015] In certain embodiments, the exact polymeric material used to produce the recycled fibers may vary. For example, recycled fibers may be made from polyethylene terephthalate, polyethylene, polypropylene, polyamide, copolyamide, recycled high-density polyethylene, low-density polyethylene, and combinations thereof. Other materials, including, for example, polystyrene and polyvinyl chloride, can also be converted and used alone or in combination with other polymeric materials. The polymeric material may be pre-polymerized and formed into other shapes or articles. Pre-formed articles can be chopped, crushed, ground, pulverized, melted, softened, or otherwise physically or chemically processed to convert the material in the article into a suitable form for use in polymer fiber production. If desired, the converted material can be mixed with virgin polymeric material before fiber production. In other embodiments, the converted material can be used to produce recycled polymeric fibers without the addition of any virgin polymeric material. The converted material may be subjected to a washing process, a depolymerization agent to convert at least a portion of the converted material into monomer units, or other physical or chemical processes. In some embodiments, the material may undergo one or more of glycolysis, methanolysis, hydrolysis, or treatment with other chemical agents or solvents before being used to make recycled polymer fibers.

[0016] In some embodiments, recycled polymer fibers can be made from pre-polymerized non-fibrous materials that are converted into a form suitable for repolymerization into recycled polymer fibers. For example, pre-polymerized non-fibrous materials can be converted into non-fibrous materials, depolymerized and / or further polymerized, and then spun into yarns or recycled polymer fibers. In other embodiments, recycled polymer fibers can be converted into non-fibrous materials that include monomers, repolymerized, and then spun into yarns or recycled polymer fibers. While not wishing to be bound by any particular scientific theory, virgin polymer fibers may differ chemically or physically from recycled polymer fibers. For example, recycled polymer fibers may have a higher degree of polymerization (DP or X) compared to virgin polymer fibers. n) or may have a different chemical makeup as a result of the regeneration process. n is typically calculated as the ratio of the molecular weight of the polymer to the molecular weight of the repeating unit. Number-average DP and weight-average DP are the two main types used to measure DP. In certain arrangements, the DP of recycled polymer fibers can be at least 10% higher than the starting material used to make the recycled polymer fibers. In other configurations, the DP of recycled polymer fibers can be at least 20% higher than the starting material used to make the recycled polymer fibers.

[0017] In certain embodiments, the exact size of the individual recycled polymer fibers may vary. For example, recycled polymer fibers can generally have a diameter greater than about 5 μm, more specifically, between about 5 μm and about 22 μm, and a length between about 5 mm and about 200 mm; more specifically, the fiber diameter may be between about 2 μm and about 22 μm, and the fiber length may be between about 5 mm and about 75 mm. The recycled polymer fibers may be twisted as a result of the fiber manufacturing process, or they may be untwisted and exist as single recycled polymer fibers that generally do not cross or intersect with other recycled polymer fibers. While not wishing to be bound by any particular configuration, untwisted recycled polymer fibers may provide a smoother surface than twisted or kinked recycled polymer fibers. The recycled polymer fibers, when present in the thermoplastic composite articles described herein, are typically randomly oriented; however, if desired, the recycled polymer fibers can be oriented in any suitable direction, such as, for example, 0 degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, 75 degrees, or 90 degrees relative to the machine direction used to manufacture the thermoplastic composite article.

[0018] In other embodiments, a thermoplastic composite article may include one or more recycled thermoplastic materials. Recycled thermoplastic materials may be used in combination with recycled polymeric fibers, or may be used in combination with non-recycled fibers, such as glass fibers, inorganic fibers, organic fibers, polymeric fibers, etc. In some configurations, the thermoplastic materials present in the composite article may be a combination of virgin and recycled thermoplastic materials. For example, virgin polyolefin materials may be blended with recycled polyolefin materials, and the blends may be used to produce the fiber-reinforced thermoplastic composite articles described herein. In some embodiments, recycled thermoplastic materials may be chemically similar or identical to virgin thermoplastic materials, but may be physically different from virgin thermoplastic materials. For example, the virgin thermoplastic and recycled thermoplastic materials may share the same underlying chemical structure, e.g., the same monomers, but the recycled thermoplastic material may have a different color, particle size, shape, average glass transition temperature, crystallinity, or other physical property than the virgin thermoplastic material. In some embodiments, the virgin thermoplastic material and the recycled thermoplastic material each comprise a polyolefin material, which may be the same or different. For example, the virgin thermoplastic material and the recycled thermoplastic material each may be polyethylene (e.g., high-density polyethylene, low-density polyethylene, linear low-density polyethylene), polypropylene (e.g., homopolymer, random copolymer, and block copolymer), polybutene (e.g., 1-butene, 2-butene, and isobutylene), and other copolymers thereof. In some cases, the recycled polyolefin may comprise a blend of different recycled polyolefins, such as a blend or mixture of polyethylene and polypropylene.

[0019] In other configurations, the recycled thermoplastic material may be recycled polystyrene, recycled acrylonitrile styrene, recycled butadiene, recycled polyethylene terephthalate, recycled polybutylene terephthalate, recycled polybutylene tetrachlorate, and recycled plasticized and unplasticized polyvinyl chloride, as well as blends of these materials with each other or with other polymeric materials. Other suitable recycled thermoplastic materials include, but are not limited to, recycled polyarylene ethers, recycled polycarbonates, recycled polyester carbonates, recycled thermoplastic polyesters, recycled polyimides, recycled polyetherimides, recycled polyamides, recycled copolyamides, recycled acrylonitrile-butyl acrylate-styrene polymers, recycled amorphous nylons, recycled polyarylene ether ketones, recycled polyphenylene sulfides, recycled polyarylsulfones, recycled polyethersulfones, recycled liquid crystalline polymers, recycled poly(1,4 phenylene) compounds commercially known as PARMAX®, recycled high-heat polycarbonates such as Bayer's APEC® PC, recycled high-temperature nylons, and recycled silicones, as well as copolymers, alloys, and blends of these materials with each other or with other polymeric materials. The recycled thermoplastic material used to form the core layer can be in powder, resin, rosin, particle, fiber, or other suitable form.

[0020] In certain embodiments, the exact total amount of thermoplastic material (virgin, recycled, or both) present in the core layer can vary, with exemplary amounts ranging from about 20% to about 80% by weight, e.g., 30-70% or 35-65% by weight, based on the total weight of the core layer. Recycled thermoplastic materials are commercially available from a number of suppliers, including, but not limited to, Solvay Chemicals, Inc. (Alorton, IL), Primex Plastics (Richmond, IN), Arkema Inc. (King of Prussia, PA), and other suppliers of recycled thermoplastic materials. In other cases, all of the thermoplastic material in the composite article may be recycled thermoplastic material, which may be combined with non-recycled fibers, recycled fibers, or both, as desired.

[0021] In certain configurations, a fiber-reinforced thermoplastic composite article may include a porous core layer comprising an open-cell structured web comprising randomly intersecting multiple recycled polymer fibers held together by a thermoplastic material, which may be a virgin thermoplastic material, a recycled thermoplastic material, or a combination thereof. Referring to Figure 1, a core layer 105 is shown comprising recycled polymer fibers and a thermoplastic material. The core layer 105 is typically porous, for example, having a porosity that can vary from greater than 0% to about 95% by volume of the porous core layer. For example, the porous core layer 105 may have a volume ratio of 0 to 30%, 10 to 40%, 20 to 50%, 30 to 60%, 40 to 70%, 50 to 80%, 60 to 90%, 0 to 40%, 0 to 50%, 0 to 60%, 0 to 70%, 0 to 80%, 0 to 90%, 10 to 50%, 10 to 60%, 10 to 70%, 10 to 100%, 10 to 100%, 10 to 200%, 10 to 200%, 10 to 300%, 10 to 400%, 10 to 50%, 10 to 60%, 10 to 70%, 10 to 100%, 10 to 200%, 10 to 300%, 10 to 400%, 10 to 50%, 10 to 60%, 10 to 70%, 10 to 100%, 10 to 200%, 10 to 200%, 10 to 300%, 10 to 400%, 10 to 50%, 10 to 60%, 10 to 7 ...300%, 10 to 400%, 10 to 50%, 10 to 60%, 10 to 70%, 10 to 200%, 10 to 300%, 10 to 400%, 10 to 50%, 10 to 60%, 10 to 70%, 10 to The void fraction or porosity may comprise 0-80% by volume, 10-90% by volume, 10-95% by volume, 20-60% by volume, 20-70% by volume, 20-80% by volume, 20-90% by volume, 20-95% by volume, 30-70% by volume, 30-80% by volume, 30-90% by volume, 30-95% by volume, 40-80% by volume, 40-90% by volume, 40-95% by volume, 50-90% by volume, 50-95% by volume, 60-95% by volume, 70-80% by volume, 70-90% by volume, 70-95% by volume, 80-90% by volume, 80-95% by volume, or any exemplary value within these exemplary ranges.

[0022] In certain embodiments, the thermoplastic material of the porous core layer 105 may include virgin and / or recycled polyolefin and / or non-polyolefin materials. For example, the thermoplastic material of the core layer 105 may include one or more of virgin and / or recycled polyolefins (e.g., one or more of polyethylene, polypropylene, etc.), polystyrene, acrylonitrile styrene, butadiene, polyethylene terephthalate, polybutylene terephthalate, polybutylene tetrachlorate, and plasticized and unplasticized polyvinyl chloride, as well as blends of these materials with each other or with other polymeric materials. Other suitable thermoplastic materials include, but are not limited to, polyarylene ethers, polycarbonates, polyester carbonates, thermoplastic polyesters, polyimides, polyetherimides, polyamides, copolyamides, acrylonitrile-butyl acrylate-styrene polymers, amorphous nylons, polyarylene ether ketones, polyphenylene sulfides, polyarylsulfones, polyethersulfones, liquid crystal polymers, poly(1,4 phenylene) compounds commercially known as PARMAX®, high-heat polycarbonates such as Bayer's APEC® PC, high-temperature nylons, and silicones, as well as copolymers, alloys, and blends of these materials with each other or with other polymeric materials. The thermoplastic material used to form the core layer 105 can be used in powder, resin, rosin, particle, fiber, or other suitable form. Exemplary thermoplastic materials in various forms are described herein and also in, for example, U.S. Patent Application Publication No. 20130244528 and U.S. Patent Application Publication No. 20120065283. The exact amount of thermoplastic material present in the core layer can vary, with exemplary amounts ranging from about 20% to about 80% by weight, e.g., 30-70% by weight or 35-65% by weight, based on the total weight of the core layer 105. Those skilled in the art will recognize that the weight percentages of all materials used in the core layer 105 add up to 100% by weight. The thermoplastic material in the core layer 105 may include only virgin materials, only recycled materials, or a combination of virgin and recycled materials.When a combination of virgin and recycled thermoplastic materials is used, the recycled material may be chemically the same or different from the virgin material. If the recycled material is chemically the same as the virgin material, it may be physically different from the virgin material; for example, the recycled material may have a different color, particle size, shape, average glass transition temperature, crystallinity, or other physical property than the virgin thermoplastic material, even though the virgin and recycled thermoplastic materials share the same underlying chemical structure.

[0023] In certain configurations, the recycled polymer fibers in the porous core layer 105 may comprise one, two, three, or more polymer materials. For example, the recycled polymer fibers in the core layer 105 may comprise one or more of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled nylon fibers, recycled copolyamide fibers, recycled high-density polyethylene fibers, glass fibers coated with recycled polymer materials, and combinations thereof. In some configurations, the fibers may comprise recycled glass fibers, for example, glass fibers that have been recycled and / or reclaimed through optional physical and / or chemical treatments before reuse. The dimensions of the different recycled polymer fibers may be the same or different. For example, the recycled polymer fibers in the core layer 105 may have a diameter greater than about 5 μm, more specifically, between about 5 μm and about 22 μm, and a length between about 5 mm and about 200 mm. More specifically, the fiber diameter may be between about 2 μm and about 22 μm, and the fiber length may be between about 5 mm and about 75 mm. The recycled polymer fibers in the core layer 105 may be twisted as a result of the fiber manufacturing process, or may be present as single recycled polymer fibers that are untwisted and generally do not cross or intersect with other recycled polymer fibers. The recycled polymer fibers in the core layer 105, when present in the porous core layer 105, are typically randomly oriented; however, if desired, the recycled polymer fibers in the core layer 105 can be oriented in any suitable direction, such as at 0 degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, 75 degrees, or 90 degrees relative to the machine direction used to manufacture the thermoplastic composite article. The recycled polymer fiber content in the porous core layer 105 can vary from about 5% to about 90% by weight, more specifically, from about 5% to about 80% by weight, e.g., from about 5 to 10%, 5 to 20%, 5 to 30%, 5 to 40%, 5 to 50%, or from about 20% to about 80% by weight, or other amounts. Depending on whether non-recycled polymeric fibers are also present in the core layer 105, the exact amount of recycled polymeric fibers in the core layer 105 may be as little or as much as desired.

[0024] In certain embodiments, the porous core layer 105 can also include reinforcing fibers that are non-regenerated polymer fibers, or non-regenerated polymer fibers, such as inorganic fibers, virgin polymer fibers, etc. For example, the non-regenerated reinforcing fibers in the core layer 105 can include glass fibers, carbon fibers, graphite fibers, synthetic organic fibers, particularly high-modulus organic fibers such as para-aramid and meta-aramid fibers, nylon fibers, polyester fibers, natural fibers, cellulose fibers, high melt flow index (MFI) resins suitable for use as fibers (e.g., 100 g / 10 min MFI, 325 g / 10 min MFI or higher), mineral fibers such as basalt, mineral wool (e.g., rock wool or slag wool), wollastonite, alumina silica, or mixtures thereof, metal fibers, metallized natural and / or synthetic fibers, ceramic fibers, spun fibers, or mixtures thereof. In some configurations, the fibers can include recycled glass fibers, e.g., glass fibers that have been recycled and / or reclaimed by optional physical and / or chemical treatment before reuse. In certain embodiments, the fibers used may be cellulose-free to avoid or reduce the possibility of mold and other microorganisms. In some embodiments, the fibers in the core layer 105 may be bicomponent fibers, such as core-sheath fibers, as described, for example, in U.S. Patent Application Publication No. 20180162107, published June 14, 2018. In some embodiments, any of the aforementioned fibers may be chemically treated prior to use to impart desired functional groups or other physical properties to the fibers, which may be chemically treated to enable reaction with thermoplastic materials, recycled polymer fibers, or both. The non-recycled polymer fiber content in the core layer may vary from about 10% to about 90% by weight of the core layer, more specifically, from about 20% to about 80% by weight of the core layer 105, e.g., from about 30% to about 70% by weight. The particular size and / or orientation of the fibers used may depend, at least in part, on the thermoplastic material used and / or the desired properties of the core layer 105. For example, the reinforcing fibers may be randomly oriented or may have a particular selected orientation, as desired.In one non-limiting example, the reinforcing fibers dispersed within the thermoplastic material and optional other additives to provide the core layer can generally have a diameter greater than about 5 μm, more specifically, from about 5 μm to about 22 μm, and a length of from about 5 mm to about 200 mm; more specifically, the fiber diameter can be from about 2 μm to about 22 μm, and the fiber length can be from about 5 mm to about 75 mm. When the reinforcing fibers are present in combination with recycled polymer fibers, the total fiber content in the core layer 105 can vary from about 10% to about 90% by weight of the core layer, more specifically, from about 20% to about 80% by weight of the core layer, such as from about 30% to about 70% by weight of the core layer 105.

[0025] In some embodiments, the core layer may include only recycled thermoplastic materials (no virgin thermoplastic materials) and only recycled fibers (no virgin fibers). Such articles meet sustainability requirements by including a significant amount of recycled thermoplastic fibers and recycled polymer fibers. In other embodiments, described below, the core layer may include multiple core layers laminated together, with one or more layers including recycled thermoplastic materials and recycled fibers and one or more layers including virgin thermoplastic materials and virgin fibers.

[0026] In certain configurations, one or more biomaterials, which may be present in particulate form, fiber form, or both, may be present along with the regenerated fibers. For example, the biomaterials may be made from one or more of rice husks, coconut shells, coffee husks, wheat husks, corn husks, wood flour, coffee bean grounds, plant by-products, and combinations thereof. In some embodiments, the bioparticles may be made from one or more of rice husks, coconut shells, coffee husks, wheat husks, corn husks, wood flour, coffee bean grounds, plant by-products, and combinations thereof. In other embodiments, the biofabric may be made from one or more of rice husks, coconut shells, coffee husks, wheat husks, corn husks, wood flour, coffee bean grounds, plant by-products, and combinations thereof. In other embodiments, the biomaterials may be made from eggshells, animal hair, animal bones, animal fat, animal meat, animal collagen, or other animal products and by-products, and combinations thereof. In some embodiments, the bioparticles can be made from eggshells, animal hair (wool, hair), insect secretions (e.g., silk), animal bones, animal fat, animal flesh, animal collagen, or other animal products and by-products, and combinations thereof. In other embodiments, the biofabric can be made from one or more of eggshells, seashells, crab shells, shrimp shells, fish shells, animal hair, animal bones, animal fat, animal flesh, animal collagen, or other animal products and by-products, and combinations thereof. In some examples, the biomaterial can be made from non-plant and non-animal products and by-products, including insects, fungi, arthropods, nematodes, and combinations thereof. For example, the bioparticles can be made from non-plant and non-animal products and by-products, including insects, fungi, arthropods, nematodes, and combinations thereof. In certain examples, the biofabric can be made from non-plant and non-animal products and by-products, including insects, fungi, arthropods, nematodes, and combinations thereof. As described herein, the biomaterial may exist as a fibrous biomaterial, a particulate biomaterial, a powder biomaterial, or may take other forms.

[0027] In some embodiments, other additives or materials may be present in the core layer 105. Such additives may be virgin or recycled additives. For example, lofting agents, flame retardants, colorants, smoke suppressants, surfactants, foams, or other materials may be present. In some instances, the core layer 105 may be a substantially halogen-free core layer or a halogen-free core layer to meet the limits of hazardous substance requirements in certain applications. In other cases, the core layer may include a halogenated flame retardant, such as one or more of F, Cl, Br, I, and At, or a compound containing such a halogen, such as tetrabromobisphenol A polycarbonate, or a monohalo-polycarbonate, dihalo-polycarbonate, trihalo-polycarbonate, or tetrahalo-polycarbonate. In some cases, the thermoplastic material used in the core layer 105 may include one or more halogens to provide a degree of flame retardancy without the addition of other flame retardants. When a halogenated flame retardant is present, it is desirable that it be present in a flame retardant amount that can vary depending on the other components present. For example, the halogenated flame retardant may be present in an amount of about 0.1% to about 15% by weight (based on the weight of the core layer), more specifically about 1% to about 15% by weight, e.g., about 5% to about 15% by weight, based on the weight of the core layer. If desired, two different halogenated flame retardants may be added to the layer. In other cases, a non-halogenated flame retardant may be added, such as a flame retardant containing one or more of N, P, As, Sb, Bi, S, Se, and Te. In some embodiments, the non-halogenated flame retardant may include a phosphide material, thereby making the layer more environmentally friendly. When a non-halogenated or substantially halogen-free flame retardant is present, it is desirable that it be present in a flame retardant amount that can vary depending on the other components present. For example, the substantially halogen-free flame retardant may be present at about 0.1% to about 15% by weight (based on the weight of the layer), more specifically about 1% to about 15% by weight, e.g., about 5% to about 15% by weight, based on the weight of the core layer.If desired, two different substantially halogen-free flame retardants can be added to one or more of the core layers described herein. In certain cases, one or more of the core layers described herein may include one or more halogenated flame retardants in combination with one or more substantially halogen-free flame retardants. When two different flame retardants are present, the combination of the two flame retardants may be present in a flame retardant amount that can vary depending on the other components present. For example, the total weight of the flame retardants present may be from about 0.1% to about 20% by weight (based on the weight of the layer), more specifically, from about 1% to about 15% by weight, e.g., from about 2% to about 14% by weight, based on the weight of the core layer. The flame retardants used in the layers described herein can be added to a mixture containing the thermoplastic material and fibers (before processing the mixture onto a wire mesh or other processing component) or can be added after the core layer 105 is formed. In some examples, the flame retardant material may include one or more of an expandable graphite material, magnesium hydroxide (MDH), and aluminum hydroxide (ATH).

[0028] In some embodiments, the lofting ability of the core layer 105 can be adjusted by including one or more added lofting agents in the core layer 105. The exact type of lofting agent used in the core layer 105 can depend on many factors, including, for example, the desired lofting temperature, the desired degree of loft, etc. In some cases, a microsphere lofting agent, such as expandable microspheres, can be used, which can increase in size under exposure to convection heating. Exemplary commercially available lofting agents are available, for example, from Kureha Corporation (Japan). In other examples, the lofting agent can be an expandable graphite material, or a combination of a microsphere lofting agent and a non-microsphere lofting agent.

[0029] In some configurations, the fiber-reinforced thermoplastic composite article 200 may include a porous core layer 105 in combination with a skin layer 210, as shown in FIG. 2 . The skin layer 210 may comprise a single layer of material or multiple layers of different materials, as desired. In some embodiments, the skin layer 210 may comprise, for example, a film (e.g., a thermoplastic film or an elastomeric film), a flim, a scrim (e.g., a fiber-based scrim), a foil, a woven fabric, a nonwoven fabric, or may be present as an inorganic coating, an organic coating, or a thermoset coating disposed on the core layer 105. In some examples, the skin layer 210 may comprise natural fibers, polymeric fibers, recycled polymeric fibers, biomaterials, or other materials described herein. In other cases, the skin layer 210 may include a limiting oxygen index of greater than about 22, measured according to ISO 4589, dated 1996. When a thermoplastic film is present as the skin layer 210 (or as part of the skin layer 210), the thermoplastic film may comprise at least one of poly(etherimide), poly(etherketone), poly(ether-etherketone), poly(phenylene sulfide), poly(arylene sulfone), poly(ether sulfone), poly(amide-imide), poly(1,4-phenylene), polycarbonate, nylon, and silicone. The film may comprise virgin material, recycled material, or both. When a fiber-based scrim is present as the skin layer 210 (or as part of the skin layer 210), the fiber-based scrim may comprise at least one of glass fiber, aramid fiber, graphite fiber, carbon fiber, inorganic mineral fiber, metal fiber, metallized synthetic fiber, and metallized inorganic fiber. The fiber-based scrim may comprise virgin material, recycled material, or both. When a thermoset coating is present as (or as part of) skin layer 210, the coating may comprise at least one of unsaturated polyurethane, vinyl ester, phenolic, and epoxy. The thermoset coating may comprise virgin materials, recycled materials, or both.When an inorganic coating is present as the skin layer 210 (or as part of the skin layer 210), the inorganic coating may include a mineral containing a cation selected from Ca, Mg, Ba, Si, Zn, Ti, and Al, or may include at least one of gypsum, calcium carbonate, and mortar. The inorganic coating may include virgin material, recycled material, or both. When a nonwoven fabric is present as the skin layer 210 (or as part of the skin layer 210), the nonwoven fabric may include a thermoplastic material, a thermosetting binder, inorganic fibers, metal fibers, metallized inorganic fibers, and metallized synthetic fibers. The nonwoven fabric may include virgin material, recycled material, or both. In some configurations, the skin layer 210 may include recycled polymer fibers that are also present in the core layer 105. For example, certain recycled polymer fibers in the core layer 105 may be the same as the recycled polymer fibers in the skin layer 210. When the skin layer 210 includes recycled polymer fibers, the recycled polymer fibers in the skin layer 210 may include one or more of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled nylon fibers, recycled copolyamide fibers, recycled high-density polyethylene fibers, and combinations thereof. In some configurations, the fibers may include recycled glass fibers, such as glass fibers that have been recycled and / or reclaimed through optional physical and / or chemical treatments prior to reuse. The exact amount of recycled polymer fibers in the skin layer 210 can vary from about 5% to about 90% by weight, more specifically from about 5% to about 80% by weight, such as from about 5% to 20%, 5% to 30%, 5% to 40%, 5% to 50%, 5% to 60%, 10% to 60%, 10% to 50%, 20% to 50%, 20% to 40%, or from about 20% to about 80% by weight, or other amounts.

[0030] In some embodiments, an adhesive layer (not shown) may be present between the skin layer 210 and the core layer 105. If an adhesive is desired, one or more thermoplastic polymer adhesives may be used. For example, it may be desirable to bond the skin layer 210 to the core layer 105 using an adhesive. In some instances, the thermoplastic component of the adhesive layer may include a thermoplastic polymer such as, for example, a polyamide, a copolyamide, or a polyolefin such as polyethylene or polypropylene. The thermoplastic component of the adhesive layer may optionally include recycled thermoplastic materials. In other cases, the thermoplastic polymer of the adhesive layer may include polystyrene, acrylonitrile styrene, butadiene, polyethylene terephthalate, polybutylene terephthalate, polybutylene tetrachlorate, and plasticized and unplasticized polyvinyl chloride, as well as blends of these materials with each other or with other polymeric materials. Other suitable thermoplastic polymers for use in the adhesive layer include, but are not limited to, polyarylene ethers, polycarbonates, polyester carbonates, thermoplastic polyesters, polyimides, polyetherimides, polyamides, acrylonitrile-butyl acrylate-styrene polymers, amorphous nylons, polyarylene ether ketones, polyphenylene sulfides, polyarylsulfones, polyethersulfones, liquid crystal polymers, poly(1,4-phenylene) compounds commercially known as PARMAX®, high-heat polycarbonates such as Bayer's APEC® PC, high-temperature nylons, and silicones, as well as alloys and blends of these materials with each other or with other polymeric materials. If desired, the adhesive can also include any thermosetting material, including, but not limited to, epoxides, epoxy resins, polyesters, polyester resins, urethanes, polyurethanes, diallyl phthalates, polyamides, cyanate esters, polycyanurates, and combinations thereof. In certain embodiments, the adhesive may also include recycled materials and / or regenerated fibers, if desired.

[0031] In other configurations, a fiber-reinforced thermoplastic composite article 300 may include a porous core layer 105 combined with a skin layer 210 and a skin layer 320, as shown in FIG. 3 . The skin layers 210, 320 may be the same or different. In certain embodiments, the skin layers 210, 320 may have a common material but different thicknesses or porosities. In some configurations, at least one of the skin layers 210, 320 includes natural fibers, biomaterials, or recycled polymer fibers. In other configurations, each of the skin layers 210, 320 includes natural fibers or recycled polymer fibers. Optionally, at least one of the skin layers 210, 320 may include both natural fibers and recycled polymer fibers. In some cases, one or both of the skin layers may include recycled thermoplastic materials.

[0032] In certain embodiments, the skin layer 320 may comprise a single layer of material or multiple layers of different materials, as desired. In some embodiments, the skin layer 320 may comprise, for example, a film (e.g., a thermoplastic film or an elastomeric film), a flim, a scrim (e.g., a fiber-based scrim), a foil, a woven fabric, a nonwoven fabric, or may be present as an inorganic coating, an organic coating, or a thermoset coating disposed on the core layer 105. In some examples, the skin layer 320 may comprise natural fibers, polymeric fibers, recycled polymeric fibers, or other materials described herein. In other cases, the skin layer 320 may comprise a limiting oxygen index of greater than about 22, measured according to ISO 4589, dated 1996. If a thermoplastic film is present as the skin layer 320 (or as part of the skin layer 320), the thermoplastic film may comprise at least one of poly(etherimide), poly(etherketone), poly(ether-etherketone), poly(phenylene sulfide), poly(arylene sulfone), poly(ether sulfone), poly(amide-imide), poly(1,4-phenylene), polycarbonate, nylon, and silicone. The film may comprise virgin material, recycled material, or both. If a fiber-based scrim is present as the skin layer 320 (or as part of the skin layer 320), the fiber-based scrim may comprise at least one of glass fiber, aramid fiber, graphite fiber, carbon fiber, inorganic mineral fiber, metal fiber, metallized synthetic fiber, and metallized inorganic fiber. The fiber-based scrim may comprise virgin material, recycled material, or both. When a thermoset coating is present as (or as part of) the skin layer 320, the coating may comprise at least one of an unsaturated polyurethane, a vinyl ester, a phenolic, and an epoxy. The thermoset coating may comprise virgin materials, recycled materials, or both.When an inorganic coating is present as the skin layer 320 (or as part of the skin layer 320), the inorganic coating may include a mineral containing a cation selected from Ca, Mg, Ba, Si, Zn, Ti, and Al, or may include at least one of gypsum, calcium carbonate, and mortar. The inorganic coating may include virgin materials, recycled materials, or both. When a nonwoven fabric is present as the skin layer 320 (or as part of the skin layer 320), the nonwoven fabric may include thermoplastic materials, thermosetting binders, inorganic fibers, metal fibers, metallized inorganic fibers, and metallized synthetic fibers. The nonwoven fabric may include virgin materials, recycled materials, or both. In some configurations, the skin layer 320 may include recycled polymer fibers that are also present in the core layer 105. For example, certain recycled polymer fibers in the core layer 105 may be the same as the recycled polymer fibers in the skin layer 320. When the skin layer 320 includes recycled polymer fibers, the recycled polymer fibers in the skin layer 320 may include one or more of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled copolyamide fibers, recycled high density polyethylene fibers, and combinations thereof.

[0033] In certain embodiments, an adhesive layer (not shown) may be present between the skin layer 320 and the core layer 105. The adhesive layer may optionally include recycled thermoplastic material. If an adhesive is desired, one or more thermoplastic polymer adhesives may be used. For example, it may be desirable to bond the skin layer 320 to the core layer 105 using an adhesive. In some instances, the thermoplastic component of the adhesive layer may include a thermoplastic polymer such as, for example, a polyamide, a copolyamide, or a polyolefin such as polyethylene or polypropylene. In other cases, the thermoplastic polymer of the adhesive layer may include polystyrene, acrylonitrile styrene, butadiene, polyethylene terephthalate, polybutylene terephthalate, polybutylene tetrachlorate, and plasticized and unplasticized polyvinyl chloride, as well as blends of these materials with each other or with other polymeric materials. Other suitable thermoplastic polymers for use in the adhesive layer include, but are not limited to, polyarylene ethers, polycarbonates, polyester carbonates, thermoplastic polyesters, polyimides, polyetherimides, polyamides, acrylonitrile-butyl acrylate-styrene polymers, amorphous nylons, polyarylene ether ketones, polyphenylene sulfides, polyarylsulfones, polyethersulfones, liquid crystal polymers, poly(1,4 phenylene) compounds commercially known as PARMAX®, high-heat polycarbonates such as Bayer's APEC® PC, high-temperature nylons, and silicones, as well as alloys and blends of these materials with each other or with other polymeric materials. Optionally, the adhesive can also include any thermosetting material, including, but not limited to, epoxides, epoxy resins, polyesters, polyester resins, urethanes, polyurethanes, diallyl phthalates, polyamides, cyanate esters, polycyanurates, and combinations thereof.

[0034] In certain configurations, a fiber-reinforced thermoplastic composite article 400 may include a porous core layer 105 in combination with a skin layer 210 and a decorative layer 430, as shown in FIG. 4 . The decorative layer 430 may be disposed directly on the porous core layer 105, or, if desired, a skin layer may be present between the decorative layer 430 and the porous core layer 105. In certain embodiments, the decorative layer 430 may be formed from a thermoplastic film, such as polyvinyl chloride, polyolefin, thermoplastic polyester, thermoplastic elastomer, paper, or the like. The film may include virgin materials, recycled materials, or both. The decorative layer 430 may also have a multi-layer structure, if desired. For example, fabrics, such as woven fabrics made from natural and synthetic fibers, organic fiber nonwoven fabrics after needlepunching or other processes, raised fabrics, knitted products, flocked fabrics, or other such materials, can be bonded to the foam core (or other structure). Fabrics can also be bonded with thermoplastic adhesives, including pressure-sensitive and hot-melt adhesives, such as polyamides, modified polyolefins, urethanes, polyolefins, and the like. The decorative layer 430 can also be manufactured using a spunbond, thermal bond, spunlace, meltblown, wetlaid, and / or drylaid process. In some embodiments, the decorative layer 430 can be embossed, textured, or have some pattern or granular structure. Optionally, the decorative layer can include recycled fibers, biomaterials, recycled thermoplastic materials, or other materials.

[0035] In some embodiments, an adhesive layer (not shown) may be present between the decorative layer 430 and the core layer 105. If an adhesive is desired, one or more thermoplastic polymer adhesives may be used. For example, it may be desirable to bond the decorative layer 430 to the core layer 105 using an adhesive. In some instances, the thermoplastic component of the adhesive layer may include a thermoplastic polymer such as, for example, a polyamide, a copolyamide, or a polyolefin such as polyethylene or polypropylene. The adhesive layer may also include recycled thermoplastic materials, if desired. In other cases, the thermoplastic polymer of the adhesive layer may include polystyrene, acrylonitrile styrene, butadiene, polyethylene terephthalate, polybutylene terephthalate, polybutylene tetrachlorate, and plasticized and unplasticized polyvinyl chloride, as well as blends of these materials with each other or with other polymeric materials. Other suitable thermoplastic polymers for use in the adhesive layer include, but are not limited to, polyarylene ethers, polycarbonates, polyester carbonates, thermoplastic polyesters, polyimides, polyetherimides, polyamides, acrylonitrile-butyl acrylate-styrene polymers, amorphous nylons, polyarylene ether ketones, polyphenylene sulfides, polyarylsulfones, polyethersulfones, liquid crystal polymers, poly(1,4 phenylene) compounds commercially known as PARMAX®, high-heat polycarbonates such as Bayer's APEC® PC, high-temperature nylons, and silicones, as well as alloys and blends of these materials with each other or with other polymeric materials. Optionally, the adhesive can also include any thermosetting material, including, but not limited to, epoxides, epoxy resins, polyesters, polyester resins, urethanes, polyurethanes, diallyl phthalates, polyamides, cyanate esters, polycyanurates, and combinations thereof.

[0036] In other embodiments, a fiber-reinforced thermoplastic composite article may include a porous core layer that does not contain any recycled polymer fibers in combination with a skin layer that includes recycled polymer fibers. Figure 5 shows a thermoplastic composite article 500 including a skin layer 550 on a porous core layer 505. The porous core layer 505 includes an open-cell structured web that includes random intersections of a plurality of non-recycled polymer fibers held together by a thermoplastic material. The core layer 505 is typically porous, for example, having a porosity that can vary from less than 0% to about 95%. For example, the porous core layer 505 may have a density of 0 to 30%, 10 to 40%, 20 to 50%, 30 to 60%, 40 to 70%, 50 to 80%, 60 to 90%, 0 to 40%, 0 to 50%, 0 to 60%, 0 to 70%, 0 to 80%, 0 to 90%, 10 to 50%, 10 to 60%, 10 to 70%, 10 to 80%, 10 to 90%, 10 to 95%, 20 to 60%, 20 to 70%, 20 to 80%, 20 to 90%, 20 to 95%, 30 to 70%, 30 to 80%, 30 to 90%, 30 to 95%, 40 to 80%, 40 to 90%, 40 to 95%, 50 to 90%, 50 to 95%, 60 to 95% It may include a void fraction or porosity of 70-80%, 70-90%, 70-95%, 80-90%, 80-95%, or any exemplary value within these exemplary ranges.

[0037] In certain embodiments, the thermoplastic material of the porous core layer 505 may include polyolefin and / or non-polyolefin materials, which may be virgin thermoplastic materials, recycled thermoplastic materials, or both. For example, the thermoplastic material of core layer 505 may include one or more of polyolefins (e.g., one or more of polyethylene, polypropylene, etc.), polystyrene, acrylonitrile styrene, butadiene, polyethylene terephthalate, polybutylene terephthalate, polybutylene tetrachlorate, and plasticized and unplasticized polyvinyl chloride, as well as blends of these materials with each other or with other polymeric materials. Other suitable thermoplastic materials include, but are not limited to, polyarylene ethers, polycarbonates, polyester carbonates, thermoplastic polyesters, polyimides, polyetherimides, polyamides, copolyamides, acrylonitrile-butyl acrylate-styrene polymers, amorphous nylons, polyarylene ether ketones, polyphenylene sulfides, polyarylsulfones, polyethersulfones, liquid crystal polymers, poly(1,4 phenylene) compounds commercially known as PARMAX®, high-heat polycarbonates such as Bayer's APEC® PC, high-temperature nylons, and silicones, as well as copolymers, alloys, and blends of these materials with each other or with other polymeric materials. The thermoplastic material used to form the core layer 505 can be used in powder, resin, rosin, particle, fiber, or other suitable form. Exemplary thermoplastic materials in various forms are described herein and also in, for example, U.S. Patent Application Publication Nos. 20130244528 and 20120065283. The exact amount of thermoplastic material present in core layer 505 can vary, with exemplary amounts ranging from about 20% to about 80% by weight, e.g., 30-70% by weight or 35-65% by weight, based on the total weight of core layer 505. One of ordinary skill in the art will recognize that the weight percentages of all materials used in core layer 505 add up to 100% by weight. The thermoplastic material may include only virgin materials, only recycled materials, or a combination of virgin and recycled materials.When a combination of virgin and recycled thermoplastic materials is used, the recycled material may be chemically the same or different from the virgin material. If the recycled material is chemically the same as the virgin material, it may be physically different from the virgin material; for example, the recycled material may have a different color, particle size, shape, average glass transition temperature, crystallinity, or other physical property than the virgin thermoplastic material, even though the virgin and recycled thermoplastic materials share the same underlying chemical structure.

[0038] In certain embodiments, the porous core layer 505 may include non-regenerated polymer fibers or reinforcing fibers that are non-regenerated polymer fibers, such as inorganic fibers, virgin polymer fibers, etc. As noted herein, the core layer 505 does not include recycled polymer fibers. For example, the non-regenerated reinforcing fibers in the core layer 505 may include glass fibers, carbon fibers, graphite fibers, synthetic organic fibers, particularly high-modulus organic fibers such as para-aramid and meta-aramid fibers, nylon fibers, polyester fibers, natural fibers, high melt flow index resins suitable for use as fibers (e.g., 100 g / 10 min MFI or greater), mineral fibers such as basalt, mineral wool (e.g., rock wool or slag wool), wollastonite, alumina silica, or mixtures thereof, metal fibers, metallized natural and / or synthetic fibers, ceramic fibers, spun fibers, or mixtures thereof. In some configurations, the fibers may include recycled glass fibers, e.g., glass fibers that have been recycled and / or reclaimed through optional physical and / or chemical treatments before reuse. In certain embodiments, the fibers used may be cellulose-free to avoid or reduce the possibility of mold and other microorganisms. In some embodiments, the fibers in the core layer 505 may be bicomponent fibers, such as core-sheath fibers, as described, for example, in U.S. Patent Application Publication No. 20180162107, published June 14, 2018. In some embodiments, any of the aforementioned fibers may be chemically treated prior to use to impart desired functional groups or other physical properties to the fibers, which may be chemically treated to enable reaction with thermoplastic materials, recycled polymer fibers, or both. The reinforcing fiber content in the core layer 505 may vary from about 10% to about 90% by weight of the core layer, more specifically, from about 20% to about 80% by weight of the core layer 505, e.g., from about 30% to about 70% by weight. The particular size and / or orientation of the fibers used may depend, at least in part, on the thermoplastic material used and / or the desired properties of the core layer 505. For example, the reinforcing fibers may be randomly oriented or may have a particular selected orientation, as desired.In one non-limiting example, the reinforcing fibers dispersed within the thermoplastic material and optional other additives to provide the core layer can generally have a diameter greater than about 5 μm, more specifically, from about 5 μm to about 22 μm, and a length of from about 5 mm to about 200 mm; more specifically, the fiber diameter can be from about 2 μm to about 22 μm, and the fiber length can be from about 5 mm to about 75 mm. When the reinforcing fibers are present in combination with recycled polymer fibers, the total fiber content in the core layer 505 can vary from about 10% to about 90% by weight of the core layer, more specifically, from about 20% to about 80% by weight of the core layer 505, such as from about 30% to about 70% by weight.

[0039] In some embodiments, other additives or materials may be present in the core layer 505. For example, lofting agents, flame retardants, colorants, smoke suppressants, surfactants, foams, or other materials may be present. In some instances, the core layer 505 may be a substantially halogen-free core layer or a halogen-free core layer to meet the limits of hazardous substance requirements in certain applications. In other cases, the core layer may include a halogenated flame retardant, such as one or more of F, Cl, Br, I, and At, or a compound containing such a halogen, such as tetrabromobisphenol A polycarbonate, or a monohalo-, dihalo-, trihalo-, or tetrahalo-polycarbonate. In some cases, the thermoplastic material used in the core layer 505 may include one or more halogens to impart a degree of flame retardancy without the addition of other flame retardants. When a halogenated flame retardant is present, it is desirable that the flame retardant be present in a flame retardant amount, which may vary depending on the other components present. For example, the halogenated flame retardant may be present in an amount of about 0.1% to about 15% by weight (based on the weight of the core layer 505), more specifically, about 1% to about 15% by weight, e.g., about 5% to about 15% by weight, based on the weight of the core layer 505. If desired, two different halogenated flame retardants may be added to the layer. In other cases, a non-halogenated flame retardant may be added, such as a flame retardant containing one or more of N, P, As, Sb, Bi, S, Se, and Te. In some embodiments, the non-halogenated flame retardant may include a phosphide material, thereby making the layer more environmentally friendly. When a non-halogenated or substantially halogen-free flame retardant is present, it is desirable that the flame retardant be present in a flame retardant amount that can vary depending on the other components present. For example, the substantially halogen-free flame retardant may be present at about 0.1% to about 15% by weight (based on the weight of layer 505), more specifically about 1% to about 15% by weight, e.g., about 5% to about 15% by weight, based on the weight of core layer 505. If desired, two different substantially halogen-free flame retardants can be added to one or more of the core layers described herein.In certain cases, one or more of the core layers described herein may include one or more halogenated flame retardants in combination with one or more substantially halogen-free flame retardants. When two different flame retardants are present, the combination of the two flame retardants may be present in a flame retardant amount that can vary depending on the other components present. For example, the total weight of the flame retardants present may be from about 0.1% to about 20% by weight (based on the weight of the layer 505), more specifically, from about 1% to about 15% by weight, e.g., from about 2% to about 14% by weight, based on the weight of the core layer 505. The flame retardants used in the layers described herein may be added to a mixture containing the thermoplastic material and fibers (before processing the mixture onto a wire mesh or other processing component) or may be added after the core layer 505 is formed. In some examples, the flame retardant material may include one or more of expandable graphite material, magnesium hydroxide (MDH), and aluminum hydroxide (ATH).

[0040] In some embodiments, the lofting ability of the core layer 505 can be adjusted by including one or more added lofting agents in the core layer 505. The exact type of lofting agent used in the core layer 505 can depend on many factors, including, for example, the desired lofting temperature, the desired degree of loft, etc. In some cases, a microsphere lofting agent, e.g., expandable microspheres, can be used, which can increase in size under exposure to convection heating. Exemplary commercially available lofting agents are available, for example, from Kureha Corporation (Japan). In other examples, the lofting agent in the core layer 505 can be an expandable graphite material, or a combination of a microsphere lofting agent and a non-microsphere lofting agent.

[0041] In certain configurations, the skin layer 550 on the core layer 505 may include a plurality of recycled polymer fibers and / or biomaterials. For example, the recycled polymer fibers in the skin layer 505 may include one or more of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled copolyamide fibers, recycled high-density polyethylene fibers, and combinations thereof. The exact amount of recycled polymer fibers in the skin layer 550 can vary from about 5% to about 90% by weight, more specifically, from about 5% to about 80% by weight, such as from about 5% to 20%, 5% to 30%, 5% to 40%, 5% to 50%, 5% to 60%, 10% to 60%, 10% to 50%, 20% to 50%, 20% to 40%, or from about 20% to about 80% by weight, or other amounts. Fibers other than recycled polymer fibers can also be present in the skin layer 550. For example, the skin layer 550 may be configured as a fiber-based scrim that may include recycled polymer fibers, optionally in combination with non-recycled polymer fibers. In certain embodiments, the skin layer 550 including recycled polymer fibers may include one or more of a film (e.g., a thermoplastic film or an elastomeric film), a flim, a scrim (e.g., a fiber-based scrim), a foil, a woven fabric, a nonwoven fabric, or may be present as an inorganic coating, an organic coating, or a thermoset coating disposed on the core layer 505. In some examples, the skin layer 550 may include natural fibers, polymer fibers, or other materials described herein. In other cases, the skin layer 550 may include a limiting oxygen index of greater than about 22, measured according to ISO 4589, dated 1996. If a thermoplastic film is present as part of skin layer 550, the thermoplastic film may comprise at least one of poly(etherimide), poly(etherketone), poly(ether-etherketone), poly(phenylene sulfide), poly(arylene sulfone), poly(ether sulfone), poly(amide-imide), poly(1,4-phenylene), polycarbonate, nylon, and silicone.If a fibrous scrim is present as (or as part of) the skin layer 550, the fibrous scrim may comprise at least one of glass fibers, aramid fibers, graphite fibers, carbon fibers, inorganic mineral fibers, metal fibers, metallized synthetic fibers, and metallized inorganic fibers. If a thermosetting coating is present as part of the skin layer 550, the coating may comprise at least one of unsaturated polyurethane, vinyl ester, phenolic, and epoxy. If an inorganic coating is present as part of the skin layer 550, the inorganic coating may comprise a mineral containing a cation selected from Ca, Mg, Ba, Si, Zn, Ti, and Al, or may comprise at least one of gypsum, calcium carbonate, and mortar. If a nonwoven fabric is present as (or as part of) the skin layer 550, the nonwoven fabric may comprise a thermoplastic material, a thermosetting binder, inorganic fibers, metal fibers, metallized inorganic fibers, and metallized synthetic fibers.

[0042] In certain configurations, an optional adhesive layer (not shown) may be present between the skin layer 550 and the core layer 505. If an adhesive is desired, one or more thermoplastic polymer adhesives may be used. For example, it may be desirable to bond the skin layer 550 to the core layer 505 using an adhesive. In some instances, the thermoplastic component of the adhesive layer may include a thermoplastic polymer (which may be virgin or recycled), such as, for example, a polyamide, a copolyamide, or a polyolefin such as polyethylene or polypropylene. In other cases, the thermoplastic polymer of the adhesive layer may include polystyrene, acrylonitrile styrene, butadiene, polyethylene terephthalate, polybutylene terephthalate, polybutylene tetrachlorate, and plasticized and unplasticized polyvinyl chloride, as well as blends of these materials with each other or with other polymeric materials. Other suitable thermoplastic polymers for use in the adhesive layer include, but are not limited to, polyarylene ethers, polycarbonates, polyester carbonates, thermoplastic polyesters, polyimides, polyetherimides, polyamides, acrylonitrile-butyl acrylate-styrene polymers, amorphous nylons, polyarylene ether ketones, polyphenylene sulfides, polyarylsulfones, polyethersulfones, liquid crystal polymers, poly(1,4 phenylene) compounds commercially known as PARMAX®, high-heat polycarbonates such as Bayer's APEC® PC, high-temperature nylons, and silicones, as well as alloys and blends of these materials with each other or with other polymeric materials. Optionally, the adhesive can also include any thermosetting material, including, but not limited to, epoxides, epoxy resins, polyesters, polyester resins, urethanes, polyurethanes, diallyl phthalates, polyamides, cyanate esters, polycyanurates, and combinations thereof.

[0043] In certain embodiments, the core layer 505 and the skin layer 550 comprising recycled polymer fibers can be used in combination with the skin layer 320 to provide the composite article 600 shown in Figure 6. The skin layer 320 of Figure 6 may include any of the materials described herein with respect to the skin layer 320 shown in Figure 3. Additionally, an optional adhesive layer may be present between the skin layer 320 and the core layer 505, if desired. The adhesive layer may include any of the materials described herein with respect to the optional adhesive layer between the skin layer 550 and the core layer 505. In other embodiments, the core layer 505 and the skin layer 550 comprising recycled polymer fibers can be used in combination with a decorative layer 430 to provide the composite article 700 shown in Figure 7. The decorative layer 430 of Figure 7 may include any of the materials described herein with respect to the decorative layer 430 shown in Figure 4. Additionally, if desired, an optional adhesive layer may be present between the decorative layer 430 and the skin layer 550. The adhesive layer may include any of the materials described herein with respect to the optional adhesive layer between the skin layer 550 and the core layer 505.

[0044] In certain configurations, a porous core layer containing recycled polymer fibers can be bonded to a porous core layer that does not contain any recycled polymer fibers. A diagram of a thermoplastic composite article 800 containing a porous core layer 105 containing recycled polymer fibers and a porous core layer 505 that does not contain recycled polymer fibers is shown in FIG. 8. The porous core layers 105, 505 may each comprise any of the materials described herein with reference to FIGS. 1 and 5. If desired, an optional adhesive layer can be used to bond the porous core layer 105 to the porous core layer 505. For example, if an adhesive is used, one or more thermoplastic polymer adhesives can be used. For example, it may be desirable to bond the core layer 105 to the core layer 505 using an adhesive. In some instances, the thermoplastic component of the adhesive layer may comprise a thermoplastic polymer, such as a polyolefin, e.g., polyethylene or polypropylene. In other cases, the thermoplastic polymer of the adhesive layer may include polystyrene, acrylonitrile styrene, butadiene, polyethylene terephthalate, polybutylene terephthalate, polybutylene tetrachlorate, and plasticized and unplasticized polyvinyl chloride, as well as blends of these materials with each other or with other polymeric materials. Other suitable thermoplastic polymers for use in the adhesive layer include, but are not limited to, polyarylene ethers, polycarbonates, polyester carbonates, thermoplastic polyesters, polyimides, polyetherimides, polyamides, acrylonitrile-butyl acrylate-styrene polymers, amorphous nylons, polyarylene ether ketones, polyphenylene sulfides, polyarylsulfones, polyethersulfones, liquid crystalline polymers, poly(1,4 phenylene) compounds commercially known as PARMAX®, high heat polycarbonates such as Bayer's APEC® PC, high temperature nylons, and silicones, as well as alloys and blends of these materials with each other or with other polymeric materials.If desired, the adhesive may also include any thermosetting material, including, but not limited to, epoxides, epoxy resins, polyesters, polyester resins, urethanes, polyurethanes, diallyl phthalates, polyamides, cyanate esters, polycyanurates, and combinations thereof.

[0045] 8 may instead include similar fibers, such as virgin and / or recycled polymer fibers, but the thermoplastic materials of core layers 105, 505 may be different. For example, layer 505 may include recycled thermoplastic material and layer 105 may include virgin thermoplastic material (or vice versa). The fibers of layers 105, 505 may be the same or different, as desired. In certain configurations, the bonded core layers 105, 505 can be used in combination with a skin layer 210 (FIG. 9) to provide a thermoplastic composite article 900. The bonded core layers 105, 505 can be used in combination with a skin layer 320 (FIG. 10) to provide a thermoplastic composite article 1000. Both skin layers 210, 320 can be present to provide a composite article 1100 shown in FIG. 11. In other cases, the bonded core layers 105, 505 can be used with a decorative layer 430 to provide a composite article 1200 shown in FIG. 12. Another skin (not shown) can be disposed on the surface of the core layer 505 in FIG. 12.

[0046] 8 to 12, core layers 105 and 505 are different, but two or more core layers of the same type can be bonded together as needed. For example, two core layers each having the composition of core layer 105 can be bonded together. Alternatively, two core layers each having the composition of core layer 505 can be bonded together. In certain embodiments, a skin layer may be present between two different core layers. Referring to Figure 13, a composite article 1300 is shown that includes a skin layer 210 present between core layer 105 and core layer 505. As described herein, an optional adhesive layer may be present between any two of the components. Alternatively, skin layer 210 itself may function to bond core layer 105 to core layer 505.

[0047] In certain embodiments, when multiple core layers are used, one or more of the core layers may comprise a recycled thermoplastic material, as described herein. Optionally, each core layer may comprise a recycled thermoplastic material. In some embodiments, one of the core layers may comprise a recycled thermoplastic material in combination with recycled fibers, while another core layer may comprise a virgin thermoplastic material in combination with recycled fibers, non-recycled fibers, or both. In other embodiments, one of the core layers may comprise a recycled thermoplastic material in combination with non-recycled fibers, while another core layer may comprise a virgin thermoplastic material in combination with recycled fibers, non-recycled fibers, or both. Other variations are possible, in which at least one core layer comprises one or more of a recycled thermoplastic material, recycled fibers, and / or non-recycled fibers. While not required, a core layer comprising a virgin thermoplastic material may be positioned near the outer surface of the article, while a core layer comprising a recycled thermoplastic material may be positioned away from the outer surface of the article.

[0048] In certain embodiments, any one or more of the core layers described herein may be configured as (or used in) a glass mat thermoplastic composite (GMT) or a lightweight reinforced thermoplastic (LWRT). The areal density of such GMT or LWRT can range from about 200 grams per square meter (gsm) to about 4000 gsm of GMT or LWRT, although depending on the needs of a particular application, the areal density can be less than 200 gsm or greater than 4000 gsm. In some embodiments, the upper density limit can be less than 4000 gsm.

[0049] In certain examples, one or more of the core layers described herein can be generally made using chopped fibers (reinforced fibers or recycled polymer fibers, or both), thermoplastic materials (virgin, recycled, or both), and optionally, lofting agents and / or other materials. For example, the thermoplastic materials (virgin, recycled, or both) and any fibers can be added or metered into a dispersed foam contained in an open-top mixing tank equipped with an impeller. If necessary, separate tanks can be used for virgin and recycled thermoplastic materials, allowing for precise control of the amount of each material in the final article. While not wishing to be bound by theory, the presence of trapped air pockets in the foam can aid in the dispersion of the fibers and thermoplastic material. In some examples, the dispersed mixture of fiber and thermoplastic material can be pumped through a distribution manifold to a headbox located above the wire section of a papermaking machine. The dispersed mixture can then be vacuum-fed through a moving wire screen, removing the foam but not the fibers and thermoplastic material, continuously producing a uniform fibrous wet web containing the fibers and thermoplastic material. The wet web can be passed through a dryer at an appropriate temperature to reduce the moisture content and melt or soften the thermoplastic material. Skin layers, decorative layers, etc. can then be applied to the web, optionally with an adhesive material between the web and other layers. The assembly can be passed through one or more sets of rollers to press the skins onto the web and / or compress the assembly to a desired thickness. The resulting thermoplastic composite article can be cut, sized, or subjected to subsequent manufacturing steps as needed. The machine direction in this process generally refers to the direction of the moving wire screen, and the cross direction refers to the direction perpendicular to the machine direction. As described herein, the reinforcing fibers, recycled polymer fibers, or both can be randomly oriented or oriented at a specific angle relative to the machine direction, as desired. It may be desirable to orient the recycled polymer fibers in the skin layers at an orientation angle of 30 degrees, 45 degrees, 60 degrees, 75 degrees, or 90 degrees relative to the machine direction.

[0050] In certain configurations, the fiber-reinforced thermoplastic composite articles described herein can be produced by adding a plurality of reinforcing fibers (e.g., a plurality of non-recycled polymer fibers), a plurality of recycled polymer fibers, and a thermoplastic material (virgin, recycled, or both) to an agitated aqueous foam solution to form a dispersed mixture. The dispersed mixture of the plurality of reinforcing fibers, recycled polymer fibers, and thermoplastic material can be deposited onto a forming support element, such as a moving wire screen or other element. The deposited dispersed mixture can be drained to form a web. The web can include, for example, fibers held in place by a thermoplastic material. The web can be heated to a temperature above the softening temperature of the thermoplastic material. This softening temperature can vary depending on the properties of the various thermoplastic materials that may be present. The heated web can be compressed to a selected or predetermined thickness, for example, from 500 μm to about 20 mm, more specifically, from about 1 mm to about 10 mm or from about 2 mm to about 8 mm. A skin layer can be disposed on the compressed web to provide a thermoplastic composite article. Alternatively, a skin layer can be disposed on the web before compression, and the resulting thermoplastic composite article can be compressed to a desired overall thickness. As described herein, the skin layers may or may not contain recycled polymeric fibers, as desired. In certain embodiments, the core layer, skin layer, and / or thermoplastic composite article described herein can be used to manufacture an interior or exterior component or part. For example, the thermoplastic composite article can be present in a vehicle panel, a vehicle underbody panel, an exterior auto part, an interior auto part, an auto headliner, a recreational vehicle panel, or a recreational vehicle part.

[0051] In certain configurations, the core layer, skin layer, and / or thermoplastic composite article described herein can be used to provide a vehicle headliner. Exemplary vehicles include, but are not limited to, automobiles, trucks, trains, subways, recreational vehicles, aircraft, ships, submarines, spacecraft, and other vehicles capable of transporting people or cargo. In some cases, the headliner typically includes at least one core layer described herein and a decorative layer, such as a decorative fabric, disposed on the core layer. The decorative layer not only provides aesthetic and / or visual appeal, but can also enhance sound absorption and may include foam, insulation, or other materials. FIG. 14 shows a diagram of a top view of a headliner. The headliner 1300 includes a main body 1410 and an opening 1420, for example, for a sunroof, moonroof, etc., although more than a single opening may be present if desired. The main body 1410 of the headliner 1400 may include one or more of the thermoplastic composite articles described herein, optionally along with a decorative layer, fabric, textile, etc. The opening 1420 is optional and can be created by trimming the headliner 1400. The "C" side or roof side of the headliner typically consists of a nonwoven scrim layer for handling purposes. The overall shape and geometry of the headliner 1300 may be selected based on the area of ​​the vehicle to which the headliner will be coupled. For example, the length of the headliner may be sized and arranged to span from the front windshield to the rear windshield, and the width of the headliner may be sized and arranged to span from the left side of the vehicle to the right side of the vehicle.

[0052] In certain cases, the core layers, skin layers, and / or thermoplastic composite articles described herein can be used to manufacture underbody shields and rear window trim pieces or components. A diagram of an underbody shield 1500 is shown in FIG. 15 , and a top view of a rear window trim 1600 is shown in FIG. 16 . The specific outer layers used in the underbody shield 1500 and rear window trim 1600 may differ from those of a headliner. For example, the underbody shield may include a scrim or other outer layer to increase its durability and / or acoustic properties. For example, the inner surface of the underbody shield located adjacent the bottom of the engine may include one or more layers designed to absorb and / or retain automotive fluids, such as motor oil, antifreeze, brake fluid, etc. While various openings are shown in the rear window trim 1600, the location and geometry of these openings may vary. Furthermore, typical rear window trim trim materials may include unlined PET carpet or PP carpet. The underbody shield 1500 and window trim 1600 may include one or more of the core layers and / or thermoplastic composite articles described herein.

[0053] In certain examples, the core layers, skin layers, and / or thermoplastic composite articles described herein may be used in composite articles configured for interior use in recreational vehicle panels, wall panels, building panels, roofs, floors, or other applications. As described herein, the composite articles are typically used as manufactured and are not molded. In certain examples, the articles described herein may be configured as ceiling tiles. Referring to FIG. 17 , a ceiling tile grid 1700 is shown including support structures 1702, 1703, 1704, and 1705 and a plurality of ceiling tiles, such as tile 1710, laid within the grid formed by the support structures. In some examples, the ceiling tile includes one or more of the core layers, skin layers, and / or thermoplastic composite articles described herein. In some examples, the ceiling tile 1710 may include a porous decorative layer, such as a fabric, textile, or other layer, disposed on a porous core layer or skin layer described herein.

[0054] In other embodiments, the core layer, skin layer, and / or thermoplastic composite article described herein can be used in non-automotive or non-recreational vehicle components. For example, the thermoplastic composite article can be used in architectural applications, including roofing, flooring, ceiling tiles or panels, cubicle panels, and other architectural applications. In certain examples, a cubicle panel can include one or more of the core layer, skin layer, and / or thermoplastic composite article. Referring to FIG. 18 , a top view of a cubicle 1800 is shown, including side panels 1810, 1830, and a center panel 1820. Any one or more of the panels 1810-1830 can include one of the core layer, skin layer, and / or thermoplastic composite article described herein. The cubicle panel can also include one or more skin layers. In some examples, a cubicle wall panel is sized and arranged to be able to be joined with another cubicle wall panel.

[0055] In certain embodiments, the core layer, skin layer, and / or thermoplastic composite article described herein may be present in a structural panel. The structural panel may be used, for example, as sub-flooring, wall sheathing, roof sheathing, as structural support for cabinets, countertops, etc., as stair treads, as a plywood replacement, and other applications. If desired, the structural panel can be bonded to another substrate, such as plywood, oriented strand board, or other building panels commonly used in residential and commercial buildings. Referring to FIG. 19 , a top view of a structural panel 1910 is shown. The panel 1910 may include any one or more of the core layer, skin layer, and / or thermoplastic composite article described herein. If desired, two or more structural panels can be sandwiched together, with one skin facing the interior of a room and the other skin of another structural panel facing away from the interior of the room. In some cases, the structural panel may also include a structural substrate 2020, as shown in FIG. 20 . The exact nature of the structural substrate 2020 may vary and may include, but is not limited to, plywood, gypsum board, wood planks, wood tile, cement board, oriented strand board, polymeric or vinyl panels, or plastic panels. In some examples, the structural substrate comprises a plywood panel, gypsum board, wood tile, ceramic tile, metal tile, wood panel, concrete panel, concrete board, or brick. Optionally, the structural panel may further include a second structural panel bonded to a skin layer of the first structural panel.

[0056] In certain cases, the core layer, skin layer, and / or thermoplastic composite article described herein may be present in a wallboard or wall panel. Wall panels can be used, for example, to cover studs or structural members of a building, to cover ceiling joints, trusses, etc. If desired, the wall panel can be bonded to another substrate, such as tile, wood paneling, gypsum, concrete backer board, or other wall panel substrates commonly used in residential and commercial buildings. Referring to FIG. 21 , a side view of a wall panel 2100 is shown. The panel 2100 may include one or more of the core layer, skin layer, and / or thermoplastic composite article described herein. For example, the wall panel 2100 may also include at least one skin 2120 bonded to a first surface of the porous core layer 2110. Although not shown, a second skin can be placed on a second surface of the core layer 2110. An optional wall substrate can be bonded to the second surface of the porous core layer 2110 and configured to support the porous core layer 2110 when the wall panel 2100 is bonded to a wall surface. In certain configurations, the wall panel 2100 further comprises a porous decorative layer disposed on the skin 2120. In certain embodiments, a second wall panel can be bonded to the skin 2120.

[0057] In certain cases, the core layer, skin layer, and / or thermoplastic composite article described herein may be present in a siding panel attached to a building, such as a residential home or commercial building. The siding panel can be used to cover, for example, house wrap, sheathing, or other materials commonly used on the exterior of a building. If desired, the siding panel can be bonded to another substrate, such as vinyl, concrete board, wood siding, brick, or other substrates commonly placed on the exterior of a building. Referring to FIG. 22 , a side view of a siding panel is shown. The panel may include any one or more of the core layer, skin layer, and / or thermoplastic composite article described herein, e.g., core layer 2210 and skin 2220. The building substrate 2230 may be composed of many different materials, including, but not limited to, vinyl, wood, brick, concrete, etc. For example, a vinyl substrate can be bonded to a first surface of skin 2220, and siding can be configured to bond to a non-horizontal surface of a building to hold the siding panel to the non-horizontal surface of the building. In some cases, the siding panel further includes a weather barrier, such as house wrap, a membrane, etc., bonded to the second surface of the flame retardant and noise-reducing layer. In some embodiments, the substrate includes a nailing flange to allow the siding to be bonded to the side of a building. In some instances, the siding panel may further include a second siding panel, which can be bonded to the second substrate. In some cases, when two siding panels are secured together horizontally, a butt joint, lap joint, etc. may be present.

[0058] In certain cases, the core layer, skin layer, and / or thermoplastic composite article described herein may be present in a roofing panel attached to a building, such as a residential home or commercial building. The roofing panel can be used, for example, to cover an attic space, to attach to roof trusses, or to cover a flat roof such as is commonly found on commercial buildings. If desired, the roofing panel can be bonded to another substrate, such as oriented strand board, plywood, or even solar cells attached to the roof to provide roof covering. Referring to FIG. 23 , a perspective view of a roofing panel 2310 attached to a house 2300 is shown. The roofing panel 2310 may include any one or more of the core layer, skin layer, and / or thermoplastic composite article described herein. If desired, two or more roofing panels can be sandwiched or used together. The roofing panel may also include a roofing substrate bonded to the first surface of the core layer, which can be bonded to the roof of the building to hold the roof panel to the roof. In some instances, the roofing panel may include or be used in conjunction with a weather barrier, such as a membrane, house wrap, tar paper, plastic film, etc. In certain cases, the roofing panel may include, overlap, or be bonded to a second roofing panel to prevent moisture from entering the home 2300.

[0059] In certain configurations, the core layer, skin layer, and / or thermoplastic composite article described herein may be present in a roofing shingle that is attached to a building, such as a residential home or commercial building, to absorb sound and provide fire retardancy. The roofing shingle can be used, for example, to cover roofs commonly found in residential and commercial buildings. If desired, the roofing shingle can be bonded to another substrate, such as asphalt, ceramic, clay tile, aluminum, copper, wood such as cedar, and other materials commonly found or used as roofing shingles. Referring to FIG. 24 , an exploded view of a roofing shingle is shown. The roofing shingle 2400 may include any one or more of the core layer, skin layer, and / or thermoplastic composite article described herein. If desired, two or more roofing shingles can be sandwiched together. In some examples, the roofing shingle may include a core layer 2410. If desired, a weather-resistant roofing shingle substrate 2430 can be bonded to the first surface and configured to bond to the building's roofing panel to provide a weather-resistant and fire-retardant roofing panel. In certain cases, a weather barrier can be bonded to the roofing shingles. In other instances, the roofing shingles include asphalt. Between the outer layer 2430 and the core layer 2410, there may be an intermediate layer 2420, such as a skin, insulation, or other material.

[0060] In certain configurations, any one or more of the core layers, skin layers, and / or thermoplastic composite articles described herein may be present in an interior panel or wall of a recreational vehicle (RV) or an interior panel of an aircraft or aerospace vehicle, such as a rocket, satellite, shuttle, or other air or space vehicle. The panel or wall may be used, for example, to cover the interior framework of the recreational vehicle or aerospace vehicle and may be bonded to foam or other insulating material between the interior and exterior of the vehicle. In some examples, the core layers, skin layers, and / or thermoplastic composite articles described herein may be part of a sandwich structure formed from the core layer or article and other layers. If desired, the interior panel may be bonded to another substrate, such as, for example, fabric, plastic, tile, etc.

[0061] Referring to FIG. 25, a side view of a recreational vehicle 2500 is shown. An interior panel 2510 may include any one or more of the core layers, skin layers, and / or thermoplastic composite articles described herein. If desired, two or more RV panels can be sandwiched or bonded together. In some examples, the RV panel includes an interior wall substrate configured as a decorative layer, such as fabric, plastic, tile, metal, wood, etc. In additional cases, the RV panel may include a second RV interior panel, which may be the same or different from the RV panel. If desired, the RV panel may include a third RV interior panel, which may be the same or different. Although not shown, similar interior panels may be present in aerospace applications / vehicles and may be placed and / or bonded to a metal or metal alloy skin or structure, e.g., aluminum, magnesium, titanium, etc. exterior skin, or other exterior structure. In certain configurations, any one or more of the core layers, skin layers, and / or thermoplastic composite articles described herein may be configured as or present within an exterior panel or wall of an aircraft, aerospace, or recreational vehicle. The panel or wall may be used, for example, to cover the exterior frame structure of the vehicle and bond to foam or other insulating material between the interior and exterior of the vehicle. In some examples, the core layer or article may be part of a sandwich structure formed from the core layer or article and other layers. If desired, the exterior panel may be bonded to another substrate, such as, for example, a metal, metal alloy, fiberglass, or the like. Referring to FIG. 26 , a side view of a recreational vehicle 2650 is shown including an exterior panel 2660 that may be configured as any one of the core layers, skin layers, and / or thermoplastic composite articles described herein. If desired, two or more RV panels may be sandwiched together, with one skin facing the interior of the RV and the other RV panel's skin facing away from the interior of the RV panel. In certain configurations, the exterior wall substrate may include fiberglass or be configured as a metal panel such as aluminum or other metallic material. In additional cases, the RV panel includes a second RV exterior panel, which may be the same or different from the RV panel. Optionally, the RV panel may include a third RV exterior panel, which may be the same or different. While not shown, similar exterior panels may be present in aerospace applications / vehicles and may be placed against and / or bonded to interior metal or metal alloy skins, e.g., aluminum, magnesium, titanium, etc., interior skins or structures, or other interior structures.

[0062] In certain examples, the core layer, skin layer, and / or thermoplastic composite article described herein may be used in an automotive vehicle 2810 ( FIG. 28 ), a recreational vehicle 2910 ( FIG. 29 ), an airplane 3010 ( FIG. 30 ), a shuttle or spacecraft 3110 ( FIG. 31 ), a rocket, a satellite, or other vehicle having a power means that may include one or more wheels, engines, motors, turbines, rockets, fuel cells, batteries, and may be solar-powered, wind-powered, gas-propelled, or otherwise used to propel the vehicle. However, as shown in FIG. 29 , a vehicle having a core layer, skin layer, and / or thermoplastic composite article described herein may be towed or coupled to another vehicle if desired, and may not have a separate motor or engine for propulsion. In some examples, the core layer, skin layer, and / or thermoplastic composite article described herein may be used in interior trim applications, such as RV interior trim, interior trim for architectural or automotive applications. The interior trim can be bonded to other materials, such as wood, PVC, vinyl, plastic, leather, or other materials. A side view of a trim piece that can be used as baseboard trim is shown in FIG. 27 . The trim piece includes a trim substrate 2720. The trim piece can be nailed or attached to a stud or wallboard 2710 as desired. The substrate 2720 faces outward and is visible within the room. The trim piece can be curved or have a two- or three-dimensional shape as desired. Optionally, one or more decorative skins can be present on the outside of the trim piece and face the interior of the room. To facilitate a better understanding of the techniques described herein, certain illustrative examples are set forth.

[0063] ( Example 1 ) Two composite article formulations were prepared and their mechanical properties were tested. Mechanical properties were measured according to ISO 178 (flexural properties) dated 2011 or ISO 527 (tensile properties) dated 2001 or equivalent methodologies, unless otherwise specified. Formulation 1 contained 20% by weight recycled polyolefin resin (a blend of PP and PE), 5% by weight recycled polyethylene terephthalate (PET) fiber, 50% by weight glass fiber, and 25% by weight virgin PP resin. Formulation 2 contained 20% by weight recycled polyolefin resin (a blend of PP and PE), 10% by weight recycled PET fiber, 45% by weight glass fiber, and 25% by weight virgin PP resin. The two formulations were compared to a Superlite (SL) control material containing 45% by weight glass fiber and 55% by weight virgin PP. The results of mechanical testing for different thicknesses are shown in Figures 32 and 33. The machine direction refers to mechanical testing in the direction of the moving support used to make the article. The cross direction refers to the direction perpendicular to the machine direction. The results are consistent with articles containing recycled materials providing similar or better performance than the control material.

[0064] ( Example 2 ) Two composite article formulations were prepared and their mechanical properties were tested. Mechanical properties were measured according to ISO 178, dated 2011, unless otherwise specified. Formulation 3 contained 10% by weight kenaf fiber, 45% by weight glass fiber, and 45% by weight virgin polyolefin resin. Formulation 4 contained 20% by weight kenaf fiber, 35% by weight glass fiber, and 45% by weight virgin polyolefin resin. The two formulations were compared to a Superlite control material containing 45% by weight glass fiber and 55% by weight virgin polyolefin. The results of the mechanical tests for different thicknesses are shown in Figures 34 and 35. The results are consistent with articles with higher kenaf fiber loading providing similar or better performance to the control material.

[0065] ( Example 3 ) Four composite article formulations were prepared and their mechanical properties were tested. Mechanical properties were measured according to ISO 178 (2011) (or equivalent methodologies, such as ASTM D790-17) unless otherwise specified. Formulation 5 contained 5% by weight of kenaf fiber, 10% by weight of recycled polyolefin resin (a blend of PP and PE), 50% by weight of glass fiber, and 35% by weight of virgin polyolefin resin. Formulation 6 contained 5% by weight of kenaf fiber, 20% by weight of recycled polyolefin resin (a blend of PP and PE), 50% by weight of glass fiber, and 25% by weight of virgin PP resin. Formulation 7 contained 10% by weight of kenaf fiber, 10% by weight of recycled polyolefin resin (a blend of PP and PE), 45% by weight of glass fiber, and 35% by weight of virgin PP resin. Formulation 8 contained 10% by weight kenaf fiber, 20% by weight recycled polyolefin resin (a blend of PP and PE), 45% by weight glass fiber, and 25% by weight virgin PP resin. The four formulations were compared to a Superlite control material containing 45% by weight glass fiber and 55% by weight virgin PP. The results of mechanical testing for different thicknesses are shown in Figures 36-43. In the machine direction, Formulations 5-8 generally had better or similar mechanical properties to the control material. The cross direction mechanical properties varied with the exact amount of material present.

[0066] ( Example 4 ) Two test core layers were prepared and compared with a control layer (SL Control). The SL Control contained 55% glass fiber and 45% polypropylene by weight. Test Sample #1 contained recycled polyethylene terephthalate fiber (5% by weight), 50% glass fiber, and 45% polypropylene by weight. Test Sample #2 contained recycled polyethylene terephthalate fiber (10% by weight), 45% glass fiber, and 45% polypropylene by weight. The ISO-Flexural Peak Load and ISO-Tensile Peak Load were tested according to ISO 178 (Flexural) dated 2011 and ISO 527 (Tensile) revised in 2001, respectively. Table 1 shows the results of the ISO-Flexural Peak Load test, and Table 2 shows the results of the ISO-Tensile Peak Load test. Average values ​​are shown in Tables 1 and 2, and the variations are shown in Figures 44-47. TS stands for Test Sample. MD refers to the machine direction, CD refers to the cross direction, and SD refers to the standard deviation. In each bar graph grouping, the left bar is the machine direction value and the right bar is the cross direction value.

[0067] [Table 1]

[0068] [Table 2] As shown in Table 1, Figures 44 and 45, at comparable mold thicknesses, the ISO Flexural Peak Load machine direction values ​​are similar to or better than the control values. The ISO Flexural Peak Load cross direction values ​​tend to be similar to or lower than the control values.

[0069] As shown in Table 2, Figures 46 and 47, at equivalent mold thicknesses, the ISO tensile peak load machine direction values ​​for Test Sample #1 improved at a mold thickness of 2.5 mm but decreased at a mold thickness of 2.75 mm. Sample #2 exhibited decreased tensile peak loads in both the machine and cross directions at both mold thicknesses. These results are consistent with the suitability of recycled fibers for use at specific weight percents and mold thicknesses.

[0070] ( Example 5 ) Several test samples were prepared containing recycled PET fibers and / or recycled resins. The sample formulations are shown in Table 3. GF stands for glass fiber, PP stands for polypropylene, and PET stands for polyethylene terephthalate. [Table 3] The ISO-Flexural Peak Load test results for different thicknesses are shown in Figures 48 and 49. The ISO-Tensile Peak Load test results for different substrate thicknesses are shown in Figures 50 and 51. MD refers to the machine direction and CD refers to the cross direction. In each bar graph grouping, the left bar is the machine direction value and the right bar is the cross direction value.

[0071] The ISO-Flexural Peak Load values ​​of the test samples were similar or comparable to the control values, indicating that the inclusion of recycled fibers and / or recycled resins provided similar or better performance. The ISO-Tensile Peak Load values ​​varied with the resin loading of the fibers and resin. For example, test samples containing recycled PET fibers generally had higher machine direction values ​​than the control sample values.

[0072] ( Example 6 ) Two test samples were prepared containing different lengths of recycled kenaf fibers, and the formulations are shown in Table 6 below. [Table 4] The ISO-Flexural Peak Load values ​​(Figures 52 and 53) and ISO-Tensile Peak Load values ​​(Figures 54 and 55) for different substrate thicknesses were measured. In each bar graph grouping, the left bar is the machine direction value and the right bar is the cross direction value. The ISO-Flexural Peak Load values ​​were similar to or better than the control values ​​at different thicknesses. The ISO-Tensile Peak Load values ​​were generally lower than the control values ​​and decreased with increasing kenaf fiber length in both the machine and cross directions.

[0073] ( Example 7 ) Several test samples were prepared containing various amounts of recycled PP resin and various skins, and the formulations are shown in Table 5 below. [Table 5] The ISO-Flexural Peak Load values ​​(Figures 56 and 57) and ISO-Tensile Peak Load values ​​(Figures 58 and 59) were measured for different substrate thicknesses. Figures 60-63 show the SAE-Flexural Peak Load for the substrate alone (Figures 60 and 61) and the SAE-Flexural Peak Load for the substrate and bonded skin (Figures 62 and 63). In each bar graph grouping, the left bar is the machine direction value and the right bar is the cross direction value.

[0074] The ISO-Flexural Peak Load values ​​were similar (within a standard deviation) or better for the test samples compared to the control samples at both substrate thicknesses. The ISO-Tensile Peak Load values ​​of the test samples were similar to or lower than the control sample values ​​in the machine direction. Increasing the basis weight of the core layer resulted in an increase in the ISO-Tensile Peak Load values. In the cross direction, the ISO-Tensile Peak Load values ​​were similar to those in the control samples for both substrates. For the SAE-Flexural Peak Load values, the test sample values ​​were similar to or better than the control values, with the higher basis weight (1100 gsm) providing higher values. The addition of a skin layer (Figures 62 and 63) increased the SAE-Flexural Peak Load values ​​compared to the equivalent substrate thickness without a skin layer. These results are consistent with recycled PP resin providing similar performance to virgin PP in the core layer.

[0075] ( Example 8 ) Several test samples were prepared containing various amounts of recycled PET fibers and various skin layers, and the formulations are shown in Table 6 below. [Table 6] The ISO-Flexural Peak Load values ​​(Figures 64 and 65) and ISO-Tensile Peak Load values ​​(Figures 66 and 67) were measured for different substrate thicknesses. Figures 68-71 show the SAE-Flexural Peak Load for the substrate alone (Figures 68 and 69) and the SAE-Flexural Peak Load for the substrate and bonded skin (Figures 70 and 71). In each bar graph grouping, the left bar is the machine direction value and the right bar is the cross direction value.

[0076] The ISO-Flexural Peak Load values ​​generally decreased as the glass fiber loading decreased and the basis weight decreased. A similar trend was observed for the ISO-Tensile values. The SAE-Flexural Peak values ​​were higher than the control values ​​at equivalent basis weights, even at low glass fiber loading levels. These results are consistent with recycled PET fibers providing similar performance to a glass-only core layer.

[0077] ( Example 9 ) Several test samples were made containing various amounts of recycled resin, recycled PET fibers, and various skin layers. The formulations are shown in Table 7 below. [Table 7] For a substrate thickness of 2.75 mm, the ISO-Flexural Peak Load values ​​(Figure 72) and ISO-Tensile Peak Load values ​​(Figure 73) were measured. Figures 74-77 show the SAE-Flexural Peak Load for the substrate alone, and Figures 78-80 show the SAE-Flexural Peak Load for the substrate and bonded skin, at different substrate thicknesses. In each bar graph grouping, the left bar is the machine direction value and the right bar is the cross direction value.

[0078] The ISO-Flexural Peak Load and ISO-Tensile Peak Load values ​​for the test samples were slightly lower in the machine direction compared to the control values. In the cross direction, the ISO-Flexural Peak Load and ISO-Tensile Peak Load values ​​were comparable at higher recycled PET fiber loadings compared to the control values. The SAE-Flexural Peak values ​​were also lower than the control values ​​at comparable substrate thicknesses. The addition of skins (Figures 78-80) slightly increased the SAE-Flexural values. These results are consistent with recycled resin and recycled fiber providing comparable performance to a core layer containing only glass fiber and virgin resin.

[0079] ( Example 10 ) Several test samples were made containing various amounts of recycled resin and / or recycled PET fibers, and various skin layers. The formulations are shown in Table 8 below. [Table 8] The ISO-Flexural Peak Load values ​​(Figure 81) and ISO-Tensile Peak Load values ​​(Figure 82) were measured for a substrate thickness of 2.75 mm. Figures 83 and 84 show the SAE-Flexural Peak Load values ​​for the substrate alone, and Figures 85-86 show the SAE-Flexural Peak Load values ​​for the substrate and bonded skin, at different substrate thicknesses. In each bar graph grouping, the left bar is the machine direction value and the right bar is the cross direction value.

[0080] The ISO-Flexural Peak Load values ​​of the test samples were similar compared to the control values ​​in the machine direction. The ISO-Tensile Peak Load values ​​in the cross direction were generally lower compared to the control values. The SAE-Flexural Peak values ​​were similar to or lower than the control values ​​at equivalent substrate thicknesses. The addition of a skin (Figures 85 and 86) increased the SAE-Flexural values ​​compared to the substrate without a skin. These results are consistent with the recycled resin providing equivalent performance to a core layer containing only virgin resin.

[0081] ( Example 11 ) Several test samples were made containing various amounts of recycled resin and / or recycled PET fibers, and various skin layers. The formulations are shown in Table 9 below. [Table 9] The ISO-Flexural Peak Load values ​​(Figures 87-90) and ISO-Tensile Peak Load values ​​(Figures 91-94) were measured for different substrate thicknesses. Figures 95-98 show the SAE-Flexural Peak Load for the substrate only, and Figures 99-102 show the SAE-Flexural Peak Load for the substrate and bonded skin, for different substrate thicknesses. In each bar graph grouping, the left bar is the machine direction value and the right bar is the cross direction value.

[0082] The ISO-Flexural Peak Load values ​​of the test samples were similar to or better than the control values ​​in the machine and cross directions. The ISO-Tensile Peak Load values ​​in the machine and cross directions were also similar to the control values. The SAE-Flexural Peak values ​​were similar to the control values ​​at equivalent substrate thicknesses. The addition of a skin (Figures 101 and 102) increased the SAE-Flexural values ​​compared to the substrate without a skin. These results are consistent with recycled resin and regenerated polymer fibers providing equivalent performance to a core layer containing only virgin resin and glass fibers.

[0083] When introducing elements of the embodiments disclosed herein, the articles "a," "an," "the," and "said" are intended to mean that there are one or more of the elements. The terms "comprising," "including," and "having" are intended to be open-ended, meaning that there may be additional elements other than the listed elements. Those skilled in the art with the benefit of this disclosure will recognize that various elements of the embodiments may be interchanged or substituted for various elements of other embodiments. While certain aspects, configurations, examples, and embodiments have been described above, those skilled in the art, having the benefit of this disclosure, will recognize that additions, substitutions, modifications, and variations of the disclosed exemplary aspects, configurations, examples, and embodiments are possible.

Claims

1. a porous core layer including an open-cell structured web including a random crossing of a plurality of reinforcing fibers and a plurality of recycled polymer fibers held together by a thermoplastic material; a skin layer disposed on a first surface of the porous core layer; 1. A thermoplastic composite article comprising:

2. 10. The thermoplastic composite article of claim 1, wherein the recycled polymer fibers are selected from the group consisting of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled copolyamide fibers, recycled high density polyethylene fibers, and combinations thereof.

3. 10. The thermoplastic composite article of claim 1, wherein the thermoplastic material of the porous core layer comprises virgin thermoplastic material, recycled thermoplastic material, or both, and the virgin thermoplastic material or recycled thermoplastic material is independently at least one of polyethylene, polypropylene, polystyrene, polyimide, polyetherimide, acrylonitrile styrene, butadiene, polyethylene terephthalate, polybutylene terephthalate, polybutylene tetrachlorate, polyvinyl chloride, polyphenylene ether, polycarbonate, polyester carbonate, polyester, acrylonitrile-butyl acrylate-styrene polymer, amorphous nylon, polyarylene ether ketone, polyphenylene sulfide, polyarylsulfone, polyethersulfone, poly(1,4 phenylene) compound, silicone, and mixtures thereof.

4. 10. The thermoplastic composite article of claim 1, wherein the plurality of reinforcing fibers of the porous core layer are selected from the group consisting of glass fibers, carbon fibers, graphite fibers, synthetic organic fibers, inorganic fibers, natural fibers, mineral fibers, metal fibers, metallized inorganic fibers, metallized synthetic fibers, ceramic fibers, biofibers, rice husk fibers, kenaf fibers, and combinations thereof.

5. 10. The thermoplastic composite article of claim 1, wherein the skin layer is selected from the group consisting of a fabric, a film, a scrim, a flim, a porous nonwoven material, a porous knit material, a decorative layer, and combinations thereof.

6. The thermoplastic composite article of claim 1 , wherein the plurality of reinforcing fibers is present at 20% to 80% by weight, based on the weight of the porous core layer.

7. 10. The thermoplastic composite article of claim 1, wherein the plurality of recycled polymeric fibers is present at 20% to 80% by weight, based on the weight of the porous core layer.

8. 10. The thermoplastic composite article of claim 1, wherein the plurality of recycled polymer fibers comprises a monomer unit that is different from a monomer unit of the plurality of reinforcing fibers.

9. 10. The thermoplastic composite article of claim 1, wherein the plurality of recycled polymer fibers and the plurality of reinforcing fibers each comprise a similar average diameter and average length.

10. 10. The thermoplastic composite article of claim 1, wherein the thermoplastic composite article is assembled and arranged as a vehicle panel, a vehicle underbody panel, an exterior automotive part, an interior automotive part, an automotive headliner, a recreational vehicle panel, or a recreational vehicle part.

11. The thermoplastic composite article of claim 1 , wherein the skin layer comprises a plurality of recycled polymeric fibers.

12. 12. The thermoplastic composite article of claim 11, wherein the plurality of recycled polymer fibers in the porous core layer and the plurality of recycled polymer fibers in the skin layers are independently selected from the group consisting of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled copolyamide fibers, recycled high density polyethylene fibers, and combinations thereof.

13. 12. The thermoplastic composite article of claim 11, wherein the plurality of recycled polymer fibers in the porous core layer and the plurality of recycled polymer fibers in the skin layers comprise different monomer units.

14. The thermoplastic material of the porous core layer may be virgin polyethylene, virgin polypropylene, virgin polystyrene, virgin polyimide, virgin polyetherimide, virgin acrylonitrile styrene, virgin butadiene, virgin polyethylene terephthalate, virgin polybutylene terephthalate, virgin polybutylene tetrachlorate, virgin polyvinyl chloride, virgin polyphenylene ether, virgin polycarbonate, virgin polyestercarbonate, virgin polyester, virgin acrylonitrile-butyl acrylate-styrene polymer, virgin amorphous nylon, virgin polyarylene ether ketone, virgin polyphenylene sulfide, virgin polyarylsulfone, virgin polyethersulfone, virgin poly(1,4 12. The thermoplastic composite article of claim 11, comprising at least one of: recycled poly(1,4 phenylene) compounds, recycled polyethylene, recycled polypropylene, recycled polystyrene, recycled polyimide, recycled polyetherimide, recycled acrylonitrile styrene, recycled butadiene, recycled polyethylene terephthalate, recycled polybutylene terephthalate, recycled polybutylene tetrachlorate, recycled polyvinyl chloride, recycled polyphenylene ether, recycled polycarbonate, recycled polyester carbonate, recycled polyester, recycled acrylonitrile-butyl acrylate-styrene polymer, recycled amorphous nylon, recycled polyarylene ether ketone, recycled polyphenylene sulfide, recycled polyarylsulfone, recycled polyethersulfone, recycled poly(1,4 phenylene) compounds, recycled silicone, and mixtures thereof.

15. 12. The thermoplastic composite article of claim 11, wherein the plurality of reinforcing fibers of the porous core layer are selected from the group consisting of glass fibers, carbon fibers, graphite fibers, synthetic organic fibers, inorganic fibers, natural fibers, mineral fibers, metallic fibers, metallized inorganic fibers, metallized synthetic fibers, ceramic fibers, and combinations thereof.

16. 12. The thermoplastic composite article of claim 11, wherein the skin layer is selected from the group consisting of a fabric, a film, a scrim, a flim, a porous nonwoven material, a porous knit material, a decorative layer, and combinations thereof.

17. 10. The thermoplastic composite article of claim 1, wherein the plurality of reinforcing fibers and the plurality of recycled polymer fibers of the porous core layer are independently present at 20% to 80% by weight, based on the weight of the porous core layer.

18. 12. The thermoplastic composite article of claim 11, wherein the plurality of recycled polymer fibers in the skin layers comprise a monomer unit that is different from a monomer unit of the plurality of reinforcing fibers in the porous core layer.

19. 2. The thermoplastic composite article of claim 1, wherein the thermoplastic material of the porous core layer comprises a virgin polyolefin material or a recycled polyolefin material or both, the plurality of reinforcing fibers of the porous core layer comprise glass fibers, and the plurality of recycled polymer fibers of the porous core layer are selected from the group consisting of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled copolyamide fibers, recycled high density polyethylene fibers, and combinations thereof.

20. 12. The thermoplastic composite article of claim 11, wherein the thermoplastic material of the porous core layer comprises a virgin polyolefin material or a recycled polyolefin material or both, the plurality of reinforcing fibers of the porous core layer comprise glass fibers, and the plurality of recycled polymer fibers of the skin layers are selected from the group consisting of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled copolyamide fibers, recycled high density polyethylene fibers, and combinations thereof.

21. a porous core layer including an open-cell web including a randomly intersecting plurality of reinforcing fibers held together by a thermoplastic material; a skin layer disposed on a first surface of the porous core layer and including a plurality of recycled polymer fibers; 1. A thermoplastic composite article comprising:

22. 22. The thermoplastic composite article of claim 21, wherein the plurality of recycled polymer fibers of the skin layers are selected from the group consisting of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled copolyamide fibers, recycled high density polyethylene fibers, and combinations thereof.

23. 22. The thermoplastic composite article of claim 21, wherein the plurality of reinforcing fibers of the porous core layer and the plurality of recycled polymer fibers of the skin layers comprise a common monomer unit.

24. 22. The thermoplastic composite article of claim 21, wherein the thermoplastic material of the porous core layer comprises virgin thermoplastic material, recycled thermoplastic material, or both, and the virgin thermoplastic material or recycled thermoplastic material is independently at least one of polyethylene, polypropylene, polystyrene, polyimide, polyetherimide, acrylonitrile styrene, butadiene, polyethylene terephthalate, polybutylene terephthalate, polybutylene tetrachlorate, polyvinyl chloride, polyphenylene ether, polycarbonate, polyester carbonate, polyester, acrylonitrile-butyl acrylate-styrene polymer, amorphous nylon, polyarylene ether ketone, polyphenylene sulfide, polyarylsulfone, polyethersulfone, poly(1,4 phenylene) compound, silicone, and mixtures thereof.

25. 22. The thermoplastic composite article of claim 21, wherein the plurality of reinforcing fibers of the porous core layer are selected from the group consisting of glass fibers, carbon fibers, graphite fibers, synthetic organic fibers, inorganic fibers, natural fibers, mineral fibers, metallic fibers, metallized inorganic fibers, metallized synthetic fibers, ceramic fibers, and combinations thereof.

26. 22. The thermoplastic composite article of claim 21, wherein the skin layer is selected from the group consisting of a fabric, a film, a scrim, a flim, a porous nonwoven material, a porous knit material, a decorative layer, and combinations thereof.

27. 22. The thermoplastic composite article of claim 21, wherein the plurality of reinforcing fibers is present at 20% to 80% by weight, based on the weight of the porous core layer.

28. 22. The thermoplastic composite article of claim 21, wherein the plurality of recycled polymer fibers in the skin layers comprise a monomer unit that is different from a monomer unit of the plurality of reinforcing fibers in the porous core layer.

29. 22. The thermoplastic composite article of claim 21, wherein the thermoplastic composite article is assembled and arranged as a vehicle panel, a vehicle underbody panel, an exterior automotive part, an interior automotive part, an automotive headliner, a recreational vehicle panel, or a recreational vehicle part.

30. 22. The thermoplastic composite article of claim 21, wherein the plurality of thermoplastic materials of the porous core layer comprise virgin polyolefin materials or recycled polyolefin materials or both, the plurality of reinforcing fibers of the porous core layer comprise glass fibers, and the recycled polymer fibers of the skin layers are selected from the group consisting of recycled polyethylene terephthalate fibers, recycled polyethylene fibers, recycled polypropylene fibers, recycled polyamide fibers, recycled copolyamide fibers, recycled high density polyethylene fibers, and combinations thereof.

31. 1. A method for making a thermoplastic composite article, comprising: adding a plurality of reinforcing fibers, a plurality of recycled polymer fibers, and a thermoplastic material to an agitated aqueous foam solution to form a dispersed mixture; depositing the dispersed mixture of the plurality of reinforcing fibers, the recycled polymer fibers, and the thermoplastic material onto a forming support element; draining the liquid from the deposited dispersed mixture to form a web; heating the web at or above the softening temperature of the thermoplastic material; compressing the heated web to a predetermined thickness; placing a skin layer on the compressed web to provide the thermoplastic composite article; A method comprising:

32. 32. The method of claim 31 , wherein the skin layer comprises a plurality of recycled polymeric fibers.

33. 32. The method of claim 31 , wherein the thermoplastic material comprises a mixture of virgin and recycled thermoplastic materials.

34. 1. A method for making a thermoplastic composite article, comprising: adding a plurality of reinforcing fibers and a thermoplastic material to an agitated aqueous foam solution to form a dispersed mixture; depositing the dispersed mixture of the plurality of reinforcing fibers and the thermoplastic material onto a forming support element; draining the liquid from the deposited dispersed mixture to form a web; heating the web at or above the softening temperature of the thermoplastic material; compressing the heated web to a predetermined thickness; disposing a skin layer comprising a plurality of recycled polymeric fibers on the compressed web to provide the thermoplastic composite article; A method comprising:

35. 35. The method of claim 34, wherein the thermoplastic material comprises a mixture of virgin and recycled thermoplastic materials.

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