Self-reinforced thermoplastic composites and methods of making self-reinforced thermoplastic composites

Abstract

The invention relates to a self-reinforced thermoplastic composite and a method of making a self-reinforced thermoplastic composite. A thermoplastic composite elongate extrudate having a thermoplastic polymer matrix material with a plurality of elongate thermoplastic liquid crystal polymer fibrils generally aligned with the extrusion direction. A method of making a thermoplastic composite includes mixing a thermoplastic polymer matrix material and a thermoplastic liquid crystal polymer wherein the thermoplastic polymer matrix material has a viscosity substantially greater than that of the thermoplastic liquid crystal polymer, and extruding the mixture to produce a composite elongate extrudate comprising the thermoplastic polymer matrix material, the thermoplastic polymer matrix material has a plurality of elongate thermoplastic liquid crystal polymer fibrils generally aligned with the extrusion direction.

Description

Technical Field

[0001] The present invention relates to a self-reinforced thermoplastic composite material and to a method of making the self-reinforced thermoplastic composite material. Background Art

[0002] The information provided in this section is for the purpose of generally introducing the background of the present disclosure. No admission is made, either explicitly or implicitly, that the work of the presently named inventors described in this section is prior art to the present disclosure, nor is it admitted that the work is prior art to the present disclosure with respect to the specification that may not have been otherwise identified as prior art at the time of filing.

[0003] Composite materials are materials made from two or more constituent materials, often with different properties, that are combined to create a material with properties different from those of its constituents. One type of composite material is reinforced plastics, such as fiber-reinforced polymers or fiberglass. Reinforced plastic composites are frequently used in structural components and are increasingly used in common automotive applications. However, these materials are difficult and expensive to manufacture, and are also difficult to recycle. Summary of the Invention

[0004] Further areas of applicability of the present disclosure will become apparent from the detailed description, claims and drawings.The detailed description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.

[0005] Embodiments of the present disclosure provide a thermoplastic extruded composite material comprising a thermoplastic polymer matrix material having a plurality of elongated thermoplastic liquid crystal polymer fibrils generally aligned in the direction of extrusion. The elongated thermoplastic liquid crystal polymer fibrils may comprise from about 20% to about 80% by weight of the composite extrudate, and in some embodiments, may comprise from about 20% to about 80% by weight of the composite extrudate.

[0006] The thermoplastic polymer matrix material may include a variety of thermoplastic polymers, copolymers, and mixtures thereof, including but not limited to PA6 (nylon 6), PA66 (nylon 66), PA12 (nylon 12), PA6,66 (nylon 6-66), PPS (polyphenylene sulfide), PEI (polyetherimide), PEEK (polyetheretherketone), PEKK (polyetherketoneketone), PAEK (polyaryletherketone), PET (polyethylene terephthalate), PC (polycarbonate), ABS (acrylonitrile butadiene styrene), and PP (polypropylene). Generally, any thermoplastic material that adheres to and can be dispersed in a liquid crystal polymer may be a suitable matrix material.

[0007] The thermoplastic liquid crystal polymer material may include various thermotropic liquid crystal polymers, including but not limited to Vectra B950, Xydar SRT-900, as long as the liquid crystal polymer is compatible with the matrix material, which is determined by the rheological properties (viscosity and elasticity) and the interfacial tension between the components.

[0008] Embodiments of the present disclosure also provide a method for making a thermoplastic composite extrudate comprising a thermoplastic polymer matrix material comprising a plurality of elongated thermoplastic liquid crystal polymer fibrils. The method may include mixing a thermoplastic liquid crystal polymer with a thermoplastic polymer matrix having a viscosity substantially greater than that of the thermoplastic liquid crystal polymer at an extrusion temperature, such that extruding the mixture produces a composite extrudate comprising the thermoplastic polymer matrix material having a plurality of elongated thermoplastic liquid crystal polymer fibrils generally aligned in the direction of extrusion.

[0009] The ratio of the viscosity of the thermoplastic polymer matrix material to the viscosity of the thermoplastic liquid crystal polymer at the extrusion temperature is greater than about 2 and can be between about 2 and about 1000. A tackifier can be added to the thermoplastic polymer matrix material. The tackifier can be at least one multi-walled carbon nanotube, carbon black, nanoclay (e.g., montmorillonite), and silicate. In some embodiments, the tackifier is more miscible with the thermoplastic polymer matrix material than with the thermoplastic liquid crystal polymer. Additionally or alternatively, a viscosity reducer can be added to the thermoplastic liquid crystal polymer material. The viscosity reducer can be boron nitride and / or fumed silica. In at least some embodiments, the viscosity reducer is more miscible with the thermoplastic liquid crystal polymer material than with the thermoplastic polymer matrix material.

[0010] The thermoplastic polymer matrix material may include a variety of thermoplastic polymers, copolymers, and mixtures thereof, including but not limited to PA6 (nylon 6), PA66 (nylon 66), PA12 (nylon 12), PA6,66 (nylon 6-66), PPS (polyphenylene sulfide), PEI (polyetherimide), PEEK (polyetheretherketone), PEKK (polyetherketoneketone), PAEK (polyaryletherketone), PET (polyethylene terephthalate), PC (polycarbonate), ABS (acrylonitrile butadiene styrene), and PP (polypropylene). Generally, any thermoplastic material having a minimum processing temperature that does not exceed the thermal or rheological processing conditions of the thermoplastic liquid crystal polymer material and having compatible viscosity, elasticity, and interfacial tension may be a suitable matrix material.

[0011] The thermoplastic liquid crystal polymer material includes a variety of thermotropic liquid crystal polymers. Generally, any polymer having a main chain consisting of repeating units of aromatic rings linked together or a main chain of repeating units of aromatic rings linked to organic groups, which can form a liquid crystal phase, such as the commercially available class, class, Grades and the like, including but not limited to Vectra B950, Xydar SRT-900, can be used, as long as the liquid crystal polymer is compatible with the matrix material and the minimum supercooling processing temperature of the thermoplastic liquid crystal polymer material does not exceed the onset temperature of thermal or rheological degradation of the matrix material.

[0012] The mixture of the thermoplastic polymer matrix material and the thermoplastic liquid crystal polymer can be extruded from a single screw extruder to produce filaments. The filaments can be used for melt filament manufacturing, or they can be pelletized.

[0013] The mixture of the thermoplastic polymer matrix material and the thermoplastic liquid crystal polymer may contain a compatibilizer to improve the interfacial bonding between the thermoplastic liquid crystal polymer and the thermoplastic polymer matrix. The compatibilizer may include at least one of an ionomer, a copolymer, maleic anhydride, PEEK, other thermoplastic liquid crystal polymers, and a polyesterimide. The performance of the compatibilizer / ionomer / copolymer can be evaluated by testing the initial morphological behavior of the blend, with improved adhesion and dispersibility at a finer scale than other blends.

[0014] The mixture of the thermoplastic polymer matrix material and the thermoplastic liquid crystal polymer may contain a stabilizer. The stabilizer may be at least one of polystyrene, poly(methyl methacrylate), or single-walled carbon nanotubes. Increasing the molar ratio of acid in the copolymer formulation of the thermoplastic liquid crystal polymer phase generally increases LC stability.

[0015] The present invention discloses the following solutions:

[0016] Embodiment 1. A thermoplastic composite elongated extrudate comprising a thermoplastic polymer matrix material having a plurality of elongated thermoplastic liquid crystal polymer fibrils generally aligned in the direction of extrusion.

[0017] Option 2. A thermoplastic composite elongated extrudate according to Option 1, wherein the elongated thermoplastic liquid crystal polymer fibrils constitute from about 20 weight percent to about 80 weight percent of the composite elongated extrudate.

[0018] Option 3. A thermoplastic composite elongated extrudate according to Option 1, wherein the thermoplastic polymer matrix material comprises at least one of PA6 (nylon 6), PA66 (nylon 66), PA12 (nylon 12), PA6,66 (nylon 6-66), PPS (polyphenylene sulfide), PEI (polyetherimide), PEEK (polyetheretherketone), PEKK (polyetherketoneketone), PAEK (polyaryletherketone), PET (polyethylene terephthalate), PC (polycarbonate), ABS (acrylonitrile butadiene styrene) and PP (polypropylene).

[0019] Option 4. A thermoplastic composite elongated extrudate according to Option 1, wherein the thermoplastic liquid crystal polymer fibrils comprise at least one of any polymers having a main chain consisting of repeating units of aromatic rings linked together or a main chain of repeating units of aromatic rings linked to organic groups, which can form a liquid crystal phase.

[0020] Scheme 5. A method for manufacturing a thermoplastic composite elongated extrudate, comprising mixing a thermoplastic polymer matrix material and a thermoplastic liquid crystal polymer, wherein the viscosity of the thermoplastic polymer matrix material is substantially greater than the viscosity of the thermoplastic liquid crystal polymer at the extrusion temperature, and extruding the mixture to produce a composite elongated extrudate comprising the thermoplastic polymer matrix material, wherein the thermoplastic polymer matrix material has a plurality of elongated thermoplastic liquid crystal polymer fibrils generally aligned with the extrusion direction.

[0021] Option 6. A method for manufacturing a thermoplastic composite material according to Option 5, wherein the ratio of the viscosity of the thermoplastic polymer matrix material to the viscosity of the thermoplastic liquid crystal polymer at the extrusion temperature is greater than about 2.

[0022] Option 7. A method for manufacturing a thermoplastic composite material according to Option 5, wherein the thermoplastic polymer matrix material comprises at least one of PA6 (nylon 6), PA66 (nylon 66), PA12 (nylon 12), PA6,66 (nylon 6-66), PPS (polyphenylene sulfide), PEI (polyetherimide), PEEK (polyetheretherketone), PEKK (polyetherketoneketone), PAEK (polyaryletherketone), PET (polyethylene terephthalate), PC (polycarbonate), ABS (acrylonitrile butadiene styrene) and PP (polypropylene).

[0023] Option 8. A method for manufacturing a thermoplastic composite material according to Option 5, wherein the thermoplastic liquid crystal polymer comprises at least one of any polymers having a main chain consisting of repeating units of aromatic rings linked together or a main chain of repeating units of aromatic rings linked to organic groups, which can form a liquid crystal phase.

[0024] Option 9. A method for manufacturing a thermoplastic composite material according to Option 5, wherein the step of extruding the mixture is performed using a single-screw extruder to produce filaments suitable for melt filament manufacturing.

[0025] Option 10. A method for producing a thermoplastic composite material according to Option 5, wherein the elongated extrudate is pelletized.

[0026] Option 11. The method for manufacturing a thermoplastic composite material according to Option 5, further comprising adding a tackifier to the thermoplastic polymer matrix material.

[0027] Option 12. A method for producing a thermoplastic composite material according to Option 11, wherein the adhesion promoter is at least one of multi-walled carbon nanotubes, carbon black, nanoclay and silicate.

[0028] Option 13. A method for producing a thermoplastic composite material according to Option 11, wherein the tackifier is more miscible with the thermoplastic polymer matrix material than with the thermoplastic liquid crystal polymer.

[0029] Option 14. The method for manufacturing a thermoplastic composite material according to Option 5, further comprising adding a viscosity reducing agent to the thermoplastic liquid crystal polymer material.

[0030] Option 15. A method for manufacturing a thermoplastic composite material according to Option 14, wherein the viscosity reducing agent is at least one of boron nitride and / or fumed silica.

[0031] Option 16. A method for producing a thermoplastic composite material according to Option 14, wherein the viscosity reducing agent is more miscible with the thermoplastic liquid crystal polymer material than with the thermoplastic polymer matrix material.

[0032] Option 17. The method according to Option 5, wherein the mixture of the thermoplastic polymer matrix material and the thermoplastic liquid crystal polymer contains a compatibilizer to improve the interfacial bonding between the thermoplastic liquid crystal polymer material and the thermoplastic polymer matrix.

[0033] Item 18. The method of Item 17, wherein the compatibilizer comprises at least one of an ionomer and / or a copolymer.

[0034] Option 19. The method according to Option 5, wherein the mixture of the thermoplastic polymer matrix material and the thermoplastic liquid crystal polymer comprises a stabilizer.

[0035] Item 20. The method of item 19, wherein the stabilizer is at least one of polystyrene, poly(methyl methacrylate), or single-walled carbon nanotubes. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The present disclosure will be more fully understood from the detailed description and accompanying drawings, in which:

[0037] Figure 1 is a schematic diagram of an apparatus for making a thermoplastic extruded composite material comprising a thermoplastic polymer matrix material having a plurality of elongated thermoplastic liquid crystal polymer fibrils according to the principles of the present disclosure;

[0038] Figure 2 is a photomicrograph showing a cross-section of a filament of a thermoplastic extruded composite material comprising a thermoplastic polymer matrix material having a plurality of elongated thermoplastic liquid crystal polymer fibrils according to an embodiment of the present disclosure;

[0039] Figure 3 yes Figure 2 Magnified micrograph of a portion of the cross section shown in;

[0040] Figure 4 is a flow chart of one embodiment of a method of making a thermoplastic extruded composite material comprising a thermoplastic polymer matrix material having a plurality of elongated thermoplastic liquid crystal polymer fibrils according to the principles of the present disclosure;

[0041] Figure 5 is a micrograph of the self-reinforced thermoplastic composite material according to Example 1 of the present disclosure; and

[0042] Figure 6 is a micrograph of the self-reinforced thermoplastic composite material according to Example 2 of the present disclosure.

[0043] In the drawings, reference numerals may be repeated to designate similar and / or identical elements. DETAILED DESCRIPTION

[0044] Embodiments of the present disclosure provide a thermoplastic extruded composite material comprising a thermoplastic polymer matrix material having a plurality of elongated thermoplastic liquid crystal polymer fibrils generally aligned with an extrusion direction. In some embodiments, these fibrils may have a diameter of 1-10 μm, and in other embodiments, may have a diameter of 1-5 μm. Typically, the diameter of the fibrils may be controlled by changing the relative viscosity of the liquid crystal polymer and the thermoplastic matrix during the extrusion process. The fibrils may have a tensile modulus of 20-40 GPa, and the entire extrudate may have a tensile modulus of 35-70 GPa. The extrudate may be in the form of a thin (e.g., 3 mm to 8 mm in diameter), elongated extrudate. The elongated thermoplastic liquid crystal polymer fibrils may account for approximately 20% to approximately 80% by weight of the composite extrudate, and in some embodiments, may account for approximately 40% to approximately 60% by weight of the composite extrudate.

[0045] The thermoplastic polymer matrix material may comprise a wide variety of thermoplastic polymers, copolymers, and mixtures thereof, including, but not limited to, PA6 (nylon 6), PA66 (nylon 66), PA12 (nylon 12), PA6,66 (nylon 6-66), PPS (polyphenylene sulfide), PEI (polyetherimide), PEEK (polyetheretherketone), PEKK (polyetherketoneketone), PAEK (polyaryletherketone), PET (polyethylene terephthalate), PC (polycarbonate), ABS (acrylonitrile butadiene styrene), and PP (polypropylene). Generally, any thermoplastic material having a minimum processing temperature that does not exceed the thermal or rheological processing conditions of the thermoplastic liquid crystal polymer material and having compatible viscosity, elasticity, and interfacial tension may be a suitable matrix material.

[0046] Thermoplastic liquid crystal polymer materials may include various thermotropic liquid crystal polymers, including but not limited to Vectra B950 and Xydar SRT-900, as long as the liquid crystal polymer is compatible with the matrix material and the minimum supercooling processing temperature of the thermoplastic liquid crystal polymer material does not exceed the onset temperature of thermal or rheological degradation of the matrix material. A thermoplastic liquid crystal polymer material having a melting point of 275-305°C can be combined with a polymer having a melting point of 270-350°C (e.g., PPS or PEI), while a thermoplastic liquid crystal polymer material having a melting point of 320-360°C can be combined with a polymer having a melting point of 310-4000°C (e.g., PEI, PEKK, PAEK, and PEEK).

[0047] Embodiments of the present disclosure also provide a method of making a thermoplastic composite extrudate comprising a thermoplastic polymer matrix material having a plurality of elongated thermoplastic liquid crystal polymer fibrils. One such method is Figure 4 Generally it is expressed as 20. Figure 4 As shown, a thermoplastic liquid crystal polymer and a thermoplastic polymer matrix are loaded into the barrel of an extruder at 22. The thermoplastic liquid crystal polymer and the thermoplastic polymer matrix are selected so that when heated to the extrusion temperature, the ratio of the viscosity of the thermoplastic polymer matrix material to the viscosity of the thermoplastic liquid crystal polymer is at least about 2 to 1 to form fibrils during the extrusion process.

[0048] As described above, the thermoplastic polymer matrix material may comprise a wide variety of thermoplastic polymers, copolymers, and mixtures thereof, including, but not limited to, PA6 (nylon 6), PA66 (nylon 66), PA12 (nylon 12), PA6,66 (nylon 6-66), PPS (polyphenylene sulfide), PEI (polyetherimide), PEEK (polyetheretherketone), PEKK (polyetherketoneketone), PAEK (polyaryletherketone), PET (polyethylene terephthalate), PC (polycarbonate), ABS (acrylonitrile butadiene styrene), and PP (polypropylene). Generally, any thermoplastic material whose minimum processing temperature of the matrix material does not exceed the thermal or rheological processing conditions of the thermoplastic liquid crystal polymer material may be a suitable matrix material.

[0049] As also described above, the thermoplastic liquid crystal polymer material may include various thermotropic liquid crystal polymers, including but not limited to Vectra B950 ((aromatic co(polyester amide)) with 2,6-dihydroxynaphthoic acid (HNA), p-aminophenol (AP) and terephthalic acid (TA) having a molar ratio of 60 / 20 / 20) and Xydar SRT-900 (a copolymer of 4-hydroxybenzoic acid, 4,4'-biphenol and terephthalic acid), as long as the liquid crystal polymer is compatible with the matrix material and the minimum supercooling processing temperature of the thermoplastic liquid crystal polymer material does not exceed the upper limit of thermal or rheological degradation of the matrix material.

[0050] Before or after loading into the extruder, one or more tackifiers can be added to the thermoplastic polymer matrix material to obtain or maintain the desirable relationship between the viscosity of the thermoplastic polymer matrix material and the thermoplastic liquid crystal polymer. Tackifier can be at least one of multi-walled carbon nanotubes, carbon black, nanoclay (such as montmorillonite), boron nitride and silicate. Tackifier can be added to the thermoplastic polymer matrix material with a loading capacity of approximately 1 % by weight to approximately 10 % by weight of the polymer matrix material. In at least some embodiments, particularly in the presence of thermoplastic liquid crystal polymer, when adding tackifier, it is possible that desirable tackifier is more miscible with the thermoplastic polymer matrix material than with the thermoplastic liquid crystal polymer.

[0051] Before or after the forcing machine barrel of packing, one or more viscosity reducers can be added in the thermoplastic liquid crystal polymer (TLP), to obtain or keep the desirable relationship between the viscosity of thermoplastic polymer matrix material and the thermoplastic liquid crystal polymer (TLP).Viscosity reducer can be the nanoparticle of polymer, metal or pottery, for example aerosil.Viscosity reducer can be added in the thermoplastic liquid crystal polymer (TLP) material with the load capacity of approximately 1 % by weight to approximately 2 % by weight of liquid crystal polymer material.In at least some embodiments, particularly in the presence of the thermoplastic polymer matrix material, add the viscosity reducer under the situation of, possible desirable viscosity reducer and the thermoplastic liquid crystal polymer material than more miscible with the thermoplastic polymer matrix material.

[0052] A compatibilizer can be added to a mixture of a thermoplastic polymer matrix material and a thermoplastic liquid crystal polymer to improve the interfacial bonding between the thermoplastic liquid crystal polymer and the thermoplastic polymer matrix. The compatibilizer can include at least one of an ionomer, a copolymer, maleic anhydride, PEEK, other thermoplastic liquid crystal polymers, and a polyesterimide. In particular, ionomers of sulfonated polystyrene can improve the interfacial adhesion between the liquid crystal polymer and the thermoplastic matrix.

[0053] A stabilizer can be added to the mixture of the thermoplastic polymer matrix material and the thermoplastic liquid crystal polymer as a UV stabilizer to prevent discoloration under UV irradiation. The stabilizer can be at least one of polystyrene, poly(methyl methacrylate), or single-walled carbon nanotubes. Increasing the molar ratio of acid in the copolymer formulation of the thermoplastic liquid crystal polymer phase generally increases LC stability.

[0054] The thermoplastic polymer matrix material and thermoplastic liquid crystal polymer mixture are passed through one or more static mixers at 24. As described above, it is desirable that the ratio of the viscosity of the thermoplastic polymer matrix material to the viscosity of the thermoplastic liquid crystal polymer at the extrusion temperature be greater than about 2 and can be up to 1000 or more.

[0055] At 26, a mixture of a thermoplastic polymer matrix material and a thermoplastic liquid crystal polymer can be extruded from a single screw extruder to produce filaments. In some embodiments, the extrusion pressure is at least about 15 kPa. At 28, the filaments can be cooled and solidified by an optional water bath. The filaments can then enter a winder and be wound for filament manufacturing, or they can be pelletized.

[0056] One approach to making filaments for 3D printing is to first compound the LCP and matrix material and pelletize them without much concern or consideration for fibril formation—fibrils would then be generated in a subsequent processing step that uses the compounded pellets to produce filaments for fused filament fabrication. In other words, pellets containing a thermoplastic polymer matrix material and a thermoplastic liquid crystal polymer can be used as starting materials to produce self-reinforced thermoplastic composite filaments for 3D printing fused filament fabrication according to embodiments of the present disclosure.

[0057] The system of method 20 is Figure 1 100. The system 100 includes a barrel 102 for melting the thermoplastic polymer matrix material and the thermoplastic liquid crystal polymer or at least softening them sufficiently to allow them to be mixed. A typical temperature range will be above the liquid crystal phase-isotropic phase transition of the thermoplastic liquid crystal polymer and between about 570°F and about 610°F.

[0058] The system 100 further includes one or more static mixers 104 for mixing the thermoplastic polymer matrix material and the thermoplastic liquid crystal polymer along with any viscosity enhancers or viscosity reducers, compatibilizers, and stabilizers.

[0059] The system 100 also has an extrusion head 106 for extruding thin filaments. The filaments are preferably cooled in a water bath 108, after which they can be sent to a winder or pelletizer.

[0060] Example 1:

[0061] 40 wt% of Vectra B950 with a pure viscosity of about 50 Pa.s and 60 wt% of polyphenylene sulfide were mixed with a mixture having a pure viscosity of about 190 Pa.s measured at 325°C and a shear rate of 1 Hz using a twin-screw mixer, compounded using a twin-screw extruder, and then injection molded. The mixture was heated to a temperature of about 325°C, which is higher than the liquid crystal phase-isotropic phase transition temperature of Vectra B950, which occurs between about 300-310°C. A tensile test bar was prepared in a mold, which was carried out at a temperature of 127°C. The resulting sample was a fully thermoplastic composite material consisting of a liquid crystal polymer fibril reinforced polymer matrix. The results of the tensile test were a modulus of 10 GPa and a tensile strength of 79 MPa. Figure 5 The image of the broken section of the tensile sample shows the presence of the liquid crystal polymer fibrils of Vectra B950 and the PPS matrix.

[0062] The present inventors believe that maintaining a viscosity ratio of the thermoplastic polymer matrix material to the thermoplastic liquid crystal polymer of at least 2:1 facilitates the formation of liquid crystal polymer fibrils.

[0063] The material can be injection molded at high production rates and has improved surface properties compared to thermoset composites. It can also be recycled and used in similar applications because it remelts and forms new fibrils in a subsequent process.

[0064] Example 2:

[0065] 40 wt% was extruded using a twin-screw extruder (LCP), 55 wt% Polyphenylene sulfide (PPS) and 5 wt% fumed silica (FS) were mixed and then injection molded. The compounded material was prepared by mixing FS with PPS before adding LCP. During the injection molding process, the melt temperature leaving the barrel was 315°C, making the LCP an isotropic melt. The viscosity ratio of the PPS-FS mixture to the LCP was about 13.5. Tensile test bars were prepared in a mold at a temperature of 140°C to allow the LCP to transition from the isotropic phase to the liquid crystal phase and form fibrils. The tensile test results were a modulus of 13 GPa and a tensile strength of 107 MPa. Figure 6 The image of the broken section of the tensile sample shows the presence of the liquid crystal polymer fibrils of Vectra B950 and the PPS matrix.

[0066] The foregoing description is merely exemplary and is absolutely not intended to limit the present disclosure, its application or use. The broad teachings of the present disclosure can be implemented in various forms. Therefore, although the present disclosure includes specific examples, the true scope of the present disclosure should not be limited thereto, because other modifications will become apparent after studying the drawings, the specification and the following claims. It should be understood that one or more steps within the method may be implemented in a different order (or simultaneously) without changing the principles of the present disclosure. In addition, although the various embodiments are described above as having certain features, any one or more features described with respect to any embodiment of the present disclosure may be implemented in any other embodiment and / or combined with the features of any other embodiment, even if the combination is not explicitly described. In other words, the embodiments are not mutually exclusive, and the mutual replacement of one or more embodiments is still within the scope of the present disclosure.

[0067] Various terms are used to describe the spatial and functional relationships between elements (e.g., between modules, circuit elements, semiconductor layers, etc.), including "connected," "engaged," "coupled," "adjacent," "next to," "on top of," "over," "under," and "disposed." Unless explicitly described as "directly," when describing a relationship between a first element and a second element in the above disclosure, the relationship can be a direct relationship in which there are no other intervening elements between the first element and the second element, or an indirect relationship in which there are one or more intervening elements (spatially or functionally) between the first element and the second element. The phrase "at least one of A, B, and C" as used herein should be interpreted to mean a logical (A or B or C) using a non-exclusive logical OR, and should not be interpreted to mean "at least one of A, at least one of B, and at least one of C."

Claims

1. A thermoplastic composite elongated extrudate comprising a thermoplastic polymer matrix material having a plurality of elongated thermoplastic liquid crystal polymer fibrils generally aligned in the direction of extrusion.

2. The thermoplastic composite elongated extrudate of claim 1 , wherein the elongated thermoplastic liquid crystal polymer fibrils comprise from about 20% to about 80% by weight of the composite elongated extrudate.

3. The thermoplastic composite elongated extrudate according to claim 1, wherein the thermoplastic polymer matrix material comprises at least one of PA6 (Nylon 6), PA66 (Nylon 66), PA12 (Nylon 12), PA6,66 (Nylon 6-66), PPS (polyphenylene sulfide), PEI (polyetherimide), PEEK (polyetheretherketone), PEKK (polyetherketoneketone), PAEK (polyaryletherketone), PET (polyethylene terephthalate), PC (polycarbonate), ABS (acrylonitrile butadiene styrene) and PP (polypropylene).

4. The thermoplastic composite elongated extrudate of claim 1 , wherein the thermoplastic liquid crystal polymer fibrils comprise at least one of any polymer having a backbone consisting of repeating units of aromatic rings linked together or a backbone of repeating units of aromatic rings linked to organic groups, which can form a liquid crystal phase.

5. A method of making a thermoplastic composite elongated extrudate comprising mixing a thermoplastic polymer matrix material and a thermoplastic liquid crystal polymer, the viscosity of the thermoplastic polymer matrix material being substantially greater than the viscosity of the thermoplastic liquid crystal polymer at an extrusion temperature, and extruding the mixture to produce a composite elongated extrudate comprising the thermoplastic polymer matrix material having a plurality of elongated thermoplastic liquid crystal polymer fibrils generally aligned in the direction of extrusion.

6. The method of making a thermoplastic composite material according to claim 5, wherein the ratio of the viscosity of the thermoplastic polymer matrix material to the viscosity of the thermoplastic liquid crystal polymer at extrusion temperature is greater than about 2.

7. The method for manufacturing a thermoplastic composite material according to claim 5, wherein the thermoplastic polymer matrix material comprises at least one of PA6 (nylon 6), PA66 (nylon 66), PA12 (nylon 12), PA6,66 (nylon 6-66), PPS (polyphenylene sulfide), PEI (polyetherimide), PEEK (polyetheretherketone), PEKK (polyetherketoneketone), PAEK (polyaryletherketone), PET (polyethylene terephthalate), PC (polycarbonate), ABS (acrylonitrile butadiene styrene) and PP (polypropylene).

8. The method for producing a thermoplastic composite material according to claim 5, wherein the thermoplastic liquid crystal polymer comprises at least one of any polymer having a main chain consisting of repeating units of aromatic rings linked together or a main chain of repeating units of aromatic rings linked to organic groups, which can form a liquid crystal phase.

9. The method of making a thermoplastic composite material according to claim 5, further comprising adding a tackifier to the thermoplastic polymer matrix material.

10. The method for manufacturing a thermoplastic composite material according to claim 5, further comprising adding a viscosity reducing agent to the thermoplastic liquid crystal polymer material.

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