Continuous Fiber Thermoplastic Composites

[0001] This patent application claims the benefit of priority from U.S. Provisional Application Serial No. 61/861,188, filed August 1, 2013, teachings of which are herein incorporated by reference in their entirety.

Field of Invention

[0002] The present disclosure relates to continuous fiber thermoplastic composites comprising a high flow, low viscosity thermoplastic resin and continuous fiber, articles of manufacture produced from the composites, and methods of production and use of the composites.

Background

[0003] Thermoplastic composites are currently being developed for metal and/or wood to plastic replacement in applications requiring a strong, yet lightweight, and cost effective solution.

[0004] For example, automakers in many parts of the world are currently facing challenging fuel economy and even more demanding greenhouse-gas emission targets that have already begun phasing in and will become more severe over the next decade. In many countries, failing to meet these targets carries significant financial penalties with the potential to put noncomplying automakers out of business. Accordingly, there is much interest in finding ways to reduce the mass of vehicle bodies through use of thermoplastic composites laminates, particularly in body in white (BIW) applications.

[0005] Additional examples where a plastic replacement for metal or wood is desirable include, but are not limited to, truck/trailer load carrying structures, aircraft floor beams, housing construction joists, etc.

[0006] Nylons have been disclosed for use as the matrix material in engineering plastics with short reinforcing fibers such as glass or carbon fiber; such engineering plastics have a higher density than pure nylon. Such thermoplastic composites with about 25% to 60% short glass fibers are frequently used in molded car components next to the engine, such as intake manifolds, where the good heat resistance of such materials makes them feasible competitors to metals. [0007] However, the modulus or stiffness of glass-filled nylons (GF nylon) is very low compared to metal. For example, short fiber reinforced nylons have a stiffness of only l/20 ^th of steel. Thus, these GF nylons are difficult to use in body in white (BIW) structure applications. Short glass fibers can vary in length and have a general diameter of 10 to 15 microns. Milled short glass fibers are approximately 1/32 inch (1.59 mm) long while chopped glass fibers are typically between 1/8 and 1/4 inch (3.18 and 6.35 mm).

[0008] Continuous fiber and nylon composites offer better specific strength (strength to density ratio) and specific modulus (modulus to density ratio), as well as stiffness comparable to those of metals, without weight penalty.

[0009] Such composites of continuous fiber and thermoplastic resin can be fed into an extruder to make a fiber reinforced tape which is then used to form laminates.

[0010] A recent study at University of Warwick compared the energy absorption characteristics of a laminate produced from unidirectional tapes of a thermoplastic composite with a continuous E-glass fiber-reinforced polyamide 6 (PA6-GF60) with structural steel and aluminum (see www2 with the extension warwick.ac.uk/fac/sci/wmg/research/lcvtp/presentations /4__presentation_-

_physical_test_programmes outcomes_by_n._reynolds_wmg.pdf, November 2011).

[0011] Various tapes and fabrics of thermoplastic composites have been disclosed including narrow tapes (0.12"~0.2") which can be used to assemble wider tape of approximately 12" containing glass fiber tow partially coated with resin on the outside, a comingled fabric wherein each fabric has multiple tows and each tow contains a mixture of nylon fiber and glass fiber, and wider tapes of 4"-6" with glass fiber tows fully wetted by resin.

[0012] Tapes and laminates prepared from a nylon 6 thermoplastic resin and continuous glass fiber with a tensile strength of 450 MPa to 770 MPa are available commercially from BASF (BASF Ultracom Composite.pdf, September 2013).

[0013] Bond Laminates also offers various thermoplastic composite tapes and laminates with tensile strengths ranging from about 405 MPa up to 785 MPa under the tradename TEPEX®.

[0014] However, attempts to apply thermoplastic composite technology to commercially viable product development have faced challenges relating to materials, product manufacturing methods and quality issues.

[0015] Accordingly, there is a need for continuous fiber thermoplastic composites with desired quality, higher production rate and acceptable cost. Summary of the Invention

[0016] The present disclosure relates to a unique continuous fiber thermoplastic composite which is suitable for production of tape and fabric products that can be stitched and/or formed into laminates of a precise shape having areas engineered to provide various targeted strengths. Laminates of this unique continuous fiber thermoplastic composite and tapes and fabrics thereof are useful in imparting anisotropic, as well as isotropic, orientations to achieve optimal stress dissipation and/or distribution in three-dimensionally molded polymer parts.

[0017] Accordingly, an aspect of the present invention relates to a continuous fiber thermoplastic composite comprising a high flow, low viscosity thermoplastic resin which adheres to or binds continuous fiber.

[0018] In one nonlimiting embodiment, the thermoplastic resin comprises a nylon, a nylon polymer, a nylon copolymer or a combination or blend thereof.

[0019] In one nonlimiting embodiment, the thermoplastic resin further comprises an agent which reduces resin viscosity and/or increases resin flow.

[0020] In one nonlimiting embodiment, the continuous fiber comprises glass, carbon, aramid and/or basalt.

[0021] In one nonlimiting embodiment, the continuous fiber further comprises an interfacial modifier which improves adhesion between the continuous fiber and the thermoplastic resin.

[0022] Another aspect of the present invention relates to a fiber reinforced tape extruded from the thermoplastic composite.

[0023] Another aspect of the present invention relates to an article of manufacture produced from the continuous fiber thermoplastic composite comprising a thermoplastic resin and continuous fiber.

[0024] In one nonlimiting embodiment, the article of manufacture is a fiber or yarn spun from the continuous fiber thermoplastic composite.

[0025] In one nonlimiting embodiment, the article of manufacture is a fiber reinforced fabric woven from the fiber or yarn.

[0026] In one nonlimiting embodiment, the article of manufacture is molded from the thermoplastic composite or fiber reinforced tape. [0027] In one nonlimiting embodiment, the molded article is used as a less expensive, lighter replacement for wood or metal products.

[0028] In one nonlimiting embodiment, the article of manufacture is injection molded from the thermoplastic composite or fiber reinforced tape.

[0029] In one nonlimiting embodiment, the article of manufacture is compression molded from the thermoplastic composite or fiber reinforced tape.

[0030] In yet another nonlimiting embodiment, the article of manufacture is a laminate prepared from one or more fiber reinforced tapes or fabrics.

[0031] Another aspect of the present invention relates to a laminate prepared from the continuous fiber thermoplastic composite or one or more tapes or fabrics thereof, said laminate having a flexural strength of at least 1000 MPa.

[0032] Another aspect of the present invention relates to a laminate prepared from the continuous fiber thermoplastic composite or one or more tapes or fabrics thereof, said laminate having a flex modulus of at least 30 GPa or 30,000 MPa.

[0033] Another aspect of the present invention relates to a laminate prepared from the continuous fiber thermoplastic composite or one or more tapes or fabrics thereof, said laminate having a tensile strength of at least 700 MPa, more preferably at least 900 MPa.

[0034] Another aspect of the present invention relates a laminate prepared from the continuous fiber thermoplastic composite or one or more tapes or fabrics thereof, said laminate having a tensile modulus of at least 40,000 MPa.

[0035] Another aspect of the present invention relates to a method for production of a continuous fiber thermoplastic composite comprising a high flow, low viscosity thermoplastic resin and continuous fiber. In this method, the thermoplastic resin is coated on the continuous fiber either through a melt process, powder process or comingled fiber process.

[0036] In one nonlimiting embodiment, the thermoplastic resin used in this method comprises a nylon, a nylon polymer, a nylon copolymer or a combination or blend thereof.

[0037] In one nonlimiting embodiment, the thermoplastic resin used in this method further comprises an agent which reduces resin viscosity and/or increases resin flow.

[0038] In one nonlimiting embodiment, the continuous fiber used in this method comprises glass, carbon, aramid and/or basalt. [0039] In one nonlimiting embodiment, the continuous fiber used in this method further comprises an interfacial modifier which improves adhesion between the continuous fiber and the thermoplastic resin.

[0040] Another aspect of the present invention relates to a method for continuous consolidation of a fiber reinforced tape or fabric into a laminate, i this method, a plurality of tapes or fabrics laid in custom tailored orientation is consolidated into a laminate, preferably in a continuous manner.

[0041] Another aspect of the present invention relates to a method for injection molding a laminate from the continuous fiber thermoplastic composite or fiber reinforced tape or fabric.

[0042] Another aspect of the present invention relates to a method for compression molding a laminate from the continuous fiber thermoplastic composite or fiber reinforced tape or fabric.

[0043] Yet another aspect of the present invention relates to a method for molding an article of manufacture from the continuous fiber thermoplastic composite or a tape or fabric thereof. In this method one or more laminates are formed from the continuous fiber thermoplastic composite or a tape or fabric thereof into defined shapes. The one or more laminates are then placed into a desired mold for the article of manufacture and a molten thermoplastic is added to the mold to overmold the one or more laminates into the article of manufacture. Thickness and fiber orientation of the composite, tapes or fabrics in the one or more laminates can be customized to achieve optimal stress dissipation and/or distribution in the molded article of manufacture

Brief Description of the Figures

[0044] Figure 1 is a diagram outlining processes for preparation of various fiber reinforced tapes and/or fabrics of the present invention.

[0045] Figure 2 is a diagram outlining processes for production of an article of manufacture from the continuous fiber thermoplastic composite and/or laminate of the present invention.

[0046] Figure 3a through 3f are diagrams of various laminate constructions and their fiber patterns. Figures 3a and 3d show a unidirectional (UD) laminate and its fiber pattern, respectively. Figures 3b and 3f show a quasi-isotropic laminate and its fiber pattern, respectively. Figures 3c and 3e show a cross-ply laminate and its fiber pattern, respectively.

[0047] Figures 4(a) through 4(c) provide an illustration of use of the present invention as a side impact beam in the side door of an automobile. Figure 4(a) shows placement of the side impact beam within the door while Figures 4(b) and 4(c) show a top view and bottom view, respectively of the side impact beam.

[0048] Figure 5 is a photograph of a side impact beam produced by compression and injection molding using Tailored Fiber Placement (TFP) in accordance with the present invention The laminate base component is depicted by A while the overmolding features inclusive of a rib- attachment point is depicted by B.

[0049] Figures 6(a) and 6(b) show a cross-sectional view of the side impact beam also depicted in Figure 4 and 5. Figure 6(a) is a schematic showing the top, vertical wall and flange while Figure 6(b) is a photograph of a cross-sectional view of the side impact beam.

[0050] Figure 7 shows various nonlimiting configurations of continuous shape laminates which can be prepared in accordance with the present invention.

[0051] Figures 8(a) and 8(b) are graphs comparing resin viscosity and melt flow index of a thermoplastic resin PA66 and a high flow, low viscosity thermoplastic resin PA66 modified with polyhydric alcohol in accordance with the present invention. In the experiments, pellet moisture was controlled at 15%.

Detailed Description of the Invention

[0052] Provided by this disclosure is a continuous fiber thermoplastic composite, articles of manufacture produced from this composite as well as methods of production and use of the continuous fiber thermoplastic composite and articles of manufacture. The articles of

manufacture produced with the compositions and methods of the present invention are useful in applications in which light weight, high strength/stiffness, high impact resistance, temperature of use from -40°C to +180°C, and corrosion resistance are of primary design interests. Such applications include, but are in no way limited to automotive side impact beams, front end modules, floor structures, aerospace floor beams, construction joists, and truck supporting structures.

[0053] The continuous fiber thermoplastic composite of the present invention comprises a thermoplastic resin. Thermoplastic resins useful in the present invention exhibit characteristics of high flow, low viscosity and easy, as well as efficient, fiber wetting capabilities.

[0054] By "high flow, low viscosity" thermoplastic resin, it is meant a thermoplastic resin having a solution viscosity ranging from 20 to 80 relative viscosity (RV), preferably from 30 to 40 RV. A nonlimiting example of the viscosity and melt flow index of a high flow, low viscosity thermoplastic resin as compared to a neat thermoplastic resin is depicted in Figures 8(a) and 8(b), respectively. Use of high flow, low viscosity resins results in easier and better fiber wetting thereby cutting processing time. Better fiber wetting also ensures that the fibers are covered by polymer. Better polymer coverage of the fiber results in improved load transfer from polymer to fiber thus enhancing mechanical properties of the thermoplastic resins, tapes extruded therefrom and articles of manufacture comprising the resins.

[0055] In one embodiment, the high flow, low viscosity thermoplastic resin comprises a nylon, nylon polymer or nylon copolymer or a combination or blend thereof. Examples of nylons, nylon polymers and nylon copolymers useful in the present invention include, but are not limited to, polyamides such as nylon 6,6, nylon 6, nylon 4,6; nylon 6,12; nylon 6,10; nylon 6T; nylon 61; nylon 9T; nylon DT; nylon DI; nylon D6; and nylon 7; polymers and copolymers thereof including, but not limited to, nylon 6,6/D6, nylon DI/DT, nylon 6I/6T, nylon 6T/DT, and nylon 6,6/6; and/or blends or combinations thereof. By "blends or combinations thereof with respect to polyamides, it is meant to include, but is not limited to, block copolymers, random copolymers, terpolymers, as well as melt blends.

[0056] In one nonlimiting embodiment, nylon 6,6 polymer having a low relative viscosity such as described in U.S. Patent 8,501 ,900, teachings of which are incorporated herein by reference in their entirety, is used.

[0057] In one nonlimiting embodiment, the viscosity of the polyamide resin is lowered by altering termination chemistry of the polyamide such as described in, for example EP 2403896, teachings of which are herein incorporated by reference in there entirety.

[0058] In one nonlimiting embodiment, the thermoplastic resin of the present invention further comprises one or more agents which increase flow and/or lower viscosity of the thermoplastic resin. In one nonlimiting embodiment, the agent comprises a polyhydric alcohol, an alkyl stearate or an organo titanate/zirconate.

[0059] In one nonlimiting embodiment of the present invention, the thermoplastic resin comprises a polyamide resin and a polyhydric alcohol as described in published U.S. Application No. 2013/0228728, teachmgs of which are herein incorporated by reference in their entirety.

[0060] The thermoplastic resin may further comprise a long term and/or short term heat stabilizer. Examples of heat stabilizers useful in the present invention include, but are not limited to, copper-based heat stabilizers, copper or copper salt in combination with potassium iodide or potassium bromide, phenolic antioxidants, aromatic amines and polyhydric alcohols as well as other agents known by those of skill in the art to act as heat stabilizers, redox reaction agents and/or antioxidants in thermoplastic polymer production.

[0061] In one nonlimiting embodiment, nylon 6,6 further comprising copper iodide and potassium bromide is used in the thermoplastic resin. In this embodiment, preferably 40-200 ppm of Cul and 40-200 ppm of KBr are used.

[0062] The high flow, low viscosity thermoplastic resin makes up about 30-80% by weight of the continuous fiber thermoplastic composite.

[0063] The continuous fiber thermoplastic composite of the present invention further comprises continuous fiber of, for example, glass, carbon, aramid and basalt. By continuous fiber, as used herein, it is meant to encompass fibers greater in length than short fibers such as used in GF nylons. Short glass fibers can vary in length but typically range between 1.59 mm and 6.35 mm. Thus, by continuous fiber as used herein it is meant to encompass fibers greater in length than 6.35 mm. In one nonlimiting embodiment, fiber roving which comprises a collection of individual glass, carbon, aramid or basalt filaments held together with or without twisting is used.

[0064] In one nonlimiting embodiment, the fiber is modified with an interfacial modifier to facilitate adhesion between the fiber and the polyamide. Examples of interfacial modifiers which can be used include, but are not limited to, maleic anhydride, organo titanate/zirconate interfacial modifiers, and glycidyl-, ester-, methy methacrylate-, urethane- or silane-based interfacial modifiers. In one nonlimiting embodiment, the continuous fiber is coated with sizing comprising maleic anhydride.

[0065] The continuous fiber makes up about 20-80% by weight of the continuous fiber thermoplastic composite.

[0066] Without being bound to any particular theory, it is believed that use of the high flow, low viscosity thermoplastic resin in combination with the continuous fiber with interfacial modifier promotes chemical bonding between the fiber and the polyamide, thereby enhancing adhesion of the resin to the fiber. [0067] The present invention is also related to fiber reinforced tapes extruded from the continuous fiber thermoplastic composite. For these tapes, the thermoplastic resin is generally melt coated onto the continuous fiber or fiber roving.

[0068] The present invention is also related to articles of manufacture produced from the continuous fiber thermoplastic composite and tapes thereof.

[0069] In one nonlimiting embodiment, the article of manufacture comprises a fiber spun from the continuous fiber thermoplastic composite.

[0070] In another nonlimiting embodiment, the article of manufacture comprises a plurality of fibers held together with or without twisting to produce a yarn.

[0071] Nonwoven and woven fabrics can then be produced from the fibers and yarns.

[0072] Tapes produced from these composites are generally of unidirectional (UD) stitch bonded construction. Nonwoven fabrics may also be unidirectional (UD). By "unidirectional or UD", as used herein, it is meant that all the fibers or fiber roving in the tape or fabric are in one direction, generally 0 degrees.

[0073] Fabrics may also be of bidirectional or multiaxial stitch bonded construction.

[0074] Processes for production of various embodiments of fiber reinforced tapes and/or fabrics of the present invention including UD narrow tape, UD woven wider tape, UD non-crimp fabric and a non-crimp/crimp fabric are depicted in Figure 1.

[0075] For purposes of the present invention, by "woven/crimp fabric it is meant that each fiber roving crosses underneath another fiber roving.

[0076] For purposes of the present invention, by "non-crimp fabric" it is meant that each fiber roving lies on top of another fiber roving without crossing.

[0077] In one embodiment, the article of manufacture is a laminate formed by laying the tapes or fabrics produced from the continuous fiber thermoplastic composite in customized layers of orientation. Figure 2 provides a diagram of examples of processes used to prepare a laminate of the present invention from either a UD narrow tape, UD wide tape or a UD woven wider tape, a UD fabric or a non-crimp/crimp fabric. Figures 3a through 3f provide diagrams of various nonlimiting embodiments of laminates which can be constructed in accordance with the present invention. Such embodiments include, but are not limited to, UD laminates (Figures 3a and 3d), cross-ply laminates wherein the tapes or fabrics are laid at 0 degrees and 90 degrees (Figures 3c and 3e), and quasi-isotropic laminates wherein the tapes or fabrics are laid at 0, 45 and 90 degrees (Figures 3b and 3f). In one embodiment, the laminate prepared from the continuous fiber thermoplastic composite or tape or fabric thereof has a flex strength of at least 1000 MPa. In one embodiment, the laminate prepared from the continuous fiber thermoplastic composite or tape or fabric thereof has a flex modulus of at least 30 GPa or 30,000 MPa. In one embodiment, the laminate prepared from the continuous fiber thermoplastic composite or tape or fabric thereof has a tensile strength of at least 700, more preferably at least 900 MPa. In one embodiment, the laminate prepared from the continuous fiber thermoplastic composite or tape or fabric thereof has a tensile modulus of at least 40,000 MPa.

[0078] Articles of manufacture of the present invention can also be injection molded and/or compression molded from the thermoplastic composite or fiber reinforced tape or fabric. In one embodiment, the article of manufacture is used as a less expensive, lighter replacement for wood or metal products. For example, the composite can be used in an automotive crash beam as depicted in Figures 4 through 6, auto body B pillars and as structural beams and components for rail transportation, trucks, shipping containers and industrial and/or home building. As shown in Figure 7, the continuous fiber thermoplastic composite of the present invention can also be molded into various continuous shape laminates including, but not limited to, I-, C-, n-, T-, Z and L-shaped laminates.

[0079] The present invention also relates to methods for production of a continuous fiber thermoplastic composite comprising a thermoplastic resin and continuous fiber. In this method, the thermoplastic resin is coated on to the continuous fiber, either through melt process, powder process, or a comingled fiber process wherein fibers of the thermoplastic resin and the continuous fiber are consolidated by heat. Preferred in these processes is that residence time in the extruder or melt pump, or special melt die head be sufficient to promote chemical bonding between the fiber and the polyamide, thereby enhancing adhesion of the resin to the fiber. As will be understood by the skilled artisan upon reading this disclosure, the length of the residence time is a function of the polymer being processed and the width of the article being extruded and may need to be increased for wider articles.

[0080] In addition, the present invention provides methods for continuous consolidation of a fiber reinforced tape or fabric extruded from the continuous fiber thermoplastic composite. In this method, tapes or fabrics are laid in a custom tailored orientation for optimum property targeting and consolidated into laminates in a continuous manner. [0081] Further, the present invention provides methods for injection molding and compression molding articles of manufacture from the thermoplastic composite or fiber reinforced tape or fabric of the present invention.

[0082] In one embodiment, one or more laminates are first formed from the thermoplastic composite or tape or fabric thereof into defined shapes. Thickness as well as fiber orientation of the composite, tapes or fabrics making up the laminate can be customized to achieve optimal stress dissipation and/or distribution in the three-dimensionally molded polymer parts comprising the laminates, thereby enhancing performance of the end product or part. For example, in the side impact beam depicted in Figures 4 through 6, the laminate was 2 mm in thickness at the top with a UD orientation of 0 degrees, 1 mm in thickness on the vertical walls with a quasi-isotropic orientation of + 45 degrees; and 3 mm in thickness on the flange with a cross-ply orientation of 90 degrees. As will be understood by the skilled artisan upon reading this disclosure, with the present invention, thicknesses and orientations of the laminate can be routinely modified depending upon the part being molded. Further, more than one laminate with similar or differing thicknesses and/or orientations may be used in a part. The one or more laminates are then placed into a desired mold for the article of manufacture. A subsequent molten

thermoplastic is then added to overmold the part into a final shape, with commercial surface quality and multi-functional design features that injection molding technology offers. See Figure 5. Examples of subsequent molded thermoplastics which can be added to overmold the part include, but are not limited to, nylon, nylon copolymer, polybutylene terephtalate (PBT), polyethylene (PE) and polypropylene (PP). Examples of end products produced in accordance with the compositions and methods of this invention include, but are not limited to, snap fit, fastener connection details, and achieving multi functional parts in one consolidated part while offering excellent structural strength as well as aesthetic and functional diversity.

[0083] In these laminate making processes, the residence time is selected to promote further wetting of the glass fibers, squeeze out excess resin, and promote chemical bonding between fiber and polymer. Preferred is that the residence time be at least 3 minutes. However, as will be understood by the skilled artisan upon reading this disclosure, this time may vary depending upon the thickness and size of the laminate. [0084] The following section provides further illustration of the thermoplastic composites, articles of manufacture and processes of the present invention. These working examples are illustrative only and are not intended to limit the scope of the invention in any way.

EXAMPLES

[0085] Example 1

[0086] Resin formulation:

1. Plain PA66 resin

2. Plain PA66 resin 100 parts, Copper-based heat stabilizer 3.1 parts

3. Plain PA66 resin 100 parts, high flow additive 5.56 parts

4. Plain PA66 resin 100 parts, high flow additive 5.28 parts, heat stabilizer 0.32 parts Reinforcement type: Glass fiber roving, compatible with polyamide

UD narrow tape production: The resin was first passed through a single- or twin-screw extruder (at temperature 270°C to 290°C) to reach molten state, and then it was pushed into a pressurized coating die. The pressurized coating die was also heated to maintain molten state and low resin viscosity for subsequent coating operation. At the same time, glass fiber roving was fed into the pressurized coating die so that the resin could fully coat (with high pressure) or partially coat (with low pressure) the glass fiber roving to produce UD narrow tape. As the UD narrow tape exited the pressurized die head, the narrow tape was cooled and wound onto a creel.

[0087] Example 2

[0088] Resin formulation:

1. Plain PA66 resin 100 parts, high flow additive 5.28 parts, heat stabilizer 0.32 parts

2. Plain PA66/D6 resin 100 parts, high flow additive 5.28 parts, heat stabilizer 0.32 parts Reinforcement type: Glass fiber roving, multiple roving, compatible with polyamide

UD wide tape production: The resin was first passed through a single- or twin-screw extruder (at temperature 270°C to 290°C) to reach molten state, and then it was pushed into a pressurized coating die. The pressurized coating die was also heated to maintain molten state and low resin viscosity for subsequent coating operation. At the same time, several glass fiber roving were first spread and passed through a series of rollers to ensure straightness and flatness of roving, and then they were placed side-by-side (no gap between two roving) and fed into the pressurized coating die so that the resin could fully coat (with high pressure) the glass fiber roving to produce UD wide tape. As the UD wide tape exited the pressurized die head, the wide tape was cooled and wound onto a creel.

[0089] Example 3

[0090] Resin for polymer yarn production:

1. Plain PA66 resin 100 parts, high flow additive 5.28 parts, heat stabilizer 0.32 parts

2. Plain PA66/D6 resin 100 parts, high flow additive 5.28 parts, heat stabilizer 0.32 parts Reinforcement type; Glass fiber roving, compatible with polyamide

Commingled fabric production: The polymer/resin was spun into monofilament (20-50 μηι in diameter) and several monofilaments are combined into a yarn. The yarn length was greater than 10 km per spool of yarn. During commingling operation, a spool of polymer yarn and a spool of glass fiber roving were individually spun at high speed (5000 rpm) so that each polymer filament and glass fiber was uniformly separated. Afterward, multiple separated polymer yarn and glass fiber were guided into a collector and immediately recombined to give commingled fiber. Using commercial textile processes, multiple commingled fiber spools were wo en/stitched into UD, crimp and non-crimp fabrics. Multi-directional (with 0, 90 and ± 45 being the most common) construction was possible during fabric construction. The width 0 commingled fabric can be as high as 50 inches. The polymer yarns embedded inside the commingled fabric will eventually melt and wet the surrounding glass fibers during the laminate making process.

[0091] Example 4

[0092] Material used: UD narrow tape, resin formulation 1&2 from Example 1

Laminate molding process: A Tailored Fiber Placement (TFP) machine was used to create a preform with a selected orientation. Typical preform orientation can be UD, 0/90 and 0/90/±45. First, the narrow tape (width of 3-5 mm) and stitching material were fed into the tip of the TFP machine, and the preforming operation began by simultaneously placing and stitching narrow tape onto a veil for support. Upon the completion of the preforming operation, the stitched preform was placed in a vacuum oven at elevated temperature of about 285°C for degassing to remove trapped air inside the preform and drying to remove moisture from the resin. Afterward, the preform was placed on a compression molding machine to produce a flat laminate. The compression molding process takes place for approximately 20 minutes, including both heating and cooling cycles with pressure. In the heating cycle, the temperature is raised to about 285 °C. In the cooling cycle the temperature is decreased to about 100 °C. The demolded part was carefully machined to obtain test specimens for various types of mechanical tests. All mechanical tests are conducted according to ASTM standards as listed in Table 1 below. The tensile and flexural strength of a UD laminate were 729 MPa and 584 MPa, respectively, at dry as molded (DAM) condition. The laminate fiber volume fraction was estimated to be approximately 50- 55%.

[0093] Example 5

[0094] Material used: UD narrow tape, resin formulation 3 from Example 1

Laminate (flat) molding process: A Tailored Fiber Placement (TFP) machine was used to create a preform with a selected orientation. Typical preform orientation can be UD, 0/90 and 0/90/±45. First, the narrow tape (width of 3-5 mm) and stitching material were fed into the tip of the TFP machine, and the preforming operation began by simultaneously placing and stitching narrow tape onto a veil for support. Upon the completion of the preforming operation, the stitched preform was placed in a vacuum oven at elevated temperature of about 285 °C for degassing to remove trapped air inside the preform and drying to remove moisture from the resin. Afterward, the preform was placed on a compression molding machine to produce a flat laminate. The compression molding process takes place for approximately 20 minutes, including both heating and cooling cycles with pressure. In the heating cycle, the temperature is raised to about 285 °C. In the cooling cycle the temperature is decreased to about 100 °C. The demolded part was carefully machined to obtain test specimens for various types of mechamcal tests. All mechanical tests are conducted according to ASTM standards as listed in Table 1 below. The tensile and flexural strength of a UD laminate were on average 920 MPa and 1,040 MPa, respectively, at dry as molded (DAM) condition. After moisture conditioning the test specimens at 50% relative humidity (RH) for one month, the tensile and flexural strength of a UD laminate were on average 830 MPa and 755 MPa, respectively. The laminate fiber volume fraction is estimated to be approximately 50-55%. [0095] Table 1

[0096] Example 6

[0097] Material used: UD wide tape, resin formulation 1&2 from Example 2

Laminate (flat and shape) molding process: An ultrasonic tacking method was used to create a preform with a selected orientation. Typical preform orientation can be UD, 0/90 and 0/90/±45. First, the 4-6 inch wide tape was cut to a desired length and laid on a layup table. The preforming operation began by ultrasonic tacking multiple wide tapes side-by-side and top-to-bottom wise. Upon completion of the preforming operation, the tacked preform was wound onto a creel and was ready for molding processing. The preform was continuously fed into an extrusion machine to produce flat and shaped ("I", "C", box, etc.) laminates. The extrusion process takes place at a throughput rate of 10 ft/hr, including both heating and cooling cycles with pressure. The laminate fiber volume fraction was estimated to be approximately 50%. Depending on the nature of application, various structural assemblies can be achieved by joining flat laminate to shaped laminate or shaped laminate to shaped laminate using mechanical, adhesive, chemical and physical methods.

[0098] Example 7

[0099] Material used: Commingled fabric, Example 3

Laminate (flat and shape) molding process: A manual or automated method was used to create a preform with a selected orientation. Typical preform orientation can be UD, 0/90 and 0/90/±45. First, the commingled fabric was cut to a desired length and laid on a layup table. The preforming operation began by ultrasonic tacking multiple fabrics top-to-bottom wise. Upon the completion of the preforming operation, the tacked preform was wound onto a creel and was ready for molding processing. The preform was continuously fed into an extrusion machine to produce flat and shaped ("I", "C", box, etc.) laminates. The extrusion process takes place at a throughput rate of 10 ft/hr, including both heating and cooling cycles with pressure. The laminate fiber volume fraction was estimated to be approximately 50%. Depending on the nature of application, various structural assemblies can be achieved by joining flat laminate to shaped laminate or shaped laminate to shaped laminate using mechanical, adhesive, chemical and physical methods.

ΙΌ01001 Example 8

[00101] Multi-stage molding process: A secondary injection molding process can also be implemented in Example 6 and 7 to furnish the laminate parts with various complex geometrical features. This process is also known as "over-molding". In this process, various types of engineered polymers such as short glass fiber-filled grade, toughened grade, etc. that are compatible with the resins used in Example 6 and 7 can be used as over-molding materials, depending on the specified design criteria.

[001021 Example 9

[00103] The parts made using methods described in Example 6, 7 and 8 can be used in applications which lightweight, high strength/stiffness, high impact resistance and corrosion resistance are of primary design interests. Such applications can include automotive side impact beam, front end module, floor structure, aerospace floor beam, construction joist, truck supporting structures etc.