权利要求：
1. A silk fibroin composite comprising:
a plurality of coupled layers wherein at least one of the layers includes a composite matrix of at least one non-silk polymer and silk fibroin material derived at least in part from expression of one or more spider silk genes within at least one living organism, the plurality of coupled layers further comprising:
at least one backing or surface layer;
a substantially honeycomb-shaped core including a plurality of cells,
wherein the honeycomb-shaped core comprises the silk fibroin material, and
the substantially honeycomb-shaped core coupled to the at least one backing or surface layer with a continuous fiber-reinforced polymer layer,
wherein the continuous fiber-reinforced polymer layer closes openings of the plurality of cells, and
wherein the continuous fiber-reinforced polymer layer comprises a phenolic resin matrix and continuous spider silk fiber and carbon fiber dispersed in the phenolic resin matrix; and
wherein the at least one of the layers of the plurality of coupled layers includes a fibrous material.
2. The composite of claim 1, wherein the silk fibroin material includes at least one of silk fiber and silk polypeptides in a non-fibrous form.
3. The composite of claim 2, wherein the silk polypeptide in a non-fibrous form forms at least a portion of the composite matrix of the at least one backing or surface layer, or at least one layer of the plurality of coupled layers.
4. The composite of claim 1, wherein the at least one non-silk polymer includes at least one of a thermoplastic polymer and a thermoset polymer.
5. The composite of claim 1, wherein the plurality of coupled layers includes at least one of a polyurethane polymer, a polycarbonate polymer, a polypropylene polymer, an acrylonitrile butadiene styrene (ABS) polymer, a polylactic acid (PLA) polymer, a polyamide (nylon) polymer, a glass-filled polyamide polymer, an epoxy resin, silver, gold, titanium, steel, stainless steel, wax, a photopolymer, high density polyethylene (HDPE), polycarbonate-acrylonitrile butadiene styrene (PC/ABS) polymer, and polyphenylsulfone (PPSU) polymer.
6. The composite of claim 1, wherein the at least one non-silk polymer comprises polyurethane reaction product of one or more isocyanates and at least one isocyanate-reactive component.
7. The composite of claim 1, wherein the silk fibroin material includes at least one of a plurality of long fibers of varying lengths and a plurality of short fibers comprised of a variety of lengths; and
wherein the long fibers have lengths of more than 3 mm and the short fibers have lengths less than the shortest of any of the lengths of the plurality of long fibers.
8. The composite of claim 7, wherein the long fibers make up 0.5 wt.% to 99 wt. % of the combined weight of the plurality of coupled layers.
9. The composite of claim 1, wherein the silk fibroin material comprises electro-spun silk.
10. The composite of claim 1, wherein the silk fibroin material includes silk weave or cloth, silk fiber, silk mat.
11. The composite of claim 1, wherein at least a portion of the composite matrix is derived by injection molding, reaction-injection molding, chopped-fiber injection, extrusion, molding, film casting, web coating, spray-coating, weaving, vacuum injection, or 3D printing.
12. The composite of claim 1, wherein at least a portion of the plurality of coupled layers includes a fibrous material that includes at least one of a silk fiber, a silk weave or cloth, and a silk mat.
13. The composite of claim 12, wherein the article of manufacture includes at least one of a load-bearing structure, non-load-bearing structure, and a decorative or aesthetic structure.
14. The composite of claim 1, wherein the plurality of coupled layers is an article of manufacture selected from a land vehicle frame, an air vehicle frame, a sea vehicle frame, a land vehicle panel, an air vehicle panel, and a sea vehicle panel.
15. The composite of claim 1, wherein the at least one backing or surface layer further comprises a polyaramid fiber.
16. A silk fibroin composite comprising:
a plurality of coupled layers wherein at least one of the layers includes a composite matrix of at least one non-silk polymer and silk fibroin material derived at least in part from expression of one or more spider silk genes within at least one living organism, the plurality of coupled layers further comprising:
at least one backing or surface layer;
a substantially honeycomb-shaped core including a plurality of cells, wherein the honeycomb-shaped core comprises the silk fibroin material, and the substantially honeycomb-shaped core coupled to the at least one backing or surface layer with a continuous fiber-reinforced polymer layer, wherein the continuous fiber-reinforced polymer layer closes openings of the plurality of cells, and wherein the continuous fiber-reinforced polymer layer comprises a phenolic resin matrix and continuous spider silk fiber and carbon fiber dispersed in the phenolic resin matrix; and
wherein the at least one of the layers of the plurality of coupled layers includes a fibrous material.
17. The composite of claim 1, wherein the honeycomb core is comprised of a hybrid fiber of silk fiber and a polyaramid fiber.
18. A method of making a silk fibroin composite comprising:
providing at least one non-silk polymer and silk fibroin material derived at least in part from expression of one or more spider silk genes in at least one living organism;
combining at least a portion of the silk fibroin material and the at least one non-silk polymer material to form a mixture;
forming a composite matrix from at least a portion of the mixture using a process of injection molding, reaction-injection molding, chopped-fiber injection, extrusion, molding, film casting, web coating, spray-coating, weaving, vacuum injection, and 3D printing;
forming a plurality of coupled layers wherein at least one of the layers includes at least a portion of the composite matrix, the plurality of layers further comprising:
at least one backing or surface layer and at least one layer including a substantially honeycomb-shaped core including a plurality of cells, wherein the honeycomb-shaped core comprises the silk fibroin material and, the substantially honeycomb-shaped core coupled to the at least one backing or surface layer with a continuous fiber-reinforced polymer layer, wherein the continuous fiber-reinforced polymer layer closes openings of the plurality of cells, and wherein the continuous fiber-reinforced polymer layer comprises a phenolic resin matrix and continuous spider silk fiber and carbon dispersed in the phenolic resin matrix; and
wherein the at least one of the layers of the plurality of coupled layers includes a fibrous material.
19. The method of claim 18, wherein the silk fibroin material includes at least one of a plurality of long fibers of varying lengths and a plurality of short fibers comprised of a variety of lengths, wherein the long fibers have lengths of more than 3 mm and the short fibers have lengths less than the shortest of any of the lengths of the plurality of long fibers.
20. The method of claim 19, wherein the long or short fibers include at least one of a silk fiber, a silk weave or cloth, and a silk mat.
21. The method of claim 18, wherein the plurality of coupled layers is an article of manufacture selected from a land vehicle frame, an air vehicle frame, a sea vehicle frame, a land vehicle panel, an air vehicle panel, and a sea vehicle panel.
22. The method of claim 21, wherein the article of manufacture includes at least one of a load-bearing structure, non-load-bearing structure, and a decorative or aesthetic structure.
23. A method of making a silk fibroin composite comprising:
feeding a silk fibroin material into an extruder, the silk fibroin material derived at least in part from expression of one or more spider silk genes in at least one living organism;
extruding a silk fiber precursor from the silk fibroin material;
passing the silk fiber precursor through a coagulation bath at one end of the coagulation bath;
forming a silk fiber from the silk fiber precursor through coagulation in the coagulation bath;
stretching at least a portion of the silk fiber using at least one set of godets;
combining at least a portion of the silk fiber with at least one non-silk polymer material to form a feedstock;
using the feedstock, forming a composite matrix using at least one of injection molding, reaction-injection molding, chopped-fiber injection, extrusion, molding, film casting, web coating, spray-coating, batch mixing, weaving, vacuum injection, and 3D printing;
forming a plurality of coupled layers wherein at least one of the layers includes at least a portion of the composite matrix, the plurality of layers further comprising:
at least one backing or surface layer and at least one layer including a substantially honeycomb-shaped core including a plurality of cells, wherein the honeycomb-shaped core comprises the silk fibroin material and, the substantially honeycomb-shaped core coupled to the at least one backing or surface layer with a continuous fiber-reinforced polymer layer, wherein the continuous fiber-reinforced polymer layer closes openings of the plurality of cells, and wherein the continuous fiber-reinforced polymer layer comprises a phenolic resin matrix and continuous spider silk fiber and carbon dispersed in the phenolic resin matrix; and
wherein the at least one of the layers of the plurality of coupled layers includes a fibrous material.
24. The method of claim 23, wherein the composite matrix includes at least one of a plurality of long fibers of varying lengths and a plurality of short fibers comprised of a variety of lengths; and wherein the long fibers have lengths of more than 3 mm and the short fibers have lengths less than the shortest of any of the lengths of the plurality of long fibers.
25. The method of claim 24, wherein the long fibers make up 0.5 wt.% to 99 wt. % of the combined weight of the composite matrix.
26. The method of claim 23, wherein the honeycomb-shaped core includes at least one of an aluminum core, a foam core, a wood core, and a carbon-fiber core.
27. The method of claim 23, further comprising mixing the feedstock with another feedstock selected from a soap material, a cosmetic material, or a paint material.
具体实施方式：
[0038]Some embodiments include materials, structures, and articles of manufacture including silk fibroin material derived at least in part from expression of one or more spider silk genes within at least one living organism. As used herein, the silk fibroin material can be any silk fiber and/or silk protein derived from the expression of the one or more spider silk genes, and the term spider silk fiber and/or spider silk protein is used herein to define the silk fibroin material. Some embodiments of the invention include load-bearing panels, materials, and products made with, and out of, spider silk fiber and/or spider silk protein, such as load-bearing composite panels, materials, and products made by surrounding them with short or long fiber and/or spider silk long-continuous fiber-cloth-proteins reinforced polyurethane resin, an assembly containing one or more load-bearing members, graphene, a structural polyurethane/resin sandwich composite and/or spider silk proteins-fiber-cloth-continuous fiber. Some embodiments of the invention provide such panels, materials, and products, and also processes for their production. The inventive load-bearing composite panel, materials, and products can be made by surrounding with a continuous spider silk fiber and/or spider silk cloth and/or long fiber reinforced polyurethane resin an assembly made from one or more load-bearing members and a structural polyurethane and/or resin sandwich composite. Some embodiments of the lightweight inventive panels, materials, and products have greater bending and buckling strength than the sum of the individual components due to the physical properties of the continuous spider silk fiber and/or spider silk cloth and/or long fiber reinforced polyurethane.
[0039]Some embodiments of the inventive composite panels, materials, and products can find use in such items as automobile floor panels, vehicle body panels, bullet-proof anti-ballistic panel products, vehicle bullet-proof-anti-ballistic body panel structures and floors, bullet-proof vests, vehicle chassis structures, monocoque chassis, motor home chassis bodies, fuselages, floors and frames for aircraft and/or UAV's, bicycle and motorcycle frames, wind turbine blade frame structures, ship and boat haul body structures, submarines body structures, shipment containers, pre-fabricated walls and associated structures of homes and other buildings, train structures and body panels and/or floor panels, solar panel supports, battery housings, walls for mobile homes, roof modules, truck beds, truck trailer floors and the like. Such composite panels, materials, and products made with, or out of, spider silk fibers and/or spider silk proteins can also be utilized in artificial organs, ligaments or tendons, artificial disc vertebrae, brushes, ropes, and 3D printed parts.
[0040]In some embodiments, the spider silk proteins and fibers can be mixed with resins, chemicals, films, etc. to improve the chemical and/or mechanical properties of different components-technologies. In some embodiments, the spider silk proteins and fibers can be used to prepare glues or adhesives, either alone or in combination with other chemical additives. In some further embodiments, the spider silk proteins and fibers can be used to prepare soaps, cosmetics, paints and other coatings, either alone or in combination with other chemical additives.
[0041]The panels, materials, and products of some embodiments of the invention can be combinations of existing fibers (such as carbon fiber, fiberglass, natural fibers, Kevlar) that are combined with spider silk fiber. In some embodiments, the spider silk proteins and/or fibers are mixed with resins, polyurethane, and other chemicals.
[0042]In some embodiments, such panels, materials, and products can be made with only the pure fibers spider silk fibers themselves or combined with the other fibers.
[0043]In some embodiments, the spider silk fibers by themselves (or combined with fibers of other materials) can be combined with honeycomb cores (such as aluminum, Kevlar, carbon fiber, Nomex, cardboard, and polypropylene) or other natural fiber cores.
[0044]In some embodiments, spider silk fibers and proteins are combined with chemicals, composites, and thermosets to improve their mechanical properties.
[0045]In some embodiments, spider silk fibers and proteins are used as additives in materials such as acrylonitrile butadiene styrene (ABS), polycarbonate (PC), polylactic acid (PLA), polyamide (nylon), glass-filled polyamide, stereo lithography materials (epoxy resins), silver, gold, titanium, steel, stainless steel, wax, photopolymers, high density polyethylene (HDPE), PC/ABS, and polyphenylsulfone (PPSU).
[0046]“Spider silk” as used herein refers to fiber or protein materials that can be created by spiders but can (and are) also artificially manufactured. U.S. Patent Appl. Publ. No. 2013/0212718 to Fraser et al. teaches chimeric spider silk and uses thereof. U.S. Patent Appl. Publ. No. 2015/0047532 to Lewis et al. teaches synthetic spider silk protein compositions and methods (which includes mixing recombinant spider silk proteins with water to form a mixture and hearing the mixture in a closed vessel to form a solution). U.S. Patent Appl. Publ. No. 2015/0202651 to Lewis et al. teaches a method of forming recombinant spider silk protein films.
[0047]For instance, protein samples of spider silk (“spider silk protein”) can be made via a fermentation process, such as shown in FIG. 1. Cells or bacteria containing the spider silk genes in their DNA (spider silk closed DNA) can be placed in a fermentation tank, and the spider silk protein is produced through a fermentation process, and the spider silk proteins extracted using a high-pressure bacterial cell lysis process, or any other conventional bacterial cell lysis process.
[0048]As shown in FIG. 2A, fibers of spider silk (“spider silk fibers”) can be made from the spider silk protein, For instance, the spider silk proteins can be processed and dried, and then electro-spun in an aqueous solution. As also shown in FIG. 2A, these spider silk proteins can be processed and dried and then are used as an additive in chemicals-plastics-composites (such as resins, polyurethanes, and other conventional polymers, etc.) to improve their mechanical properties.
[0049]FIG. 2B illustrates a process 250 utilizing spider silk protein and/or spider silk to prepare spider silk fiber used in at least one embodiments of the invention described herein. In some embodiments of the invention, a piston/extruder 251 can be used to extrude spider silk spin dope. In some embodiments, constant pressure can be applied to the spin dope to extrude a silk fiber 260 into a coagulation bath 252. In some embodiments, isopropanol (or other solvents) can be used to help with fiber formation and to extract solvents used in the spin dope. In some embodiments, using a Teflon® brand or other low friction material guide 253, the fiber 260 can be fed to one or more godets 254 (shown as 254a, 254b, 254c) that are sets of wheels that spin in synchronization along which the fiber runs). In some embodiments, one or more sets of godets 254 can be programmed to rotate at different speeds independently and this allows stretch to be applied to the fiber 260. Further in some embodiments, a stretch bath 255 can be used as the fiber 260 is stretched by a difference in speed between two or more godets 254, and the fiber 260 can run through a stretch bath 255 to aid in protein motif formation and alignment. In some embodiments, a drying unit 256 can be used with either heat or a slight air current, and the solvents used in the stretch bath can be driven off prior to entering the water bath or before going into the winder. In some embodiments, using a water bath 257, the fiber 260 can run through water or a water/alcohol or water/salt mix to further strengthen and align the fiber 260. In some embodiments, a stretch can also be applied here between the second and third godet sets (254b, 254c). Finally, a winder 258 can be used so that the fiber 260 is guided for collection. Other embodiments can use more or less godets 254 and more or less numbers and types of baths 255, 257.
[0050]FIG. 3 is a photograph that includes samples of spider silk materials, namely a cloth with square of spider silk fibers 301 (dyed green) and a cloth with spider silk fibers 302 (white). A close-up view of the square of spider silk fibers 101 is shown in FIG. 4. These materials can be prepared using the processes described above and shown in FIG. 2B.
[0051]Some embodiments provide load-bearing composite panels, materials, and products made from long and/or short fiber reinforced polyurethane surrounding an assembly made from one or more load-bearing members and a structural polyurethane sandwich composite. Some embodiments of the provide a process involving surrounding a short or long or continuous spider silk fiber and/or spider silk cloth and/or spider silk proteins reinforced polyurethane and/or resin and assembly made from one or more load-bearing members and a structural polyurethane sandwich composite. In some embodiments, the surrounding can additionally incorporate a long fiber. In some embodiments, as load-bearing members can be natural (e.g., wood), synthetic (e.g., polyurethane and other polymers) and metal (e.g., steel and aluminum) tubes, rods, beams, slabs, plates, planks and stampings and/or a combination of all the aforementioned materials. The load-bearing members can be hollow or solid in some embodiments. In some embodiments, the structural polyurethane or resin sandwich composite can encase or abut (contact) these load-bearing member(s) as the panels/materials/products’ intended use may necessitate. In some embodiments, the structural polyurethane or resin sandwich composites can be made from one or more spider silk mats, glass fiber mats, a rigid or flexible polyurethane foam, aluminum honeycomb, Nomex® honeycomb, steel honeycomb, carbon fiber honeycomb, Kevlar® honeycomb and a paper honeycomb.
[0052]Some embodiments include long and/or short fiber (which can include long and/or short spider silk fibers and/or spider silk proteins)-reinforced polyurethane contains reinforcing fibers whose nature is such as to prevent the use of a conventional high pressure mixing head. In some embodiments, the long fibers can be introduced into the polyurethane by means, for example, of chopped fiber injection (“CFI”) techniques, known to those skilled in the art. CFI machines and processes are available from a number of suppliers including Krauss-Maffei (LFI-PUR), The Cannon Group (InterWet) and Hennecke GmbH (FipurTec). In some embodiments, the long fibers useful in some embodiments of the invention can be more than about 3 mm, or more than about 10 mm, and/or from about 12 mm to 75 mm in length. In some embodiments, the long fibers can make up from 5 to 75 wt. %, or from 10 to 60 wt. %, or from 20 to 50 wt. % of the long fiber-reinforced polyurethane. The long fibers can be present in the long fiber-reinforced polyurethane of the inventive load-bearing composite panel in an amount ranging between any combinations of these values, inclusive of the recited values.
[0053]In some embodiments, the long fibers can be incorporated in the form of mats or cloth into the polyurethane. Examples of suitable types of long fibers, mats or cloth for use in some embodiments of the invention include, but are not limited to, glass fibers; spider silk fibers; natural fibers, such as those of flax, jute or sisal; and synthetic fibers, such as polyamide fibers, Kevlar® fibers, polyester fibers, carbon fibers and polyurethane fibers. Glass and spider silk fibers are particularly preferred as long fibers in some embodiments of the invention.
[0054]In some embodiments of the invention, spider silk protein can be added and/or mixed with the polyurethane and/or resin mixture-liquid in different percentages (e.g., between 0.01% and 99.99%) to increase the mechanical properties of the inventive load-bearing composite panel. In some embodiments of the invention, the polyurethanes are the reaction products of polyisocyanates with isocyanate-reactive compounds, and optionally reacted in the presence of blowing agents, catalysts, auxiliaries and additives. In some embodiments, suitable isocyanates, polyether polyols, blowing agents, catalysts, auxiliaries, and additives are identified in Cageao. For example, in some embodiments, suitable isocyanates include unmodified isocyanates, modified polyisocyanates, and isocyanate prepolymers. In some further embodiments, the organic polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic polyisocyanates of the type described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136. Some example embodiments include isocyanates represented by the formula Q(NCO)n, where n is a number from 2-5, preferably 2-3, and Q is an aliphatic hydrocarbon group containing 2-18, preferably 6-10, carbon atoms; a cycloaliphatic hydrocarbon group containing 4-15, preferably 5-10, carbon atoms; an araliphatic hydrocarbon group containing 8-15, preferably 8-13, carbon atoms; or an aromatic hydrocarbon group containing 6-15, preferably 6-13, carbon atoms. In some embodiments, examples of suitable isocyanates include ethylene diisocyanate; 1,4-tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; 1,12-dodecane diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,3- and -1,4-diisocyanate, and mixtures of these isomers; 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate; e.g., German Auslegeschrift 1,202,785 and those disclosed in U.S. Pat. No. 3,401,190); 2,4- and 2,6-hexahydrotoluene diisocyanate and mixtures of these isomers; dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI, or HIVIDI); 1,3- and 1,4-phenylene diisocyanate; 2,4- and 2,6-toluene diisocyanate and mixtures of these isomers (TDI); diphenylmethane-2,4′- and/or -4,4′-diisocyanate (MDI); naphthylene-1,5-diisocyanate; triphenylmethane-4,4′,4″-triisocyanate; polyphenyl-polymethylene-polyisocyanates of the type which can be obtained by condensing aniline with formaldehyde, followed by phosgenation (crude MDI), which are described, for example, in GB 878,430 and GB 848,671; norbornane diisocyanates, such as described in U.S. Pat. No. 3,492,330; m- and p-isocyanatophenyl sulfonylisocyanates of the type described in U.S. Pat. No. 3,454,606; perchlorinated aryl polyisocyanates of the type described, for example, in U.S. Pat. No. 3,227,138; modified polyisocyanates containing carbodiimide groups of the type described in U.S. Pat. No. 3,152,162; modified polyisocyanates containing urethane groups of the type described, for example, in U.S. Pat. No. 3,394,164 and 3,644,457; modified polyisocyanates containing allophanate groups of the type described, for example, in GB 994,890, BE 761,616, and NL 7,102,524; modified polyisocyanates containing isocyanurate groups of the type described, for example, in U.S. Pat. No. 3,002,973, German Patentschriften 1,022,789, 1,222,067 and 1,027,394, and German Offenlegungsschriften 1,919,034 and 2,004,048; modified polyisocyanates containing urea groups of the type described in German Patentschrift 1,230,778; polyisocyanates containing biuret groups of the type described, for example, in German Patentschrift 1,101,394, U.S. Pat. Nos. 3,124,605 and 3,201,372, and in GB 889,050; polyisocyanates obtained by telomerization reactions of the type described, for example, in U.S. Pat. No. 3,654,106; polyisocyanates containing ester groups of the type described, for example, in GB 965,474 and GB 1,072,956, in U.S. Pat. No. 3,567,763, and in German Patentschrift 1,231,688; reaction products of the above-mentioned isocyanates with acetals as described in German Patentschrift 1,072,385; and polyisocyanates containing polymeric fatty acid groups of the type described in U.S. Pat. No. 3,455,883. In some embodiments, it is also possible to use the isocyanate-containing distillation residues accumulating in the production of isocyanates on a commercial scale, optionally in solution in one or more of the polyisocyanates mentioned above. Moreover, mixtures of any two or more polyisocyanates described above can also be used in some embodiments.
[0055]Some embodiments include isocyanate-terminated prepolymers for the preparation of the polyurethanes. In some embodiments, prepolymers can be prepared by reacting an excess of organic polyisocyanate or mixtures thereof with a minor amount of an active hydrogen-containing compound as determined by the well-known Zerewitinoff test, as described by Kohler in Journal of the American Chemical Society, 49, 3181(1927). In some embodiments, although any isocyanate-reactive compound can be used to produce the polyurethanes of the inventive composite, polyether polyols are preferred as isocyanate-reactive components. Suitable methods for preparing polyether polyols are known and are described, for example, in EP-A 283 148, U.S. Pat. Nos. 3,278,457; 3,427,256; 3,829,505; 4,472,560; 3,278,458; 3,427,334; 3,941,849; 4,721,818; 3,278,459; 3,427,335; and 4,355,188.
[0056]In some embodiments, polyether polyols can be used, including those resulting from the polymerization of a polyhydric alcohol and an alkylene oxide. Some example embodiments include ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, glycerol, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, or 1,2,6-hexanetriol. Any suitable alkylene oxide can be used such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide, and mixtures of these oxides. In some embodiments, the polyoxyalkylene polyether polyols can be prepared from other starting materials such as tetrahydrofuran and alkylene oxide-tetrahydrofuran mixtures, epihalohydrins such as epichlorohydrin, as well as aralkylene oxides such as styrene oxide. In some embodiments, the polyoxyalkylene polyether polyols can have either primary or secondary hydroxyl groups. Included among the polyether polyols are polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polytetramethylene glycol, block copolymers, for example, combinations of polyoxypropylene and polyoxyethylene glycols, poly-1,2-oxybutylene and polyoxyethylene glycols and copolymer glycols prepared from blends or sequential addition of two or more alkylene oxides. The polyoxyalkylene polyether polyols can be prepared by any known process.
[0057]In some embodiments of the invention, blowing agents to produce foamed products (or foamed portions of the product). In some embodiments, water can be used as a chemical blowing agent. In some embodiments, physical blowing agents include inert (cyclo) aliphatic hydrocarbons having from 4 to 8 carbon atoms which evaporate under the conditions of polyurethane formation.
[0058]In some embodiments of the invention, one or more catalysts can be used for the polyurethane formation, and can be used to accelerate the reaction of the isocyanate with the isocyanate-reactive component. In some embodiments of the invention, the suitable catalysts include tertiary amines and/or organometallic compounds. Examples of compounds useful in one or more embodiments of the invention can include, but not be limited to, triethylenediamine, aminoalkyl- and/or aminophenyl-imidazoles, e.g. 4-chloro-2,5-dimethyl-1-(N-methylaminoethyl)imidazole, 2-aminopropyl-4,5-dimethoxy-1-methylimidazole, 1-aminopropyl-2,4,5-tributyl-imidazole, 1-aminoethyl-4-hexylimidazole, 1-aminobutyl-2,5-dimethylimidazole, 1-(3-aminopropyl)-2-ethyl-4-methylimidazole, 1-(3-aminopropyl)imidazole and/or 1-(3-aminopropyl)-2-methylimidazole, tin(II) salts of organic carboxylic acids, examples being tin(II) diacetate, tin(II) dioctoate, tin(II) diethylhexoate, and tin(II) dilaurate, and dialkyltin(IV) salts of organic carboxylic acids, examples being dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate. In some embodiments, the polyurethane forming reaction can take place, if desired, in the presence of auxiliaries and/or additives, such as cell regulators, release agents, pigments, surface-active compounds and/or stabilizers to counter oxidative, thermal or microbial degradation or aging
[0059]In some embodiments of the invention, the load-bearing composite panels of some embodiments of the invention described herein can be produced by reaction injection molding (RIM) techniques, which are known to those skilled in the art. The mixture of the long fiber reinforced polyurethane and/or resin producing components with the fibers, including the spider silk fibers and/or proteins, can be accomplished according to the long fiber injection (LFI) process. In this instance, polyurethane can be used with a mixture of spider silk protein. Referring to FIGS. 5A-5D, illustrating conventional load-bearing composite panels described in United States Patent Appl. Publ. No. 2007/0160793, as described, FIG. 5A shows a cross section taken through a load-bearing composite panel 410. The load-bearing composite panel 410 has hollow load-bearing member 412 surrounded by a polyurethane sandwich composite 16. The entire assemblage is encased in long fiber reinforced polyurethane 414 to form the load-bearing composite panel 410. Further, FIG. 5B depicts a cross section taken through load-bearing composite panel 420 having a hollow load-bearing member 422 abutting (contacting) a structural polyurethane sandwich composite 426. In some embodiments, the entire assemblage is enclosed in long and/or short spider silk fiber and/or spider silk proteins reinforced polyurethane (or resins) 424 to form the load-bearing composite panel 420. Further, FIG. 5C illustrates a cross-section taken through an embodiment of the load-bearing composite panel 430 mounted in brackets. The load-bearing composite panel 430 includes a hollow load-bearing member 432 abutting (contacting) a structural polyurethane sandwich composite 436. A second, solid load-bearing member 438, in this case made of a different material than load-bearing member 432, also abuts (contacts) the structural polyurethane sandwich composite 436. In some embodiments, the entire assemblage is surrounded by long and/or short spider silk fiber and/or spider silk proteins fiber reinforced polyurethane (and/or resins) 434 to form the load-bearing composite panel 430 which is shown seated in brackets 437. Further, FIG. 5D provides a cross section taken through load-bearing composite panel 440 having a load-bearing member 442 made from a metal stamping abutting a structural polyurethane sandwich composite 446. The entire assemblage is encapsulated in long or short spider silk fiber and/or spider silk proteins reinforced polyurethane (and/or resins) 444 to form the load-bearing composite panel 440. In some embodiments of the invention, the entire assemblage shown in FIGS. 5A-5D can be encased in spider silk material (such as spider silk long fiber, spider silk protein, spider silk mat, or spider silk cloth) reinforced polyurethane to form the load-bearing composite panel. In some embodiments, the spider silk material is enclosed with long fiber.
[0060]In some embodiments, conventional injection molding processes can be used to produce composite materials and structures including spider silk fibers and/or spider silk proteins. For example, in some embodiments, spider silk fibers and/or spider silk proteins can be used within thermo-polymer pellets for injection molding applications to improve the mechanical properties of any polymer that can be produced via injection molding. In other embodiments, spider silk fibers and/or spider silk proteins can be separately added into an injection mold machine (e.g., such as by adding into a hopper that feeds into a screw-scroll of an injection molding machine) along with thermopolymer pellets. As with other processing methods described herein, in some embodiments, the spider silk fibers can include long fibers, short fibers, or combinations thereof.
[0061]The composite panels of some embodiments of the invention encompass a variety of arrangements, configurations and combinations of load-bearing members within the structural polyurethane sandwich composite. For example, the structural polyurethane sandwich composite can encase a first load-bearing member and abut (contact) a second load-bearing member, or the structural polyurethane sandwich composite can enclose several load-bearing members and abut (contact) one or no second load-bearing member. The specific configuration and arrangement will be determined by the particular application for which the panel is intended.
[0062]The load-bearing composite panels of some embodiments of the invention can be incorporated into such items as automobile floor panels, vehicle body panels, bullet-proof anti-ballistic panels-products, vehicle bullet-proof anti-ballistic body panels, structures and floors, tires, wheels, bullet-proof vests, vehicle chassis structures, monocoque chassis, motor home chassis bodies, fuselages, floors and frames for aircraft and/or UAV's, bicycle and motorcycle frames, wind turbine blade frame structures, ship and boat haul body structures, submarines body structures, shipment containers, pre-fabricated walls and associated structures of homes and other buildings, train structures and body panels and/or floor panels, solar panel supports, battery housings, walls for mobile homes, roof modules, truck beds, truck trailer floors and the like. Such composite panels, materials, and products made with, or out of, spider silk fibers and/or spider silk proteins can also be utilized in artificial organs, ligaments or tendons, artificial disc vertebrae, ropes, and 3D printed parts.
[0063]As described earlier, by utilizing spider silk protein and fibers in various processes, the mechanical properties and/or performances can be improved (such as by mixing the spider silk proteins with the chemicals and/or using spider silk fibers to improve the mechanical properties of the components manufactured). Some embodiments of useful processes are detailed below. For example, some embodiments include utilizing spider silk protein and fibers in processes to make load-bearing composite panels, such as shown in the examples from Cageao (in paragraphs [0038]-[0061] and detailed further below.
[0064]In some embodiments, materials useful for preparing the composites can include, but not be limited to, Polyol A a sucrose-based polyether polyol having an OH number of 365-395; Polyol B an amine-initiated propylene oxide-extended hydroxyl-terminated triol having a weight average molecular weight of 240; Polyol C an ethylene diamine-based polyether polyol having an OH number of 600-660; Polyol D a polypropylene oxide-based triol having a weight average molecular weight of 160; Polyol E a polyester polyol containing oleic acid, adipic acid and pentaerythritol having an OH number of 51; Catalyst a 62/38 weight percent blend of glycol and potassium acetate, respectively; Release agent, the reaction product of adipic acid, pentaerythritol, and oleic acid, having an acid number of less than 15 and a hydroxyl number of less than 15; Pigment black pigment available as DR-2205 from Plasticolors, Inc.; Isocyanate A a polymeric diphenylmethane diisocyanate having an NCO group content of about 31.5%, a functionality of about 2.8, and a viscosity of about 196 mPa·s at 25° C.; and Isocyanate B an isocyanate-terminated prepolymer made by combining 90 parts Isocyanate A with 10 parts Polyol E, and having an NCO group content of about 28.5%.
[0065]In some embodiments, a structural polyurethane sandwich composite can comprise a polyurethane A produced by reacting isocyanate B at a ratio of isocyanate to polyol of 0.1.39:1.00 with polyol A 53.75 parts, polyol B 35.75 parts, fatty acid 5.0 parts, catalyst 0.5 parts, and pigment 5.0 parts. In some embodiments, structural polyurethane sandwich composite plaques can be produced by wrapping a piece of paper honeycomb in glass and/or spider silk fiber mat. The thickness of the honeycomb used can be determined by the thickness of the part required. The amount or weight of glass and/or spider silk fiber mat used can vary as well depending upon the strength characteristics desired. In most cases, the glass weight can vary from 225 g/m2 to 1200 g/m2. In some embodiments, Polyurethane A can be applied to both sides of the composite in amounts equal to the weight of glass on either side of the packet. Upon completion of spraying, the packet can be placed in a heated mold (200° F.-230° F.) where it can be compressed into its final shape.
[0066]In some further embodiments, a polyurethane B can comprise an Isocyanate A reacted at a ratio of isocyanate to polyol of 1.72:1.00 with the following polyol blend: Polyol B 40 parts, Polyol C 31 parts, Polyol D 17 parts, Quaternary amine salt 4 parts, release agent 6 parts, pigment 2 parts. Other embodiments can include a composite comprising steel tubing, structural polyurethane sandwich composite plaques and Polyurethane B. In some embodiments, to produce a composite panel, the following five pieces were arranged in the mold: 1) Structural polyurethane sandwich composite (5 in.×24 in.×1 in.), 2) Steel tubing (2 in.×24 in.×1 in.); 3) Structural polyurethane sandwich composite (10 in.×24 in.×1 in.); 4) Steel tubing (2 in.×24 in.×1 in.); and 5) Structural polyurethane sandwich composite (5 in.×24 in.×1 in.).
[0067]In some embodiments, a composite panel can be produced using long fiber technology (LFT), in which lengths of glass and/or spider silk fiber can be chopped and injected simultaneously with Polyurethane B into a heated mold at 150-175° F. After injection, the mold can be closed and the part cured. The panel can be coated on one side with Polyurethane B, removed from the mold, trimmed, and reinserted in the mold so that the second side could be coated using the LFT process.
[0068]In some embodiments of the invention, polyurethane sandwich composite plaques can be produced utilizing such processes by wrapping pieces of aluminum, Kevlar®, Nomex® honeycomb with spider silk mat, long fiber and cloth. These can be produced by mixing spider silk protein with the polyurethane. In some embodiments, various lengths of spider silk fibers (with or without the glass fibers) can also be chopped and injected in the processes set forth in paragraphs of Cageao. For example, in some embodiments, a composite panel can be produced using long fiber technology (LFT), in which lengths of glass fiber can be chopped and injected simultaneously with Polyurethane B into a heated mold at 150-175° F. After injection, the mold can be closed and the part cured. In some embodiments, the panel can be coated on one side with Polyurethane B, removed from the mold, trimmed, and reinserted in the mold so that the second side can be coated using the LFT process. A non-limiting example embodiment can be a floor of a car chassis or an entire vehicle chassis made by wrapping a honeycomb core with spider silk mat or knitted cloth, which is then sprayed with the polyurethane and chopped fibers. In some embodiments, the chopped long or short fibers can be from any source (fiberglass, Kevlar®, carbon fiber), and including spider silk fibers. In some embodiments, the “sandwich” can be placed in a pre-heated doubled-sided mold and pressed for around 1 to 2 minutes to make the floor of the chassis or the entire vehicle chassis structure (which is ready to be used). In some embodiments, spider silk proteins can be at least partially pre-mixed with the polyurethane.
[0069]Some embodiments include utilizing spider silk protein and fibers in processes to make fiber-reinforced polymer materials/products, such as the processes, materials, and products described in https://en.wikipedia.org/wiki/Fiber-reinforced_plastic. For example, spider silk fibers can be utilized to manufacture car body panels or airplane fuselages, such as indicated in below. Also, for example, a monocoque chassis can be manufactured using spider silk cloth (knitted in different weaves). For example, some embodiments can include two-dimensional and/or three-dimensional orientations. For example, some embodiments include a two dimensional fiber-reinforced polymer characterized by a laminated structure in which the fibers are only aligned along the p