Fabric impregnation for improved mechanical, transport, and functional properties.

Abstract

The method comprises a) impregnating a woven fabric, nonwoven fabric, or knitted fabric with a silk fibroin solution. The method comprises b) curing the silk fibroin solution to form the cured silk polymer matrix in which the woven fabric, nonwoven fabric, or knitted fabric is embedded. The fiber-reinforced polymer composite material contains the cured polymer matrix in an amount of at least 25%, at least 50%, at least 75%, or at least 100% by weight of the woven fabric, nonwoven fabric, or knitted fabric. The cured polymer matrix contains silk fibroin in an amount of at least 10% by weight.

Description

[Technical Field]

[0001] (Claiming priority) This application claims the benefit of the following provisional applications (which are incorporated herein by reference in their entirety for all purposes): U.S. Patent Application No. 63 / 489,362 filed 9 March 2023; and U.S. Patent Application No. 63 / 505,543 filed 1 June 2023.

[0002] (Statement regarding research funded by the U.S. federal government) Not applicable.

[0003] (Reference to sequence listings) Not applicable. [Background technology]

[0004] (background) The textile and apparel industry is estimated to produce 110 million tons of new textile products worldwide every year, and this production volume is constantly increasing, coupled with the generation of textile waste, due to fast fashion. Globally, textile waste generation reaches 92 million tons per year, with 17 million tons generated in the United States alone, and it is projected to reach 134 million tons by 2030. Although 95% of textile waste could be reused and recycled, only 15% of it is actually recovered from the waste stream, and thus the textile and apparel industry is one of the largest contributors to the generation of enormous amounts of waste and greenhouse gas emissions. More specifically, textile production is the world's second-largest polluting industry after the petroleum industry, contributing 1.2 billion tons of greenhouse gas emissions, and it is estimated that by 2050 it will use up to 25% of the global carbon budget. In this context, there is a growing need for strategies to address the negative environmental impacts of the textile and apparel industry and to promote the recovery of textile waste from landfills, thereby giving that textile waste a second life through a circular economy approach.

[0005] This disclosure focuses on the impregnation of fabrics using silk fibroin solutions to impart new and improved properties to expand the application areas of fabrics, with the aim of recycling textile waste and reusing it for other purposes. To date, fabric functionalization has been widely used, with interest focused on improving fabric properties (e.g., dyeability, wrinkle resistance, antimicrobial activity, flame retardancy, and water resistance). In the context of fabric functionalization, silk fibroin has been used in combination with crosslinking agents to improve wrinkle recovery in cotton, in combination with antimicrobial agents to obtain medical antimicrobial textile products, and in combination with silica nanoparticles to improve dyeability. After these functionalization procedures, the fabrics undergo pressing and washing processes to remove unbound silk fibroin. The interaction between silk fibroin and fabrics, as well as its effects on mechanical, transport, and thermal properties, has not been investigated. In fact, the functionalization of textile products aims to improve the performance of new, pristine fabrics (e.g., personal protective equipment, technical sportswear) in the textile and apparel industry to meet consumer needs in specific situations, but does not involve exploring fabric recycling or reusing them for other purposes in other applications. Furthermore, functionalized textile products are designed to acquire specific functional properties without sacrificing comfort by compromising their softness and breathability. Consequently, enhancement of mechanical properties, barrier properties, and shapeability was not a goal of fabric functionalization. The functionalization of fabrics is not intended to extend the applicability of fabrics beyond the textile and apparel industry.

[0006] On the other hand, textile products have been used as reinforcements in the manufacture of composite materials. In particular, interest in natural fiber-reinforced composites has been rapidly increasing due to their environmentally friendly properties, low cost, biodegradability, light weight, and good mechanical properties, which have enabled their commercial application in the automotive and construction industries. Fiber-reinforced composites exhibit a variety of properties based on the shape and length of the fibers, such as discontinuous fibers, continuous aligned fibers, and woven or knitted fabrics. Discontinuous randomly oriented fibers offer the advantage of producing isotropic materials but require carefully designed dispersion techniques to avoid aggregation. Continuous aligned fibers provide maximum tensile strength in the direction parallel to the fibers but require complex manufacturing techniques to ensure alignment. Composites containing fabric are easier to manufacture and can be used to obtain pseudo-isotropic materials. Fabric reinforcement has been used in the aforementioned industries to improve the mechanical properties of polymer materials, ceramic materials, or cement-based materials, as well as in the packaging industry to improve the barrier properties of plastics. In fact, the presence of fibers in a polymer matrix increases the coefficient of inflection for the diffusion of gas molecules, which reduces permeability. The approach presented herein differs from previously reported studies using textile products as reinforcing materials, which focus on the effects of fibers and fabrics on the properties of the matrix (which is the main component of the composite material). Here, the composite material is, conversely, primarily composed of fabric (10 wt.% to 45 wt.%) and shaped using a polymer material (i.e., silk fibroin) to increase its stiffness and barrier properties. The interaction between knitted fabrics and silk fibroin has not yet been investigated in studies reported in the literature.

[0007] Traditionally, composite materials containing fabric as an internal structural material embedded within a cured resin have been widely applicable across industries ranging from the medical to the automotive sector. However, conventionally, the cured resins in these composite materials are not sustainable and environmentally unfriendly. Their processing requires the use of potentially harmful solvents, and the resulting products are not easily biodegradable. [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] There is a need for composite materials that can achieve some of the performance of conventional composite materials, but that contain a cured resin component without the drawbacks of conventional cured resins. [Means for solving the problem]

[0009] (overview) Methods for impregnating fabrics for improved mechanical, transport, and functional properties are disclosed herein. In some embodiments, the techniques described herein relate to a method for producing a fiber-reinforced polymer composite material comprising a cured silk polymer matrix in which a woven, nonwoven, or knitted fabric is embedded, the method comprising: a) impregnating a woven, nonwoven, or knitted fabric with a silk fibroin solution; and b) curing the silk fibroin solution to form a cured silk polymer matrix in which the woven, nonwoven, or knitted fabric is embedded; wherein the fiber-reinforced polymer composite material comprises the cured polymer matrix in an amount of at least 25%, at least 50%, at least 75%, or at least 100% by weight of the woven, nonwoven, or knitted fabric, and the cured polymer matrix comprises at least 10% by weight of silk fibroin.

[0010] In some embodiments, the techniques described herein relate to a method for producing a fiber-reinforced silk polymer composite material comprising a cured silk polymer matrix impregnated into a woven, nonwoven, or knitted fabric substrate, the method comprising: a) impregnating a woven, nonwoven, or knitted fabric with a silk fibroin solution, wherein the woven, nonwoven, or knitted fabric has a native porosity of at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%; b) curing the silk fibroin solution to form the cured silk polymer matrix within the pores of the woven, nonwoven, or knitted fabric, thereby producing a fiber-reinforced silk polymer composite material, wherein the fiber-reinforced polymer composite material has a composite porosity at least 50% less than the native porosity of the woven, nonwoven, or knitted fabric substrate, and the cured polymer matrix contains silk fibroin in an amount of at least 10% by weight.

[0011] These and other systems, methods, purposes, features, and advantages of this disclosure will become apparent to those skilled in the art from the following detailed description and drawings of preferred embodiments.

[0012] All documents referenced herein are incorporated herein by reference in their entirety. References to items in the singular form should be understood to include multiple items unless otherwise explicitly stated or evident from the text, and vice versa. Grammatical conjunctions are intended to indicate any disjunctive and conjunctive combination of connected clauses, sentences, phrases, etc., unless otherwise explicitly stated or evident from the context.

[0013] The following detailed description of this disclosure and its particular embodiments can be understood by referring to the following drawings. [Brief explanation of the drawing]

[0014] [Figure 1]Figure 1 shows a manufacturing method and a fiber reinforced polymer composite material according to an aspect of the present disclosure.

[0015] [Figure 2] Figure 2 shows the following: A) SEM micrographs of the cross-section (top) and surface (bottom) of the composite material. B) The weight of the composite material with varying concentrations of the silk fibroin solution. C) The thickness of the composite material with varying concentrations of the silk fibroin solution. D) Color analysis in the RGB color space. The blue value of the composite material with varying concentrations of the silk fibroin solution.

[0016] [Figure 3] Figure 3 shows the following thermal and mechanical properties of the composite material: A) Thermogravimetric analysis. B) Derivative thermogravimetry. C) Differential scanning calorimetry. D) Stress-strain curve. E) Young's modulus. D) Elongation at break.

[0017] [Figure 4] Figure 4 shows the following: A) The bending angle of the composite material. B) Photographs of the composite material formed in the following various shapes: noodle box (left), cup (upper right), corrugated cardboard (lower right). C) Imprint of a diffraction grating on the composite material. Macroscopic photograph (left), SEM micrograph (right).

[0018] [Figure 5] Figure 5 shows the following mechanical properties of the recycled composite material: A) Tensile strength, B) Young's modulus. C) Elongation at break.

[0019] [Figure 6] Figure 6 shows sensors including the following: A) Temperature sensor. B) Cold chain monitoring. C) Oxygen sensor.

[0020] [Figure 7] Figures 7A and 7B show that an increase in the silk fibroin solution concentration corresponds to a linearly increasing Young's modulus and a composite material with a higher tensile strength.

[0021] Figure 7C shows the various increases that resulted from the data presented in Figures 7A and 7B. This shows a twill fabric using the added silk fibroin concentration.

[0022] [Figure 8] Figure 8 shows the mechanical characterization (comparison of Young's modulus [GPa] / tensile strength [MPa]) of various materials, including twill-silk fibroin composite materials.

[0023] [Figure 9] Figure 9A shows that increasing the concentration of the silk fibroin solution corresponds to a decrease in the bending angle, and Figure 9B shows an image of the material tested in Figure 9A. [Modes for carrying out the invention]

[0024] (Detailed explanation) Before this disclosure is described in further detail, it should be understood that this disclosure is not limited to the specific embodiments described herein. It should also be understood that the terminology used herein is intended solely to describe, and not to limit, specific embodiments. The scope of this disclosure is limited only by the claims. Where used herein, the singular forms “a,” “an,” and “the” include multiple embodiments unless the context explicitly states otherwise.

[0025] It will be apparent to those skilled in the art that many further modifications are possible without departing from the concept of the present invention, in addition to those already described. In interpreting this disclosure, all terms should be interpreted in the broadest possible form that is consistent with their context. Variations of the term “includes” should be interpreted as referring to an element, component, or process in a non-exclusive manner, and thus the mentioned element, component, or process may be combined with other elements, components, or processes not explicitly mentioned. Embodiments that refer to a particular element as “includes” are also intended to “essentially consist of” and “consist of” those elements. Where two or more ranges are listed for a particular value, this disclosure intends all combinations of those ranges with upper and lower limits not explicitly listed. For example, an enumeration of values ​​between 1 and 10 or between 2 and 9 also intends values ​​between 1 and 9 or between 2 and 10.

[0026] As used herein, “silk fibroin” refers to silk fibroin protein, whether produced by silkworms, spiders, or other insects, or otherwise generated (Lucas et al., Adv. Protein Chem., 13:107-242 (1958)). Any type of silk fibroin may be used in the various embodiments described herein. Silk fibroin produced by silkworms (e.g., Bombyx mori) is the most common and represents an environmentally friendly renewable resource. For example, silk fibroin used in silk films can be obtained by extracting sericin from B. mori cocoons. Organic silkworm cocoons are also commercially available. However, there are many different types of silk that can be used, including spider silk (e.g., obtained from Nephila clavipes), transgenic silk, genetically modified silk (e.g., silk derived from bacteria, yeast, mammalian cells, transgenic animals, or transgenic plants), and their variants. See, for example, WO97 / 08315 and U.S. Patent No. 5,245,012 (each of which is incorporated herein by reference in whole).

[0027] The interaction between silk fibroin and fabric (new and recycled) can be achieved through impregnation to obtain improved properties (e.g., mechanical properties, transport properties, and sensing properties) that expand the application areas of the fabric, with the aim of addressing real-world problems. While we do not wish to be constrained by any particular theory, it is conceivable that silk fibroin can be used to modify the mechanical properties of fabric to impart stiffness and shapeability, as well as to improve its barrier properties to regulate its permeability to oxygen and water vapor. In this way, textile waste can be functionalized and shaped with the long-term goal of being recovered from waste flows and reused for other purposes in other industries. For example, using this approach, recovered fabric can be converted into packaging material, which can have the dual benefit of reducing both plastic packaging waste and textile waste.

[0028] The methods described herein differ from previously reported methods for functionalizing fabrics, as they focus on improving the performance of fabrics in the textile and apparel industry but do not aim for their recycling or reuse for other purposes in other fields. At the same time, this approach also differs from the use of textiles as reinforcing materials for polymer matrices and cement-based matrices. Here, the fabric is, conversely, shaped using a polymer material (i.e., silk fibroin), which is the primary component and defines its rigidity and barrier properties.

[0029] Accordingly, the disclosures herein include characterizing the effect of silk fibroin on the properties of fabrics; studying the recyclability of fabric / silk fibroin composites; and enhancing their functionality for the development of colorimetric sensors using fabric / silk fibroin composites as substrates and stabilizers. Regarding the fabrication and characterization of fabric / silk fibroin composites, composites using silk fibroin (aqueous solution) to modify the surface and bulk of fabric (solid) to characterize the effect of silk fibroin on its properties are disclosed herein. In embodiments, fabrics may be impregnated with silk fibroin solutions of various concentrations to produce composites having a wide range of compositions and properties, which can be characterized by evaluating the effect of silk fibroin on macroscopic and microscopic morphology, thermal properties, tensile properties, stiffness, wettability, and transport properties. Furthermore, the formability of the material can be studied at both the macro and micro scales. Regarding the investigation of the recyclability of fabric / silk fibroin composites, the feasibility of closed-loop recycling of the composites is disclosed. Silk fibroin can be extracted from the composite material to re-obtain the original fabric, and such fabric can be re-impregnated with silk fibroin to obtain a new composite material. This cycle can be repeated several times (e.g., 5 cycles), and the properties of the recycled composite material (in particular, changes in mechanical and transport properties) can be evaluated after each cycle. Regarding the imparting of functional sensing properties to the fabric / silk fibroin composite material, colorimetric sensing inks (e.g., temperature sensors, cold chain sensors, and oxygen sensors) are disclosed herein, which can either be printed on the fabric before impregnation with silk fibroin or printed directly on the composite material. Silk can also be used as a stabilizer for unstable molecules used for sensing.

[0030] Referring to Figure 1, a method 100 for producing a fiber-reinforced polymer composite material 150 comprising a cured silk polymer matrix in which a woven, nonwoven, or knitted fabric is embedded according to the present disclosure may include (a) impregnating a woven, nonwoven, or knitted fabric 120 with a silk fibroin solution 110, and (b) curing the silk fibroin solution 110 to form a cured silk polymer matrix in which the woven, nonwoven, or knitted fabric 120 is embedded.

[0031] The adoption of silk as a resin for fabrics (and other large objects) as a substitute for petrochemical-derived binders is a highly unexpected application. The inventors have surprisingly discovered that an impressive range of material properties could be achieved with the fiber-reinforced polymer composite material 150. While we do not wish to be constrained by any particular theory, the pursuit of sustainable alternatives for conventional polymers and resins has historically been a difficult one, facing more failures than successes. Consequently, the likelihood of benchmark success is low, and achieving performance approaching that of conventional polymers by using sustainable alternatives is highly unexpected. The conventional use of silk in textiles makes it a particularly good binder for the conversion of textile waste into molded objects, for example, due to its ability to integrate the material universe of textiles while simultaneously adding structural properties suitable for the use of recycled silk fibroin solutions and polymorphic transitions.

[0032] In some embodiments, the fiber-reinforced polymer composite material 150 may contain a cured silk polymer matrix in an amount of at least 20% by weight of its woven, nonwoven, or knitted fabric. For example, the silk fibroin content of the fiber-reinforced polymer composite material may be at least 20% by weight of its woven, nonwoven, or knitted fabric after curing (e.g., when the fiber-reinforced polymer composite material is dry), which may provide good results in some embodiments. However, embodiments are not limited thereto, and in some embodiments, the fiber-reinforced polymer composite material may contain its cured polymer matrix in an amount of at least 25% by weight of its woven, nonwoven, or knitted fabric, at least 50% by weight of its woven, nonwoven, or knitted fabric, at least 75% by weight of its woven, nonwoven, or knitted fabric, or at least 100% by weight of its woven, nonwoven, or knitted fabric, each range offering various advantages.

[0033] In some embodiments, the cured (e.g., dried) polymer matrix may contain silk fibroin in an amount of at least 10% by weight. In some embodiments, the cured (e.g., dried) polymer matrix may contain silk fibroin in an amount between 10% and 100% by weight. In some embodiments, the cured (e.g., dried) polymer matrix may contain silk fibroin in an amount between 30% and 100% by weight. In some embodiments, the cured (e.g., dried) polymer matrix may contain silk fibroin in an amount between 50% and 100% by weight. In some embodiments, the cured (e.g., dried) polymer matrix may contain silk fibroin in an amount between 70% and 100% by weight. In some embodiments, the cured (e.g., dried) polymer matrix may contain silk fibroin in an amount between 90% and 100% by weight.

[0034] A method for producing a fiber-reinforced silk polymer composite material 150, which includes a cured silk polymer matrix impregnated into a woven, nonwoven, or knitted fabric substrate according to certain embodiments, may include (a) impregnating the woven, nonwoven, or knitted fabric 120 with a silk fibroin solution 110. In certain embodiments, the woven, nonwoven, or knitted fabric 120 may have a native porosity of at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%, each range offering various advantages.

[0035] A method according to certain embodiments may further include the step of (b) curing the silk fibroin solution to form the cured silk polymer matrix in the pores of a woven, nonwoven, or knitted fabric to form a fiber-reinforced silk polymer composite material. In some embodiments, the fiber-reinforced polymer composite material may have a composite porosity at least 50% smaller than the native porosity of the woven, nonwoven, or knitted fabric substrate. Furthermore, in some embodiments, the cured polymer matrix may contain silk fibroin in an amount of at least 10% by weight. In some cases, the cured polymer matrix contains silk fibroin in an amount between 10% and 100% by weight. In some cases, the cured polymer matrix contains silk fibroin in an amount between 30% and 100% by weight. In some cases, the cured polymer matrix contains silk fibroin in an amount between 50% and 100% by weight. In some cases, the cured polymer matrix contains silk fibroin in an amount between 70% and 100% by weight. In some cases, the cured polymer matrix contains silk fibroin in an amount between 90% and 100% by weight.

[0036] In some embodiments, the silk fibroin solution may contain silk fibroin in an amount between 0.1% and 30% by weight. In some cases, favorable results (e.g., impressive mechanical stiffness) are achieved when the silk fibroin solution contains silk fibroin in an amount between 10% and 30% by weight. In some cases, favorable results (e.g., impressive mechanical stiffness) are achieved when the silk fibroin solution contains silk fibroin in an amount between 0.1% and 10% by weight.

[0037] In some embodiments, the woven, nonwoven, or knitted fabric and the silk fibroin solution may be present in a mold having a negative imprint of a certain shape during the curing of the silk fibroin solution (e.g., in step b). Thereafter, the fiber-reinforced polymer composite material may exhibit a solid form that includes at least a portion of its shape.

[0038] In some embodiments, the shape may be a cup, a box, a corrugated sheet, or a combination thereof.

[0039] In some embodiments, the mold may have a negative imprint of a fine pattern, thereby providing the fine pattern to at least a portion of the surface of the fiber-reinforced polymer composite material.

[0040] In some embodiments, the impregnation (for example, in step a) may be carried out at an impregnation pressure of 1 atm. However, embodiments are not limited thereto, and in some examples, the impregnation may be carried out within an impregnation pressure range between 0.1 atm and 20 atm, between 0.2 atm and 10 atm, or between 0.5 atm and 5 atm. In some cases, the impregnation pressure may be between 0.1 atm and 20 atm. In some cases, the impregnation pressure may be between 0.2 atm and 10 atm. In some cases, the impregnation pressure may be between 0.5 atm and 5 atm.

[0041] In some embodiments, the impregnation (for example, in step a) may be carried out at an impregnation temperature between 4°C and 50°C, between 10°C and 40°C, or between 18°C ​​and 25°C, each range offering various advantages. In some cases, the impregnation temperature may be between 4°C and 50°C. In some cases, the impregnation temperature may be between 10°C and 40°C. In some cases, the impregnation temperature may be between 18°C ​​and 25°C.

[0042] In some embodiments, curing (for example, in step b) may be carried out at curing pressures between 0.1 MPa and 50 MPa, between 4 MPa and 40 MPa, or between 10 MPa and 30 MPa, each range offering various advantages. In some cases, the curing pressure may be between 0.1 MPa and 50 MPa. In some cases, the curing pressure may be between 4 MPa and 40 MPa. In some cases, the curing pressure may be between 10 MPa and 30 MPa.

[0043] In some embodiments, curing (for example, in step b) may be carried out at curing temperatures between 18°C ​​and 250°C, between 60°C and 200°C, or between 120°C and 180°C, each range offering various advantages. In some cases, the curing temperature may be between 18°C ​​and 250°C. In some cases, the curing temperature may be between 60°C and 200°C. In some cases, the curing temperature may be between 120°C and 180°C.

[0044] In some embodiments, curing (for example, in step b) may be carried out at curing relative humidity between 0% and 90%, between 10% and 60%, or between 20% and 40%, each range offering various advantages. In some cases, the curing relative humidity may be between 0% and 90%. In some cases, the curing relative humidity may be between 10% and 60%. In some cases, the curing relative humidity may be between 20% and 40%.

[0045] In some embodiments, curing (for example, step b) may include drying at a curing temperature between 100°C and 150°C, a curing pressure between 20 MPa and 30 MPa, and a curing relative humidity between 0% and 40%.

[0046] In some embodiments, the method may further include the step of forming a fine pattern on the fiber-reinforced silk polymer composite material.

[0047] In some embodiments, the method may further include the step of attaching embedded functional sensing spots to the woven, nonwoven, or knitted fabric prior to impregnation.

[0048] Functional sensing spots (e.g., embedded or external) described in some aspects of this specification may include pH-sensing inks, temperature-sensing inks, cold chain monitoring inks, and shock-sensing inks, which provide unexpectedly good results, for example, in their sensing capabilities.

[0049] In some embodiments, the step of attaching the embedded functional sensing spot may include printing the embedded functional sensing spot from the embedded functional sensing ink.

[0050] In some embodiments, the method may further include the step of attaching exposed functional sensing spots to a fiber-reinforced silk polymer composite material.

[0051] In some embodiments, the step of attaching the exposed functional sensing spot may include printing the exposed functional sensing spot from the exposed functional sensing ink.

[0052] In some embodiments, the fiber-reinforced silk polymer composite material 150 may comprise a cured silk polymer matrix and a woven, nonwoven, or knitted fabric 120 embedded within the cured polymer matrix. The fiber-reinforced polymer composite material may contain the cured polymer matrix in an amount equal to or greater than the amount of the woven, nonwoven, or knitted fabric by weight, and the cured polymer matrix may contain silk fibroin in an amount of at least 10% by weight.

[0053] In some embodiments, the fiber-reinforced silk polymer composite material 150 may contain silk fibroin that permeates the fiber bundles of the fabric 120, such that the silk may be present between the individual fibers of the fabric 120 rather than simply coating the outer surface of the fabric 120.

[0054] In some embodiments, the fiber-reinforced silk polymer composite material 150 may include a woven fabric substrate, a nonwoven fabric substrate, or a knitted fabric substrate. In some embodiments, the fabric substrate may have a native porosity (e.g., macroscopic porosity, not referring to pores within the fibers themselves) of at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%, each range offering various advantages. In some cases, its native porosity is at least 50%. In some cases, its native porosity is at least 60%. In some cases, its native porosity is at least 70%. In some cases, its native porosity is at least 80%. In some cases, its native porosity is at least 90%.

[0055] Furthermore, the fiber-reinforced silk polymer composite material 150 may include a cured silk polymer matrix impregnated into a woven, nonwoven, or knitted fabric substrate, the cured silk polymer matrix may contain silk fibroin in an amount of at least 10% by weight. The fiber-reinforced polymer composite material 150 may have a composite material porosity (e.g., macroscopic) that is at least 50% smaller than the native porosity of the woven, nonwoven, or knitted fabric substrate.

[0056] In some embodiments, the woven, nonwoven, or knitted fabric 120 may be selected from cotton jersey or other types of fabric (e.g., other types of cotton (canvas, twill, sateen, etc.), linen, silk fabric (organza, crepe, satin, etc.)) and combinations thereof. In some embodiments, synthetic and semi-synthetic fabrics (e.g., rayon, polyester, nylon, acrylic fibers) may also be used. In one example, the woven, nonwoven, or knitted fabric 120 is cotton jersey.

[0057] In some embodiments, the cured silk polymer matrix may further contain additives, which may include plasticizers (e.g., glycerol) or crosslinking agents for silk (e.g., acids or alcohols), and combinations thereof. Furthermore, the additives may include small amounts of antioxidants and / or antimicrobial agents, which may enhance the functionality of the fiber-reinforced silk polymer composite material 150 for packaging applications.

[0058] In some embodiments, the fiber-reinforced silk polymer composite material 150 may have a thickness between 0.1 mm and 5 mm. In some embodiments, the fiber-reinforced silk polymer composite material 150 may have a thickness between 0.4 mm and 2 mm.

[0059] In some embodiments, the fiber reinforced silk polymer composite material 150 may have a tensile strength between 2 MPa and 80 MPa, between 8 MPa and 40 MPa, or between 10 MPa and 20 MPa. In some cases, the tensile strength may be between 2 MPa and 80 MPa. In some cases, the tensile strength may be between 8 MPa and 40 MPa. In some cases, the tensile strength may be between 10 MPa and 20 MPa.

[0060] In some embodiments, the fiber reinforced silk polymer composite material 150 may have an elongation at break between 0.1% and 800%, between 2% and 400%, or between 20% and 200%. In some cases, the elongation at break may be between 0.1% and 800%. In some cases, the elongation at break may be between 2% and 400%. In some cases, the elongation at break may be between 20% and 200%.

[0061] In some embodiments, the fiber reinforced silk polymer composite material 150 may have a Young's modulus between 0.5 MPa and 20 GPa, between 100 MPa and 10 GPa, or between 200 MPa and 2 GPa. In some cases, the Young's modulus may be between 0.5 MPa and 20 GPa. In some cases, the Young's modulus may be between 100 MPa and 10 GPa. In some cases, the Young's modulus may be between 200 MPa and 2 GPa.

[0062] In some embodiments, the fiber reinforced silk polymer composite material 150 has a mass density between 0.1 g / cm 3 and 5 g / cm 3 , between 0.3 g / cm 3 and 2 g / cm 3 or between 0.4 g / cm 3 and 1 g / cm 3 In some cases, the mass density may be between 0.1 g / cm 3 and 5 g / cm 3 In some cases, the mass density may be between 0.3 g / cm 3 and 2 g / cm 3It can be between these two values. In some cases, the substance density is 0.4 g / cm³. 3 and 1 g / cm³ 3 It could be between these two.

[0063] In some embodiments, the fiber-reinforced silk polymer composite material 150 may include at least one patterned surface. Furthermore, in some embodiments, the at least one patterned surface may include a pattern selected from diffraction gratings, lotus leaf patterns, gecko feet patterns, micropyramids, cubes, spheres, or cone arrays, and combinations thereof.

[0064] A method for recycling the fiber-reinforced silk polymer composite material 150 according to certain embodiments may include the steps of dissolving at least a portion of a cured silk polymer matrix impregnating a woven, nonwoven, or knitted substrate, and separating at least a portion of the cured silk polymer matrix from the woven, nonwoven, or knitted substrate. In certain embodiments, the fiber-reinforced silk polymer composite material 150 may be a fiber-reinforced silk polymer composite material 150 prepared according to and / or certain embodiments described herein. In one exemplary embodiment, the dissolving step may use a LiBr salt solution.

[0065] A specific logical set of operations (e.g., the methods or procedures of this disclosure) is provided to illustrate aspects of this disclosure. Operations are described and / or depicted schematically, and operations may be combined, divided, reordered, added or removed in a manner consistent with the disclosure herein. While it is understood that the context of the description of operations may require the ordering of one or more operations and / or the order of one or more operations may be explicitly disclosed, the order of operations should be understood more broadly where any equivalent set of operations to provide equivalent work results is specifically contemplated herein. For example, if a value is used in a particular operation, the determination of that value may be required before that operation in certain circumstances (e.g., when a time delay in data for an operation is important to achieve a particular effect), but not before that operation in other circumstances (e.g., when the use of that value derived from a previous execution cycle of the operation is sufficient for that purpose). Accordingly, in some embodiments, the order and set of operations described herein are expressly intended, and in some particular embodiments, changes in the order, subdivision, and / or different sets of operations are expressly intended herein.

[0066] The methods and systems described herein can transform physical and / or intangible objects from one state to another. The methods and systems described herein can also transform data representing physical and / or intangible objects from one state to another.

[0067] Elements described and depicted in this specification (including flowcharts, block diagrams, and / or descriptions of operations) are for illustrative purposes only and depict and / or describe specific illustrative configurations of the elements.

[0068] While this disclosure has been made in connection with preferred embodiments described in detail, various modifications and improvements to this disclosure will be readily apparent to those skilled in the art. Therefore, the intent and scope of this disclosure should not be limited by the examples given above, but should be understood in the broadest sense permitted by law. [Examples]

[0069] (Example 1: Fabrication and characterization of cloth / silk fibroin composite material)

[0070] This specification discloses an analysis of the effect of silk fibroin solution concentration on the properties of cloth / silk fibroin composite materials. Cloth is impregnated with an aqueous silk fibroin solution, thereby providing improved properties that enable the use of these cloths in various fields (e.g., packaging and disposable plastic substitutes). Since the adhesion between these two materials directly affects the properties of this composite, it is important to understand the influence of manufacturing conditions and material characteristics on their interaction. To do this, the thickness, weight, and color of the composite material are quantified, and macroscopic and microscopic morphology is characterized using SEM analysis. FTIR and thermal analysis are used to investigate the interaction between the cloth and silk fibroin, as well as the secondary structure of the silk fibroin. Mechanical properties, barrier properties, and formability are carefully evaluated, as they represent important parameters for explaining the use of cloth in the packaging industry.

[0071] (Experimental Method - Fabrication of Fabric / Silk Fibroin Composite Material): Regenerated silk fibroin solution was extracted from Bombyx mori cocoons using an established protocol (see Rockwood, DN; Preda, RC; Yucel, T.; Wang, X.; Lovett, ML; Kaplan, DL Materials Fabrication from Bombyx Mori Silk Fibroin. Nat. Protoc. 2011, 6(10), 1612-1631). Cotton jersey fabric (100% organic cotton, 190g / m)2 A piece of fabric (purchased from Organic Cotton Plus (USA)) is laser-cut into a square (side length 5 cm). A certain volume of silk fibroin solution at various concentrations (i.e., 2 wt. / v%, 6 wt. / v%, 10 wt. / v%, 14 wt. / v%, 18 wt. / v%, 22 wt. / v%) is then impregnated into the square of fabric and dried overnight at room temperature (Figure 1).

[0072] (Characterization): The weight change of the sample before and after silk fibroin infiltration is measured using a chemical balance. The thickness is measured using a micrometer. Images are collected using a scanner and ImageJ, and their color is analyzed and quantified in the RGB color space. The morphological features of the composite material are studied using a scanning electron microscope (SEM).

[0073] The secondary structure of silk fibroin on the surface of the composite material is analyzed using Fourier transform infrared (FTIR). The decomposition temperature and glass transition temperature of the composite material are determined by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).

[0074] The tensile strength, elongation at break, and Young's modulus of the composite material are evaluated using an Instron tensile testing machine according to ASTM D5035. Its stiffness is measured by measuring the bending angle of a rectangular piece of material fixed at one end and bent under its own weight. Its water vapor transmission rate and oxygen transmission rate are measured according to ASTM E96M and ASTM F3136, respectively. Its macroscopic formability is investigated by thermoforming using hydraulic hot press and vacuum forming. The fine pattern-forming capability of the composite material is evaluated by imprinting a diffraction grating during drying. The pattern transfer is confirmed using SEM analysis.

[0075] (Results and Expected Outcomes): Macroscopic characteristics of materials (e.g., thickness and weight) play a crucial role in determining their properties (e.g., mechanical properties and transport properties), and these characteristics can influence their applicability in specific fields. Consequently, the effect of silk fibroin solution concentration on the thickness, weight, and color of the cloth / silk fibroin composite material is analyzed (Figure 2). The results show that increasing the concentration of the silk fibroin solution from 2 wt. / v% to 22 wt. / v% increases the thickness and weight of the composite material, and changes its color from white to yellow (corresponding to a decrease in the blue value in the RGB color space). In the context of composite materials, achieving a uniform distribution of various phases is important to ensure that the final composite material has uniform properties. SEM micrographs show the uniform distribution of silk fibroin on the surface and bulk of the composite material (Figure 2). The increase in silk fibroin concentration corresponds to an increase in the amount of silk fibroin covering the surface of the fibers and filling the space between the fibers and bundles.

[0076] The presence of silk fibroin on the surface of the composite material is further confirmed by FTIR analysis. Given its shallow penetration depth, FTIR analysis cannot provide information about the secondary structure of silk fibroin in the bulk material, which is useful for inferring the interaction between silk fibroin and cotton fabric. Furthermore, the secondary structure of silk fibroin directly correlates with its mechanical and barrier properties. Since several previously reported studies describe the formation of β-sheets in silk / cellulose composite materials, it is predicted that silk fibroin exhibits a crystalline structure (i.e., β-sheet) induced by the presence of cotton. Since it has been reported that increasing the crystallinity of silk fibroin leads to an increase in its glass transition temperature, measuring the glass transition temperature of silk fibroin in the composite material using DSC can overcome the lack of information about the secondary structure of silk fibroin in the bulk material of that composite material. The glass transition temperature of the initial state silk fibroin film is 183°C, while it increases to 189°C for silk fibroin in the composite material, confirming the formation of β-sheets (Figure 3). Furthermore, TGA analysis revealed an increase in the on-set degradation temperature in the composite material compared to the initial silk fibroin film. While we do not wish to be constrained by any particular theory, silk fibroin improves the thermal stability of cotton fabric by generating a layer of carbon that protects the underlying material. The initial cotton showed a residual weight of 8%. This residual weight increased with increasing silk fibroin concentration, ranging between 15% and 25% (Figure 3).

[0077] Tensile tests confirm that the mechanical properties of a fabric can be modified and its stiffness increased using silk fibroin. Increasing the concentration of silk fibroin increases the Young's modulus of the composite material, while decreasing its elongation at break (Figure 3). The stiffness of the composite material can also be evaluated by measuring the flexion angle formed in its horizontal plane, which decreases with increasing silk fibroin concentration, indicating the composite material's ability to maintain its shape (Figure 4a).

[0078] While we do not wish to be constrained by any particular theory, water vapor and oxygen permeability may decrease by increasing the silk fibroin concentration and may be lower compared to the permeability of the initial silk fibroin film and the initial fabric. While we do not wish to be constrained by any particular theory, the interaction between the fabric and silk fibroin, and the formation of β-sheets in the silk matrix, may increase barrier properties. While we do not wish to be constrained by any particular theory, the permeability of the fabric may be influenced by the interfiber distance within the bundle and the stiffness of the weave, which create voids that allow for the transport of vapors and gases. In this composite material, the silk fibroin fills these voids, thereby reducing its permeability. At the same time, the presence of the fabric increases the coefficient of inflection for the diffusion of vapors and gas molecules, which reduces its permeability compared to the initial silk fibroin film. The wettability of the composite material can be evaluated by contact angle measurement.

[0079] This composite material exhibits the ability to hold a wide range of complex shapes (Figure 4b). Examples can range from simpler shapes (e.g., cup-like shapes) to more complex shapes (such as noodle boxes or corrugated cardboard sheets). Furthermore, the surface of this composite material can be micro-patterned as shown by the imprinting of a diffraction grating (Figure 4c). Using the same approach, the hydrophobicity of this composite material can be increased by imprinting a lotus leaf pattern or a gecko foot pattern.

[0080] While we do not wish to be constrained by any particular theory, the effects of drying conditions (temperature and relative humidity (RH)) on the properties of this composite material may exist. Cotton jersey was chosen because it is one of the most commonly used fabrics in the apparel industry. The same approach could be applied to other types of fabrics.

[0081] This specification discloses information regarding methods for precisely tuning the mechanical and barrier properties of fabrics in order to produce composite materials having a wide range of compositions and properties. In particular, when combined with post-treatment of silk fibroin (e.g., water annealing or alcohol treatment) and surface patterning, this approach can make it possible to obtain a library of materials (ranging from soft to hard, from permeable to impermeable, and combinations thereof) in which applications can be found in various situations.

[0082] (Example 2: Investigation of the recyclability and biodegradability of cloth / silk fibroin composite materials): The determination of a recycling process for cloth / silk fibroin composite materials, its effect on their properties, and an analysis of their biodegradability are disclosed herein. This disclosure enables the production of composite materials in a fully circular approach. Both silk fibroin solution and cloth are obtained from waste, and after use, they are recovered and reused to form new composite materials. After the composite material is produced, the silk fibroin can be removed and the cloth recovered, and these can be reused to produce new cloth / silk fibroin composite materials. Since the ability to withstand this recycling process is important for practical applications (e.g., packaging), the mechanical properties and barrier properties of the composite material are evaluated in relation to the effects of this recycling process. Various processes for removing silk fibroin from cloth are tested.

[0083] (Experimental Method): Recycling of cloth / silk fibroin composite material. A square of cotton jersey cloth is impregnated with a silk fibroin solution (6 wt. / v%) and dried overnight at room temperature. Two separate processes are tested to remove the silk fibroin: 1) immersion of the composite material in deionized (DI) water under agitation for 8 hours; and 2) impregnation of the composite material in lithium bromide aqueous solution (9.3 M) at 60°C for 4 hours, followed by rinsing in deionized (DI) water. Then, such cloth is impregnated with a silk fibroin solution (6 wt. / v%) and dried overnight at room temperature on a silicone mat. This process (impregnation-removal-impregnation) is named the "recycling cycle" and is repeated up to 5 times.

[0084] (Characterization): The weight of the fabric before and after the infiltration of silk fibroin, and after its removal, is measured using a chemical balance. After each recycling cycle, the tensile strength, elongation at break, Young's modulus, water vapor permeability, and oxygen permeability of the recycled composite material are evaluated.

[0085] (Results and Expected Outcomes): Removal of silk fibroin by immersion in water yields unsatisfactory results. After immersion, the composite material loses only 2% of its weight, which corresponds to incomplete removal, given that the solid content of silk fibroin in the composite material is 17%. Silk fibroin has good water solubility when in an amorphous state, while it becomes insoluble in water when in its crystalline state (e.g., after the formation of a β-sheet secondary structure). Although we do not wish to be constrained by any particular theory, the poor solubility of silk fibroin in the composite material, based on the reported interactions between silk fibroin and cellulose, as well as the analysis of its glass transition temperature, suggests the formation of a crystalline structure.

[0086] The second approach described above (which relies on the dissolution of silk fibroin in a LiBr solution) allows for the complete removal of silk fibroin. The mechanical properties of the composite material are evaluated after 1 to 5 recycling cycles (Figure 5). Its tensile strength is unaffected by this recycling process. After the initial changes following the first recycling cycle, its elongation at break and Young's modulus are unaffected by this recycling process. A moderate increase in Young's modulus and a decrease in elongation after the first recycling cycle suggest hardening of the composite material, which may be due to the accumulation of silk fibroin residue in the material bulk. The minimal impact of this recycling process on the mechanical properties of the material indicates its promising potential for recycling.

[0087] Based on these results, and without wishing to be constrained by any particular theory, it is possible that its water vapor and oxygen permeability are unaffected by this recycling process. In some embodiments, minimal accumulation of silk fibroin in the bulk material may further reduce its porosity, resulting in improved barrier properties.

[0088] To optimize the recovery of silk fibroin from composite materials and reuse it to create new composite materials, a minimum volume of LiBr solution and a minimum volume of water can be used for rinsing to dissolve the silk fibroin. The molecular weight of the recovered silk can be measured, and any changes in its properties can be investigated. Since dissolution in lithium bromide should not change its molecular weight, the properties of the silk may not be impaired by this recycling.

[0089] In some embodiments, after rinsing the composite material, the concentration of silk fibroin in the water may be low, and this protein may gel immediately after dialysis (required to remove LiBr used for removing silk fibroin from the fabric) or during the concentration process. Such a silk fibroin gel may be coagulated, its silk solid may be dissolved, and the resulting solution may be used to develop new composite materials. Furthermore, its silk solid may serve as a resource for other applications.

[0090] (Example 3: Functionalization of fabric / silk fibroin composite material to impart sensing properties)

[0091] This specification discloses the functionalization of a cloth / silk fibroin composite material for imparting sensing properties using a colorimetric sensing ink, which is either printed on the cloth before the silk fibroin is impregnated or printed directly on the composite material. This disclosure enables the production of sensing composite materials that may be relevant to the packaging industry. Such sensing packaging produced would ensure optimal storage conditions for delicate products. This approach can be extended to various types of colorimetric sensors. For example, colorimetric sensing can be combined with packaging for detecting food spoilage.

[0092] (Preparation of sensing ink): A temperature-sensing ink can be prepared by mixing a thermochromic pigment with a mixture of alginate solution, silk fibroin solution, a thickener, and a fixative. A pH-sensing ink can be prepared by mixing a pH indicator (nitrazine yellow, phenol red, or bromocresol green sodium salt) with a mixture of alginate solution, silk fibroin solution, a thickener, and a fixative. A cold chain monitoring sensor can be prepared by imparting functionality to one side of a cloth piece with pH-sensing ink, drying it once, impregnating the other side with a citric acid solution (pH 3), and then storing the piece in a freezer at -20°C. An oxygen sensor can be fabricated under a nitrogen atmosphere by mixing a chromogenic substrate (3,5-dichloro-2-hydroxybenzenesulfonate, 4-aminoantipyrine, acid yellow), enzymes (horseradish peroxidase (HRP) and lactate oxidase (LOx)), and lactate in a silk fibroin solution (4 wt. / v%). This mixture formulation was previously tested to produce a printable lactate-sensing, wearable patch. The mixture was then converted to a hydrogel using acetone. Finally, the acetone was removed to obtain the oxygen-sensing hydrogel.

[0093] (Characterization): To characterize the colorimetric reactions of these temperature sensors, cold chain sensors, pH sensors, and oxygen sensors, they were exposed to increasing temperatures, pH, and oxygen concentrations, respectively, and the reactions were recorded by acquiring images with a camera. These images were then analyzed using ImageJ to quantify the color changes in the RGB color space.

[0094] (Results and Expected Outcomes): These temperature-sensing inks are reversible inks that can be used in a variety of situations. This is because their sensing range can be changed by altering the thermochromic pigment. For example, one ink can change color from gray to transparent at temperatures between 70°C and 75°C, and can be applied in the context of temperature monitoring of hot beverages and food (Figure 6a). In fact, hot beverages (e.g., tea or coffee) are usually served at temperatures higher than 70°C, which can cause burns to the mucous membranes of the tongue and esophagus. Such sensors can be applied to food containers to indicate when the contents can be safely consumed without causing damage.

[0095] Cold chain monitoring sensors can be used to monitor temperature-sensitive products (e.g., pharmaceuticals, biologics, foods) that need to be transported at sub-zero temperatures because suboptimal conditions during transport and storage can impair their quality (Figure 6b). When removed from the freezer, a citric acid solution migrates along a piece of cloth and reacts with pH-sensing ink, causing a color change from blue to yellow in the central part of the cloth. The reaction time can be evaluated by exposing these sensors to increasing temperatures. Furthermore, the reaction time can be adjusted by varying the length of the cloth to obtain faster or slower colorimetric reactions.

[0096] Oxygen sensors can be used to ensure optimal storage conditions for products that need to be stored in a modified atmosphere (i.e., certain medical devices and meat products) (Figure 6c). These oxygen sensors can be based on the LOx / HRP cascade reaction. In the presence of oxygen, LOx (lactate oxidase) oxidizes lactate to produce pyruvate and hydrogen peroxide, which is then used by HRP (horseradish peroxidase) to oxidize the chromogenic substrate, resulting in a visible color change from yellow to red. In a nitrogen atmosphere, this colorimetric reaction does not occur, and the sensor is yellow. When exposed to air, the sensor turns red. In this situation, silk fibroin can act as a stabilizer for these enzymes used for detection, increasing the effective lifespan of the sensor. Its detection limit, sensitivity, and stability are evaluated by recording the color change while the sensor is exposed to increasing concentrations of oxygen.

[0097] In some embodiments, these oxygen sensors are fabricated in hydrogel form (because they do not exhibit a colorimetric reaction in a dry state), and a hygroscopic component (e.g., glycerol) can be added to their formulation to maintain the sensors in a moist state.

[0098] (Example 4: Twill and silk fibroin composite material: Mechanical properties)

[0099] Referring to Figures 7A and 7B, increasing the concentration of the silk fibroin solution corresponds to a linear increase in Young's modulus (Figure 7B). Using twill (a fabric commonly used to produce strong cloth, e.g., denim) or other fabrics (such as those made using warp / weft weaving methods) as starting materials resulted in composite materials with higher tensile strength (Figure 7A). Figure 7C shows twills with various increasing silk fibroin concentrations, which yielded the data presented in Figures 7A and 7B. Figure 8 shows the mechanical characterization (comparison of Young's modulus [GPa] / tensile strength [MPa]) of various materials, including cotton jersey (a knitted fabric commonly used to produce stretchy cloth, e.g., T-shirts), elastomers, silk foam, polymers, metals, non-technical ceramics, foams, and twill-silk fibroin composite materials. Figure 9A shows that increasing the concentration of the silk fibroin solution corresponds to a decrease in the bending angle (e.g., an increase in stiffness), and Figure 9B shows an image of the material tested in Figure 9A. The twill and silk fibroin composite material exhibits formability with respect to folding (e.g., for forming takeout containers), thermoforming (e.g., for forming bowls, plates, etc.), and combinations thereof. The twill and silk fibroin composite material can be used to form articles containing multiple layers of twill (e.g., utensils, eyewear, etc.).

Claims

1. A method for producing a fiber-reinforced polymer composite material comprising a cured silk polymer matrix in which a woven, nonwoven, or knitted fabric is embedded, a) The process of impregnating a woven fabric, nonwoven fabric, or knitted fabric with a silk fibroin solution; b) A step of curing the silk fibroin solution to form the cured silk polymer matrix in which the woven fabric, nonwoven fabric, or knitted fabric is embedded. Includes, The fiber-reinforced polymer composite material comprises the cured silk polymer matrix in an amount equal to at least 25%, at least 50%, at least 75%, or at least 100% by weight of the woven, nonwoven, or knitted fabric. The method wherein the cured silk polymer matrix contains silk fibroin in an amount of at least 10% by weight.

2. A method for producing a fiber-reinforced silk polymer composite material containing a cured silk polymer matrix, which is impregnated into a woven fabric substrate, a nonwoven fabric substrate, or a knitted fabric substrate, a) A step of impregnating the woven fabric substrate, nonwoven fabric substrate, or knitted fabric substrate with a silk fibroin solution, wherein the woven fabric substrate, nonwoven fabric substrate, or knitted fabric substrate has a native porosity of at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%; b) A step of curing the silk fibroin solution, thereby forming the cured silk polymer matrix in the pores of the woven fabric substrate, nonwoven fabric substrate, or knitted fabric substrate, and producing the fiber-reinforced silk polymer composite material. Includes, The fiber-reinforced silk polymer composite material has a composite material porosity that is at least 50% smaller than the native porosity of the woven fabric substrate, nonwoven fabric substrate, or knitted fabric substrate. The method wherein the cured silk polymer matrix contains silk fibroin in an amount of at least 10% by weight.

3. The method according to claim 1 or 2, wherein the silk fibroin solution contains silk fibroin in an amount between 0.1% and 30% by weight.

4. The method according to any one of the claims, wherein the woven fabric, nonwoven fabric, or knitted fabric and the silk fibroin solution are present in a mold having a negative imprint of a certain shape during the curing of step b), so that the fiber-reinforced polymer composite material exhibits a solid form including at least a portion of the shape.

5. The method according to the preceding claim, wherein the shape is a cup, a box, a corrugated sheet, or a combination thereof.

6. The method according to any one of the two preceding claims, wherein the mold has a negative imprint of a fine pattern, thereby providing the fine pattern to at least a portion of the surface of the fiber-reinforced silk polymer composite material.

7. The method according to any one of the claims, wherein the impregnation in step a) is carried out at an impregnation pressure between 0.1 atm and 20 atm, between 0.2 atm and 10 atm, between 0.5 atm and 5 atm, or at an impregnation pressure of 1 atm.

8. The method according to any one of the claims, wherein the impregnation in step a) is carried out at an impregnation temperature between 4°C and 50°C, between 10°C and 40°C, or between 18°C ​​and 25°C.

9. The method according to any one of the claims, wherein the curing in step b) is carried out at a curing pressure between 0.1 MPa and 50 MPa, between 4 MPa and 40 MPa, or between 10 MPa and 30 MPa.

10. The method according to any one of the claims, wherein the curing in step b) is carried out at a curing temperature between 18°C ​​and 250°C, between 60°C and 200°C, or between 120°C and 180°C.

11. The method according to any one of the claims, wherein the curing in step b) is carried out at a curing relative humidity between 0% and 90%, between 10% and 60%, or between 20% and 40%.

12. The method according to any one of the claims, wherein the curing in step b) includes drying at a curing temperature between 100°C and 150°C, a curing pressure between 20 MPa and 30 MPa, and a curing relative humidity between 20% and 40%.

13. Steps to form a fine pattern on the aforementioned fiber-reinforced silk polymer composite material. The method according to any one of the claims, further comprising:

14. The process of attaching embedded functional sensing spots to the woven, nonwoven, or knitted fabric before impregnation. The method according to any one of the claims, further comprising:

15. The method according to the preceding claim, wherein the step of attaching the embedded functional sensing spot includes printing the embedded functional sensing spot from an embedded functional sensing ink.

16. A step of attaching exposed functional sensing spots to the fiber-reinforced silk polymer composite material. The method according to any one of the claims, further comprising:

17. The method according to the preceding claim, wherein the step of attaching the exposed functional sensing spot includes printing the exposed functional sensing spot from the exposed functional sensing ink.

18. With a cured silk polymer matrix; The woven, nonwoven, or knitted fabric embedded in the aforementioned cured silk polymer matrix A fiber-reinforced silk polymer composite material including, The fiber-reinforced silk polymer composite material contains the cured silk polymer matrix in an amount equal to or greater than that of the woven fabric, nonwoven fabric, or knitted fabric by weight. The cured silk polymer matrix is ​​a fiber-reinforced silk polymer composite material containing at least 10% by weight of silk fibroin.

19. Woven fabric substrates, nonwoven fabric substrates, or knitted fabric substrates having a native porosity of at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%; A cured silk polymer matrix impregnated into the aforementioned woven fabric substrate, nonwoven fabric substrate, or knitted fabric substrate. A fiber-reinforced silk polymer composite material including, The cured silk polymer matrix contains silk fibroin in an amount of at least 10% by weight. The fiber-reinforced silk polymer composite material has a composite material porosity that is at least 50% smaller than the native porosity of the woven fabric substrate, nonwoven fabric substrate, or knitted fabric substrate.

20. The fiber-reinforced silk polymer composite material or method according to any one of the claims, wherein the woven, nonwoven, or knitted fabric is selected from the group consisting of cotton jersey or other types of fabric including various types of cotton (canvas, twill, satine, etc.), linen, silk fabric (organza, crepe, satin, etc.), and combinations thereof.

21. The fiber-reinforced silk polymer composite material or method according to any one of the claims, wherein the woven fabric, nonwoven fabric, or knitted fabric is cotton jersey.

22. The fiber-reinforced silk polymer composite material or method according to any one of the claims, wherein the cured silk polymer matrix further comprises an additive, the additive being selected from the group consisting of plasticizers or crosslinking agents for silk, and combinations thereof.

23. The fiber-reinforced silk polymer composite material or method according to the immediately preceding claim, wherein the plasticizer comprises glycerol and the crosslinking agent for silk comprises an acid or an alcohol.

24. The fiber-reinforced silk polymer composite material or method according to any one of the claims, wherein the fiber-reinforced silk polymer composite material has a thickness between 0.1 mm and 5 mm or between 0.4 mm and 2 mm.

25. The fiber-reinforced silk polymer composite material or method according to any one of the claims, wherein the fiber-reinforced silk polymer composite material has a tensile strength between 2 MPa and 80 MPa, between 8 MPa and 40 MPa, or between 10 MPa and 20 MPa.

26. The fiber-reinforced silk polymer composite material or method according to any one of the claims, wherein the fiber-reinforced silk polymer composite material has elongations at break between 0.1% and 800%, between 2% and 400%, and between 20% and 200%.

27. The fiber-reinforced silk polymer composite material or method according to any one of the claims, wherein the fiber-reinforced silk polymer composite material has a Young's modulus between 0.5 MPa and 20 GPa, between 100 MPa and 10 GPa, or between 200 MPa and 2 GPa.

28. The fiber-reinforced silk polymer composite material is 0.1 g / cm³ ３ and 5 g / cm ３ Between these two points, 0.3 g / cm³ ３ and 2 g / cm ３ Between, or 0.4 g / cm³ ３ and 1 g / cm ３ A fiber-reinforced silk polymer composite material or method according to any one of the claims, having a material density between [a certain value] and [a certain value].

29. The fiber-reinforced silk polymer composite material or method according to any one of the claims, wherein the fiber-reinforced silk polymer composite material includes at least one patterned surface.

30. The fiber-reinforced silk polymer composite material or method according to the preceding claim, wherein the at least one patterned surface includes a pattern selected from the group consisting of diffraction gratings, lotus leaf patterns, gecko foot patterns, micropyramids, cubes, spheres, or cone arrays, and combinations thereof.

31. A step of dissolving at least a portion of a cured silk polymer matrix to impregnate a woven fabric substrate, a nonwoven fabric substrate, or a knitted fabric substrate; and A step of separating at least a portion of the cured silk polymer matrix from the woven fabric substrate, nonwoven fabric substrate, or knitted fabric substrate. A method for recycling fiber-reinforced silk polymer composite materials, including [specific material].

32. The method according to the preceding claim, wherein the fiber-reinforced silk polymer composite material is the fiber-reinforced silk polymer composite material described in any one of claims from claim 1 to the claim immediately preceding the preceding claim, or the fiber-reinforced silk polymer composite material produced by the method according to any one of claims from claim 1 to the claim immediately preceding the preceding claim.

33. The method according to any one of claims 31 to the immediately preceding claim, wherein the dissolution step uses a LiBr salt solution.

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