TW202413515A - Gel casting methods for manufacture of textile materials - Google Patents

Abstract

Methods for making a biocomposite material include depositing a fluid mixture into a desired spatial configuration, where the fluid mixture includes a carrier fluid, biomass, and a gelling agent; triggering gelling of the fluid mixture to form a biomass gel; and removing at least a portion of the carrier fluid to form the biocomposite material. Biocomposite materials as disclosed herein may have advantageous mechanical and aesthetic properties that make the materials especially suitable for use as textile materials, including but not limited to leather analog textile materials.

Description

Gel casting method for making textile materials

The present invention relates generally to methods for preparing textile materials, and more particularly to methods for forming textile materials by gel casting.

Methods for making leather-like materials or other composite textile materials from non-animal derived biomaterials (e.g., size-reduced particles of filamentous fungal biomats) have recently received a great deal of attention and investment. Such materials have been known to be formed by one of two methods: (1) wet-laying of biomaterial-containing films, whereby a dilute (2 to 4 wt%) mixture of biomass and other components in a liquid medium (usually all or mostly water) is cast onto a filter that allows the liquid medium to drain, or (2) slurry casting/blade smearing, whereby a slurry with a slightly higher solids content (18 to 24 wt%) is cast onto a sheet and a blade is used to spread the viscous mixture into a cohesive film. However, both known methods have major disadvantages: in the practice of wet web forming, it may be difficult to control the content of plasticizers and other water-soluble components (because these plasticizers and components are discharged through the filter together with the liquid medium) and it is difficult to add large amounts of high molecular weight components such as polymers (because these components may clog the filter and hinder the discharge of the liquid medium), and the slurry casting/blade smearing method also has a limited capacity for high molecular weight additives (because these additives often make the slurry too viscous to be effectively spread), and is generally ineffective for forming materials with a flat or smooth surface and/or uniform thickness due to the rheology of the slurry.

Therefore, there is a need in the art for methods of preparing biocomposites from particulate non-animal derived biomaterials that allow for the increased use of water soluble and/or high molecular weight components, as well as improved surface texture and thickness uniformity.

In one aspect of the invention, a method for producing a biocomposite comprises (a) depositing a fluid mixture comprising a carrier fluid, biomass, and a gelling agent into a desired spatial configuration, wherein the biomass comprises a portion that is at most slightly soluble in the carrier fluid; (b) triggering gelation of the fluid mixture to form a biomass gel; and (c) removing at least a portion of the carrier fluid from the biomass gel to form a biocomposite, wherein the carrier fluid comprises no more than about 95 wt%, no more than about 80 wt%, no more than about 65 wt%, or no more than about 50 wt% of the biocomposite.

In an embodiment, the method may further include depositing a second fluid mixture comprising a second carrier fluid, a second biomass, and a second gelling agent into a second desired spatial configuration, wherein the second biomass includes a portion that is at most slightly soluble in the second carrier fluid; triggering gelation of the second fluid mixture to form a second biomass gel; prior to step (c), layering the biomass gel and the second biomass gel that are in physical contact with each other; and removing at least a portion of the second carrier fluid from the second biomass gel, wherein the biocomposite material includes a first layer and a second layer that are adhered to each other.

In embodiments, the biomass may comprise fermented biomass.

In embodiments, the biomass may comprise fungal mycelium.

In embodiments, the biomass may comprise microbial biomass. The biomass may, but need not, comprise bacterial biomass.

In embodiments, the biomass may comprise plant biomass.

In embodiments, the biomass may comprise algal biomass.

In an embodiment, the mass ratio of biomass to gelling agent in the fluid mixture may be about 1:18 to about 18:1. The mass ratio of biomass to gelling agent in the fluid mixture may be, but need not be, no more than about 10:3.

In an embodiment, the fluid mixture may further comprise a filler. The filler may be, but need not be, selected from the group consisting of microfibrillated cellulose, nanofibrillated cellulose, recycled fibers, recycled particles, polymerized fibers, polymerized particles, and combinations thereof.

In embodiments, step (a) may comprise casting a fluid mixture.

In an embodiment, step (a) may include extruding or spraying the fluid mixture into a first desired spatial configuration. The method may, but need not, further include depositing a second mixture having a different composition than the fluid mixture into a second desired spatial configuration, the second desired spatial configuration having a preselected spatial relationship to the first desired spatial configuration. Step (a) may, but need not, include extruding the fluid mixture onto a surface.

In an embodiment, step (a) may include casting or patterning the fluid mixture by printing.

In embodiments, step (a) may comprise forming fibers of the fluid mixture by solution spinning. At least a portion of the carrier fluid may, but need not, gel during step (a). At least a portion of the carrier fluid may, but need not, evaporate from the fluid mixture during step (a).

In an embodiment, the carrier fluid may be selected from the group consisting of water, one or more alcohols, and combinations thereof.

In embodiments, the fluid mixture may further comprise a dispersed or emulsified compound that is insoluble in the carrier fluid and is entrapped in the biomass gel during step (b).

In embodiments, in step (a), the fluid mixture may be cast onto a substantially flat surface, i.e., to form a layer or sheet that is substantially "two-dimensional" in that its length and width are substantially greater than its thickness.

In an embodiment, in step (a), the fluid mixture may be cast into or onto a cavity or mold. The cavity or mold may have any suitable three-dimensional shape (e.g., the shape of an article to be made from the biocomposite material).

In an embodiment, step (b) can be performed by at least one of: reducing the temperature of the fluid mixture, increasing the temperature of the fluid mixture, changing the pH of the fluid mixture, adding metal ions to the fluid mixture, inducing polymerization of monomers in the fluid mixture, and exposing the fluid mixture to electromagnetic radiation of a selected wavelength.

In embodiments, step (b) may be performed by removing at least a portion of the carrier fluid.

In embodiments, the fluid mixture may remain fluid for about five seconds to about twelve hours after step (a).

In an embodiment, between step (a) and step (b), the fluid mixture may be self-leveled.

In an embodiment, the method may further comprise mechanically agitating the fluid mixture between step (a) and step (b).

In embodiments, the gelling agent may comprise a polymer having a molecular weight of at least about 80,000 daltons. The polymer may, but need not, be a polysaccharide, a polypeptide, a protein, a starch, a block copolymer, a polyelectrolyte, or a plant gum. The polymer may, but need not be, a hydrophilic colloid selected from the group consisting of iota-carrageenan, kappa-carrageenan, lambda-carrageenan, agar, starch, modified starch, galangal, guar gum, locust bean gum, gum arabic, acacia gum, gum karaya, tragacanth gum, alginate, pectin, methylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, and combinations thereof.

In an embodiment, the gelling agent may include one or more monomers. The gelling agent may, but need not, further include an initiator.

In an embodiment, the gelling agent may include at least one of a colloid and a mutagenic agent.

In embodiments, the gelling agent may comprise an amphiphilic molecule.

In an embodiment, the fluid mixture may further comprise at least one cation. The at least one cation may, but need not, comprise an organic cation, a metal cation, or both.

In embodiments, the fluid mixture may further comprise at least one plasticizer. The at least one plasticizer may, but need not be, insoluble, nearly insoluble, very slightly soluble, or slightly soluble in the carrier fluid. The at least one plasticizer may, but need not be, slightly soluble, soluble, freely soluble, or very freely soluble in the carrier fluid. The at least one plasticizer may, but need not, comprise from about 10 wt % to about 85 wt % of the total solid content of the biocomposite.

In embodiments, the fluid mixture may further comprise one or more functionalizing compounds or crosslinking agents. The one or more functionalizing compounds or crosslinking agents may, but need not, comprise at least one of carboxylic acids, esters, anhydrides, epoxides, amidoamines, epichlorohydrins, carbodiimides, peptides, oligopeptides, polypeptides, proteins, and enzymes, which may, but need not, comprise transglutaminase. The method may, but need not, further comprise covalently functionalizing or crosslinking at least one of the biomass and the gelling agent during or after step (c).

In embodiments, the fluid mixture may further comprise at least one non-gelling polymer. The at least one non-gelling polymer may, but need not be, soluble in the carrier fluid. The at least one non-gelling polymer may, but need not be, comprise a polysaccharide. The at least one non-gelling polymer may, but need not be, partially soluble or insoluble in the carrier fluid; the at least one non-gelling polymer may, but need not be, selected from the group consisting of lignin, rubber (which may, but need not be, natural latex rubber), and combinations thereof.

In an embodiment, step (c) can be performed by freeze drying or critical point drying.

In embodiments, the biomass gel may be pinned during step (c). The biomass gel may, but need not, be pinned by compression. The biomass gel may, but need not, be pinned by uniaxial or biaxial tension.

In an embodiment, during step (c), the biomass gel may be in contact with a release layer and the adhesion between the biomass gel and the release layer may be strong enough to prevent the biomass gel from delaminating, and after step (c), the adhesion between the biocomposite material and the release layer may be weak enough to allow the biocomposite material to be peeled off from the release layer. The release layer may, but need not, comprise wax, polytetrafluoroethylene, polyethylene, polypropylene, polysilicone, or a combination thereof.

In an embodiment, the biocomposite material may be uniaxially or biaxially stretched after step (c). The biocomposite material may, but need not, be heated while being uniaxially or biaxially stretched.

In an embodiment, the method may further comprise embossing the biomass gel. The embossing step may, but need not, be performed simultaneously with step (c). Step (c) may, but need not, be initiated before the embossing step.

In an embodiment, the method may further include introducing at least one gas into the fluid mixture before step (a). After the introducing step, the fluid mixture may be, but need not be, a foam. The at least one gas may be, but need not be, selected from the group consisting of air, carbon dioxide, nitrogen, and combinations thereof.

In an embodiment, the method may further include introducing a foaming agent into the fluid mixture. The foaming agent may, but need not be, a surfactant, and the method may further include introducing at least one gas into the fluid mixture; the at least one gas may, but need not be, selected from the group consisting of air, carbon dioxide, nitrogen, and combinations thereof, and the surfactant may, but need not, be introduced in an amount of about 0.1 wt % to about 4 wt % of the fluid mixture. The foaming agent may, but need not be, a blowing agent, which may, but need not, be selected from the group consisting of bicarbonate, compressed gas, hydride salt, and combinations thereof.

In an embodiment, step (c) can be performed by heating the biomass gel, applying negative pressure to the biomass gel, radio frequency irradiation of the biomass gel, microwave irradiation of the biomass gel, or a combination thereof.

In embodiments, the rate at which the carrier fluid is removed from the biomass gel during step (c) can be controlled, optimized, selected or adjusted to provide a preselected porosity to the biocomposite.

In an embodiment, step (a) may include casting the fluid mixture onto a temperature-controlled surface. The method may, but need not, further include controlling a spatial temperature gradient of the temperature-controlled surface. During step (a), at least a portion of the temperature-controlled surface may, but need not, be cooled to a temperature below the freezing point of the carrier fluid. The fluid mixture may, but need not, further comprise a liquid additive, and during step (a), at least a portion of the temperature-controlled surface may, but need not, be cooled to a temperature below the freezing point of the liquid additive so that the liquid additive freezes and forms a frozen additive; the liquid additive may, but need not, be immiscible with the carrier fluid, insoluble, nearly insoluble, very slightly soluble, or slightly soluble in the carrier fluid, and the method may, but need not, further comprise removing at least a portion of the frozen additive after step (a).

In an embodiment, step (a) may include depositing the fluid mixture in physical contact with a backing material. The backing material may, but need not, be a woven material (e.g., a flat woven web), which may, but need not, comprise cotton (which may, but need not, be selected from the group consisting of cotton cheesecloth, muslin, and combinations thereof) and may, but need not, comprise resistant polyester. The backing material may, but need not, be selected from the group consisting of foamed materials, nonwovens, knitted fabrics, and combinations thereof. The backing material may, but need not, comprise a cellulose fabric.

In another aspect of the invention, the biocomposite comprises about 0.01 wt % to about 95 wt %, about 0.01 wt % to about 80 wt %, about 0.01 wt % to about 65 wt %, or about 0.01 wt % to about 50 wt % of a carrier fluid; biomass, wherein the biomass is at most slightly soluble in the carrier fluid; and at least one gelling agent, wherein the biocomposite has a tensile strength of at least about 3 MPa.

In an embodiment, the biocomposite material may further comprise at least one additive selected from the group consisting of fillers, functionalized compounds, crosslinkers, polymers, sizing agents, hydrophobic agents, plasticizers, pigments, dyes, antifoaming agents, defoaming agents, flocculants, deflocculating agents, antimicrobial agents, antistatic agents, UV stabilizers, surface modifiers, foaming agents, foaming agents, and flame retardants. The at least one additive may, but need not, comprise a functionalized compound or crosslinker, wherein the functionalized compound or crosslinker is a carboxylic acid, an ester, an anhydride, or an epoxide. The at least one additive may, but need not, comprise a deep eutectic solvent. The at least one additive may, but need not, include a surface modifier selected from the group consisting of a texture modifier, a slip agent, an anti-slip agent, a matting agent, and a gloss agent.

In embodiments, at least one gelling agent may comprise a polymer, and the polymer may comprise between about 1 wt% and about 90 wt% of the biocomposite. The polymer may, but need not be, a polysaccharide, a polypeptide, a protein, a starch, a block copolymer, a polyelectrolyte, or a plant gum. The polymer may, but need not be, a hydrophilic colloid selected from the group consisting of iota-carrageenan, kappa-carrageenan, lambda-carrageenan, agar, starch, modified starch, safflower gum, guar gum, locust bean gum, gum arabic, acacia gum, karaya gum, tragacanth gum, alginate, pectin, methylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, and combinations thereof. The at least one gelling agent may, but need not, further comprise at least one hydrophobic modifier covalently bonded to the polymer. The at least one hydrophobic modifier may, but need not, non-covalently bond to the polymer, and may, but need not, bond to the polymer by electrostatic interactions. The at least one gelling agent may, but need not, further comprise at least one cation complexed to the polymer; the at least one cation may, but need not, comprise an organic cation, a metal cation, or both, and may, but need not, crosslink the first portion of the polymer with the second portion of the polymer and at least one of the polymeric components of the biomass. The polymer may, but need not, have a molecular weight of at least about 80,000 Daltons.

In an embodiment, at least one gelling agent may include one or more monomers. At least one gelling agent may, but need not, further include an initiator.

In embodiments, the gelling agent may include a colloid or a mutagenic agent.

In embodiments, the gelling agent may comprise an amphiphilic molecule.

In embodiments, the gelling agent may be a peptide or an oligopeptide.

In an embodiment, the biocomposite material may further comprise at least one of a plasticizer, a filler and a crosslinking agent.

In embodiments, the biocomposite may include a plasticizer, wherein the plasticizer comprises about 10 wt % to about 85 wt % of the total solid content of the biocomposite.

In embodiments, the mass ratio of gelling agent to biomass may be at least about 0.3.

In an embodiment, the biocomposite material may further include a backing material. The backing material may, but need not, include a woven material (e.g., a flat woven mesh), which may, but need not, include cotton (which may, but need not, be selected from the group consisting of cotton gauze, plain woven cloth, and combinations thereof) and may, but need not, include resistant polyester. The backing material may, but need not, include a nonwoven fabric, a knitted fabric, or both. The backing material may, but need not, include a cellulose fabric.

In another aspect of the invention, a biocomposite gel comprises a carrier fluid; biomass, wherein the biomass is at most slightly soluble in the carrier fluid; and at least one gelling agent.

In embodiments, the biocomposite gel may include first and second polymer networks, wherein the first polymer network includes a gelling polymer. The first and second polymer networks may, but need not, interpenetrate each other. The second polymer network may, but need not, include a gelling polymer. The second polymer network may, but need not, include a non-gelling polymer.

In embodiments, the mass ratio of gelling agent to biomass may be at least about 0.3.

In an embodiment, the biocomposite gel may further include a backing material. The backing material may, but need not, include a woven material (e.g., a flat woven mesh), which may, but need not, include cotton (which may, but need not, be selected from the group consisting of cotton gauze, plain woven cloth, and combinations thereof) and may, but need not, include resistant polyester.

Although specific embodiments and applications have been illustrated and described, the present invention is not limited to the exact configuration and components described herein. Various modifications, changes and variations that will be apparent to those skilled in the art may be made to the configuration, operation and details of the methods and systems disclosed herein without departing from the spirit and scope of the entire disclosure.

As used herein, unless otherwise specified, when used with respect to a numerical limitation or range, the terms "about", "approximately", etc., mean that the limitation or range may vary by up to 10%. By way of non-limiting example, "about 750" may mean as little as 675 or as much as 825, or any value therebetween. When used in relation to a ratio or relationship between two or more numerical limits or ranges, the terms "about," "approximately," and the like, mean that each of the limits or ranges can vary by up to 10%; by way of non-limiting example, a statement that two quantities are "approximately equal" can mean that the ratio between the two quantities is as little as 0.9:1.1 or as much as 1.1:0.9 (or any value therebetween), and a statement that the four-way ratio is "about 5:3:1:1" can mean that the first number in the ratio can be any value from at least 4.5 to no more than 5.5, the second number in the ratio can be any value from at least 2.7 to no more than 3.3, and so on.

The embodiments and configurations described herein are neither complete nor exhaustive. As should be appreciated, other embodiments may utilize one or more of the features described above or in detail below, alone or in combination.

Cross-reference to related applications This application claims priority to U.S. Provisional Patent Application No. 63/350,395 filed on June 8, 2022; U.S. Provisional Patent Application No. 63/399,577 filed on August 19, 2022; and U.S. Provisional Patent Application No. 63/427,698 filed on November 23, 2022. Each of the above-mentioned applications is incorporated herein by reference in its entirety.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. All patents, applications, published applications and other publications referenced herein are incorporated herein by reference in their entirety. Unless otherwise stated, if there are multiple definitions for a term in this document, the definition provided in the invention content shall prevail.

As used herein, unless otherwise specified, the term "aqueous" refers to any mixture or solution that includes water. Therefore, it should be clearly understood that in the term "aqueous" solution as used herein, water can be the only solute, one of two or more solutes, the only solvent, or one of two or more solvents.

As used herein, unless otherwise specified, the term "backing material" or "backing layer" refers to a material or material layer that is added to a composite article to impart one or more desired mechanical and/or structural characteristics (e.g., improved tensile modulus, improved fracture strain, increased stiffness/hardness, etc.). It should be expressly understood that the backing material or backing layer, as those terms are used herein, need not be placed on the "back" (i.e., rear, front) aspect of the composite article, but may be placed on any exterior aspect (front, back, top, bottom, side, etc.) or internal (e.g., distributed throughout the article, "sandwiched" between other material layers, etc.) of the article.

As used herein, unless otherwise specified, the term "biodegradable" refers to a material that biodegrades at least 10% faster than "real" (i.e., animal) leather under a given set of conditions (e.g., those specified in ISO 20136:2017, "Leather-determination of degradability by micro-organisms").

As used herein, unless otherwise specified, the term "biomass" refers to the mass of living or formerly living organisms, including microbial and plant biomass. Microbial biomass sources may include bacterial, fungal (including higher fungi), and microalgae biomass sources. Plant biomass sources may include any source of plant-based biopolymers such as cellulose, lignin, and pectin. By way of non-limiting example, the phrase "filamentous fungal biomass" as used herein refers to the mass of living or formerly living filamentous fungi. Filamentous fungal biomass may include biomats (as that term is used herein) and filamentous fungi produced by submerged fermentation, such as, but not limited to, mycoprotein pastes as described in U.S. Patent No. 7,635,492 to Finnigan et al. and/or filamentous fungal biomass as described (or produced by the methods described) in U.S. Patent No. 11,058,137 to Pattillo, or filamentous fungi produced by solid substrate fermentation.

As used herein, unless otherwise specified, the term "biomat" refers to a cohesive mass of filamentous fungal tissue comprising a network of interwoven hyphae filaments. As used herein, a biomat may be characterized, but need not be, by one or more of the following: a density between about 50 and about 200 grams per liter, a solids content between about 5 wt% and about 20 wt%, and a tensile strength sufficient to be substantially completely raised from the surface of a growth substrate (e.g., a liquid growth medium, a solid fungal composite, or a solid film or mesh). As used herein, the biomat may be produced by any one or more fungal fermentation methods known in the art, such as, by way of non-limiting example, the methods described in PCT Application Publications 2020/176758, 2019/099474, and 2018/014004.

As used herein, unless otherwise specified, the term "biological material" refers to any tissue or other physical material derived from one or more living or formerly living organisms other than animals (e.g., filamentous fungi, plants, bacteria, algae, yeast, etc.). As used herein, the term "biological material" may be biomass or a portion thereof, but may also be a material derived directly or indirectly from an organism (e.g., an extract, a metabolite, etc.).

As used herein, unless otherwise specified, the term "cohesive" refers to any material having sufficient structural integrity and tensile strength to be picked up by hand and/or physically manipulated as a solid object without tearing or collapsing.

As used herein, unless otherwise specified, the term "colloid" refers to a mixture in which particles of one substance (the "dispersed phase") are dispersed throughout a volume of a different substance (the "dispersed medium"); for example, the dispersed phase may include or consist of microscopic or macroscopic bubbles, particles, etc. Where the dispersed phase and the dispersed medium of a colloid are specifically identified herein, the dispersed phase and the dispersed medium are separated by a hyphen, wherein the dispersed phase is identified first, e.g., reference herein to an "oil-water colloid" refers to a colloid in which oil is the dispersed phase and water is the dispersed medium.

As used herein, unless otherwise specified, the term "degree of expansion" refers to the relative change in the mass of a solid item when the solid is saturated with a liquid. By way of non-limiting example, a solid item having a mass of 200 g when dry and a mass of 300 g when saturated with water has a degree of expansion in water of 50% or 0.5. In the case where the term "degree of expansion" is used herein without explicitly identifying a liquid, it can be assumed that the liquid is water.

As used herein, unless otherwise specified, the term "deposition" means casting, laying, placing or placing a deformable mass of material in a desired spatial configuration, such as by extrusion or other suitable technique.

As used herein, unless otherwise specified, the term "durable" refers to a material having at least one of a tear strength of at least about 5 N/mm, a tear force of at least about 5 N, and a tensile strength of at least about 1.5 MPa.

As used herein, unless otherwise specified, the term "emulsion" refers to a colloid in which both the dispersed phase and the dispersion medium are liquids. As the term is used herein, examples of emulsions include, but are not limited to, lotions, latex, and various biofilms.

As used herein, unless otherwise specified, the term "filamentous fungus" refers to any multicellular fungus capable of forming an interconnected network of hyphae (either vegetative hyphae or aerial hyphae, and most commonly both) called a "mycelium." As the term is used herein, examples of filamentous fungi include, but are in no way limited to, the following genera: Acremonium , Alternaria , Aspergillus , Cladosporium , Fusarium , Mucor , Penicillium , Rhizopus , Stachybotrys , Trichoderma , and Trichophyton , as well as many other genera, with specific examples including Fusarium strain flavolapis (ATCC Accession No. PTA-10698) and Fusarium venenatum . It is to be expressly understood that filamentous fungi, as the term is used herein, may be capable of forming other fungal structures besides hyphae/hyphae, such as fruiting bodies.

As used herein, unless otherwise specified, the term "foam" refers to a colloid in which the dispersed phase is a gas and the dispersion medium is a liquid. Examples of foams, as the term is used herein, include but are not limited to shaving creams, soap bubbles, and the "top layer" of carbonated or nitrogenated beverages.

As used herein, unless otherwise specified, the terms "fungal mycelial matter" and "fungal mycelial biomass" are interchangeable and each refers to any material comprising at least about 50 wt% fungal mycelial matter on a dry weight basis (i.e., without taking into account the mass of any water). More specifically, as used herein, unless otherwise specified, the term "consisting essentially of fungal mycelial matter" refers to any material comprising at least about 95 wt% fungal mycelial matter on a dry weight basis.

As used herein, unless otherwise specified, the term "gel" refers to a colloid in which the dispersed phase is a liquid and the dispersion medium is a solid. Examples of gels, as the term is used herein, include but are not limited to agar, hair gel, and opal. As the term is used herein, a gel may behave as a solid or a semisolid and generally has a storage modulus greater than its loss modulus in a linear strain state under dynamic deformation at a frequency of 0.1 Hz to 100 Hz, and therefore does not flow easily.

As used herein, unless otherwise specified, the terms "animal hide leather" and "genuine leather" are interchangeable and each refers to a durable, flexible material made by tanning animal hides or skins.

As used herein, unless otherwise specified, the term "inactivated" refers to filamentous fungal biomass in which the fungal cells have been rendered nonviable (hereinafter referred to as "viability inactivation"), or enzymes capable of degrading or causing chemical transformations within the biomass have been inactivated (hereinafter referred to as "enzyme inactivation"), or both. By extension, the term "inactivation" refers to any method or process by which filamentous fungal biomass can be inactivated, such as, by way of non-limiting example, boiling, immersion in an organic liquid (e.g., alcohol, peracetic acid, etc.), irradiation, pressure treatment, washing, size reduction, steaming, and temperature cycling.

As used herein, unless otherwise specified, the term "impregnation" refers to the penetration and/or impregnation of a solution into a mass of a solid but permeable and/or porous material such that the solution or a portion thereof is distributed in a mass of solid material, such as and not limited to a polymer solution penetrating the pore spaces in a fungal biomass comprising hyphae. Without being bound by theory, impregnation of fungal hyphae biomass with a solution comprising components such as polymers and plasticizers, after removal of the solvent by curing, produces a textile material having such components distributed in the biomass. This distribution may be substantially uniformly distributed or non-uniformly distributed.

As used herein, unless otherwise specified, the term "liquid aerosol" refers to a colloid in which the dispersed phase is a liquid and the dispersion medium is a gas.

As used herein, unless otherwise specified, the term "loading ratio" refers to the weight ratio of fungal biomass relative to polymer in a fungal textile composition.

As used herein, unless otherwise specified, the term "mass loss after immersion" refers to the relative mass lost by a solid object after being immersed in a liquid, without taking into account the mass of the liquid absorbed by the solid object. By way of non-limiting example, a solid object having a mass of 100 grams when dry and a mass of 95 grams after being immersed in water (without taking into account the mass of the absorbed liquid) has a 5% mass loss after being immersed in water. In the case where the term "mass loss after immersion" is used herein without explicitly identifying a liquid, it can be assumed that the liquid is water.

As used herein, unless otherwise specified, the term "particle" refers to a small, discrete, localized object that can be attributed to chemical or physical properties such as volume, density and/or mass. As used herein, a "particle" can be microscopic or macroscopic; can be in the gas phase (e.g., bubbles), liquid phase (e.g., droplets of the dispersed phase in an emulsion), or solid phase (e.g., particles of a powder); and can be in any of a variety of shapes (e.g., spheres, oblate spheroids, fibers, tubes, rods, etc.). Particles in the solid phase may be referred to herein as "microparticles" or "microparticle matter."

As used herein, unless otherwise specified, the term "sheet" refers to a layer of solid material having a generally flat or planar shape and a high ratio of surface area to thickness.

As used herein, unless otherwise specified, the term "sol" refers to a colloid in which the dispersed phase is a solid and the dispersion medium is a liquid. Examples of sols as the term is used herein include, but are not limited to, blood, soil, paint, and colored ink.

As used herein, unless otherwise specified, the term "solid aerosol" refers to a colloid in which the dispersed phase is a solid and the dispersion medium is a gas. Examples of solid aerosols as the term is used herein include smoke, ice clouds, and atmospheric particulates.

As used herein, unless otherwise specified, the term "solid foam" refers to a colloid in which the dispersed phase is a gas and the dispersion medium is a solid. Examples of solid foams as used herein include, but are not limited to, aerogels, pumice, and styrofoam.

As used herein, unless otherwise specified, the term "solid sol" refers to a colloid in which both the dispersed phase and the dispersion medium are solid. Examples of solid sols as used herein include cranberry glass.

As used herein, unless otherwise specified, the term "tannin" generally refers to any molecule that forms a strong bond with a protein structure, and more specifically, refers to a molecule that, when applied to hides and leathers, binds strongly to the protein portion of the collagen structure of the skin to improve the strength and resistance to degradation of the leather. The most commonly used types of tannins are vegetable tannins, i.e., tannins extracted from trees and plants, and chromic tannins such as chromium (III) sulfate. Other examples of tannins, as the term is used herein, include modified naturally derived polymers, biopolymers, and metal salts other than chromium salts, such as aluminum silicates (sodium aluminum silicate, potassium aluminum silicate, etc.).

As used herein, unless otherwise specified, the term "water absorption" refers to the degree of swelling of a solid material when the solid material is saturated with water.

The present invention provides biocomposites having advantageous and beneficial properties, and methods of making biocomposites by gel casting. In general, the methods of the present invention comprise (a) casting (e.g., into a cavity/mold or onto a surface by extrusion) or otherwise depositing (e.g., by solution spinning) a fluid mixture comprising a carrier fluid, biomass, and a gelling agent into a desired spatial configuration, wherein the biomass comprises a portion that is at most slightly soluble in the carrier fluid, (b) triggering gelation of the fluid mixture to form a biomass gel, and (c) removing at least a portion of the carrier fluid of the fluid mixture from the biomass gel to form a biocomposite. By way of non-limiting example, a fluid mixture may be produced by reducing the size of cohesive biomass (e.g., cohesive fungal hyphae biomass) by any suitable method, thoroughly blending, combining and/or mixing the size-reduced biomass with a carrier fluid, and vacuum degassing the mixture to remove entrapped gases.

When deposition or casting of a fluid mixture is performed by extrusion, the mixture is fed into the feed zone of the extruder. The temperature and screw speed of the extruder are set to ensure proper mixing of the material in the extruder barrel. Multiple feed ports can be used to adjust the relative loading of the various components during the extrusion process. Vacuum ports can also be used after the mixing section of the screw to remove air bubbles before the material leaves the extruder through the extruder die, which can be appropriately shaped to achieve the desired cross-section of the material and can be temperature controlled. After mixing and degassing, the material leaves the die at the end of the extruder in the form of a sheet or other desired shape and gel. The resulting monolithic gel is collected and may be dehydrated and dried.

In embodiments of the methods disclosed herein, the fluid mixture has an overall solids content that allows such mixtures to flow easily but achieves a thickness of the resulting biocomposite that is similar to existing conventional fabrics and thus allows the biocomposite to be used as an analog to such conventional fabrics (e.g., about 0.5 to about 1.5 mm in the case of leather analogs). Typically, such solids content is intermediate between that in mixtures used for wet lay film processes (2 to 4 wt%) and that in mixtures used for slurry casting/blade shaving (18 to 24 wt%); most typically, the solids content of the fluid mixtures used in embodiments disclosed herein is about 10 to about 14 wt%. The solids of the fluid mixture used in the gel casting method disclosed herein include at least non-animal biomass (such as, by way of non-limiting example, particles of cohesive fungal hyphae biomass with reduced size) and a gelling agent, but may include one or more additives such as, by way of non-limiting example, plasticizers, polymers, crosslinking agents (such as metal ions) and the like. These solid components are provided as a mixture with a carrier fluid to form a fluid mixture.

In many embodiments, the biomass used in the methods according to the present invention is filamentous fungal biomass, which is the biomass of one or more fungi that produce a network of interconnected hyphae called mycelium. Specifically, in many embodiments, the filamentous fungal biomass can be fungal mycelial biomass as that term is defined herein (although other filamentous fungal biomass is also encompassed, such as biomass containing a large amount of material derived from the fruiting body of a filamentous fungus, and is within the scope of the present invention). Most typically, the fungal mycelial biomass used in accordance with the present invention is a particle derived (e.g., by size reduction) from cohesive fungal mycelial biomass, i.e., mycelial biomass having sufficient structural integrity and tensile strength to be picked up by hand and physically manipulated without tearing or collapsing; non-limiting examples of cohesive fungal mycelial biomass that may be suitable for forming a fluid mixture in embodiments of the present invention include fungal mycelial biomass produced by a liquid surface fermentation process or a membrane fermentation process as described in PCT Application Publication No. 2019/046480 (the entire contents of which are incorporated herein by reference), and/or fungal mycelial biomass produced by a solid substrate fermentation process as described in PCT Application Publication No. 2016/149002 (the entire contents of which are incorporated herein by reference).

In embodiments of the methods disclosed herein, the biomass may include at least one portion (e.g., carbohydrates and/or proteins) that is extremely soluble, freely soluble, soluble, or slightly soluble in a carrier fluid (i.e., at least slightly soluble in a carrier fluid); and at least a second portion (e.g., lipids and/or other hydrophobic compounds) that is insoluble, nearly insoluble, extremely soluble, or slightly soluble in a carrier fluid (i.e., at most slightly soluble in a carrier fluid). In some such embodiments, the fluid mixture may be an emulsion in which at least a portion of the second portion is emulsified and substantially uniformly distributed prior to gelation. Incorporation of a hydrophobic, insoluble component into a fluid mixture, and thus into a biomass gel and ultimately into a biocomposite, may be desirable to render the finished biocomposite resistant to fluid absorption (e.g., water resistant where the biocomposite is intended for use as a leather analog). In embodiments where the biomass includes an insoluble, nearly insoluble, very slightly soluble, or slightly soluble portion, such a portion is generally present in an amount of about 20 to about 80 wt % of the biomass, or any subrange therebetween.

Many different gelling agents including, by way of non-limiting example, polysaccharides, polypeptides, proteins, starches, block copolymers, polyelectrolytes, and plant gums may be suitably used in the fluid mixtures of the methods disclosed herein. In some embodiments, the gelling agent may preferably comprise one or more polysaccharides, may more preferably comprise one or more carrageenans, may even more preferably comprise at least one of iota-carrageenan, kappa-carrageenan, and lambda-carrageenan, and may most preferably comprise kappa-carrageenan. In many embodiments, the amount of gelling agent is selected to be low enough to allow the mixture to flow when heated but high enough to form a gel upon cooling (e.g., cooling to room temperature); by way of non-limiting example, in embodiments where the gelling agent is κ-carrageenan, the amount of κ-carrageenan may be from about 10 to about 30 wt % of the total solids content of the fluid mixture, or any subrange thereof, or alternatively from about 2 to about 4 wt % of the total fluid mixture, or any subrange thereof. In some embodiments, the concentration of a single gelling agent and/or the relative amounts of two or more gelling agents (e.g., polysaccharides and metal cations) can be varied to achieve desired characteristics of the gelling properties of the fluid mixture; by way of non-limiting example, gelling can be slowed or accelerated depending on the gelling agent provided, for example, the gelling agent and its concentration can be selected to provide a gelling time of about five seconds to about twelve hours under standard temperature and pressure conditions. In some embodiments, the ratio of biomass to gelling agent can also be an important determinant of the combination of mechanical performance and aesthetic "look and feel" of the finished biocomposite; most typically, the mass ratio of biomass to gelling agent in the fluid mixture is from about 1:18 to about 18:1, or any subrange therebetween, on a dry weight basis. In other embodiments, the mass ratio of biomass to gelling agent is at least about 1:18, at least about 1:17, at least about 1:16, at least about 1:15, at least about 1:14, at least about 1:13, at least about 1:12, at least about 1:11, at least about 1:10, at least about 1:9, at least about 1:8, at least about 1:7, at least about 1:6, at least about 1:5, at least about 1:4, at least about 1:3, at least about 1:2, at least about 1:1, at least about 2:1, at least about 3:1, at least about 4:1, at least about 5:1, at least about 6:1, at least about 7:1, at least about 8:1, at least about 9:1, at least about 10:1, at least about 11:1, at least about 12:1, at least about 13:1, at least about 14:1, at least about 15:1, at least about 16:1, or at least about 17:1; and/or no more than about 18:1, no more than about 17:1, no more than about 16:1, no more than about 15:1 1, no more than about 14:1, no more than about 13:1, no more than about 12:1, no more than about 11:1, no more than about 10:1, no more than about 9:1, no more than about 8:1, no more than about 7:1, no more than about 6:1, no more than about 5:1, no more than about 4:1, no more than about 3:1, no more than about 2:1, no more than about 1:1, no more than about 1:2, no more than about 1:3, no more than about 1:4, no more than about 1:5, no more than about 1: 6, no more than about 1:7, no more than about 1:8, no more than about 1:9, no more than about 1:10, no more than about 1:11, no more than about 1:12, no more than about 1:13, no more than about 1:14, no more than about 1:15, no more than about 1:16 or no more than about 1:17; and/or within any range with a lower limit of A:B and an upper limit of C:D, wherein each of A, B, C and D is any integer greater than or equal to 1 and less than or equal to 18.

In many embodiments, it may be necessary or preferred to heat the fluid mixture to above room temperature prior to casting or deposition to improve its fluidity. The fluidity of the heated fluid mixture may have the additional benefit of enabling the fluid mixture to "self-level," i.e., naturally form a flat or smooth layer of substantially uniform thickness when cast, thereby eliminating the need for the labor-intensive, energy-intensive, and/or costly step of spreading or otherwise leveling the fluid mixture prior to gelling.

In some embodiments, the casting or deposition step may include two or more separate casting or deposition sub-steps to provide a layered structure to the resulting biocomposite material. Even more specifically, some embodiments of the method may include a first casting sub-step, in which a first layer of a fluid mixture is cast into a desired spatial orientation; a reinforcement sub-step, in which a layer of a reinforcement material (e.g., natural and/or synthetic fibers, membranes, mesh scaffolds, etc.) is placed on top of the first layer of the fluid mixture; and a second casting sub-step, in which a second layer of the fluid mixture is cast into the desired spatial orientation on top of the reinforcement material layer. Of course, this sequence of steps may be repeated any number of times to produce a "sandwiched" material (i.e., having a first layer of reinforcing material between a first layer and a second layer of fluid mixture, having a second layer of reinforcing material between a second layer and a third layer of fluid mixture, etc.). In some, but not all, embodiments, a previously cast or deposited layer of fluid mixture may be gelled prior to casting or depositing a subsequent layer of fluid mixture, while in other embodiments this is not the case. Advantageously, this process of placing a layer of reinforcing material between layers of the fluid mixture may allow the reinforcing material to be "embedded" or "hidden" within the finished biocomposite material such that it provides structural integrity to the biocomposite material and/or enhances or improves the physical characteristics or properties of the biocomposite material (e.g., ability to withstand stitching, flexibility, tensile strength, etc.) without being visible to an observer (e.g., a consumer purchasing an article of apparel or other product made from the biocomposite material), and/or may eliminate the need for an adhesive or glue to bond the fungal biomass layer to the reinforcing material layer. In other embodiments, more particularly, some embodiments of the method may include a first reinforcing sub-step, in which a layer of reinforcing material (e.g., natural and/or synthetic fibers, membranes, mesh scaffolds, etc.) is placed in a certain position; and a second casting sub-step, in which a layer of the fluid mixture is cast to a desired spatial orientation atop the layer of reinforcing material. In all such embodiments, the reinforcing material may be placed in an appropriate position and maintained under tension for a desired period of time. For example, the reinforcing material may be maintained under tension until the fluid mixture is cast, but before it has gelled or until the fluid mixture is completely gelled. For example, maintaining the reinforcing material under tension until the cast material gelates can improve the texture or smoothness of the resulting product, such as reducing or eliminating wrinkles in the final material.

After the fluid mixture has been cast or otherwise deposited into the desired spatial configuration (most often, but not necessarily always, a flat or planar sheet), gelation of the fluid mixture is triggered by any suitable method to form a biomass gel. Most commonly, gelation can be triggered by cooling the fluid mixture (actively or passively), for example, to room or ambient temperature, but other gelation mechanisms may also be possible depending on the composition of the fluid mixture; non-limiting examples of additional or alternative gelation triggering mechanisms include changing the pH of the fluid mixture, adding metal ions to the fluid mixture, initiating polymerization reactions in the fluid mixture, and exposing the fluid mixture to selected wavelengths of electromagnetic radiation. The self-leveling properties of the fluid mixture and the many mechanisms that can be used for gelation not only provide the possibility of reducing the energy requirements of the manufacturing process (for example, the fluid mixture can be gelled simply by exposing it to ambient conditions without any active energy), but also simplify and reduce the equipment requirements of the manufacturing process by making filters, scrapers, etc. optional or redundant as appropriate.

In some embodiments, the surface on which the fluid mixture is deposited may be temperature controlled, and in particular may have at least one region having a temperature below the freezing point of the carrier fluid and/or additives in the fluid mixture. By way of non-limiting example, in embodiments where the fluid mixture is an emulsion comprising water, biomass, a water-soluble gelling agent, and a hydrophobic wax, the solution may be cast on a surface having a temperature below the freezing point of the wax, thereby inducing the freezing of the wax and the phase separation of the water-soluble/water-dispersible components; after removing the water in a drying step, a sheet-like biocomposite having alternating layers of hydrophobic and hydrophilic materials may be produced.

One particular advantage and benefit of biocomposites prepared by the methods disclosed herein is that they can be picked up, handled, and/or moved after gelation but before removal of the carrier fluid (i.e., before the material dries) without breaking or disintegrating, which is generally not true for wet-laid or slurry-cast membranes. This feature makes subsequent processing of the biocomposite easier, as the material can be easily hung to air dry, transferred to an oven for drying, embossed with a pattern, etc. In some embodiments, the biomass gel can be embossed or textured before removal of any carrier fluid and/or during the drying step (i.e., when removal of the carrier fluid is incomplete and ongoing).

The use of gel casting to produce biocomposites as disclosed herein results in the production of strong, tough biocomposites that have mechanical characteristics similar to conventional textiles (e.g., leather) and in many cases have aesthetic (i.e., "look and feel") characteristics. In particular, the combination of fungal biomass, gelling agents, and, in some embodiments, plasticizers can give the desired look and feel of conventional textiles.

In some embodiments, the biocomposite materials disclosed herein can have a tensile strength suitable for a variety of applications of known materials. For example, the material can have a tensile strength greater than about 3 MPa, greater than about 4 MPa, greater than about 5 MPa, greater than about 6 MPa, greater than about 7 MPa, greater than about 8 MPa, greater than about 9 MPa, greater than about 10 MPa, greater than about 11 MPa, greater than about 12 MPa, greater than about 13 MPa, greater than about 14 MPa, greater than about 15 MPa, greater than about 16 MPa, greater than about 17 MPa, greater than about 18 MPa, greater than about 19 MPa, or greater than about 20 MPa.

In some embodiments, the biocomposite materials disclosed herein can have a tensile modulus suitable for a variety of applications of known materials. For example, the material can have a tensile modulus greater than about 20 MPa, greater than about 25 MPa, greater than about 30 MPa, greater than about 35 MPa, greater than about 40 MPa, greater than about 45 MPa, greater than about 50 MPa, greater than about 60 MPa, greater than about 70 MPa, greater than about 80 MPa, greater than about 90 MPa, greater than about 100 MPa, greater than about 125 MPa, greater than about 150 MPa, greater than about 175 MPa, or greater than about 200 MPa.

The materials of the present invention can achieve a combination of beneficial properties, such as having both high tensile strength values and high tensile modulus values. For example, such materials can have a tensile strength of greater than about 3 MPa (or any other tensile strength value mentioned above) while also having a tensile modulus of greater than about 20 MPa (or any other tensile modulus value mentioned above).

Other components in the fluid mixture (e.g., polymers, crosslinking agents, such as metal ions, etc.) can enhance the mechanical performance of the biocomposite after gelation and removal of the carrier fluid, for example, by crosslinking gelling agents and/or functional moieties (e.g., carboxylic acids of surface proteins) of the biomass. In some embodiments, the biocomposite can include as an additive at least one functionalizing agent or crosslinking agent selected from the group consisting of carboxylic acids, esters (e.g., fatty acids, fatty acid esters, waxes, esterified waxes, triglycerides and their derivatives), anhydrides, and epoxides. In some embodiments, the biocomposite can be partially dried and then exposed to another aliquot of the fluid to introduce additional components, such as crosslinking agents, metal ions, etc., into the biocomposite via injection/absorption of the fluid into the biocomposite.

The parameters of the drying/carrier fluid removal step can be selected to provide the desired characteristics of the finished biocomposite. By way of a first non-limiting example, freeze drying or critical point drying can be employed to retain high porosity in the finished biocomposite. By way of a second non-limiting example, the biomass gel can be "fixed" by compression, uniaxial tension, or biaxial tension during and/or after the drying step to prevent the biomass gel from curling during drying and/or to improve the toughness and cracking of the finished biocomposite. By way of a third non-limiting example, the rate at which the carrier fluid is removed can be selected to provide the desired porosity and/or thermal conductivity to the biocomposite, as faster removal of the carrier fluid generally produces a more porous material.

In some embodiments, the fluid mixture may be a foam, that is, one or more gases (e.g., air, carbon dioxide, nitrogen, etc.) may be incorporated into the fluid mixture to provide desired thermal characteristics (e.g., insulating characteristics) and/or textural characteristics and/or strength to porosity ratios in the biocomposite. In some embodiments, the fluid mixture may be a sol-gel precursor that forms a sol-gel upon gelation; embodiments of this type may be particularly useful for forming biocomposite materials that include metal and/or ceramic components.

In some embodiments, one or more reinforcing materials, such as natural or synthetic fibers, or combinations thereof, may be added to the fluid mixture prior to the drying/carrier fluid removal step to strengthen the resulting biocomposite and provide additional structural integrity to the resulting biocomposite. Non-limiting examples of suitable reinforcing materials include cellulose fibers, cardboard, and paper. Most typically, reinforcing materials such as fibers may be added to the fluid mixture in an amount of about 2 wt % to about 10 wt %, more preferably about 2.5 wt % to about 9 wt %, and most preferably about 3 wt % to about 8 wt % of the fluid mixture on a dry weight basis (i.e., excluding water), or any sub-range of any of these ranges.

In some embodiments, one or more vegetable oils may be added to the fluid mixture prior to the drying/carrier fluid removal step. Vegetable oils may be used in the biocomposite as any one or more of the following: a fragrance, an insecticide or pesticide, a preservative, a lubricant, a dirt-proofing or dirt resistance agent, a stain-proofing or stain resistance agent, and a water-proofing or water-repellent agent. Non-limiting examples of suitable vegetable oils include cedar oil. Most typically, a vegetable oil, such as cedar oil, can be added to the fluid mixture in an amount of about 0.1 wt % to about 0.5 wt %, more preferably about 0.15 wt % to about 0.35 wt %, and most preferably about 0.2 wt % of the fluid mixture on a dry weight basis (i.e., excluding water), or any sub-range of any of these ranges.

In some embodiments, one or more salts may be added to the fluid mixture prior to the drying/carrier fluid removal step. Salts may be useful as part of a saline rinse to separate organic contaminants, to promote "salting out" of dye precipitates, to blend with concentrated dyes, to provide cationic charge to promote absorption of anionic dyes (or vice versa), as antimicrobial and/or preservatives, as humectants, as desiccants, and the like. Non-limiting examples of suitable salts include sodium chloride, sodium benzoate, and sodium hydroxide. Most typically, a salt (e.g., sodium chloride) may be added to the fluid mixture in an amount of about 0.1 wt % to about 2 wt % of the fluid mixture on a dry weight basis (i.e., excluding water), or any sub-range thereof.

In some embodiments, the fluid mixture prior to the drying/carrier fluid removal step may include, on a dry weight basis (i.e., excluding water), about 25 wt% to about 60 wt% fungal biomass, about 15 wt% to about 30 wt% plasticizer, about 15 wt% to about 30 wt% polymer, about 2 wt% to about 10 wt% reinforcing material (e.g., natural or synthetic fibers, such as cellulose fibers), about 0.1 wt% to about 0.5 wt% vegetable oil (e.g., cedar oil), and about 0.1 wt% to about 2 wt% salt (e.g., sodium chloride, sodium benzoate, and/or sodium hydroxide), or any subranges therein.

In some embodiments, one or more water-resistant or anti-swelling crosslinking agents may be added to the fluid mixture prior to the drying/carrier fluid removal step. The water-resistant or anti-swelling crosslinking agents may be useful for reducing the water absorption of the finished biocomposite, i.e., reducing the tendency of the finished biocomposite to absorb water. Non-limiting examples of suitable crosslinking agents include polyamideamine-epichlorohydrin (PAE) resins, epoxides, and acrylates. Most typically, the water-resistant or anti-swelling crosslinking agent, such as a PAE resin, may be added to the fluid mixture in an amount of about 0.1 wt % to about 10 wt % of the fluid mixture on a dry weight basis (i.e., excluding water), or any subrange thereof. Additionally or alternatively, the biocomposite may be treated with or otherwise include a water repellent or water repellent such as lecithin and/or beeswax in an amount between about 0.1 wt % and about 50 wt %, or alternatively within any range having a lower limit of ten percent of any number between 0.1 wt % and 40 wt % and an upper limit of ten percent of any other number between 0.1 wt % and 40 wt %. In some embodiments, the moisture absorption of the finished biocomposite material may be no more than about 80%, no more than about 75%, no more than about 70%, no more than about 65%, no more than about 60%, no more than about 55%, no more than about 50%, no more than about 45%, no more than about 40%, no more than about 35%, no more than about 30%, no more than about 25%, no more than about 20%, no more than about 15%, no more than about 10%, no more than about 5%, no more than about 4%, no more than about 3%, no more than about 2%, or no more than about 1%.

Embodiments of the present invention enable the production of biocomposite materials that are resilient to repeated flexion. By way of non-limiting example, the materials of the present invention may be able to withstand at least about 5,000, at least about 10,000, at least about 15,000, at least about 20,000, at least about 25,000, at least about 30,000, at least about 35,000, or at least about 40,000 flexion cycles in a flexion cycle test according to BS EN ISO 5402:2009.

The biocomposite material according to the present invention can be manufactured so that it is characterized by a desired fracture strain. In some embodiments, by way of non-limiting example, the biocomposite can be made to have a fracture strain of at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, or at least about 65%, or no more than about 70%, no more than about 65%, no more than about 60%, no more than about 55%, no more than about 50%, no more than about 45%, no more than about 40%, no more than about 35%, no more than about 30%, no more than about 25%, no more than about 20%, no more than about 15%, no more than about 10%, or alternatively in any range having a lower limit of any integer percentage between 1% and 70% and an upper limit of any other integer percentage between 1% and 70%.

In some embodiments, a biocomposite material according to the present invention can be made into a multi-layer fabric by adhering, laminating or otherwise attaching to a non-fungal material (e.g., a cotton liner, a resistant polyester liner, a cardboard liner, a paper liner, etc.) and/or one or more liner layers of different fungal or biocomposite materials. Non-limiting examples of non-fungal fabrics that can be adhered, laminated or otherwise attached to a biocomposite according to the present invention to form a multi-layer fabric include acrylic fabrics, alpaca fabrics, angora fabrics, cashmere fabrics, coir fabrics, cotton fabrics, eisengarn fabrics, linen fabrics, Jute fabric, Kevlar fabric, linen fabric, microfiber fabric, mohair fabric, nylon fabric, olefin fabric, pashmina fabric, polyester fabric, pineapple fiber (piña) fabric, ramie fabric, rayon fabric, seaweed fiber fabric, silk fabric, sisal fabric, spandex fiber fabric, spider silk fabric, wool fabric and combinations thereof. In some embodiments, the backing layer may be a porous or mesh material having a pore size between about 5 μm and about 25.4 mm, between about 25 μm and about 5.60 mm, between about 0.165 mm and about 2.00 mm, between about 15 μm and about 400 μm, or alternatively within any range having a lower limit of any integer number of microns between 1 μm and 25.4 mm and an upper limit of any other integer number of microns between 1 μm and 25.4 mm. The adhesion between a layer of biocomposite and a layer of non-fungal or other fungal or biocomposite material can be at least about 1 N, at least about 2 N, at least about 3 N, at least about 4 N, at least about 5 N, at least about 6 N, at least about 7 N, at least about 8 N, at least about 9 N, at least about 10 N, at least about 11 N, at least about 12 N, at least about 13 N, at least about 14 N, or at least about 15 N, and the multi-layer fabric can, but need not, be engineered such that the adhesion failure mode between the layers is adhesive or cohesive.

Biocomposites according to the present invention can be manufactured such that they are characterized by a desired tear strength. In some embodiments, by way of non-limiting example, the biocomposite can be manufactured to have a tear strength of at least about 5 N/mm, at least about 10 N/mm, at least about 15 N/mm, at least about 20 N/mm, at least about 25 N/mm, at least about 30 N/mm, at least about 35 N/mm, at least about 40 N/mm, at least about 45 N/mm, at least about 50 N/mm, at least about 55 N/mm, at least about 60 N/mm, at least about 65 N/mm, at least about 70 N/mm, at least about 75 N/mm, at least about 80 N/mm, at least about 85 N/mm, at least about 90 N/mm, at least about 95 N/mm, or at least about 100 N/mm.

In some embodiments, one or more gases (e.g., air, carbon dioxide, nitrogen, etc.) may be incorporated into a biocomposite according to the present invention to produce a "foamed" biocomposite having a significantly lower mass density than a corresponding "non-foamed" biocomposite. Conversely, in other embodiments, it may be necessary to degas the pregelatinized slurry to remove any air bubbles and thereby increase the mass density of the biocomposite. In some embodiments, the biocomposite material may be "non-foamed" and have a mass density of at least about 1 g/cm ³ , at least about 1.05 g/cm ³ , at least about 1.1 g/cm ³ , at least about 1.15 g/cm ³ , at least about 1.2 g/cm ³ , at least about 1.25 g/cm ³ , at least about 1.3 g/cm ³ , at least about 1.35 g/cm ³ , at least about 1.4 g/cm ³ , at least about 1.45 g/cm ³ , or at least about 1.5 g/cm ³ . In other embodiments, the biocomposite can be "foamed" such that the density of the biocomposite is reduced by at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least about 95% relative to a corresponding "non-foamed" biocomposite, such as such that the "foamed" biocomposite has a density of no more than about 1 g/cm ³ , no more than about 0.95 g/cm ³ , no more than about 0.9 g/cm ³ , no more than about 0.85 g/cm ³ , no more than about 0.8 g/cm ³ , no more than about 0.75 g/cm ³ , no more than about 0.7 g/cm ³ , , no more than about 0.65 g/cm ³ , no more than about 0.6 g/cm ³ , no more than about 0.55 g/cm ³ , no more than about 0.5 g/cm ³ , no more than about 0.45 g/cm ³ , no more than about 0.4 g/cm ³ , no more than about 0.35 g/cm ³ , no more than about 0.3 g/cm ³ , no more than about 0.25 g/cm ³ , no more than about 0.2 g/cm ³ , no more than about 0.15 g/cm ³ , no more than about 0.1 g/cm ³ , or no more than about 0.05 g/cm ³ .

Biocomposites according to the present invention can be manufactured so that they are characterized by a desired thickness. In some embodiments, by way of non-limiting example, the biocomposites can be manufactured to have a thickness between about 0.1 mm and about 10 cm, or alternatively a thickness within any range having a lower limit of ten millimeters of any number between 0.1 mm and 10 cm and an upper limit of ten millimeters of any other number between 0.1 mm and 10 cm.

In some embodiments, an emulsifier and/or surfactant may be provided in the fungal slurry to improve the incorporation of hydrophobic materials into the fungal slurry. Non-limiting examples of such emulsifiers and/or surfactants include epoxidized soybean oil, cationic lipids, polysorbates, and alkyl polysaccharides. The emulsifier and/or surfactant may be provided in any amount within any range between about 2 wt % and about 20 wt %, or alternatively with a lower limit of any integer percentage between 2 wt % and 20 wt % and an upper limit of any other integer percentage between 2 wt % and 20 wt %.

It is expressly understood that the methods and systems disclosed herein are applicable to making biocomposites from fibrous or particulate non-animal biomass other than fungal biomass. Non-limiting examples of such fibrous or particulate, non-animal, non-fungal biomass include corn stover, sugarcane bagasse, coconut coir, fruit waste, vegetable waste, and used coffee grounds. The use of certain biomasses, particularly those that may be waste materials from other agricultural or industrial processes, may advantageously produce biocomposites having desirable overall mechanical, aesthetic, and/or textural properties while mitigating the environmental impact (e.g., carbon emissions) of producing such materials.

The biocomposite materials made according to the methods described above can have advantageous mechanical properties compared to known or currently known materials. By way of a first non-limiting example, the biocomposite materials made according to the present invention can have a moisture absorption of no more than about 140%, no more than about 130%, no more than about 120%, no more than about 110%, no more than about 100%, no more than about 90%, no more than about 80%, no more than about 70%, no more than about 60%, no more than about 50%, or no more than about 40% after 24 hours. By way of a second non-limiting example, the biocomposite materials made according to the present invention can have a moisture absorption of no more than about 140%, no more than about 130%, no more than about 120%, no more than about 110%, no more than about 100%, no more than about 90%, no more than about 80%, no more than about 70%, no more than about 60%, no more than about 50%, or no more than about 40% after 24 hours. flex) test to withstand at least about 10,000 flexion cycles, at least about 20,000 flexion cycles, at least about 30,000 flexion cycles, at least about 40,000 flexion cycles, at least about 50,000 flexion cycles, at least about 60,000 flexion cycles, at least about 70,000 flexion cycles, at least about 80,000 flexion cycles, at least about 90,000 flexion cycles, at least about 100,000 flexion cycles , at least about 110,000 flexion cycles, at least about 120,000 flexion cycles, at least about 130,000 flexion cycles, at least about 140,000 flexion cycles, at least about 150,000 flexion cycles, at least about 160,000 flexion cycles, at least about 170,000 flexion cycles, at least about 180,000 flexion cycles, at least about 190,000 flexion cycles, or at least about 200,000 flexion cycles. By way of a third non-limiting example, a biocomposite material made according to the present invention may have a fracture strain of about 10% to about 70%, or alternatively between a lower limit of any integer percentage of 10% to 70% and an upper limit of any other integer percentage of 10% to 70%. By way of a fourth non-limiting example, a biocomposite material made according to the present invention may have a tensile strength of at least about 1 MPa, at least about 2 MPa, at least about 3 MPa, at least about 4 MPa, at least about 5 MPa, at least about 6 MPa, or at least about 7 MPa.

Biocomposites prepared according to the methods described above may have a combination of particularly beneficial properties, such as having high tensile strength values and the ability to withstand a large number of flexion cycles in a bally flex test. For example, such materials may have a tensile strength of greater than about 3 MPa (or any other tensile strength value mentioned above) while also withstanding at least about 40,000 flexion cycles (or any other number of flexion cycles mentioned above) in a bally flex test.

Embodiments of the present invention are further described by means of the following illustrative and non-limiting examples.

Example 1 A fluid mixture comprising 90 wt% water, 5 wt% size-reduced particles of a biomass mat of the filamentous fungus Scyphodium luteum strain, 2.4 wt% glycerol, 2 wt% kappa-carrageenan, and 0.6 wt% urea was prepared. This mixture was heated until it flowed easily, cast onto a PTFE sheet, allowed to gel (by cooling to room temperature), passively dried overnight at room temperature while pressed between two wire racks, and subsequently baked in an oven at 100°C for 6 hours. FIG. 1 shows a section of the biomass gel after casting and gelling, and FIG. 2 shows several sections of the biomass gel during the ambient air drying step. The biomass gel had a thickness of approximately 6.6 mm before any water removal; the finished biocomposite had a thickness of approximately 0.95 mm.

The mechanical properties of the resulting biocomposite were then tested. The biocomposite passed the double bend test and survived 21,350 bending cycles in the flexion cycle test, with a tensile modulus of 39.5 MPa, a tensile strain at break of 42.13%, and a tensile strength of 6.11 MPa.

Example 2 Biomats of the filamentous fungus Scyphodium luteum strain grown on liquid growth medium were boiled to inactivate the fungus and rinsed with water to remove any residual growth medium. These biomats were then placed in a standard kitchen blender and reduced in size and blended with water until a homogenous aqueous slurry was obtained. 0.1 wt% sodium benzoate was added to the slurry as a preservative.

To each of these slurries were added (a) potassium chloride, (b) glycerol and urea as plasticizers, (c) Fiberlean ^™ cellulose fibers as a reinforcing material, (d) iron (III) oxide (Fe ₂ O ₃ ) as a pigment, and (e) kappa-carrageenan as a gelling agent. In some cases, additional water was added to obtain a desired total solids content of 5 to 8 wt %. Each slurry contained 36.9 wt% fungal biomass, 18.0 wt% κ-carrageenan, 1.1 wt% potassium chloride, and 2.0 wt% iron (III) oxide on a dry weight basis (i.e., excluding water); the amounts of plasticizer and cellulose varied relative to each other but in all cases totaled 42 wt% of the dry components.

Each slurry is heated in a pot with continuous stirring until a smooth, free-flowing mixture is obtained. This free-flowing mixture is then placed in a vacuum chamber for a short period of time to degas (i.e., to remove air). After degassing, each mixture is cast into a preheated mold, and the mold is then agitated to ensure uniform casting and to remove any surface bubbles. The mold is then allowed to cool to room temperature under ambient conditions.

After cooling, a monolithic gel is obtained from each mold. These gels are transferred to a dehydrator and dried at 40°C for 24 hours. The resulting material is then stretched, clamped to a solid substrate, and placed in an oven at 60°C for another 24 hours, after which each material is in the form of a smooth, bubble-free sheet. The composition of each slurry is given in Table 1, and the tensile strength and elongation at break of the obtained smooth, bubble-free sheets are shown in Figures 3A and 3B, respectively; it should be noted that in Table 1, the proportions of plasticizer and Fiberlean are reported on a dry mass basis (i.e., excluding water), while the "solid proportion" is the mass of all non-aqueous components of the initial slurry relative to the entire initial slurry (i.e., including water). Table 1 Urea ( dry wt% ) Glycerol ( dry wt% ) Fiberlean ( dry wt%) Solid content (wt%) 7.8 31.2 3.0 8.0 7.6 30.4 4.0 5.0 7.4 29.6 5.0 5.0 6.8 27.2 8.0 5.0

Example 3 Biomats of the filamentous fungus Scyphodium luteum strain grown on liquid growth medium were boiled to inactivate the fungus and rinsed with water to remove any residual growth medium. These biomats were then placed in a standard kitchen blender and reduced in size and blended with water until a homogenous aqueous slurry was obtained. 0.1 wt% sodium benzoate was added to the slurry as a preservative.

To each of these slurries was added (a) sulfuric acid, (b) glycerol and urea as plasticizers, (c) Fiberlean cellulose fibers as a reinforcing material, (d) iron (III) oxide ( _Fe2O3 ) as a pigment, and (e) kappa- _carrageenan as a gelling agent. In some cases, additional water was added to obtain a desired total solids content of 5 to 6 wt%. Epoxidized soybean oil was also added to some of the slurries and mixed until a uniform emulsion was formed; this demonstrates that the slurries according to the present invention are capable of uniformly and uniformly incorporating and distributing hydrophobic materials. Each slurry contained 18.0 wt% κ-carrageenan, 0.5 wt% sulfuric acid, and 1.0 wt% iron (III) oxide on a dry weight basis (ie, excluding water).

Each slurry is heated in a pot with continuous stirring until a smooth, free-flowing mixture is obtained. This free-flowing mixture is then placed in a vacuum chamber for a short period of time to degas (i.e., to remove air). After degassing, each mixture is cast into a preheated mold, and the mold is then agitated to ensure uniform casting and to remove any surface bubbles. The mold is then allowed to cool to room temperature under ambient conditions.

After cooling, a monolithic gel was obtained from each mold. These gels were transferred to a dehydrator and dried at 40° C. for 24 hours. The resulting material was then stretched, clamped to a solid substrate, and placed in an oven at 60° C. for another 24 hours, after which each material was in the form of a smooth, bubble-free sheet. The composition of each slurry is given in Table 2, and the tensile strength and elongation at break of the obtained smooth, air-free sheets are shown in Figures 4A and 4B, respectively; it should be noted that in Table 2, the amounts of biomass, plasticizer, epoxidized soybean oil, and Fiberlean are reported on a dry mass basis (i.e., excluding water), while the "solids content" is the mass of all non-aqueous components of the initial slurry relative to the entire initial slurry (i.e., including water). Table 2 Urea ( dry wt%) Glycerol ( dry wt%) Biomass ( dry wt%) Epoxidized soybean oil ( dry wt%) Fiberlean ( dry wt%) Solid content (wt%) 7.0 28.0 37.5 5.0 3.0 6.0 6.0 24.0 37.5 10.0 3.0 6.0 7.0 28.0 35.5 5.0 5.0 5.0 6.0 24.0 35.5 10.0 5.0 5.0 6.0 24.0 47.5 0.0 3.0 6.0 6.0 24.0 45.5 0.0 5.0 5.0

Example 4 Biopads of the filamentous fungus Scyphodium luteum strain grown on liquid growth medium were boiled to inactivate the fungus and rinsed with water to remove any residual growth medium. These biopads were then placed in a standard kitchen blender and reduced in size and blended with water until a homogenous aqueous slurry was obtained. 0.1 wt% sodium benzoate was added to the slurry as a preservative.

To this slurry, kappa-carrageenan, Thermolec 57 lecithin, beeswax, sodium hydroxide, and potassium chloride were added. The slurry contained 43.4 wt% fungal biomass, 15.0 wt% kappa-carrageenan, 0.5 wt% Thermolec 57, 38.3 wt% beeswax, 1.9 wt% sodium hydroxide, and 0.9 wt% potassium chloride on a dry weight basis (i.e., excluding water), and had a total solids content of 13.0 wt% slurry.

Heat the slurry in a pan with continuous stirring until a smooth, free-flowing mixture is obtained. This free-flowing mixture is then cast into a pre-heated mould and the mould is subsequently stirred to ensure uniform casting and to remove any surface bubbles. The mould is then allowed to cool to room temperature at ambient conditions.

After cooling, a monolithic gel was obtained from the mold. This gel was transferred to a dehydrator and dried at 38°C for 24 hours. The resulting material was clamped to a solid substrate and dried at 60°C for another 6 hours, then cut into two parts; one sample was heated to 130°C for 3 hours, and the other sample was heated to 150°C for 3 hours. Two samples of the finished material were then weighed, immersed in water for 1 hour, and weighed again to determine their water absorption. Both samples showed strong water absorption; the sample heated to 130°C had a water absorption of 1.60%, and the sample heated to 150°C had a water absorption of 1.58%.

Example 5 Biomats of the filamentous fungus Scyphodium luteum strain grown on liquid growth medium were boiled to inactivate the fungus and rinsed with water to remove any residual growth medium. These biomats were then placed in a standard kitchen blender and reduced in size and blended with water until a homogenous aqueous slurry was obtained. 0.1 wt% sodium benzoate was added to the slurry as a preservative.

To this slurry, glycerol, urea, iota-carrageenan, potassium chloride, Fiberlean cellulose fibers, and cedar oil were added. The slurry contained 38.7 wt% fungal biomass, 27.2 wt% glycerol, 6.8 wt% urea, 18.0 wt% iota-carrageenan, 1.1 wt% potassium chloride, 8.0 wt% Fiberlean, and 0.2 wt% cedar oil on a dry weight basis (i.e., excluding water), and had a total solids content of 2.0 wt% slurry.

The slurry was mixed and heated until a free-flowing, relatively non-viscous fluid was obtained, and this fluid was cast into a glass pan; after cooling to room temperature under ambient conditions, the fluid was qualitatively observed to be slightly more viscous but still free-flowing. The glass pan was then heated to 90°C for 24 hours to dry. As shown in Figure 5, the thick solution did not dry into a continuous film, which may be because iota-carrageenan did not gel.

Example 6 Biomats of the filamentous fungus Scyphodium luteum strain grown on liquid growth medium were boiled to inactivate the fungus and rinsed with water to remove any residual growth medium. These biomats were then placed in a standard kitchen blender and reduced in size and blended with water until a homogenous aqueous slurry was obtained. 0.1 wt% sodium benzoate was added to the slurry as a preservative.

To each of these slurries was added (a) potassium chloride, (b) glycerol and urea as plasticizers, (c) Fiberlean cellulose fibers as reinforcing material, (d) iron (III) oxide (Fe ₂ O ₃ ) as pigment, and (e) κ-carrageenan as gelling agent. In some cases, additional water was added to obtain a desired total solids content of 5 to 8 wt %. Each slurry contained 36.9 wt % fungal biomass, 18.0 wt % κ-carrageenan, 1.1 wt % potassium chloride, and 2.0 wt % iron (III) oxide on a dry weight basis (i.e., excluding water); the amounts of plasticizer and cellulose varied relative to each other, but in all cases totaled 42 wt % of the dry components.

Each slurry is fed into the feed zone of the extruder. The temperature and screw speed of the extruder are set to ensure proper mixing of the materials in the extruder barrel. In some cases, multiple feed ports are used to adjust the relative loading of the components during the extrusion process. A vacuum port may also be used after the mixing section of the screw to remove air bubbles before the material leaves the extruder.

After mixing and degassing, the material leaves the temperature-controlled die at the end of the extruder in the form of flakes and gel. The resulting monolithic gel is collected, transferred to a dehydrator, and dried at 40°C for 24 hours. The resulting material is then stretched, clamped to a solid substrate, and placed in an oven at 60°C for another 24 hours, after which each material is in the form of a smooth, bubble-free flake. The composition of each slurry is given in Table 3; it should be noted that in Table 3, the portions of plasticizer and Fiberlean are reported on a dry mass basis (i.e., excluding water), while the "solid portion" is the mass of all non-aqueous components of the initial slurry relative to the entire initial slurry (i.e., including water). Table 3 Urea ( dry wt%) Glycerol ( dry wt%) Fiberlean ( dry wt%) Solid content (wt%) 7.8 31.2 3.0 8.0 7.6 30.4 4.0 5.0 7.4 29.6 5.0 5.0 6.8 27.2 8.0 5.0

Example 7 Biopads of the filamentous fungus Scyphodium luteum strain grown on liquid growth medium were boiled to inactivate the fungus. These biopads were then blended in deionized water in a standard kitchen blender until a flowable and substantially homogeneous mixture was produced.

Glycerin, additional deionized water, microfibrillated cellulose, and acyl gellan gum were added to the mixture; the total solids content of the mixture was 5 wt%, and on a dry solids basis, the mixture consisted of about 36 wt% fungal biomass, about 36 wt% glycerin, about 20 wt% acyl gellan gum, and about 8 wt% microfibrillated cellulose. The mixture was blended in a standard kitchen blender until it appeared to form a viscous and substantially homogeneous slurry. The slurry was then poured into a stainless steel container and stirred while heated by an induction heating plate until a free-flowing mixture was formed; the free-flowing mixture was then poured into a heated pan and allowed to cool at room temperature for about 30 minutes, during which time gelling of the mixture occurred to form a hydrogel.

After cooling to room temperature, the hydrogel was removed from the pan and dried in a drying oven at an elevated temperature of about 70°C on a non-stick PTFE sheet. After 8 hours at this elevated temperature, the dried gel was removed and its tensile properties were evaluated according to ISO 3376. The tensile modulus of the dried gel was found to be 84.77 ± 10.72 MPa, the tensile strength was 9.80 ± 1.51 MPa and the elongation at break was 27.90% ± 3.97%.

Example 8 A substantially homogeneous aqueous slurry having a total solids content of 8 wt% (i.e., 92 wt% water) and consisting, by dry weight, of 34.4 wt% fungal (Yellowstone sickle fungus strain) biomass, 30.0 wt% glycerol, 7.6 wt% urea, 18.0 wt% κ-carrageenan, 1.0 wt% potassium chloride, 8.0 wt% microfibrillated cellulose, and 1.0 wt% magnetite pigment was prepared by mixing all components in a standard kitchen blender and transferring the contents to an induction cooker. The mixture was then heated on an induction burner until its temperature exceeded 60°C, at which point it became free-flowing. The mixture was then degassed in a vacuum chamber for 2.5 minutes.

Separately, three different types of woven substrates, unbleached 90 mesh cotton gauze, unbleached plain muslin, and food grade polyester mesh with a pore size of 400 μm were soaked in deionized water, placed in an 18''×24'' (45.7 cm×61.0 cm) aluminum baking pan, stretched tight and clamped to the edge of the pan using binder clips; the pan was preheated on a heating pad to maintain a surface temperature above 40°C. Optical microscopy images of the gauze substrate are shown in Figures 6A and 6B, optical microscopy images of the plain muslin substrate are shown in Figures 6C and 6D, and optical microscopy images of the polyester substrate are shown in Figure 6E.

The fungal slurry was cast in aluminum pans on woven backings, and the pans were shaken on a shaker table to evenly distribute the slurry inside the pans. The pans were then cooled to room temperature so that the slurry formed a hard hydrogel that could be manually removed from the pans. The hydrogel/backing composite was transferred to a drying rack, and the composite was dried in an oven at 45°C for 8 hours, followed by drying at 70°C for another 8 hours. Control samples containing only cast fungal slurry without a woven backing were prepared by a similar procedure. All samples were then baked at 100°C for 1 hour and placed in an environmental chamber under controlled environmental conditions of 25°C and 50% relative humidity for 24 hours.

The tear strength of the four materials was tested using a single-sided tear test in an Instron machine by cutting 4.5 cm x 7 cm samples of each material and making a slit in the middle of each sample to leave exactly 2 cm intact. The tear strength was evaluated as the average peak force in five tests and normalized to the thickness of the test sample. The adhesion of the fungal gel to the backing material was also evaluated using a T-peel test with a sample strip 6 inches (15.2 cm) long and 1 inch (2.5 cm) wide. The data are summarized in Table 4 below; as shown in Table 4, the tear strength of the finished material was increased by more than an order of magnitude by casting the fungal slurry directly onto the backing material. Table 4 Lining material Average adhesion (N) Adhesion failure mode Thickness of mycelium composite (mm) Average tear strength of mycelium composite (N) Thickness of lining (mm) Average tear strength of lining (N) without - - 0.53 1.7 - - 90 mesh cotton (500 pore size) 7.2 Cohesion 0.795 21.7 0.20 21.3 Plain woven cloth (175 micron pore size) 2.9 Adhesion 0.831 11.1 0.33 11.2 300 micron nylon mesh 1.7 Adhesion 0.978 44.1 0.27 98.5

Example 9 Several substantially homogeneous aqueous slurries having a total solids content of 5-10 wt% and whose dry ingredients consisted of 32.0 wt% glycerol, 3.6 wt% urea, 2.0 wt% pigment and varying amounts of fungal (Yellowstone sickle fungus strain) biomass, kappa-carrageenan and potassium chloride were prepared by mixing all components in a standard kitchen blender and transferring the contents to an induction cooker; in all cases, kappa-carrageenan and potassium chloride were provided in a 20:1 weight ratio. The slurries were then heated on an induction burner until the temperature exceeded 60°C, at which point the slurries became free-flowing. These slurries were then cast into a Pyrex pan preheated to 90°C, which was shaken on a shaker table to evenly distribute the slurry in the pan. The pan was then cooled to room temperature so that the slurry formed a hard hydrogel that could be manually removed from the pan. The hydrogel material was transferred to a drying rack and the composite was dried in an oven at 50°C for 12 hours, then at 70°C for 5 hours, and then at 100°C for 1 hour. Five samples were cut from each material for tensile testing, the average results of which are summarized in Table 5 below and are illustrated in Figure 7A (tensile strength) and Figure 7B (tensile modulus). As shown in Table 5, as the content of gelling agent (in this case, κ-carrageenan) increases, the tensile modulus and tensile strength also increase, with a six-fold increase in strength achieved by increasing the gelling agent/fungal biomass ratio from 1:17.35 (3.4 wt% gelling agent) to 1:1.03 (30.0 wt% gelling agent). Table 5 κ -Carrageenan ( dry wt%) Tensile modulus (MPa) Elongation at break (%) Tensile strength (MPa) 3.4 19.29 ± 5.34 26.53 ± 1.60 2.66 ± 0.41 6.0 30.36 ± 5.50 28.96 ± 4.37 4.24 ± 0.19 10.0 40.63 ± 19.03 34.68 ± 4.42 5.68 ± 1.24 15.0 69.57 ± 17.13 34.58 ± 5.40 7.77 ± 0.51 20.0 63.63 ± 11.88 34.65 ± 2.11 11.39 ± 0.71 25.0 96.99 ± 25.68 32.31 ± 2.27 13.80 ± 0.46 30.0 277.70 ± 80.38 24.39 ± 4.13 16.08 ± 1.70

Example 10 Two substantially homogeneous aqueous slurries having a total solids content of 8 wt % were prepared by mixing all components in a standard kitchen blender and transferring the contents to an induction cooker, wherein the dry components of the first slurry consisted of 31.0 wt % fungal (Yellowstone sickle fungus strain) biomass, 30.0 wt % glycerol, 10.0 wt % urea, 18.0 wt % κ-carrageenan, 6.0 wt % microfibrillated cellulose, 2.0 wt % cationic lipid liquid (Catalix LX) and 3.0 wt % Epoxol 9-5, and the dry components of the second slurry consisted of 34.4 wt % fungal (Yellowstone sickle fungus strain) biomass, 30.0 wt % glycerol, 7.6 wt % urea, 18.0 wt % κ-carrageenan, 1.0 wt% potassium chloride, 8.0 wt% microfibrillated cellulose and 1.0 wt% magnetite pigment. The slurries were then heated on an induction burner until the temperature exceeded 60°C, at which point the slurries became free-flowing; during the heating period, the first slurry was intermittently mixed with a hand-held homogenizer to incorporate air, which was stabilized by a lipid liquid to form a stable air-in-water foam. Both slurries (the "foaming" and "non-foaming" slurries) were cast into aluminum pans preheated to 90°C and allowed to cool to room temperature over a period of 15 minutes so that the slurries formed a hard hydrogel that could be manually removed from the pan. These hydrogels were transferred to a drying oven and dried at 70°C for 24 hours. The dry material produced by the foamed slurry was a flexible, closed-cell solid foam with an average density of 0.243 ± 0.010 g/ ^cm3 , while the dry material produced by the non-foamed slurry had a mass density of about 1.289 g/ ^cm3 . Cross-sectional micrographs of the dry materials produced by the foamed and non-foamed slurries are shown in Figures 8A and 8B, respectively.

Example 11 Two substantially homogeneous aqueous slurries, "Slurry A" and "Slurry B", having a total solid content of 8 wt% were prepared and formed into a dry gel by mixing all components in a Vitamix blender, transferring to a pot and heating the solution to 65°C, transferring the pot to a vacuum chamber and subjecting the mixture to vacuum for 150 seconds, and pouring the contents into a Pyrex dish. The mixture gelled as it cooled to room temperature. After gelling, the material was dried in a dehydrator oven at 70°C for 24 hours. The two slurries contained 18.0 wt% κ-carrageenan, 1.0 wt% potassium chloride and 8.0 wt% microfibrillated cellulose by dry weight, but differed in the plasticizer used; slurry A contained 35.4 wt% fungal (Yellowstone sickle fungus strain) biomass, 30.0 wt% glycerol and 7.6 wt% urea by dry weight, while slurry B contained 33.0 wt% fungal (Yellowstone sickle fungus strain) biomass and 40.0 wt% deep eutectic solvent (DES), where DES was a 3:2 molar mixture of urea and trimethylglycine. The dried sheet prepared from slurry A was measured to have a tensile modulus of 68.10 ± 1.42 MPa, a tensile strain at break of 34.71% ± 1.49%, and a tensile strength of 11.44 ± 0.20 MPa, while the dried sheet prepared from slurry B was measured to have a tensile modulus of 102.76 ± 12.12 MPa, a tensile strain at break of 48.10% ± 1.76%, and a tensile strength of 11.97 ± 1.73 MPa.

Example 12 Biopads of the filamentous fungus Scyphodium luteum strain grown on liquid growth medium were boiled to inactivate the fungus. These biopads were then blended in deionized water in a standard kitchen blender until a flowable and substantially homogeneous mixture was produced.

Three mixtures were produced by adding glycerol, urea, additional deionized water, microfibrillated cellulose, potassium chloride, and kappa-carrageenan to fungal biomass and deionized water; the total solid content of each mixture was 7 wt%. Each mixture was blended in a standard kitchen blender until it appeared to form a viscous and substantially homogeneous slurry. This slurry was then poured into a stainless steel container and stirred while being heated by an induction heating plate until a free-flowing mixture was formed; during the heating and stirring period, an aqueous solution of polyamide-epichlorohydrin (PAE) resin was added to two of the three slurries and allowed to mix for 1 minute. On a dry weight basis, each of the three slurries contained 30.0 wt% glycerol, 7.6 wt% urea, 18.0 wt% κ-carrageenan, 1.0 wt% potassium chloride, and 8.0 wt% microfibrillated cellulose; the remainder of the dry components in each slurry (35.4 wt%) consisted of fungal biomass and PAE resin. Each slurry was then briefly degassed using a vacuum pump, then poured into a preheated pan and allowed to cool at room temperature for 15 minutes, during which time gelation of the slurry was performed to form a hydrogel.

After cooling to room temperature, the hydrogel was removed from the pan and dried in a drying oven at approximately 40°C for 16 hours on a non-stick PTFE sheet, followed by drying at 71°C for approximately 5 hours, and then drying at 100°C for 1 hour. Samples were cut from each sheet and immersed in water for 1 hour to assess the extent of swelling. The results are given in Table 6. Table 6 PAE resin ( dry wt%) Water mass absorption (%) 0 215 3 84 5 61

Example 13 Yellowstone sickle fungus strain biomass was prepared by immersion (stirred tank) fermentation. After the fungus fermentation, steam was injected into the stirred tank fermentation tank until a temperature of about 80°C was reached in the fermentation tank to inactivate the fungus. The inactivated biomass was then washed with deionized water and collected as a wet mixture with a solid content of about 25 wt%. This wet mixture was then spray dried to a solid content of about 98 wt%. The particle size distribution of this spray-dried biomass was determined by sequential screening and is shown in Table 7 below. Table 7 Particle size range (μm) Particles in range % ＞ 500 0.00 250-500 0.14 150-250 0.28 75-150 52.41 53-75 11.95 25-53 29.19 ＜ 25 6.03

Separately, biomass of the S. lutea strain was produced as a whole biomat by liquid surface fermentation, inactivated by boiling, and blended with water in a conventional kitchen blender to produce a slurry with a fungal solids content of 7.7 wt%.

Each of the two fungal biomasses (submerged fermentation, spray dried biomass and surface fermentation slurry) was mixed with water and other components in a conventional kitchen blender to obtain a substantially homogeneous aqueous slurry having a total solid content of 7 wt% and consisting of 35.4 wt% fungal biomass, 30.0 wt% glycerol, 7.6 wt% urea, 18.0 wt% kappa-carrageenan, 1.0 wt% potassium chloride and 8.0 wt% microfibrillated cellulose on a dry weight basis. These mixtures were heated in a pot on an induction burner until their temperature exceeded 60°C, at which point they became substantially free-flowing. Each mixture was then degassed in a vacuum chamber for 3 minutes and cast into a preheated pan; the pan was agitated to ensure uniformity and homogeneity of the cast mixture and to remove any surface bubbles. The pan was allowed to cool to room temperature at ambient conditions, whereupon each mixture formed an elastic hydrogel. These hydrogels were removed from the pan and dried in a drying oven at about 40°C on a non-stick PTFE sheet for 18 hours, followed by drying at 100°C for 1 hour, followed by cooling at ambient conditions for 1 hour.

The tensile properties of each dried biocomposite were then evaluated according to ISO 3376. The biocomposite containing the surface fermentation-derived biomass was found to have a tensile modulus of 681.6 ± 1.4 MPa, a tensile strength of 11.4 ± 0.2 MPa, and an elongation at break of 34.7% ± 1.5%, while the biocomposite containing the submerged fermentation-derived biomass was found to have a tensile modulus of 44.5 ± 5.4 MPa, a tensile strength of 8.1 ± 0.6 MPa, and an elongation at break of 51.8% ± 2.3%. Thus, this example demonstrates that submerged fermentation and/or spray drying/screening procedures can allow for the tuning of a wide range of mechanical properties and surface textures of fungal biocomposites by controlling the composition and size of the fungal hyphae particles.

Example 14 A portion of a coconut shell fiber brick was cut and manually washed with deionized water; the resulting coconut shell fiber slurry was manually pressed in a 400 μm nylon mesh to remove water until a solid content of 12 wt % was obtained (measured by thermogravimetric analysis). This washed coconut shell fiber material was mixed with water and other components in a conventional kitchen blender to form a substantially homogeneous aqueous slurry having a total solid content of 7 wt % and consisting of 43.4 wt % coconut shell fiber, 30.0 wt % glycerol, 7.6 wt % urea and 18.0 wt % kappa-carrageenan on a dry weight basis. This mixture is transferred to a pot and heated on an induction burner until its temperature exceeds 60°C, at which point it becomes substantially free-flowing. The mixture is then degassed in a vacuum chamber for 2.5 minutes and cast into a preheated Pyrex pan; the pan is agitated to ensure uniformity and homogeneity of the cast mixture and to remove any surface bubbles. The pan is allowed to cool to room temperature under ambient conditions, whereupon each mixture forms an elastic hydrogel. This hydrogel is removed from the pan and allowed to dry on a non-stick PTFE sheet in a drying oven at 70°C for 24 hours, followed by baking at 100°C for 1 hour, followed by equilibration for 24 hours in an ambient room at a temperature of 30°C and a relative humidity of 50%.

The tensile properties of the dried biocomposites were then evaluated according to ISO 3376. The biocomposite containing coconut coir fibers was found to have a tensile modulus of 629.9 MPa, a tensile strength of 14.1 MPa, and an elongation at break of 12.7%.

Example 15 A substantially homogeneous aqueous biomass slurry was prepared by blending an inactivated surface fermentation-derived Scyphoblastoma styracifluum strain, nanofibrillated cellulose, and shredded coconut coir fiber with water and other components in a known kitchen blender. The resulting mixture had a total solids content of 8 wt% and consisted of 26.6 wt% fungal biomass, 30.0 wt% glycerol, 7.6 wt% urea, 15.0 wt% kappa-carrageenan, 0.8 wt% potassium chloride, 12.0 wt% coconut coir fiber, and 8.0 wt% nanofibrillated cellulose on a dry weight basis. This mixture was transferred to a pot and heated on an induction burner until its temperature exceeded 60°C, at which point it became substantially free-flowing. The mixture was then degassed in a vacuum chamber for 2.5 minutes and cast into a preheated Pyrex pan; the pan was agitated to ensure uniformity and homogeneity of the cast mixture and to remove any surface bubbles. The pan was allowed to cool to room temperature under ambient conditions, whereupon each mixture formed an elastic hydrogel. This hydrogel was removed from the pan and allowed to dry on a non-stick PTFE sheet in a drying oven at 70°C for 24 hours, followed by baking at 100°C for 1 hour, followed by equilibration in an ambient room at 30°C and 50% relative humidity for 24 hours.

The tensile properties of the dried biocomposites were then evaluated according to ISO 3376. The biocomposite containing fungal biomass/cellulose/coconut husk fiber was found to have a tensile modulus of 68.2 MPa, a tensile strength of 6.1 MPa, and an elongation at break of 34.3%.

Example 16 A substantially homogeneous aqueous slurry was prepared by blending recycled copy paper with water and other components in a known kitchen blender. The resulting mixture had a total solids content of 7 wt% and consisted of 44.4 wt% recycled copy paper, 30.0 wt% glycerol, 7.6 wt% urea, and 18.0 wt% kappa-carrageenan on a dry weight basis. This mixture was transferred to a pot and heated on an induction burner until its temperature exceeded 60°C, at which point it became substantially free-flowing. The mixture was then degassed in a vacuum chamber for 3 minutes and cast onto a preheated Pyrex pan; the pan was agitated to ensure uniformity and homogeneity of the cast mixture and to remove any surface bubbles. The pan was allowed to cool to room temperature at ambient conditions, whereupon each mixture formed an elastic hydrogel. This hydrogel was removed from the pan and dried on a non-stick PTFE sheet in a drying oven at about 40°C for 18 hours, followed by baking at 100°C for 1 hour, followed by cooling to room temperature at ambient conditions for 1 hour.

The tensile properties of the dried biocomposites were then evaluated according to ISO 3376. The biocomposite containing recycled paper was found to have a tensile modulus of 57.6 ± 16.9 MPa, a tensile strength of 9.13 ± 0.8 MPa, and an elongation at break of 30.7% ± 2.1. The tear strength of the biocomposite containing dried recycled paper was also evaluated using a single-edge tear test in an Instron instrument with a tear length of 2 cm; the tear strength, defined as the average peak force in five tests, was found to be 5.99 ± 0.18 N/mm.

The concepts illustratively disclosed herein can be suitably practiced in the absence of any element not specifically disclosed herein. However, it is obvious to those skilled in the art that many changes, variations, modifications, other uses and applications of the invention are possible, and the invention is deemed to cover changes, variations, modifications, other uses and applications that do not depart from the spirit and scope of the invention.

The foregoing discussion has been presented for purposes of illustration and description. The foregoing is not intended to limit the invention to one or more forms disclosed herein. For example, in the foregoing embodiments, various features are grouped together in one or more embodiments for the purpose of streamlining the invention. Features of the embodiments may be combined in alternative embodiments other than the embodiments discussed above. This approach to the invention should not be interpreted as reflecting an intent to claim more features than are expressly described in each technical solution. In fact, as reflected in the following claims, aspects of the invention lie in less than all of the features of a single previously disclosed embodiment. Therefore, the following claims are hereby incorporated into this embodiment, with each technical solution acting on its own as a separate embodiment.

In addition, although the present invention has included a description of one or more embodiments and certain variations and modifications, other variations, combinations and modifications are within the scope of the present invention, such as those within the skill and knowledge of those skilled in the art after understanding the present invention. It is contemplated that the right to alternative embodiments, including alternative, interchangeable and/or equivalent structures, functions, ranges or steps of the claimed structures, functions, ranges or steps, whether or not such alternative, interchangeable and/or equivalent structures, functions, ranges or steps are disclosed herein, is not intended to exclusively disclose any patentable subject matter.

FIG. 1 shows a biocomposite comprising filamentous fungal biomass prepared by a gel casting method five minutes after casting according to an embodiment of the present invention. FIG. 2 shows a biocomposite comprising filamentous fungal biomass during a drying step of a gel casting method according to an embodiment of the present invention. FIG. 3A and FIG. 3B are graphs of tensile strength and elongation at break of a cellulose fiber loaded gel cast sheet according to an embodiment of the present invention, respectively. FIG. 4A and FIG. 4B are graphs of tensile strength and elongation at break of a gel cast sheet containing epoxidized soybean oil, respectively, according to an embodiment of the present invention. FIG. 5 is a diagram of a cracked, poorly cohesive gel casting sheet containing iota-carrageenan according to an embodiment of the present invention. FIG. 6A and FIG. 6B are optical microscopic images of a cotton gauze backing according to an embodiment of the present invention. FIG. 6C and FIG. 6D are optical microscopic images of a plain woven gauze backing according to an embodiment of the present invention. FIG. 6E is an optical microscopic image of a nylon backing according to an embodiment of the present invention. FIG. 7A and FIG. 7B are graphs showing the relationship between tensile strength (FIG. 7A) or tensile modulus (FIG. 7B) and the fungal biomass/gelling agent mass ratio according to an embodiment of the present invention. FIG. 8A and FIG. 8B are diagrams of foamed and non-foamed gel casting sheets according to an embodiment of the present invention, respectively.

Claims (131)

A method for producing a biocomposite material comprising: (a) depositing a fluid mixture comprising a carrier fluid, a biomass, and a gelling agent into a desired spatial configuration, wherein the biomass comprises a portion that is at most slightly soluble in the carrier fluid; (b) triggering gelation of the fluid mixture to form a biomass gel; and (c) removing at least a portion of the carrier fluid from the biomass gel to form the biocomposite material, wherein the carrier fluid comprises no more than about 95 wt%, no more than about 80 wt%, no more than about 65 wt%, or no more than about 50 wt% of the biocomposite material. The method of claim 1, further comprising: depositing a second fluid mixture comprising a second carrier fluid, a second biomass, and a second gelling agent into a second desired spatial configuration, wherein the second biomass comprises a portion that is at most slightly soluble in the second carrier fluid; triggering gelation of the second fluid mixture to form a second biomass gel; prior to step (c), layering the biomass gel and the second biomass gel in physical contact with each other; and removing at least a portion of the second carrier fluid from the second biomass gel, wherein the biocomposite comprises a first layer and a second layer that are adhered to each other. The method of claim 1 or claim 2, wherein the biomass comprises fermented biomass. The method of any one of claims 1 to 3, wherein the biomass comprises fungal mycelium. The method of any one of claims 1 to 4, wherein the biomass comprises microbial biomass. The method of claim 5, wherein the biomass comprises bacterial biomass. The method of any one of claims 1 to 6, wherein the biomass comprises plant biomass. The method of any one of claims 1 to 7, wherein the biomass comprises algal biomass. A method as in any one of claims 1 to 8, wherein the mass ratio of the biomass to the gelling agent in the fluid mixture is about 1:18 to about 18:1. The method of claim 9, wherein the mass ratio of the biomass to the gelling agent in the fluid mixture does not exceed about 10:3. A method as in any one of claims 1 to 10, wherein the fluid mixture further comprises a filler. The method of claim 11, wherein the filler is selected from the group consisting of microfibrillated cellulose, nanofibrillated cellulose, recycled fibers, recycled particles, polymerized fibers, polymerized particles, and combinations thereof. A method as claimed in any one of claims 1 to 12, wherein step (a) comprises casting the fluid mixture. A method as in any one of claims 1 to 13, wherein step (a) comprises extruding or spraying the fluid mixture into the first desired spatial configuration. The method of claim 14, further comprising: Depositing a second mixture having a different composition than the fluid mixture into a second desired spatial configuration, the second desired spatial configuration having a preselected spatial relationship with the first desired spatial configuration. The method of claim 14 or claim 15, wherein step (a) comprises extruding the fluid mixture onto a surface. A method as in any one of claims 1 to 16, wherein step (a) comprises casting or patterning the fluid mixture by printing. A method as claimed in any one of claims 1 to 17, wherein step (a) comprises forming fibers of the fluid mixture by solution spinning. The method of claim 18, wherein at least a portion of the carrier fluid gels during step (a). The method of claim 18 or claim 19, wherein at least a portion of the carrier fluid evaporates from the fluid mixture during step (a). The method of any one of claims 1 to 20, wherein the carrier fluid is selected from the group consisting of water, one or more alcohols, and combinations thereof. A method as in any one of claims 1 to 21, wherein the fluid mixture further comprises a dispersed or emulsified compound that is insoluble in the carrier fluid and is entrapped in the biomass gel during step (b). A method as in any one of claims 1 to 22, wherein in step (a), the fluid mixture is cast onto a substantially flat surface. A method as claimed in any one of claims 1 to 23, wherein in step (a), the fluid mixture is cast into or onto a cavity or a mould. A method as in any one of claims 1 to 24, wherein step (b) is performed by at least one of: lowering the temperature of the fluid mixture, increasing the temperature of the fluid mixture, changing the pH of the fluid mixture, adding metal ions to the fluid mixture, inducing polymerization of monomers in the fluid mixture, and exposing the fluid mixture to electromagnetic radiation of a selected wavelength. A method as in any one of claims 1 to 25, wherein step (b) is performed by removing at least a portion of the carrier fluid. A method as in any of claims 1 to 26, wherein the fluid mixture remains fluid for about five seconds to about twelve hours after step (a). A method as in any one of claims 1 to 27, wherein between step (a) and step (b), the fluid mixture self-levels. The method of any one of claims 1 to 28, further comprising mechanically agitating the fluid mixture between step (a) and step (b). The method of any one of claims 1 to 29, wherein the gelling agent comprises a polymer having a molecular weight of at least about 80,000 daltons. The method of claim 30, wherein the polymer is a polysaccharide, a polypeptide, a protein, a starch, a block copolymer, a polyelectrolyte or a plant gum. The method of claim 30, wherein the polymer is a hydrophilic colloid selected from the group consisting of iota-carrageenan, kappa-carrageenan, lambda-carrageenan, agar, starch, modified starch, galangal, guar gum, locust bean gum, gum arabic, acacia gum, gum karaya, tragacanth gum, alginate, pectin, methylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, and combinations thereof. The method of any one of claims 1 to 32, wherein the gelling agent comprises one or more monomers. The method of claim 33, wherein the gelling agent further comprises an initiator. The method of any one of claims 1 to 34, wherein the gelling agent comprises at least one of a colloid and a mutagenic agent. The method of any one of claims 1 to 35, wherein the gelling agent comprises an amphiphilic molecule. A method as in any of claims 1 to 36, wherein the fluid mixture further comprises at least one cation. The method of claim 37, wherein the at least one cation comprises an organic cation, a metal cation, or both. A method as in any one of claims 1 to 38, wherein the fluid mixture further comprises at least one plasticizer. The method of claim 39, wherein the at least one plasticizer is insoluble, nearly insoluble, very slightly soluble, or slightly soluble in the carrier fluid. The method of claim 39, wherein the at least one plasticizer is slightly soluble, soluble, readily soluble, or very readily soluble in the carrier fluid. The method of any one of claims 39 to 41, wherein the at least one plasticizer comprises about 10 wt % to about 85 wt % of the total solid content of the biocomposite. The method of any one of claims 1 to 42, wherein the fluid mixture further comprises one or more functionalizing compounds or crosslinking agents. The method of claim 43, wherein the one or more functionalizing compounds or crosslinking agents comprise at least one of the following: carboxylic acids, esters, anhydrides, epoxides, amidoamine epichlorohydrins, carbodiimides, peptides, oligopeptides, polypeptides, proteins, and enzymes. The method of claim 44, wherein the one or more functionalizing compounds or cross-linking agents comprise transglutaminase. The method of any one of claims 43 to 45, further comprising covalently functionalizing or cross-linking at least one of the biomass and the gelling agent during or after step (c). A method as in any one of claims 1 to 46, wherein the fluid mixture further comprises at least one non-gelling polymer. The method of claim 47, wherein the at least one non-gelling polymer is soluble in the carrier fluid. The method of claim 47 or claim 48, wherein the at least one non-gelling polymer comprises a polysaccharide. The method of claim 47 or claim 49, wherein the at least one non-gelling polymer is partially soluble or insoluble in the carrier fluid. The method of claim 50, wherein the at least one non-gelatinous polymer is selected from the group consisting of lignin, rubber, and combinations thereof. The method of claim 51, wherein the at least one non-gelatinous polymer comprises rubber and the rubber is natural latex rubber. The method of any one of claims 1 to 52, wherein step (c) is performed by freeze drying or critical point drying. The method of any one of claims 1 to 53, wherein the biomass gel is pinned during step (c). The method of claim 54, wherein the biomass gel is fixed by compression. The method of claim 54, wherein the biomass gel is fixed by uniaxial or biaxial tension. A method as claimed in any one of claims 1 to 56, wherein during step (c), the biomass gel is in contact with a release layer and the adhesion between the biomass gel and the release layer is strong enough to prevent the biomass gel from delaminating, and after step (c), the adhesion between the biocomposite material and the release layer is weak enough to allow the biocomposite material to be peeled off from the release layer. The method of claim 57, wherein the release layer comprises wax, polytetrafluoroethylene, polyethylene, polypropylene, polysilicone or a combination thereof. A method as claimed in any one of claims 1 to 58, wherein the biocomposite is subjected to uniaxial or biaxial stretching after step (c). The method of claim 59, wherein the biocomposite is heated while being uniaxially or biaxially stretched. The method of any one of claims 1 to 60, further comprising embossing the biomass gel. A method as claimed in claim 61, wherein the embossing step is performed simultaneously with step (c). The method of claim 61, wherein step (c) begins before the embossing step. A method as in any one of claims 1 to 63, further comprising introducing at least one gas into the fluid mixture prior to step (a). A method as claimed in claim 64, wherein after the introducing step, the fluid mixture is a foam. The method of claim 64 or claim 65, wherein the at least one gas is selected from the group consisting of air, carbon dioxide, nitrogen, and combinations thereof. The method of any one of claims 1 to 66, further comprising introducing a foaming agent into the fluid mixture. A method as claimed in claim 67, wherein the foaming agent is a surfactant and the method further comprises introducing at least one gas into the fluid mixture. The method of claim 68, wherein the at least one gas is selected from the group consisting of air, carbon dioxide, nitrogen, and combinations thereof. The method of claim 68 or claim 69, wherein the surfactant is introduced in an amount of about 0.1 wt % to about 4 wt % of the fluid mixture. The method of any one of claims 67 to 70, wherein the foaming agent is a blowing agent. The method of claim 71, wherein the foaming agent is selected from the group consisting of bicarbonate, compressed gas, hydride salt and combinations thereof. A method as in any one of claims 1 to 72, wherein step (c) is performed by heating the biomass gel, applying negative pressure to the biomass gel, radio frequency irradiating the biomass gel, microwave irradiating the biomass gel, or a combination thereof. The method of any one of claims 1 to 73, wherein the rate at which the carrier fluid is removed from the biomass gel during step (c) is controlled, optimized, selected or adjusted so that the biocomposite has a preselected porosity. A method as in any of claims 1 to 74, wherein step (a) comprises casting the fluid mixture onto a temperature controlled surface. A method as claimed in claim 75, further comprising controlling the spatial temperature gradient of the temperature-controlled surface. A method as claimed in claim 75 or claim 76, wherein during step (a), at least a portion of the temperature-controlled surface is cooled to a temperature below the freezing point of the carrier fluid. A method as in any of claims 75 to 77, wherein the fluid mixture further comprises a liquid additive and during step (a), at least a portion of the temperature-controlled surface is cooled to a temperature below the freezing point of the liquid additive so that the liquid additive freezes and forms a frozen additive. The method of claim 78, wherein the liquid additive is immiscible with the carrier fluid, insoluble, nearly insoluble, very slightly soluble, or slightly soluble in the carrier fluid. The method of claim 79, further comprising removing at least a portion of the cryogenic additive after step (a). The method of any one of claims 1 to 80, wherein step (a) comprises depositing the fluid mixture in physical contact with a backing material. The method of claim 81, wherein the backing material is a woven material. The method of claim 82, wherein the woven material comprises cotton. The method of claim 83, wherein the woven material is selected from the group consisting of cotton cheesecloth, muslin, and combinations thereof. The method of any of claims 82 to 84, wherein the woven material comprises resistant polyester. The method of any one of claims 82 to 85, wherein the woven material is a woven mesh. A method as claimed in claim 81, wherein the backing material is selected from the group consisting of foamed materials, non-woven fabrics, knitted fabrics and combinations thereof. A method as in any one of claims 81 to 87, wherein the backing material comprises a cellulose fabric. A biocomposite comprising: about 0.01 wt% to about 95 wt%, about 0.01 wt% to about 80 wt%, about 0.01 wt% to about 65 wt%, or about 0.01 wt% to about 50 wt% of a carrier fluid; biomass, wherein the biomass is at most slightly soluble in the carrier fluid; and at least one gelling agent, wherein the biocomposite has a tensile strength of at least about 3 MPa. The biocomposite material of claim 89 further comprises at least one additive selected from the group consisting of fillers, functionalized compounds, crosslinking agents, polymers, sizing agents, hydrophobic agents, plasticizers, pigments, dyes, antifoaming agents, defoaming agents, flocculants, deflocculating agents, antibacterial agents, antistatic agents, UV stabilizers, surface modifiers, foaming agents, foaming agents and flame retardants. The biocomposite material of claim 90, wherein the at least one additive comprises a functionalizing compound or a cross-linking agent, wherein the functionalizing agent or the cross-linking agent is a carboxylic acid, an ester, an anhydride or an epoxide. The biocomposite material of claim 90 or claim 91, wherein the at least one additive comprises a deep eutectic solvent. A biocomposite material as in any one of claims 90 to 92, wherein the at least one additive comprises a surface modifier selected from the group consisting of a texture modifier, a slip agent, an anti-slip agent, a matting agent, and a gloss agent. The biocomposite material of any one of claims 89 to 93, wherein the at least one gelling agent comprises a polymer, wherein the polymer comprises between about 1 wt % and about 90 wt % of the biocomposite material. The biocomposite material of claim 94, wherein the polymer is a polysaccharide, a polypeptide, a protein, a starch, a block copolymer, a polyelectrolyte or a plant gum. The biocomposite material of claim 94, wherein the polymer is a hydrophilic colloid selected from the group consisting of iota-carrageenan, kappa-carrageenan, lambda-carrageenan, agar, starch, modified starch, galangal, guar gum, locust bean gum, gum arabic, acacia gum, karaya gum, tragacanth gum, alginate, pectin, methylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, and combinations thereof. A biocomposite material as in any one of claims 94 to 96, wherein the at least one gelling agent further comprises at least one hydrophobic modifier covalently bonded to the polymer. The biocomposite of claim 97, wherein the at least one hydrophobic modifier is non-covalently bonded to the polymer. A biocomposite material as in claim 98, wherein the at least one hydrophobic modifier is bonded to the polymer via electrostatic interactions. A biocomposite material as in any one of claims 94 to 99, wherein the at least one gelling agent further comprises at least one cation complexed with the polymer. A biocomposite material as in claim 100, wherein the at least one cation comprises an organic cation, a metal cation, or both. A biocomposite material as in claim 100 or claim 101, wherein the at least one cation cross-links the first portion of the polymer with the second portion of the polymer and at least one of the polymeric components of the biomass. The biocomposite of any one of claims 94 to 102, wherein the polymer has a molecular weight of at least about 80,000 Daltons. A biocomposite material as in any one of claims 89 to 103, wherein the at least one gelling agent comprises one or more monomers. The biocomposite material of claim 104, wherein the at least one gelling agent further comprises an initiator. A biocomposite material as claimed in any one of claims 89 to 105, wherein the gelling agent comprises a colloid or a mutagenic agent. A biocomposite material as in any one of claims 89 to 106, wherein the gelling agent comprises an amphiphilic molecule. The biocomposite material of any one of claims 89 to 107, wherein the gelling agent is a peptide or an oligopeptide. The biocomposite material of any one of claims 89 to 108, further comprising at least one of a plasticizer, a filler and a crosslinking agent. The biocomposite of any one of claims 89 to 109, wherein the biocomposite comprises a plasticizer, wherein the plasticizer accounts for about 10 wt % to about 85 wt % of the total solid content of the biocomposite. A biocomposite material as in any one of claims 89 to 110, wherein the mass ratio of the gelling agent to the biomass is at least about 0.3. The biocomposite material of any one of claims 89 to 111, further comprising a backing material. The biocomposite material of claim 112, wherein the backing material comprises a woven material. A biocomposite material as claimed in claim 113, wherein the woven material comprises cotton. The biocomposite material of claim 114, wherein the woven material is selected from the group consisting of cotton gauze, plain woven cloth, and combinations thereof. A biocomposite material as in any one of claims 113 to 115, wherein the woven material comprises resistant polyester. A biocomposite material as in any one of claims 113 to 116, wherein the woven material is a woven mesh. A biocomposite material as in any one of claims 112 to 117, wherein the backing material comprises a nonwoven fabric, a knitted fabric, or both. A biocomposite material as in any one of claims 112 to 118, wherein the backing material comprises a cellulose fabric. A biocomposite gel comprising: a carrier fluid; biomass, wherein the biomass is at most slightly soluble in the carrier fluid; and at least one gelling agent. The biocomposite gel of claim 120, further comprising a first polymer network and a second polymer network, wherein the first polymer network comprises a gelling polymer. The biocomposite gel of claim 121, wherein the first polymer network and the second polymer network interpenetrate each other. The biocomposite gel of claim 121 or claim 122, wherein the second polymer network comprises a gelling polymer. A biocomposite gel as in any one of claims 121 to 123, wherein the second polymer network comprises a non-gelling polymer. A biocomposite gel as claimed in any one of claims 120 to 124, wherein the mass ratio of the gelling agent to the biomass is at least about 0.3. The biocomposite gel of any one of claims 120 to 125, further comprising a backing material. The biocomposite gel of claim 126, wherein the backing material comprises a woven material. The biocomposite gel of claim 127, wherein the woven material comprises cotton. The biocomposite gel of claim 128, wherein the woven material is selected from the group consisting of cotton gauze, plain woven cloth, and combinations thereof. The biocomposite gel of claim 127, wherein the woven material comprises resistant polyester. A biocomposite gel as claimed in any one of claims 127 to 130, wherein the woven material is a woven mesh.