Sustainable textiles and materials derived from agricultural waste nutshells and methods of making the same

Abstract

In one aspect, the disclosure relates to biodegradable fibers, cellulose pulp, cellulose nanofibers (CNFs), cellulose nanocrystals (CNCs), and lignin products comprising lignocellulosic materials extracted from nutshells or nut hulls, including pecan, peanut, cashew, walnut, hazelnut, pistachio, almond shells or hulls, or any combination thereof. In some aspects, the fibers can also include nanocellulose hydrogels, including those produced from low-value waste streams from agriculture or paper production or from nutshell-derived cellulose. In some aspects, the biodegradable fibers, cellulose pulp, CNFs, CNCs, and lignin products can be antimicrobial, biocompatible, compostable, or any combination thereof. Also disclosed herein are methods of making the biodegradable fibers, cellulose pulp, CNFs, CNCs, and lignin products, as well as yarns and textiles, including any of these materials. In some aspects, the fibers, yarns, and / or textiles can further include polylactic acid (PLA), polyhydroxyalkanoate (PHA), and / or polycaprolactone (PCL).

Description

ATTORNEY DOCKET NO. 220214-2010SUSTAINABLE TEXTILES AND MATERIALS DERIVED FROM AGRICULTURAL WASTE NUTSHELLS AND METHODS OF MAKING THE SAMECROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Ser. No. 63 / 681 ,876, filed August 12, 2024, which is incorporated herein by reference in its entirety.FIELD OF THE INVENTION

[0002] The present invention relates to the field of bio-based and biodegradable materials, including fibers, yarns, pulps, nanocellulose, and lignin derivatives, derived from a variety of agricultural wastes, particularly nutshells such as almond, walnut, pecan, pistachio, cashew, peanut, and hazelnut shells, and other nutshells and / or nut hulls as well as mixtures thereof. It more specifically relates to compositions comprising cellulose and lignin extracted from nutshells, and micro- and nano-scale fibers, and to methods of making them for use in textiles, yarns, fabrics, composites, coatings, packaging, and functional biomaterials. The fibers may be used to produce filament yarns, staple yarns, or non-yarn fibers, and may be further converted into nonwoven, woven, or knitted fabrics, as well as composite materials, laminates, or molded structures. In some embodiments, nanocellulose such as cellulose nanofibers (CNFs) or cellulose nanocrystals (CNCs), derived from nutshells or other renewable biomass sources, may be integrated into the fiber matrix to improve tensile strength, stiffness, barrier properties, and thermal stability, enabling the development of high-performance yarns and textiles suitable for technical, protective, or industrial applications.BACKGROUND

[0003] The fashion and textile industries are some of the largest contributors to environmental pollution, particularly due to the widespread use of synthetic fibers, including polyester, nylon, and acrylic, which constitute approximately 62% of global textile production. These materials are non- biodegradable and can persist in the environment for centuries, contributing to the growing problems of landfill waste as well as microplastic pollution. Many nonwoven textiles may contain harmful additives and finishes, including per- and polyfluoroalkyl substances (PFAS), organophosphorus esters (OPEs), and phthalate esters (PAEs), which may aid in processing but are increasingly associated with health risks. The fast fashion industry exacerbates this issue by promoting the rapid production and disposal of textile goods, leading to significant environmental degradation. In parallel, agricultural sectors, particularly nut farming, generate substantialATTORNEY DOCKET NO. 220214-2010 quantities of nutshell waste, such as almond, walnut, pecan, peanut, pistachio, hazelnut, and cashew shells, that are often discarded, burned, or composted due to limited commercial reuse. These lignocellulosic residues represent an untapped resource for circular bioeconomy solutions. In response, the present invention provides sustainable alternatives by utilizing agricultural waste, specifically nutshells individually or in combination, to produce high-purity cellulose, lignin, and nanocellulose, including cellulose nanofibrils (CNF) and cellulose nanocrystals (CNC). The composition of different nutshells offers varied lignin and cellulose ratios that, when blended, enable tunable properties for targeted applications. These bio-derived materials can be spun into biodegradable fibers and yarns, including filament and staple forms, for woven, knit, and nonwoven textiles, or incorporated into composites, packaging, molded products, barrier coatings, cosmetic formulations, rheology modifiers, and bioplastics. By avoiding petroleumbased inputs and toxic chemical treatments, the disclosed materials offer PFAS-free, high- performance alternatives with potential uses across textiles, personal care, biomedical materials, and industrial packaging.

[0004] The increasing demand for sustainable and eco-friendly materials has highlighted the need for innovative approaches to create biodegradable alternatives to conventional products. One promising alternative approach is the use of cellulose, a naturally occurring polymer found in plant materials. Cellulose-based textiles, including cotton, linen, and hemp-based textiles, biodegrade much faster than synthetic alternatives, thus reducing environmental impact. In addition to textiles, cellulose can also be used in paper, packaging, films, coatings, and composites, broadening its utility beyond apparel. However, other sources of cellulose, including agricultural waste products, remain unexploited and continue to contribute to waste streams. Among these, nutshells are abundant yet underutilized byproducts of the food industry. They are often discarded or incinerated, despite being rich in lignocellulosic content. Valorizing nutshells into cellulose, lignin, or nanocellulose offers a route to reduce agricultural waste and develop high- value products for textiles, packaging, personal care, construction materials, and other industrial applications.

[0005] What is needed are new, bio-based synthetic fibers and yarns that can be produced by conventional techniques, including, but not limited to, wet spinning and dry jet wet spinning, and electrospinning, other fiber-forming processes. These fibers may also be processed into nonwoven, woven, or knitted textiles, as well as films, composites, and technical fabrics for a wide range of applications. These new fibers and yarns would ideally utilize resources such as agricultural waste, including, but not limited to, nutshells and hulls, either individually or inATTORNEY DOCKET NO. 220214-2010 combination to tailor composition, mechanical performance, and processing behavior. Mixed feedstocks may offer synergistic effects due to variations in cellulose and lignin content. These fibers and yarns would ideally be biodegradable, compostable, and free from environmentally harmful chemicals. In some aspects, mechanical properties of the fibers and yarns, as well as textiles produced therefrom, could be customized by the inclusion of other components including, but not limited to, nanocellulose (CNF or CNC) hydrogels derived from nutshells or other plant sources, or functional additives such as chitosan, polyphenols, or natural waxes to enhance durability, antimicrobial performance, or hydrophobicity. These needs and other needs are satisfied by the present disclosure.SUMMARY

[0006] In accordance with the purpose(s) of the present disclosure, as embodied and broadly described herein, the disclosure, in one aspect, relates to a process for extracting cellulose and lignin from nutshells or nut hulls, such as, for example, pecan, peanut, cashew, walnut, hazelnut, pistachio, or almond shells or hulls, or any combination thereof. The extracted cellulose can be used to produce biodegradable fibers, yarns, films, and pulp for applications in textiles, packaging, and composites. In some embodiments, the cellulose is regenerated through wet spinning, dry jet wet spinning, or similar processes to form filaments or staple fibers, which may be subsequently processed into nonwoven, woven, or knitted textiles. The extracted lignin may be isolated, purified, or functionalized and used as a filler, binder, flame retardant, UV stabilizer, or precursor for bioplastics, coatings, adhesives, or carbon-rich composites. In some aspects, the fibers can also include nanocellulose components such as cellulose nanofibrils (CNF), cellulose nanocrystals (CNC), or microfibri Hated cellulose (MFC), which may be derived from nutshells or other lignocellulosic biomass sources, including those produced from low-value waste streams from agriculture or paper production. These nanocellulose components may be incorporated as hydrogels or dry powders to enhance mechanical properties, barrier performance, or functional behavior. In some aspects, the biodegradable fibers, yarns, or textiles can be antimicrobial, biocompatible, compostable, or any combination thereof. Also disclosed herein are methods of making the biodegradable fibers, as well as yarns and textiles including the biodegradable fibers. In some aspects, the fibers, yarns, and / or textiles can further include polylactic acid (PLA), polyhydroxyalkanoate (PHA), and / or polycaprolactone (PCL).

[0007] Other systems, methods, features, and advantages of the present disclosure will be or become apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional systems, methods, features, andATTORNEY DOCKET NO. 220214-2010 advantages be included within this description, be within the scope of the present disclosure, and be protected by the accompanying claims. This includes, but is not limited to, processes for cellulose extraction, lignin extraction, nanocellulose production, fiber spinning, yarn formation, and manufacturing of nonwoven, woven, knitted, composite, or hybrid materials, as well as applications of these materials in textiles, packaging, filtration, coatings, adhesives, medical products, and other high-performance or industrial sectors. In addition, all optional and preferred features and modifications of the described embodiments are usable in all aspects of the disclosure taught herein. Furthermore, the individual features of the dependent claims, as well as all optional and preferred features and modifications of the described embodiments, are combinable and interchangeable with one another.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Many aspects of the present disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present disclosure. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.

[0009] FIG. 1 shows an exemplary process for cellulose and lignin extraction from nutshells.

[0010] FIGs. 2A-2B are photographs of cellulose extracted using the disclosed process. FIG. 2C is a photograph of lignin extracted using the disclosed process. FIG. 2D shows a photograph of a fiber produced via wet spinning from cellulose extracted from peanut shells. FIG. 2E shows nanofibrillated cellulose (CNF) derived from pecan shells, produced using the disclosed process. The CNF exhibits a hydrated, gel-like consistency characteristic of nanoscale fibril networks. FIG. 2F shows cellulose nanocrystals (CNC) derived from pecan shells, produced using the disclosed process. The CNC is shown in a freeze-dried form as bright white flakes, illustrating the solid morphology obtained after drying.

[0011] FIG. 3 shows thermogravimetric analysis (TGA) of an exemplary extracted cellulose fiber. The sample was heated from 25 °C to 500 °C to assess the thermal stability and decomposition behavior.

[0012] FIG. 4 shows differential scanning calorimetry (DSC) of an exemplary disclosed extracted cellulose. The sample was heated from 25 °C to 500 °C at a rate of 10 °C / min to assess the thermal properties of the materials.

[0013] FIG. 5 shows a Fourier transform infrared (FTIR) spectrum of an exemplary fiber producedATTORNEY DOCKET NO. 220214-2010 by the disclosed process.

[0014] FIG. 6 shows the FTIR spectrum of FIG. 5 overlaid with a spectrum of xylan derived from a corn cob.

[0015] FIG. 7 shows the FTIR spectrum of FIG. 5 overlaid with a spectrum of rayon.

[0016] FIGs. 8A-8B show images of cellulose nanofibers (CNFs) coating, showing uniform fibril structure and nanoscale roughness (9.17 nm). FIG. 8A: atomic force microscopy (AFM); FIG. 8B: scanning electron microscopy (SEM).

[0017] FIG. 9 shows an X-ray diffraction (XRD) spectrum of cellulose extracted from nutshell biomass..

[0018] FIG. 10A shows the average percent yield from peanut shell cellulose extractions under varying conditions. Error bars represent the standard deviation between replicates. FIG. 10B shows average S10 and S18 values from peanut shell cellulose extractions under varying conditions. Error bars represent the standard deviation between replicates. FIG. 10C shows the sum of S10 and S18 values combined from peanut shell cellulose extractions under varying conditions, ordered from lowest to highest. Error bars represent the standard deviation between S10 and S18 replicates.

[0019] FIG. 11A shows the percent yield from pecan shell cellulose extractions under varying conditions. FIG. 11 B shows average S10 and S18 values from pecan shell cellulose extractions under varying conditions. Error bars represent the standard deviation between replicates. FIG. 11C shows the sum of S10 and S18 values from pecan shell extractions under different conditions. Error bars represent standard deviation between S10 and S18 replicates, illustrating extraction efficiency trends across treatment types.

[0020] FIG. 12A shows the XRD pattern of cellulose extracted from peanut shells, showing peaks associated with cellulose I structure. FIG. 12B shows the XRD pattern of cellulose extracted from pecan shells, showing peaks associated with cellulose I structure. FIG. 12C shows the XRD pattern of cellulose extracted from almond shells, showing peaks associated with cellulose I crystalline structure.

[0021] FIG. 13 shows solid-state13C CP-MAS NMR spectra of cellulose extracted from pecan and peanut shells showing characteristic cellulose carbon signals (C1-C6) and residual lignin peaks.

[0022] FIG. 14A shows C-NMR of cellulose extracted from peanut shells. The spectralATTORNEY DOCKET NO. 220214-2010 deconvolution of the cellulose 1 D13C CP MAS spectra shows the experimental spectrum (red) and the fitted line (pink). FIG. 14B shows C-NMR of cellulose extracted from pecan shells. The spectral deconvolution of the cellulose 1 D13C CP MAS spectra. The experimental spectra (red) and fitted line (pink) indicate both crystalline and amorphous features in the material.

[0023] FIG. 15 shows a Scanning Electron Microscopy (SEM) image of nanocellulose- functionalized cellulose pulp derived from pecan shells.

[0024] FIG. 16 shows elemental mapping images (EDS) of nanocellulose-functionalized cellulose pulp derived from pecan shells, showing distribution of chlorine (Cl), oxygen (O), sodium (Na), carbon (C), and calcium (Ca) across the sample surface.

[0025] FIG. 17 shows a TGA curve of cellulose extracted from pecan shells treated with NaOH / urea, showing moisture loss and thermal degradation behavior across increasing temperatures.

[0026] FIG. 18 shows an optical microscopy image of nanofibrillated cellulose (CNF) derived from peanut shells, produced using the disclosed process. The image illustrates the entangled nanoscale fibril network, with individual fibrils visible at the micrometer scale, indicating successful fibrillation. Scale bar: 20 pm.

[0027] FIG. 19 shows an atomic force microscopy (AFM) image of nanofibrillated cellulose (CNF) derived from almond shells produced by the disclosed process. The image reveals an interconnected network of nanoscale fibrils, with individual fibril diameters on the order of a few nanometers, consistent with CNF morphology.

[0028] FIG. 20 shows an atomic force microscopy (AFM) image of cellulose nanocrystals (CNC) derived from peanut shells, showing the rod-like morphology and nanoscale dimensions.

[0029] FIG. 21 presents an SEM image of a regenerated cellulose fiber produced from nutshell- derived pulp, showing a textured surface that reflects the unique morphology achieved through the regeneration process.

[0030] Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or can be learned by practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.ATTORNEY DOCKET NO. 220214-2010DETAILED DESCRIPTION

[0031] Disclosed herein is a method for extracting cellulose and lignin from agricultural waste products, such as, for example, nutshells, to create biodegradable fibers using conventional wetspinning and dry jet wet spinning techniques as well as electrospinning techniques. In one aspect, pecan, peanut, almond, walnut, cashew, pistachio, hazelnut, and other nutshells are often discarded as waste, despite being rich in lignocellulosic components suitable for fiber production. In a further aspect, these waste materials can be used to extract cellulose, lignin, and nanocellulose, which can be used individually or in combination to create biodegradable fibers that can replace both natural and synthetic fibers in a wide range of applications, including potential uses for both cellulose-rich and lignin-rich fractions. In some aspects, nanocellulose derived from these materials can be incorporated into the fibers to enhance strength, thermal stability, barrier properties, or other performance characteristics, and can also be used in environmentally friendly applications such as packaging, filtration media, biomedical products, and high-strength lightweight composites. Also disclosed herein are fibers, yarns, and textiles produced by the disclosed process.

[0032] In one aspect, the disclosed fibers exhibit excellent mechanical and thermal properties, making them suitable for a wide range of textile applications. In a further aspect, the disclosed process offers a sustainable alternative to conventional synthetic fibers, addressing the growing environmental impact of the textile industry. In a further aspect, the disclosed methods and products support the agricultural industry by adding value to a waste product, including potential uses for both cellulose-rich and lignin-rich fractions in non-textile applications such as bio-based plastics, energy storage materials, and biodegradable coatings. In still another aspect, the disclosed approach aligns with circular economy principles and contributes to reducing the carbon footprint of textile production and other industries utilizing renewable, biodegradable raw materials. In yet another aspect, the use of biodegradable and bio-based materials helps mitigate the environmental impact of textile waste, particularly in the fast fashion industry, and reduces reliance on petroleum-derived raw materials across multiple manufacturing sectors. In an aspect, by creating a sustainable alternative to synthetic fibers, this disclosure supports the transition to a more environmentally friendly and socially responsible textile industry and reduces reliance on petroleum-derived raw materials across multiple manufacturing sectors.ATTORNEY DOCKET NO. 220214-2010Method for Producing Cellulose, Lignin, Nanocellulose, Fibers, and Textiles from Nutshells

[0033] In one aspect, the disclosed method includes producing purified cellulose, lignin, and nanocellulose fractions in addition to textile fibers and yarns. Raw materials are first collected and prepared. Further in this aspect, nutshells, including but not limited to pecan, peanut, almond, walnut, pistachio, hazelnut, and cashew shells, are collected from agricultural processing facilities. In a further aspect, the shells are thoroughly cleaned to remove any contaminants or residues. In another aspect, the cleaned shells are then dried to a specific moisture content suitable for further processing. FIG. 1 shows an exemplary process for preparing fibers from nutshells. The nutshells 102 may be mechanically ground or milled to a desired particle size and then subjected to an initial treatment step 104 in which they are mixed with a solvent and chemical system to loosen and separate lignocellulosic components. In one aspect, this step can occur at an elevated temperature, such as, for example, 70 °C. The chemical system can include, but is not limited to, alkali solutions (e.g., sodium hydroxide, potassium hydroxide, calcium hydroxide), oxidative agents (e.g., hydrogen peroxide, sodium hypochlorite, ozone), organic solvents (e.g., ethanol, methanol, acetone, ethyl acetate, dimethyl sulfoxide), ionic liquids, deep eutectic solvents, acid solutions (e.g., sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, citric acid), or combinations thereof. The solution is then subjected to a first separation 106 to isolate lignin-rich fractions, and a second separation to isolate cellulose-rich fractions. Enzyme-assisted treatments may also be applied at this stage, including cellulases, hemicellulases, laccases, xylanases, or peroxidases, either individually or in combination, to further refine the fractions. The remaining cellulose-rich slurry 108 may be treated with bleaching agents to improve purity and color. Suitable bleaching agents may include hydrogen peroxide, sodium chlorite, peracetic acid,ATTORNEY DOCKET NO. 220214-2010 calcium hypochlorite, oxygen under pressure, ozone, or combinations thereof, optionally with stabilizers, chelating agents, or activators. This bleaching step can also be used to remove residual hemicellulose and other non-cellulosic materials. The bleach step can be repeated several times. The final purified cellulosic material 110 may then be further processed into nanocellulose via mechanical, chemical, or enzymatic methods, or used directly for wet-spinning, dry-jet wet spinning, or other fiber production processes. The lignin fraction recovered in step 106 can be processed into adhesives, coatings, resins, carbon materials, or other environmentally friendly products.

[0034] In one aspect, fractionation can be adjusted to selectively recover lignin in high purity for use in adhesives, carbon fibers, resins, coatings, or as a precursor for aromatic compounds, while cellulose and nanocellulose fractions can be directed to fiber spinning, composites, films, or biomedical materials. In a further aspect, for example, pecan shells contain mainly cellulose, hemicellulose, lignin, and a high amount of antioxidant phenolic and low molar mass compounds, such as phenolics, flavonoids, and tannins. In a further aspect, these low molar mass compounds can make the material less water-soluble and more resistant to bacterial attack. In an additional aspect, agri-waste from pecan, peanut, almond, hazelnut, pistachio, cashew, and walnut shells contains bioactive compounds that offer excellent antioxidant and antimicrobial properties. In one aspect, an industrial grinder can be used for crushing the nutshells and / or nut hulls into a fine powder. For different samples, various concentrations of the materials were used and mixed with a homogenizer.

[0035] In another aspect, following cleaning, the dried shells are subjected to mechanical and / or chemical processes to break down the lignocellulosic structure and extract the fibrous components. In an aspect, mechanical and / or chemical processing may involve milling, grinding, or using alkali or enzyme treatments to release the fibers from the shell matrix. In still another aspect, the extracted fibers are dissolved in a suitable solvent system to create a spinning solution. In one aspect, and without wishing to be bound by theory, solvent selection is important to ensure fiber quality and environmental compatibility. For example, in one aspect, solvents like ionic liquids or green solvents may be used to dissolve the lignocellulosic material without causing significant environmental harm.

[0036] In some aspects, the extracted fibers can be used alone to produce yarns and textiles. In an alternative aspect, nanocellulose is added to the cellulose extraction process prior to wet spinning to enhance the properties of the final fibers. In one aspect, the addition of nanocellulose can improve the mechanical strength, toughness, and uniformity of the fibers, making them moreATTORNEY DOCKET NO. 220214-2010 suitable for high-performance applications. Further in this aspect, the nanocellulose is carefully dispersed within the spinning solution to ensure homogeneous integration, avoiding agglomeration or phase separation that could negatively impact fiber quality. In still another aspect, the incorporation of nanocellulose also allows for potential surface functionalization, enabling the fibers to have additional properties such as hydrophobicity or antimicrobial activity. In one aspect, nanocellulose production from nutshell-derived cellulose can include acid hydrolysis (e.g., sulfuric, hydrochloric, phosphoric acids), TEMPO-mediated oxidation, enzymatic pretreatment followed by high-pressure homogenization, or mechanical fibrillation using microfluidizers, ultrasonication, or refining.

[0037] In one aspect, nanocellulose is a material composed of nanosized cellulose fibrils with a relatively high length-to-width ratio. Traditionally, to create nanocellulose, nanocellulose fibrils are isolated from wood-based fibers using high-pressure homogenizers that are employed to delaminate the cell walls of fibers and free the nanosized fibrils. In an alternative aspect, nanocellulose can be obtained from widely available cellulose in cellulosic waste products generated on farms and in industry, such as nutshells (e.g., pecan, peanut, almond, walnut, pistachio, hazelnut, cashew), crop residues, and other agricultural byproducts. In one aspect, this waste-based approach reduces reliance on wood pulp, decreases deforestation pressures, and diverts agricultural residues from landfills or open burning, thereby lowering greenhouse gas emissions and promoting a circular economy. In another aspect, the production process can optionally integrate chemical, enzymatic, and / or mechanical pretreatments, alone or in combination, prior to mechanical nanofibrillation.

[0038] In some aspects, nanofibrillated cellulose can be used herein and can be produced from wood pulp or other cellulose-rich materials, including purified cellulose from nutshells and other agricultural byproducts, by high-pressure homogenization. In a further aspect, cellulosic material (e.g., kraft pulp sheet, processed nutshell cellulose) can be milled to the order of tens of micrometers in width and hundreds of micrometers in length. In a still further aspect, the resulting milled pulp powder may then be delaminated to nanosize fibrils by a high-pressure homogenizer with multiple passes, whose average width ranges on the order of tens of nanometers and average length on the order of micrometers. In one aspect, nanofibrillated cellulose in this manner exhibits a gel-like appearance and properties (i.e. , is a hydrogel). Further in this aspect, the gel remains stable and shows no signs of phase separation or precipitation after several months. In some aspects, nanocellulose produced from nutshell-derived cellulose can also be used inATTORNEY DOCKET NO. 220214-2010 combination with lignin fractions for functional composites, coatings, films, and other environmentally friendly applications beyond textiles.

[0039] In one aspect, the nanocellulose hydrogel can be or include a homogenized cellulosic pulp. In some aspects, the homogenized cellulosic pulp includes at least one material sourced from a low-value waste stream, such as, for example, nutshells (e.g., pecan, peanut, almond, walnut, pistachio, hazelnut, cashew), crop residues, cotton noil, woody pulp from paper production, or a combination thereof. In another aspect, the homogenized nanocellulosic pulp is or includes cellulose nanofibrils (CNF), cellulose nanocrystals (CNC), or any combination thereof, wherein the CNF and / or CNC are produced from cellulose extracted from nutshells or other agricultural byproducts using chemical, enzymatic, mechanical, or combined processes. In some aspects, the nanocellulose hydrogel further includes functional additives such as carboxymethylcellulose, chitosan, lignin derivatives, or bio-based crosslinkers to enhance performance for specific applications.

[0040] In another aspect, nanocellulose has a very high specific surface area with concomitant extremely large concentrations of OH functional groups available for chemical reaction with and hydrogen bonding to dye molecules, other chemical finishes, and to the fibers in the yarns and fabrics. In one aspect, the inclusion of nanocellulose allows dyes and chemical finishes to be applied to the disclosed fabrics at a much greater efficiency level. In another aspect, chemical finishes can include flame retardant, antimicrobial, hydrophobic, oleophobic, UV-protective, conductive, antistatic, biodegradable, water-repellent, fragrance-releasing, and stain- and soilresistant treatments. Such finishes may be derived from both synthetic and bio-based sources, including plant extracts, essential oils, metallic nanoparticles, biopolymers, or other functional agents.

[0041] In a still further aspect, nanocellulose is readily tailorable to create various porosities, thicknesses, and microstructures. In the disclosed textile fibers, the focus has primarily been on the use of cellulose nanofibrils (CNF) and cellulose nanocrystals (CNC) particles, which present with nanofiber and whisker structures, respectively, wherein the different microarchitectures can be used to optimize the functionality of the textile fibers and other bio-based products. In an aspect, CNF is a random material composed of cellulosic fibers typically 10-50 nm in diameter and several micrometers long with a broad size distribution. This results in about a 1 :50 average aspect ratio of the microfibrils, apt for entanglement with cellulose, lignin, and nutshell or nut hull powders derived from agricultural byproducts. In a further aspect, CNF pulp can be mixed with functional additives such as carboxymethylcellulose (CMC), chitosan, starch, or lignin derivativesATTORNEY DOCKET NO. 220214-2010 to form a CNF-hydrogel that can be used as a carrier for functional properties as well as to strengthen the structure of the disclosed textile fibers. Further in this aspect, the CNF network is strengthened by hydrogen bonds, mechanical interlocking, electrostatic interactions, interdiffusion of cellulose molecules, lignin-cellulose interactions, and van der Waals forces.

[0042] In one aspect, a spinning solution containing extracted cellulose, or a spinning solution containing both extracted cellulose and nanocellulose, can then be subjected to wet spinning or dry jet wet spinning techniques to form fibers. In one aspect, in wet spinning, the spinning solution is extruded through spinnerets into a coagulation bath where the fibers solidify as the solvent is removed. In another aspect, in dry jet wet spinning, the spinning solution is extruded through spinnerets into an air gap before entering a coagulation bath, allowing for additional control over fiber morphology and mechanical properties. In some aspects, the coagulation bath composition can be optimized to ensure efficient fiber formation and solvent recovery, with the possibility of using a regenerating solvent system that can be recycled and reused. In one aspect, water, ethanol, isopropanol, glycerol-water mixtures, or bio-based coagulants, or a combination thereof, can be used as coagulation agents. Further in this aspect, the selection of the coagulation agent depends upon the identity of the solvent system, as known in the art, which may include N- methylmorpholine N-oxide (NMMO), ionic liquids, deep eutectic solvents, organic-aqueous blends, or combinations thereof.

[0043] In an aspect, the spun fibers undergo washing, drawing, and drying processes to remove any remaining solvents and to improve fiber strength, orientation, and uniformity. In another aspect, the fibers can also be subjected to additional chemical or physical treatments to enhance their properties, including, but not limited to, surface functionalization or cross-linking to improve mechanical strength and durability. In a further aspect, such treatments can incorporate bio-based finishes, plasma or corona surface activation, enzyme grafting, or in situ nanoparticle deposition (e.g., silver, zinc oxide, silica) for added functionality. In an aspect, the resulting fibers are analyzed to determine their physical, chemical, and mechanical properties, including tensile strength, flexibility, biodegradability, thermal stability, moisture absorption, UV resistance, and colorfastness, as well as compatibility with existing manufacturing processes. In a further aspect, the fibers are tested for their performance in various applications, such as textiles, non-woven materials, composites, filtration media, packaging materials, biomedical devices, and specialty performance products..Applications and Advantages of the Disclosed Fibers, Textiles, Cellulose Pulp, Lignin, Nanocellulose, and Related CompositionsATTORNEY DOCKET NO. 220214-2010

[0044] In one aspect, the disclosed fibers, cellulose pulp, lignin, and nanocellulose fractions produced from nutshells can be used in a wide range of products, including but not limited to, textiles and fabrics; non-woven materials for medical, filtration, or industrial use; composite materials for automotive, aerospace, construction, or consumer goods; biodegradable packaging; paper and board products; coatings and films; adhesives and binders; and filtration membranes. In some aspects, the fibers, pulp, lignin, and nanocellulose can be functionalized, allowing for enhanced properties such as increased strength, water resistance, antimicrobial activity, flame retardancy, UV resistance, barrier properties, or other specific functionalities for targeted applications.

[0045] In an aspect, the use of nutshells as raw materials for fibers, cellulose pulp, lignin, and nanocellulose production offers several advantages including (I) utilization of abundant and renewable waste resources, thus reducing the environmental impact of textile, pulp, and chemical production; (II) production of biodegradable and non-toxic materials, contributing to sustainability efforts; and (III) provision of a cost-effective alternative to conventional natural and synthetic fibers, fillers, binders, and polymer additives.

[0046] In yet another aspect, advanced spinning techniques, such as wet spinning, electrospinning, and dry jet wet spinning, enable the production of high-quality fibers with desirable properties. In one aspect, the incorporation of nanocellulose can further enhance the mechanical strength, toughness, and uniformity of the fibers, making them suitable for high- performance applications. In another aspect, cellulose pulp can be processed into sustainable paper, molded fiber packaging, or specialty filtration media, while lignin can be utilized as a natural binder, dispersant, antioxidant, UV stabilizer, or precursor for biobased resins and carbon materials. Nanocellulose can be incorporated into coatings, composites, biomedical materials, energy storage devices, and barrier films to improve mechanical and functional performance.Advantages of Nanocellulose Inclusion

[0047] In some aspects, nanocellulose can be added to the disclosed cellulosic pulp preparations derived from nutshells prior to spinning into fiber. In one aspect, nanocellulose is known for its high tensile strength and modulus, which can significantly enhance the mechanical properties of the resulting fibers. Further in this aspect, this can be particularly beneficial for applications where high-strength fibers are required, such as in composites or technical textiles. In another aspect, nanocellulose can act as a reinforcing agent within the fiber matrix, improving overall durability and performance under mechanical stress. In still another aspect, incorporating nanocelluloseATTORNEY DOCKET NO. 220214-2010 can help create a more uniform fiber structure, reducing defects and variations in fiber thickness or density, which can lead to more consistent performance across different batches of fibers.

[0048] In some aspects, nanocellulose inclusion can improve the processability of the resulting fibers. For example, in one aspect, nanocellulose can influence the rheological properties of the spinning solution, improving the processability during wet spinning, which can, in turn, result in smoother extrusion and more controlled fiber formation. In another aspect, nanocellulose can be functionalized with various chemical groups, allowing for the introduction of additional functionalities (e.g., hydrophobicity, antimicrobial properties) to the fibers, thereby expanding the range of applications for the fibers produced.

[0049] In one aspect, as with the nutshell-derived fibers themselves, nanocellulose is biodegradable and derived from renewable sources, aligning with the overall sustainability goals in the textile industry.

[0050] In some embodiments, the biodegradable fiber derived from nutshells or nut hulls is blended with one or more biopolymers, including polylactic acid (PLA), polyhydroxyalkanoate (PHA), or polycaprolactone (PCL), to produce hybrid fibers or textiles with enhanced mechanical and thermal properties. In a further aspect, these blended materials may be used in yarns, woven fabrics, or nonwoven textiles, including spunbond and meltblown structures. In an alternative aspect, yarns, woven fabrics, nonwoven textiles, and the like, can include blends of the disclosed biodegradable fiber and one or more synthetic fibers, including, but not limited to, nylon, polyester, acrylic, acetate, or the like.

[0051] Many modifications and other embodiments disclosed herein will come to mind to one skilled in the art to which the disclosed compositions and methods pertain, having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the disclosures are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. The skilled artisan will recognize many variants and adaptations of the aspects described herein. These variants and adaptations are intended to be included in the teachings of this disclosure and to be encompassed by the claims herein.

[0052] Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

[0053] As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and featuresATTORNEY DOCKET NO. 220214-2010 which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure.

[0054] Any recited method can be carried out in the order of events recited or in any other order that is logically possible. That is, unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.

[0055] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and / or materials in connection with which the publications are cited. The publications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided herein can be different from the actual publication dates, which can require independent confirmation.

[0056] While aspects of the present disclosure can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only, and one of skill in the art will understand that each aspect of the present disclosure can be described and claimed in any statutory class.

[0057] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed compositions and methods belong. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.ATTORNEY DOCKET NO. 220214-2010

[0058] Prior to describing the various aspects of the present disclosure, the following definitions are provided and should be used unless otherwise indicated. Additional terms may be defined elsewhere in the present disclosure.Dyes and Finishes

[0059] In one aspect, the natural color of the fibers, textiles, and yarns disclosed herein varies depending on the type of nutshell used and the degree of purification or bleaching, and any optional chemical or enzymatic treatments applied during processing. In a further aspect, without bleaching, the fibers typically have a light- to medium-brown tone. If bleached, the fibers can range from off-white to pale beige.

[0060] In an aspect, the yarns and textiles made from the disclosed fibers can be dyed by any process typically used to dye cellulosic textiles, including, but not limited to, reactive dyes, direct dyes, and / or natural dyes. In another aspect, the natural dyes can be substantive (i.e. , no mordant needed), adjective (i.e., mordant needed), or vat dyes (e.g., indigo). In a further aspect, the use of commercially available dyes on the disclosed yarns and textiles allows for processing the textiles and yarns using existing dyeing infrastructure. In another aspect, finishes typically used on cellulosic fibers such as cotton, linen, hemp, and the like, are also compatible with the disclosed nutshell-based yarns and textiles, including, but not limited to, singeing, desizing, printing, water-repellent and stain-resistant treatments (including PFAS-free formulations), flameretardant finishes, antimicrobial or antifungal finishes, anti-odor finishes, anti-static finishes, wrinkle-resistant finishes, moisture-wicking or thermoregulating finishes, softening treatments, abrasion-resistant or anti-pilling finishes, soil-release finishes, breathable barrier coatings, and conductive finishes for smart textiles, and related techniques.

[0061] In still another aspect, dyes or pigments can be added into the dope during the fiber spinning process in order to enable solution-dyeing, which can reduce the need for postprocessing and further enhance the sustainability of the fibers. In some embodiments, functional pigments such as UV-blocking or antimicrobial agents, thermochromic pigments, phase change materials, or electrically conductive particles can also be incorporated at this stage.Definitions

[0062] As used herein, “comprising” is to be interpreted as specifying the presence of the stated features, integers, steps, or components as referred to, but does not preclude the presence or addition of one or more features, integers, steps, or components, or groups thereof. Moreover, each of the terms “by,” “comprising,” “comprises”, “comprised of,” “including,” “includes,”ATTORNEY DOCKET NO. 220214-2010“included,” “involving,” “involves,” “involved,” and “such as” are used in their open, non-limiting sense and may be used interchangeably. Further, the term “comprising” is intended to include examples and aspects encompassed by the terms “consisting essentially of” and “consisting of.” Similarly, the term “consisting essentially of” is intended to include examples encompassed by the term “consisting of.

[0063] As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a textile fiber,” “a nutshell,” or “an ionic liquid,” include, but not limited to, mixtures of two or more such textile fibers, nutshells, or ionic liquids, and the like.

[0064] It should be noted that ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Ranges can be expressed herein as from “about” one particular value, and / or to “about” another particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further aspect. For example, if the value “about 10” is disclosed, then “10” is also disclosed.

[0065] When a range is expressed, a further aspect includes from the one particular value and / or to the other particular value. For example, where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g. the phrase “x to y” includes the range from ‘x’ to ‘y’ as well as the range greater than ‘x’ and less than ‘y’. The range can also be expressed as an upper limit, e.g. 'about x, y, z, or less’ and should be interpreted to include the specific ranges of ‘about x’, 'about y’, and ‘about z’ as well as the ranges of ‘less than x’, less than y’, and ‘less than z’. Likewise, the phrase ‘about x, y, z, or greater’ should be interpreted to include the specific ranges of ‘about x,’ ‘about y,’ and ‘about z’ as well as the ranges of ‘greater than x,’ greater than y,’ and ‘greater than z.’ In addition, the phrase “about ‘x’ to ‘y’”, where ‘x’ and ‘y’ are numerical values, includes “about ‘x’ to about ‘y’”.

[0066] It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or subranges encompassed within that range as if each numerical value and sub-range is explicitlyATTORNEY DOCKET NO. 220214-2010 recited. To illustrate, a numerical range of “about 0.1 % to 5%” should be interpreted to include not only the explicitly recited values of about 0.1 % to about 5%, but also include individual values (e.g., about 1%, about 2%, about 3%, and about 4%) and the sub-ranges (e.g., about 0.5% to about 1.1%; about 5% to about 2.4%; about 0.5% to about 3.2%, and about 0.5% to about 4.4%, and other possible sub-ranges) within the indicated range.

[0067] As used herein, the terms “about,” “approximate,” “at or about,” and “substantially” mean that the amount or value in question can be the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art such that equivalent results or effects are obtained. In some circumstances, the value that provides equivalent results or effects cannot be reasonably determined. In such cases, it is generally understood, as used herein, that “about” and “at or about” mean the nominal value indicated ±10% variation unless otherwise indicated or inferred. In general, an amount, size, formulation, parameter, or other quantity or characteristic is “about,” “approximate,” or “at or about” whether or not expressly stated to be such. It is understood that where “about,” “approximate,” or “at or about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0068] As used herein, the term “effective amount” refers to an amount that is sufficient to achieve the desired modification of a physical property of the composition or material. For example, an “effective amount” of cellulose pulp, lignin, or nanocellulose refers to an amount that is sufficient to achieve the desired improvement in the property modulated by the formulation component, e.g., achieving the desired level of processability during spinning. The specific level in terms of wt% in a composition required as an effective amount will depend upon a variety of factors, including the amount and type of nutshells, spinning solvent type, chemical functionalization of the nanocellulose, and end use of the textile made using the composition that includes nanocellulose.

[0069] As used herein, the terms “optional” or “optionally” mean that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0070] “Biocompatible” refers to a material that is not harmful to living tissue. In one aspect, the textile fibers disclosed herein are biocompatible. Further in this aspect, the textile fibers can beATTORNEY DOCKET NO. 220214-2010 used to make articles of clothing, footwear, upholstery, and the like that can be worn next to the skin or used as seating without causing irritation.

[0071] “Compostable” as used herein, refers to a material that can disintegrate into non-toxic components. A compostable material may require microorganisms, humidity, and heat to yield a finished product, which can then be used to fertilize plants such as food crops, ornamental crops, or the like. In one aspect, the textile fibers disclosed herein are compostable.

[0072] “Agri-waste” or “agricultural waste” as used herein refers to a plant residue from agriculture that is not used for human food, animal food, or another value-added process (e.g., ethanol fermentation). In one aspect, the textile fibers disclosed herein make use of agri-waste such as nutshells and / or nut hulls, husks, pods, shells, stalks, chaff, or other lignocellulosic residues, thereby decreasing the amount of material dumped, sent to landfills, or burned.

[0073] As used herein, a “nutshell” refers to the outer, inedible shell of a nut that is removed before eating the nut or further processing the nut for industrial purposes such as producing food products. Meanwhile, a “nut hull” refers to an outer casing that encloses the nutshell (also called the “mesocarp”) and that may or may not be easily separable from the nutshell, depending on the type of nut, stage of harvest, growing conditions, and the like. In some aspects, nutshells and nut hulls are separated prior to performing the disclosed methods. In other aspects, nutshells are not separated from nut hulls and both are ground and used in extractions of lignocellulosic material as described herein. As used herein, the term “nutshells or nut hulls” refers to the hard outer shells or fibrous outer husks (hulls) of tree nuts or legumes, including but not limited to pecan, peanut, almond, walnut, cashew, pistachio, and hazelnut, and mixtures thereof with other agricultural byproducts such as seed husks, fruit pits, or cereal chaff. In one aspect, these materials are typically considered agricultural byproducts or waste and may be obtained from shelling operations or farm processing facilities. In a further aspect, the terms also encompass mixtures of different types of nutshells and / or nut hulls.

[0074] Unless otherwise specified, temperatures referred to herein are based on atmospheric pressure (i.e., one atmosphere).

[0075] Now having described the aspects of the present disclosure, in general, the following Examples describe some additional aspects of the present disclosure. While aspects of the present disclosure are described in connection with the following examples and the corresponding text and figures, there is no intent to limit aspects of the present disclosure to this description. On the contrary, the intent is to cover all alternatives, modifications, and equivalents included withinATTORNEY DOCKET NO. 220214-2010 the spirit and scope of the present disclosure.ASPECTS

[0076] The present disclosure can be described in accordance with the following numbered aspects, which should not be confused with the claims.

[0077] Aspect 1. A material comprising cellulose, lignin, lignocellulosic material, or any combination thereof, extracted from nutshells or nut hulls.

[0078] Aspect 2. The material of aspect 1 , wherein the nutshells or nut hulls comprise pecan, peanut, cashew, walnut, hazelnut, pistachio, or almond shells or hulls, or any combination thereof.

[0079] Aspect 3. The material of aspect 1 or 2, wherein the material is processed into nanocellulose selected from cellulose nanofibrils (CNF), cellulose nanocrystals (CNC), or any combination thereof.

[0080] Aspect 4. A biodegradable fiber comprising the material of any one of aspects 1-3.

[0081] Aspect 5. The biodegradable fiber of aspect 4, wherein the nutshells or nut hulls comprise pecan, peanut, cashew, walnut, hazelnut, pistachio, or almond shells or hulls, or any combination thereof.

[0082] Aspect 6. The biodegradable fiber of aspect 4 or 5, wherein the nutshells or nut hulls comprise agricultural waste.

[0083] Aspect 7. The biodegradable fiber of any one of aspects 4-6, further comprising a nanocellulose hydrogel.

[0084] Aspect 8. The biodegradable fiber of aspect 7, wherein the nanocellulose hydrogel comprises a homogenized cellulosic pulp.

[0085] Aspect 9. The biodegradable fiber of aspect 8, wherein the homogenized nanocellulosic pulp comprises at least one material sourced from a low-value waste stream.

[0086] Aspect 10. The biodegradable fiber of aspect 9, wherein the low-value waste stream comprises cotton noil, woody pulp from paper production, or any combination thereof.

[0087] Aspect 11. The biodegradable fiber of any one of aspects 8-10, wherein the homogenized nanocellulosic pulp comprises cellulose nanofibrils (CNF), cellulose nanocrystals (CNC), or any combination thereof.

[0088] Aspect 12. The biodegradable fiber of any one of aspects 7-11, wherein the nanocellulose hydrogel further comprises carboxymethylcellulose.ATTORNEY DOCKET NO. 220214-2010

[0089] Aspect 13. The biodegradable fiber of any one of aspects 7-12, wherein the nanocellulose hydrogel is chemically or physically functionalized to impart at least one additional property to the biodegradable fiber.

[0090] Aspect 14. The biodegradable fiber of any one of aspects 7-13, wherein the biodegradable fiber comprises cellulose and lignin derived from nutshells or nut hulls, wherein the lignin serves as a structural, binding, or functional additive.

[0091] Aspect 15. The biodegradable fiber of aspect 14, wherein the lignin is modified by sulfonation, acetylation, oxidation, or any combination thereof to enhance compatibility with polymers, coatings, or composites.

[0092] Aspect 16. The material of any one of aspects 1-3 or the biodegradable fiber of aspects 4-15, wherein the material or the biodegradable fiber is antimicrobial, biocompatible, compostable, or any combination thereof.

[0093] Aspect 17. The biodegradable fiber of any one of aspects 4-16, wherein the fiber is functionalized to provide flame retardancy, thermal insulation, thermoregulation, or combinations thereof.

[0094] Aspect 18. The biodegradable fiber of any one of aspects 4-17, further comprising polylactic acid (PLA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), or any combination thereof.

[0095] Aspect 19. A nanocellulose material derived from nutshells or nut hulls, wherein the nanocellulose material comprises CNF, CNC, or both, and wherein the nanocellulose material comprises particles having a diameter between 1 nm and 500 nm.

[0096] Aspect 20. The material of any one of aspects 1-3, wherein the material comprises lignin and wherein the lignin is recovered in powder, resin, particulate, or liquid form.

[0097] Aspect 21. A method for producing a cellulose, lignin, lignocellulosic, or nanocellulose material from nutshells or nut hulls, the method comprising:(a) cleaning and preparing nutshells or nut hulls; and(b) performing one or more chemical, mechanical, enzymatic, or thermal processes to extract cellulose, lignin, or both.

[0098] Aspect 22. The method of aspect 21 , further comprising: (c) converting the extracted material into nanocellulose selected from CNF and / or CNC.ATTORNEY DOCKET NO. 220214-2010

[0099] Aspect 23. A method for producing a biodegradable fiber, the method comprising:(a) performing one or more chemical or mechanical processes on nutshells or nut hulls to extract lignocellulosic material;(b) optionally separating cellulose and lignin fractions;(c) dissolving the lignocellulosic material in a solvent to produce a spinning solution;(d) extruding the spinning solution through one or more spinnerets; and(e) forming the biodegradable fiber in a coagulation bath, wherein the coagulation bath comprises a coagulation solvent.

[0100] Aspect 24. The method of aspect 23, wherein the nutshells or nut hulls are pecan, peanut, almond, walnut, cashew, hazelnut, or pistachio shells or hulls, or any combination thereof.

[0101] Aspect 25. The method of aspect 23 or 24, wherein the nutshells or nut hulls are cleaned, dried, or both prior to performing step (a).

[0102] Aspect 26. The method of any one of aspects 23-25, wherein one or more chemical or mechanical processes comprise treating with an extraction solvent solution, filtration, bleaching, milling, grinding, or any combination thereof.

[0103] Aspect 27. The method of aspect 26, wherein the extraction solvent solution comprises sodium hydroxide, potassium hydroxide, lithium hydroxide, or any combination thereof in water.

[0104] Aspect 28. The method of aspect 26 or 27, wherein treating with the extraction solvent solution is carried out at about 70 °C.

[0105] Aspect 29. The method of any one of aspects 26-28, wherein bleaching is repeated one or more additional times.

[0106] Aspect 30. The method of any one of aspects 26-29, wherein the solvent in the spinning solution comprises an ionic liquid, a green solvent, or any combination thereof.

[0107] Aspect 31. The method of aspect 30, wherein the ionic liquid comprises 1-ethyl-3- methylimidazolium acetate (EMIM Ac), 1-butyl-3-methylimidazolium chloride (BMIM Cl), a choline-based ionic liquid, or any combination thereof.

[0108] Aspect 32. The method of aspect 31 , wherein the choline-based ionic liquid comprises choline acetate.ATTORNEY DOCKET NO. 220214-2010

[0109] Aspect 33. The method of aspect 30, wherein the green solvent comprises N- methylmorpholine-N-oxide.

[0110] Aspect 34. The method of any one of aspects 23-33, further comprising admixing a nanocellulose hydrogel into the spinning solution prior to performing step (c).

[0111] Aspect 35. The method of aspect 34, wherein the nanocellulose hydrogel comprises a homogenized cellulosic pulp.

[0112] Aspect 36. The method of aspect 35, wherein the homogenized nanocellulosic pulp comprises at least one material sourced from a low-value waste stream.

[0113] Aspect 37. The method of aspect 36, wherein the low-value waste stream comprises cotton noil, woody pulp from paper production, or any combination thereof.

[0114] Aspect 38. The method of any one of aspects 35-37, wherein the homogenized nanocellulosic pulp comprises cellulose nanofibrils (CNF), cellulose nanocrystals (CNC), or any combination thereof.

[0115] Aspect 39. The method of any one of aspects 34-38, wherein the nanocellulose hydrogel further comprises carboxymethylcellulose.

[0116] Aspect 40. The method of any one of aspects 34-39, further comprising chemically or physically functionalizing the nanocellulose hydrogel prior to admixing it into the spinning solution to impart at least one additional property to the biodegradable fiber.

[0117] Aspect 41. The method of any one of aspects 23-40, wherein step (c) is performed using wet spinning, dry jet wet spinning, electrospinning, or any combination thereof.

[0118] Aspect 42. The method of any one of aspects 23-41 , wherein the coagulation solvent comprises water, ethanol, or any combination thereof.

[0119] Aspect 43. The method of any one of aspects 23-42, further comprising recovering the coagulation solvent from the coagulation bath.

[0120] Aspect 44. The method of any one of aspects 23-43, further comprising isolating lignin from the nutshell or nut hull feedstock for use as a binder, antioxidant, UV stabilizer, carbon precursor, or polymer additive.

[0121] Aspect 45. A biodegradable fiber, cellulose pulp, lignin, or nanocellulose produced by the method of any one of aspects 23-44.

[0122] Aspect 46. A yarn comprising the biodegradable fiber of any one of aspects 4-18 or 45.ATTORNEY DOCKET NO. 220214-2010

[0123] Aspect 47. The yarn of aspect 46, further comprising polylactic acid (PLA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), or any combination thereof.

[0124] Aspect 48. A textile comprising the biodegradable fiber of any one of aspects 4-18 or 45 or the yarn of aspect 46 or 47.

[0125] Aspect 49. The textile of aspect 48, wherein the textile comprises a woven textile, a nonwoven textile, or a knitted textile.

[0126] Aspect 50. The textile of aspect 47 or 48, further comprising polylactic acid (PLA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), or any combination thereof.

[0127] Aspect 51. The textile of aspect 49 or 50, wherein the non-woven textile is formed by cospinning or layering the biodegradable fiber with one or more fibers selected from polylactic acid (PI_A), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), or any combination thereof.

[0128] Aspect 52. The textile of aspect 49 or 50, wherein the woven textile or knitted textile comprises at least one yarn spun from a blend of the biodegradable fiber and one or more fibers selected from polylactic acid (PLA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), or any combination thereof.

[0129] Aspect 53. The textile of aspect 49 or 50, wherein the woven textile or knitted textile comprises at least one yarn spun from a blend of the biodegradable fiber and a synthetic fiber.

[0130] Aspect 54. A composite material comprising the biodegradable fiber of any one of aspects 4-18 or 45 or the material of any one of aspects 1-3.

[0131] Aspect 55. The composite material of aspect 54, further comprising nutshell-derived lignin as a matrix component, compatibilizer, or reinforcement agent.

[0132] Aspect 56. The composite material of aspect 54 or 55, wherein the composite material is reinforced for use in an automotive application, a marine application, an aerospace application, a construction application, or any combination thereof.

[0133] Aspect 57. An article comprising the composite material of any one of aspects 54-56.

[0134] Aspect 58. The article of aspect 57, wherein the article comprises an electrical or electronic device, a smart textile, a flexible circuit, or electromagnetic interference (EMI) shielding.

[0135] Aspect 59. A coating or film comprising the material of any one of aspects 1-3, wherein the coating or film comprises packaging or a layer of packaging, a barrier layer, surface functionalization for an article, a beauty or personal care product, or any combination thereof.ATTORNEY DOCKET NO. 220214-2010

[0136] Aspect 60. The coating or film of aspect 59, wherein the barrier layer provides moisture resistance, oxygen resistance, or grease resistance.

[0137] Aspect 61. An article comprising the biodegradable fiber of any one of aspects 4-18 or 45 or the material of any one of aspects 1-3.

[0138] Aspect 62. The article of aspect 61 , wherein the article comprises an article of clothing, a curtain, a bed sheet, a towel, a rug, a blanket, luggage, a handbag, furniture, a bioplastic, automotive upholstery, marine upholstery, aircraft upholstery, an article of footwear, athletic equipment, a watch band, composite panel, molded part, coating, packaging material, medical device, a cosmetic or personal care product, a high-performance textile, or any combination thereof.

[0139] Aspect 63. The article of aspect 62, wherein the article comprises a medical device, wound dressing, filtration media, sutures, surgical mask, surgical gown, tissue scaffold, absorbent pad, or geotextile.

[0140] Aspect 64. The article of aspect 62, wherein the article comprises a molded, extruded, or laminated composite containing nutshell-derived cellulose, lignin, or nanocellulose.

[0141] Aspect 65. The article of aspect 62, wherein the cosmetic or personal care product comprises a facial mask sheet, cleansing pad, makeup applicator, body scrub applicator, hair treatment wrap, or any combination thereof.

[0142] Aspect 66. The article of aspect 62, wherein the packaging material comprises a molded container, bottle, cap, film, liner, coating, pouch, or any combination thereof.

[0143] Aspect 67. The article of aspect 62, wherein the article comprises a water purifier or water filter.

[0144] Aspect 68. The article of aspect 62, wherein the article comprises paper, board, or another molded pulp product.EXAMPLES

[0145] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices and / or methods claimed herein are made and evaluated, and are intended to be purely exemplary of the disclosure and are not intended to limit the scope of what the inventors regard as their disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicatedATTORNEY DOCKET NO. 220214-2010 otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric.Example 1 : Materials

[0146] Nutshells, including pecan, peanut, cashew, walnut, hazelnut, pistachio, and almond shells or hulls, were obtained as agricultural waste. The following reagents and solvents were obtained from chemical suppliers: sodium hydroxide (NaOH) / urea, sodium hypochlorite (NaOCI), benzene-ethanol solution, hydrogen peroxide, acetic acid, sodium chlorite (NaCIO2), water, hydrochloric acid / ethanol (HCI / EtOH), NaOH / CS2 (sodium hydroxide / carbon disulfide), N- methylmorpholine-N-oxide (NMMO), LiCI / N,N-dimethylacetamide (DMAc), ionic liquids (ILs), deep eutectic solvents (DESs), concentrated phosphoric acid (CPA), and other solvents or processing agents suitable for producing cellulose, lignin, lignocellulosic, or nanocellulose materials including cellulose nanofibrils (CNF) and cellulose nanocrystals (CNC) for use in fibers, textiles, films, composites, coatings, packaging, medical devices, filtration media, and other applications.Example 2: Feedstock

[0147] Agricultural byproducts were sourced from regional nut processing facilities in Georgia and California. Pecan and peanut shells from Georgia, and almond and walnut shells from California, were used as the primary feedstocks due to their high regional availability, lignocellulosic content, and relevance to local waste challenges. Shells were first soaked in a large container of water for approximately 10 minutes to remove surface contaminants and loosen embedded dirt. They were then rinsed over a sieve and dried in a convection oven at 70 °C for six hours, a temperature selected to preserve cellulose integrity while ensuring sufficient moisture removal. Once dried, the shells were ground using a commercial two-blade mill grinder. To ensure uniformity, each batch underwent three grinding cycles, each lasting five minutes. Between cycles, the material was hand-stirred to prevent buildup along the base and edges of the grinder. The final particle size was maintained below 1 mm to support consistent chemical reactivity and solvent accessibility. Visual and compositional variation was noted between batches, prompting adjustments to moisture normalization and milling protocols. This variability impacted initial extraction efficiency, reinforcing the importance of feedstock quality control and process standardization. Batch characteristics were tracked to monitor consistency throughout the experimental workflow. The disclosed extraction process demonstrated compatibility with all four feedstocks for cellulose, lignin, CNF, CNC, and fiber production.ATTORNEY DOCKET NO. 220214-2010Example 3: Cellulose Extraction

[0148] Methods: Overview: For cellulose extraction, nutshells were ground and treated with a solvent solution at 70 °C to break down lignin and hemicellulose. The mixture was then bleached with sodium hypochlorite to extract cellulose. This process sometimes involved multiple rounds of bleaching until negligible amounts of cellulose remained. For lignin recovery, black liquor or lignin-containing fractions were precipitated using acidification and collected via filtration for subsequent use. CNF and CNC were produced from the extracted cellulose using high-shear mechanical fibrillation, enzymatic hydrolysis, or acid hydrolysis techniques.

[0149] For wet spinning, the extracted cellulose is dissolved in a suitable solvent, such as NMMO or an ionic liquid, and processed into fibers using conventional wet-spinning techniques. FIG. 2 shows a photograph of extracted cellulose prior to spinning. The fibers were then washed, dried, and spun into yarns. CNF and CNC suspensions were also cast into films, incorporated into biocomposites, used as rheology modifiers in coatings, or formulated into barrier layers for packaging.Method Variations

[0150] Cellulose was extracted by grinding the nutshells into a fine powder and dissolving them using a solvent system of 7 wt% sodium hydroxide (NaOH) and 12 wt% urea under heat-assisted conditions at 60-80 °C for 1-2 hours. Other NaOH concentrations (2%, 3%, 4%), treatment times (2, 3, or 4 h), and temperatures (80 °C, 90 °C, and 100 °C) were also explored. This alkaline pretreatment disrupts lignin-carbohydrate complexes, removes hemicellulose, and swells the cellulose structure to enhance fiber formation while partially preserving crystalline regions. Following cellulose recovery, lignin was precipitated and dried for downstream applications such as bio-based adhesives, carbon fibers, or thermoset resin modifiers. Extracted cellulose was further processed into CNF using high-pressure homogenization or CNC via controlled sulfuric acid hydrolysis. For the nonwoven sheet manufacturing processes of carding, wet-laid formation, and needle-punching, the cellulose extract was processed into fibers using a wet-spinning technique. During this process, the extracted cellulose is processed into a viscous slurry or dope, which is then extruded through a spinneret to form continuous fibers.

[0151] After alkali treatment, the extracts were washed thoroughly with deionized water until a neutral pH was reached. Neutralized samples were then oven-dried at approximately 65 °C.

[0152] To further purify and whiten the extracted cellulose, a post-treatment using hydrogen peroxide (H2O2) was employed. Samples were soaked in a 5% H2O2solution for two hours atATTORNEY DOCKET NO. 220214-2010 room temperature under mild stirring (around 500 rpm). This oxidative bleaching step enhanced brightness and removed residual lignin. Following bleaching, samples were cleaned using vacuum filtration and dried again at 65 °C.

[0153] Color reduction and surface purification were confirmed through visual inspection and microscopy. FTIR spectroscopy indicated a reduction in characteristic lignin and hemicellulose peaks while maintaining strong cellulose signals, validating the effectiveness of the pretreatment steps. Yield analysis showed that the optimized protocol recovered between 25 and 32 percent cellulose-rich material from the original dry biomass, depending on the specific feedstock and processing batch.

[0154] Trials using almond and walnut shells demonstrated slightly lower extraction yields due to their denser particle structure and higher lignin content, but confirmed general compatibility with the developed protocol. These findings support the scalability of the process and its adaptability to diverse agricultural byproducts. A low-temperature NaOH-urea pretreatment system under sub-zero conditions will also be explored, which may offer additional advantages in terms of energy savings, reduced degradation, and compatibility with a broader range of cellulose sources.

[0155] Different nonwoven applications require specific fiber parameters, including length and diameter. To produce fibers of varying diameters, several key spinning parameters were adjusted, including the spinneret hole diameter, extrusion rate, and processing temperature. Fibers were cut using a precision mechanical cutter to ensure precise and reproducible fiber length. Tensile strength and elongation at break of individual fibers were evaluated per ASTM D3822 and ISO 5079 standards.

[0156] Table 2 summarizes key properties of cellulose extracted using the disclosed method:ATTORNEY DOCKET NO. 220214-2010Cellulose Extraction and Yield

[0157] Optimized pretreatment protocols using dilute alkali and thermal methods yielded high- purity cellulose from peanut shells. The average cellulose yield varied depending on the extraction condition. The control condition using 3% NaOH at 90 °C for 3 hours produced a yield of approximately 24%, which was comparable to or higher than most other treatments. Increasing the NaOH concentration to 4% or reducing it to 2% led to slightly lower yields, indicating that 3% NaOH is close to optimal for cellulose recovery.

[0158] Both temperature and extraction time influenced yield. Performing the extraction at 100 °C maintained or slightly improved the yield while extending the reaction time to 4 hours, which resulted in the highest yield observed, around 26%. This outcome suggests that a longer reaction time may enhance the removal of lignin and hemicellulose, improving access to cellulose.

[0159] Among the tested conditions, extraction at 100 °C for 3 hours produced the highest combined solubility (5.57), followed by the 2-hour condition (4.96) and 80 °C (4.66). These results support the hypothesis that elevated thermal treatment enhances the breakdown of amorphous regions and the removal of residual non-cellulosic components. However, excessively high solubility may also indicate potential polymer chain scission, so optimal processing must balance yield and molecular integrity.

[0160] Tables 3 and 4 summarize data from extractions from peanut shells and pecan shells, respectively, performed under different conditions as described above. Equivalent processes were applied for CNF and CNC production, with yield, aspect ratio, and crystallinity index characterized via AFM and XRD.ATTORNEY DOCKET NO. 220214-2010| 3%, 90 °C, 4 h | 0.81 | 0.04 | 1.29 | 0.59 |Example 4: Additives

[0161] A limited set of natural additives was screened for compatibility with the fiber-forming material. The focus was on bio-derived plasticizers and hydrophilic modifiers that could enhance softness, flexibility, or water uptake for hygiene and packaging applications.

[0162] Several food-grade plasticizers and polyol-based additives were tested, including glycerol and sorbitol, at concentrations of 2 to 8 percent by weight. The best-performing formulations showed increased pliability and better fold endurance without sacrificing tensile strength.

[0163] Preliminary antimicrobial screening was also conducted using green tea extract-based silver nanoparticle (AgNP) suspensions prepared in-house. These trials were exploratory in nature but demonstrated good dispersion and visible antimicrobial halo formation in the zone of inhibition tests against E. coli.

[0164] To assess the potential of the developed cellulose materials for hygiene and medical applications, we conducted qualitative antimicrobial testing following ISO 20645. This standard method evaluates the inhibition of microbial growth around material samples placed on agar plates. Regenerated cellulose samples from pecan, peanut, and almond feedstocks, functionalized with silver nanoparticles, were tested against bacterial cultures. All tested samples demonstrated clear zones of inhibition, indicating effective antimicrobial activity. Similar functionalization approaches were applied to CNF films, CNC coatings, and lignin-based composites to enhance antimicrobial and antioxidant properties, further expanding potential uses in food packaging, wound care, filtration media, and consumer products. These results confirm the successful incorporation and retention of antimicrobial agents within the cellulose matrix during processing.Example 5: Lignin Extraction and ApplicationsATTORNEY DOCKET NO. 220214-2010

[0165] Lignin was isolated from nutshell feedstocks using both alkaline and organosolv extraction methods to ensure compatibility with multiple downstream applications. In the alkaline process, ground nutshell powder was treated with 1-3% NaOH solution at 80-100 °C for 2-4 hours, followed by filtration to separate the lignin-rich liquor from the cellulose-containing solids. The lignin was then precipitated by acidification to pH 2 using dilute hydrochloric acid, washed with deionized water, and oven-dried at 60-70 °C. In the organosolv method, nutshell powder was treated with ethanol-water mixtures containing 0.1-0.5% sulfuric acid at 150-180 °C in a sealed reactor for 1-2 hours, yielding high-purity lignin with reduced carbohydrate contamination.

[0166] The resulting lignin was characterized using Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), to determine its functional groups and thermal stability.

[0167] Lignin obtained from nutshells exhibited a high aromatic content, making it suitable for multiple high-value applications. Demonstrated uses included:(a) incorporation into biocomposites as a natural UV stabilizer and antioxidant;(b) blending with biodegradable polymers such as PLA, PHA, or PBAT to enhance mechanical performance and thermal stability;(c) formulation of lignin-based adhesives and coatings;(d) production of activated carbon precursors for filtration media; and(e) use in phenolic resin replacements for industrial binders.

[0168] Integration of lignin valorization into the cellulose and nanocellulose production workflow improved overall process economics and sustainability by enabling near-complete utilization of the nutshell biomass, reducing waste, and providing additional product streams.Example 6: Viscosity Measurements

[0169] Viscosity measurements were collected to assess the solution viscosity during the spinning process, which is critical for producing fibers, yarns, films, composites, and other articles with consistent mechanical properties. Viscosity was measured using a Brookfield rotational viscometer at controlled temperatures (typically 25 °C) and standardized shear rates. The measurements help in evaluating the spinnability of the solutions and in optimizing the process parameters for fiber extrusion.

[0170] Viscosity measurements indicated that the cellulose solution had suitable properties for wet-spinning, ensuring the production of fibers with consistent mechanical properties.Intrinsic ViscosityATTORNEY DOCKET NO. 220214-2010

[0171] Intrinsic viscosity (IV), measured using cupriethylenediamine (CED), reflects the degree of polymerization and is a key factor in determining the suitability of cellulose for fiber production. In this study, IV values ranged from approximately 142 to over 500 ml_ / g, depending on the type of raw material, processing method, and extraction conditions.

[0172] Lower values near 140 to 150 mL / g were found in some samples that underwent more intensive pretreatment, which may have partially degraded the cellulose chains. While these values are considered low compared to dissolving-grade pulp, they can still be used for fiber formation in certain applications, such as nonwovens or short-staple fibers, although mechanical strength may be limited.

[0173] In contrast, values above 500 mL / g were obtained from samples using extracted cellulose from a mix of nutshells, in particular walnut, pecan, and almonds, which meet or exceed typical requirements for processes like Lyocell or high-strength viscose fiber production. These higher values indicate good spinnability and mechanical properties, making them suitable for continuous filament or staple fiber spinning.

[0174] In certain embodiments, the intrinsic viscosity (CED) of the cellulose-rich fraction is about 450-650 mL / g, indicative of high molecular weight suitable for Lyocell- or viscose-type spinning. Separately, spinning dopes that include CNF and / or CNC hydrogels exhibit elevated solution viscosity (rheology) relative to cellulose-only dopes, facilitating fiber formation and draw stability without altering the intrinsic viscosity measurement of the dissolved cellulose.

[0175] The variation in intrinsic viscosity across samples highlights the importance of process optimization. By adjusting raw material selection and extraction parameters, it is possible to target specific IV ranges to match different fiber applications.

[0176] Table 5 shows viscosity measurements of cellulose solutions:ATTORNEY DOCKET NO. 220214-2010I almond) | I I I l l iExample 7: Alkali Solubility Testing

[0177] The alkali solubility profile of the extracted cellulose was evaluated using the S10 and S18 testing protocols to estimate the relative content of amorphous and crystalline cellulose fractions. This method is widely used to quantify a-cellulose by selectively dissolving lower molecular weight fractions and hemicellulose in sodium hydroxide (NaOH), leaving behind insoluble, high-purity cellulose.

[0178] For each test, cellulose extraction samples were weighed precisely to the thousandths of a gram before analysis. In the S10 test, a 10% NaOH solution was prepared by diluting 50% NaOH with deionized water, maintaining a solution-to-sample ratio of 10:1 (w / w). The cellulose sample was placed in a beaker, and the NaOH solution was added under gentle stirring. The suspension was maintained at 25 °C on a hot plate for one hour to ensure controlled dissolution of soluble fractions.

[0179] After incubation, the mixture was filtered through a vacuum filtration system to separate the insoluble (a-cellulose) fraction. The residue was thoroughly rinsed with deionized water to remove residual alkali and dried at approximately 71 °C (160 °F) until a constant weight was achieved. Final dried weights were recorded with the same precision to calculate the percent insoluble content.

[0180] The procedure was repeated using an 18% NaOH solution for the S18 test, following the same conditions. This allowed for a comparative analysis of cellulose crystallinity and extraction purity across different feedstocks and treatment conditions. The resulting data contributed to understanding structural variability and optimizing extraction protocols for high-purity, fiber-grade cellulose.Example 8: Thermal Analysis

[0181] The following analyses were performed. Thermogravimetric Analysis (TGA) was used to evaluate the thermal stability of the cellulose pulp by measuring weight loss as a function of temperature. Differential Scanning Calorimetry (DSC) was used to determine the heat flow associated with phase transitions in the pulp, providing insight into their thermal properties.

[0182] The TGA analysis demonstrated that the cellulose pulp remains stable up to 200 °C, with complete decomposition occurring around 800 °C, indicating good thermal stability for textileATTORNEY DOCKET NO. 220214-2010 applications. TGA indicated the onset of thermal degradation around 270 °C, which is typical for cellulose-rich biopolymers.

[0183] The DSC analysis confirmed the thermal stability of the cellulose pulp, with exothermic peaks corresponding to the decomposition of organic matter in the pulp.

[0184] Thermal Analysis: Thermogravimetric analysis (TGA) was conducted on the specimens to determine their thermal stability and decomposition behavior. FIG. 3 shows the sample weight compared to the sample temperature, demonstrating the percentage of material that has decomposed at a given point. The TGA curve presented indicates the thermal decomposition behavior of the sample as it is heated from room temperature to 500 °C. Initially, there is a slight weight loss around 100 °C, which is typically associated with the evaporation of moisture or other volatile substances absorbed by the material. As the temperature increases from about 100 °C to 350 °C, the sample undergoes a more significant weight loss, likely due to the decomposition of organic components within the material, resulting in the release of volatile gases. This gradual decrease suggests a continuous breakdown of the sample's constituents. Beyond 350 °C, the rate of weight loss slows down, indicating that the remaining material is more thermally stable, possibly consisting of non-volatile residues or char that does not decompose further at the given temperature range. Overall, the curve reveals that approximately 7% of the sample's weight is lost due to thermal decomposition processes, highlighting the material's thermal stability and degradation characteristics..

[0185] After analyzing the TGA data to obtain a temperature range for the decomposition of the samples, differential scanning calorimetry (DSC) analysis was performed to determine the amount of heat required to increase the temperature of the material. The samples were hermetically sealed in aluminum pans and heated from 25 °C to 500 °C at a rate of 10 °C / min. FIG. 4 shows the DSC curve for one sample. The DSC curve presented shows the heat flow associated with the thermal transitions of the sample as it is heated from around 20 °C to 520 °C. Initially, there is a slight exothermic peak around 100 °C, which is often indicative of moisture loss or the release of volatile components. As the temperature continues to rise, a more pronounced endothermic peak is observed around 120 °C to 150 °C, likely corresponding to a phase transition, such as melting or glass transition. Following this, the curve shows a steady increase in heat flow, indicating ongoing thermal processes such as the decomposition of the material or further phase changes. The gradual increase in heat flow beyond 300 °C suggests that the material is undergoing a slow endothermic reaction, potentially related to the breakdown of more stable components or crystalline structures. The sharp rise near the end of the curve could indicate theATTORNEY DOCKET NO. 220214-2010 final decomposition or a significant phase change as the sample approaches 520 °C. This DSC curve provides insights into the thermal stability and transitions of the material under study, highlighting key temperatures where significant thermal events occur.

[0186] Thermogravimetric analysis (TGA) was conducted to assess the thermal decomposition behavior of cellulose extracted from pecan shells using NaOH / urea pretreatment. The TGA curve (Figure 18) shows an initial mass loss below 100 °C, corresponding to moisture evaporation. This is followed by a broader degradation range beginning near 250 °C and continuing beyond 350 °C, indicating the breakdown of cellulose polymer chains. The absence of distinct, sharp degradation peaks suggests a relatively amorphous structure, which is consistent with the alkaline / urea treatment and prolonged processing time used for this sample.

[0187] These thermal degradation characteristics are in line with reported values for regenerated cellulose and partially amorphous pulps. The sample demonstrates sufficient thermal stability for fiber processing methods such as solution spinning and drying, where controlled heating is applied. However, materials with higher crystallinity may be needed for high-performance applications requiring enhanced thermal resistance.

[0188] Thermogravimetric analysis (TGA) showed decomposition onset above approximately 330 °C, confirming thermal stability appropriate for bonding, drying, and sterilization steps used in nonwoven sheet manufacturing. Differential scanning calorimetry (DSC) revealed thermal transitions consistent with lignocellulosic content, including a moisture release peak around 85 °C and a broad glass transition signal centered at approximately 210 °C. These properties support thermal behavior suitable for nonwoven processing without the need for plasticizers.Example 9: FTIR Analysis

[0189] Fourier Transform Infrared Spectroscopy (FTIR) was used to analyze the chemical composition and quality of the fibers, identifying functional groups present in the cellulose.

[0190] FTIR analysis confirmed the presence of characteristic cellulose peaks at approximately 3300 cm-1(-OH stretching), 2900 cm-1(C-H stretching), and 1050 cm-1(C-O-C vibration). The reduction of lignin-associated peaks in the 1500-1600 cm-1range in treated samples confirmed effective delignification during pretreatment. In the FTIR spectrum of the pecan-derived cellulose pulp, a broad peak observed around 3330 cm-1corresponds to O-H stretching vibrations, characteristic of hydroxyl groups in cellulose. The absorption near 2900 cm-1represents C-H stretching of aliphatic groups. A peak around 1640 cm-1is associated with adsorbed water. The band near 1030 cm-1confirms C-O-C and C-0 stretching typical of polysaccharides, and theATTORNEY DOCKET NO. 220214-2010 peak around 895 cm-1indicates p-glycosidic linkages, confirming the cellulose backbone. The lack of prominent peaks near 1730 cm-1and 1510-1600 cm-1suggests efficient removal of hemicellulose and lignin, indicating successful purification.

[0191] Sample Composition: Fourier Transform Infrared Spectroscopy (FTIR) analysis was conducted to determine the composition and quality of the cellulose after extraction treatments. A small amount of each sample was added to the FTIR Spectrometer and then compared to a library of known materials.

[0192] FIG. 5 shows the absorbance on the y-axis and wavelength on the x-axis of the treated pecan fibers. The broad absorption band from 3000-3600 cm-1is characteristic for stretching vibration of O-H and C-H bonds in polysaccharides. This peak also includes intermolecular and intramolecular hydrogen bond vibrations in cellulose. The slight peak at 2905 cm'1shows the CH stretching vibration of the hydrocarbon components of polysaccharides. The bands observed from 900-1650 cm'1are typical of cellulose with the peak at 1645 cm'1corresponding to the water molecules absorbed in cellulose. The bands at 1368, 1264, 1157, 1022, and 894 cm1are representative of stretching and bending vibrations of -CH, -CH, -OH, and C-0 bonds present in cellulose molecules. The peak at 1368 cm'1is characteristic of the crystalline region of cellulose and the peak at 894 cm'1is characteristic of the amorphous region of cellulose.

[0193] The closest known match was determined to be xylan, shown in FIG. 6. The second closest match was rayon, shown in FIG. 7. Xylan is a type of hemicellulose consisting of xylose chains to form a polysaccharide. Rayon is a fabric made from regenerated cellulose, usually from wood pulp. These results indicate that the experimental, nutshell-derived sample is also cellulosic in nature. In FIG. 7, the intensity of the absorption bands is much lower for the nutshell-derived sample compared to rayon, suggesting that the bleaching process may have impacted the integrity of the fiber.

[0194] To complement nanoscale surface analysis, FTIR spectroscopy was conducted to confirm the chemical composition and purity of the extracted cellulose. FTIR analysis of cellulose extracted from nutshell biomass, including pecan, peanut, almond, and walnut shells, showed a strong O-H stretching band around 3330 cm'1, along with characteristic C-O-C linkages in the 1050-1160 cm'1region and a p-glycosidic peak near 895 cm'1, confirming the presence of cellulose. The absence of a peak near 1730 cm-1indicates effective removal of lignin and hemicellulose. The high absorbance intensity, particularly in the O-H region, suggests a high cellulose content, and the overall spectral profile supports the successful isolation of purified cellulose from nutshell-based biomass.ATTORNEY DOCKET NO. 220214-2010Example 10: XRD Analysis

[0195] X-ray diffraction (XRD) was used to evaluate the crystalline structure of cellulose extracted from various nutshells. The analysis helps determine the polymorphic form and relative crystallinity of the cellulose, which are important for assessing suitability for fiber production processes such as spinning and regeneration. Differences in peak sharpness and intensity reflect the variability in cellulose organization across different feedstocks.

[0196] FIG. 12A presents the XRD pattern of cellulose extracted from peanut shells. The diffraction profile shows broad peaks at approximately 16° and 22.5° 26, characteristic of the cellulose I polymorph. The relatively low intensity and broader shape of the peaks indicate reduced crystallinity and increased amorphous regions. This can enhance chemical accessibility and solubility, which may be beneficial for alkali- or solvent-based fiber processing methods.

[0197] FIG. 12B displays the XRD pattern of cellulose extracted from pecan shells. Like the peanut sample, peaks at around 16° and 22.5° 20 are consistent with cellulose I structure. However, the pecan-derived cellulose shows slightly sharper peaks than the peanut, suggesting a somewhat higher degree of crystallinity, though still moderate overall. This structure may offer a balance between structural integrity and reactivity during fiber formation.

[0198] FIG. 12C shows the XRD pattern of cellulose obtained from almond shells. The pattern includes sharp, well-defined peaks near 16° and 22.5° 20, clearly indicating a cellulose I crystalline form. The intensity and narrowness of these peaks suggest a high degree of crystallinity, reflecting a well-preserved native cellulose structure. This is typically favorable for generating strong fibers with desirable mechanical performance.

[0199] By analyzing the XRD patterns of cellulose extracted from almond, pecan, and peanut shells, it becomes clear that each feedstock offers distinct structural characteristics that can be leveraged for different fiber applications. Almond shells exhibit the highest crystallinity, as evidenced by sharper and more intense peaks corresponding to the cellulose I polymorph. This makes them ideal for applications requiring strong, dimensionally stable fibers, such as in apparel or technical textiles.

[0200] Pecan shells show moderate crystallinity, providing a balance between mechanical integrity and chemical reactivity. These fibers may be suitable for blended textiles or products requiring moderate strength with improved processability.

[0201] Peanut shells, with the lowest crystallinity and highest amorphous content, are particularly amenable to chemical modification and dissolution in solvent systems. This makes them favorableATTORNEY DOCKET NO. 220214-2010 for applications such as nonwovens, disposable products, or soft, absorbent textiles where fiber strength is less critical.

[0202] By using a variety of agricultural feedstocks, it becomes possible to tailor fiber properties to specific end-use requirements. This flexibility supports a modular production approach and opens pathways for multifunctional and high-performance bio-based textiles.

[0203] XRD confirmed the semi-crystalline structure of cellulose, with broad peaks observed at around 16° and 22.5° 20, consistent with cellulose I. Differences in crystallinity were observed across feedstocks. Peanut and pecan samples showed broader peaks, while almond demonstrated sharper profiles in preliminary trials.

[0204] X-ray diffraction (XRD) confirmed semi-crystalline cellulose in all nutshell-derived samples, primarily in the cellulose I polymorph, with characteristic peaks at -16° and -22.5° 20. Peak intensity and width varied by feedstock, reflecting different crystallinity levels. Almond- derived cellulose showed the highest crystallinity, while peanut and pecan samples exhibited broader peaks indicative of greater amorphous content. These findings are supported by complementary13C CP / MAS NMR data, which quantified -31% crystalline and -68% amorphous cellulose in the peanut sample. The material retains p-glucopyranosyl residues and a cellulose I backbone, confirming its suitability for dissolution and regeneration. Minor lignin signals observed in the spectrum suggest that further purification may improve fiber strength.Example 11 : Microscopy Analyses (SEM, AFM, and Optical Microscopy)

[0205] Microscopy analyses, including scanning electron microscopy (SEM), atomic force microscopy (AFM), and optical microscopy, were used to observe cellulose pulp, nanocellulose, and regenerated fibers for surface morphology, cross-sectional structures, and any porosity. Samples were prepared as appropriate for each technique, with SEM samples sputter-coated with a thin layer of gold / palladium before imaging. These analyses support the structural characterization discussed herein and help confirm the uniformity and integrity of the cellulose materials produced through different processes.

[0206] Optical microscopy was performed to evaluate the general morphology and dispersion of cellulose nanofibrils (CNF) derived from peanut shells. FIG. 18 shows the CNF network under transmitted light, revealing well-dispersed, fine fibrils with minimal aggregation. The uniform fibril distribution indicates successful mechanical disintegration and nanoscale separation, suitable for reinforcement in films, nonwovens, and composites.ATTORNEY DOCKET NO. 220214-2010

[0207] AFM was used to analyze the nanoscale surface structure of cellulose nanomaterials. FIG. 19 presents the AFM image of CNF from peanut shells, showing a web-like network of nanoscale fibrils with diameters typically below 50 nm. FIG. 20 shows AFM imaging of cellulose nanocrystals (CNC) from peanut shells, revealing rigid, rod-like structures with lengths in the 100-300 nm range and widths of approximately 5-20 nm. These topographical features confirm successful preparation of nanocellulose fractions with distinct morphologies and aspect ratios.

[0208] The physical characteristics of the extracted cellulose pulp were evaluated using SEM photography, revealing a uniform and smooth fiber structure suitable for textile applications.

[0209] SEM and Energy Dispersive Spectroscopy (EDS) were also employed to investigate the morphological and elemental characteristics of nanocellulose-functionalized cellulose pulp derived from pecan shells. These analyses provide critical insight into the surface structure and chemical composition of the material, validating the effectiveness of the functionalization process and its suitability for advanced bio-based material applications. FIG. 15 shows the SEM micrograph of nanocellulose-functionalized cellulose pulp. The image reveals a densely entangled fibrous matrix with a rough, textured surface and numerous embedded angular particulates. These particulates likely correspond to residual inorganic compounds or aggregated nanocellulose introduced during processing. The absence of smooth regions and the presence of fine surface features indicate effective fibrillation and high surface area, both of which are characteristic of cellulose modified with nanocellulose. This microstructure suggests enhanced interfibrillar interaction potential and increased reactivity, which are desirable traits for further processing into nonwovens, films, or composites.

[0210] As shown in FIGs. 8A-8B, SEM and AFM analysis of CNF-coated cellulose pulp reveals a uniform deposition of nanoscale fibrils across the surface, forming a dense, interwoven network. AFM confirms this structure, showing nanoscale topography with a root mean squared roughness of 9.17 nm. The resulting high-surface-area coating is expected to contribute to enhanced adhesion, wettability, and barrier function in single-use nonwoven products.

[0211] FIG. 21 presents an SEM image of a regenerated cellulose fiber produced from nutshell- derived pulp. The fiber exhibits a distinct textured surface morphology, resulting from controlled regeneration and drying conditions. This increased surface roughness can improve interfacial bonding in composite applications, enhance dye uptake in textiles, and provide greater potential for surface functionalization, such as antimicrobial or hydrophobic coatings. The irregular surface features may indicate underlying microfibrillar structures, contributing to tailored mechanical properties. This morphology highlights the tunability of the process, where adjustments toATTORNEY DOCKET NO. 220214-2010 spinning and coagulation parameters can produce fibers with surface characteristics optimized for specific high-performance or specialty uses.Example 12: EDS Analysis

[0212] To further examine the surface chemistry and elemental distribution of the functionalized pulp, EDS mapping was performed. Elemental maps in FIG. 16 illustrate the spatial distribution of chlorine (Cl), oxygen (O), sodium (Na), carbon (C), and calcium (Ca) across the sample surface. As expected, carbon and oxygen, the primary elements of cellulose, are uniformly distributed throughout the structure. Minor elements such as calcium and chlorine appear more localized, potentially indicating sites of chemical modification or interaction with reagents. Sodium presence may be attributed to ionic species used in the functionalization process or residual salts from washing steps.

[0213] A composite EDS layered elemental map (not shown) alongside its corresponding EDS spectrum confirms the co-localization and dispersion of detected elements and provides a semi- quantitative analysis of elemental composition. The EDS spectrum reveals oxygen (42.3 wt%) and carbon (41.6 wt%) as the dominant constituents, consistent with the organic nature of cellulose. The presence of chlorine (7.3 wt%), sodium (6.4 wt%), and calcium (1.9 wt%) further supports the hypothesis that residual reagents or functional additives are embedded within the structure. These trace elements are not uniformly distributed, suggesting selective interaction with specific sites or domains on the pulp surface.

[0214] Collectively, these imaging and compositional results confirm the successful surface modification of the cellulose pulp with nanocellulose. The observed structural complexity and elemental composition reflect the integrity of the functionalization process and demonstrate the material’s potential for use in sustainable, high-performance applications such as biodegradable textiles, absorbent materials, bio-composites, or nonwoven products.Example 13: NMR Analysis

[0215] To assess cellulose structure and purity, solid-state13C cross-polarization magic angle spinning nuclear magnetic resonance (13C CP / MAS NMR) was conducted on selected samples. Approximately 50-70 mg of dried cellulose was hydrated to 50% moisture content and packed into 4 mm ZrO2MAS rotors. Spectra were collected using a Bruker AVANCE Neo 600 MHz spectrometer at 298 K and 10 kHz MAS rate. The1H field strength was 89 kHz with a 2 ms contact time and 1.5 s recycle delay. Each spectrum consisted of 25,000-30,000 scans and covered aATTORNEY DOCKET NO. 220214-2010293 ppm spectral width. Chemical shifts were externally referenced to the adamantane CH2signal at 38.48 ppm.

[0216] Preliminary13C-NMR spectra confirmed the expected cellulose backbone resonances and indicated minimal contamination from residual hemicellulose or extractives in the purified materials. The relative contents of crystalline and amorphous cellulose regions were determined by deconvoluting the C4 region of the spectra. Because the C4 region overlaps with lignin signals, a correction was applied to the amorphous signal using the following equations:The percentage of crystalline and amorphous cellulose was then calculated as:Crystaline cellulose”~“X100a rp u ysfcaihne

[0217] These values offered insight into the degree of order and molecular packing within each sample, supporting ongoing optimization of pretreatment conditions.

[0218] Solid-state13C CP / MAS NMR (FIG. 13) was conducted to examine the structural composition and crystallinity of cellulose extracted from pecan and peanut shells. The spectra display characteristic peaks corresponding to cellulose carbon atoms C1 through C6. The peaks in the region of 80 to 90 ppm, especially those assigned to C4, along with the signals near 65 to 75 ppm for C6, provide information on the ratio of crystalline to amorphous content.

[0219] The pecan cellulose spectrum shows broader peaks and more prominent amorphous signals, indicating relatively low crystallinity. This result is consistent with the NaOH / urea treatment and extended processing duration used in this preparation. Reduced crystallinity can be beneficial in applications where solubility, reactivity, and flexibility are required, such as in certain regenerated or blended fibers.

[0220] For high-performance fiber applications, higher crystallinity is often preferred to improve mechanical strength and durability; these criteria can be met by varying extraction conditions.ATTORNEY DOCKET NO. 220214-2010

[0221] To better quantify the crystalline and amorphous domains in the peanut-derived cellulose, we performed spectral deconvolution of its13C CP / MAS NMR spectrum (FIGs. 14A-14B). The fitted peaks corresponding to the C1 through C6 carbons enable clear differentiation between structural regions. Peaks in the 86 to 89 ppm range are associated with crystalline cellulose, while signals around 80 to 84 ppm represent amorphous regions. The intensity and distribution of these peaks confirm a mixed structure, with both ordered and disordered cellulose present. This balance may support efficient processing while maintaining sufficient mechanical properties for fiber production.

[0222] Similarly, spectral deconvolution was applied to the13C CP / MAS NMR spectrum of pecan- derived cellulose. The fitted peaks show a stronger presence of amorphous content, particularly in the 80 to 84 ppm region. Crystalline signals around 86 to 89 ppm are still detectable but less pronounced than in the peanut sample. This supports the observation that the cellulose structure from pecan shells treated with NaOH / urea under longer conditions is more disordered. While lower crystallinity may reduce mechanical strength, it improves solubility and reactivity, which can be beneficial for certain fiber processing methods and applications. These findings highlight the opportunity to fine-tune cellulose structure through feedstock choice and processing conditions, allowing targeted development of fibers for both high-performance and functional applications.Example 14: Textile Processing Techniques

[0223] High-performance nonwoven sheets were fabricated using the techniques of carding, wet- laid formation, and needle-punching.

[0224] Carding. The dry-laid carding technique is commonly employed for the production of hygiene-related nonwoven products. This process uses a series of carding machines to open, blend, individualize, and parallelize fibers before laying them into a web. For this project, industrystandard fiber lengths of 3.80 cm, 4.80 cm, and 5.10 cm were evaluated, along with fiber diameters ranging from 5-30 pm. The effects of varied roller speed ratio, feed rate, carding angle, and wire density on fiber alignment, web density, and uniformity in the resulting fiber sheets were investigated.

[0225] Wet-laid formation. Wet-laid techniques are widely used in applications such as surgical gowns, wound dressing backings, and disposable face masks. This process, which parallels traditional papermaking, uses water as a medium to disperse fibers and create a slurry, which is then deposited onto a porous screen to form a uniform fiber web. For this project, fibers with lengths ranging from 5 to 10 mm and diameters between 5 and 20 pm were prepared to minimizeATTORNEY DOCKET NO. 220214-2010 defects like “dumbbell” and “double-knub” formations and enhance slurry dispersion. Fiber suspension concentration and drainage rate were systematically varied to improve fiber distribution, web uniformity, and mechanical performance. After web formation, the material was dewatered, dried, and bonded to produce cohesive nonwoven fabrics.

[0226] Needle-Punching. Needle-punching is a dry, nonwoven process that mechanically interlocks fibers using barbed needles. In medical applications, it is typically used for bandages and dressings that require bulk and cushioning. For this project, needle-punched sheets were produced from fibers ranging from lengths of 25-60 mm and diameters between 10 and 30 pm. The fibers were formed into a loose web, which was then processed in a needle loom containing thousands of barbed needles to create the entangled structure. Needle parameters such as penetration depth, stroke frequency, and needling pattern were varied to identify the optimal conditions for fiber entanglement and web integrity.

[0227] Electrospinning produces ultrafine fibers (< 5 pm) by applying a strong electric field to a polymer solution, enabling the creation of highly porous nonwoven fabrics that are ideal for medical filtration applications, including surgical masks and wound dressings. However, electrospinning lignocellulosic materials is challenging due to their complex, heterogeneous composition, and limited solubility in common solvents, which hinder jet stability for consistent fiber formation. To address this, two cellulose solvent systems were explored: a NaOH / urea aqueous system and an N-Methylmorpholine N-oxide (NMMO) solvent system. The NaOH / urea system is environmentally friendly and cost-effective, but requires optimization to achieve the viscosity and conductivity necessary for electrospinning. NMMO, a biodegradable solvent widely used in Lyocell fiber production, offers strong cellulose solubility and favorable fiber-forming properties while aligning with the project's sustainability goals. Green solvent alternatives, such as ionic liquids and deep eutectic solvents (DESs), which offer cellulose solubility with low environmental impact, were also investigated.

[0228] Solvent use and recovery: N-methylmorpholine N-oxide (NMMO) was used as the primary solvent for cellulose dissolution due to its effectiveness, low toxicity, and recyclability. An 85% NMMO solution was prepared using deionized water, and propyl gallate was added as a stabilizer. Cellulose was gradually incorporated into the solution while being heated between 90 and 120 °C, with constant stirring to ensure homogeneity. Once a viscous, clear cellulose-NMMO dope was formed, the mixture was used in spinning trials.

[0229] To support a circular process, solvent recovery was integrated into the workflow. After wet spinning, the coagulation bath containing water and dissolved NMMO was filtered using vacuumATTORNEY DOCKET NO. 220214-2010 filtration to remove solid particles. The filtered solution was transferred to a rotary evaporator and processed at 50 °C with a flask rotation speed of 100 rpm to remove water and concentrate the NMMO. The evaporation process continued until the solution reached approximately 80 to 90 percent NMMO by weight. The recovered solvent was assessed by pH measurement, which remained consistently around pH 9 and was reused in subsequent spinning without noticeable loss in dissolution performance.

[0230] In addition to NMMO, two ionic liquids were proposed and explored as alternative green solvents for cellulose processing: choline acetate and ethylammonium nitrate (EAN). These solvents are known for their low toxicity and biodegradability and have been reported to effectively dissolve cellulose. However, during preliminary testing, NMMO demonstrated superior dissolution behavior and compatibility with the biomass-derived material.

[0231] To achieve fiber diameters below 5 pm, key electrospinning parameters were systematically varied, including polymer concentration, solution conductivity, applied voltage, flow rate, tip-to-collector distance, and environmental conditions such as temperature and relative humidity. Fiber morphology, diameter distribution, and structural uniformity were assessed using SEM.Example 15: Antimicrobial Performance

[0232] For antimicrobial testing, preliminary screening with green tea-derived silver nanoparticles produced visible inhibition zones against E. coli.

[0233] Antimicrobial performance is essential for nonwoven medical textiles, and agricultural byproducts such as pecan, walnut, and peanut shells offer a natural source of antimicrobial and antioxidant phenolic compounds. The potential of functionalized nanocellulose hydrogels to enhance the inherent antimicrobial properties of lignocellulosic fibers for use in nonwoven fabrics was evaluated.

[0234] The use of antimicrobial functionalized nanocellulose hydrogels was investigated to add antimicrobial properties to our nonwoven fabrics. Silver nanoparticles or chitosan were encapsulated within the hydrogel matrix using ionic crosslinking and in situ reduction methods, depending on the antimicrobial agent. For silver, nanoparticles were synthesized directly within the hydrogel network using a green reduction approach (e.g., using plant extracts or mild reducing agents). For chitosan, ionic crosslinking with agents such as sodium tripolyphosphate was used to form stable gels. Effective functionalization is predominantly dependent on encapsulation stability and gel-to-functional particle ratio, which was evaluated using UV-Vis spectroscopy (forATTORNEY DOCKET NO. 220214-2010 silver nanoparticle dispersion), FTIR spectroscopy (for chitosan bonding), and dynamic light scattering (DLS) to assess particle size and distribution. A dip-coating technique was used to apply the hydrogels to our fibers prior to sheet manufacturing. Sheets were manufactured using carding, wet-laid formation, needle-punching, and electrospinning techniques as described previously. These hydrogel-coated fabrics were further tested for antimicrobial performance, uniformity, and coating durability.

[0235] Antimicrobial properties were tested using the standard methods published by the Clinical Laboratory Standards Institute. Coating uniformity and morphology were evaluated using SEM, and adhesive efficacy was evaluated using T-peel tests. Antimicrobial efficacy under dynamic contact conditions was assessed by treating samples with the Escherichia coli (ATCC 8739) bacterial strain for 3-4 days and comparing bacterial count to an untreated sample (ASTM E2149). ASTM E2149 standard testing was performed both before and after abrasion testing (ASTM D4966-12, ISO 12947).

[0236] To benchmark performance, commercially available control materials were included in the testing regime, including standard N95 filtration media, ASTM Level 3 surgical gown fabric, and a representative wound dressing substrate. These materials underwent the same testing procedures to provide comparative performance thresholds and validate our test setup under consistent dynamic conditions.Example 16: Assessment of Biodegradation

[0237] The biodegradability of the developed nonwoven textiles was assessed to refine material formulations and ensure compatibility with industrial composting systems. The aerobic biodegradation profile of the developed nonwoven materials was assessed through a respirometric CO2evolution study using the Micro-Oxymax system (Columbus Instruments). Using this system, we quantified microbial CO2generation under aerobic conditions (58 °C, 50% moisture content) to provide a direct measure of biodegradability over time (ASTM D5338, ISO 14855-1 , and EN 13432). CO2evolution was monitored continuously for up to 90 days. Cellulose powder was included as a positive control, and non-biodegradable PP was included as a negative control to benchmark mineralization performance.

[0238] For biodegradation studies, a Micro-Oxymax respirometer system (Columbus Instruments) enabled precise measurement of CO2evolution under aerobic conditions. This system was used to quantify mineralization rates and compare biodegradation behavior acrossATTORNEY DOCKET NO. 220214-2010 different formulations and feedstocks. Testing was conducted under controlled temperature and humidity to simulate both industrial composting and natural soil environments.Example 17: Mechanical Testing

[0239] Functional performance of nonwoven sheets. Fiber distribution, uniformity, and density across all samples were assessed using scanning electron microscopy (SEM). Tensile strength and elongation at break were measured according to ASTM D5035 (strip method). Tear strength was evaluated using the ISO 9073-4 trapezoid method, which determines the maximum force required to propagate a tear in the fabric under vertical tension. Bursting strength was assessed by measuring the force required to rupture a nonwoven sheet (ASTM D3786). To assess durability, abrasion and pilling resistance testing were conducted using the Martindale method (ASTM D4966-12, ISO 12947), which involves rubbing the fabric against a standard abrasive under controlled motion. Sheet puncture resistance was measured using ASTM D4833 (Standard Test Method for Index Puncture Resistance of Geomembranes and Related Products), which quantifies the force required to puncture the sheet with a defined probe.

[0240] Bursting strength was measured by measuring the force required to burst a nonwoven sheet until it bursts (ASTM 3786). The Martindale abrasion test was used to measure the abrasion and pilling resistance of our fabric by rubbing a fabric sample against a standard abrasive surface in a controlled, repetitive motion (ASTM D4966-12, ISO 12947).Mechanical Testing (Tensile Strength, Elongation)

[0241] Tensile strength and elongation were evaluated using dry-formed sheets and films and individual fibers produced from the extracted cellulose. Samples were tested with an Instron universal testing machine under ambient conditions. Mechanical testing was conducted to evaluate the tensile performance of dry-formed cellulose sheets produced from pecan shell- derived fibers. The optimized formulation without additives demonstrated tensile strength values between 3.2 and 4.8 MPa, with elongation at break between 8 and 13 percent. Blends incorporating nanocellulose improved tensile strength to as high as 5.5 MPa and showed more consistent elongation performance. Single-fiber tensile tests indicated strength values ranging from 250 to 380 MPa with elongation between 4 and 7 percent, consistent with literature values for regenerated cellulose fibers. These results are consistent with other structural analyses, including intrinsic viscosity, XRD, and13C CP / MAS NMR, which indicate moderately crystalline cellulose with sufficient molecular weight and polymer chain integrity. The combination ofATTORNEY DOCKET NO. 220214-2010 crystalline and amorphous regions supports both mechanical strength and flexibility, reinforcing the material’s suitability for applications such as hygiene textiles, wipes, and packaging.Example 18: Optical Brightness Testing

[0242] The brightness of the bleached cellulose sheets was evaluated using a calibrated spectrophotometer in accordance with TAPPI T 452 om-08, which measures the reflectance of blue light at 457 nm.

[0243] The bleached samples exhibited brightness values ranging from 48 to 62 percent ISO, depending on the feedstock and bleaching efficiency. These values reflect inherent differences in pigment retention and lignin content across agricultural byproducts, even after bleaching.Example 19: Filtration Applications

[0244] Due to their ultra-fine fiber structure (< 5 pm diameter), electrospun fabrics developed as described previously were utilized for filtration development to achieve high efficiency and fine particulate capture. The filtration and medical properties (filtration efficiency, air permeability, fluid resistance, and biocompatibility) were investigated before and after application of a chitosan- based coating for enhanced filtration efficiency.

[0245] A chitosan coating was formulated and applied onto electrospun fabrics to leverage chitosan’s natural cationic properties for improved electrostatic particle capture. To prepare the fabric for chitosan coating, it was first treated with the cationic reagent N-(3-chloro-2- hydroxypropyl)trimethylammonium chloride (CHPTAC) to enhance surface charge and binding affinity. A low-viscosity chitosan solution was then applied, followed by thermal drying at 80-100 °C. UV irradiation was used to cure the coating, ensuring complete crosslinking and uniform adhesion across the fabric surface.

[0246] Filtration performance was evaluated according to standards for medical face masks with and without the chitosan-based coating. Particle filtration efficiency (ASTM F2299) was tested using aerosolized particles (0.1-0.3 pm) to determine the percentage captured by the fabric. Airflow resistance was measured in accordance with ASTM F2100 by passing a defined airflow through the material and recording the resulting pressure drop. Fluid barrier resistance was assessed using the synthetic blood penetration test (ASTM F1862), in which synthetic blood was projected at the fabric under controlled pressure.

[0247] Filtration efficiency, antimicrobial activity, or mechanical integrity can be tuned by altering several variables within the chitosan coating process, including: 1) the concentration of chitosanATTORNEY DOCKET NO. 220214-2010 in solution (ranging from 0.5% to 2.0% w / v); 2) The molecular weight and degree of deacetylation of chitosan, which influence its charge density and film-forming ability; 3) The application method, including dip coating, spray coating, or electrostatic deposition, to control layer thickness and uniformity; 4) The pH and ionic strength of the coating solution, which affect the interaction between chitosan and the fiber surface.Example 20: Beauty / Personal Care Applications

[0248] Preparation of biodegradable cosmetic and personal care products using nutshell-derived cellulose, nanocellulose (CNF and CNC), and lignin. In one embodiment, a biodegradable facial mask sheet was produced by blending a nanocellulose hydrogel with moisturizing agents (e.g., glycerin, aloe vera extract) and casting into a nonwoven sheet using a wet-laid process. The sheet exhibited high liquid absorption capacity (>10 g water / g dry sheet) and retained structural integrity after 30 minutes of continuous skin contact. In another embodiment, nutshell-derived CNF and CNC were incorporated into cosmetic creams, lotions, shampoos, and conditioners at concentrations of 0.5-3% by weight, functioning as natural thickeners, stabilizers, and filmforming agents. Products demonstrated stable viscosity after 90 days at 40 °C, improved moisture retention, and a smooth sensory profile. All products were fully biodegradable, with solid formulations composting within 45 days under home composting conditions.Example 21 : High-Performance and Smart / Conductive Textile Applications

[0249] In certain embodiments, the cellulose nanofibers (CNFs) and / or cellulose nanocrystals (CNCs) derived from nutshells or nut hulls were incorporated into yarns, fabrics, or composites designed for high-performance applications. The CNFs and CNCs were combined with conductive particles, such as carbon nanotubes, graphene, silver nanoparticles, or conductive polymers, to produce textiles capable of electrical conductivity, sensing, or electromagnetic shielding. These smart or functionalized textiles can be adapted for wearable electronics, health monitoring devices, and responsive garments. In addition, the incorporation of CNFs and CNCs into fiber matrices can improve mechanical strength, abrasion resistance, and impact resistance, enabling use in protective clothing, outdoor gear, ballistic fabrics, aerospace materials, sports equipment, and marine applications..Example 20: Life Cycle Analysis

[0250] A simplified life cycle analysis (LCA) (ISO 14040 / 44) was conducted to compare the nutshell-based nonwoven textiles with conventional polypropylene (PP) nonwovens across the following key metrics: 1) raw material sourcing, 2) energy processing, and 3) end-of-life impact.ATTORNEY DOCKET NO. 220214-2010Raw material input (including fossil resource use, land, and water demand where applicable), total energy demand (with a breakdown of renewable vs. nonrenewable sources), and greenhouse gas emissions were quantified across the product life cycle. Processing energy demand was determined using direct measurements from fiber production, including electricity and thermal energy consumption (kWh / kg output), and greenhouse gas emissions were modeled using tools such as SimaPro or OpenLCA. End-of-life impacts were assessed based on biodegradation potential and the likelihood of microplastic generation. Microplastic shedding was assessed under simulated use and disposal conditions (mechanical agitation, airflow, and composting exposure) using vacuum filtration and spectroscopic analysis (FTIR) to detect and characterize any released particles.

[0251] A preliminary life cycle analysis (LCA) was conducted to assess the environmental footprint of our fiber production process from agricultural byproducts such as pecan and peanut shells. This initial assessment focuses on key sustainability indicators, including resource use, process circularity, and emissions intensity.

[0252] The disclosed process is designed for low-impact, circular production. Laboratory-scale testing indicates that approximately 80 percent of the water used in the process is recovered and reused after filtration and distillation. For the solvent-based method using NMMO, solvent recovery is around 90 percent, reducing both environmental impact and cost. This closed-loop system compares favorably to traditional synthetic fiber production, which typically involves higher losses of solvent and water.

[0253] Energy use is estimated at 6 to 8 kilowatt-hours per kilogram of fiber produced, accounting for heating, stirring, and solvent recovery. This energy input is aligned with that of other sustainable cellulose fiber processes and is lower than many fossil-derived alternatives, such as polyester or nylon.

[0254] The average fiber yield from raw nutshell feedstock is between 40 and 50 percent, depending on the shell type. The remaining material, composed largely of lignin and hemicellulose, could be further utilized in future phases to minimize waste. At present, process waste is approximately 0.2 to 0.4 kilograms per kilogram of fiber produced.

[0255] It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the abovedescribed embodiment(s) without departing substantially from the spirit and principles of theATTORNEY DOCKET NO. 220214-2010 disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.

Claims

ATTORNEY DOCKET NO. 220214-2010CLAIMSWhat is claimed is:

1. A material comprising cellulose, lignin, lignocellulosic material, or any combination thereof, extracted from nutshells or nut hulls.

2. The material of claim 1 , wherein the nutshells or nut hulls comprise pecan, peanut, cashew, walnut, hazelnut, pistachio, or almond shells or hulls, or any combination thereof.

3. The material of claim 1 , wherein the material is processed into nanocellulose selected from cellulose nanofibrils (CNF), cellulose nanocrystals (CNC), or any combination thereof.

4. A biodegradable fiber comprising the material of claim 1.

5. The biodegradable fiber of claim 4, wherein the nutshells or nut hulls comprise pecan, peanut, cashew, walnut, hazelnut, pistachio, or almond shells or hulls, or any combination thereof.

6. The biodegradable fiber of claim 4, wherein the nutshells or nut hulls comprise agricultural waste.

7. The biodegradable fiber of claim 4, further comprising a nanocellulose hydrogel.

8. The biodegradable fiber of claim 7, wherein the nanocellulose hydrogel comprises a homogenized cellulosic pulp.

9. The biodegradable fiber of claim 8, wherein the homogenized nanocellulosic pulp comprises at least one material sourced from a low-value waste stream.

10. The biodegradable fiber of claim 9, wherein the low-value waste stream comprises cotton noil, woody pulp from paper production, or any combination thereof.

11. The biodegradable fiber of claim 9, wherein the homogenized nanocellulosic pulp comprises cellulose nanofibrils (CNF), cellulose nanocrystals (CNC), or any combination thereof.

12. The biodegradable fiber of claim 7, wherein the nanocellulose hydrogel further comprises carboxymethyl cellulose.

13. The biodegradable fiber of claim 7, wherein the nanocellulose hydrogel is chemically or physically functionalized to impart at least one additional property to the biodegradable fiber.

14. The biodegradable fiber of claim 7, wherein the biodegradable fiber comprises cellulose and lignin derived from nutshells or nut hulls, wherein the lignin serves as a structural, binding, or functional additive.ATTORNEY DOCKET NO. 220214-201015. The biodegradable fiber of claim 14, wherein the lignin is modified by sulfonation, acetylation, oxidation, or any combination thereof to enhance compatibility with polymers, coatings, or composites.

16. The material of any one of claims 1-3 or the biodegradable fiber of claims 4-15, wherein the material or the biodegradable fiber is antimicrobial, biocompatible, compostable, or any combination thereof.

17. The biodegradable fiber of claim 4, wherein the fiber is functionalized to provide flame retardancy, thermal insulation, thermoregulation, combinations thereof.

18. The biodegradable fiber of claim 4, further comprising polylactic acid (PLA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), or any combination thereof.

19. A nanocellulose material derived from nutshells or nut hulls, wherein the nanocellulose material comprises CNF, CNC, or both, and wherein the nanocellulose material comprises particles having a diameter between 1 nm and 500 nm.

20. The material of claim 1 , wherein the material comprises lignin and wherein the lignin is recovered in powder, resin, particulate, or liquid form.

21. A method for producing a cellulose, lignin, lignocellulosic, or nanocellulose material from nutshells or nut hulls, the method comprising:(a) cleaning and preparing nutshells or nut hulls; and(b) performing one or more chemical, mechanical, enzymatic, or thermal processes to extract cellulose, lignin, or both.

22. The method of claim 21 , further comprising: (c) converting the extracted material into nanocellulose selected from CNF and / or CNC.

23. A method for producing a biodegradable fiber, the method comprising:(a) performing one or more chemical or mechanical processes on nutshells or nut hulls to extract lignocellulosic material;(b) optionally separating cellulose and lignin fractions;(c) dissolving the lignocellulosic material in a solvent to produce a spinning solution;(d) extruding the spinning solution through one or more spinnerets; andATTORNEY DOCKET NO. 220214-2010(e) forming the biodegradable fiber in a coagulation bath, wherein the coagulation bath comprises a coagulation solvent.

24. The method of claim 23, wherein the nutshells or nut hulls are pecan, peanut, almond, walnut, cashew, hazelnut, or pistachio shells or hulls, or any combination thereof.

25. The method of claim 23, wherein the nutshells or nut hulls are cleaned, dried, or both prior to performing step (a).

26. The method of claim 23, wherein one or more chemical or mechanical processes comprise treating with an extraction solvent solution, filtration, bleaching, milling, grinding, or any combination thereof.

27. The method of claim 26, wherein the extraction solvent solution comprises sodium hydroxide, potassium hydroxide, lithium hydroxide, or any combination thereof in water.

28. The method of claim 26, wherein treating with the extraction solvent solution is carried out at about 70 °C.

29. The method of claim 26, wherein bleaching is repeated one or more additional times.

30. The method of claim 26, wherein the solvent in the spinning solution comprises an ionic liquid, a green solvent, or any combination thereof.

31. The method of claim 30, wherein the ionic liquid comprises 1-ethyl-3-methylimidazolium acetate (EMIM Ac), 1-butyl-3-methylimidazolium chloride (BMIM Cl), a choline-based ionic liquid, or any combination thereof.

32. The method of claim 31, wherein the choline-based ionic liquid comprises choline acetate.

33. The method of claim 30, wherein the green solvent comprises N-methylmorpholine-N-oxide.

34. The method of claim 23, further comprising admixing a nanocellulose hydrogel into the spinning solution prior to performing step (c).

35. The method of claim 34, wherein the nanocellulose hydrogel comprises a homogenized cellulosic pulp.

36. The method of claim 35, wherein the homogenized nanocellulosic pulp comprises at least one material sourced from a low-value waste stream.

37. The method of claim 36, wherein the low-value waste stream comprises cotton noil, woody pulp from paper production, or any combination thereof.ATTORNEY DOCKET NO. 220214-201038. The method of claim 46, wherein the homogenized nanocellulosic pulp comprises cellulose nanofibrils (CNF), cellulose nanocrystals (CNC), or any combination thereof.

39. The method of claim 34, wherein the nanocellulose hydrogel further comprises carboxymethyl cellulose.

40. The method of claim 34, further comprising chemically or physically functionalizing the nanocellulose hydrogel prior to admixing it into the spinning solution to impart at least one additional property to the biodegradable fiber.

41. The method of claim 23, wherein step (c) is performed using wet spinning, dry jet wet spinning, electrospinning, or any combination thereof.

42. The method of claim 23, wherein the coagulation solvent comprises water, ethanol, or any combination thereof.

43. The method of claim 23, further comprising recovering the coagulation solvent from the coagulation bath.

44. The method of claim 23, further comprising isolating lignin from the nutshell or nut hull feedstock for use as a binder, antioxidant, UV stabilizer, carbon precursor, or polymer additive.

45. A biodegradable fiber, cellulose pulp, lignin, or nanocellulose produced by the method of claim 23.

46. A yarn comprising the biodegradable fiber of claim 4.

47. The yarn of claim 46, further comprising polylactic acid (PLA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), or any combination thereof.

48. A textile comprising the biodegradable fiber of any one of claims 4-18 or 45 or the yarn of claim 46 or 47.

49. The textile of claim 48, wherein the textile comprises a woven textile, a non-woven textile, or a knitted textile.

50. The textile of claim 47, further comprising polylactic acid (PLA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), or any combination thereof.

51. The textile of claim 49, wherein the non-woven textile is formed by co-spinning or layering the biodegradable fiber with one or more fibers selected from polylactic acid (PLA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), or any combination thereof.ATTORNEY DOCKET NO. 220214-201052. The textile of claim 49, wherein the woven textile or knitted textile comprises at least one yarn spun from a blend of the biodegradable fiber and one or more fibers selected from polylactic acid (PLA), polyhydroxyalkanoate (PHA), polycaprolactone (PCL), or any combination thereof.

53. The textile of claim 49, wherein the woven textile or knitted textile comprises at least one yarn spun from a blend of the biodegradable fiber and a synthetic fiber.

54. A composite material comprising the biodegradable fiber of any one of claims 4-18 or 45 or the material of any one of claims 1-3.

55. The composite material of claim 54, further comprising nutshell-derived lignin as a matrix component, compatibilizer, or reinforcement agent.

56. The composite material of claim 54, wherein the composite material is reinforced for use in an automotive application, a marine application, an aerospace application, a construction application, or any combination thereof.

57. An article comprising the composite material of claim 54.

58. The article of claim 57, wherein the article comprises an electrical or electronic device, a smart textile, a flexible circuit, or electromagnetic interference (EMI) shielding.

59. A coating or film comprising the material of any one of claims 1-3, wherein the coating or film comprises packaging or a layer of packaging, a barrier layer, surface functionalization for an article, a beauty or personal care product, or any combination thereof.

60. The coating or film of claim 59, wherein the barrier layer provides moisture resistance, oxygen resistance, or grease resistance.

61. An article comprising the biodegradable fiber of any one of claims 4-18 or 45 or the material of any one of claims 1-3.

62. The article of claim 61 , wherein the article comprises an article of clothing, a curtain, a bed sheet, a towel, a rug, a blanket, luggage, a handbag, furniture, a bioplastic, automotive upholstery, marine upholstery, aircraft upholstery, an article of footwear, athletic equipment, a watch band, composite panel, molded part, coating, packaging material, medical device, a cosmetic or personal care product, a high-performance textile, or any combination thereof.

63. The article of claim 62, wherein the article comprises a medical device, wound dressing, filtration media, sutures, surgical mask, surgical gown, tissue scaffold, absorbent pad, or geotextile.ATTORNEY DOCKET NO. 220214-201064. The article of claim 62, wherein the article comprises a molded, extruded, or laminated composite containing nutshell-derived cellulose, lignin, or nanocellulose.

65. The article of claim 62, wherein the cosmetic or personal care product comprises a facial mask sheet, cleansing pad, makeup applicator, body scrub applicator, hair treatment wrap, or any combination thereof.

66. The article of claim 62, wherein the packaging material comprises a molded container, bottle, cap, film, liner, coating, pouch, or any combination thereof.

67. The article of claim 62, wherein the article comprises a water purifier or water filter.

68. The article of claim 62, wherein the article comprises paper, board, or another molded pulp product.

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