Articles of manufacture containing nanocellulose elements

Abstract

The present invention provides formulations comprising a suspension of nanocellulose (NC) elements and a drying / dispersing additive selected from the group consisting of temperature responsive polymers, small molecule additives in volatile systems and blocking agents, as well as methods of preparing such formulations, and further provides NC-containing materials, composite materials and useful articles of manufacture made therefrom.

Description

[Technical field]

[0001] Related Applications This application claims the benefit of U.S. Provisional Application No. 63 / 208,577, filed June 9, 2021, U.S. Provisional Application No. 63 / 219,686, filed July 8, 2021, and U.S. Provisional Application No. 63 / 309,730, filed February 14, 2022. The entire contents of the above applications are incorporated herein by reference.

[0002] FIELD OF THEINVENTION The present application relates to nanocellulosic materials. [Background technology]

[0003] 2. Background of the Invention Cellulose, the main building block of wood and plant fibers, is an abundant resource for the paper, textile and chemical industries. It is a high molecular weight homopolymer of 1,4-linked β-D-glucopyranose units with each unit rotated 180° with respect to adjacent units. Each monomeric glucopyranose unit contains three hydroxyl groups that present themselves on alternate opposite faces of the polymer due to the rotational pattern of the linear arrangement of the hydroxyl groups within the polymer. The alternating orientation of the hydroxyl groups along the length of the cellulose molecule allows single chains of cellulose to readily form hydrogen bonds with adjacent polymer chains. These hydrogen bonds allow the formation of stable, strong, tightly bound multi-chain complexes.

[0004] In biological systems, individual polymeric cellulose molecules form larger units with similar molecules. Biosynthesis in plants can tightly bind about 36 individual molecules together, thereby forming the most basic building blocks of plant cell walls. These building blocks are called elementary fibrils (also called microfibrils). Elementary fibrils formed during cellulose biosynthesis in biological entities can be about 5 nm in diameter and several micrometers long. Each elementary fibril is a flexible, elongated strand composed of crystalline regions of cellulose interspersed with disordered, amorphous domains of cellulose. The crystalline regions are segments of cellulose chains that are rigidly stabilized by a strong intersecting network of hydrogen bonds; the amorphous regions are more flexible while still being held together by hydrogen bonds. These elementary fibrils (microfibrils) are packed together in biological systems to form larger units called microfibrillated cellulose, which have diameters in the range of about 20-50 nm. In biological systems, microfibrillated cellulose units are aggregated and linked via hemicellulose moieties and embedded within a pectin matrix to form the visible cellulose fibers found in plant cell walls.

[0005] The structure of basic cellulose fibrils and microfibrillated cellulose allows two distinct cellulose forms to be extracted from plant-derived cellulose raw materials. Crystalline cellulose can be extracted in granular form to produce products called cellulose nanocrystals or cellulose microcrystals depending on the size of the particles. Cellulose can also be extracted as fibers to produce products called cellulose nanofibers or cellulose microfibers depending on the size of the fibers. Cellulose crystals and cellulose micro / nanofibers are extracted by different techniques to produce different morphologies with different properties. The two fibrous materials, cellulose nanofibers and cellulose microfibers, are extracted from plant entities by different techniques, so their morphologies and properties are different. Cellulose nanofibers and cellulose microfibers can be distinguished from one another based on their size and shape: cellulose nanofibers (CNF, also known as "nanofibrillated cellulose" or "NFC") are much smaller in diameter than cellulose microfibers (CMF, also known as "microfibrillated cellulose" or "MFC") and are straight rod-like, whereas CMFs can be larger in diameter, more flexible in appearance, and irregular in shape. Although the literature cites a range of dimensions for CNFs and CMFs, CNF fibers are nanoscale (e.g., having diameters of 4-20 nm), whereas CMFs can be much larger: CMF fibers typically still have diameters in the nano range, e.g., 20-100 nm or larger.

[0006] More specifically, CMF fibers are produced by mechanical processing of cellulosic feedstocks with or without chemical or enzymatic pretreatment. CMF fibers can be elongated with high aspect ratios and contain crystalline and amorphous regions similar to native cellulose to form a three-dimensional network. The size distribution of CMF fibers in a fiber population is broad, with smaller nanoscale fibers interspersed among larger fibers in the CMF network. In contrast, for CNF fibers, different processing methods are included to create a population of individual fibrils with a narrow size distribution within the population. The dimensions in the CNF material are more consistently nanoscale compared to the CMF fiber population. As used herein, all three species (crystalline cellulose, CNF, and CMF) shall be included in the umbrella term "nanocellulose" or "nanocellulose elements" (NCEs).

[0007] Nanocellulose (NC) materials hold enormous promise for commercial applications due to their biodegradable nature, low density, abundant source material, and high mechanical performance. However, while the nano-sized geometry and hydrophilic nature of these cellulosic materials offer opportunities, these properties also present challenges. Several applications have been developed that exploit the geometry and hydrophilicity of NCs. As an example, certain nanocelluloses can be dry mixed with inorganic powders such as stucco and cement to deliver a mechanical barrier to the structure upon hydration and hardening. However, because they are hydrophilic, NC materials require modification so that they can be used in hydrophobic environments. Even in hydrophilic environments or within composites that use NC as a hydrophilic component, satisfactory NC dispersion can be difficult, limiting the usefulness of NC elements in many applications. Furthermore, limitations imposed by NC drying and dispersion techniques limit the usefulness of these materials for commercial applications.

[0008] NCs are usually made by a series of mechanical and / or chemical procedures carried out in aqueous media, which loosen the hydrogen bonds between cellulose fibers and facilitate delamination of the aqueous suspensions, resulting in the formation of NC derivatives with a more useful degree of polymerization and crystallinity and higher aspect ratios. Typically, NC materials are dispersed in aqueous media at low concentrations (<5 wt%) because their high water absorption capacity causes them to form highly viscous suspensions even at low solids concentrations due to entanglement of the high aspect ratio NC elements.

[0009] However, these aqueous suspensions of NCs are difficult to manage and expensive to transport. Therefore, drying techniques have been devised to convert NC suspensions into dry powder form. However, drying of NC suspensions using conventional techniques (e.g., evaporating water at high temperatures) promotes the formation of aggregates ("flocculation") and hydrogen bonds due to the interaction of hydroxyl groups on the surface of cellulose molecules. This flocculation process caused by conventional drying, also called hornification, is characterized by bonds between hydroxyl groups on the NC particles or fibers that are irreversible or only partially reversible.

[0010] Despite a decade-long series of academic and industrial efforts, successful low-cost and effective drying and redispersion have eluded NC manufacturers. The twin difficulties of (a) drying NC from the aqueous medium in which it is suspended and (b) redispersing the dried NC are caused by two factors: (1) the tendency of cellulose polymers to form hydrogen bonds with each other, attaching adjacent cellulosic elements into irreversible aggregates (i.e., collections of particles that are permanently attached to each other and resist redispersion in suspension); and (2) the large surface area (per unit weight) associated with the size and morphology of the NCEs, which greatly exacerbates adhesion due to hydrogen bonding. When an aqueous slurry of NCs is dried in a standard oven, a hard, closely entangled, brick-like mass forms at the bottom of the drying vessel. This dense network of aggregated cellulosic elements cannot be easily scraped out of the vessel and can only be redispersed in water using vigorous mechanical agitation. Instead, attempts at redispersion result in large clumps of NC aggregates that remain in the redispersion medium even after several hours of agitation. This resistance to redispersion precludes the use of dry NC materials in composite products (cement, concrete, paving materials, artificial stone, ceramics, stucco, mortar, jointing compounds, etc.) where the dry mix of NC reinforcing additive must be uniformly dispersed throughout the composite.

[0011] This tendency toward aggregation and keratinization and subsequent resistance to redispersion eludes a cost-effective solution, thus eliminating the opportunity for using NC materials in a wide range of attractive applications. Although various drying techniques, such as freeze-drying, spray-drying, supercritical fluid drying and atomization, have been investigated by researchers, they have at best produced small samples of redispersed NC elements using processes whose high cost, energy requirements and specialized equipment requirements preclude their widespread adoption.

[0012] Therefore, there is a need in the art for a commercial-scale drying technique for NC material that avoids clumping and keratinization problems so that a solid mass of NC can be created for later redispersion. There remains a further need in the art for such a technique that is low-cost, suitable for commercial equipment, without excessive energy requirements, and without specialized equipment requirements. Summary of the Invention

[0013] Summary of the Invention In an embodiment, a liquid formulation is disclosed herein that includes a suspension of nanocellulose (NC) elements and a drying / dispersing additive, the drying / dispersing additive being selected from the group consisting of a temperature-responsive polymer, a small molecule additive in a volatile system, and a blocking agent. In an embodiment, the nanocellulose elements are derived from lignocellulosic materials that may include untouched biomass, the untouched biomass including special purpose grains; in other embodiments, the lignocellulosic materials include waste materials. In an embodiment, the NC elements include or consist essentially of crystalline cellulose or cellulose nanofibers. In an embodiment, the drying / dispersing additive is a temperature-responsive polymer that may be a lower critical solution temperature (LCST) polymer or a short-chain oligomer derived from a LCST polymer. The LCST polymer may be selected from the group consisting of methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, polyvinylcaprolactam, poly(methylvinylether), poly(N-isopropylacrylamide), poly(N,N-diethylacrylamide), block copolymers of poly(ethylene oxide) and poly(propylene oxide), and elastin poly(pentapeptide). In an embodiment, the drying / dispersing additive is a small molecule additive in a volatile system that may be non-ionic or cationic and may be biodegradable. The small molecule additive may be selected from the group consisting of tri(propylene glycol) butyl ether, di(propylene glycol) propyl ether, propylene glycol butyl ether, propylene glycol propyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol diacetate, ethylene glycol diacetate, benzyl alcohol, 1-heptanol, and 1-hexanol. The small molecule additive may be selected from the group consisting of ethylenediamine, diethylenetriamine, tetraethylenepentamine, 1,3-pentanediamine, piperazine, 1,2-cyclohexanediamine, aniline, pyridine and piperazine.In an embodiment, the drying / dispersible additive is a blocking agent. The blocking agent may be a non-volatile chemical additive which may be a purine or a pyrimidine. In an embodiment, the non-volatile chemical additive is a purine, the purine being a xanthine or a xanthine derivative. In an embodiment, the blocking agent is a humectant, the humectant may be selected from the group consisting of glycerin, caprylyl glycol, ethylhexylglycerin, tribehenin, hydrolyzed soy protein, propylene glycol, methyl gluceth-20, phenyl trimethicone, hyaluronic acid, sorbitol, and gelatin. In an embodiment, the blocking agent may be a fatty acid. In an embodiment, the blocking agent comprises nanoscale particles. In an embodiment, the liquid formulation may further comprise an adjuvant.

[0014] Also disclosed herein in embodiments is a method of treating a cellulosic feedstock to form a redispersible dry NC-containing material comprising an NC component, comprising the steps of: mechanically defibrillating the cellulosic feedstock to form an initial nanocellulose suspension comprising an NC component; treating the cellulosic feedstock with a drying / dispersing additive before or after mechanically defibrillating the cellulosic feedstock to form a treated nanocellulose suspension comprising an NC component; and drying the treated nanocellulose suspension to form a redispersible dry NC material comprising an NC component. The method may further comprise chemically pretreating the cellulosic feedstock either before or after mechanically defibrillating the cellulosic feedstock, the chemical pretreatment step being carried out using a pretreatment agent selected from the group consisting of enzymes, alkaline solutions, acid solutions, ionic liquids, short chain amines and positive oligomeric species. In an embodiment, the pretreatment agent is selected from the group consisting of ethylenediamine, o-phenylenediamine, diethylenetriamine, tetraethylenepentamine, 1,3-diaminopentane, ethanolamine, triethynolamine, melamine, and EDTA. In an embodiment, the method further comprises treating the cellulosic feedstock with a chelating agent before or after mechanically defibrillating the cellulosic feedstock. In an embodiment, the method further comprises adding a second drying / dispersing additive to the cellulosic feedstock before, after, or simultaneously with treating the cellulosic feedstock with the drying / dispersing additive.

[0015] Also disclosed herein is a dry NC-containing material produced by the above-mentioned method.Furthermore, disclosed herein is a method for producing a formulation comprising NC elements suspended in a fluid medium, comprising the steps of providing a fluid medium, adding the above-mentioned redispersible dry NC material to the fluid medium, and mixing the redispersible dry NC material in the fluid medium, thereby suspending the NC elements in the fluid medium.In an embodiment, the fluid medium is an aqueous fluid.Also disclosed herein is a formulation comprising NC elements redispersed in the fluid medium produced by the above-mentioned method.

[0016] In an embodiment, disclosed herein is a method of making a redispersible dry NC-containing material having nanocellulose elements embedded therein, comprising providing a liquid formulation as described herein, wherein the liquid formulation comprises nanocellulose elements, and the liquid formulation comprises a drying / dispersibility additive; and drying the liquid formulation to form a dry NC-containing material having embedded nanocellulose elements, wherein the redispersibility of the dry NC-containing material is greater than that of a dry control material prepared by drying a control suspension of nanocellulose elements in a liquid medium, the control suspension lacking the drying / dispersibility additive. The method may further comprise adding a pretreatment agent to the liquid formulation prior to drying the liquid formulation; the pretreatment agent may be added prior to or simultaneously with the addition of the drying / dispersibility additive. In an embodiment, the pretreatment agent is a chemical pretreatment material, which may be selected from the group consisting of ethylenediamine, o-phenylenediamine, diethylenetriamine, tetraethylenepentamine, 1,3-diaminopentane, ethanolamine, triethynolamine, melamine, and EDTA. The chemical pretreatment agent may be a chelating agent. Further disclosed is a redispersible dry NC-containing material in which nanocellulose elements are embedded, made by the method disclosed above. In an embodiment, the nanocellulose elements are formed as a matrix that may be a support or container for the active agent. Advantageously, the matrix may act as a container, and the container may be foamed. In an embodiment, the matrix may be shaped as a formed article. In another embodiment, the matrix may be formed as a film, and the film may encase the active agent. In an embodiment, the formed article is adapted for rupture by a physical, chemical or biological mechanism, and the rupture allows for the release of the active agent. In an embodiment, the formed article includes a first matrix that acts as a support for the active agent, and the first matrix is ​​formed as a sheet. In another embodiment, the formed article includes a first matrix formed as a sheet and a second matrix formed as a sheet, and the active agent is disposed between the first matrix and the second matrix, and the active agent may be enclosed between the first matrix and the second matrix.In embodiments, the active agent is selected from the group consisting of laundry products, soaps, detergents, surfactants, bleaches, enzymes, hair maintenance products, pigments, colorants, odor-related agents, softeners, cosmetics, pharmaceutical products, medical products, and agricultural active ingredients. In embodiments, the matrix further comprises filler particles that can act as pore-closing materials. In embodiments, the matrix has abrasive properties. In embodiments, the NC-containing material further comprises a barrier-making material that can be deployed as a coating on the upper or lower surface (e.g., top or bottom) of the matrix or mixed into the matrix. In embodiments, the barrier-making material provides the NC-containing material with oil and grease resistance properties or provides the NC-containing material with water resistance or water vapor resistance properties. In embodiments, the barrier-making material comprises a biopolymer.

[0017] In an embodiment, also disclosed herein is a method of redispersing nanocellulose elements, comprising providing a redispersible dry NC-containing material as described above, and adding a redispersion fluid to the dry NC-containing material, thereby redispersing the NCEs embedded in the redispersible dry NC-containing material. The redispersion fluid can be an aqueous fluid. Further disclosed herein is a redispersed NC-containing formulation comprising NC elements suspended in a redispersion fluid, wherein the redispersed NC formulation is made by the method described above. In an embodiment, the formulation can be foamed. In an embodiment, the formulation further comprises an active agent attached to the NC elements or embedded in a matrix formed with the NC elements. In an embodiment, the active agent can be a skin treatment substance or a pharmaceutical or nutraceutical product or a cosmetic product or an odor-related active agent or an agricultural active ingredient. Also disclosed herein is a method of producing a formed article, comprising drying the formulation described above into a selected shape, which when dried creates the formed article. Also disclosed herein is a method of treating a surface, comprising applying the formulation described above to the surface and drying the formulation. In an embodiment, the surface is a hair shaft or a skin surface. In an embodiment, disclosed herein is a method for treating a skin disorder or condition comprising applying the above-described formulation to a selected area of ​​the skin in need of treatment. Also disclosed herein is a method for treating an agricultural product comprising applying the above-described formulation to the agricultural product.

[0018] Further, in an embodiment, a method of making a composite matrix is ​​disclosed herein, comprising providing an existing matrix composition and incorporating a population of additional NCEs into the existing matrix. The existing matrix composition may comprise or consist essentially of an organic material, which may be a pulp or pulp-based material. In an embodiment, the existing matrix composition is coated or impregnated with the additional NCEs. Also disclosed herein is a composite material prepared by the aforementioned method. In an embodiment, the existing matrix is ​​a hydrophobic matrix, and the additional NCEs are hydrophobized for use in the hydrophobic matrix. In an embodiment, the existing matrix comprises a biodegradable polymer, which may be a natural polymeric material. In an embodiment, at least a portion of the additional NCEs act as fillers or pore-closers in the existing matrix. In an embodiment, the composite material further comprises a secondary additive, which may be a plasticizer or a hydrophobic cellulose additive. In an embodiment, the composite material exhibits special properties, which may be selected from the group consisting of mechanical properties, barrier properties, and additive properties. In an embodiment, the special properties are mechanical properties, which may be an enhancement of the mechanical characteristics of the existing matrix. In embodiments, the special property is a barrier property that may be an oleophobic barrier property, a hydrophobic barrier property, or both. In embodiments, the special property is an additional property that may be a conductive property. In such embodiments, the population of additional NCEs may include a subpopulation of NCEs with conductive properties, and the conductive property of the subpopulation may be created in the subpopulation via a silver mirror reaction. In embodiments, the composite material may be a foamed article that may include cellulose microfibers in the population of additional NCEs; in embodiments, the foamed article may include a barrier-making material. Further disclosed herein is an article of manufacture that includes the composite material disclosed above. In embodiments, the article of manufacture is selected from the group consisting of a recreational facility article, an athletic shoe, an architectural coating product, a building material, a durable ink, and a 3D printing material. In embodiments, the article of manufacture may include the composite material disclosed above, and the composite material exhibits special properties.Such articles of manufacture may be formed as drinking straws, films, sheets, or fibers or nonwoven fabrics; such fibers or nonwoven fabrics may exhibit optimized properties, and they may be formed into artificial leather. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] Detailed Description of the Invention 1. Building Blocks for Redispersible Nanocellular Materials It is understood that the NC material suitable for processing by the system and method disclosed herein can be derived from all kinds of cellulosic raw materials, especially cellulosic raw materials from plants, which can also be referred to as lignocellulosic materials. Lignocellulosic materials are formed of cellulose polymers as described above combined with various amounts of lignin. Lignocellulosic materials can include intact biomass found in naturally occurring plants such as trees, shrubs and grasses. Lignocellulosic materials may include waste materials from consumption or from industries such as agriculture (e.g., corn straw and corn cobs, sugarcane bagasse, straw, empty oil palm fruit bunches, pineapple leaves, apple stalks, coir fiber, mulberry bark, rice grains, bean husks, soybean husks (or "soyhulls"), cotton linters, blue agave waste, North African glass, banana pseudostem residues, groundnut shells, pistachio nut shells, grape pomace, shea nut shells, passion fruit peels, fique fiber waste, sago nut shells, kelp waste, junk plant stems, etc.), or forestry (sawmill and paper mill waste). Lignocellulosic materials may include special purpose crops such as switchgrass and elephantgrass that are grown for uses such as biofuel, allowing multiple harvests. Plants with uses as lignocellulosic materials may be woody (e.g., trees with stiff stems and perennial growth cycles) or non-woody with weak stems and annual or limited perennial growth cycles. Non-woody plants are particularly advantageous because they typically have low amounts of lignin relative to the amount of cellulose they contain. As will be appreciated by those skilled in the art, different techniques are available for processing various lignocellulosic materials to extract NC materials therefrom.

[0020] In embodiments, additives are disclosed herein that can be used to inhibit or disrupt hydrogen bonding of NC materials at high temperatures (e.g., upon drying) while retaining high inherent hydrophilicity, allowing for easy redispersion in aqueous media. The formulations and methods disclosed herein include several different categories of additives (referred to as "drying / dispersing additives"): (1) certain temperature-responsive polymers that can introduce space between NC particles or fibers (collectively "NC elements") upon drying, preventing them from clumping; (2) certain volatile small molecules that can create space between NC elements upon drying; and (3) certain non-volatile small or large molecules that prevent hydrogen bonding between or within NC elements upon drying. All of these materials act to disrupt hydrogen bonding at high temperatures or under other circumstances, while creating gaps between or within NC elements upon further drying that allow for subsequent redispersion.

[0021] As used herein, the term "drying" for an initial suspension of NC elements (referred to as "initial NC suspension" and understood to be the suspension containing NC elements that is first created during the defibrillation process when exemplified in the ensuing description) refers to the application of heat and / or any other dehydration technique to the initial NC suspension that results in a reduction in the water content of the initial NC suspension so as to convert the initial NC suspension into a solid or semi-solid material containing the NC elements that were present in the initial NC suspension. This dried solid or semi-solid material may be referred to as a "dry NC material." As used herein, the term "redispersion" refers to a process in which the dry NC material is suspended in a fluid medium (either aqueous or non-aqueous) such that there is substantially complete dissolution of the dry NC material (either semi-solid or solid) into its constituent NC elements. In embodiments, an aqueous resuspension fluid may be used; in other embodiments, a non-aqueous resuspension fluid may be used, such as a fluid having hydrophobic or amphiphilic properties. In embodiments, redispersion results in suspension of the NC elements such that the NC elements are formed as individual NC elements or as amalgamations of individual NC elements (both referred to herein as "resuspended particles"), where such resuspended particles have an aspect ratio greater than 10. In embodiments, the resuspended particles have an aspect ratio of about 10 to about 300 or about 10 to about 200. In embodiments, the resuspended particles have an aspect ratio of about 50 to about 150. In embodiments, the resuspended particles have an aspect ratio of about 25 to about 75. In other embodiments, the resuspended particles have an aspect ratio of about 75 to about 125.

[0022] While certain additives (e.g., certain LCST polymers described below) are suitable for use as single agents to facilitate drying and redispersion, other additives are useful for use as adjuvants in combination with a primary drying / dispersing additive, either administered to the initial NC suspension simultaneously with the primary additive, or as pretreatments to the initial NC suspension or any of its precursors prior to the addition of the primary additive, or as posttreatments to the initial NC suspension after the addition of the primary drying / dispersing additive. Drying / dispersing additives include, without limitation, temperature-responsive polymers, small molecule additives in volatile systems, and blocking agents. The primary drying / dispersing additives and adjuvant additives used in combination with a source of NC elements to produce the liquid formulations and derivative redispersible dry materials of the present invention are collectively referred to as "primary additives."

[0023] a. Temperature-responsive polymers In embodiments, certain temperature-responsive polymers can be used to create spaces between NC elements upon drying, thereby preventing the NC elements from agglomerating during the drying process. Particularly suitable temperature-responsive polymers for this purpose are those that exhibit a phenomenon known as LCST (lower critical solution temperature) phase behavior. It is understood that certain LCST polymers are hydrophilic below their LCST transition temperature and become reversibly hydrophobic above their LCST transition temperature. That is, below the LCST point, the polymer exhibits high affinity for water, consistent with its inherent molecular hydrophilicity. However, above the LCST point, the polymer repels water and avoids hydrogen bonding. This is manifested by the observed thermogelation of polymer solutions above this transition temperature. When polymeric or oligomeric LCST additives self-assemble (in the form of a monolayer or a few molecular layers) on the surface of the NC elements, the drying of the NC elements is influenced in such a way that their eventual redispersion is facilitated.

[0024] More specifically, the LCST polymer can be added to the initial NC suspension at a temperature below the transition temperature of the LCST polymer. When water evaporates from the initial NC suspension upon drying, its temperature increases and reaches the boiling point of water, exceeding the transition temperature of the LCST polymer, at which point the LCST polymer loses its hydrophilic character and becomes hydrophobic. When it becomes hydrophobic, the LCST polymer interferes with the hydrogen bonds that form between the NC elements. Here, the hydrophobic nature of the LCST polymer determines the aggregation or disaggregation of the NC elements, instead of these processes being driven by the interactions of the cellulosic units of the NC elements.

[0025] In embodiments, the selected LCST polymer can significantly or completely prevent the dense aggregation of NC elements during drying. In embodiments, the ability of the selected LCST polymer to disrupt the aggregation of NC elements is independent of the choice of equipment and the mode of drying. For example, the suspension containing the LCST polymer and the NC elements can remain stationary during drying. To achieve aggregation-free drying, a wide range of drying temperatures and pressures can be applied to the initial NC suspension in the presence of the selected LCST polymer. The dried NC material made using the selected LCST polymer described herein can be easily redispersed in water by gentle agitation or stirring, with minimal or no clumping or residual aggregation identified in the redispersed suspension. These features result in a wide latitude in processing parameters.

[0026] In embodiments, the following list provides examples of LCST polymers and their analog short chain oligomers that can be used to prevent aggregation and facilitate redispersion of NC elements. Methylcellulose Hydroxyethylcellulose Hydroxypropyl cellulose Hydroxypropyl methylcellulose Ethyl hydroxyethyl cellulose Polyvinylcaprolactam Poly(methyl vinyl ether) Poly(N-isopropylacrylamide) Poly(N,N-diethylacrylamide) Block copolymers of poly(ethylene oxide) and poly(propylene oxide) Elastin poly(pentapeptide)

[0027] Note that the thermal gelation temperatures of the cellulose derivatives listed above depend on the type and degree of substitution and can be tuned by structural design. Advantageously, the LCST polymers selected for use as drying / dispersing additives may have transition temperatures above ambient temperature (e.g., >25°C), so that the polymer remains in solution until the drying process is initiated.

[0028] b. Volatile small molecule additive systems In embodiments, volatile systems containing small molecule additives can be used to create spaces between NC elements upon drying, either alone or in combination with other additives, to prevent the NC elements from agglomerating during the drying process. The small molecule additives selected for use with volatile systems are miscible with water and have a boiling point higher than that of coexisting water. Small molecule additives useful in volatile systems are further characterized by their rather low hydrogen bonding tendency compared to water. When an additive-loaded volatile system containing NC and a selected small molecule undergoes drying, the water molecules preferentially evaporate, leaving behind the small molecule additive due to its high boiling point, thereby increasing the concentration of additive in the solution remaining between adjacent NC elements. In embodiments, the molecular segments of the volatile small molecule additives contain both polar and non-polar functional groups. Without being bound by theory, it is envisioned that the polar segments are attracted to the cellulose hydroxyl groups, while the non-polar segments simultaneously interfere with the hydroxyl-hydroxyl interactions, thus reducing adhesion between and within the NC elements. Then, as the temperature in the system increases, the additive evaporates, leaving behind the NC elements surrounded by air. The resulting dry material containing NC elements separated from each other by air can be easily redispersed without any observable agglomerate / clump formation or concentration change. The redispersed suspension contains resuspended NC particles with a uniform distribution in the suspension, where the NC elements retain their nano-sized characteristics, and redispersion can be achieved with only very gentle stirring / agitation.

[0029] In embodiments, the following list provides examples of small molecule additives that can be used in the aforementioned volatile systems to prevent aggregation and facilitate redispersion of NC elements. Exemplary additives can be divided into two categories: nonionic and cationic compounds.

[0030] Non-ionic candidates include, but are not limited to: · Tri(propylene glycol) butyl ether (TPnB) Di(propylene glycol) propyl ether (DPnP) Propylene glycol butyl ether (PnB) Propylene glycol propyl ether (PnP) Ethylene glycol monobutyl ether Propylene glycol monomethyl ether acetate Propylene glycol diacetate Ethylene glycol diacetate Benzyl alcohol 1-Heptanol 1-Hexanol may be mentioned.

[0031] Cationic candidates include, but are not limited to: Ethylenediamine Diethylenetriamine Tetraethylenepentamine 1,3-Pentanediamine Piperazine 1,2-Cyclohexanediamine Aniline Pyridine Piperazine may be mentioned.

[0032] In embodiments, small molecule additives can completely evaporate from the initial NC suspension, leaving only NC elements behind without any additive residue. However, in other embodiments, traces of small molecule additives can remain. For example, certain cationic additives can attach their cationic groups to cellulose molecules, so that after complete drying, traces of additives remain attached to cellulose. For most industrial applications, the remaining traces of these additives do not present health or environmental problems. However, in embodiments, biodegradable cationic small molecules, such as 1,3-pentanediamine, are advantageous.

[0033] c. Blocking agent In embodiments, non-volatile small or large molecule additives can be used by themselves apart from the above-mentioned volatile systems to prevent hydrogen bonding and / or create spaces between NC elements upon drying, thereby preventing interactions between NC elements and thus preventing NC elements from agglomerating during the drying process. In embodiments, surface-functionalized nanoscale particles can be used in the same manner. Such non-volatile small or large molecule additives and nanoscale particles that perform this blocking function are referred to herein as blocking agents or blocking agents. As used herein, the term "blocking agent" or "blocking agent" includes any non-volatile chemical additive or nanoscale particulate material that itself prevents hydrogen bonding or creates spaces in NC elements, whether the material is intercalated between or within NC elements, or whether the material provides temporary competitive binding sites for NC elements, or otherwise. As an example, caffeine and other xanthine derivatives are small molecule blocking agents that can be advantageously used to facilitate the isolation and redispersion of NC elements. Without being bound by theory, it is envisioned that aromatic nitrogen atoms in certain purines (e.g., caffeine and other xanthines or xanthine derivatives) and pyrimidines may hydrogen bond with hydroxy groups of cellulose to present a flat, relatively non-polar, molecularly smooth, water-screening outer surface, thus preventing adhesion between and within the NC elements. Advantageously, caffeine and other xanthines and xanthine derivatives can typically be used in amounts that do not present health or environmental concerns, even when used in doses sufficient to facilitate NC dispersion.

[0034] As another example, certain humectant substances can be used as blocking agent molecules. The humectants have multiple hydrophilic sites (hydroxyl, ester and ammonium groups) that can form hydrogen bonds with the surface of NC elements, thus shielding these elements from interacting with each other via hydrogen bonds, thereby preventing aggregation. Moreover, these hygroscopic substances are biocompatible and already widely used in the pharmaceutical, cosmetic and food industries. Exemplary short and long humectant candidates include, but are not limited to: glycerin, caprylyl glycol, ethylhexylglycerin, tribehenin, hydrolyzed soy protein, propylene glycol, methyl gluceth-20, phenyl trimethicone, hyaluronic acid, sorbitol and gelatin.

[0035] As another example, fatty acids can also be used as blocking agents. Fatty acids contain hydrophilic sites and hydrophobic tails. The hydrophilic sites can form hydrogen bonds with the surface of NC elements, thus shielding the interaction of these elements with each other through hydrogen bonds, thereby preventing aggregation. Advantageously, fatty acids can be selected that do not contain too many hydrophilic sites and many hydrogen bonds occur between the fiber and the blocking agent. In embodiments where too many hydrogen sites can cause aggregation, the hydrophobic tails of the fatty acid blocking agent can act to physically prevent or impede hydrogen bonding, thereby preventing aggregation of NC elements. In embodiments, the blocking agent can be a fatty acid, such as stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, caproic acid, etc. For dispersion purposes, water-soluble fatty acids can be preferred.

[0036] 2. Further processing options It is understood that the drying / dispersing additives disclosed herein can be introduced into the NC-containing suspension individually or in combination to improve the drying process for NC and to facilitate its redispersion. The drying / dispersing additives can also be used in combination with other agents to enhance their efficacy, even if the other agents are not effective as drying / dispersing additives when used alone; such agents used in combination with the drying / dispersing additives to enhance their efficacy are referred to as "adjuvants". It is further understood that one or more of the drying / dispersing additives or adjuvants can act together in a synergistic manner. Furthermore, the combination of drying / dispersing additives can be introduced sequentially during the preparation of the initial NC suspension and / or before, after or during the process used to make the initial NC suspension from the cellulosic feedstock feedstock, with or without the addition of an adjuvant. For example, non-polymeric additives can be added during the process used to make the initial NC suspension from the feedstock, but desirably after chemical pretreatment.

[0037] Processes for forming NC-containing suspensions (i.e., initial NC suspensions) suitable for processing using the formulations and methods disclosed herein are well known in the art. To form such NC-containing suspensions, the cellulose feedstock can be treated using mechanical techniques and optional chemical treatments to extract the constituent cellulose nanomaterials and retain them for suspension in the liquid medium. The NC elements thus extracted from the initial NC suspension can be processed using the formulations and methods disclosed herein.

[0038] More specifically, mechanical treatments such as high pressure homogenization, microfluidization, super-grinding, freeze-fracturing, steam explosion, purification and high-density ultrasonication are known in the art to break down cellulose feedstocks to produce their constituent NC elements; other mechanical techniques are well known to those skilled in the art. Such mechanical treatments are referred to as forms of mechanical defibrillation. However, mechanical treatments require a significant amount of energy. Therefore, in order to reduce energy consumption during the mechanical defibrillation process, various chemical and enzymatic strategies have been used to pretreat cellulose feedstocks prior to mechanical treatment, collectively referred to herein as "chemical pretreatment." Chemical modification of NC elements can also be carried out after mechanical defibrillation to change their properties.

[0039] The drying / dispersing additives disclosed herein can be used in various suspensions of partially treated cellulose feedstocks instead of or in addition to being used to treat the first NC suspension resulting from the extraction of NC elements from the cellulose feedstock feedstock. In an exemplary embodiment, a single drying / dispersing additive can be used to treat a feedstock suspension of partially treated cellulose feedstocks, such as a suspension of cellulose feedstocks that has been chemically pretreated but not yet subjected to mechanical defibrillation. For example, a volatile additive can be used in this method. The volatile additive can typically be formulated as a non-viscous fluid that can be injected directly into the pulp feedstock suspension, for example, after its chemical pretreatment and / or just before it undergoes a mechanical defibrillation process (homogenization, microfluidization, grinding, high-intensity ultrasonication, etc.). In this manner, the volatile portion is intermingled between and within the individual fibers as the fibers are pulled away from the larger pulp (cellulose) chains, an artifact that is retained during mechanical defibrillation.

[0040] In another embodiment, non-volatile additives or temperature-responsive polymers, such as LCST polymers, can be used to treat the partially processed cellulose feedstock instead of or in addition to treating the initial NC suspension using dry / dispersible additives. Non-volatile additives and LCST polymers generally occur as viscous fluids or powdered solids that are dissolved in aqueous solutions. Due to their high viscosity, these components are desirably added after mechanical defibrillation, either by direct application / dissolution or by combining a concentrated solution of the additive with the NC suspension effluent.

[0041] In other embodiments, pretreatment with various pretreatment agents may be useful prior to adding the drying / dispersible formulations disclosed herein. For example, the cellulosic feed may be subjected to certain chemical pretreatment materials prior to mechanical defibration as described above. Chemical pretreatment materials such as enzymes, alkaline-acid solutions and / or ionic liquids may, for example, destroy lignin and hemicellulose in the cellulosic feed while preserving the cellulose portion. These chemical pretreatment materials assist in reducing the energy consumption of subsequent mechanical treatments as previously described. Additionally, chemical pretreatment materials may make the surface chemistry of the extracted NC elements more receptive to treatment with the drying / dispersible additives disclosed herein. The surface chemistry of NC elements is known to vary depending on the raw cellulosic material feed (e.g., softwood, hardwood, soybean husk, wheat straw, bagasse, sugar beet pulp, etc.) and the treatment technique performed (e.g., Kraft vs. Sunburst). Additionally, further chemical treatments such as carboxymethylation, oxidation and sulfonation may be performed during industrial processes to generate permanent anionic charges on the NC surface. To optimize the surface chemistry of a population of NC elements for treatment with the drying / dispersibility additives disclosed herein, these elements may be pretreated with short amine or positive oligomer species to reduce ionic forces between the NC elements; such pretreatment may be performed prior to or together with the addition of the drying / dispersibility additive. Examples of such pretreatment agents include: ethylenediamine, o-phenylenediamine, diethylenetriamine, tetraethylenepentamine, 1,3-diaminopentane, ethanolamine, triethynolamine, melamine, and EDTA; other pretreatment agents will be familiar to those skilled in the art.

[0042] In some embodiments, chelating agents such as EDTA or equivalent chelating agents such as MGDA (methylglycine diacetic acid trisodium salt), GLDA (glutamic acid tetrasodium diacetate), GEDTA (EGTA) (ethylene glycol-bis(β-aminoethyl ether)-N,N,N',N'-tetraacetic acid), etc. are useful as pretreatments when a hard water feed is used to suspend NC elements. In embodiments, LCST polymers can be selected as drying / dispersing additives to be used in the NC suspension after or at the same time as using EDTA to chelate hard water cations. In embodiments, chelating agents such as EDTA can be used to treat the initial NC suspension, thereby complexing divalent cations remaining in the suspending fluid.

[0043] Other useful pretreatments can be readily envisioned by one of ordinary skill in the art.

[0044] 3. Exemplary Articles of Manufacture In embodiments, the nanocellulose elements (NCEs) prepared according to the systems and methods disclosed herein can be incorporated into various articles of manufacture. NCEs offer significant advantages for forming commercial products.

[0045] In embodiments, these materials can be engineered to provide a matrix that supports other active agents in a formulation or composition; such materials advantageously provide a vehicle with properties such as optical transparency and mechanical strength to conveniently carry and deliver active agents to their intended use. As used herein, the term "active agent" refers to any substance that produces a desired chemical, physical, or biological effect, where the substance can produce a chemical, physical, or biological effect independently of its association with an NCE product as disclosed herein (matrix, coating, material, filler, etc.). Such active agents can be included in (e.g., transported within, encapsulated by, distributed from, or otherwise directed to the site of activity by) an NCE-based product as disclosed herein. By way of non-limiting example, active agents may include laundry products (e.g., materials such as laundry detergents, bleaches, enzymes, and fabric softeners), soaps, cosmetics, pharmaceutical products, agricultural active ingredients, and the like (certain of which are described in more detail below); such active agents may be supported by an NCE matrix embedded therein, attached thereto, or otherwise bound thereto, where the matrix allows the active agent to be delivered to the site of activity for the active agent. In certain embodiments, the NCE-based matrix may support the encapsulation of active agents that have their own properties but are intended to modify the inherent properties of the matrix itself, such as pigments, dyes or other colorants to add or change color, fragrances, odor absorbers, disinfectants, and the like; such active agents may be incorporated into articles of manufacture that include the matrix to thereby impart their properties to the final formed article.

[0046] In other embodiments, materials including NCEs can be integrated into non-NCE matrices to enhance the properties of such non-NCE matrices, such as enhanced strength and resilience, among others. Despite the properties of NCEs, which are cheap, abundant, sustainable, and biodegradable, as described above, their widespread adoption in articles of manufacture has been limited by drawbacks associated with suspensions of these particles: once suspended, NCEs require the transport of significant volumes of liquid; when the suspension dries, it undergoes irreversible keratinization, preventing the resuspension of the NCEs contained therein. The methods and compositions disclosed herein render NCEs resuspendable and therefore available for inclusion in various products, examples of which are described in this disclosure.

[0047] a. NCE as a matrix: general characteristics Dispersed NCEs made as disclosed herein can be formed into highly porous three-dimensional nanoscale networks capable of retaining functional or active agents within their pores, and can be engineered to optimize their own inherent properties, with or without the addition of other ingredients. Such matrices can be formulated as solids, gels, liquids, etc., to meet the needs of a particular product. Furthermore, once made, the matrices can be shaped or molded into any convenient geometric structure as required by the product category, such as chips, strips, balls, cubes, sheets, etc., to create an article of manufacture. Once formed, the NCE matrices can be used as is or redispersed in water or other aqueous redispersion fluid to form the final product.

[0048] In embodiments, the NCE-based matrix manufactured article is intended to encase, contain, surround, support or otherwise deliver an active agent. In embodiments, the NCE-based matrix serves as a carrier for other active agents, which are embedded in, attached to or supported by the matrix structure; under such circumstances, the matrix may be referred to as a support for the active agent. In other embodiments, the NCE-based matrix surrounds or encases the active agent, serving as a container for the active agent. In either case, the matrix serves to transport the active agent to its site of activity, and the matrix is ​​engineered to deliver the active agent to its site of activity. An article of manufacture may be constructed that includes an NCE-based matrix that serves as a support, a container, or both. In embodiments, such articles of manufacture may be adapted for disintegration by physical, chemical, or biological mechanisms, thereby releasing the active agents that they support or contain. Such articles of manufacture may be engineered to produce, for example, fragile or soluble or other properties that permit disintegration (e.g., digestible by microorganisms or hydrolyzable by enzymes) so that they are adapted for delivery of the active agent they contain, for example, upon encounter with mechanical forces (e.g., tearing, squeezing, piercing, etc.) or upon encounter with chemical solvents such as aqueous fluids or upon encounter with disruptive biological entities. Encounter between the article of manufacture and such physical, chemical or biological mechanisms may compromise the integrity of the article of manufacture sufficiently for the article of manufacture to deliver the active agent it contains or supports to an area, surface, material, etc., indicated for activity of the active agent.

[0049] In other embodiments, the structure of the NCE matrix itself provides the desired properties to the manufactured article. The NCE matrix can be shaped to provide the structural and engineered properties that a particular application requires. Under these circumstances, the NCE matrix produces the desired effect in the product due to its mechanical or structural properties. In embodiments, the NCE matrix can incorporate secondary additives that provide the matrix itself with other advantageous properties apart from the ability of the matrix as a carrier for the active agent.

[0050] Examples of NCE matrices as carriers for active agents and as structural units or building blocks are described below to illustrate the principles of the present invention.

[0051] NCE matrices as carriers: product distribution vehicles The NCE matrix is ​​suitable for use in a variety of product distribution applications and can easily serve as a convenient vehicle for distributing products embedded within the matrix. Without being bound by theory, it is understood that active agents can be introduced into the NCE matrix so that they penetrate and reside within the interstices or coat the matrix framework, or both. Various advantageous properties can be imparted to articles made from the NCE matrix by introducing secondary additives into the matrix that convey the desired properties. For example, special release papers can be prepared using silicone adhesives in the NCE matrix, thus requiring less adhesive backings.

[0052] In embodiments, the NCE matrix can act as a vehicle for active agents used in the household products and personal care industries. Because they can be dehydrated and redispersed, the NCE compositions prepared according to the methods disclosed herein can be used as vehicles for active agents in detergents, bleaches, fabric softeners, soaps, fragrances, skin care items, cosmetics, and the like.

[0053] Once the desired NCE matrix suspension is formed with the active agent and other secondary additives disposed therein, it may be dried for use as a formed article. The dried NCE suspension with the desired active agent within the NCE interstices may be formed as dried or gelatinized sheets, chips, balls, cubes, etc., which may then be rehydrated with resuspension and release of the active agent. These form factors allow for convenient transportation and storage for the formulation without the need for large fluid volumes.

[0054] For example, a sheet can be formed using an NCE-based matrix to distribute a product or active agent within a desired environment for a desired period of time. A sheet can be formed from an NCE-based (mased) matrix with detergent and / or other cleaning agents (e.g., enzymes or bleach) disposed within the matrix interstices; this sheet can be delivered to a washing machine or dishwasher, where it comes into contact with water, delivering the cleaning agent(s), and the NCE-based matrix is ​​eventually dissolved due to the dispersion of the NCE components.

[0055] Thus, as another example, redispersible dry chips, plaques, strips, etc., can support various actives in a convenient dry vehicle, releasing them as a final formulation upon simple rehydration or redispersion. As an example, soap or shampoo chips can be made from NCE suspensions containing the desired soap product by dehydrating the suspension to produce a solid composition. Lightweight, conveniently sized chips can be rehydrated by the consumer with water to form the final liquid formulation reconstituted to the required standard. In commercial embodiments, manufacturers can make precisely measured chips for use with proprietary containers of known volume, allowing the consumer to simply insert the chip and fill the container with a specified amount of water. In embodiments, the container for reconstituting the NCE-based composition can be reusable, allowing manufacturers to avoid using plastic or glass containers to transport, display and store household products or cosmetics. In other embodiments, no container is required, and the chip of the NCE-based composition can be held on the hand while washing with water. Thus, reconstitution occurs during the process of washing hands, which can be particularly useful for travel or in areas where water is not readily available.

[0056] Although a flat chip shape is described as an exemplary embodiment, it is understood that the NCE-based compositions can be formed in any desired geometric structure, including, but not limited to, regular or irregular spheres, rectangles, cubes, cylinders, thick sheets, rolls, etc., with shapes selected to provide an attractive form for consumer use.

[0057] Examples of useful active agents in NCE-based matrices for household use include bleach, laundry detergents and combinations thereof, dishwasher soaps and dishwasher treatments, toilet bowl cleaners, and other industrial heavy soil cleaning products such as oven cleaners, floor cleaners, etc. These products can be formulated to incorporate other advantageous properties such as sustained release. Similar NCE-based products can be envisioned for other areas, such as medical products, where the active agent can be carried within the matrix of the NCE composition.

[0058] In an embodiment, active agents such as those exemplified above can be embedded in a sheet formed of NCE matrix delivered in a fabric dryer as a substitute for well-known dryer sheets. Conventional dryer sheets are fibrous sheets, usually made of compressed polyester or cellulose fibers, which are coated in a thin waxy layer of laundry products such as fabric softeners, fragrances, static electricity reducing agents, etc. When used in a high temperature dryer, these laundry substances melt out of the dryer sheet fibers and are distributed evenly throughout the laundry load, applying all the benefits of the listed materials. However, the materials used in conventional dryer sheets can be petroleum-derived and resistant to biodegradation, resulting in the accumulation of these materials in landfills. As an alternative, NCEs can be used as a carrier matrix for laundry products, replacing conventional nonwoven materials and providing an environmentally friendly, biodegradable alternative to conventional dryer sheets. In an embodiment, NFC, MFC or mixtures thereof can be used alone or in combination with other matrix materials, such as pulp or pulp-based materials, to make articles such as dryer sheets disclosed herein. Advantageously, the use of an NCE matrix provides high strength and biodegradability while forming a porous material that can act as a carrier for active agents distributed within the dryer.

[0059] To this end, formulations for NCE redispersion disclosed herein may be modified to have higher concentrations of hydrophobic cellulose polymers, such as hydrophobic cellulose polymers (e.g., methylcellulose) in the range of about 0% to about 10%, resulting in a strong network of fibers. In embodiments, the plasticizer should preferably be hydrophobic to protect the sheet from saturation and weakening by water. Plasticizers such as diesters and triesters of certain acids, e.g., triethyl citrate or diethyl phthalate, and diesters and triesters of certain alcohols, e.g., triacetin and vegetable oils, are advantageous. More hydrophobic plasticizers may be difficult to mix with water-based NCE suspensions, but mechanical mixing may overcome their limited solubility to impart the desired hydrophobic properties to the dryer sheets thus formed, so that they will withstand the stresses imposed by heat and movement within the fabric dryer. Fatty acids may also be used as plasticizers, especially in more hydrophobic applications.

[0060] After the NCE matrix is ​​formed, materials that typically coat dryer sheets can then be applied using techniques well known in the art, such as aerosolized sprays that disperse particles of wax, including materials such as fabric softeners, antistatic chemicals, and natural fragrances suspended therein. This wax-like material is then cured on the surface of the sheet so that it can melt out of the sheet and coat the fabric in a heated dryer. In embodiments, active agents can be premixed into the NCE matrix before it is dried to form a sheet. In other embodiments, the NCE matrix can be formed, extruded, and dried first, and the wax containing the active agent(s) is applied thereafter. The use of an NCE matrix provides a larger available surface area for each sheet compared to conventional laundry sheets of similar dimensions due to the increased surface area and more interstices inherent in the much smaller fibers. The larger surface area allows each sheet to carry a larger volume of active agent per sheet, reducing the required number of sheets required for a single load of laundry.

[0061] In embodiments, laundry sheets can be made as a single sheet using NCE dispersion technology previously described, for example, using cellulose polymers and plasticizers to facilitate such dispersion. When a matrix is ​​formed with redispersed NCE, suitable actives, such as laundry detergents, cleaning products, and / or surfactants, laundry actives such as bleaches and enzymes, and optional ingredients such as chelating agents, antifoaming agents, emulsifiers, etc., can be added before forming it into a single sheet. The mixture of redispersed NCEs, actives and secondary additives can then be vigorously mixed; in embodiments, sufficient mixing can be applied so that the mixture is exposed to air and foams. The mixture can then be formed into a sheet using conventional techniques and dried. Once prepared and cooled, the resulting sheet can provide a stable substrate layer that contains laundry agents, such as detergents / surfactants or other cleaning products, within its material core, but also provides a platform for supporting other more active agents such as enzymes and bleaches that do not withstand heat treatment.

[0062] In other embodiments, the NCE matrix configured as a sheet can be used to enclose actives in a layered arrangement. For example, two outer layers formed of NCE-based sheets can encase laundry detergent, cleaning products or other actives between them like a sandwich. Such actives can then be dispersed on the surface of the prepared sheet, which is then covered by another sheet, and the two layers are gently pressed together to trap the actives in the sheet "sandwich" without applying heat or force that would damage these more delicate components. Thus, the composite laminate structure becomes available to distribute both the actives (detergents, surfactants, emulsifiers, chelating agents for hard water treatment, etc.) embedded in the matrix during sheet formation, and any actives or secondary additives that are dispersed on the surface of the matrix and are not subjected to heat or excessive pressure. When the laminate carrier structure is exposed to water and decomposes, all the components become available during the washing process, releasing all of the actives and / or other additives that it supports.

[0063] The active agent may be present in a solid form, for example as a compressed powder, or may be suspended / emulsified in a viscous gel, or not. A dispersible NCE layer may release the active agent when required by a particular application, for example when contacted with water (or hot water) during a wash cycle. In other embodiments, multiple NCE layers may be arranged with different active agents layered therebetween. Such NCE layers may have the same release / redispersion properties or different ones, which may allow for differential release of different active agents consistent with the selected application.

[0064] LCST polymers can be used together with laundry or soap or other cleaning sheets or alone, and their proportions can be selected based on their lower critical solution temperature or the temperature at which their hydrophilicity transitions. The amount of plasticizer can also be adjusted to fine-tune the timing at which the sheet dissolves. Furthermore, adjusting the dispersibility by varying the type and amount of LCST polymer can be useful for applications requiring different temperatures, and adjusting the amount of plasticizer can allow for faster or slower dissolution.

[0065] In embodiments, an NCE-based matrix containing a soap product with fragrances, softeners, etc., can be formulated for convenient use while traveling, so that it delivers actives upon contact with water, thereby allowing hand washing, dish washing, etc., without prior reconstitution. As discussed in more detail below, additives such as colorants and fragrances can be incorporated into the NCE-based matrix using oil- or water-based delivery vehicles to affect the properties of the matrix, to accompany other actives, or to act as the primary active itself. As used herein, a color-forming additive can be any pigment, dye, fragrance, or other colorant that changes the perceived color of the matrix or article by absorbing or scattering different wavelengths of light along the visible spectrum. A variety of color-forming additives for various industrial, household, cosmetic, fabric, and other products are compatible with the NCE-based formulations and matrices disclosed herein.

[0066] For example, sheets or formed articles (e.g., balls or cubes) can be formed using NCE-based matrices with fragrances in the matrix interstices, which can be used, for example, for odor control purposes in closed spaces. More specifically, NCE-based matrices can be used to contain odor blocking chemicals or natural fragrances adapted for release in small rooms with high levels of odoriferant materials, such as closets, sports bags, suitcases, etc., or adapted for use in personal items prone to odor release (e.g., shoe insoles or linings). NCE matrices adapted for these purposes can incorporate plasticizers or other additives to tailor the release of odor control agents or to tailor their release to specific environmental conditions (e.g., shoe linings that release odor control substances when in contact with warm feet). Similarly, NCE-based matrices can be formulated with deodorants or odor-inhibiting substances in the matrix interstices, which serve to allow for more durable application of such products to the skin.

[0067] Base formulations for odor control articles may include an NCE supply treated with plasticizers, e.g., cellulose polymers such as glycerol and methylcellulose, with ratios of these two actives to the dry NCE ranging from 1:1 to 12:1. This creates an NCE-based matrix in which other more hydrophobic chemicals, e.g., aromatic and oil-based fragrances, may be suspended, resulting in a more hydrophobic environment that may provide additional benefits such as preventing degradation upon contact with moisture or aqueous solutions.

[0068] Whether odor control, odor blocking or odor generation is intended, these odor-related actives (e.g., odor prevention, odor blocking or odor (fragrance) generating agents) can be mixed into the NCE-based matrix at the desired concentration (e.g., in the range of about 1% to about 30% or 10% to about 20%) to achieve the required odor intensity. When finished, a viscous liquid is formed that can be spread to form a sheet having a thickness that can typically range from 0.1 mm to 3 mm, or the viscous liquid can be formed into any other desired shape by using techniques well known in the art for forming articles. For the above-mentioned films or sheets, after spreading, they can be dried in a low temperature oven to form a dry paper-like layer that can be used separately or integrated into other manufactured articles. The article thus formed, whether a flat sheet or a three-dimensional shape, can constantly release the desired odor at a rate determined by the amount of plasticizer used. The flexible geometry that the sheets provide can be useful in areas that are more difficult to access, such as sneakers or thin crevices in the home. It is understood that different geometries distribute the fragrance differentially. In embodiments, the fragrance can be suspended within these sheets or shapes, such as pods or cases.

[0069] In embodiments, various fragrances may be used by the systems disclosed herein. The term "fragrance" as used herein refers to various odors that may be purposefully integrated into and delivered by the matrices, shapes, and vehicles described. For example, pleasant fragrances may be used for cosmetic or aesthetic purposes, or to mask unpleasant odors. Fragrances may be used for medical, veterinary, or agricultural purposes to act as insect repellents, pesticides, pheromones, growth hormones, and the like. Fragrances may be provided from volatile aromatic compounds, such as essential oils, hydrosols, fragrance microcapsules, and the like. Exemplary supplies may incorporate biological oils and chemical supplies suspended in solution for easy application or mixing. Other supplies for fragrances may be water-based, such as hydrosols. The biodegradable nature of NCE-based vehicles makes them particularly useful for delivering fragrances or other active agents that are released naturally into the environment: degradation of the vehicle (e.g., the sheet) facilitates release of the active agent; the rate of release can be controlled by careful selection of the active agent and vehicle components and by modifying the ratio of each component.

[0070] Other examples of the fragrance-based technology based on the formulations disclosed herein include, but are not limited to, agricultural insecticides, fragrances and odor neutralizers for domestic use, and pet hormones to promote calm behavior around the home.By controlling the rate of release through careful manipulation of the base technology, applications can be personalized for different consumer needs, for example, agricultural products that release insecticide quickly during the planting season and more slowly when the plants are fully grown.

[0071] In an embodiment, the NCE matrix containing agricultural active ingredients can be applied to agricultural products used in the treatment of agricultural products, where such treatments can include additives, fertilizers, pesticides, hormones, nutrients, or other treatments intended to improve the life or health or post-harvest condition of agricultural products or to improve harmful conditions associated with the products, as understood by those skilled in the art. As an example, the NCE matrix containing agricultural active ingredients can be used as a coating by spray for plants or seeds. For live plants or plant materials, the NCE matrix can include active agents intended to repel or kill insects, fungi, etc., or can include nutrients or other beneficial agents or other agricultural active ingredients. For seeds, the NCE coating can be used to mark or designate the seeds, to allow color grading or other differentiation, or to repel moisture, dust, or other physical contaminants. The NCE matrix can support active agents intended to promote growth or protect against pests and fungi, such as sustained release formulations of such active agents, and can also protect against mechanical damage. In embodiments, the NCE matrix for seed coating can contain precisely formulated agents (e.g., fertilizers, micronutrients, crop protection chemicals and biologicals, temperature-sensitive polymers, water-retaining materials, colorants, beneficial organisms, etc.) that can be distributed over appropriate time intervals after application. The NCE matrix can further be formed into a structure that can support seeds pre-loaded with protective substances such as nutrients, fertilizers, or herbicides embedded within the matrix at precisely positioned intervals, optionally combined with materials that can retain water around the seed itself, thereby facilitating planting and optimizing seed growth.

[0072] For example, as previously described, matrices containing fragrant materials can be easily formed from NCE matrices, optionally in combination with plasticizers to control the release of odoriferants. This technology can be adapted for agricultural purposes, for example, using pheromones as agricultural active ingredients. Pheromones are understood to be secreted or excreted chemicals that trigger a social response in members of the same species. Although they may not have an "odor" as the term is commonly understood, pheromone receptors are typically located in the olfactory epithelium or vomeronasal organ, indicating that they are conventionally processed in similar pathways. Thus, pheromones are considered to be odor-related active agents for the purposes of this disclosure.

[0073] Certain pheromones are known to have applications in agriculture as pesticides or artificial growth hormones. The pheromones can be suspended in an NCE matrix and formed into sheets or formed articles, and the pheromones are released into the environment at a controlled rate as the NCE matrix degrades. The rate of release can be controlled by careful selection of the plasticizer and modification of its amount in the matrix substrate. Hydrophobicity can be controlled by selection of additives that impart hydrophobic properties to the matrix, such as cellulosic polymer additives (e.g., polymers of higher or lower hydrophobicity). NCE matrices containing more hydrophobic materials take longer to degrade and release the pheromones into the environment at a slower rate, promoting long-term growth. An additional benefit of this technology is the contribution of cellulose to the soil, which promotes the activity of beneficial insects in the environment to aerate the soil and to decompose the cellulose into materials useful to the plant, such as carbon dioxide.

[0074] It is understood that other active agents having agricultural effects can be similarly incorporated into the NCE matrix for application to growing plants. For example, in embodiments, growth hormones can be included in the matrix and released in a controlled manner as described above. In other embodiments, insecticides, fungicides, pesticides, and the like can be incorporated into the NCE matrix. For these purposes, the matrix itself can contain a plasticizer to facilitate diffusion of the active agent into the ambient air, if that is the appropriate mechanism of action; such plasticizers can be advantageously hygroscopic to aid in the diffusion of the active agent when it is airborne. To retain the active agent within the NCE matrix without premature release and without damaging the matrix itself, the matrix material can be thickened using thickening agents such as cellulose polymers, starches, gelatins, and the like. Similar techniques can be used for insect repellents such as DEET, permethrin, picaridin, and the like. These materials can be incorporated into the NCE sheet and applied directly to the skin or articles of clothing. When the sheet dissolves, the remaining active agent deposits locally and continues to provide insect repellent activity. Proper selection of the plasticizer can extend the release of the insect repellent to extend protection.

[0075] Also, matrices used for agricultural purposes can be coated or formulated with hydrophobic components to protect agricultural active agents and prevent them from washing away after application. This ability to protect active agents and provide controlled release can be useful for distributing fertilizer to plants over an extended or predetermined time period. In contrast, current fertilizer formulations are water-soluble, so they can be easily washed away on rainy days. It is understood that the more hydrophobic selection of components for the NCE vehicle (facilitated by the selection of more hydrophobic cellulose materials, such as methylcellulose, or by the addition of oils or waxes) will take longer to decompose in moist environments, such as the ground or areas with high humidity, releasing pesticides, hormones, fertilizers, etc., to the environment at a slower rate, promoting long-term growth. An additional benefit of this technology is the contribution of cellulose to the soil, which promotes the activity of useful insects in the environment to aerate the soil and to break down the cellulose into materials useful to the plant, such as carbon dioxide. The NCE-based technology disclosed herein can cooperate with agricultural active agents to promote healthy growth of plants for stronger and more abundant crops.

[0076] ii. NCE matrix as structure: solubility properties NCE matrices have mechanical properties due to their incorporation into the structural framework of themselves, so that matrices can be used to support or cover structures for formed articles that have advantageous mechanical properties such as strength and stability, but are also engineered to be dissolvable at a time appropriate for consumer use.

[0077] This property allows the container to be constructed with sufficient durability to hold the contents of the container during consumer use, but also allows for easy decomposition and biodegradability of the container after use.This property allows the container to be constructed for more short-lived purposes, such as containers for fertilizers or agricultural products that are intended to dissolve in a short time to release the agricultural products into the environment.This property also allows the container to be constructed to deliver active agents, such as for laundry or other home care purposes, to dissolve quickly when encountering water.

[0078] For example, sheets, strips, etc. formed with an NCE matrix can be used to provide a wrapper or container for covering or otherwise delivering an active agent therein, providing an easily dissolving (dispersible) container for useful materials, making such materials more conveniently dispersible for consumers. For example, an active agent, such as a cleaning product, laundry detergent, or dishwasher soap, can be enclosed in a biodegradable sheet containing a dispersible NCE matrix. One or more compartments can be formed with the NCE-based packaging material, so that various active agents can be kept separate within a single article when necessary. In embodiments, sheets formed with an NCE matrix can be joined together to form a container for covering an active agent, such as a laundry product, as a payload within a closed NCE envelope; such sheets themselves can also contain active agents within their interstices, so that more than one type of laundry product is delivered, each one kept separate from the other(s). The differential solubility profile may allow the active agent within the NCE matrix sheet itself to be delivered first, followed by sufficient dissolution of the encapsulating sheet structure around the payload to compromise its integrity, allowing delivery of the payload.

[0079] In embodiments, the NCE-based packaging material may enclose a paste or gel, for example, containing a laundry detergent or other cleaning product in powdered or gel or liquid form, and optionally containing other actives such as bleach, enzymes for stain removal, fabric softeners, etc. In embodiments, actives such as those exemplified above (e.g., cleaning or laundry products) may be wrapped in the NCE-based packaging material to form a pod-like container for the actives. In embodiments, the packaging material formed of the NCE matrix sheet may wrap completely around the product, or the packaging material may be placed above and below the actives and sealed to enclose the actives. Sealing two NCE packaging sheets may be performed using heat (searing) or by applying a natural polymeric adhesive to stick them together. In embodiments, a thin, lightweight sheet formed of the redispersible matrix, weighing about 1 gm, may be shaped as a pod or envelope to contain up to about 30 gm of detergent powder within it. In other embodiments, the NCE-based matrix can be extruded from a circular die as an open, elongated tube. The tube, with or without an active agent inside, can be cut to the desired length and the ends can be sealed by pinching, baking or gluing. Alternatively, a hollow tube can be cut to the desired length, one end sealed, and then the desired components are filled into the hollow interior.

[0080] In yet other embodiments, the NCE-based matrix may be used as a packaging or container for cleaning products, such as toilet bowl cleaners, allowing for the creation of disposable, biodegradable toilet cleaning pads or cleaning brushes that are used in place of traditional systems for toilet bowl cleaning, including reusable brushes and cleaning products that are dispensed into the toilet bowl. In such embodiments, the cleaning product may be encased within one or more external NCE matrices to form a single-use, flushable, biodegradable cleaning pad or brush, which may be attached by the user to a wand, extendable member, or other applicator before using the cleaning pad to scrub toilet surfaces. Upon completion of the cleaning process, the cleaning pad may be removed from the applicator and flushed with the water in the bowl used to rinse the cleaning product. Advantageously, the cleaning pad may be removable by the user via a mechanism on the proximal end of the applicator, so that the user does not have to directly contact the flushable pad or brush to remove it. As a further advantage, the NCE-based matrix containing the cleaning product may have abrasive properties (described in more detail below), and these properties may be optimized so that the scrubbing surface of the pad is adapted to clean the toilet bowl surface. This system, which includes an applicator and flushable pad or brush, is a hygienic alternative to conventional toilet bowl cleaning systems, since there is no multi-use toilet brush that must be stored between exposures to the contaminated surfaces of the toilet. Instead, the applicator can be made of a smooth plastic material that resists attachment of contaminated material; instead, the contaminants remain attached to the exterior NCE-based matrix of the cleaning pad, and the pad itself is washed away. The biodegradability of the NCE-based matrix allows the pad to quickly degrade after cleaning is accomplished, minimizing the risk of clogging plumbing after flushing.

[0081] The paste or gel enclosed within the dispersible NCE matrix-based container may be formed by suspending the active agent in a vehicle formed of a water-soluble, non-aqueous, viscous liquid polymer, such as poly(propylene) glycol, polyethylene glycol, polyethylene oxide, polyoxyethylene, and the like, and derivatives thereof. A thickener that is soluble in the water-soluble, non-aqueous, viscous liquid polymer, such as a cellulose polymer, such as hydroxypropylmethylcellulose, methylcellulose, and the like, may be optionally added, optionally in combination with a dispersible (i.e., water-soluble), hygroscopic plasticizer, such as glycerol. In embodiments, the paste or gel may be formed by combining the detergent and the cellulose polymer or combination of polymers in a ratio of 8:1 to 15:1, a range of 2:1 to 8:1 ratios of dispersible viscous polymer to activity modifier of cellulose polymer and hygroscopic plasticizer, and a ratio of 50 / 50 to 95 / 5 of cellulose polymer to hygroscopic plasticizer. Compositions containing these substances can be highly viscous and create a medium for gels in which cleaning or laundry products, such as detergents, bleaches, enzymes, fabric softeners, etc., can be suspended. In embodiments, powdered or other concentrated forms (e.g., concentrated liquids, gels, emulsions, etc.) for the active agent(s) provide advantages, such as the coexistence within a gel of several different chemicals that normally cannot be physically combined due to their interactions when they are mixed together as aqueous fluids; in powdered or other concentrated forms, these chemicals can coexist within a gel without requiring separate compartments to store them apart. Furthermore, due to the powdered or concentrated forms of the active agent(s), the volume for each unit can be reduced to improve transport efficiency.This composition, including the active agent(s) suspended or emulsified within the paste or gel matrix, can then be packaged within a sheet or wrapper formed with the NCE as described herein to create a sealed, single-use container, such as a single or multi-chamber pouch, pod, or otherwise appropriately shaped packet that can be placed directly into a washing machine or dishwasher using safe, biodegradable materials that readily dissolve and release their contents upon contact with water. It will be appreciated that the active agents dispersed within the polymeric gel medium can be aligned to facilitate specialized cleaning, for example, within a layer, such as a layer of bleach-containing gel attached to a detergent gel for extreme cleaning strength, and they can be separated by a layer of sheet material therebetween.

[0082] The NCE-based packaging material enclosing the active agent(s) can further be engineered to tailor the release of the active agent, for example to create a time-release container or a container that requires a specific water temperature before dissolution. In embodiments, this timed or tailored release can be achieved by adjusting the amount of cellulose additives (dispersant materials) that can dissolve at different times. For example, one or more LCST polymers can be used to form the NCE-based packaging material, and their ratios can be selected based on their lower critical solution temperatures or the temperatures at which their hydrophilicity transitions. The amount of plasticizer can also be adjusted to fine-tune the timing of the dissolution of the packaging material. Furthermore, tailoring the dispersibility by varying the type and amount of LCST polymer can be useful for applications that require different temperatures, and tailoring the amount of plasticizer can allow for faster or slower dissolution, for example when using packaging materials with different properties to separate different compartments containing different active agents.

[0083] iii. NCE matrix as structure: barrier properties NCE matrices prepared for use as containers or films can be optimized for these applications to impart oil and grease resistance (OGR) and / or water vapor or water resistance (WVR) properties to the NCE-based structure. WVR properties are often expressed in gm / m 2 / day or g / 100in 2 The water vapor transmission rate (WVTR) is a measure of the water vapor permeability of a material per unit of water per day. Collectively, these coatings, formed articles, and material treatments that improve resistance to grease permeability and / or improve resistance to water vapor permeability and / or improve resistance to other fluids (liquids or gases) are referred to as "barrier treatments" or "barrier-making" materials. The resistance to selected fluids that they impart to the material or substrate matrix into which they are formed, such as OGR and / or WVR properties, are referred to as "barrier properties." Barrier properties can be tailored to allow differential permeability of various fluids or a selected degree of permeability of various fluids. By way of example, in embodiments, a barrier-making formulation can impart both OGR and WVR properties to the article it treats, and the relative strength of each property can be adjusted by adjusting the components selected for the formulation itself and / or by adjusting the relative amounts of the components, for example to emphasize hydrophobicity or oleophobicity.

[0084] In embodiments, the barrier formulation may be prepared to emphasize OGR or WVR properties or both; in embodiments, the barrier formulation may include both types of properties, and the formulation components may be adjusted to enhance or balance either the OGR or WVR properties. The barrier formulation may include components such as NCEs, cellulose polymers, filler particles, plasticizers, film-forming biopolymers, and the like, with different compositions and different amounts of such compositions being selected to emphasize OGR or WVR features in the barrier treatment, as applicable to the particular article being treated and formed. For example, since there is a range of cellulose polymers in which various polymers have different degrees of hydrophobicity or oleophobicity, the cellulose polymer may be selected to produce the desired degree of OGR and / or WVR. OGR technology may include cellulose derivatives and those that are specifically more hydrophobic. Overall, the cellulose derivatives previously described are oleophobic (hydrophilic), so it is beneficial to mix other materials that are more hydrophobic into the matrix to provide higher water resistance or higher overall OGR / VWR. For example, methylcellulose provides good resistance, although not as high as water resistance. A mixture of methylcellulose and cellulose acetate can be provided to tailor both OGR and WVR properties. The LCST polymers discussed work well for oil resistance, but films / coatings made with them are soluble at room temperature, making the water resistance properties less effective. Cellulose acetate and lipids are some examples of additives that can be used to tailor the OGR coating to be more hydrophobic, and a combination of this with a more oleophobic material can provide both oil and water resistance. Similarly, certain fillers have more hydrophobic or oleophobic properties: for example, fillers such as waxes can be selected to increase hydrophobicity or, for example, many excess NCEs can be added as pore blockers to increase oleophobicity. Fatty acids can also be used to increase hydrophobicity. Advantageously, the barrier formulation can be sprayable to allow easy application to either the surface of the formed article or the substrate itself for mixing.

[0085] More specifically, depending on the balance and amount of ingredients, barrier treatments can be formulated for use in three general categories: 1) with a barrier profile that balances OGR and WVR properties, with both OGR and WVR being effective; 2) with some WVR but significant OGR; and 3) with some OGR but significant WVR. Articles treated with category 1 barrier formulations can be used for applications such as food packaging where both oil repellency and water repellency are advantageous. Articles treated with category 2 barrier formulations can be used for those applications where oil resistance is a more important property, for example in containers for oil or greasy materials, and for packaging for oil-based products such as pre-measured amounts of salad dressing or cosmetic lotion, or for use as a more durable container that can contain motor oil and similar fluids instead of metal containers in this purpose. Articles treated with Category 3 barrier formulations may be used for those applications where water repellency (also waterproofing) is a more important property, such as in six-pack holders for coffee cups and beverage cans, or in grocery bags and other containers or packaging that are intended to be substantially water-resistant or leak-proof.

[0086] In embodiments, film-forming biopolymers can be added to barrier formulations, such as those intended for mix-in use. As used herein, the term "biopolymer" refers to those polymers produced by living organisms during the organism's lifespan. Such biopolymers can include, but are not limited to, exopolysaccharides such as bacterial cellulose, kefir, pullulan, levan, gellan, and other polysaccharides such as alginate, cellulose, carrageenan, gum arabic, starch, and plant glycomannan-like locust bean gum, mannan, guar gum, and the like. Biopolymers can also include biopolyesters such as polyhydroxy-alkanoates and polylactic acid derivatives. Advantageously, certain exopolysaccharides such as pullulan, kefir, cellulose, levan, gellan, and the like can be used to form films, for example for packaging applications. The addition of biopolymers useful as film formers or with other useful mechanical or barrier properties may allow the barrier formulation to be tailored and customized for specific purposes.

[0087] In embodiments, additional measures may be useful to address the porosity of the NCE matrix in which the formulation is supported. Addition to the base formulation, such as stearic acid or other long chain fatty acids to promote the hydrophobic properties of the barrier or wax beads as pore fillers to create a more hydrophobic base matrix for the formed article, may be provided.

[0088] Under certain circumstances, blocking of pores in the matrix is ​​advantageous to allow the barrier treatment to work or to improve its effectiveness. When blocking of pores is desired, the barrier treatment formulation (e.g., comprising a cellulosic polymer with varying hydrophobicity, a plasticizer, and an NCE) can be used in combination with additional pore-blocking materials, such as filler particles, to block the pores in the NCE matrix and improve the ability of the matrix to block oil, grease, and / or water. Such filler particles can include, but are not limited to, large or small particles of any shape or mixtures of different sizes and shapes made of natural or artificial materials, such as organic or inorganic components; by way of example, particles useful for this purpose include, but are not limited to, sand materials, pottery materials, resin materials, glass materials, polymeric materials, rubber materials, organic materials, such as nut shells (e.g., walnuts, pecans, coconuts, almonds, ivory palm, Brazil nuts, etc.) that have been appropriately cracked, ground, crushed, or crushed, and powdered materials that have been appropriately cracked, ground, crushed, or crushed. Other plant-derived materials such as crushed or crushed seed shells or fruit pits (e.g. plum, olive, peach, cherry, apricot, etc.), cracked, ground, crushed or crushed corn cobs, solid glass, glass microspheres, fly ash, silica, alumina, fumed carbon, carbon black, graphite, mica, boron, zirconia, talc, kaolin, titanium dioxide, calcium carbonate (e.g. precipitated calcium carbonate (PCC)), calcium silicate, and other specific particles, as well as combinations or composites of these or other similar materials. Advantageously, in some embodiments, filler particles may be selected that may be naturally hydrophobic or may be rendered hydrophobic, for example by linking or coating them with hydrophobic materials such as stearic acid or oleic acid (e.g. functionalized PCC). In embodiments, the filler particles may include waxes, either as a material for the particle itself or as a coating for other particles, and these waxes may be in wax form or in emulsion form (oil-in-water wax emulsion).For example, waxy materials such as beeswax, soy wax, carnauba wax, etc., may be used either as base particles or as coatings for other filler particles. As used herein, the term "wax" refers to any hydrocarbon that is a lipophilic, malleable solid near ambient temperature and typically has a melting point above about 40°C. By way of example, waxes may include long chain aliphatic hydrocarbons, typically having 20-40 carbon atoms per molecule, or fatty acid / alcohol esters, typically containing 12-32 carbon atoms per molecule, such as myricyl cerotenate, found in beeswax and carnauba wax. Filler particles may be mixed into the barrier formulation to impart pore-clogging functionality.

[0089] It is desirable in some embodiments to prepare the barrier formulation as a viscous suspension, with or without the presence of pore-blocking filler particles; for example, it has been determined that viscosity enhances the pore-clogging properties of the formulation and improves its grease-resistant properties. However, in other embodiments, for example when used as a mix-in formulation, it is advantageous to prepare a more dilute suspension: in embodiments, using a less viscous barrier formulation can improve the mixing of the barrier-making components with the pulp or pulp-based matrix material used to form the formed article. As used herein, the term "pulp-based" refers to those materials derived from pulp by processing, forming or treating while leaving the pulp or pulp derivatives in their material. Pulp and pulp-based materials can be used with the formulations, compositions and methods disclosed herein to be formed or shaped as components of or substrates for manufactured articles of any useful shape, such as sheets, fibers, solid articles, molded articles, etc.

[0090] In embodiments, the NCE-based OGR and WVR materials disclosed herein can be used as barrier treatments, such as (i) coatings on top of matrices or articles made therefrom to impart barrier properties to them; (ii) compound additives incorporated into other compositions or substances used to form articles themselves to impart barrier properties to them; (iii) films or packages with barrier properties to contain other substances or materials; or (iv) any combination of the above. More specifically, OGR and / or WVR formulations can be used as coatings or mixed into NCE-based slurries and shaped (e.g., thermoformed) into products. For example, in embodiments, containers formed of NCE matrices with OGR and / or WVR properties can be prepared, allowing the containers to reliably contain liquids or gels for delivery to consumers for other purposes.

[0091] In embodiments, the barrier-making components can be mixed into the NCE-based matrix formulation at any concentration (as described above); then, prior to molding / thermoforming, the mixture can be heated to just above the lower critical solution temperature of the LCST polymer of the barrier formulation. This procedure causes the LCST polymer to disperse within the mixture and precipitate (or "crash out") onto the surface of the fibrous NCE-based matrix. In other embodiments, the barrier-making formulation can be applied onto the surface of the article of manufacture using conventional application procedures such as painting or blade painting, curtain coating, etc., or spraying if the formulation is of a viscous nature that is compatible with the selected spraying equipment.

[0092] Films, sheets or formed articles with barrier properties provide important advantages when used in commercial products. For example, OGR or WVR pouches, pods or other packaging articles formed with NCEs as disclosed herein can serve as containers for condiments, dressings or other liquid or gel food substances, allowing consumers to open the package and dispense the food substances as desired. Such packages can conveniently contain and dispense water- or oil-based food substances such as soy sauce, ketchup, mustard, mayonnaise, salad dressings, dairy products, etc., thereby reducing the plastic consumption associated with conventional packaging for such food substances.

[0093] NCE packaging materials can be tailored to maximize other protective elements of the package, optimize oil resistance for oils or oil suspensions or optimize water resistance for aqueous solutions or suspensions, add strength, or reduce gas permeability to provide more sealed packaging properties. For example, packaging materials and sheets formed with NCEs having OGR and / or WVR properties can be used as components or full containers for liquids such as milk (e.g., shelf-stable milk cartons) that are sterilizable by techniques such as ultraviolet sterilization and other methods well known to those skilled in the art. In embodiments, these OGR and / or WVR packaging materials can be transparent or translucent with excellent mechanical properties such as tear resistance or stiffness, providing a viable alternative to traditional packaging and hermetic films made of polyolefins. In embodiments, OGR and / or WVR materials incorporating NCEs as disclosed herein can be modified by adding additional polymers or particles to the matrix material (e.g., PVA, PVOH, hydroxyethyl butyrate, exfoliated clay, etc.) to improve their sealing properties.

[0094] iv. NCE materials as structures: inherent properties The NCE matrix has certain inherent mechanical properties, including hardness, toughness, brittleness, rigidity, adhesion, durability, impact resistance, optical transparency, etc., which can also be enhanced or tailored for specific applications by incorporating the NCEs prepared as disclosed herein, optionally together with suitable secondary additives. Such inherent mechanical properties can be exploited in useful articles. These inherent mechanical properties can be advantageous alone or in combination with other features of the NCE matrix, such as their ability to act as a carrier, act as a dissolving container, or act as an oil, grease and / or water resistant barrier. In embodiments, NCE matrices can be prepared with inherent mechanical properties that are advantageous for specific applications while also providing a suspension framework for embedded active agents.

[0095] For example, nanoscale abrasive compositions can be formed by engineering the inherent mechanical properties of the NCE matrix to achieve a desired degree of hardness, strength and robustness. It is understood that during abrasion, the surface of the abrasive material forms an irregular interface with the abraded surface that tears or wears away particles on the abraded surface. Since NCE matrices are formed with their surface irregularities on the order of nanoscale, these matrices can be engineered for applications that require minimal gentle abrasion. As an example, NCE matrices can be used for minimal abrasion as removal pads for facial makeup or pads for skin exfoliation. In other embodiments, NCE matrices can be combined with soap products or body / face cleaners as exfoliants. In still other embodiments, NCE matrices can be used for minimal abrasion in dentifrices for oral hygiene to remove plaque or as dental products for professional use. NCE matrix formulations may be particularly advantageous for dental products such as toothpaste or tooth powder, by adhering the plaque to be polished to the excess surface area of ​​the matrix itself, facilitating the removal of plaque particles.In yet another embodiment, NCE matrix may be used to polish uneven or damaged biological surfaces, such as those found in bone or blood vessels.In an embodiment, NCE matrix used for polishing purposes may support embedded active agents, such as anticoagulants, which are applied to the polished arterial plaque to prevent subsequent platelet adhesion during the healing period.

[0096] Properly modified NCE matrices are suitable for use as household scrubbers, cleaners and wipes. For example, NCE matrix materials can be fashioned as scrubs or sponges, optionally preloaded with cleaning chemicals. In such articles of manufacture, the NCE structure can provide excess surface area within the matrix, allowing for extremely high capture of oil, grease, dirt or other spilled materials, while also providing abrasiveness that facilitates scrubbing. As an added advantage, the NCE matrix is ​​itself made of plant-derived products, making it disposable and compostable.

[0097] Properly modified NCE matrices can be easily converted into sheets or liquid foams that can be dried to form substitutes for conventional articles such as paper packaging or Styrofoam. Unfoamed sheets can be used as substitutes for paper wrapping, butcher paper, sandwich wraps, etc., where foam properties are not necessary; foams can be used in special situations where properties such as insulation, like packing peanuts, are advantageous or where light weight per unit volume is advantageous. In embodiments, barrier properties can be introduced into the foam using techniques to make the formulation more hydrophobic or oleophobic, as described above. In embodiments, grease-resistant properties can be imparted to the foam by making some or all of the NCE particles more oleophobic, and / or by using a matrix to support an oleophobic coating material, and / or by introducing other oleophobic additives; similarly, water vapor-resistant properties can be imparted to the foam by making some or all of the NCE particles more hydrophobic, and / or by using a matrix to support a hydrophobic coating material, and / or by introducing other hydrophobic additives. As described herein, foamed or non-foamed formulations can be customized to emphasize either oleophobic or hydrophobic properties, and such formulations may exhibit both types of properties to a greater or lesser extent.

[0098] More specifically, materials containing NCE matrices can provide a replacement for traditional foam products such as those found in synthetic Styrofoam packaging materials. Traditional packaging materials and containers are well suited for their end use because they are lightweight, shock absorbing and water repellent; however, these materials are made of petroleum-based plastics such as polystyrene that cannot be recycled and are therefore relegated to landfills, and they take centuries to decompose. The foamed NCE matrices can provide a biodegradable alternative with good inherent mechanical properties, or the NCEs can be used with other biodegradable materials to improve their properties for applications such as packaging materials, as described in detail below. To form sheets or liquid foams, the NCEs for forming the matrices can be treated to allow redispersibility as described above. In embodiments, the slurry of NCE redispersed at 2-3% can then be mixed with a cellulosic polymer and optional plasticizer, and / or combined with a hydrophobic or oleophobic material to impart the desired barrier properties; in other embodiments, the hydrophobic or oleophobic material can replace the cellulosic polymer, and in still other embodiments, the cellulosic polymer itself can provide the desired hydrophobic or oleophobic properties. Barrier-making additives, such as hydrophobic starch, hydrophobic cellulosic polymer, fatty acid, surfactant, or water-in-oil wax emulsions, can be added in ratios ranging from 1:1 barrier additive to NCE to 15:1 barrier additive to NCE, and preferably 3:1 to 9:1. In embodiments, foams can be easily made with NCE suspensions due to the high viscosity of these materials and their response to vigorous agitation or whipping, and barrier properties can be easily introduced into the foam. Foaming can be facilitated by adding a surfactant to the NCE suspension. Once the NCE suspension is foamed, flash drying can result in a fixed, foam-like feel in the sheet or formed article. As an example, by rolling or vacuum forming sheets of unfoamed or foamed NCE matrix, NCE-based products can be made into insulated, lightweight cups, plates, bowls, food packaging, take-out containers or trash bags with the added benefit of being biodegradable.As an example, a highly effective, lightweight insulation material can be made from the dried NCE foam with optionally exploitable barrier properties (OGR and / or WVR properties), a customizable feature.

[0099] The durability of the NCE matrix when dried on the skin may support a variety of other cosmetic and medical products, including, but not limited to, bandages and wound dressings based on the NCE matrix with disinfecting or clotting aids, insect repellents, anti-itch medications, pain relievers, topical anesthetics, vehicles for sustained delivery of health or wellness agents such as CBD oil, or diagnostic products or monitors for glucose monitoring, ionic conductivity, pH, etc. In other embodiments, the NCE matrix may be ingestible, for example for use with probiotics or pharmaceuticals, providing a controlled slow release.

[0100] The use of NCE matrices is particularly advantageous with active agents in certain personal care applications, such as hair hold formulations and cosmetics, due to the optical transparency of NCE suspensions. In embodiments, shampoos, hair conditioners, hair hold and hair color preparations can be formulated by including active agents in an NCE matrix with the matrix and then drying as a transparent layer on the underlying hair shaft surface. Hair products for temporary hair styling can also use NCE matrices to hold hair in a particular shape or style. More specifically, it is understood that hair sprays, mousses, gels, etc. are designed and used to hold many different hairstyles in place for hours at a time. These conventional products tend to use harsh chemicals to provide the desired "hold", and products lacking this class of chemicals tend to produce unsatisfactory hair hold: they may not hold well, or they may cause the hair to feel "crisp", or they may produce a stiff or unnatural look. Alternatively, the NCE matrix formulation may contain an active agent such as chitosan, which firmly adheres the NCE matrix to the hair strand and provides shape retention benefits. The product may be washed off the hair with water and regular shampoo. NCE-based formulations with chitosan or similar reinforcing secondary additives may produce durable hair hold with a soft, natural feel without the use of harsh chemicals.

[0101] NCE matrix can be used with a single active agent, but it can also support a combination of hair care products in a single formulation, such as shampoo, conditioner and shape retention agent, all applied at once as a single product.NCE can also be used to impart color to hair in an easy and gentle manner without the use of harsh chemicals.In other embodiments, NCE can be pre-colored before being suspended and / or incorporate colored particles such as lignin into their matrix, allowing convenient application to hair, such as dark gray hair, without the need for harsh chemical treatments used in conventional products.

[0102] In other embodiments, the NCE matrix formulation can be used to apply cosmetic or skin care (i.e., treat skin disorders or skin conditions, such as wrinkles or hyperpigmentation) products. As an example, skin creams can be formulated by suspending skin treatment substances (e.g., vitamins, lipoic acid, collagen, emollients, sunscreens, etc.) in an NCE matrix to form a product that is invisible on the skin after application due to the optical transparency of the NCE matrix. As another example, an NCE-based cream or lotion can be spread on the skin surface to smooth the skin surface and smooth wrinkles. With higher concentrations of NCEs, the formulation will shrink when dry and pull the skin as taught; with proper positioning and orientation of the applied formulation, it can exert a force that counteracts skin wrinkles or provides smoothness to the skin surface. As yet another example, an NCE matrix for sunscreen or sunblock is particularly advantageous due to its inherent strength after application, so that it forms a durable layer of sunscreen protection on the skin. In embodiments, pigments may also be added to mask the chalky appearance of sunscreens such as zinc oxide or titanium dioxide.As another example, skin creams or face masks may be formulated as shape-retaining materials that temporarily flatten wrinkles after application and drying due to the strength properties of the NCE matrix when dry; in embodiments, the matrix may be engineered to shrink when dry, thus exerting forces in a favorable direction on loose or wrinkled skin.

[0103] Vehicles can be prepared for medical skin treatment or transdermal pharmaceutical delivery using the NCE matrix. Pharmaceutical products, nutraceutical products, moisturizers, antioxidants, etc. can be incorporated into the NCE matrix and applied to the skin so that the active agent can pass through the matrix to the skin. As an example, application of an NCE matrix containing moisturizers, antioxidants, and topical retinol can be used as an overnight mask, which keeps the active agent in place while providing a dry outer surface for contact with bedclothes. Similarly, the NCE matrix can be used to apply pharmaceuticals or other beneficial products to localized areas of the skin. Topical products for acne or rosacea (e.g., salicylic acid, azelaic acid, topical retinoids, benzoyl peroxide (for acne), metronidazole, ivermectin (for rosacea), topical antibiotics (for both) embedded in the NCE matrix can be applied to the affected area for topical treatment. NCE matrices are typically translucent or transparent, but pigments can be included to opacify the product and hide the lesions underneath the treatment.

[0104] NCE matrix can be engineered for transdermal delivery of pharmaceutical products, especially those used as sustained release agents.For example, active agents such as nicotine, opioids, hormones, nitroglycerin, methylphenidate, MAO inhibitor antidepressants, clonidine, scopolamine, vitamin B12 and cyanocobalamin are compatible for delivery as transdermal patches that can be formed with NCE matrix.For certain applications, the patch formed with NCE matrix can support an array of microneedles, thus forming a microneedle transdermal patch that can be used for the controlled release of other pharmaceutical products.The presence of NCE in these patch products can improve the strength and durability of the patch.

[0105] Various biomedical and cosmetic manufactured articles may incorporate NCEs as a matrix for the delivery of medical or cosmetic actives, and may further incorporate NCEs as a filler for added strength. When used as a matrix, NCEs may form a framework for roll-on, spread-on or spray-on patches or liquid bandages. Such devices may be used to deliver pharmaceutical, nutraceutical or cosmetic products as actives, such as collagen, vitamins, retinoids, hyaluronic acid, etc. Such products may be delivered as liquid form factors, such as concentrates that can be further diluted or as easy-to-use liquids, or as solid form factors that are dissolved or suspended in water by the consumer, who then applies the reconstituted formulation to the affected area. In embodiments, NCEs may be applied as a film, i.e., a series of layers across the affected area, to cover and protect skin wounds and promote healing. Liquid NCE-based formulations may dry to form a thin, solid, flexible protective barrier, optionally transparent or translucent, so that healing can be monitored. Antiseptics or antibiotics or other special active agents may be included in the formulation to prevent or combat infection in the area covered by the barrier.

[0106] NCE formulations with oil, grease and / or water resistant properties can be combined with the NCE matrix so that the film applied to the skin will stay in place and be more resistant to wear and tear. For applications that incorporate an NCE as a delivery vehicle for active agents (e.g. creams, patches, bandages, etc.), the OGR / WVR component of the formulation can extend the useful life of the product on the skin. For example, adding an OGR / WVR formulation to an NCE matrix with an active agent is useful for those topical applications (whether for medical or cosmetic purposes) where a permanent period of skin contact is desired. OGR / WGR formulations can also be added to those compositions used in transdermal patches to protect the patch from water, sweat, skin oils, etc. that could otherwise loosen the patch and impair the delivery of their active agents.

[0107] NCE vehicles applied to the skin may be used in other applications such as semi-permanent tattoos or application of conductive lines or shapes to the skin to interface with sensors and transmit information (e.g., RFID tokens for wireless payment, portable medical records, biometrics, health monitoring, etc.) Other NCE-based formulations may be used for specialty inks, paints, adhesives, or conductive coatings or elements, where the NCE matrix provides support for the active agent or active particulate material.

[0108] In advantageous embodiments, lignin or other specialty materials, such as melanin or other dyes or pigments, may be incorporated into the matrix formed with the suspended NCEs to produce colored formulations for use in hair, nails, fabrics, etc. The natural affinity of NCEs with skin supports the development of nail formulations with pigments or other aesthetic elements within the NCE matrix to provide strong, chip-resistant nail polish for cosmetic applications or to treat brittle or damaged nails without the need for varnishes or harsh organic solvents. In other embodiments, NCEs may be used as strengthening agents for conventional nail polishes to improve their strength and chip resistance or to treat brittle or damaged nails.

[0109] In embodiments, the NCE matrix can be shaped to provide structural and architectural features for a particular article of manufacture. As an example, a foamed NCE matrix, optionally combined with a material such as hydroxyapatite, can provide a strong bone graft that can act as a scaffold for osteoblasts to develop into bone tissue. Alternatively, the NCE matrix can be shaped as a solid bone graft that is not foamed but contains other reinforcing and / or osteogenic materials within the matrix. In embodiments, the NCE can also be used as a scaffold for biomaterials that are not intended to degrade quickly, such as a scaffold for surgical meshes, semi-permanent sutures, or bioengineered implants, due to the durability of the NCE in the body. In embodiments, the NCE material can be engineered to have higher or lower biological durability depending on the application envisioned. In embodiments, the NCE matrix can also be formed as threads, drawn fibers, etc. for specialized applications. As an example, elongated threads formed with an NCE matrix can be used alone or with incorporated protein materials such as collagen as dissolving suture materials or biocompatible meshes with customizable degradation rates and customizable strengths that can be engineered into materials for specific applications.

[0110] b. NCEs as additives in composites: general characteristics In embodiments, the population of NCEs may be incorporated into an existing matrix composition (referred to as "existing matrix"), for example, organic matrices such as paper matrices, plastic matrices, liquid resin matrices, wood-based composites such as TREX, and inorganic matrices such as cement and plaster. Such matrices formed with a population of redispersible or redispersible NCEs incorporated into an existing matrix are referred to as "composite matrices". More specifically, the NCEs incorporated into an existing matrix to form a composite matrix may be provided as redispersible dry NC-containing materials with NC elements embedded therein as described herein, or they may be provided as NC elements redispersed and suspended within a redispersion formulation as described herein. In either case, the NCEs so prepared and provided are referred to as "additional NCEs" with reference to their inclusion in the composite matrix. Thus, the composite matrix is ​​understood to be a combination of an additional NCE and an existing matrix composition.

[0111] In embodiments, the matrix-forming material is coated and / or immersed in additional NCEs to form a composite material. As a result, the composite material may have special properties that exceed or are not found in the original matrix-forming material. For example, the composite material may exhibit special inherent mechanical properties such as strength, hardness, toughness, brittleness, stiffness, adhesion, durability, impact resistance, optical transparency, etc., where such properties are present in the original matrix-forming material, but the presence of the NCE in the composite article enhances such special properties. As another example, the composite material may exhibit barrier properties such as hydrophobic, oleophobic or water-resistant properties that may be present in the original matrix-forming material but are enhanced in the composite material, or that are not present in the original matrix-forming material but are provided in the composite material. As yet another example, the composite material may exhibit additional properties, i.e. properties that are not present in the original matrix-forming material but result from the use of the NCE in their normal or modified state. One such additional special property, i.e., a property not typically present in the original matrix-forming material but imparted through the incorporation of an NCE formulation in the composite, is electrical conductivity, which can be introduced into the composite through the use of NCEs and the silver mirror effect, etc., as discussed in more detail below.

[0112] Although the special properties of composite materials using NCEs are already contemplated in industry, their application is hindered by the redispersion problems mentioned above. The redispersion techniques disclosed herein facilitate the transport of NCE compositions, which can then be resuspended to be combined with other matrix-forming materials to produce composite materials. In embodiments, these redispersion techniques can produce a homogeneous mixture of high aspect ratio NCEs within the main matrix-forming material, allowing for the enhancement of desired special properties in the final composite, such as inherent mechanical properties such as strength, hardness, toughness, brittleness, stiffness, adhesion, durability, impact resistance, optical transparency, etc., as described in more detail above. In other embodiments, the use of NCE formulations made using the redispersion techniques disclosed herein can introduce or enhance special properties, such as barrier properties that allow the composite to have a desired degree of oil and / or water vapor resistance. In yet other embodiments, the use of NCE formulations made using the redispersion techniques disclosed herein can provide composite materials with new special properties, such as electrical conductivity, that are not present in the original matrix-forming materials.

[0113] i. NCEs as Fillers: Exemplary Articles Fillers are understood to improve the mechanical properties of organic and in organic materials or to make products cheaper, lighter, etc. Fillers can improve composite properties such as strength, hardness, toughness, brittleness, stiffness, adhesion, durability, impact resistance, optical clarity, etc. NCEs are already used as fillers in consumer products, but their use is limited due to the redispersibility issues described herein. The methods for NCE redispersion disclosed herein may enable wider adoption of these additives as reinforcing agents for paper, resins, cements, and plastics, further enabling a dramatic expansion of new applications. As used herein, the term "reinforcing" refers to the improvement of mechanical characteristics belonging to strength, hardness, toughness, brittleness, stiffness, adhesion, durability, impact resistance, optical clarity, etc. found in an existing matrix; a composite matrix having improved mechanical properties compared to a constitutive existing matrix may be referred to as "reinforced" due to the reinforcement of the composite due to the presence of NCEs.

[0114] Although NCEs are inherently hydrophilic, they can also be used as fillers in hydrophobic environments.For use in hydrophobic environments, NCEs can be surface-modified to match the properties of the hydrophobic matrix in which they are incorporated, so that they are compatible with the matrix and can be uniformly dispersed therein.In an embodiment, the surface modification of the additional NCEs prepared according to the method disclosed herein can be carried out, for example, using a hydrophobic monolayer on the NCE. Such NCEs that have been hydrophobized for use in hydrophobic matrices are not only redispersible upon drying (as are unmodified NCEs in hydrophilic environments), but their hydrophobic coatings also make them compatible with a variety of polymeric "plastic" materials, such as thermoplastic and thermoset matrices (e.g., polypropylene, polyethylene, polystyrene, polyester, poly(acrylate / methacrylate), rubber, silicone, urethane, epoxy, etc.), to produce strong, lightweight, non-porous solids for molding and extrusion, as well as open- or closed-cell foams for other applications. In embodiments, hydrophobically modified NCEs can provide renewable, lightweight, high-performance fillers for advanced composite hydrophobic materials for applications such as vinyl siding, deck flooring, composite roofing, injection molded plastic parts, reinforced Styrofoam products such as automotive bumpers, fenders and dashboards, insulation blocks and ceiling tiles. In other embodiments, NCEs can be dispersed in adhesives that are commonly added to matrix materials, such as oriented strand board or other wood-based building materials, thereby improving the strength of the adhesive itself and the strength of the matrix material.

[0115] The lightweight and environmentally friendly nature of the NCE reinforcing fillers makes them particularly suitable for medical applications where the NCEs can be used to add strength to medical articles, such as those that may be intended for temporary use. For example, the NCEs can be added to mold materials to strengthen them without adding weight. As another example, the NCEs can be added to bandage materials to strengthen them. When incorporated into traditional bandages or hydrogel bandages, the NCEs make the bandages more durable while adding some structural protection to healing wounds. Similarly, the NCEs can provide reinforcement when used in cosmetic products. Patches with pharmaceutical, nutraceutical or cosmetic active agents can gain significant strength gains with low doses of the NCEs dispersed in the product. The NCE fillers can be used with traditional polymeric matrices, such as hydrogels, polyethylene, PVC and other dressing materials, allowing for increased strength and durability while allowing for lighter and thinner bandages. The NCE fillers can also be used with NCE matrices to improve strength and durability, as previously discussed. Similarly, cosmetic products such as face masks, nose strips and acrylic (fake) nails may benefit from the strength imparting properties of adhesives and NCE fillers.

[0116] As another example, NCEs incorporated as fillers into other polymeric matrices may provide an environmentally attractive option for reinforcing recreational facility articles. In embodiments, NCE-reinforced polymers may serve as substitutes for synthetic materials used in surfboards and boat hulls (e.g., fiberglass resin, polyurethane or polystyrene foam core (surfboards), carbon fiber, fiberglass, polyethylene (skulls)) with less weight and retaining strength in a more environmentally conscious manner. NCE additives may also be used to improve the strength and elasticity of recycled plastics. They may also facilitate the transition from petroleum sources of plastic materials to more sustainable sources of plastics that often lack the performance characteristics of petroleum-based materials. For example, Lego has experimented with using biopolyethylene derived from sugarcane, but this material may not be able to be used as a substitute for the petroleum-based acrylonitrile-butadiene-styrene (ABS) copolymer used to form its bricks; NCE additives may improve the toughness and strength of materials similar to biopolyethylene, allowing reinforced bio-based composites to be used as a potential substitute for materials such as ABS.

[0117] As yet another example, for athletic shoes, the sole can be made of NCE reinforced polymers or as composites using an NCE matrix to reduce the amount of materials such as ethyl vinyl acetate and polyurethane and silicone gel used in the shoe, thus providing a more environmentally friendly product. NCE matrix foams or foams containing NCE reinforced fillers can be used in these applications to provide support and comfort to the wearer. The inclusion of this NCE can increase bending-torsion-tear resistance due to the reinforcing effect of the fibers while keeping the shoe sole lightweight and shape-retaining. As an added benefit, viscoelastic damping can be imparted by the fiber matrix throughout the sole, blocking the transmission of physical shock waves through the sole to the wearer's body with small, stiff fibers to absorb some of the physical forces.

[0118] As a further example, architectural coating products containing resuspended NCEs can be formulated to be intrinsically injected, allowing for ready use on drywall, wood, concrete, brick, etc. The presence of NCEs in coating products can provide improved substrate adhesion and drip control, crack resistance, and resistance to corrosion. There are other opportunities to improve building materials by incorporating NCEs to create high performance materials such as sag-free stucco, lightweight and strong sheetrock (drywall), oriented strand board and similar composites, easy to work with and crack resistant faux wood concrete countertops, synthetic flooring and bath tile, stucco moldings, interlocking compounds, artificial lightweight carved stone, recycled glass cement-NFC / MFC composites, etc. Opportunities also exist to create durable inks that can be used for fertilizer-able products through the use of NCE-filled resins. Wheeled vehicles such as cars, trucks, aircraft, ATVs, motorcycles, scooters, bicycles, wheelchairs, etc. can also benefit from NCE-filled tires to improve wear resistance, strength, and durability. Lightweight, foamed versions of the NCE-containing materials can be formed for specific applications.

[0119] NCEs can be used as fillers in a variety of environments, as shown in the examples above. Once redispersed, NCEs can be provided with an appropriate coating to allow them to interact with the selected polymeric matrix. As such, they can add strength and elasticity without weighing down the composites incorporating them. They can also substitute for existing fillers to provide a plant-derived alternative to traditional petroleum-derived or inorganic fillers. For example, 3D printing materials are typically plastics such as ABS, polylactic acid, polyvinyl alcohol, polyethylene terephthalate glycol, nylon, and various resins that can be reinforced with fillers such as carbon fiber, Kevlar, and glass fiber. NCEs can substitute for inorganic fibers as a more sustainable component of the overall 3D printing substrate.

[0120] ii. NCEs as Matrix Pore Closures: Exemplary Articles Nano-sized NCEs allow them to be incorporated into the pores of existing matrices, resulting in advantageous properties for the resulting composite article, where the advantageous properties are based on their presence in the pores to reduce the porosity of the native matrix. Thus, in embodiments, NCEs can be used as coating products for existing matrices, such as paper products, to fill the pores in the paper matrix to create high-value specialty paper products. As an example, a paper product with NCEs embedded in its pores can provide grease resistance. As another example, a paper product with NCEs embedded in its pores can be engineered to form a releasable label backing or selective adhesive. In embodiments, all forms of cellulose, hydrophobic emulsions, fatty acids, any film-forming material, etc. can be used for these types of applications, where NCE-based formulations are used to provide advantageous properties in the composite article. All such additives can be used alone as single additives, added together, or added sequentially.

[0121] iii. NCEs as Substrate Components: Exemplary Articles Although films, sheets, formed articles, and the like may be formed substantially entirely of an NCE matrix, as discussed above, additional NCEs may be incorporated into existing matrices made of other polymeric materials to create composites with advantageous and / or special properties. Such existing polymeric matrices that are receptive to the addition of additional NCEs prepared by the methods disclosed herein may be provided in formulations suitable for the incorporation of additional NCEs, optionally including other additives with advantageous properties. By selection of appropriate polymers and additives for the existing matrix into which the NCEs are incorporated to form a composite, properties such as structural strength, resilience, elasticity, water resistance, oil resistance, etc., combined with biodegradability, may be imparted to useful articles formed therefrom. These polymeric matrices and formulations into which additional NCEs are added to create composite matrices are referred to as "constructive polymeric substrates (CPS)."

[0122] In embodiments, the addition of NFC / MFC to CPS can be done directly from a low concentration suspension (about 2 wt%) or can be added in dry form with redispersion additives to cut water, costs, and enhance redispersion. The final NCE-containing polymer formulation can be prepared at high concentration for industrial-scale extrusion process. The extruded films can then be dried and / or formed into their final geometric structures (bags, lids, containers, films, etc.). Illustrative examples are provided below.

[0123] (a) Example: Films and sheets For example, films used as packaging materials for food products can be made using conventional biodegradable and naturally derived materials such as cellulose ethers, cellulose esters, starch ethers, starch esters, polyvinyl alcohol, hydroxyethyl butyrate, or any combination thereof, in combination with the above-mentioned NCE and dispersibility additives incorporated to impart inherent mechanical properties to the film, such as, but not limited to, improved mechanical strength for tear resistance and firmness. In an embodiment, the NCE additive can be a film-coated fiber to provide grease resistance and / or water resistance. Cellulose acetate or other hydrophobic stretchable materials can be added to impart elasticity to the coated fiber or incorporated into the polymer matrix to provide flexibility and extensibility to the product. For products that require gas barrier properties, polyvinyl alcohol or polyvinyl acetate / polyvinyl alcohol copolymers are advantageous.

[0124] Composite films or sheets incorporating NCEs may be transparent or translucent if desired, and have excellent mechanical properties such as tear resistance along with biodegradability. In contrast, plastic films and sheets, such as those used in Ziplock bags, garbage bags, grocery bags, and the like, are typically formed of polyolefins such as polyethylene and polypropylene, which are petroleum-derived and slow to degrade. In embodiments, films and sheets formed by incorporating NCEs described herein may be used in many other packaging applications where strength is desirable, to provide a biodegradable alternative to traditional polyolefin-based packaging materials. Such films and sheets may also be formed with barrier properties (e.g., OGR or WVR or both) using the techniques disclosed herein. Such composites containing NCEs prepared according to the methods disclosed herein and having barrier properties are referred to as barrier materials. Barrier materials may be advantageously formed as films, sheets, containers, or other articles of manufacture where the barrier properties indicated are desirable.

[0125] More specifically, in embodiments, the barrier material may be prepared from a base formulation of biodegradable materials, such as cellulose ethers, cellulose esters, starch ethers, starch esters, polyvinyl alcohol, hydroxyethyl butyrate, polyvinyl acetate, or any combination thereof, with additives to impart specific properties to meet specific needs. For example, a barrier material requiring gas barrier properties may include polyvinyl alcohol, polyvinyl acetate, copolymers thereof, and mixtures thereof. For water and oil repellency, methylcellulose is a desirable additive. To improve mechanical strength, NCEs may be added at concentrations ranging from 1 wt% to 10 wt%. In embodiments, the base formulation may be prepared with a specific polymer(s) selected for optimal physical integrity, with polymers having molecular weights ranging from tens of thousands of g / mol to millions of g / mol; advantageously, high molecular weight versions (e.g., molecular weights ranging from hundreds of thousands of g / mol to millions of g / mol) may be selected. To impart flexibility, the addition of plasticizers may be incorporated in a concentration range of, for example, about 1 wt% to about 50 wt%, or about 1 wt% to about 10 wt%, or about 5% to about 15%. Plasticizers may include, but are not limited to, 1,2-propanediol, xylitol, erythritol, maltitol, and mannitol, or fatty acids such as caprylic acid, caproic acid, etc. Fatty acids used as plasticizers may be beneficial for barrier applications due to their hydrophobic nature. The addition of NCEs may be made directly from low concentration suspensions (about 2 wt%) or may be added in dry form and redispersed using the redispersants described herein. For large-scale processing, sufficient formulation (including redispersed polymer(s), NFC / MFC, plasticizer, and desired additives) may be mixed in a large tank and pumped into an extruder with a slit mold. The extruded sheet may then be roller compressed and / or perforated. After drying (heated rollers or oven), the compressed sheet may be gathered into a roll or further formed into a bag or sachet.

[0126] An exemplary formulation for making a packaging or container or sachet for an oxygen non-sensitive substance (e.g. salt / pepper) would contain the following ingredients (by weight per 100 g total formulation weight): Methylcellulose (MC): 85.5g Xylitol: 4.5g NCE: 10g may include.

[0127] An exemplary formulation for making a packaging material or container for oxygen sensitive materials (e.g., a see-through film for metal trays) contains the following ingredients (by weight per 100 g total formulation weight): Polyvinyl alcohol (PVA): 23.75g Polyvinyl acetate (PVAc): 23.75g Methylcellulose (MC): 42.75g Maltitol: 4.75 NCE: 5g may include.

[0128] (b) Example: Textiles and nonwoven fabrics In embodiments, the formulations used to make films and sheets reinforced with NCEs can be used to make other useful shapes or forms, such as threads and fibers. The formulations previously described can be used in combination with NCEs as composite matrix materials that can be formed into strong biodegradable fibers that can be used in many applications, including (but are not limited to) healthcare specialty products (sutures, meshes, implantable drug delivery vehicles, etc.), nonwoven materials (wipes, coffee filters, tea bags, cloth, dryer sheets, etc.), and fibrous reinforcements for building or packaging materials to add strength, shock absorption, and resilience.

[0129] As previously described, NCE matrices useful for these purposes can be formed as NCE materials alone. However, this section illustrates the creation of composites incorporating NCEs within polymeric matrices made with other non-NCE materials. For example, composites can be formed as previously described using the natural biodegradable polymers disclosed herein to form CPSs to which NCEs can be added to improve strength, toughness, brittleness, stiffness, adhesion, durability, impact resistance, etc. The CPSs can also incorporate other secondary additives to impart advantageous special properties to the overall composition, such as mechanical properties, barrier properties (e.g., hydrophobic / hydrophilic, grease resistance, etc.) and additional properties (e.g., electrical conductivity, elasticity, malleability, etc.). The final CPS with all the desired additives and containing the NCE can then be formed into a variety of useful articles.

[0130] In an embodiment, the composites described above can be formed into fibers or nonwoven materials. As a first step, a CPS, such as a viscous polymer formulation containing one or more biodegradable polymers, is prepared. Biodegradable polymers that can be used in the CPS for this purpose include polymers such as fully or partially hydrolyzed polyvinyl alcohol, polyvinyl acetate, cellulose derivatives (cellulose ethers and esters, such as methylcellulose (MC), hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC), etc.), polylactic acid, polygalactic acid, polyhydroxybutyrate, polyvinylpyrrolidone, and mixtures thereof. Polyvinyl alcohol is advantageous for certain applications due to its oxygen impermeability. Other natural polymers that can be used in the CPS include chitosan, zein, pectin, and natural proteins (soybean, whey, pea, etc.).

[0131] NCEs can be added to CPS to impart special properties such as inherent mechanical properties, barrier properties, and additive properties. The desired special properties can be inherent mechanical properties such as excessive strength, hardness, toughness, brittleness, stiffness, adhesion, durability, impact resistance, or selected optical properties such as transparency, translucency, etc. Once included in the CPS, the NCEs can remain deployed as fibers and can be aligned with themselves in a straight or randomly oriented manner to form networks or other internal artifacts within the CPS. In embodiments, the amount of NCE in the final matrix can range from about 1 wt% to about 30 wt%.

[0132] Before or after adding NCE to CPS, the special properties of a particular formulation can be optimized. In an embodiment, the optimized special property is a mechanical property. In an embodiment, the optimized special property is a barrier property. In an embodiment, the optimized special property is an additive property. Optimization of CPS can result in formed or manufactured articles such as fibers or nonwoven fabrics with optimized special properties.

[0133] For example, the hydrophobicity / hydrophilicity of the CPS can be adjusted depending on the final application by adding materials selected to impart these desired properties, such as increased strength or adjusted hydrophobicity / hydrophilicity. For more hydrophilic fibers, biodegradable gums or other hydrocolloids can be used in conjunction with or in place of the biodegradable polymers mentioned above, such as adding xanthan gum to the CPS or replacing certain structural polymers in the CPS with xanthan gum. For more hydrophobic fibers, more hydrophobic biodegradable polymers such as methylcellulose can be used; additionally or alternatively, small amounts of very hydrophobic materials, such as waxes, oils or emulsions thereof, can be added to impart additional hydrophobicity. When waxes are added, the CPS may be more prone to forming emulsions instead of suspensions, in which case surfactants such as fatty acids or others are used to enhance the incorporation of the wax into the overall CPS.

[0134] After the CPS is formulated to incorporate the NCE and any desired secondary additives, it provides a viscous matrix for further shaping, for example, forming fibers. Optionally, glycerol or other small molecules that interact with or insert themselves between the constituent polymer chains can be added to the matrix to act as a plasticizer, which can result in the formation of less brittle and more malleable fibers once shaped. Plasticizers that can be used include, but are not limited to, the aforementioned substances such as glycerol, propanediol, erythritol, xylitol, mannitol, maltitol, sorbitol, and fatty acids such as stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, and caproic acid.

[0135] After the composite matrix (i.e., a suspension of the NCE in the constituent polymer formulation with appropriate secondary additives) is formulated, it can be shaped using techniques well known in the art for processing viscous or molten substrates to form fibers. More specifically, the substrate can be prepared at the appropriate viscosity so that it can be directed by an extruder or spinneret system. The viscosity of the substrate can be adjusted by adding more or less water to it, by incorporating secondary additives such as thinning or thickening agents, by changing its temperature, or by other mechanisms well known in the art.

[0136] Once the composite matrix achieves the appropriate viscosity, it acts as an amorphous substrate that can be forced through an extruder or spinneret, i.e., a die containing several holes or channels. The passage of the amorphous substrate through the holes of the extruder or spinneret results in the elongation of the substrate to form one or more fibers. As will be understood by those skilled in the art, the number of holes in the spinneret can result in a defined number of fibers that will intertwine with each other to form a thread or yarn in a subsequent process. As will also be understood by those skilled in the art, a single hole extruder can be used to form a continuous single fiber or yarn, which can then be mechanically divided into smaller fibrils, for example, by cutting the single fiber longitudinally or transversely. In embodiments, NCE fibrils can be directionally aligned within a single or multiple extruded polymeric fibers to enhance their resistance to transverse or longitudinal stress.

[0137] After the extrusion process, the fibers may pass through an area that solidifies them for the fiber's intended use. For example, if the fibers are from a heated substrate and they still retain heat after extrusion, they may be cooled to the temperature of their intended use or reheated as needed, for example to drive off excess water. Or, for example, if the extruded fibers are still too soft or stretchable, they may be solidified by exposure to a coagulation bath to crosslink some of the component polymers, or to an air gap to drive off volatile components of the substrate and allow subsequent solidification. After optimization of the extruded fibers, they may be combined to form a thread or yarn, which may then be further processed by spin finishing, if necessary, consistent with techniques well known to those skilled in the art. The thread or yarn may be further processed using one or more godet rolls running at an appropriate speed and temperature to align the polymeric materials with each other and with the NCEs within the fiber, and to eliminate voids within the fiber, thereby making the material stronger. In embodiments, fibers or filaments made from the biodegradable, NCE-containing CPS substrates disclosed herein can be used in several applications.

[0138] In embodiments, these NCE-containing products can be used to form biodegradable nonwoven materials, advantageously providing an alternative to conventional nonwovens made of non-biodegradable materials such as polypropylene or polyester. It is understood that nonwoven fabrics can be formed of fibers or filaments attached together in a random pattern to form a mat, without the need to convert the fibers or filaments into twisted or knitted yarns. Thus, the formation of nonwoven fabrics differs from traditional weaving, knitting or braiding techniques for forming fibers or filaments into fabrics. The formation of nonwoven fabrics includes two main processes: textile formation and textile reinforcement. The use of these techniques with fibers or filaments made of NCE-containing CPS substrates can result in biodegradable nonwoven materials with advantageous properties. The textile formation process for making such biodegradable materials subjects the fibers and filaments made as described above to techniques such as carding, air laying, wet laying, spun-bonding, melt-blowing and more recently electrospinning, as will be understood by those skilled in the art. Textile reinforcement processes for making such biodegradable materials can include techniques such as needle-punching, spunlacing, chemical bonding and thermal bonding.

[0139] Fibers or nonwoven materials formed with NCE-containing CPS substrates can be made into fibers or fabrics that exhibit optimized properties such as fabric handling and drape, elongation properties, abrasion resistance, pilling and wash stability, dyeing and printing compatibility, and other features that allow these biodegradable materials to be used in various applications. In embodiments, products formed with these biodegradable materials are customized so that they retain sufficient integrity and strength for their desired purpose while being susceptible to biodegradation after disposal. Examples include, but are not limited to, cleaning towels (similar to microfiber cleaning cloths), wipes, absorbent materials, tea bags, coffee filters and similar food-related filters, filters for industrial and consumer use such as HEPA filters, vacuum bags, and medical gowns, drapes, covers, masks, bandages and other wound dressings, and packaging systems, in addition to the aforementioned dryer sheets and similar products.

[0140] As another example, man-made fabrics and fibers that are derived from NCEs can be formed to make artificial leather. Conventional artificial leathers are made by taking an artificial fabric such as polyester and dipping / coating it with polyurethane, polyvinyl chloride or wax. These products have poor performance against natural leathers, and they are made with synthetic, non-biodegradable plastic materials. As an alternative, naturally derived artificial leathers can be made using fibers or fabrics made with NCEs. As described above, NCE-based fabrics can be made that form the basic substrate for artificial leather, and reinforcement can be added from fibers spun from the NCE or from the NCE itself acting as filler particles (or both). Using the techniques described above, OGR / WVR coatings can be added to the fibers. Cellulose acetate or other hydrophobic stretching materials can be added to impart elasticity to the coated fibers and therefore the final leather product. The addition of strength from NFC / MFC and elasticity from cellulose acetate can create a durable, naturally derived leather alternative. Hydrophobic plasticizers such as triacetin or citrate esters, fatty acids, etc. may also be used to impart elasticity.

[0141] (c) Example: drinking straw An application that combines the features of biodegradability, strength and barrier properties is the use of NCE materials to form articles of manufacture formed as biodegradable drinking straws. Straws are intended to be used at various temperatures with various liquids such as alcohol, fat, sour, etc., and since straws need sufficient strength to resist deformation during normal use, non-biodegradable more durable plastics tend to be used; biodegradable materials alone lack the liquid tolerance and strength to withstand the stresses that straws normally encounter. The use of NCE materials alone or in combination with other biodegradable materials can provide the necessary liquid tolerance and strength while making the product biodegradable. As previously described, NCE matrices alone can be formed as sheets and rolled into hollow cylinders to act as straws. In other embodiments, composite materials can be formed using derivatized cellulose, such as methylcellulose, combined with, for example, an NCE, where methylcellulose or similar biodegradable LCST polymers or other materials such as cellulose acetate, lipids, polyvinyl alcohol or polyvinyl acetate / polyvinyl alcohol copolymers, wax, wax emulsions hydrophobic starch, fatty acids, or other hydrophobic cellulosic polymers, or any other similar hydrophobic polymers can increase the hydrophobicity of the material.

[0142] In embodiments, dry forms of methylcellulose (MC), cellulose acetate, lipids, polyvinyl alcohol or polyvinyl acetate / polyvinyl alcohol copolymers, wax, wax emulsion hydrophobic starch, fatty acids, or other hydrophobic cellulosic polymers, or any other similar hydrophobic polymers, can be combined with a dry redispersible NCE that is pretreated with a redispersion additive, such as a combination of a small molecule plasticizer and a biodegradable polymer, such as a cellulosic polymer, as described above, where the MC and NCE mixture is ground to a powder form. The powdered mixture can then be stirred into water to create a viscous mixture, which can then be formed into a sheet or extruded into a hollow cylinder. In embodiments, the ratio of redispersion additive (e.g., small molecule and biodegradable polymer) to NCE component can range from about 1:1 to about 15:1, or from about 3:1 to about 12:1, or about 6:1 ratio, and various balances between biodegradable cellulosic polymer and small molecule plasticizer are available, such as a 70 / 30 balance between polymer and small molecule, or a 50 / 50 balance between polymer and small molecule, or a 0 / 100 balance between polymer and small molecule, or any balance of the two components between the exemplary ratios are provided. For embodiments engineered to have barrier properties, the ratio of OGR or WVR component to NCE can be about 1:1 to about 12:1, or about 3:1 to about 9:1. In another embodiment, a 2-3% suspension of NCE can be mixed with MC or other cellulose-containing suspension. In embodiments, the NCE formulation may contain CMF and CNF, or may contain more CMF than CNF, or may consist essentially of CMF, with the ratio of CMF to CNF adjusted to optimize the strength of the final formulation. In embodiments, standard pulp may be used in addition to or in place of derivatized cellulose in the mixture. The stiffness of the straw product may be improved by eliminating or reducing the amount of glycerol or other plasticizers used in the formulation. Spun hydrogel fibers may be added to the composite to improve strength and flexibility.

[0143] (d) Example: Biodegradable alternatives to conventional products As previously described, the composite matrices disclosed herein provide a biodegradable alternative to conventional products.

[0144] For NCE / starch composites, cellulose microfibers are advantageous as additives to starch-based CPS, either alone or in combination with cellulose nanofibers. Foaming can be produced by mechanical means or by incorporating foam-forming elements such as surfactants into the mixture. Bicarbonate crystals can also be incorporated into the mixture as foam-forming elements, with acid being added at a later stage to activate foaming. Secondary additives such as linseed oil or more hydrophobic cellulose additives, such as methylcellulose, cellulose acetate, lipids, polyvinyl alcohol or polyvinyl acetate / polyvinyl alcohol copolymers, waxes, wax emulsions, hydrophobic starches, fatty acids, other hydrophobic cellulosic polymers, or any other similar hydrophobic polymers, can be added to improve hydrophobicity; alternatively or additionally, NCE additives with OGR properties can be prepared.

[0145] In an embodiment, the composite matrix made using biodegradable materials as existing matrices can be used to make foams and foam articles. Conventional foam products made with biodegradable materials, such as foams made with starch, typically have poor performance against petroleum-derived foams, and often lack the strength and hydrophobicity of petroleum-derived products. NCE-based foams, which are mainly derived from NCE matrices, can act as a substitute for conventional foams for applications such as packaging materials, as described above. Composite materials comprising a mixture of NCEs and biodegradable materials such as starch or derivatized cellulose (e.g., cellulose ether or cellulose acetate) can also be prepared as foam articles and used as substitutes for conventional foams, combining the benefits of biodegradability with the desired strength, impact absorption, light weight and water resistance required by packaging materials and containers.

[0146] In an embodiment, the redispersible or redispersible NCE additive prepared according to the technology disclosed herein can be used as a carrier to impart barrier properties to existing biodegradable matrices, such as those formed with pulp or pulp-based materials. To do this, the NCE can be first treated in the same manner as previously described to allow for redispersibility. A cellulosic polymer mixed with a plasticizer can be added to the 2-3% NCE slurry, if acceptable, which can be dried into a sheet or any other form or shape. Once dried, the product can then be ground to small particles resembling a powder. To this novel powder, one or more hydrophobic or oleophobic materials can be added to impart barrier properties. The barrier-making material can advantageously be, for example, a hydrophobic starch, a more hydrophobic cellulosic polymer, such as methylcellulosic, or something that is soluble or solubilizable in water to facilitate the handling of fatty acids. The barrier-making material may be added in ratios ranging from 1:1 barrier additive to NCE to 15:1 barrier additive to NCE, and preferably 3:1 to 9:1. The barrier-making material may also be an oil-in-water emulsion or a wax emulsion. Secondary additives such as plasticizers may also be added to this step. The composition made is either a powder or a paste material, which may be shipped in its concentrated form and then dissolved in water and added to a selected biodegradable pre-existing matrix to make a composite matrix with barrier properties. For example, a slurry of the components may be used as a mixed barrier additive for pulp molding or pulp-based products as previously described, or it may be used as a coating for already made pulp or pulp-based products as previously described. It may also be used to impart barrier properties to fibers: the composite matrix containing the barrier treatment may be molded into a product, extruded to form fibers, spun into fibers, or otherwise treated to yield a composition or formed article with barrier properties. The composition or formed article is then dried to enable it to exhibit barrier properties in the dry form.

[0147] In embodiments, composite matrices can be made from existing biodegradable matrices that have a combination of special properties, such as advantageous mechanical and barrier properties. As an example, packaging materials can be made from previously described natural polymeric materials, such as starch or derivatized cellulose (cellulose ether or cellulose acetate), optionally with the addition of barrier polymers or optionally with the addition of barrier-treated NCE foam, where the natural polymeric materials are reinforced with NCE reinforced fibers. In embodiments, the natural polymeric materials can be spun into yarns or fibers, and the NCE tufts are aligned within the spun fibers to create strong reinforced fibers. Foamed products, such as packing peanuts made from previously described natural materials, can be reinforced with these NCE reinforced polymer fibers to form packaging materials that are lightweight networks with shock absorbing properties. Bundled balls of small fibers or longer reinforced fibers can be used as reinforcement in the overall packaging material matrix for increased shock absorbing properties. NCE tufts for this purpose can have inherent hydrophobicity and can be optionally treated with materials to improve their grease resistance. Overall, these natural materials and NCE reinforcements (NCE fibers and / or NCE reinforced polymer fibers) can be used in many packaging applications such as packing peanuts, bags, cardboard boxes, etc.

[0148] (e) Example: Conductive materials In embodiments, the additional NCE population may include subpopulations of NCEs that are modified via the silver mirror reaction to enable their use in conductive applications.

[0149] The silver mirror reaction produces a layer of metallic silver on a surface as a result of a redox reaction resulting from the interaction of an ammoniacal complex of silver with an aldehyde. The first step of the silver mirror reaction using Thoren's reagent (ammoniacal solution of silver oxide) is represented by the following equation EQ.1:

number

[0150] The second step of the silver mirror reaction, which shows the reaction of silver diamine hydroxide with an aldehyde R-CH=O, is shown in the following equation EQ.2: EQ.2: R-CH=O + 2[Ag(NH 3 ) 2 ]OH → 2Ag↓ + R-COONH 4 + 3NH 3 + H 2 O where [Ag(NH 3 ) 2 ] is silver diamine hydroxide produced by dissolving a metal oxide in an ammoniacal solution, where the products include amine carbonate, ammoniacal solution, and a silver precipitate forming a "silver mirror."

[0151] When a subpopulation of NCEs, whether NFC, MFC or mixtures thereof, is immersed in an aldehyde, and aldehyde groups are present on the surface of the NCE, a redox reaction occurs on the surface of these NCEs. Aldehydes useful for this reaction may include glutaraldehyde, cinnamaldehyde, vanillin, etc. These aldehyde-bearing NCEs may then be exposed to an ammonia complex of silver, resulting in the deposition of a silver precipitate on the surface of the NCE. As a result, a conductive and reflective coating may be deposited on the NCE subpopulation. When this subpopulation is included in a composite matrix prepared as disclosed herein, the composite matrix has conductive properties, allowing it to be used in conductive and / or reflective applications. By way of example, conductive and highly reflective NCEs may be used in applications where a combination of strength and conductivity is advantageous, such as in fitness, health care and medical industries, as well as in cable cladding, EMI shielding, circuit board manufacturing and overall electrode construction. Other applications in which the elongated structure, high surface area and ability to be dispersed and coated provide advantages will be apparent to those of skill in the relevant art. EXAMPLES

[0152] Working Example The materials used in Examples 1 to 4 are: NFC suspensions in water (obtained from various sources including Performance Biofilaments, SAPPI, University of Maine, and Auburn University) Chemicals (all obtained from Sigma Aldrich unless otherwise indicated) Tri(propylene glycol) butyl ether (TPnB) ○Di(propylene glycol) propyl ether (DPnP) Propylene glycol butyl ether (PnB) Propylene glycol propyl ether (PnP) Butylene glycol ethyl ether Ethylene glycol monobutyl ether (2-butoxyethanol) Propylene glycol monomethyl ether acetate Propylene glycol diacetate Ethylene glycol diacetate Benzyl alcohol ○1-Heptanol ○1-Hexanol Caffeine Glycerol Piperazine Pyridine Methylcellulose (MC) Hydroxyethyl cellulose (HEC) Hydroxypropyl cellulose (HPC) Hydroxypropyl methylcellulose (HPMC) Poly(methyl vinyl ether) Melamine Triethanolamine ○Dytek EP (1,3 diaminopentane) Ethylenediamine ○Diethylenetriamine Tetraethylenepentamine ○1,2-Diaminocyclohexane Polyethyleneimine (PEI) Ethylenediaminetetraacetic acid (EDTA) Luviskol Plus (Polyvinylcaprolactam) (BASF) Corning Stir Plate ·BINDER Forced Convection Oven Examples include:

[0153] Example 1: Direct additive application to NFC suspension This experiment may test the direct application of redispersion additives to NFC suspensions. In this experiment, a 2.1 wt% NFC slurry may be diluted to 0.1 wt% with tap water and stirred slowly for at least 5 hours to fully disperse the NFC fibers. 50 mL aliquots of the diluted NFC suspension may be measured and individually treated with the direct addition of exemplary redispersion additives. Each additive may be mixed directly into 50 mL of the 0.1 wt% NFC suspension for 5 minutes on a stir plate. The resulting mixture may be dried at 110° C. in a BINDER forced convection oven. After drying, the resulting mat of dry fibers may be immersed in 80 mL of tap water and resuspended on a stir plate for 5 minutes. The suspended material may be qualitatively evaluated using the following criteria to assess the degree of redispersion: a) High redispersion effectiveness: Complete separation of the full fiber mat from the beaker and total break-up of clusters / agglomerates into separate fibers, resulting in an opaque / translucent suspension with no visible lumps. b) Medium redispersion effectiveness: Sufficient separation of fiber mats from a medium to full beaker in which small / medium NFC agglomerates (1-5 mm diameter) are suspended in aqueous medium. c) Low redispersion effectiveness: There is little or no sufficient separation of the fiber mat from the beaker and there are medium / large NFC agglomerates (>5mm diameter) suspended in the aqueous medium.

[0154] The expected results for redispersion effectiveness for selected redispersion additives are listed as follows: HPC, HPMC, and glycerol added in amounts between 100% and 300% of the weight of NFC in the suspension are expected to produce high redispersion effectiveness. Caffeine, ethylenediamine, tetraethylenepentamine, Dytek EP, MC, Luvskol Plus, DPnP and TPnB added in amounts 2 to 5 times the weight of NFC in the suspension are expected to produce moderate redispersion effectiveness. · Other additives are expected to produce low redispersion effectiveness and / or require a larger relative volume of additive to produce moderate redispersion.

[0155] Example 2: Binary / Tertiary Direct Additive Application to NFC Suspensions NFC suspensions similar to those described in Example 1 can be diluted, stirred and measured into 50 mL aliquots for processing. Two or three additives (binary or ternary) can be combined and each NFC sample can be processed following the method described in Example 1. All processed samples can be dried and tested for redispersion following the same protocol as in Example 1. Redispersion efficacy for binary and ternary components can be predicted for various combinations of additives using the redispersion efficacy criteria described in Example 1 to evaluate the effect of each combination of additives on redispersion.

[0156] The additive combinations may be introduced to the NFC samples in various ratios. An additive combination of HPC and HPMC in a 1:1 ratio may be added in an amount three times greater than the amount of NFC in the mixture, and high redispersion effectiveness is expected. An additive combination of HPMC and MC in a 1:1 ratio may be added in an amount three times greater than the amount of NFC in the mixture, and high redispersion effectiveness is expected. Other possible combinations are expected to produce moderate or low redispersion effectiveness and / or require significantly greater amounts of additives in proportion to the amount of NFC being processed. The possible combinations of additives are listed in Table 1 below, along with their expected redispersion effectiveness. [Table 1]

[0157] Example 3: Single-element processing of NFC after filtration In this example, a 1 L suspension of diluted NFC (0.3-1.0 wt%) can be prepared according to Example 1 and combined with the diluted pulp suspension (0.3-0.75 wt%). The combined stock suspension can be vigorously mixed on a stir plate for 15 minutes, then it can be filtered through a 70 mesh screen in a Büchner funnel and drained into a 250 mL graduated cylinder to remove excess water, thereby forming an NFC / pulp mat on the mesh screen. A vacuum can be used to increase the final solids content of the NFC / pulp mat (approximately 10 wt%). Each selected additive can be mixed with a spatula into the filtered solids in separate beakers to thoroughly mix the resulting mat of NFC / pulp fibers and redispersed additives for testing.

[0158] Additives to test resuspension ability may include LCST polymers and non-volatile additives. LCST polymers or non-volatile additive candidates may first be dissolved in concentrated aqueous solutions (ranging from 5 wt% to 40 wt%) before adding them to the NFC / pulp solids. These solutions, each containing a single additive, may then be added to the NFC / pulp solution material and processed using methods similar to those described in Example 1. All resulting samples of the treated NFC / pulp mixtures may then be deposited into spherical hemispherical (1.5 cm diameter) silicone molds and dried at 110°C to produce a consistent sample shape, size and density for comparison purposes.

[0159] Redispersion of the samples may be performed as described in the Examples above. The results of the redispersion test may be qualitatively evaluated using the redispersion effectiveness criteria described above. HPMC used in an amount 1.5-2 times the amount of NFC is expected to produce low or moderate redispersion effectiveness, and glycerol in an amount 3-4 times the amount of NFC is expected to produce high redispersion effectiveness.

[0160] Example 4: Binary processing of NFC after filtration In this experiment, the NFC and pulp suspension may be prepared and filtered according to Example 3. The treatment solution used to dose the filtered solid fiber may be prepared to contain two active additives, such as HPMC and glycerol or HPMC and 2-butoxyethanol. Various ratios of additive and amount of additive to amount of NFC may be tested. Ratios of HPMC to glycerol of about 0.4:1 to 2:1 are expected to produce moderate or high redispersion effectiveness, using the criteria for qualitative results provided above, and a ratio of HPMC to 2-butoxyethanol of 0.6:1 is expected to produce moderate redispersion effectiveness. For the HPMC:glycerol additive mixture, larger additive-to-NFC ratios, such as 3:1, 4:1 or more, are expected to produce higher redispersion effectiveness than lower relative amounts of additive to NFC.

[0161] The materials used in Examples 5 and 6 are: Corning Stir Plate ·BINDER Forced Convection Oven ·NFC (2.1wt% in water): Auburn University ·Sigma Aldrich Chemicals Tri(propylene glycol) butyl ether (TPnB) ○Di(propylene glycol) propyl ether (DPnP) Propylene glycol butyl ether (PnB) Propylene glycol propyl ether (PnP) Butylene glycol ethyl ether Ethylene glycol monobutyl ether (2-butoxyethanol) Propylene glycol monomethyl ether acetate Propylene glycol diacetate Ethylene glycol diacetate Benzyl alcohol ○1-Heptanol ○1-Hexanol Caffeine Glycerol Piperazine Pyridine Methylcellulose (MC) Hydroxyethyl cellulose (HEC) Hydroxypropyl cellulose (HPC) Hydroxypropyl methylcellulose (HPMC) Poly(methyl vinyl ether) Melamine Triethanolamine ○Dytek EP (1,3 diaminopentane) Ethylenediamine ○Diethylenetriamine Tetraethylenepentamine ○1,2-Diaminocyclohexane Polyethyleneimine (PEI) Ethylenediaminetetraacetic acid (EDTA) Sodium dodecyl sulfate (SDS) Other chemicals Luviskol Plus (Polyvinylcaprolactam): BASF ○Capryl glucoside: Amazon ○Decyl glucoside: Amazon ○Cocoglycoside: Amazon Examples include:

[0162] Example 5: Treatment of charged NCE fibers In this experiment, the direct application of redispersion additives to NFC suspensions was tested. Soybean hulls are a biological source of NCE fiber (NFC) that was mechanically and chemically processed at Auburn University to produce NFC suspensions at 2.1 wt% solids. Various ratios of HPMC and glycerol, listed in Table 2 below, were combined to form solutions for direct processing of 2.1 wt% NFC suspensions. The highly viscous processed suspensions were then spread on silicone sheets at a thickness of 1 mm to 3 mm and dried at 75°C in a BINDER forced convection oven to obtain NFC sheets.

[0163] The resulting treated and control NFC sheets were resuspended at 5 wt% solids in glass vials with DI water by vigorously shaking by hand for 3 minutes. The vials were then qualitatively observed for redispersion effectiveness, with the results shown below in Table 2. The following descriptions of redispersion effectiveness were used to indicate the qualitative results observed from these redispersion tests.

[0164] Redistribution Efficiency: a) High redispersion effectiveness: Complete disintegration of the fiber sheet into separate fibers resulting in an opaque / translucent suspension with no visible lumps. b) Medium redispersion effectiveness: Medium disintegration of fiber sheets with small / medium NFC agglomerates (1-5 mm diameter) suspended in aqueous medium. c) Low redispersion effectiveness: Little to no disintegration of the fiber sheet and presence of medium / large agglomerates of NFC (>5mm diameter) suspended in the aqueous medium. [Table 2]

[0165] Example 6: Redispersion of surfactant-loaded nanocellular elements In this experiment, a 2.1 wt% soybean husk-derived nanocellular element (NFC) suspension from Auburn University was used to act as a carrier for the chemical of interest (in this case, a surfactant) when redispersed in water. For this experiment, all NFC samples were dosed with a redispersion additive in a ratio of 6:1 with the NFC fiber. The redispersion additive consisted of HPMC and glycerol in a ratio of 19:1, respectively. After a binary redispersion additive solution was applied directly to the 2.1 wt% NFC suspension to form a treatment suspension, various surfactants were mixed into the treatment suspension individually, and the resulting mixture was dried and tested for redispersibility according to the procedure outlined in Example 5. Redispersibility was observed qualitatively according to the redispersion effectiveness criteria described in Example 5. Table 3 below lists the surfactants tested and their effect on NFC redispersion. [Table 3]

[0166] These samples, which could be dried and redispersed with high redispersion efficiency, produced thick surfactant-containing liquids that could be useful as soaps. The results suggest that certain surfactants can be incorporated into the redispersible NFC sheets to allow for reconstitution as liquid surfactant-containing materials for applications such as soaps, shampoos, etc. It is hypothesized that other active agents (particularly bleaches, cationic surfactants for fabric softeners, fragrances, softeners, etc.) can be similarly incorporated into the redispersible NFC sheets, either alone or in combination with other ingredients.

[0167] Materials used in Example 7 include: Corning Stir Plate Soybean husk NFC (2.1wt% in water) (Auburn University) Butcher Paper - Uncoated (Amazon) DI Water ·Carrington Farms Organic Coconut Cooking Oil ·oven Baking pan ·Sigma Aldrich Chemicals Glycerol Methylcellulose (MC) Examples include:

[0168] Example 7: Oil and fat resistance In this experiment, the ability of the treated NFC to impart grease resistance to food contact paper was tested. Soy husk NFC suspension (2.1% concentration) was used in this experiment. A 4.5% stock solution of MC and glycerol in DI water was made on a stir plate with 95% of the active being HPMC and 5% being glycerol. Five gram samples of the 2.1% soy husk NFC suspension were added to three small beakers and a corresponding amount of MC / glycerol solution was added along with the NFC suspension resulting in treatments of 3:1, 6:1 and 9:1 of active dispersant to dry NFC. The 3:1 sample contained 7 grams of the 4.5% MC / glycerol solution, the 6:1 sample contained 14 grams of the MC / glycerol solution and the 9:1 sample contained 21 grams of the MC / glycerol solution. There was also a sample with 5 grams of 2.1% NFC suspension without the HPMC / glycerol treatment, but 7 grams of additional DI water was added to ensure a lower viscosity coating and to better match the viscosity of the other samples. This was treated as the control sample. The suspension was mixed by hand and set aside.

[0169] Separately, uncoated brown butcher paper was cut into small 1.5" x 1.5" squares. Each of the four suspensions made in the previous step was poured into its own weigh boat and three different butcher paper squares were dipped (one at a time) into each suspension. Once each square was fully immersed and adequately coated, it was removed with tweezers and held over the weigh boat for one minute to allow excess suspension to drain from the paper. Each piece of butcher paper was then placed in an oven and dried at 75°C for 30-60 minutes. After the squares were adequately dry, three drops each of DI water and liquid coconut oil were applied to each square. The squares were observed at two intervals: immediately after application of the water and oil droplets (time 1) and 15 minutes after application of the droplets (time 2). When observed at time 1 (immediately after application of the droplets), all four samples appeared to repel water. The water droplets retained their shape and the contact angle (observed qualitatively) was relatively high, characteristic of a non-wetting droplet. No color change occurred on the brown butcher paper beneath the droplet, indicating that the droplet had not penetrated into the pores of the butcher paper. When observed at time 1, the oil droplet on the control sample had a contact angle (observed qualitatively) close to zero, such that the droplet did not continue to reside on the paper. The droplet spread over a large area (approximately 3x the size of the droplet), the paper became wet, and the color became darker brown, indicating that the oil had penetrated into the pores of the paper. The 3:1 treated sample had a slightly higher contact angle than the control, such that the droplet remained visible, and the dark brown spot beneath the droplet was smaller than the control and approximately twice the size of the original droplet. The contact angle of the oil droplet on the 6:1 sample was slightly higher than that on the 3:1 sample, but otherwise appeared nearly identical. The oil droplet on the 9:1 sample had the highest contact angle of all samples and no dark brown spots were visible under the droplet, indicating that the oil did not penetrate into the pores of the butcher paper. When observed at time 2 (15 minutes after application of the droplet), the water droplet remained the same as previously described for all samples. When observed at time 2, the appearance of the oil droplet changed.The brown spot from the oil droplet from the control and 3:1 samples grew to cover approximately 1 / 3 of the area of ​​the square, indicating increased wetting over time. The contact angle of the oil droplet on the 6:1 sample decreased over time, and the brown spot from the droplet grew to cover approximately 1 / 5 of the area of ​​the square. However, for the 9:1 sample, the size and contact angle of the oil droplet and the lack of a dark brown spot remained unchanged at time 2, indicating persistent lack of wetting over time.

[0170] Materials used in Example 8 include: Corning Stir Plate ·NFC suspension (2.1wt% in water) (Auburn University) DI Water ·Revlon Blow Dryer Hair ties ·tape Stir bar receiver ·Full Shine Remy Human Hair:Amazon ·Sigma Aldrich Chemicals Glycerol Low molecular weight chitosan Hydroxypropyl methylcellulose (HPMC) Acetic acid Other chemicals ○Xiameter OFX-0193 PEG-12 Dimethicone: Dow Chemical Examples include:

[0171] Example 8: NFC Hair Retention In this experiment, the ability of the processed NFC to aid hair hold and replace the use of hairsprays and harsh chemicals was tested. NFC suspension (2.1% concentration) was used in this experiment. A 9.43% solution of HPMC and glycerol with 90.57% DI water was made; a 100gm stock solution was made with 9.43 grams of HPMC / glycerol (8.96 grams HPMC and 0.47 grams glycerol) and 90.57g DI water; this solution with 95% of the active being HPMC and 5% being glycerol is the HPMC / glycerol solution used as follows: 5.95 grams of the 2.1% NFC suspension was added to a small beaker and 3.98 grams of the HPMC / glycerol solution was added with the NFC suspension to give a 3:1 ratio of active dispersant to dry NFC. The suspension was mixed by hand and set aside.

[0172] Separately, a 1% low molecular weight chitosan solution with NFC in 1% acetic acid was made. To do this, 40.06 grams of DI water was added to the beaker with the NFC suspension (previously treated with the previously prepared HPMC / glycerol solution) for further dilution. 0.5 grams of acetic acid was then added dropwise to the beaker and stirred with a stir plate. 0.5 grams of chitosan powder was slowly added to the beaker while vigorously stirring the suspension. The suspension was left stirring for about an hour until it appeared homogeneous. Once the chitosan appeared to be fully dissolved, 2.5 grams of Dow Chemical's Xiameter OFX-0193 PEG-12 Dimethicone was added to the beaker and stirred for a few seconds. This formulation was set aside to test as a hair treatment.

[0173] The formulations were then tested against a control sample to verify their effectiveness as a hair treatment. Two samples of 0.5 grams of hair were cut from a Full Shine Remy human hair wig. Each sample was cut to a length of 12 inches. Each sample was tied at one end using a small hair tie and secured to a table using tape. The hair of each sample was thoroughly wetted with DI water until no dry hair remained. The control hair sample was left wet with water only, and then the experimental hair sample was wetted with 0.2 grams of the previously described hair treatment. The hair treatment was applied with a syringe and then rubbed thoroughly over the entire length of the hair sample. Both samples were then curled snugly around the stirring bar receptacle and blow-dried for 3 minutes. After 3 minutes, the stirring receptacle was removed from the hair and the curl was observed. The curl was observed even after pinching the curl along the length of the hair and stretching it 3-4 times.

[0174] Results immediately after blow drying the control and experimental samples showed similar curls. The curls were very dense with curls exactly the size of the stir bar receiver diameter. The control sample showed slightly less dense hair tufts than those of the experimental sample, with slightly greater spacing between each tuft. After pinching and stretching the hair, the curls of the control sample were farther apart and did not provide any "bounce". The diameter of the tufts grew to nearly twice the diameter of the stir bar receiver and the hair became frizzy, where each tuft was farther apart from one another. The experimental sample bounced back to its original shape with no change in the diameter of the tufts, spacing between tufts or spacing between hair tufts. All curls from both the control and experimental samples were soft to the touch with no "crispness".

[0175] While the present invention has been particularly shown and described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details can be made therein without departing from the scope of the invention encompassed by the appended claims.

Claims

1. A suspension of nanocellulose (NC) elements in a liquid medium, where the NC elements include cellulose nanofibers or cellulose microfibers; and A liquid formulation comprising a drying / dispersing additive, the drying / dispersing additive being selected from the group consisting of temperature responsive polymers, small molecule additives in volatile systems and blocking agents.

2. 2. The liquid formulation of claim 1, wherein the nanocellulose elements are derived from lignocellulosic materials.

3. The liquid formulation of claim 1 , wherein the NC component consists essentially of cellulose nanofibers.

4. The liquid formulation of claim 1 , wherein the drying / dispersing additive is a temperature responsive polymer.

5. The liquid formulation of claim 4, wherein the temperature-responsive polymer is a low critical solution temperature (LCST) polymer or a short-chain oligomer derived from an LCST polymer.

6. 6. The liquid formulation of claim 5, wherein the LCST polymer is selected from the group consisting of methylcellulose, hydroxyl ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, ethyl hydroxyethyl cellulose, polyvinyl caprolactam, poly(methyl vinyl ether), poly(N-isopropylacrylamide), poly(N,N-diethylacrylamide), block copolymers of poly(ethylene oxide) and poly(propylene oxide), and elastin poly(pentapeptide).

7. The liquid formulation of claim 1 , wherein the drying / dispersible additive is a small molecule additive in a volatile system.

8. The liquid formulation of claim 7 , wherein the small molecule additive is non-ionic.

9. 9. The liquid formulation of claim 8, wherein the small molecule additive is selected from the group consisting of tri(propylene glycol) butyl ether, di(propylene glycol) propyl ether, propylene glycol butyl ether, propylene glycol propyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol diacetate, ethylene glycol diacetate, benzyl alcohol, 1-heptanol, and 1-hexanol.

10. The liquid formulation of claim 7 , wherein the small molecule additive is a fatty acid.

11. The liquid formulation of claim 5 , wherein the small molecule additive is cationic.

12. 12. The liquid formulation of claim 11, wherein the small molecule additive is selected from the group consisting of ethylenediamine, diethylenetriamine, tetraethylenepentamine, 1,3-pentanediamine, piperazine, 1,2-cyclohexanediamine, aniline, pyridine and piperazine.

13. 2. The liquid formulation of claim 1, wherein the drying / dispersibility additive is a blocking agent.

14. 14. The liquid formulation of claim 13, wherein the blocking agent is a non-volatile chemical additive.

15. 15. The liquid formulation of claim 14, wherein the non-volatile chemical additive is a purine or a pyrimidine.

16. 16. The liquid formulation of claim 15, wherein the non-volatile chemical additive is a purine, the purine being a xanthine or a xanthine derivative.

17. 14. The liquid formulation of claim 13, wherein the blocking agent is a wetting agent.

18. 18. The liquid formulation of claim 17, wherein the humectant is selected from the group consisting of glycerin, caprylyl glycol, ethylhexylglycerin, tribehenin, hydrolyzed soy protein, propylene glycol, methyl gluceth-20, phenyl trimethicone, hyaluronic acid, sorbitol and gelatin.

19. 14. The liquid formulation of claim 13, wherein the blocking agent comprises a nanoscale particle.

20. mechanically defibrillating the cellulosic feedstock, thereby forming an initial nanocellulose suspension containing NC components; treating the cellulosic feedstock with a drying / dispersing additive before or after mechanically defibrating the cellulosic feedstock to form a treated nanocellulose suspension containing NC elements; and drying the treated nanocellulose suspension to form a redispersible dry NC material containing the NC elements. A method for treating a cellulosic feedstock to form a redispersible, dry NC-containing material comprising an NC component, the method comprising:

21. 21. A dried NC-containing material made by the process of claim 20.

22. providing a fluid medium; adding the redispersible dry NC material of claim 1 to a fluid medium; and mixing the redispersible dry NC material in a fluid medium, thereby suspending the NC elements in the fluid medium; A method of making a formulation comprising NC elements suspended in a fluid medium, comprising:

23. 23. The method of claim 22, wherein the fluid medium is an aqueous fluid.

24. 23. A formulation comprising NC elements redispersed in a fluid medium produced by the process of claim 22.

25. Providing a liquid formulation according to claim 1, wherein the liquid formulation comprises nanocellulose elements and the liquid formulation comprises a drying / dispersing additive; and drying the liquid formulation to form a redispersible dry NC-containing material in which the nanocellulose elements are embedded, wherein the redispersibility of the dry NC-containing material is greater than that of a dry control material prepared by drying a control suspension of the nanocellulose elements in a liquid medium, the control suspension lacking a drying / dispersibility additive; A method for making a redispersible dry NC-containing material having nanocellulose elements embedded therein, comprising:

26. 26. A redispersible dry NC-containing material having nanocellulose elements embedded therein produced by the method of claim 25.

27. 27. The NC-containing material of claim 26, wherein the nanocellulose elements are formed as a matrix.

28. 28. The NC-containing material of claim 27, wherein the matrix is ​​acting as a support for the active agent or a container for the active agent.

29. 29. The NC-containing material of claim 28, wherein the matrix acts as a container.

30. 30. The NC-containing material of claim 29, wherein the container is foamed.

31. 30. The NC-containing material of claim 28, wherein the matrix is ​​shaped as a formed article.

32. 32. The NC-containing material of claim 31 , wherein the matrix is ​​formed as a film, and the film encapsulates the active agent.

33. 32. The NC-containing material of claim 31, wherein the formed article is adapted for rupture by physical, chemical, or biological mechanisms, and rupture allows for release of the active agent.

34. 32. The NC-containing material of claim 31 , wherein the formed article comprises a first matrix that acts as a support for the active agent, the first matrix being formed as a sheet.

35. 32. The NC-containing material of claim 31 , wherein the formed article comprises a first matrix formed as a sheet and a second matrix formed as a sheet, the active agent being disposed between the first matrix and the second matrix.

36. 36. The NC-containing material of claim 35, wherein the active agent is enclosed between the first matrix and the second matrix.

37. 29. The NC-containing material of claim 28, wherein the active agent is selected from the group consisting of cleaning or laundry products, soaps, detergents, surfactants, bleaches, enzymes, hair maintenance products, pigments, colorants, odor-related agents, softeners, cosmetics, pharmaceutical products, medical products, and agricultural active ingredients.

38. 28. The NC-containing material of claim 27, wherein the matrix further comprises filler particles.

39. 28. The NC-containing material of claim 27, further comprising a barrier-creating material.

40. 40. The NC-containing material of claim 39, wherein the barrier-creating material is deployed as a coating on the top or bottom surface of the matrix.

41. 40. The NC-containing material of claim 39, wherein the barrier-creating material is mixed into a matrix.

42. 40. The NC-containing material of claim 39, wherein the barrier-creating material imparts oil and grease resistant properties to the NC-containing material.

43. 40. The NC-containing material of claim 39, wherein the barrier-creating material imparts water-resistant or water vapor-resistant properties to the NC-containing material.

44. Providing a redispersible dry NC-containing material according to claim 25; and adding a redispersion fluid to the dry NC-containing material, thereby redispersing the NC elements embedded in the redispersible dry NC-containing material; A method for redispersing nanocellulose elements, comprising:

45. 45. The formulation of claim 44, wherein the redispersion fluid is an aqueous fluid.

46. 45. A redispersed NC-containing formulation comprising NC elements suspended in a redispersion fluid, the redispersed NC formulation being made by the method of claim 44.

47. 47. The formulation of claim 46, which is effervescent.

48. 47. The formulation of claim 46, further comprising an active agent attached to the NC element or embedded in a matrix formed by the NC element.

49. 49. The formulation of claim 48, wherein the active agent is a pharmaceutical or nutraceutical product.

50. 49. The formulation of claim 48, wherein the active agent is a cosmetic product.

51. 49. The formulation of claim 48, wherein the active agent is an odor-related active agent.

52. 49. The formulation of claim 48, wherein the active agent is an agricultural active ingredient.

53. 46. ​​A method of making a shaped article comprising drying the formulation of claim 45 into a selected shape, which when dried produces the shaped article.