Foamed manufactured articles containing nanocellulose elements

Abstract

The present invention includes a simple NCE-based material comprising a simple NCE-based matrix, the simple NCE-based matrix comprising a population of redispersible NCEs treated with a drying / dispersing additive; the matrix provides a structural framework for the simple NCE-based material; and the simple NCE-based material comprises a barrier formulation. The present invention also includes a foamed composite NCE-containing material comprising a composite NCE-containing matrix, the composite NCE-containing matrix comprising a population of redispersible NCEs treated with a drying / dispersing additive, and an existing matrix; the NCEs are incorporated into the existing matrix, the existing matrix provides a structural framework for the composite NCE-containing material; and the composite NCE-containing material comprises a barrier formulation. The present invention further includes manufactured articles comprising NCE-containing materials, formed articles made therefrom, and methods for manufacturing them.

Description

Technical Field

[0001] Related Applications This application claims the benefit of U.S. Provisional Application 63 / 458,276, filed Apr. 10, 2023. The entire content of the above application is incorporated herein by reference.

[0002] Field of the Invention This application relates to a formulation comprising a nanocellulose material for use in the formation of foamed manufactured articles.

Background Art

[0003] Background of the Invention Industrial foams are widely used in several commercial applications. Foaming a material provides the material with certain mechanical properties, such as shock absorbency, using the foam as a container, packaging materials, cushioning materials, low-density structural materials, and wearable members for cushioning and impact protection. Foaming a material also improves the insulating properties of the material, so it can be used for thermal insulation as well as for thermally specialized manufactured articles such as coolers and heat-resistant or thermally insulating products. Foams can also provide acoustic insulation, preventing sound energy from moving into or out of a designated area. Foaming minimizes cost by reducing the amount of material required to produce the desired effect, so foams are particularly useful in situations where low weight per unit volume is advantageous. Thus, foams are commonly used as containers or packaging materials, such as wraps, protective package inserts, and space fillers such as packing peanuts, where the foamed material encloses, contains, confines, or otherwise protects other articles from external damage such as collision, impact, vibration, extreme temperatures, and insect / animal intrusion.

[0004] Furthermore, foams can be combined with additives that provide other properties to foamed articles, such as water or oil resistance. Additives can be integrated with the foam or used to coat the foam to form articles for special purposes where additional properties are important. For example, containers in general, especially those for food and beverages, can be formed with foams in which suitable additives can provide resistance to leakage, spillage, absorption, contamination, and fluid ingress. As an example, food can be securely contained in foamed cups, plates, dishes, trays, etc., which, in addition to providing a barrier against fluid ingress or egress, induce mechanical protection from the foamed material itself. Such articles are commercially well-received: single-use food and beverage containers are everywhere, offering an inexpensive, convenient, and lightweight alternative to reusable articles. The hygienic benefits of single-use containers, in addition to their convenience, are related to improved human hygiene and overall human health and well-being.

[0005] These advantages translate to high environmental costs. Foamed products are primarily made from petroleum-derived plastics (e.g., polystyrene, expanded polystyrene, extruded polystyrene, polypropylene, polyethylene terephthalate, high-density and low-density polyethylene, polyurethane, polycarbonate). These petroleum-derived substrates are lightweight, low-cost, and resistant to oil and water vapor, such as expanded polystyrene (EPS, trade name STYROFOAM). TMThis process produces (commonly sold) and extruded polystyrene. The production of petroleum-derived plastics themselves requires the consumption of non-renewable resources and results in substantial greenhouse gas emissions. The processes for producing certain foams, especially extruded foams, require considerable energy. Foams are also associated with ozone depletion and climate change due to the use of toxic blowing agents, such as chlorofluorocarbons and hydrofluorocarbons. Foams, especially polyurethane foams, are often synthesized and catalyzed using toxic and corrosive chemicals, such as isocyanates and strong acids, to form heavily cross-linked structures that dramatically slow down the decomposition of the foam (and cause little to no biodegradation).

[0006] Furthermore, many of these items made from foam are designed for single-use applications. However, conventional petroleum-derived plastic foam products are not biodegradable; therefore, although they can be recycled under certain limited circumstances, after single use they are usually dumped in landfills. Once these items reach landfills, they can take 450 to 1000 years or more to decompose, and if broken down, they produce microplastic particles. It is estimated that less than 1% of EPS cups are recovered and recycled, but an estimated 500 billion single-use cups are used and discarded worldwide every year. Moreover, single-use containers are often improperly disposed of and experience disintegration over long periods of time in places such as waterways, beaches, and roadsides, where they can come into contact with aquatic or terrestrial animals in these localized environments.

[0007] Concerns about the environmental impact of discarded and broken-down plastic materials are prompting manufacturers to consider bio-based alternatives. Materials composed of whole or significant parts of biological products or renewable agricultural or forestry materials are designated “bio-based” by the USDA. Biopolymers derived from bio-based materials can be used to form bioplastic materials that offer alternatives to conventional petroleum-based plastics.

[0008] Biopolymers can be produced by biological systems (microorganisms, plants, animals) or chemically synthesized from biological materials such as proteins, starches, and sugars. The primary sources of biopolymers are renewable materials such as agricultural feedstocks or waste products. Many biopolymers are biodegradable, meaning they can be broken down into carbon dioxide, water, and other organic compounds via the enzymatic action of microorganisms. These bio-based plastics, made from precursors such as polylactic acid (PLA), polyhydroxyalkanoates (PHA), and cellulose, are typically considered biodegradable and can be broken down in the environment by microorganisms under certain conditions (e.g., high heat and long duration for PLA). Certain biodegradable materials are further considered "compostable," meaning they can be broken down by microorganisms to form nutrient-rich organic materials that can enrich the soil, producing end products similar to those produced during natural compost formation.

[0009] While these bio-based plastic alternatives, such as polylactic acid plastics, starch-derived plastics, or cellulosic plastics, are of great interest as substrates for the manufacture of plastic materials, their use in general consumer applications, such as durable formed articles, containers, and packaging, remains limited, partly due to performance limitations. These materials tend to be hydrophilic and / or lipophilic, and have a high affinity for water and / or lipids. Therefore, these materials can become waterlogged or immersed in oils, making them unsuitable as containers for food and other products containing water or oil. When water or oil penetrates durable articles, they begin to solvate the container or packaging material, affecting their mechanical properties, thus making them structurally weak and prone to inadequacy. These limitations of bio-based plastics are often overcome by coating bioplastic materials with substances that have strong hydrophobic and oleophobic properties, usually petroleum-derived organic substances, such as polyethylene, polyethyleneimine, PVC, or fluorocarbons, materials with well-recognized environmental impacts. Furthermore, while such coatings improve water and oil resistance in bio-based materials, these materials still lack rigidity and mechanical strength. Also, conventional processes for producing foam from such materials are costly, partly because the formulations used for foaming contain a large amount of water that must be removed during processing.

[0010] To address these limitations, manufacturers are adding inorganic and organic materials as granular or fibrous fillers to bio-based formulations to improve their mechanical properties and streamline their processes. Compared to these materials using inorganic fillers, alternative bioplastics incorporating natural particles or fibers offer advantages such as renewability, high strength, relatively easy processing, and other desired properties. Nanoscale and microscale cellulose fibers, such as nanofiberized cellulose (NFC), microfiberized cellulose (MFC), nanocrystalline cellulose (NCC), and microcrystalline cellulose (MCC), are particularly attractive fillers for improving strength. These nanoscale and microscale cellulose fibers and crystals (collectively referred to as “nanocellulose elements,” “NC elements,” or “NCE”) have potential for use in biopolymer products, but with limitations. Firstly, since NCE fibers themselves are hydrophilic, they do not contribute to the water resistance of the resulting product. Therefore, water-repellent treatment is still necessary for articles containing NCE. More importantly, NCE requires to be transported to its intended use in a highly diluted suspension (<5–10 wt%) to prevent it from entangling with itself. This entanglement causes it to harden into a dense, viscous mass that resists resuspension; if this tightly packed network of aggregated cellulose elements is further dehydrated, it hardens further in a process called hornification. Complete drying of an NCE suspension forms a solid, brick-like mass that is substantially nondispersible. Therefore, in order to maintain an NCE suspension in a usable state so that the properties of the NCE it contains are available for use in other materials, the NCE must be maintained in a highly diluted form.

[0011] Despite a decade of academic and industrial efforts, the success of low-cost and effective drying and redispersion of NCE has not been found by commercial nanocellulose manufacturers. Two difficulties arise from two factors: (a) drying or concentrating aqueous media in which NCE is suspended and (b) subsequently redispersing them: (1) the properties of cellulose polymers in NCE that form hydrogen bonds with each other, causing adjacent cellulose elements to adhere to irreversible aggregates consisting of aggregates of particles that permanently bond to each other and resist redispersion; and (2) the large surface area per unit weight associated with the size and morphology of NCE, which greatly increases the exposure of NCE surfaces to each other and worsens adhesion due to hydrogen bonding. These two factors combined result in keratinization associated with concentrated and dried NCE suspensions. The tendency of NCE suspensions toward keratinization necessitates that these materials be transported in large volumes of water, significantly adding to the costs associated with their transport and use. Furthermore, when forming foams using highly diluted NCE-containing suspensions, excess water is incorporated into the foam and must be removed by a drying technique that allows the NCE to be uniformly dispersed within the foam-forming matrix. Drying techniques such as freeze-drying, spray-drying, supercritical fluid drying, and atomization have been investigated by researchers, but these techniques have resulted in at best small samples of redispersed NC elements, using processes whose high cost, energy requirements, and the need for specialized equipment have eliminated their widespread suitability. This resistance to redispersion has hindered the suitability of NCE as a matrix for forming bio-based foams and further hindered the use of NCE as an additive for other bio-based foaming materials.

[0012] Therefore, there remains a need in the technical field for methods and formulations that provide satisfactory mechanical strength and water / oil resistance to bio-based foam-based manufactured articles, a need that could provide commercially viable alternatives to petroleum-derived plastics for foamed manufactured articles such as containers and packaging materials. There is a need to enable their commercial implementation at low cost, without excessive energy requirements or the need for special equipment, to the extent that NCE is incorporated into bio-based foam-forming materials for such articles. To achieve these latter goals, there remains an unaddressed need to make nanocellulose-containing formulations redispersible and keratinization-resistant so that these formulations can be economically transported and introduced into bio-based foam-forming composites as concentrates or dry granular additives. [Overview of the project]

[0013] Summary of the Invention In some embodiments, a simple NCE material comprising a simple NCE matrix is ​​disclosed herein, the simple NCE matrix comprising a collection of redispersed NCEs, the simple NCE matrix providing a structural framework for the simple NCE material, and the simple NCE material being foamed. In some embodiments, the simple NCE material comprising a plurality of sub-matrices. In some embodiments, pulp or a pulp-based material is incorporated into the simple NCE matrix; the simple NCE matrix may be pulp-dominant. In some embodiments, the simple NCE material further comprises a foam-forming material. In some embodiments, the simple NCE matrix further comprises a reinforcing agent or barrier formulation. In some embodiments, the matrix comprises a reinforcing agent which may contain a further amount of NCE. In some embodiments, the matrix comprises a barrier formulation which may contain methylcellulose and produce oleophobicity. In other embodiments, the matrix comprises a barrier formulation which may contain a resin acid or a combination of resin acids and produce hydrophobicity. Manufactured articles comprising the simple NCE material described above are also disclosed herein. In some embodiments, the manufactured articles further comprise a barrier formulation. In this embodiment, the article is formed into a shaped article which can be formed into a plate or bowl or a floating sheet or floating particles.

[0014] (a) A method for producing a simple NCE foam material is also disclosed herein, comprising the steps of (i) providing a redispersed suspension containing redispersed NC elements, wherein the redispersed suspension is produced by (i) providing an initial NCE suspension containing NC elements suspended in a liquid medium; (ii) adding a drying / dispersing additive to the initial NCE suspension to form a suspension of redispersible NCE; (iii) drying the suspension of redispersible NCE to produce a dried material containing redispersible NCE; and (iv) suspending the dried material in a resuspension fluid to produce a redispersed suspension; (b) drying or concentrating the redispersed suspension to produce a simple NCE matrix, wherein the simple NCE matrix provides a structural framework for a simple NCE material; (c) adding an additive substance before or after the drying or concentrating step to produce a simple NCE material; and (d) foaming at least one of the simple NCE matrix and the simple NCE material to produce a simple NCE foam material. In one embodiment, the simple NCE matrix comprises a plurality of submatrices. In one embodiment, the additive substance is a filler that may contain pulp or a pulp-based material. In one embodiment, the additive substance is a barrier formulation that produces oleophobicity, which may contain methylcellulose. In one embodiment, the additive substance is a barrier formulation that produces hydrophobicity, which may contain a resin acid or a combination of resin acids. In one embodiment, the foaming step comprises exposing the simple NCE matrix to the action of a foam-forming material and at least one action of a foam-foaming process. In one embodiment, the foaming step comprises exposing the simple NCE material to the action of a foam-forming material and at least one action of a foam-foaming process.

[0015] A composite NCE-containing material comprising a composite NCE-containing matrix is ​​further disclosed herein, the composite NCE-containing matrix comprising a group of additive NCEs and an existing matrix, the additive NCEs being incorporated into the existing matrix, the existing matrix providing a structural framework for the composite NCE-containing material, and the composite NCE-containing material being foamed. In an embodiment, the existing matrix is ​​bio-based. In an embodiment, the composite NCE-containing material further comprises one or more additive substances, each additive substance selected from the group consisting of reinforcing agents, barrier formulations and bulking agents. In an embodiment, the composite NCE-containing material further comprises a foam-forming material. Manufactured articles comprising the composite NCE-containing material described above are also disclosed herein. Manufactured articles may be selected from the group consisting of packaging materials, insulators, sports and personal protective articles, aquatic entertainment articles, bio-based flotation articles, vehicles and containers for the delivery of activators.

[0016] Furthermore, a method for producing a composite NCE-containing foamed material is disclosed herein, comprising the steps of: providing a group of additive NCEs, incorporating the group into an existing matrix to form a composite NCE-containing matrix; adding additive substances to the composite NCE-containing matrix to produce a composite NCE-containing material; and foaming at least one of the composite NCE-containing matrix and the composite NCE-containing material to form a composite NCE-containing foamed material. In an embodiment, the foaming step includes exposing the composite NCE-containing matrix to the action of at least one of a foam-forming material and a foam-foaming process. In an embodiment, the foaming step includes exposing the composite NCE-containing material to the action of at least one of a foam-forming material and a foam-foaming process.

[0017] In yet another embodiment, a simple NCE material comprising a simple NCE matrix is ​​disclosed herein, the simple NCE matrix comprising a collection of redispersible NCEs treated with a drying / dispersible additive comprising a low critical solution temperature (LCST) polymer; the simple NCE matrix provides a structural framework for the simple NCE material; the simple NCE material comprises a barrier formulation or barrier substance; and the simple NCE material is foamed. In an embodiment, the barrier formulation comprises a substance selected from the group consisting of cellulose polymers, lipids, proteins, fillers, fatty acids, resin acids, and combinations of resin acids. In one aspect, the NCE material comprises a barrier substance, the barrier substance selected from the group consisting of cellulose polymers, lipids, proteins, fillers, fatty acids, resin acids, and combinations of resin acids. In one embodiment, the barrier formulation comprises an oleophobic substance selected from the group consisting of MC, HPMC, CMC, NaCMC, CA, CAB, chitosan, rosin, lignin, and plant proteins; in another embodiment, the barrier formulation comprises a hydrophobic substance selected from the group consisting of MC, CA, CAB, chitosan, rosin, hydrophobized starch, lignin, and plant proteins. In a particular further embodiment, the barrier substance is an oleophobic substance selected from the group consisting of MC, HPMC, CMC, NaCMC, CA, CAB, chitosan, rosin, lignin, and plant proteins; in another embodiment, the barrier substance is a hydrophobic substance selected from the group consisting of MC, CA, CAB, chitosan, rosin, hydrophobized starch, lignin, and plant proteins. In an embodiment, the simple NCE-based material further comprises one or more additive substances selected from the group consisting of bulking agents, reinforcing agents, nucleating agents, plasticizers, thickening agents, and appearance modifiers or combinations thereof. In one embodiment, one or more additive substances are fillers that may include pulp or pulp-based materials or filler particles, the filler particles may include plant-derived organic materials. In one embodiment, one or more additive substances are nucleating agents. In one embodiment, one or more additives are plasticizers that can be selected from the group consisting of glycerol, triglycerin, triacetin, triethyl citrate, triethyl acetyl citrate, tributyl citrate, oleic acid, levulinic acid, PEG, and polysorbate.In some embodiments, one or more additive substances are thickeners selected from the group consisting of xanthan gum, guar gum, agar gum, gellan gum, MC, CMC, and HPMC. In some embodiments, the simple NCE-based materials further comprise foam-forming materials. Furthermore, manufactured articles comprising these simple NCE-based materials are disclosed herein and can be formed into molded articles such as plates, bowls, floating sheets, or floating particles.

[0018] In some embodiments, a method for producing a foamed article containing a simple NCE material is also disclosed herein, comprising the steps of (a) producing a simple NCE material containing redispersible NC elements, wherein the simple NCE material is produced by the sub-steps of (i) providing an initial suspension containing NC elements suspended in a fluid medium; (ii) combining a drying / dispersible additive with the initial suspension to form a suspension of redispersible NCE; and (iii) adding an additive substance to the suspension of redispersible NCE to thereby form a simple NCE material; (b) exposing the simple NCE material to the action of a foam-forming substance or a foam-forming process to provide a foamed simple NCE material; and (c) forming or shaping the foamed simple NCE material into a desired configuration to produce a foamed article. In some embodiments, the additive substance is selected from the group consisting of barrier formulations, barrier substances, fillers, reinforcing agents, nucleating agents, plasticizers, thickeners and appearance modifiers or combinations thereof. In some embodiments, the forming or shaping step includes extrusion molding.

[0019] In some embodiments, a foamed composite NCE-containing material comprising a composite NCE-containing matrix is ​​further disclosed herein, the composite NCE-containing matrix comprising a population of redispersible NCEs treated with a drying / dispersible additive comprising a low critical solution temperature (LCST) polymer and an existing matrix; the redispersible NCEs are incorporated into the existing matrix, the existing matrix providing a structural framework for the composite NCE-containing material; the composite NCE-containing material comprises a barrier formulation or barrier substance; at least one of the composite NCE-containing matrix, the existing matrix, or the composite NCE material is exposed to a foam-forming formulation or foam-forming process, and the composite NCE-containing material is converted into a foamed composite NCE-containing material. In some embodiments, the existing matrix comprises a bio-based polymer comprising a cellulose derivative. In some embodiments, the existing matrix comprises a petroleum-derived polymer which may be derived from recycled plastic material. In some embodiments, the barrier formulation comprises a substance selected from the group consisting of cellulose polymers, lipids, proteins, fillers, fatty acids, resin acids, and combinations of resin acids. In one aspect, the NCE-containing material includes a barrier substance, which is selected from the group consisting of cellulose polymers, lipids, proteins, fillers, fatty acids, resin acids, and combinations of resin acids. In one embodiment, the barrier formulation includes an oleophobic substance selected from the group consisting of MC, HPMC, CMC, NaCMC, CA, CAB, chitosan, rosin, lignin, and plant proteins; in another embodiment, the barrier formulation includes a hydrophobic substance selected from the group consisting of MC, CA, CAB, chitosan, rosin, hydrophobized starch, lignin, and plant proteins. In a specific further embodiment, the barrier substance is an oleophobic substance selected from the group consisting of MC, HPMC, CMC, NaCMC, CA, CAB, chitosan, rosin, lignin, and plant proteins; in another embodiment, the barrier substance is a hydrophobic substance selected from the group consisting of MC, CA, CAB, chitosan, rosin, hydrophobized starch, lignin, and plant proteins. In this embodiment, the composite NCE-containing material further comprises one or more additive substances selected from the group consisting of bulking agents, reinforcing agents, nucleating agents, plasticizers, thickening agents, and appearance modifiers.In an embodiment, one or more additive substances are fillers that may include pulp or pulp-based materials or filler particles, the filler particles may include plant-derived organic materials. In an embodiment, one or more additive substances are nucleating agents. In an embodiment, one or more additive substances are plasticizers that can be selected from the group consisting of glycerol, triglycerin, triacetin, triethyl citrate, triethyl acetyl citrate, tributyl citrate, oleic acid, levulinic acid, PEG, and polysorbate. In an embodiment, one or more additive substances are thickeners that can be selected from the group consisting of xanthan gum, guar gum, agar gum, gellan gum, MC, CMC, and HPMC. In an embodiment, the foamed composite NCE-containing material further comprises a foam-forming material. Also disclosed herein are manufactured articles containing these foamed composite NCE-containing materials that can be formed into articles such as plates, bowls, floating sheets, or floating particles.

[0020] In one embodiment, (a) a step of providing a composite NCE-containing material comprising redispersible NC elements, wherein the composite NCE-containing material comprises: (i) providing an initial suspension comprising NC elements suspended in a fluid medium; (ii) combining a dry / dispersible additive with the initial suspension to form a suspension of redispersible NCE; (iii) incorporating the suspension of redispersible NCE into an existing matrix to form a composite NCE-containing matrix; and (iv) adding an additive substance to at least one of the initial suspension, the suspension of redispersible NCE, the existing matrix, and the composite NCE-containing matrix. Disclosed herein are methods for producing a formed article containing a foamed composite NCE-containing material, comprising the sub-step of adding a composite NCE-containing material to thereby form a composite NCE-containing material; (b) a step of thoroughly exposing at least one of an initial suspension, a suspension of redispersible NCE, an existing matrix, and a composite NCE-containing matrix to a foaming formulation or foaming process to convert the composite NCE-containing material into a foamed composite NCE-containing material; and (c) a step of forming or shaping the foamed composite NCE-containing material into a desired configuration to thereby produce a formed article. In embodiments, the additive substance is selected from the group consisting of barrier formulations, fillers, reinforcing agents, nucleating agents, plasticizers, thickeners, and appearance modifiers. In embodiments, the exposure step involves exposing at least one of the initial suspension, an existing matrix, and a composite NCE-containing matrix to a foaming process. In embodiments, the forming or shaping step includes extrusion molding. [Brief explanation of the drawing]

[0021] Brief explanation of the drawing [Figure 1] Figure 1 is a block diagram showing the process for creating a matrix containing redispersed nanocellulose elements. [Figure 2] Figure 2 is a block diagram showing the process for creating a matrix containing redispersed nanocellulose elements. [Figure 3] Figure 3 is a block diagram showing the process for creating a matrix containing redispersed nanocellulose elements. [Figure 4]FIG. 4 is a block diagram showing a process for making a foamed material containing redispersed nanocellulose elements.

DETAILED DESCRIPTION OF THE INVENTION

[0022] Detailed Description of the Invention 1. Components of the Redispersible Nanocellulose Element Formulation a. General Redispersible Nanocellulose Elements The nanocellulose element (NCE) can be processed to be redispersible in formulations for making useful manufactured articles using the formulations and methods described in U.S. Patent Application Publication No. 20220412010A1 (U.S. Patent Application No. 17 / 834,521, filed June 7, 2022; the ‘521 application), the contents of which are incorporated herein by reference in their entirety. It has been unexpectedly discovered that using the methods of these inventions, formulations can be prepared that contain NCE, are concentrated or dried, and can then be redispersed without keratinization. Such formulations containing redispersed NCE can then be used to make foamed materials, which can then be used for the manufacture of useful articles. The formulation itself can be dried and formed to make a manufactured article, or the formulation can be integrated into an existing matrix to form a composite having improved properties relative to the existing matrix itself or a composite having additional properties not present within the existing matrix.

[0023] Suitable substrates for processing by the systems and methods disclosed herein (i.e., NFCs and MFCs, as well as NCCs and MCCs, collectively known as NCEs) can be derived from all types of cellulose raw materials, particularly plant-derived cellulose raw materials. Plant-derived cellulose raw materials include lignocellulose materials: lignocellulose materials consist of cellulose polymers bound together with a variable amount of lignin. All types of lignocellulose materials are suitable for producing NCEs or other lignocellulose materials, such as pulp. Plants having use as lignocellulose materials may be woody (e.g., trees with hard trunks and perennial growth cycles) or non-woody with weak trunks and annual or limited perennial growth cycles. Lignocellulose materials may include specialty-use grains such as switchgrass and elephantgrass, which are cultivated for applications such as biofuels and are capable of multiple harvests. Suitable materials for pulp production may, without limitation, originate from industries such as agriculture (e.g., corn stalks and leaves after the kernels have been removed and corn cobs, sugarcane bagasse, straw, bundles of empty oil palm fruits, pineapple leaves, apple stalks, coir fiber, mulberry bark, rice hulls, bean pods, soybean pods (or "soy hulls")), cotton linters, blue agave waste, North African grass, banana pseudo stem residue, American groundnut hulls, pistachio nut shells, grape pomace, shea butter nut shells, passion fruit peels, fique fiber waste, sago seed shells, kelp waste, rush stalks, etc.) or forestry (sawmill and paper mill waste).

[0024] In some embodiments, NCE is conventionally prepared from precursor lignocellulose material or other plant-derived cellulose raw materials by a series of mechanical and / or chemical procedures performed in an aqueous medium, where the aqueous suspension loosens the hydrogen bonds between the cellulose filaments to facilitate delamination, resulting in the formation of NCE. Since NFCs and MFCs are extracted from plants by different techniques, their forms and properties differ. NFCs and MFCs can be distinguished from each other based on their size and shape: cellulose nanofibers are considerably smaller in diameter than cellulose microfibers and can be straight and rod-shaped, while cellulose microfibers are larger in diameter, more flexible, and have a more varied and irregular appearance. While the literature cites a range of dimensions for NFCs and MFCs, NFC fibers are nanoscale (e.g., have a diameter of 4–20 nm), and MFCs are even larger, but typically in the nano range, with a diameter of 20–100 nm or more. After forming NCE from precursor cellulose material, the NCE is dispersed in an aqueous medium at low concentrations (<10 wt%) because, as mentioned above, their high water absorption capacity and tendency to form hydrogen bonds cause entanglement due to hydrogen bonding in high aspect ratio NC elements, resulting in the formation of highly viscous suspensions even at low solid concentrations.

[0025] As described in the 521 application, additives that can be used to prepare NCE have been discovered and are redispersible after being formulated in solution. Such additives are referred to herein as “drying / dispersing additives.” Without being bound by theory, these additives function to inhibit or disrupt hydrogen bonding between NCE and each other, in particular, usually at high reaction temperatures, thus preventing hardening and keratinization while retaining their inherent high hydrophobicity, which allows for easy redispersion in aqueous media. As used herein, the term “redispersion” and its grammatical derivatives and homogeneities mean the process by which dried or concentrated NCE, prepared to be redispersible as described herein, is suspended in a fluid medium (whether aqueous or non-aqueous), referred to as a resuspension fluid, where there is substantially complete dissolution of the dried or concentrated NCE to release its NCE components to be resuspended in the resuspension fluid. In some embodiments, aqueous suspension fluids may be used; in other embodiments, non-aqueous suspension fluids may be used, such as fluids having hydrophobic or amphiphilic properties.

[0026] As used herein, the term “redispersible” means these NCEs treated with a drying / dispersing additive as disclosed herein, which makes the NCEs redispersible. Formulations containing such redispersible NCEs may exist in liquid, dry, or partially dry states. In a fully dry or partially dry state, NCEs in a formulation are redispersible by suspending them in a resuspension fluid. Redispersible NCEs (i.e., NCEs treated with a drying / dispersing additive as disclosed herein) are present in a liquid formulation before they are dried; the presence of the drying / dispersing additive makes such NCEs redispersible, so they may subsequently experience redispersion when dried or concentrated. Redispersible NCEs also exist in a liquid formed by adding a redispersion fluid to a dry or concentrated formulation containing redispersible NCEs; their presence when resuspended in such a liquid indicates that they are indeed redispersible and therefore redispersible. To avoid any doubt, this last group of redispersible NCEs, which are formulated to be redispersible by definition and resuspended in a resuspension fluid that actually redisperses them, may also be more specifically referred to as “redispersed NCEs”; all redispersed NFCs are redispersible by definition, but not all redispersible NFCs are redispersible.

[0027] In one embodiment, the redispersion results in suspensions of NCEs, which are formed as individual NCEs or amorphous aggregates of individual NCEs (both referred to herein as “resuspended particles”), and such resuspended particles have an aspect ratio greater than 10. In one embodiment, the resuspended particles have an aspect ratio of about 10 to about 300 or about 10 to about 200. In one embodiment, the resuspended particles have an aspect ratio of about 50 to about 150. In one embodiment, the resuspended particles have an aspect ratio of about 25 to about 75. In another embodiment, the resuspended particles have an aspect ratio of about 75 to about 125.

[0028] These formulations and methods include several different categories of drying / dispersing additives: (1) certain temperature-responsive polymers that can introduce spaces between NC elements during drying, thereby preventing their aggregation; (2) certain volatile small molecules that can create spaces between NC elements during drying; and (3) certain non-volatile small or large molecules ("blocking agents") that disrupt hydrogen bonding between or within NC elements during drying. The drying / dispersing additives include, but are not limited to, temperature-responsive polymers, volatile small molecule additives, and blocking agents. All of these materials act to disrupt hydrogen bonding at high temperatures or otherwise, while creating gaps between or within NC elements, and are subsequently redispersed by further drying.

[0029] Certain additives (e.g., the specific LCST polymers listed below) are suitable for use as single agents to facilitate drying and redispersion, while other additives are intended for use as adjuvants in combination with the main drying / dispersing additive, either when administered to the initial NC suspension simultaneously with the main additive, or as a pretreatment to the initial NC suspension or any of its precursors before the addition of the main additive, or as a posttreatment to the initial NC suspension after the addition of the main drying / dispersing additive.

[0030] b. Drying / dispersing additives It is understood that the drying / dispersing additives disclosed herein, individually or in combination, may be introduced into initial NCE-containing suspensions to improve the drying process of NCE and facilitate their redispersion. Drying / dispersing additives may also be used in combination with other agents that enhance their efficiency, even if these other agents are not effective as drying / dispersing additives when used alone; such agents used in combination with drying / dispersing additives to enhance their efficiency are referred to as “adjuvants.” It is further understood that one or more drying / dispersing additives and / or adjuvants may act together in a synergistic manner. Furthermore, combinations of drying / dispersing additives may be introduced sequentially, with or without the addition of adjuvants, during and / or before, after, or during the process used to prepare initial NC suspensions from feedstock materials of a cellulose source. For example, nonpolymeric additives may be added during the process used to prepare initial NC suspensions from feedstock materials, but preferably after the chemical pretreatment of initial NCE derived from cellulose or lignocellulose precursor material.

[0031] i. Temperature-responsive polymers In some embodiments, certain temperature-responsive polymers may be used to create spaces between NC elements during drying, thereby preventing the NC elements from aggregating during the drying process. By preventing high-density aggregation and curing of NCEs, temperature-responsive polymers redisperse them upon contact with a resuspended fluid. Temperature-responsive polymers particularly suitable for this purpose are those that exhibit a phenomenon known as LCST (Low Critical Solution Temperature) phase behavior. Certain LCST polymers are understood to be hydrophilic below their LCST transition temperature and reversibly hydrophobic above their LCST transition temperature. That is, below the LCST point, the polymer exhibits a high affinity for water, consistent with its intrinsic molecular hydrophilicity. However, above the LCST point, the polymer repels water and avoids hydrogen bonding. This is evident from the observed thermogelation of polymer solutions above this transition temperature. When polymeric or oligomeric LCST additives self-assemble on the surface of NC elements (in the form of monolayers or layers of several particles), the drying of the NC elements and the resulting form of the NC-containing material in the dry state are influenced to facilitate the final redispersion of such NCEs.

[0032] For use in this setup, the LCST polymer can be added to the initial NC suspension at a temperature below the transition temperature of the LCST polymer. The initial NC suspension is then heated to allow it to dry. As water evaporates from the initial NC suspension during drying, its temperature rises to the boiling point of water, exceeding the transition temperature of the LCST polymer, at which point the LCST polymer loses its hydrophilic properties and becomes hydrophobic. Once it becomes hydrophobic, the behavior of the LCST polymer changes: it interferes with the hydrogen bonding that would otherwise occur between the NC elements. Here, the hydrophobic nature of the LCST polymer drives the aggregation or disaggregation of the NC elements instead of these processes driven by the interaction of the hydrophilic cellulose units of the NC elements.

[0033] In some embodiments, the selected LCST polymer can significantly or completely prevent high-density aggregation and curing of NC elements during drying. In some embodiments, the ability of the selected LCST polymer to disrupt high-density aggregation and curing of NC elements is independent of the selection of equipment and the mode of drying. For example, a suspension containing the LCST polymer and NC elements may remain stationary during 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 to achieve drying without aggregation. Dried NC materials incorporating the selected LCST polymer described herein can be easily redispersed in water by gentle agitation or stirring, with minimal or no clumping, or with any remaining high-density aggregation or curing identified in the redispersed suspension. These features allow for a wide tolerance in parameters for redispersion and for handling the material being redispersed.

[0034] In this embodiment, the following list provides examples of LCST polymers and their analog short-chain oligomers that can be used as drying / dispersible additives to prevent high-density aggregation and hardening of NC elements, thereby facilitating the subsequent redispersion of NC elements. Methylcellulose Carboxymethylcellulose • Sodium carboxymethylcellulose • Hydroxyethylcellulose • Hydroxypropylcellulose Hydroxypropylmethylcellulose Ethyl hydroxyethyl cellulose • Polyvinyl caprolactam • Poly(methyl vinyl ether) • Poly(N-isopropylacrylamide) • Poly(N,N-diethylacrylamide) • Block copolymer of poly(ethylene oxide) and poly(propylene oxide) • Poly(pentapeptide) of elastin

[0035] Note that the thermal gelation temperatures of the specific additives listed above depend on the type and degree of substitution and are adjustable by structural design. Advantageously, LCST polymers selected for use as drying / dispersing additives may have transition temperatures higher than ambient temperature (e.g., >25°C), so the polymer remains in solution until the drying process begins.

[0036] ii. Volatile small molecule additive systems In some embodiments, a volatile system containing small molecule additives may be used, alone or in combination with other additives, to act as a drying / dispersing additive by creating spaces between NC elements during drying, thereby preventing the NC elements from aggregating during the drying process. Selected small molecule additives for use in 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 considerably lower hydrogen bonding tendency compared to water. When an additive-loaded volatile system containing NCE and selected small molecules undergoes drying, water molecules preferentially evaporate, while the small molecule additives remain due to their higher boiling point, thereby increasing the concentration of the additive in the remaining solution between adjacent NC elements. In some embodiments, the molecular segmentation of the volatile small molecule additive includes both polar and nonpolar functional groups. Without being constrained by theory, it is conceivable that adhesion between and within NC elements is reduced, as polar segmentation is attracted to cellulose hydroxyl groups, and nonpolar segmentation simultaneously interferes with hydroxy-hydroxyl interactions. Subsequently, as the temperature in the system rises, the additives evaporate, leaving behind the NC elements surrounded by air, and thus separating from each other. The resulting dry material, containing NC elements separated from each other by air, can be readily redispersed without forming any indicators of aggregation, hardening, or concentration change, such as observable aggregates / clumps. The redispersed suspension contains resuspended NC particles with a uniform distribution in the suspension, where the NC elements retain their nanoscale characteristics, and redispersion can be achieved by very gentle stirring / agitation only.

[0037] In this embodiment, the following list provides examples of small molecule additives that can be used as drying / dispersing additives in the aforementioned volatile systems to prevent high-density aggregation and hardening, thereby facilitating the subsequent redispersion of NC elements. The exemplary additives can be divided into two categories: nonionic and cationic compounds.

[0038] Without limitation, nonionic candidates include: • 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 These could be cited.

[0039] Without limitation, cationic candidates include: Ethylenediamine • Diethylenetriamine • Tetraethylenepentaamine • 1,3-pentanediamine • Piperazine • 1,2-Cyclohexanediamine Aniline Pyridine • Piperazine These could be cited.

[0040] In some embodiments, the small molecule additive may completely evaporate from the initial NC suspension, leaving only the NC elements in suspended or dry form, without any residue of the additive. However, in other embodiments, trace amounts of the small molecule additive may remain. For example, certain cationic additives may have cationic groups that adhere to cellulose molecules, so that after complete drying, trace amounts of the additive remain adhered to the cellulose. For most industrial applications, the residue of these additives does not pose health or environmental problems. However, in some embodiments, biodegradable cationic small molecules, such as 1,3-pentanediamine, may be selected to avoid such problems.

[0041] iii. Blocking agent In embodiments, non-volatile small or large molecular additives may be used separately from the volatile systems described above to prevent hydrogen bonding and / or create spaces between NC elements during drying, thereby preventing interaction between NC elements and thus preventing aggregation of NC elements during the drying process. In embodiments, surface-functionalized nanoscale particles may be used in the same manner. Such non-volatile small or large molecular additives and nanoscale particles used to perform this blocking function are referred to herein as blocking agents or barriers. As used herein, the terms “blocking agent” or “barrier” include any non-volatile chemical additive or nanoscale granular material that, whether the substance is inserted between or into NC elements, or whether the substance provides a transient competitive bonding site for NC elements, or otherwise, prevents hydrogen bonding or creates spaces within NC elements.

[0042] As an example, caffeine and other xanthine derivatives are small molecule blockers that can be advantageously used to facilitate the isolation of NC elements from each other and their subsequent redispersion during drying or concentration processes. Without being constrained by theory, it is conceivable that certain purines (e.g., caffeine and other xanthines or xanthine derivatives) and aromatic nitrogen atoms in pyrimidines can hydrogen bond with the hydroxyl groups of cellulose, presenting a flat, relatively nonpolar, molecularly smooth outer surface for water-screening to the NCE, thus preventing adhesion between and within NC elements. Caffeine and other xanthines and xanthine derivatives can typically be used in amounts that do not pose health or environmental problems, even when used in doses sufficient to facilitate NC dispersion.

[0043] As another example, certain wetting agents can be used as blocking molecules. Wetting agents have multiple hydrophilic sites, such as hydroxyl, ester, and ammonium groups, that can form hydrogen bonds with the surface of NC elements, thereby shielding the interaction of these elements with each other via hydrogen bonding, and thus preventing high-density aggregation and hardening. Furthermore, these hygroscopic substances are biocompatible and are already widely used in the pharmaceutical, cosmetic, and food industries. Examples of short and long wetting agent candidates, though not limited to these, include glycerin, caprylyl glycol, ethylhexylglycerin, tribehenin, hydrolyzed soy protein, various amino acids, propylene glycol, methyl gluceth-20, phenyl trimethicone, hyaluronic acid, sorbitol, and gelatin.

[0044] As yet another example, fatty acids can also be used as blocking agents. Fatty acids include a hydrophilic moiety and a hydrophobic tail. The hydrophilic moiety can form hydrogen bonds with the surface of the NC elements, thereby shielding the interaction of these elements with each other via hydrogen bonding, and thus preventing aggregation. Preferably, fatty acids may be selected that do not contain so many hydrophilic moieties that excessive hydrogen bonding occurs between the NCE particles and the fatty acid. However, in embodiments where a very large number of hydrogen moieties can cause high-density aggregation and hardening, the hydrophobic tail of the fatty acid blocking agent may act to physically prevent high-density aggregation and hardening of the NC elements by preventing or hindering hydrogen bonding. In embodiments, the blocking agent may be fatty acids, such as stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, caproic acid, etc. Water-soluble fatty acids may be selected to facilitate the dispersion of fatty acids in aqueous solutions of NC elements.

[0045] 2. Redispersibility of NC elements and redispersed suspensions The block diagram in Figure 1 schematically shows process 100 involved in the preparation of a redispersible suspension of NC elements, which can be further processed to produce a redispersible suspension of NC elements and materials made therefrom. As shown in Figure 1, process 100 for producing a suspension of redispersed NC elements comprises four steps.

[0046] Step 1 involves suspending a collection of NCE 102 in a suspension fluid 104 to produce an initial NCE suspension 108. Processes for forming an initial NCE suspension suitable for further processing using the formulations and methods disclosed herein are well known in the art. To form such an NCE-containing suspension, a cellulose source may be treated using conventional mechanical techniques and any chemical treatments to extract the constituent cellulose nanomaterials (i.e., NCEs) and hold them as suspensions in a liquid or other fluid medium. The NC elements thus extracted form an initial NC suspension, which may be treated to make them redispersible in subsequent steps using the formulations and methods disclosed.

[0047] In step 2, the drying / dispersing additive 110 described above is added to the initial NCE suspension 108 to produce a suspension of redispersible NCE 112. As previously discussed, the drying / dispersing additive 110 makes the NCE in the initial NCE suspension 108 redispersible. The redispersible suspension of NCE 112 is dried in step 3 to produce a dry material 114 containing the redispersible NCE. The dry material 114 containing the redispersible NCE is then either ground / minced and used as a dry component, or suspended in the resuspension fluid 118 in step 4 to produce a suspension 120 of the redispersible NCE produced as described above at a desired concentration; such redispersible NCE treated by suspension in the resuspension fluid as described in step 4 may also be referred to as “redispersed NC”. In one embodiment, the subsequently redispersed suspension 120 of NCE may be treated alone by drying or concentrating, for example, as shown in step 5a, to form a simple NCE system matrix 122 of dried, resuspended NCE, which is formed as a continuous sheet. At the microscopic level, the structure is three-dimensional, highly porous, and typically forms a large, structurally amorphous network structure; however, when nanocrystalline elements are used and / or when crosslinking strategies such as the incorporation and esterification of carboxylic acids into the surface of NCE are employed, semi-crystalline NCE matrices can be synthesized. As used herein, the term “amorphous” refers to any solid composition in which the constituent elements are not organized into a distinct repeating lattice pattern. Amorphous structures typically enhance degradability. Additionally, additive substances (not shown) can be readily integrated into the amorphous simple NCE system matrix 122 to produce advantageous features such as malleability, processability, heat resistance, strength, or oleophobic or hydrophobic properties.

[0048] To reduce the amount of NCE required to produce the desired properties for the matrix, NCE-free pulp-based or pulp-containing additives may also be added. As used herein, the term “pulp-based” means these materials derived from pulp, obtained by processing, forming, or treating them while retaining pulp or pulp derivatives within them.

[0049] Pulp is understood to be produced from materials containing cellulose or lignocellulose fibers, such as wood, non-wood raw materials, special-purpose grains, paper waste, recycled paper, agricultural residues, etc. Non-wood raw materials such as bagasse, grain straw, bamboo, reeds, African sedge, jute, flax, and sisal hemp are well known in the art as sources of cellulose fibers; certain non-limiting examples of materials containing lignocellulose fibers are also provided herein. Wood and other plant materials used to produce pulp contain three main non-aqueous components: cellulose, lignin, and hemicellulose. Chemical and / or mechanical processes for producing pulp are intended to break down the mass structure of the plant material source into constituent fibers, thereby producing a fibrous, cellulose-containing material known in the art as pulp. Pulp can also be formed from previously processed materials such as paper scraps or recycled paper or certain fabrics; such materials may lack some or all of the components found in wood or other pulp materials, but can be subjected to appropriate chemical or mechanical processes to form them into pulp.

[0050] Pulp and pulp-based materials may be used in conjunction with the formulations, compositions, and methods disclosed herein to form or shape as components or substrates for manufactured articles of any useful shape, such as sheets, fibers, solid articles, and molded articles. Such additives may act as low-cost fillers to add volume to a matrix so that a larger amount of simple NCE-based matrix is ​​produced; in such a matrix, redispersible or redispersed NCE may be added in combination with a filler (e.g., conventional pulp or other pulp-based material) so that the final matrix has desired mechanical properties.

[0051] NCE is understood to be an additive substance that causes the organizational and structural characteristics of the matrix having the performance properties to be obtained, and other additives may be added to the matrix to produce any of the advantageous properties or other desired properties described above. For example, appearance-modifying additives, such as dyes or other colorants, may be added to the matrix, or other additives may be intended to provide desired properties such as odor-related agents, emollients, cosmetics, pharmaceuticals, medical and agricultural active ingredients, fragrances and scents. Other relevant additives may be included in the matrix to enable a particular additive to achieve its intended purpose. For example, an NCE matrix may contain odor-blocking chemicals or natural scents that are adapted for release in enclosed, confined spaces with high levels of odoriferant material in items such as gym bags and suitcases, or adapted for use in personal items that may emit odors (e.g., shoe inserts or linings). NCE matrices adapted for these purposes may incorporate plasticizers or other additives (e.g., shoe linings that release odor-controlling substances when in contact with body-temperature feet) to regulate the release of deodorants or adapt their release to specific environmental conditions. Similarly, NCE matrices may be formulated with deodorant or antiperspirant substances in the matrix interstitial spaces, and the NCE matrices work to allow for more durable application of such products to the skin. As a further example, various fragrances may be used by the systems disclosed herein. The term “fragrance,” as used herein, means various odors that may be intentionally incorporated into and delivered by the matrices described herein. 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, etc. Aromas can be supplied from volatile aromatic compounds, such as essential oils, hydrosols, or aromatic microcapsules. Exemplary supplies may integrate biological oils and chemical supplies suspended in solution for easy application or mixing. Other sources for aromas may be aqueous systems, such as hydrosols.Other examples of fragrance-based technologies based on the formulations disclosed herein include, but are not limited to, insecticides for agricultural use, fragrances and odor neutralizers for household use, and pet hormones to promote calming behavior around the home. By controlling the rate of release through careful manipulation of the base technology, applications can be personalized for agricultural products that release insecticides rapidly, for example, during planting season and more slowly when plants are fully grown, to suit the needs of various consumers. The technologies disclosed herein can be readily adapted for agricultural purposes, for example, by using pheromones as agricultural active ingredients. Pheromones are understood to be secreted or excreted chemical substances that elicit 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 processed in a similar pathway as conventionally. Thus, pheromones are considered odor-related activators for the purposes of this disclosure; they are known to be useful in the agricultural industry as pesticides or artificial growth hormones. The examples described herein are illustrative and not limiting. Other examples of additive substances useful with the matrices disclosed herein can be readily conceived by those skilled in the art.

[0052] Additive substances may be integrated into or added to the simple NCE system matrix 122 before, during, or after processing in step 5a: the additive substance(s) may be added to the suspension 120 of NCE redispersed before processing step 5a, and / or added so that the suspension 120 dries or concentrates, and / or added to the simple NCE system matrix 122. A material comprising the simple NCE system matrix 122, which provides a structural framework to the material, and further comprising any additive substances, may be referred to as a “simple NCE system material.” Where the term “matrix” is used herein as in “simple NCE system matrix,” it is understood that the matrix formation process described above does not require the creation of a single continuous simple NCE system matrix, but instead may create multiple simple NCE system matrices that are more loosely linked or discontinuous to one another. Where multiple simple NCE system matrices are created by the process disclosed herein, the interrelationships of the matrices thus formed may provide an organization or structure that can be carried over to the final simple NCE system material. More specifically, when redispersed, NCE can form entanglements or adhesions with one or more matrices that make up one or more matrices. Physical mixing of a liquid formulation containing redispersed NCE can fragment one or more matrices into smaller ones that are more loosely bound to one another. This bonding of smaller matrices can provide desirable structural stability for simple NCE-based materials. This alignment is compatible with the addition of pulp or pulp-based materials that can act as fillers, etc. The structure of the simple NCE-based matrix allows pulp or pulp-based materials to be incorporated into the overall matrix without substantially impairing their strength, stability, and / or durability.

[0053] In another embodiment, the suspension 120 may be added to another existing matrix 124, as shown in step 5b, to form a composite NCE-containing matrix 128. The redispersed NCE in the suspension 120 may be referred to as “additive NCE” when used in step 5b to be added to the existing matrix 124. In this embodiment, the existing matrix 124 provides a structural framework for the composite NCE-containing matrix, and the NCE is integrated into the composite NCE-containing matrix 128. The existing matrix 124 may provide an amorphous host matrix or produce a more recognizable ordered pattern of atoms or molecules in a regular lattice-like array, as may be found in crystals. In the composite NCE-containing matrix 128, the NCE is inserted into the existing matrix 124 to form the composite NCE-containing matrix 128. The more additive NCE the composite NCE-containing matrix 128 contains, the more the performance of the composite NCE-containing material 128 exhibits the performance that can be contributed to by the NCE. For example, formulations containing additive NCE and pulp-based extenders may provide significant strength to the composite NCE-containing matrix 128, and the presence of pulp-based extenders adds volume to the composite NCE-containing matrix 128, potentially making its production less expensive. Other properties of the composite NCE-containing matrix 128 may be provided in interaction with any structural organization or other properties provided by the existing matrix 124 alone or by the additive NCE.

[0054] In some embodiments, other additive substances may be included in the composite NCE-containing matrix to add or improve desired properties such as malleability, processability, heat resistance, strength, or oleophobic or hydrophobic properties. Such additive substances may be available to or added to the composite NCE-containing matrix 128 before, during, or after the addition of the NCE population redispersed from the suspension 120 to the existing matrix 124. In some embodiments, the existing matrix 124 already contains some or all of the desired additive substances, and their presence is carried over to the composite NCE-containing matrix 128. In other embodiments, the additive substances are included when the redispersed NCE and the existing matrix 124 are combined in step 5b to form the composite NCE-containing matrix 128. In yet another embodiment, the additive substances may be introduced into the composite NCE-containing matrix 128 after it has been formed. The composite NCE-containing matrix 128 having its included additive substances provides a material that can be further processed, shaped, or otherwise formed into a manufactured article. A material comprising a composite NCE-containing matrix 128, which provides a structural framework to the material, and further comprising any additive substances, may be referred to as a "composite NCE-containing material".

[0055] Both the simple NCE matrix 122 and the composite NCE-containing matrix 128 may be used to provide a structural framework to a material containing redispersible NCE as shown in this figure, such material may be formed or shaped to produce a manufactured article. In other embodiments not shown in this figure, the simple NCE matrix or the composite NCE-containing matrix may be used to provide a structural framework to a material containing redispersible NCE.

[0056] 3. Redispersibility and redispersed nanocellulose elements in substrates for manufacturing articles. As described above, redispersible or redispersed NC elements produced according to the systems and methods disclosed herein may be included in matrices used to form NCE-containing materials, both as components of simple NCE-system materials formed preferentially from redispersible or redispersed NCE, either alone or without another existing matrix, and as components of composite NCE-containing materials including composite NCE-containing matrices having redispersible or redispersed NCE inserted into an existing matrix. Both simple NCE-system materials and composite NCE-containing materials may be used as substrates or components of substrates, such as plastic substrates and components of plastic substrates, which may be formed in other manufactured articles. As used herein, the term “plastic” means a material that integrates a three-dimensional framework (or “matrix”) and retained flexibility, thereby resulting in a flexible NCE-system or NCE-containing material. Such a plastic material may be formed or shaped from its flexible state into a desired structure, and further fixed in the desired structure, which is retained for a specified period. The process of shaping or forming a material from a flexible state into a desired structure can be achieved by many techniques well known in the art, such as extrusion, calendering, injection molding, thermoforming, and blow molding. Similarly, the process of fixing the material into a desired structure can be achieved by many techniques well known in the art, such as heating, application of extended pressure and / or hardening, and incorporation of additives that enable fixing or curing. The specified period for holding the material in a desired structure is determined based on its intended use in the manufactured article and the intended use of the manufactured article itself (e.g., temporary vs. relatively permanent use), as well as the intended process for the disposal of the material and the disposal of the manufactured article at the end of its lifespan.

[0057] Simple NCE-based materials Simple NCE-based materials can be used as plastic substrates for forming articles of various shapes, and the mechanical properties of such formed articles depend on the structural framework provided by the matrix of dry, redispersible, or redispersed NCE, which is at least partially incorporated into the simple NCE-based material. Therefore, simple NCE-based materials can be used to form articles that have advantageous mechanical properties such as strength and stability, but can also be remodeled to dissolve or decompose within a reasonable time for consumer use. Such articles are conceived to have relatively temporary durability and can be treated by biodegradation or composting.

[0058] For example, this combination of mechanical properties and solubility / degradability allows containers to be constructed from materials that are durable enough to hold their contents during consumer use, but are also susceptible to degradation at the end of their intended lifespan. As used herein, the term “container” is broadly interpreted to mean any storage container, vessel, or enclosure that can be used in conjunction with an item or product to hold, disperse, deliver, separate, suspend, construct, package, store, or divide an item or product, or to provide similar functions derived from the partial or complete enclosure of the item or product therein. Exemplary containers include storage containers, vessels, or enclosures of all shapes and geometry, whether rigid or flexible, and intended for either temporary or permanent use. Non-limiting examples include cylindrical containers such as bottles, jars, cups, straws, barrels, cans, drums, and tubs; containers enclosed in straight lines such as boxes, crates, cartons, and cases; flat containers such as plates, trays, dishes, lids, and holders; and delivery systems such as pill capsules or soluble foams for delivering pharmaceuticals, pesticides, or other active ingredients to targeted areas for application, protection, or treatment. Advantageously, containers can provide protection from impact, collision, and mechanical damage, as well as from external environmental elements such as weather, pests, and microorganisms; furthermore, containers can provide protection from the ingress of oil, grease, and water, as well as from leakage of fluids seeping out due to the products they contain. For these reasons, containers are particularly useful for protecting food.

[0059] This combination of mechanical properties and biodegradability also allows containers to be constructed from simple NCE-based materials for intentionally short-term purposes, such as containers for fertilizers or agricultural products intended to decompose over a very short period of time to release the product into the environment. This combination of properties also allows containers to be constructed for delivering activators for purposes such as laundry or other household care, as they dissolve rapidly or immediately upon contact with water. Simple NCE-based materials, whose structure is based on a three-dimensional array of NCE alone, are bio-based overall, as they are formed from NC elements. Therefore, they offer a significant alternative to petroleum-derived formulations used to produce conventional manufactured articles used for similar purposes and provide vehicles for remaking foamed articles with combinations of mechanical properties and solubility that match the specific purpose of the article.

[0060] A significant limitation to the use of simple NCE-based materials is their vulnerability to oils, greases, and water: simple NCE-based materials tend to offer virtually no inherent resistance to the ingress and passage of water or oils / greases into the material and are often made from NCE in combination with other, often cheaper filler materials, such as pulp and pulp-derived materials. This vulnerability is exacerbated by the cost of NCE itself: NCE can be mixed with cheaper fillers or bulking agents to reduce the overall cost of the NCE-based material. Pulp or pulp-derived materials are frequently used for this purpose. However, such materials, referred to as "pulp-dominant," are particularly susceptible to the effects of water and greases. In pulp-dominant materials without any other treatment, exposure to water or oils / greases can result in a loss of structural strength or an actual loss of the integrity of the formed articles made from such materials.

[0061] As used herein, the term “pulp-dominant” means a matrix or material in which pulp or pulp-based material is present in sufficient quantity to have a substantial effect on the material’s mechanical properties. A pulp-dominant matrix may require further NCE or other reinforcement to make it as strong, stable, or durable as a non-pulp-dominant simple NCE-based material, depending on the final intended use of the material; further, such material may be treated with barrier formulations to make them resistant to the effects of water, oil, and grease, depending on the final intended use of the NCE-based material. For example, a pulp-dominant simple NCE-based material may be used to form sheets for personal care items such as cosmetic paper or toilet paper with little or no further reinforcement, while a similar material intended for use as paper towels may require more reinforcement because its final intended use requires greater strength and resistance. A pulp-dominant material may also benefit from treatments to improve its oil and grease resistance and / or its water resistance, depending on the final intended use for such material.

[0062] Therefore, simple NCE matrix can be treated with formulations that impart oil and grease resistance (oleophobicity) and / or water resistance (hydrophobicity) to the matrix itself or to these materials containing such a matrix. Water resistance in a material is often measured by the water vapor transfer rate, which is expressed as gm / m 2 Units are / day or g / 100in 2 The permeability of a material to water vapor is measured daily; therefore, the term “water resistance” (WR) includes resistance to liquid water and resistance to water vapor. Thus, oil and grease resistance (OGR) and water resistance (WR, and together with OGR, “OGWR”) properties can be incorporated into the material itself or articles formed therefrom. These OGWR properties may also be referred to as “barrier properties,” and a substance or formulation that produces one or more barrier properties may be referred to as a “barrier-producing formulation” or “barrier formulation.” A “barrier substance” refers to a substance that produces barrier properties. Both oil / grease resistance (or oleophobicity) and water resistance (or hydrophobicity) may be referred to individually as barrier properties.

[0063] Barrier properties can be tuned within a simple NCE-containing material to allow differential permeability of the material to various fluids (whether oil, grease, or water). For example, in some embodiments, a barrier-forming formulation can impart both OGR and WVR properties to the article it processes, and the relative intensity of each property can be adjusted by adjusting a component selected for the formulation itself and / or by adjusting the relative amount of that component, for example, to emphasize hydrophobicity or oleophobicity.

[0064] In some embodiments, NCE alone, or NCE modified with barrier-forming materials such as lignin, wax, or fatty acids, can impart some degree of oleophobicity or hydrophobicity to simple NCE-based materials, and their concentrations can be adjusted to optimize these barrier properties. Without being constrained by theory, it is believed that dense encapsulation of NCE can enhance the barrier properties they provide. Furthermore, regardless of their inherent hydrophilicity, NCE (either alone or modified with barrier-forming materials) can be sufficiently densely encapsulated in simple NCE-based materials under certain conditions, imparting water-resistant or water vapor-resistant barrier properties to these materials.

[0065] In some embodiments, a wide range of additive components may be combined to provide desired barrier properties. For example, a barrier-forming formulation suitable for use with a simple NCE matrix may contain cellulose ethers such as methylcellulose and / or resin acids. Alternative cellulose components for barrier-forming formulations include, but are not limited to, CMC (carboxymethylcellulose), CMCNa (sodium carboxymethylcellulose salt), CA (cellulose acetate), CDA (cellulose diacetate), cellulose triacetate (CTA), CAB (cellulose acetate butyrate), CAPh (cellulose acetate phthalate), CAP (cellulose acetate propionate), EC (ethylcellulose), HEC (hydroxyethylcellulose), EHEC (ethyl hydroxyethylcellulose), HPC (hydroxypropylcellulose), HPMC (hydroxypropyl methylcellulose), HPMCP (hydroxypropyl methylcellulose phthalate), and HPMCAS (hydroxypropyl methylcellulose acetate). Methylcellulose is particularly advantageous in barrier formulations for simple NCE-based matrices due to its oil and grease resistance, high viscosity, and its characteristic low critical solution temperature (LCST) that causes gelation when heated. Resin acids and their combinations (rosin, gum rosin, pitch, etc.) can be used alone or in combination with methylcellulose to provide water resistance. Cellulose acetate is also a particularly advantageous component in barrier formulations, especially food and beverage containers, assuming that it can produce both oleophobic and hydrophobic properties.

[0066] More specifically, resin acids are bio-derived rubbers that are sticky and water-insoluble in their natural state, and are based on empirical formula C 19 H 29These are characterized as unsaturated diterpene carboxylic acids having a COOH group and a phenanthrene ring structure. Examples of resin acids include abietic acid, pulsed phosphoric acid, levopimaric acid, neoabietic acid, dehydrogenated ibuptic acid, pimaric acid, isopimaric acid, and sandaracopimalic acid. They can be separated into two categories, abietic-type resin acids and pimaric-type resin acids, according to their chemical structure. The monomeric molecules of abietic-type resin acids have two conjugated double bonds and one isopropyl group. Dehydrogenated abietic acid, abietic acid, pulsed phosphoric acid, and levopimaric acid are examples of abietic-type resins. The monomeric molecules of pimaric-type resins have methyl and vinyl at the C13 position and two independent double bonds. This type of structure is mainly found in the resins and pine resins of pine, such as pimaric acid, isopimaric acid, sandaracopimalic acid, and pimaric resin acids.

[0067] The carboxyl groups (one or more) of resin acids can react with polyols (e.g., glycerol, erythritol, etc.) to form esters (thus, three or four resin acid molecules can come together to form basic resin acid construct blocks, e.g., "oligomers" of abietic acid). Resin acids tend to be glassy and rigid at room temperature. Depending on plasticization, they can soften with increasing temperature and the amount of plasticizer used. Resin acids are compatible and miscible with various oils / waxes to modulate their thermal or physical properties (e.g., glass transition temperature, malleability, and hydrophobicity, but not limited to these). For example, beeswax and carnauba wax are soluble in certain resin acids, thus affecting their melting point and glass transition temperature, while also decreasing their solubility in the solvent. Other examples of suitable oils and waxes for mixing with resin acids include, but are not limited to: • Mineral oil and wax (paraffin) Beeswax Carnauba wax • Linseed wax Candelilla ·lard • Coconut oil Flaxseed oil • Eucalyptus essential oil • Cocoa butter ·Sweet tonsil oil ·olive oil Palm oil Castor oil • Sunflower oil Canola oil These are some examples.

[0068] The proportions of these components in the barrier-forming formulation are adjusted to optimize its OGR and WVR properties, so that the desired amount of OGWR in the simple NCE-based material formed by adding a specific barrier-forming formulation to a simple NCE-containing matrix can be skillfully managed.

[0069] The block diagram in Figure 2 schematically illustrates how barrier-forming formulations may be added during the formation of a simple NCE system matrix and its subsequent processing. Process 200 in Figure 2 begins by providing a dry material 202 containing redispersible NCE, therein prepared substantially as described with respect to Figure 1. The dry material 202 containing redispersible NCE is then ground / minced and used as a dry component or suspended in a resuspension fluid 204 to resuspend the NCE in the dry material 202 and form a suspension 208 of redispersed NCE of a desired concentration, substantially as described with respect to Figure 1. The suspension 208 of redispersed NCE is then subjected to drying 210 to produce a simple NCE system matrix 212, which can then be used to form a simple NCE system material substantially as described with respect to Figure 1. Barrier-forming formulations 214 may be added at points A, B, C and / or D. More specifically, the barrier-forming formulation 214 may be added as part of step 206, and the dried material 202 containing redispersible NCE is treated with the resuspension fluid 204 to produce a suspension of redispersed NCE 208. For example, the barrier-forming formulation 214 may be added to the redispersion fluid 204 as indicated by its introduction at point A. The barrier-forming formulation 214 may also be added to the suspension of redispersed NCE 208 as indicated by its introduction at point B. The barrier-forming formulation 214 may also be added during the drying step 210 in which the suspension of redispersed NCE 208 is treated, ultimately forming a simple NCE-based material 212 as indicated by its introduction at point C. Finally, the barrier-forming formulation may be added to the simple NCE-based material 212 as indicated by its introduction at point D. Although a single barrier-forming formulation 214 is shown in this figure, it will be understood that multiple barrier-forming formulations or barrier-forming formulation components may be added at different introduction points. The first barrier-forming formulation may be added at one introduction point, and the second barrier-forming formulation may be added at a second introduction point.Barrier-forming formulations and combinations of their components can be introduced at any point during the process by using methods well known in the art, such as (without limiting) mixing them in the formulation, spraying them onto or into a indicated substrate, or coating them onto its surface. Such barrier-forming formulations may contain redispersed NCE to enhance performance and cause the coating to act as closer pores in their interaction with the surface of the deposited NCE-containing material. Barrier-forming formulations without redispersed NCE may also be applied to impart enhanced performance.

[0070] Exemplary simple NCE-based materials having OGWR properties can be prepared as follows, and the barrier-forming formulation is added to a redispersible or redispersed suspension of NCE. A redispersible (in this case, redispersed) suspension of NCE prepared as described above is provided, to which methylcellulose (MC) is added with or without a sugar alcohol plasticizer (glycerol, xylitol, maltitol, sorbitol, erythritol, mannitol, etc.). The addition of these components is intended to produce oleophobicity. Such a redispersible or redispersed suspension of NCE may contain NFC, MFC or both. Such a redispersible or redispersed suspension of NCE may also contain fillers, such as pulp or pulp-based components, to provide a larger volume in the final simple NCE-based matrix and the resulting material. Separately, a solution of rosin is prepared by mixing rosin with an alcohol or ketone solvent (e.g., ethanol or acetone) to achieve a 10-100 wt% (wt rosin / wt solvent) solution of rosin in the solvent. After preparing this solution, the solution can be emulsified in water using appropriately dissolved rosin, preferably with polyethylene glycol (PEG) at 1-25% relative to the weight of the rosin, and preferably using a linearly aligned homogenizer, or the solution can be directly mixed with a redispersible or redispersed MC-containing suspension of NCE. A small amount of solvent used to prepare the mixture may be added to the NCE suspension before adding the rosin mixture to promote homogenization. The mixing process can be carried out vigorously, for example, by slowly pouring the rosin formulation onto the NCE-containing resuspension with moderate to high shear force, or by spraying the solution as a fine mist with relatively low shear force, thereby agglomerating the fine rosin suspensions in the liquid phase of the MC-NCE-containing suspension. Since it is advantageous to add the rosin solution as a high-pressure stream or to create an aqueous emulsion, the rosin particle size is small. After the combination of these components, the resulting mixture can be dried to create a simple NCE matrix which can be processed to produce a simple NCE-based material.

[0071] Rosin addition improves the hydrophobicity of the matrix. The hydrophobicity of rosin can be increased by heat-treating the rosin before dissolving it in the solvent, for example, by heating the rosin at about 200°C for about 10-30 minutes to remove impurities such as terpentine. Heat treatment also increases the softening point of the rosin from 45°C to 59°C, making it more elastic when subjected to heat during the subsequent stages of treatment. In some embodiments, rosin may be loaded in an amount of about 35 wt% relative to the dry pulp weight, but amounts of rosin in the range of about 5 wt% to about 50 wt%, about 5 wt% to about 10 wt%, about 8 wt% to about 25 wt%, about 20 wt% to about 40 wt%, or about 35 wt% to about 55 wt% relative to the dry pulp weight may be used. In some embodiments, the ratio of redispersible or redispersed NCE to MC is about 1:3. Other ratios of NCE to MC in the range of 5:1 to 1:3 may be used.

[0072] A simple NCE matrix with OGWR properties can be prepared by combining the above-mentioned components. This matrix can then be formed into a simple NCE material that can be used to produce manufactured articles. Retention aids can be added to the simple NCE matrix to improve the retention of other additives in the simple NCE material. Retention aids, which are typically cationic polymers or surfactants, are well known in the paper industry; for example, substances such as chitosan or PDADMAC can be used as retention aids.

[0073] In exemplary embodiments, the OGR and WVR materials disclosed herein may be used as barrier-forming formulations together with simple NCE-based materials, either as coatings applied to the surface of a material or as mixed additives. More specifically, the OGR and / or WVR formulations may be used as coatings or mixed with simple NCE-based materials as described above, which may then be formed into a product (e.g., thermoformed).

[0074] For example, foamed containers or foamed portions of containers formed from simple NCE-based materials are prepared to have OGR and / or WVR properties, enabling the container to reliably contain liquids, gels, or wet solids for delivery to consumers for other purposes. Such simple NCE-based materials may be pulp-dominant, and appropriate adjustments are made to the amounts of NCE and barrier-forming formulations based on the amount of pulp or pulp-based material they contain. In some embodiments, the barrier-forming formulation may also be applied to the surface of the simple NCE-based material before its formation or shaping into a formed article, or the barrier-forming formulation may be applied to a formed article after formation or shaping has taken place. For example, the barrier-forming formulation may be applied surfacely to a precursor material or a manufactured article using conventional coating procedures such as paint or blade coating, curtain coating, or by spraying if the formulation has a viscosity that is compatible with a selected spraying apparatus. In other embodiments, the barrier-forming formulation may be incorporated into a simple NCE-based formulation at any concentration (as described above); the mixture may then be heated to slightly above the low critical solution temperature of the LCST polymer components of the barrier-forming formulation before molding / thermoforming. This procedure involves dispersing the LCST polymer within the mixture and allowing it to precipitate (or fall) onto the fibers or surface of a simple NCE-containing matrix structure.

[0075] In some embodiments, a filler such as pulp or a pulp-based material may be added to a simple NCE matrix to form a pulp-dominant simple NCE material as described above. In such a material, NCE may interact with the pulp or pulp-based filler so that it coats them or fills the pores between the pulp fibers or the fibers of the pulp-based material. In this capacity, the matrix formed in the simple matrix or simple NCE material may act as a pore-closing agent, filling gaps in the pulp material. This pore closing allows this type of simple NCE material to be used with pulp or a pulp-based material to form high-value special paper products having properties that reflect the behavior of the NCE matrix. As an example, since an embedded NCE matrix blocks pores in the paper material that would otherwise allow oils to pass through the product, a paper product with an NCE matrix embedded in its pores may provide or improve oil and grease resistance (particularly with respect to other barrier materials). As another example, a paper product with NCE embedded in its pores may be remodeled to form a releaseable label backing or selective adhesive. In one embodiment, the barrier-forming formulation can be added to a simple NCE-based material to enhance the effect of the NCE matrix as a pore-closing agent by imparting, for example, oleophobic or hydrophobic properties to the material, which can then be carried over to products of the type of pulp-dominant paper produced therefrom, as described above.

[0076] In some embodiments, filler particles may be added to simple NCE-based matrices and materials to provide a bulking effect and / or to act as pore-closing agents. These filler particles may be used in addition to or in place of barrier-forming formulations; in either case, the filler particles may interact with pulp fibers and simple NCE matrices to impart barrier properties such as oleophobicity and / or hydrophobicity; furthermore, the filler particles may influence mechanical properties such as strength, toughness, flexibility, and elasticity.

[0077] Such filler particles may include, but are not limited to, large or small particles of any shape made from natural or artificial materials and produced by any processing method (e.g., physical grinding, precipitation, emulsification), or mixtures of different sizes and shapes, such as organic or inorganic components; for example, particles useful for this purpose may include, but are not limited to, sand particles, ceramic particles, biomass materials or particles, mineral particles, resin materials, glass materials, polymeric materials, rubber materials, composite granular materials, chemically active materials such as fatty acids, surfactants, and sugar alcohols, organic materials such as wood or nut shells that have been finely ground, crushed, pulverized, or broken to an appropriate size (e.g., walnuts, pecans, coconuts, almonds, ivory palms, Brazil nuts, etc.), seed shells or fruit kernels that have been finely ground, crushed, pulverized, or broken to an appropriate size (e.g., plums, olives, mozzarella). Finely ground, crushed, pulverized or broken materials of other plant origin such as corn cob, oak, cherry, apricot, etc., coffee grounds, pine cone pollen, sisal, rice husk ash, rice husks, coconut shells, cotton stalks, etc., certain inorganic particles, such as solid glass, glass microspheres, fly ash, silica, alumina, fumigated carbon, carbon black, graphite, mica, boron, zirconia, talc, kaolin, titanium dioxide, Calcium carbonate (e.g., precipitated calcium carbonate (PCC) or ground calcium carbonate (GCC)), wood powder, lignin, mica, dolomite, wollastonite, halloysite, calcium silicate, flame retardants (e.g., but not limited to halogenated (chlorinated or bromised), phosphorus-based, nitrogen-based, inorganic / mineral-based flame retardants, e.g., hexabromocyclododecane (HBCD), triphenyl phosphate (TPP), tricresyl phosphate (TCP), isopropylated phenol, phosphate 3:1 (PIP 3:1), etc.), and combinations or composites of these or similar different materials.In some embodiments, plant-derived organic materials, such as (without limiting) wood or nut shells that have been finely ground, crushed, pulverized or broken to an appropriate size (e.g., walnuts, pecans, coconuts, almonds, ivory palms, Brazil nuts, etc.); seed shells or fruit kernels that have been finely ground, crushed, pulverized or broken to an appropriate size (e.g., plums, olives, peaches, cherries, apricots, etc.); coffee grounds, pine cone pollen, sisal, rice husk ash, rice husks, coconut shells, cotton stalks, etc.; and other plant-derived finely ground, crushed, pulverized or broken materials such as corn cobs are particularly advantageous for use as filler particles.

[0078] Advantageously, in one embodiment, filler particles may be selected that are naturally hydrophobic or can be made hydrophobic by linking or coating the particles with a hydrophobic material, such as stearic acid or oleic acid (e.g., functionalized PCC). In one embodiment, the filler particles may contain wax either as the substance of the particles themselves or as a coating for other particles, and these waxes may be in wax form or emulsion form (oil-in-water wax emulsion). For example, waxy substances such as beeswax, soy wax, and carnauba wax may be used either as substrate particles or as a coating for other filler particles. As used herein, the term “wax” means any hydrocarbon that is a lipophilic and malleable solid having a melting point typically higher than about 40°C near ambient temperature. Examples of waxes include long-chain aliphatic hydrocarbons having typically 20 to 40 carbon atoms per molecule or fatty acid / alcohol esters having typically 12 to 32 carbon atoms per molecule, such as myricyl cellotates found in beeswax and carnauba wax. The filler particles can be mixed into a barrier-forming formulation to impart a pore-sealing function.

[0079] b. Composite NCE-containing material Composite NCE-containing materials, formed from composite materials in which redispersible or redispersed NCE is integrated into an existing matrix, can be used as plastic substrates for forming a variety of products. After mixing them with the existing matrix, the additive NCE can be utilized as particles or as more elongated fibrous structures, aligning themselves in a straight or randomly oriented manner, and combined with the existing matrix embedded within the composite NCE-containing material to form a network or other internal structure. In some embodiments, the three-dimensional matrix framework of the existing matrix material is coated with and / or immersed therein to form a composite NCE-containing matrix, and the presence of the additive NCE imparts specialized properties that exceed or are not found in the existing matrix. For example, composite NCE-containing materials can exhibit specialized mechanical properties such as strength, hardness, toughness, brittleness, rigidity, cohesiveness, durability, impact resistance, and light transmittance, where the presence of NCE in the composite NCE-containing material produces or enhances these specialized mechanical properties.

[0080] As another example, composite NCE-containing materials may exhibit specialized barrier properties, such as OGWR properties, that may be present in the existing matrix but are enhanced in the composite NCE-containing material, or that are absent in the existing matrix but provided in the composite NCE-containing material. In some embodiments, NCE alone or NCE modified with barrier-forming materials, such as lignin, wax, or fatty acids, may impart some degree of oleophobicity or hydrophobicity to the composite NCE-containing material, and their concentrations may be adjusted to optimize these barrier properties. Without being constrained by theory, it is thought that dense packing of NCE can enhance the barrier properties they provide. Furthermore, regardless of their inherent hydrophilicity, NCE (either alone or modified with barrier-forming materials) can be packed sufficiently densely in a composite NCE-containing material to impart water-resistant or water vapor-resistant barrier properties to these materials under certain circumstances.

[0081] Combining redispersible or redispersed NCE with an existing matrix may allow the presence of NCE to act as a pore-closing agent in its interaction with the existing matrix. Under these circumstances, the redispersible or redispersed NCE may interact with the existing matrix, either coating it or filling pores or gaps in the network structure provided by the existing matrix. In some embodiments, these pore-closing effects may be enhanced when used in combination with other oil- and grease-repellent additives. In this ability, NCE and any matrix they form may act as pore-closing agents, filling gaps in the existing matrix, thereby acting as a plug to prevent certain molecules, such as oils and greases, from passing through the composite NCE-containing matrix. This mechanism is similar to the behavior of simple NCE-based materials or NCE as a pore-closing agent. Furthermore, filler particles may be added to the composite NCE-containing matrix in the same way that filler particles may be added to a simple NCE-based matrix. The role of filler particles has been described in detail above with respect to simple NCE-based materials; this description may be applied to the use of filler particles for composite NCE-containing materials with necessary modifications. Briefly, filler particles may be added to composite NCE-containing matrices for bulking effect and / or act as pore-closing agents for simple pulp-based matrices, either alone or in combination with other barrier materials. In various embodiments, filler particles may be used in addition to or in place of barrier-forming formulations; in either case, filler particles may interact with existing matrices and / or composite NCE-containing matrices to impart barrier properties such as oleophobicity and / or hydrophobicity.

[0082] More generally, the process of preparing composite NCE-containing materials from composite NCE-containing matrices can be modified to produce desired material properties. The generation of OGWR properties by incorporating barrier-forming formulations in such materials is one example of how composite NCE-containing matrices can be modified to produce such material properties. Existing matrices can be prepared to be particularly suitable for combining with redispersible or redispersed NCE in order to form composite NCE-containing matrices and to produce composite NCE-containing materials. For example, the degree of flexibility in products formed from composite NCE-containing materials can be finely tuned by changing the composition of the existing matrix, the amount of additive NCE used in the existing matrix to form the composite NCE-containing matrix, and / or the amount of various additives intended to optimize the properties of the final composite NCE-containing material. By selecting appropriate additives and polymers for the existing matrix into which the NCE is integrated to form the composite material, such additives, along with biodegradability, can produce properties such as structural strength, elasticity, resilience, water resistance, oil and grease resistance in the manufactured articles formed therefrom.

[0083] The block diagram in Figure 3 schematically illustrates how barrier-forming formulations may be added during the formation of the composite NCE-containing matrix and subsequent processing. Process 300 in Figure 3 begins with providing a dry material 302 containing redispersible NCE, such dry material 302 is prepared substantially as described with respect to Figure 1. The dry material 302 is then treated with a resuspension fluid 304 in a resuspension step 306 to form a suspension 308 of redispersed NCE, substantially as described with respect to Figure 1. The suspension 308 of redispersed NCE is then combined with an existing matrix 310 to produce a composite NCE-containing matrix 312, substantially as shown in step 5a of Figure 1. The composite NCE-containing matrix 312 may be combined with additives and / or further processed to form a composite NCE-containing material 314. The barrier-forming formulation 318 may be added at points A and B, substantially as described with respect to Figure 1. Alternatively or additionally, the barrier-forming formulation 318 may be added at one or more points W, X, Y, and Z. More specifically; the barrier-forming formulation 318 may be added so that the redispersed NCE suspension 308 is mixed with the existing matrix 310, as indicated by point W; the barrier-forming formulation 318 may be added to the existing matrix 310 before it is mixed with the redispersed NCE suspension 308, as indicated by point X; the barrier-forming formulation 310 may be added to the composite NCE-containing matrix 312 so that it is treated to become the composite NCE-containing material 314, as indicated by point Y; and / or the barrier-forming formulation 310 may be added to the composite NCE-containing material 314, as indicated by point Z. Advantageously for this last type of application, the barrier-forming formulation may be sprayed to allow for easy application to either the surface of the composite NCE-containing material 314 or the surface of a formed article manufactured therefrom (not shown). Although this figure shows a single barrier-forming formulation 318, it is understood that multiple barrier-forming formulations or barrier-forming formulation components may be added at different introduction points W, X, Y, or Z. A first barrier-forming formulation may be added at one introduction point, and a second barrier-forming formulation may be added at a second introduction point. Combinations of formulations and / or barrier-forming formulation components may be introduced at any point during the process.

[0084] In this embodiment, barrier-forming formulations containing biopolymers may be prepared as additives to impart OGWR properties or other useful properties to composite NCE-containing materials, as well as how such additives may be used in conjunction with barrier-forming formulations combined with simple NCE-based materials. Such additives may be added to barrier-forming formulations, which may then be combined with composite NCE-containing matrices as described above. Examples of biopolymers include biopolyesters such as polyhydroxy-alkanoates and polylactic acid derivatives. Advantageously, certain exopolysaccharides, such as pullulan, kefiran, cellulose, levan, guerane, etc., may be used to form films, which may be advantageous for these barrier-forming formulations and useful articles produced therefrom, which are used as coatings for composite NCE-containing materials. Such biopolymers may also include, but are not limited to, exopolysaccharides such as bacterial cellulose, kefiran, pullulan, levan, guerane, other naturally occurring polysaccharides such as arginine, lignin, carrageenan, gum arabic, starch, and plant glucomannan-like locust bean gum, mannan, guar gum, etc., and cellulose derivatives. As used herein, these products prepared by modification of natural cellulose polysaccharides are referred to as "cellulose derivatives," "cellulose polymers," or "cellulose-derived products (cellulosic)." Such modifications may include chemical modifications, such as cellulose degradation and derivatization of -OH groups. Acids / bases, oxidizing agents, biopharmaceuticals, and mechanical treatments are all examples of degradation reactions. Modifications that introduce novel functional groups to the cellulose backbone include carboxymethylation, oxidation, and addition reactions. Other reactions such as esterification, acylation, transplantation, and esterification can also produce cellulose derivatives. Other examples of reactions for producing cellulose derivatives are well known in the art.

[0085] While various specialized properties of composite materials using NCE have already been envisioned in industry, their use has been hindered by the previously mentioned redispersion problems. The redispersion techniques disclosed herein facilitate the transport of NCE compositions that can be concentrated or dried and then resuspended to combine with an existing matrix to produce a composite NCE-containing material. In some embodiments, these redispersion techniques can produce a homogeneous mixture of high-aspect-ratio NCE within the main matrix-forming material, enabling the enhancement of desired specialized properties of the final composite, including mechanical properties such as those described above. In other embodiments, NCE formulations prepared using the redispersion techniques disclosed herein can be prepared to introduce or enhance specialized properties, such as barrier properties, which enable the composite NCE-containing material to have a desired degree of oil and grease resistance and / or water vapor resistance.

[0086] Redispersible or redispersed NCEs prepared as described herein can act as fillers in composite NCE-containing matrices. Fillers are understood to improve the mechanical and barrier properties of materials such as organics and plastics, and / or make them more economical to manufacture or transport, for example, by requiring less expensive components or by making them lighter. Redispersible and redispersed NCEs prepared as described herein can also be combined with other fillers, such as pulp or pulp-based materials, to increase the final volume of composite NCE-containing matrices while maintaining strength during the presence of additive NCEs. Although NCEs are already used as fillers in plastics, their use is limited by their resistance to redispersibility.

[0087] The methods for NCE redispersion disclosed herein may enable a wider range of applications for NCE, such as reinforcement of composite materials and plastic substrates, and may further allow for a dramatic expansion of novel applications. As used herein, the term “reinforcement” means an improvement in mechanical properties observed in an existing matrix in terms of strength, hardness, toughness, brittleness, rigidity, cohesiveness, flexibility, durability, or impact resistance, or the provision of such mechanical properties if they are not already present in the existing matrix. A composite NCE-containing matrix having improved mechanical properties compared to an existing matrix may be referred to as “reinforced” by the reinforcement of the composite NCE-containing matrix due to the presence of NCE. NCE can be used as a filler in a variety of environments, as the examples above illustrate.

[0088] In one embodiment, the composite NCE-containing matrix is ​​formed from an existing petroleum-derived matrix into which redispersible or redispersed NCE is incorporated. In another embodiment, the composite NCE-containing matrix is ​​formed from an existing bio-based matrix into which redispersible or redispersed NCE is incorporated.

[0089] i. Existing petroleum-derived matrix In some embodiments, petroleum-derived polymers are used to form an existing matrix that is combined with an additive (redispersible or redispersed) NCE to form a composite NCE-containing matrix having advantageous properties. Various petroleum-derived polymers can be used as existing matrices to form a composite matrix using NCEs such as polyvinyl alcohol, high-density polyethylene, low-density polyethylene, polyvinyl chloride, acrylonitrile butadiene styrene, polypropylene, polylactic acid, polybutylene succinate, polyethylene succinate, and polypropylene succinate. The addition of NCEs to these matrices can provide specialized properties such as increased mechanical properties, such as increased strength and / or flexibility, or barrier properties, such as oleophobic or hydrophobic properties or water vapor resistance properties. Furthermore, redispersible or redispersed NCEs can be added to the matrix as components in a formulation that also includes a filler, such as pulp or a pulp-based material. Such a formulation can provide an additional volume of NCE components to the resulting composite NCE-containing matrix while retaining or improving their mechanical properties compared to the existing matrix. The use of such formulations containing redispersible or redispersed NCE and bulking agents may reduce the need for other expensive components, thereby lowering the overall cost of the resulting composite NCE-containing matrix and the materials produced therefrom.

[0090] However, the use of redispersible or redispersed NCE as an additive NCE combined with an existing hydrophobic matrix presents difficulties because NCE itself is hydrophilic. Incorporation of additive NCE into an existing hydrophobic matrix may present problems due to the weak interfacial strength between the hydrophobic polymer matrix and the hydrophilic NC elements, but redispersible or redispersed NCE can be further modified to become more hydrophobic, resulting in a stronger interface. For use in hydrophobic environments, NCE can be surface-modified to match the properties of the existing hydrophobic matrix into which they are incorporated, so that they become compatible with the existing matrix and can be regularly dispersed within it. In some embodiments, surface modification of additive NCE prepared according to the methods disclosed herein can be carried out, for example, by using a hydrophobic monolayer on the NCE. Methods for this modification may include silane coupling, alkali treatment, acetylation, carbonylation, TEMPO oxidation, polymer transplantation, bacterial modification, surfactant addition, and the like. In some embodiments, hydrophobized NCEs for use in hydrophobic matrices may be prepared such that they are not only redispersible upon drying but also compatible with various existing hydrophobic polymeric matrices, such as thermoplastic and thermosetting matrices (e.g., polypropylene, polyethylene, polystyrene, polyester, poly(acrylate / methacrylate), rubber, silicone, urethane, epoxy, etc.), for their hydrophobic coating, resulting in strong, lightweight composite NCE-containing materials for further processing to provide manufactured articles. Other modifications may include the incorporation of other additives having polar heads and nonpolar tails (e.g., fatty acids or surfactants) that enhance interfacial adhesion between the hydrophobic matrix and the hydrophilic NCE; it is understood that these additives may interact with both the hydrophobic matrix and the hydrophilic NCE to improve their adhesion to each other.

[0091] As previously described, other additives to obtain desired properties may be added to a composite NCE-containing matrix to produce a composite NCE-containing material useful as a plastic substrate. Such additives may be added at any stage in the production of a composite NCE-containing material, for example, to an existing matrix or composite NCE-containing matrix or composite NCE-containing material. For example, plasticizers such as phthalates may be used to make the material more flexible and versatile. Such a composite NCE-containing material containing plasticizers can then be formed by conventional techniques such as extrusion, calendering, injection molding, thermoforming, and blow molding to produce formed articles. The redispersible or redispersed NCE embedded in the composite NCE-containing matrix acts as a reinforcing agent, such as a filler, particle, or fiber, to improve the mechanical properties of the material softened by the plasticizer.

[0092] ii. Existing bio-based matrices In some embodiments, a bio-based polymer is used to form an existing matrix that is combined with additive NCE to form a composite NCE-containing matrix having advantageous properties. Under these circumstances, all structural components of the composite NCE-containing matrix are bio-based, as are the composite NCE-containing material formed from the composite NCE-containing matrix. This composite NCE-containing material can be used as a plastic substrate formed in manufactured articles. Fabricating this plastic substrate from bio-based components (i.e., redispersible or redispersed (additive) NCE and a bio-based existing matrix) offers sustainability advantages in both eliminating reliance on petrochemical raw materials and facilitating the decomposition and disposal of products formed from such plastic materials.

[0093] In these embodiments where bio-based polymers are used to form an existing matrix, the constitutive bio-based polymer forming the existing matrix may be a homopolymer, copolymer, polymer mixture, or any combination thereof. Additive components may be combined with the constitutive bio-based polymer to optimize the properties of the existing matrix. For example, cellulose acetate (CA) and cellulose butyrate (CAB) may be mixed together in an acetone solution to form an existing matrix; alternatively, one of the two cellulose polymers may be used independently. Additional or alternative cellulose polymers that may be used in the existing matrix include cellulose acetate propionate, methylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, sodium carboxymethylcellulose, carboxymethylcellulose, cellulose acetate phthalate, hydroxyethylcellulose, chitosan, and the like.

[0094] Polyhydroxyalkanoates (PHAs), including poly-3-hydroxybutyrate (PHB), polyhydroxyvalerate (PHV), and polygydroxyhexanoate (PHH), may also be used to form a matrix. Polybutylene succinate (PBS), polybutylene succinate co-adipate (PBSA), and the like, made from biomass, may also be used to form a matrix. In some embodiments, one or more plasticizers may be added to an existing matrix to soften it and increase its flexibility. Bio-based plasticizers may be added to an existing matrix and may include fatty acids, polyols, epoxidized triglyceride vegetable oils, alkyl esters of adipic acid and citrate, etc.; examples of such plasticizers, without limitation, include triglycerin, tributyl citrate, triethyl citrate, triethyl acetyl citrate, polyethylene glycol, epoxidized soybean oil, oleic acid, etc. Bio-based resinous materials, such as gum rosin, may be added to an existing matrix to hydrophobize, soften, and / or bond it to limit its degree of flexibility; such materials have other advantages, such as acting as adhesives to fix matrix fragments together or to form crosslinks between them. Such materials may have the further advantage of aiding the hydrophobicity of the matrix and any subsequent materials derived therefrom, if water resistance is desired for the final application. Further additives may be included to optimize material properties for the final use application. For example, fillers and bulking agents may be included: pulp may be added to an existing matrix as a filler or bulking agent to reduce costs and improve composition; wood flour, sawdust, ash, mineral powder, lignin, and other low-cost filler granules may be used to reduce costs and / or to close pores in the matrix; precipitated calcium carbonate and stearic acid may be added to an existing matrix to improve hardness and hydrophobicity; precipitated calcium carbonate may be added alone to act as a nucleating agent or to provide brightness.Alternatively, or in combination with other additives, oil-glue-resistant and / or water-resistant (OGWR) formulations can be incorporated into existing matrices to obtain hydrophobic and oleophobic properties as desired. Biodegradation-promoting additives can be used to aid in the rapid decomposition of materials after disposal; for example, silica particles can be incorporated into CAB de-degradation matrices.

[0095] For example, photocatalysts, pro-oxidants, and enzymes can be used to accelerate the decomposition of NCE-containing materials once they enter landfills. Using the example of enzymes, and without being constrained by theory, it is understood that the activity of certain biodegradable accelerators can be explained by the following mechanisms: To decompose different cellulose derivatives, it may be necessary to first decompose the functional groups, and then further decompose the β-1,4-bonds in the cellulose backbone. Unmodified cellulose can be decomposed by cellulase and β-glucosidase enzymes. Lipase or acetylesterase are examples of enzymes that can be used to hydrolyze acetyl groups in cellulose acetate. By incorporating enzymes into a matrix, their activity can accelerate its decomposition, for example, it is present in waste facilities or landfills. Methods for incorporating enzymes into a matrix may include physical adsorption, covalent bonding, crosslinking, and encapsulation. Furthermore, enzymes can be immobilized on particles and then incorporated into existing matrices for better retention and distribution. In addition, enzyme loading and enzyme selection can be adjusted to accelerate or slow the decomposition rate under different circumstances. For example, enzymes that are active within a specific temperature range and pH environment may be selected to initiate decomposition when the material is destined for home composting or soil, or when it is intended for a slower decomposition process, such as when the material is instead sent to a landfill.

[0096] Ultraviolet (UV) resistance can also be imparted to existing matrices or composite NCE-containing matrices using additives that absorb or stabilize UV ​​irradiation. For example, carbon black or other dyes that absorb UV light can be added as pigments. In one embodiment, a bio-based material containing lignin, phenol units capable of imparting UV resistance, ketones, chromophores, and conjugated double bonds, and containing different UV functional groups, can be incorporated into a polymer matrix as a UV-absorbing additive to enhance long-term stability. In one embodiment, lignin can be combined with an NCE-containing matrix in manufactured articles that are typically exposed to UV light (e.g., sunglass frames).

[0097] In some embodiments, an existing matrix or a composite NCE-containing matrix may be magnetized with an additive such as gamma iron oxide. Although it has been stated that the additives are added to the existing matrix, it is understood that they may be introduced directly into the composite matrix formulation (i.e., after the additive NCE is combined with the existing matrix) in addition to or instead of introducing them into the existing matrix.

[0098] In this embodiment, a composite NCE-containing matrix for use in composite NCE-containing materials may be prepared as follows. In this embodiment, a bio-based existing matrix is ​​prepared to contain performance-enhancing additives, and this existing matrix is ​​then combined with redispersible or redispersed (additive) NCE. In this embodiment, to prepare a bio-based existing matrix, the matrix-forming components are dissolved in a solution of acetone or water, depending on the solubility parameter of the matrix, to form a solution containing about 1 wt% to about 25 wt%, about 5 wt% to about 15 wt%, about 5 wt% to about 50 wt%, or about 20 wt% to about 75 wt%, for example, a 12 wt% solution of these components. The matrix-forming components include constitutive polymer components (e.g., cellulose acetate (CA), cellulose acetate butyrate (CAB), etc.) and other cellulose ethers (e.g., methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, hydroxymethylcellulose, etc.), polyhydroxyalkanoates (PHA), such as poly-3-hydroxybutyrate (PHB), polyhydroxyvalerate (PHV), and polyhydroxyhexanoates (polyhydroxyhexanoates) e) (PHH), polybutylene succinate (PBS), etc., or combinations of such polymer components) may be included and combined with rosin or its derivatives, fillers, e.g., calcium carbonate or silica, bulking agents, e.g., pulp or pulp-based materials, and / or fatty acids (preferably saturated), e.g., stearic acid, lauric acid, palmitic acid, oleic acid, etc., along with plasticizers (e.g., triacetin, triethyl citrate, triethyl acetyl citrate, glycerol, xylitol, trehalose, sorbitol, mannitol, polyethylene glycol, polypropylene glycol, epoxidized soybean oil, castor oil, palm oil, etc.). For example, CAB or other biopolymers may be added in the range of about 60% to about 90%; plasticizers may be added in the range of about 0.1% to about 20%; gum rosin may be added in the range of about 5% to about 50%.As another example, CAB or other biopolymers may be added in the range of approximately 55% to approximately 95%; plasticizers may be added in the range of approximately 0.1% to approximately 20%; stearic acid may be added in the range of approximately 5% to approximately 25%; calcium carbonate may be added in the range of approximately 0.5% to approximately 17%; the ratio of stearic acid to calcium carbonate is approximately 3:2. In yet another example, HPC or other biopolymers may be added in the range of approximately 20% to approximately 95%; plasticizers may be added in the range of approximately 5% to approximately 40%; gum rosin may be added in the range of approximately 5% to approximately 50%. In yet another example, HPC or other biopolymers may be added in the range of approximately 5% to approximately 50%; plasticizers may be added in the range of approximately 0.5% to approximately 30%.

[0099] For example, components containing rosin, plasticizers, and cellulose acetate butyrate (or any other biopolymer or combination of biopolymers) are combined with other additives; under certain circumstances, the order of combination may be important. In one embodiment, the least viscous components are combined first (rosin, PCC, stearic acid), then CAB is added, followed by the plasticizer. The solution is stirred until the mixture is homogeneous and no aggregates remain. The solution is thickened to provide an existing matrix into which the additive NCE is incorporated.

[0100] In parallel, the additive NCE is prepared. In one embodiment, a selected amount of the dry, redispersible NC-containing material prepared as described above is resuspended in a resuspension fluid such as water and thoroughly mixed by an overhead mixer.

[0101] In this method, a formulation of the redispersed additive NCE is prepared. In this embodiment, the formulation of the redispersed NCE may contain a suitable amount of redispersed NCE to achieve the desired properties in the composite NCE-containing material. The amount of redispersed NCE in the range of about 1% to about 50% (wt%) of the total composite NCE-containing matrix may be used, with a range of about 5% to about 40% being preferable. The use of less water in this formulation facilitates the drying of the material into which the additive NCE is incorporated and aids in its moldability. This formulation of the additive NCE is then combined with an existing matrix to prepare a composite NCE-containing matrix. In this embodiment, since suitable components have already been added to the existing matrix, no further components are added to the composite NCE-containing matrix. Surfactants such as caprylic glycosides may be added; not bound by theory, it is understood that such additives may crosslink polar and nonpolar components during mixing and processing. Next, the composite NCE-containing matrix and any other desired components may be mixed with high shear force using an overhead stirrer, high-shear-force mixer, twin-screw extruder, etc., to produce a composite NCE-containing material. This initial forming process may be adjusted based on the viscosity requirements for the manufacturing process used to produce articles formed from the composite NCE-containing material.

[0102] 4. Foamed manufactured articles a. Foaming method for NCE-based materials and NCE-containing materials In exemplary embodiments, foaming formulations may be prepared as follows: Firstly, a group of NCEs may be treated to allow for redispersibility and may be dried and redispersed in any number of volumes, or may be used without drying in their aqueous forms, all as described above. Next, unsaturated, saturated, or supersaturated solutions of cellulose polymers (e.g., but not limited to MC (methylcellulose), CMC (carboxymethylcellulose), CMCNa (sodium carboxymethylcellulose salt), CA (cellulose acetate), CDA (cellulose diacetate), CTA (cellulose triacetate), CAB (cellulose acetate butyrate), CAPh (cellulose acetate phthalate), CAP (cellulose acetate propionate), EC (ethylcellulose), HEC (hydroxyethylcellulose), EHEC (ethyl hydroxyethylcellulose), HPC (hydroxypropylcellulose), HPMC (hydroxypropyl methylcellulose), HPMCP (hydroxypropyl methylcellulose phthalate), HPMCAS (hydroxypropyl methylcellulose acetate)) are prepared in their appropriate solvents, with plasticizers optionally added. Depending on the selected cellulose polymer, suitable plasticizers may be polyols (e.g., glycerol, xylitol, diglycerol), fatty acids (e.g., oleic acid), triacetin, triethyl citrate, triethyl acetyl citrate, tributyl citrate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, levulinic acid, PEG, polysorbate, or any blocking agent to reduce physical or chemical interactions, such as hydrogen bonding. Redispersible NCE may be added to this solution in its aqueous formulation or dry state before drying, or they may be redispersed as a slurry of 1-10% NCE before addition. If the cellulose polymer solution and the redispersible NCE slurry are not miscible, small amounts of dispersing aids, such as surfactants (e.g., capryl glucoside), may be added to promote homogenization of the mixture. Pentane, often mixed with ethanol, is added to the solution as a foaming agent.

[0103] Foaming can be readily produced in such mixtures due to their high viscosity. Therefore, the addition of a viscosifier or thickener can provide phase interface stabilization, induce crosslinking, and increase the elasticity of the sample. Exemplary thickeners include, but are not limited to, xanthan gum, guar, agar, locust bean, tamarind, arabic, guerlain, guaran, carrageenan, and other gums. With interface stabilization in mind, the mixture can respond to foaming processes such as vigorous stirring or foaming or other methods well known in the art, and barrier properties can be readily introduced into the foam. Foaming can be facilitated by adding foaming substances, such as surfactants, to the mixture before or during the foaming process, due to their ability to stabilize the phase interface.

[0104] The foam-forming mixture may optionally be combined with a barrier-forming formulation as previously described. In embodiments, the hydrophobic barrier-forming formulation includes agents such as surface-modified NCE, mono-, di-, or triacetates (CA) and their derivatives, oils, resinous materials, waxy materials, proteins, lignin and its derivatives, and lignocellulose; without limitation, examples of which may be used include resins, rosin, beeswax, carnauba wax, zein, pea protein, etc. In embodiments, an oleophobic barrier-forming formulation may be used that includes agents such as NCE (in various aspect ratios and sizes), surface-modified NCE, lignin-containing NCE, CA and its derivatives, lignin and its derivatives, MC, pulp, wood flour, chitosan, silicon dioxide, calcium carbonate, and calcium carbonate coated with stearic acid. For example, barrier-forming formulations comprising hydrophobic starch, hydrophobic cellulose polymer, fatty acid, surfactant, or oil-in-water resin or wax emulsion may be added in a ratio of 1:3 barrier additive to NCE to 15:1 barrier additive to NCE, and preferably in the range of 3:1 to 9:1, by dry weight, to produce the desired barrier properties. In one embodiment, the barrier-forming formulation may act as a substitute for or concurrently with the cellulose polymer, while in yet another embodiment, the cellulose polymer itself may provide the desired hydrophobicity or oleophobicity.

[0105] More specifically, barrier-forming formulations for use with the foaming formulations disclosed herein may be prepared to emphasize OGR properties, WVR properties, or both; in embodiments, barrier-forming formulations may include both types of properties, and formulation components may be adjusted to further enhance either the OGR or WVR properties or to balance them. For example, since there is a range of cellulose polymers with varying degrees of hydrophobicity or oleophobicity, a cellulose polymer may be selected to produce a desired degree of OGR and / or WVR. Barrier-forming formulations for producing water resistance may include various cellulosic polymers and those that are more hydrophobic in particular. Overall, since cellulosic polymers tend to be oleophobic (hydrophilic), it may be beneficial to include other materials in the barrier-forming formulation if higher water resistance is desired. For example, methylcellulose provides good oil / grease resistance, though not as high as water resistance. Mixtures of methylcellulose (MC) and cellulose acetate (CA) may be provided to adjust both OGR and WVR properties. While the LCST polymers discussed perform well in terms of oil resistance, the films / coatings made using them are soluble at room temperature, resulting in a less pronounced effect on water resistance. Cellulose acetate and lipids are some examples of additives that can be used to adjust barrier formulations to be more hydrophobic, and combinations of these components with more oleophobic materials can provide both oil and water resistance. Notably, cellulose acetate can provide both hydrophobic and oleophobic properties. Cellulose acetate and other cellulose acetate derivatives (e.g., cellulose acetate butyrate, without limitation) are unique in that they possess some degree of oleophobicity in addition to their strong hydrophobicity. Similarly, certain fillers have more hydrophobic or oleophobic properties: for example, fillers such as waxes can be selected to increase hydrophobicity, or, for example, a lot of excess NCE can be added as a pore-blocking agent to increase oleophobicity. Fatty acids, either by themselves or paired with charge-binding agents such as minerals (e.g., calcium carbonate paired with stearic acid) can also be used to increase hydrophobicity.

[0106] In some embodiments, substances such as MC, HPMC, CMC, NaCMC, CA, CAB, chitosan, rosin, lignin, plant proteins (e.g., pea protein, zein, etc.) and / or any combination thereof may be used as oleophobic substances to provide oil resistance; in some embodiments, substances such as MC, CA, CAB, chitosan, rosin, hydrophobic starch, lignin, plant proteins (e.g., pea protein, zein, etc.) and / or any combination thereof may be used as hydrophobic substances to provide water and / or water vapor resistance.

[0107] When an NCE suspension is foamed by a foaming process such as mechanical stirring and / or heating with any activation of the foaming agent, drying methods such as, but not limited to, conventional baking methods, flash drying, freeze-drying / lyophilization, vacuum drying, microwave drying, and extrusion can ensure that the foamed composition of the material is preserved as the material is dried, and that the structure can be further processed into a sheet or formed article in which the structure is formed. After the foaming process is started or completed, the foam formulation can be further processed and shaped to produce a formed manufactured article. For example, the foam formulation can be extruded as a billet and thermoformed into articles such as take-out containers. More specifically, by rolling up, steam molding, or vacuum forming sheets of such foamed material, heat-insulating and lightweight cups, plates, bowls, food wraps, take-out containers, or other commercially useful containers or packaging materials with the added advantage of biodegradability similar to bio-based products can be produced. As another example, high efficiency, light weight, and thermal insulation can result from dried and foamed materials, and barrier properties and customizable properties (e.g., highly water-soluble, or highly water and vapor resistant, oxygen and / or vapor resistant, and / or oil resistant) are available when needed.

[0108] In another exemplary embodiment, a formulation for producing OGWR foaming material from an NCE matrix (either simple or composite) may be prepared as follows: 1) A collection of NCEs may be treated to enable redispersibility and may be optionally dried and redispersed in some volumes as described above, or used in their undried aqueous forms, to form either a simple NCE-based matrix or a composite NCE-containing matrix; 2) A redispersible or redispersed aqueous solution of NCE may be combined with methylcellulose and / or other cellulose derivatives (cellulose esters, ethers, etc.) and / or fillers or bulking materials (e.g., without limitation, softwood pulp, hardwood pulp, long fiber pulp, short fiber pulp, kraft pulp, SunBurst pulp, agricultural waste such as Miscanthus, soybeans, rice husks or bagasse, fast-growing tree seeds such as eucalyptus, wood flour, sawdust, ash, shredded recycled plastics, or optionally shredded pulp derived from recycled pulp immersed in a liquid foaming agent); 3) Optionally wax and other foaming agents. Prepare a non-aqueous solution of one or more selected resin acids containing a plasticizer (e.g., triglycerides such as corn oil), cellulose acetate and / or other cellulose derivatives and foam-forming materials in an alcohol (e.g., ethanol) or non-polar solvent (e.g., acetone); 4) Non-cellulose thickeners (gums such as xanthan gum, guar, locust bean, tamarind, guerlain, agar, guaran, etc.), cellulosic thickeners (MC, CMC, HPMC, etc.), and nucleating agents (e.g., calcium carbonate, SiO2, TiO2, etc.). Additives such as talc, kaolin, calcium sulfate, magnesium hydroxide, calcium tungstate, magnesium oxide, lead oxide, barium oxide, zinc oxide, boron nitride, magnesium carbonate, lead carbonate, zinc carbonate, barium carbonate, calcium silicate, aluminosilicate, carbon black, graphite, alumina, zinc stearate, and calcium metasilicate may also be added to any of the solutions; 5) Ethanol is added to the aqueous solution (to promote miscibility), and then an alcohol or acetone-based solution is mixed together;6) Fine resin acid particles precipitate from the solution, depositing themselves onto the surface of the NCE, producing the desired OGWR properties; 7) The resulting mixture can be processed in a desired manner to be foamed as is, or it can be dried or concentrated for transport to the end user for subsequent reconstitution and foaming. The foamed material produced from this mixture can be further formed into formed foamed manufactured articles. For example, the mixture can be redispersed or diluted to be foamed and formed into bowls, plates, cups, etc., as either a simple NCE-based material or an NCE-containing component mixed with an existing matrix material to form a composite NCE-containing material.

[0109] Foaming of such mixtures can be carried out by several methods. In one embodiment, two solutions are prepared and combined, one of which is aqueous and the other is mainly nonpolar. In aqueous solution, the redispersible or redispersed NCE can be combined with any combination of the following components: further doses of one or more cellulose derivatives (e.g., methylcellulose), filler materials (e.g., pulp, wood flour), nucleating agents (e.g., PCC), surfactants, compatibility agents (e.g., capryl glucoside, ethanol), thickeners (e.g., xanthan gum, guar gum, pectin), plasticizers (e.g., glycerol), and blowing agents (e.g., pentane). If the blowing agent is immiscible with water, the blowing agent can be mixed with something that is miscible with water, such as ethanol or acetone. A mixture of pentane and ethanol can be prepared in a pentane to ethanol ratio of 1:1 to 1:5.

[0110] Without being constrained by theory, it is understood that this aqueous solution is sufficiently viscous to trap very fine bubbles introduced and suspended in a solution of redispersible NCE and cellulose derivatives (one or more) by moderate to high shear force mixing. Thus, when a foaming agent is added to the solution, air-derived bubbles and the foaming agent are dynamically constrained by the high viscosity (and slow diffusion) and charge interactions of the mixture. It is further understood that the uniform distribution and size of these bubbles result in more uniform cells, closed or open, in the final foaming product.

[0111] The second primary nonpolar solution has the option of adding one or more nonpolar solvents (e.g., acetone, ethanol), resin acids (e.g., gum rosin, polymerized rosin, abietic acid), and one or more foaming agents (e.g., pentane), surfactants, compatibilizers (e.g., capryl glucoside), nucleating agents (e.g., precipitated calcium carbonate), cellulose derivative suspensions or solubilizers (e.g., methylcellulose, hydroxypropyl methylcellulose, hydroxypropylcellulose, cellulose acetate, cellulose acetate butyrate), thickeners (e.g., xanthan gum, guar, agar), and plasticizers to the resin acid and / or cellulose derivative (e.g., corn oil, epoxidized soybean oil, triacetin, glycerol, triacetin, triethyl acetyl citrate). In embodiments, the presence of capryl glucoside and an ethanol / pentane mixture in either or both solutions aids homogenization when the two solutions are combined by moderate to high shear force mixing. Once combined, the foam may be heated or microwaved to induce expansion, and then dried (by any preferred curing method listed above, for example) to ensure a foamed open or closed cell structure.

[0112] In another embodiment, rosin or resin acid is in a mixture of a nonpolar solvent (ethanol, acetone, methane, etc.) and n-pentane. Other additives and plasticizers, such as one or more cellulose derivatives, are mixed in. This solution is then mixed with a dry or concentrated mixture of other potential aforementioned components for redispersible / redispersible NCE and aqueous solutions. When the rosin / n-pentane solution is mixed with an aqueous NCE resuspended, the rosin and n-pentane form a granular emulsion of rosin-coated n-pentane embedded in the NCE-containing matrix. The rosin-coated bubbles of n-pentane expand upon heating to inflate the NCE-containing matrix.

[0113] In yet another embodiment, a nonpolar alcohol-based solution is prepared containing rosin or resin acid, stearic acid or other fatty acids, methylcellulose or other cellulose derivatives, and plasticizers such as corn oil. Separately, an aqueous solution is prepared containing bicarbonate or other foaming agent and redispersed / redispersible NCE. The two solutions are combined using a high-RPM whisking. Chemical foaming begins when the two mixtures are combined and foamed, but this foaming can be delayed or controlled by adjusting the amount of water in the system and consequently its viscosity. The rate of foaming can also be modified (accelerated) by heating the system. Foaming can be delayed by embedding bicarbonate foaming agents in molten wax and by crushing solidified wax-coated bicarbonates and then adding them to the solution: under these circumstances, the wax dissolves and releases the foaming agent into the solution, performing foam formation. Foaming can also be delayed by adding solid stearic acid to the solution and then heating the solution so that the stearic acid dissolves and enters the solution, thereby encountering and reacting with the bicarbonate. In yet another embodiment, an aqueous solution of methylcellulose is formed by high shear force, optionally by adding ethanol to the solution to accelerate the solubilization of methylcellulose. A blowing agent such as n-pentane may be added to the emulsion. In an embodiment, redispersible or redispersed NCE is added to the MC solution; a blowing agent may also be added. Separately, a solution is prepared in which rosin or other resin acids (one or more) are sufficiently dissolved in alcohol. This solution may be added directly to the NCE-containing aqueous mixture with high shear force, or it may be emulsified in water using a surfactant such as PEG and then added to the NCE-containing aqueous mixture. To foam this mixture, mechanical energy using mechanical forces such as mixing, foaming, aeration, pressurizing or depressurizing, and / or heat using a heat source such as oven heating (40-150°C), microwaves, or steam may be used.

[0114] Other orders of adding the components may be used. In one embodiment of the invention, cellulose acetate is dissolved in acetone, and then stearic acid is added. Separately, rosin or other resin acids (one or more), oil as a plasticizer, and acetone are combined. In a third container, a dry or concentrated mixture of redispersed / redispersible NCE is combined with bicarbonate in an aqueous suspension. The rosin-containing solution and the NCE-containing mixture are combined, and then the cellulose acetate-containing solution is added. In another embodiment of the invention, stearic acid is dissolved in ethanol. Separately, ethanol, rosin or other resin acids (one or more), a plasticizer such as oil, and methylcellulose are combined. In a third container, a dry or concentrated mixture of redispersed / redispersible NCE is combined with bicarbonate in an aqueous suspension. The rosin-containing solution and the NCE-containing suspension are mixed, and the stearic acid-containing solution is added to the mixture. If necessary, additional water may be added to stimulate the bicarbonate / acid gas formation reaction, and a thickener (e.g., xanthan gum, guar, agar, guerlain, etc.) may be added to slow the diffusion rate of the gas into the sample.

[0115] In yet another embodiment of the invention, an acetone-based solution is filled with a nucleating agent, then a resin acid (e.g., gum rosin) and a cellulose polymer, e.g., cellulose acetate (or CTA, CAB, CAP, or CAPh), are dissolved in the solution, and then a foaming agent (e.g., pentane) and either a redispersible NCE, e.g., redispersed NCE suspended in a resuspension fluid, or a solution of dried, fragmented redispersible NCE, are added. Prior to the addition of the NCE, there is an option to add a surfactant, another cellulose derivative (e.g., a suspension in an acetone solution of a water-soluble cellulose derivative that concentrates upon addition of the redispersed NCE to a potentially aqueous solution), a fatty acid, and / or a thickener (e.g., xanthan gum).

[0116] In each case, after preparing the foam formulation, it may be heated in an oven, such as a convection oven or vacuum oven, within a temperature range (50-120°C) appropriate to the formulation to expand it, and then the foam may be solidified, initiating a thermosetting process without heating the formulation to the point where it melts, collapses, burns, or thermally decomposes. The heat, especially when provided by hot air, forms a solid film at the top of the foam. Once this film has hardened and the sample is almost dry, though not completely, the sample may be optionally microwaved for about 3-120 seconds (depending on the wattage and liquid concentration in the formulation) in a perforated container to avoid vapor bursting / explosion, and then optionally quenched (rapidly cooled) or placed at the back of the oven to harden the expanded structure. Alternatively, the sample may be extruded, microwaved, calcined, quenched and / or sublimated, and any combination thereof, such as extruded and then calcined. During heating, a temperature gradient is formed across the sample. Therefore, the high vapor pressure solvent evaporates more quickly at the surface, allowing the rosin or resin acid components of the formulation to supersaturate the surface and aggregate there, creating a hydrophobic, sealed outer layer for the solid foam article. For applications requiring strict hydrophobicity, further sprays on the coating (e.g., cellulose acetate and rosin) may be added to the sample before or after molding.

[0117] In formulations containing fatty acids, these substances may dissolve upon heating, interact directly with bicarbonates, and release CO2. When bicarbonates are embedded in wax, heating can melt the wax and release the bicarbonates, thus initiating a gas formation reaction. The released CO2 may be trapped in the matrix components of the formulation, including rosin or resin acids (one or more) or NCE, increasing the volume of the foam. As the formulation cools, the viscosity of the rosin increases, the foam solidifies, and the CO2 is trapped in the matrix; this effect can also be achieved by quenching (with the option of sublimating any trapped water if necessary).

[0118] Both simple NCE-based materials and composite NCE-containing materials can be incorporated into foams that can be used in a wide range of manufactured articles, as described in more detail below. The foams may be made from either a simple NCE-based matrix or a composite NCE-containing matrix, such matrices formed from redispersible or redispersed suspensions of NCE as described above. Both the simple NCE-based matrix and the composite NCE-containing matrix can act as foaming substrates, similar to the simple NCE-based materials or composite NCE-based materials. The foaming substrates may further be conferred with or combined with other additives that provide advantageous properties, such as barrier properties.

[0119] As used herein, the term “foam” refers to a multilayer system of dispersed media, including gaseous bubbles distributed in a liquid or solid matrix, where the density of the multilayer system is lower than the density of the liquid or solid matrix alone. The term “foaming” refers to the process of producing a foam; articles, materials, matrices, etc., “foamed” include foam and are formed at least partially by foaming. The foaming process may occur by exposing a material or matrix to a foaming formulation or foaming process. If the precursor for forming a foaming material is foamed itself, the foaming precursor material may impart its foaming characteristics to the subsequent substrate and may influence its foaming. For example, a composite NCE-containing matrix may be foamed before encountering its existing matrix, resulting in the formation of a foamed composite NCE-containing material. Similarly, an existing matrix may be foamed before encountering its composite NCE-containing matrix, resulting in the formation of a foamed composite NCE-containing material. Foamed composite NCE-containing materials can also be formed by combining a non-foamed composite NCE-containing matrix with an existing non-foamed matrix, and then exposing such combination to a foam-forming formulation or foam-forming process. If at least one of the composite NCE-containing matrix, the existing matrix, or the composite NCE material is sufficiently exposed to a foam-forming formulation or foam-forming process, the resulting composite NCE-containing material can be converted into a foamed composite NCE-containing material.

[0120] For the purposes of this disclosure, references to solid foams include open-cell foams and closed-cell foams. Closed-cell foams are recognized as having particular utility for shock absorption and thermal insulation, making them useful for packaging materials and containers and other foam-based manufactured articles. Open-cell foams are useful for articles used in comfort-enhancing items (cushions, car seats, etc.) and articles such as sponges used for cleaning. Open-cell foams are also useful for sound insulation because sound waves can travel within the open-cell structure and be absorbed therein. Examples of foam applications include, but are not limited to, manufactured goods such as shock-absorbing articles (for indoor and outdoor furniture, mattresses, car seats and parts, pillows, pet beds, cat litter, toilet pads, sponges, foaming soaps and laundry sheets, face masks, viscoelastic "memory" foam, pad mats, carpet pads, and equipment padding (e.g., sheets for exercise equipment)); building materials (e.g., rigid and lightweight structural components, sealants, fireproofing materials, thermal and sound insulators, space fillers, adhesives, etc.); flexible plastics for grips or wraps; waterproof articles such as surfboards, rigid materials for boat manufacturing, water tanks, and cooler boxes; packaging materials such as shock-absorbing packaging inserts, shape retainers within packages, packaged peanuts or similar items and packaging materials; and containers.

[0121] To produce a foam in a simple NCE-based material or a composite NCE-containing material, the substrate or its precursor matrix may be exposed to the action of a foam-forming substance, or to the action of a foam-forming process, or both. These substrates, which are combined with a foam-forming substance, or subjected to a foam-forming process, or both, are referred to as a “foam-forming formulation” for the purpose of producing a foam. As used herein, the term “foam-forming substance” means a chemical substance that performs a foaming process for a foam-forming formulation, facilitating the foaming process or improving the quality of the foam formed in the foam-forming formulation. As used herein, the term “foam-forming process” means an operation, such as heating or mechanical foaming, that performs a foaming process for a foam-forming formulation, facilitating the foaming process or improving the quality of the foam formed in the foam-forming formulation. Exposure of a simple NCE-based material or a composite NCE-containing material to the action of a foam-forming substance or a foam-forming process results in foaming of such material, producing a foamed NCE-based or NCE-containing material that can be formed or shaped to produce a manufactured article, for example, by forming or shaping it into a desired structure.

[0122] An exemplary process for forming a foamed material from a simple NCE-based matrix or a composite NCE-containing matrix is ​​schematically shown in the block diagram of Figure 4. Process 400 in Figure 4 begins by providing a dry material 402 containing redispersible NCE, which is prepared substantially as described with respect to Figure 1. The dry material 402 is then treated with a resuspension fluid 404 to resuspend the NCE contained in the dry material 402 to form a suspension 408 of redispersed NCE, substantially as described with respect to Figure 1. The suspension 408 of redispersed NCE can then be treated as a simple NCE-based matrix 410, substantially as described above with respect to Figures 2 and 3, or it can be combined with an existing matrix 412 to form a composite NCE-containing matrix 414.

[0123] The foam-forming substance 418 can be added to any of these substances (a suspension of redispersed NCE 408, a simple NCE-based matrix 410, or a complex NCE-containing matrix 414) to initiate foam formation within the substance or to prepare a substance for a further foam-forming process. Examples of foam-forming substances are well-known in the art and are not limited to: surfactants (nonionic, anionic, cationic, amphoteric) and chemicals that reduce the surface tension of the culture medium, thereby reducing the effort required to produce foam. Examples of foam-forming agents include, but are not limited to, compounds such as glucosides (e.g., caprylic, caprin, lauryl, coco, decyl, etc.), SLS (sodium lauryl sarcosinate), SCI (sodium cocoyl isethionate), SDS (sodium dodecyl sulfate), SMCT (sodium cocoyl methyl taurate), SOS (sodium cocoyl sulfate), and SCS (sodium caprylyl sulfonate), which also assist in homogenizing polar and nonpolar solutions.

[0124] In one embodiment, the foam-forming material may include a gas-producing reagent that forms a gas that is subsequently trapped in a support medium of the foam; this gas trap produces foam. Such reagents may readily decompose or evaporate at a given temperature to produce a gas or vapor. In another embodiment, the foam-forming material may include a two-reactant system in which two reactants combine to produce a gaseous product; typically, one reagent (gas-producing agent) reacts with another chemical substance to produce CO2 or another foam-forming gas from the gas-producing agent. When such substrates are incorporated into a precursor material that forms foam, they can be used to form foam by creating closed cell structures by decomposing within the precursor material and releasing trapped bubbles during the solidification of the precursor material. Since such foam-forming materials produce gas and foam through chemical changes or reactions, they may be referred to as foaming agents, particularly chemical foaming agents.

[0125] Chemical blowing agents such as calcium bicarbonate or sodium bicarbonate are gas-generating reagents that can be added to foam-forming formulations and exposed to an acidic environment to release CO2 gas into a support medium. Calcium bicarbonate is advantageous because it is environmentally friendly, has low solubility in foam-forming formulations, and therefore tends to form many fine bubbles when exposed to acid; such bubbles tend to form closed-cell foams that have greater resistance to the inclusion of oil or water. In embodiments, carboxylic acids may be included in the formulation to provide the acidification necessary to release CO2 from the gas-generating reagent. Carboxylic acids selected for this purpose may be derived from bio-based sources, such as fatty acids, e.g., stearic acid, oleic acid, etc. The long aliphatic tails on fatty acids enhance their compatibility with other components of the foaming mixture. Other chemical blowing agents include, but are not limited to, isocyanates and water, azodicarbonamides and hydrazines.

[0126] In other embodiments, foam-forming materials include inert gases introduced into a precursor material to form a foam under pressure without any chemical change or reactivity: instead, they form the foam by expanding within the precursor material. The resulting diffusion of the inert gas through the precursor material generally produces open-cell foam, allowing the pressurized gas to penetrate the precursor material and reach the external environment. Such foam-forming materials may also be called blowing agents, specifically physicoblasting agents, since they are already in their final chemical state as inert gases, and they form the foam by expanding within the precursor material as a result of a temperature or pressure difference. Examples of physicoblasting agents include, but are not limited to, H2O, liquid carbon dioxide, supercritical carbon dioxide, hydrocarbons (e.g., n-pentane, isopentane, cyclopentane), hydrochlorofluorocarbons, and chlorofluorocarbons. Mixtures of chemical and physicoblasting agents may be used to regulate expansion in the foam and to avoid thermal decomposition of the system.

[0127] As is well known in the field of foams, blowing agents can be added to or dissolved in foam-forming formulations (in a temperature and pressure-dependent manner) to induce nucleation, growth, and stabilization of bubbles therein. The small gas pockets then created by the blowing agent can expand under different conditions such as heat or pressure and can be stabilized using specific additives (e.g., viscosity enhancers, electrostatic stabilizers) or by dynamically restricting gas diffusion through quenching or thermosetting. N-pentane is a well-known blowing agent in the field of foams due to its extensive use in the formation of expanded polystyrene beads. Many other blowing agents are available for use with the formulations disclosed herein and can produce the expansion of a desired amount of bubbles at a temperature desirable for foaming.

[0128] As shown in Figure 4, the simple NCE matrix 410 and the composite NCE-containing matrix 414 can be further processed to produce the simple NCE material 420 or the composite NCE-containing material 422, respectively. As previously described with respect to Figure 1, the simple NCE material 420 is understood to include the simple NCE matrix 410, which provides the structural framework for the material and further includes any other additive substances. Similarly, as previously described with respect to Figure 1, the composite NCE-containing material 422 is understood to include the composite NCE-containing matrix 414, which provides the structural framework for the material and further includes any other additive substances. As shown in Figure 4, either the matrix alone or the material formed therefrom can act as a substrate for foaming.

[0129] Specifically, as described above, Figure 4 shows foam-forming materials 418 introduced into optionally redispersed NCE suspensions 408 and / or simple NCE system matrices 410, the presence of which these additives may initiate foaming or prepare materials for further foaming processes; Figure 4 further shows that foam-forming materials 418, optionally introduced as a simple NCE system matrix 410, are processed to form a simple NCE system material 420, and a composite NCE-containing matrix 414 are processed to form a composite NCE-containing material 422; Figure 4 also shows foam-forming materials 418 optionally introduced into a composite NCE system matrix 414. Optionally, although not shown in Figure 4, foam-forming materials may also be introduced into an existing matrix 412. The figure shows matrix-to-material transitions as strategic sites for foaming, either from a simple NCE system matrix to a simple NCE system material as part of processing step 424, or from a composite NCE-containing matrix to a composite NCE-containing material as part of processing step 428.

[0130] In addition to these options for foaming by the action of foam-forming materials, foaming can also be produced in a simple NCE-based material matrix or material or a composite NCE-containing matrix or material by the action of a foam-forming process, in addition to or as an alternative to the action of foam-forming materials. The preferred locations for the action of the foam-forming process for producing foam are shown in Figure 4 by the symbol π. Foam-forming processes are not limited to: high-RPM mixing ("foaming") or low-RPM mixing ("stirring") for physically incorporating air; high-to-low pressure extrusion; sublimation; exposure to electromagnetic radiation (e.g., microwaves) to create pores from irritating solvent molecules; and time- and temperature-dependent heating, quenching, and / or freeze-drying. These methods may be combined and / or circulated to achieve the desired foam viscosity, density, stiffness, and pore size. In some embodiments, mechanical methods are particularly advantageous as one of the later stages of process 400 shown in Figure 4.

[0131] As previously mentioned, plasticizers, filler particles, film-forming biopolymers, and other additives can be added to the NCE matrix (either simple or composite) to form similar materials (either simple or composite). For these materials intended for foaming, additives that are suitable for foam formation and maintenance may be selected.

[0132] Examples of such reagents include, but are not limited to: • Fatty acids (e.g., stearic acid) Alcohols, such as methanol and ethanol ·acetone • Resin acid • Natural resins such as camphor, terpentine, dammar gum, and shellac • Fat-soluble vitamins (A, D, E, K) • Mineral powders such as titanium dioxide, talcum powder, calcium carbonate, silica, and titanium dioxide. • Starches such as corn starch • Selected rubber and elastomers These are some examples.

[0133] b. Exemplary foamed manufactured article The ubiquity of foam products provides a wide range of other opportunities to use the NCE-containing foam substrates described herein as a replacement for conventional petroleum-derived foams currently in use. Considering the environmental changes associated with the production and disposal of conventional petroleum-derived foams, the NCE-containing foaming substrates disclosed herein offer a welcome alternative.

[0134] Appropriately modified simple NCE systems or composite NCE-containing matrices or materials can be readily converted into liquid foams, which can be dried to form substitutes for conventional articles such as packaging materials (e.g., paper packaging or packing peanuts) or styrofoam. For example, foams formed from simple NCE system matrices or materials or composite NCE-containing matrices or materials can be used in special situations such as as insulators, where properties such as thermal insulation are advantageous or where light weight per unit volume is advantageous, as in packing peanuts. In embodiments, barrier properties can be introduced into the foam using techniques to make the formulation more hydrophobic or oleophobic, as described above. In some embodiments, oil and grease resistance properties may be imparted to a foam by making some or all of the NCE particles more oleophobic and / or by preparing a composite NCE-containing matrix having oleophobic properties, or by introducing an oleophobic barrier-forming formulation into a suitable NCE system / NCE-containing matrix or material; similarly, water resistance properties may be imparted to a foam by making some or all of the NCE particles more hydrophobic and / or by preparing a composite NCE-containing matrix having hydrophobic properties, or by introducing a hydrophobic barrier-forming formulation into a suitable NCE system / NCE-containing matrix or material. As described herein, foaming formulations may be customized to emphasize either oleophobic or hydrophobic properties, and foaming formulations may be tuned to exhibit both types of properties to a higher or lower degree.

[0135] Appropriately modified materials, including NCE matrices, disclosed herein may provide substitutes for conventional foam products, such as those found in synthetic styrofoam packaging materials. Conventional packaging materials and containers are well-suited to their end uses because they are lightweight, cushioned, and water-repellent; however, these materials are made from petroleum-based plastics such as polystyrene, which, as mentioned above, cannot be recycled and are therefore destined for landfills, taking centuries to decompose. Foamed NCE materials (either simple or composite) may provide biodegradable alternatives to such conventional products, possessing good inherent mechanical properties.

[0136] Foamed composite NCE-containing materials provide a bio-based alternative to conventional molded foams for athletic and personal protective equipment such as paddings and helmets, offering support and comfort to the wearer. For example, foam soles in athletic shoes can be made from composite NCE-containing materials to reduce the amount of materials used in the shoes, such as ethyl vinyl acetate, polyurethane, and silicone gel, thus providing a more environmentally friendly product. The amount of NCE can be adjusted to improve the flex-torsion-tear resistance of the shoe sole while keeping it lightweight and shape-retaining. An additional benefit is that reduced viscoelasticity can be imparted by the foam material used as the shoe sole, as the foam cells interrupt the transmission of physical shock waves through the sole to the wearer's body, which can optionally be supplemented by other additives such as small, stiff fibers to absorb some of the physical force.

[0137] Foamed composite NCE-containing matrices can provide environmentally conscious alternatives to synthetic materials used in underwater recreational items such as surfboards and boat hulls, replacing fiberglass resin, polyurethane or polystyrene foam cores (surfboards), carbon fiber, fiberglass, and polyethylene (skulls) while being lighter and retaining strength. Composites containing redispersible NCE can be used to create lightweight, foamed, bio-based versions of similar materials.

[0138] Advantageously, the redispersible or redispersed NCE-containing foam materials disclosed herein can be remodeled to a density lower than water, so they float. Floating foam articles can be designed for specific applications where their buoyancy is a critical factor in their use. Bio-based foam products can be used in waterways to deliver activators to water while floating on the water surface. Such products can be modified to be biodegradable after a certain period of time, so they leave no residue or plastic waste material on or in the water. For example, a bio-based floating foam product can act as a delivery vehicle for aqueous treatment (e.g., to combat algal blooms or other undesirable species invading waterways); after delivering the treatment, the bio-based floating foam article biodegrades. As another example, a bio-based floating foam article can be used to cover the surface of waterways to temporarily act as a heat or sunlight reflector. Such products may be brightly colored (and therefore reflective) or may have reflective material embedded to reflect heat or sunlight. As yet another example, bio-based floating foam articles can be used as carriers for agents intended to absorb pollutants from the atmosphere and may be designed to biodegrade once the agent is sufficiently saturated with pollutants. For example, bio-based floating foam articles may have olivine, a mineral capable of absorbing / adsorbing CO2 from the atmosphere, embedded in them and may be deployed as sheets, as a series of continuous or discontinuous sheets, or as sprayable or otherwise dispersible particles lying on top of the water surface. Many floating foam particles with embedded olivine may be deployed to cover a large surface area of ​​water to absorb large amounts of CO2. Such particles may be modified to biodegrade once the olivine is saturated, and the olivine-CO2 composite will sink to the bottom of the waterway, harmlessly trapping and retaining the CO2 there. Simple NCE-based materials may be used for this purpose when their limited lifespan and durability are not a significant factor. However, if a longer lifespan is desired for the floating foam particles, composite NCE-containing materials may offer advantages.

[0139] Simple NCE-based materials and composite NCE-containing materials possess specific mechanical properties for their incorporation within the structural framework of the NCE itself. In some embodiments, such foamed materials can be modified to dissolve at a specific rate to produce a time-delayed release of activators embedded within or covering the material. Such materials can be induced to have a specific release profile, for example, by reducing the crystallinity of the foam with or without the use of hydrophobic additives (lower crystallinity corresponds to faster dissolution), and by optimizing the plasticizer concentration at a high level to promote faster dissolution (higher concentrations result in faster dissolution). Compared to bulky materials, foams also tend to dissolve more quickly because a larger surface area is exposed, giving foam an advantage in situations where solubility is desirable.

[0140] The ability to dissolve is particularly useful in combination with activators intended for specific purposes. Examples of such activators include pesticides, pharmaceuticals, and personal care products. Solubility allows foam containers to be configured for shorter-term purposes with a more limited time, such as containers or carriers. For example, a soluble container used as a carrier may deliver an activator to a target site and then dissolve when its usefulness is exhausted. In embodiments, NCE-containing foam-forming materials may be modified to have greater or less biological durability, depending on the intended application. Certain foams may be designed to dissolve fairly quickly, while others remain in place for a longer duration. The former type of foam may be useful for the delivery of fertilizers, seeds, pesticides or other agricultural products or activators, where the container is intended to dissolve quickly to release its contents into the environment; such foams may also serve as carriers for cosmetic products or medical / veterinary activators, where it is desirable to dissolve the container after the product or activator has been delivered. The latter type of form can be modified to achieve structural stability, for example, as a template for orthopedic reconstruction that gradually dissolves as bone regeneration occurs; such forms may contain and deliver activators such as hormones, cells, or bone growth-supporting agents, including, but not limited to, bone morphogenetic proteins (BMP-2 to BMP-4 and BMP-7), insulin-like growth factor, fibroblast growth factor (FGF), vascular growth factor (VEGF), platelet-derived growth factor (PDGF), and mesenchymal stem cells. In this context, the form acts as a container for the delivery of the activators and is intended to gradually dissolve as the bone heals. As an example, a foamed NCE matrix, optionally combined with materials such as hydroxyapatite, can provide a robust bone graft that can act as a skeleton for osteoblasts adept at creating bone tissue.

[0141] As previously stated, the term “container” is interpreted broadly. By modifying the mechanical and barrier properties of these materials used to form the foam, the formed foam articles can be used as containers that are durable enough to hold their contents during consumer use, and furthermore, that are easily decomposed and biodegradable after use. For example, in agricultural settings, foam containers (e.g., sprayed foam) can be used to deliver fillers (e.g., agricultural products such as seeds or agricultural activators) to desired target areas (e.g., soil or plant surfaces). Similarly, soluble foams can be used as carriers or delivery vehicles for pharmaceutical activators in medical or veterinary settings, and foam containers can be used to deliver fillers to desired internal or external target areas. Foams used in medical or veterinary settings can be modified to target specific areas requiring treatment and / or to release therapeutic agents systemically, enabling delayed or sustained release of the desired therapeutic agent. In other settings, soluble foam containers can contain activators within them. The aforementioned activators may be intended to transport and release substances such as skin nutrients, cosmetics, fragrances, enzymes, insecticides, insect repellents, fertilizers, seeds, mushroom spores, cleaning agents, topical or ingested medicines, topical functional foods, or health treatments for consumer use.

[0142] In any case, whether the NCE-containing material is a matrix formed primarily from NCE or a composite containing NCE as an additive to another substrate, a foam can be produced by mixing, aeration, or other treatments. The components of the foam-forming formulations disclosed herein may include redispersible or redispersed NCE with or without other matrix materials, and may include foaming or foaming agents that have undergone or have not undergone a foam-forming process. Foam-forming processes include, but are not limited to, heating of the formulation, pressure changes, sublimation, mechanical foaming, etc. Surfactants may be optionally added for special purposes, as described below. For example, performance-modifying additives for imparting oil, grease, and water resistance may be incorporated as barrier treatments, as described below. The mixture of redispersible or redispersed NCE, surfactants, and performance-modifying additives may then be vigorously mixed; in embodiments, sufficient mixing may be applied so that the mixture is aerated into a foam.

[0143] In some embodiments, the composite matrix is ​​made using biodegradable materials so that the existing matrix is ​​particularly suitable for foaming and for producing foamed manufactured articles. Conventional foaming products made from biodegradable materials, such as foams formed from starch, typically perform poorly compared to petroleum-derived foams and often lack the strength and water / oil resistance of petroleum-derived products. NCE-based foams, mainly derived from NCE matrices, can serve as substitutes for conventional foams for use in common manufactured articles such as containers and packaging materials, as described above. Composite materials containing mixtures of NCE and biodegradable materials such as starch or derivatized cellulose (e.g., cellulose ether or cellulose acetate) can also be prepared as foamed articles and can similarly be used as substitutes for conventional foams, combining the advantages of biodegradability with the desired strength, shock absorption, light weight, and water resistance required by consumer articles such as packaging materials and containers.

[0144] For existing composite NCE-containing materials containing starch as a matrix, cellulose microfibers are advantageous either alone or in combination with cellulose nanofibers. The composite materials may also contain a pulp-based matrix or a starch-pulp matrix to form a total cellulose composite NCE-containing material. Foaming of composite matrices incorporating NCE can be produced by incorporating foam-forming factors such as surfactants or foaming agents into the mixture by several methods well known and previously described in the art, e.g., mechanical foaming techniques. As an example, bicarbonate crystals may also be incorporated into the mixture as foam-forming factors, and the subsequent addition of an acid activates foaming. More hydrophobic cellulose additives such as linseed oil, or methylcellulose, cellulose acetate, lipids, polyvinyl alcohol or polyvinyl acetate / polyvinyl alcohol copolymers, waxes, wax emulsions, hydrophobic starch, fatty acids, resins, other hydrophobic cellulose polymers, or other similar hydrophobic polymers may be added to improve hydrophobicity; alternatively or additionally, NCE additives having OGR properties can be prepared. In some embodiments, chitosan and aluminum sulfate are used to enhance o-resistance ratio (OGR). In other embodiments, cellulose and cellulose-derived materials having a high hydroxyl content may be used for OGR. To modulate the mechanical properties of the foam, additives such as, but not limited to, plasticizers (e.g., polyols such as glycerol), viscosifiers or thickeners (e.g., xanthan gum, guar gum, etc.), flame retardants (e.g., but not limited to, metal hydroxides such as aluminum trihydrate (ATH) and magnesium hydroxide, halogenated compounds (bromide species allow the resin to retain its mechanical properties), and polydopamine), and nucleating agents such as, but not limited to, minerals (e.g., precipitated calcium carbonate, silicon dioxide) are used to modulate the pore size and density of the foam.

[0145] The concentration of NCE in the foaming substrate can be adjusted to produce appropriate mechanical and barrier properties in the final foamed material. For example, the amount of NCE in the substrate can be varied to achieve softer or harder foams; the former is useful for applications such as space fillers, packaging materials, and packing peanuts, while the latter is useful for more structural applications, such as containers, foamed packing inserts for brittle items, and foams used in building materials. The general range of NCE in the final substrate is 1-10% for softer foams and 20-50% for harder foams, but very soft foams such as packing peanuts may contain as little as 0.1 wt%, while foams for building materials may contain up to 90 wt%. [Examples]

[0146] Examples Example 1: Preparation of a redispersible NCE sheet The redispersible NCE sheet was prepared by combining a drying / dispersing additive with an NCE slurry and then drying it at a high temperature in an oven. There are various combinations and many ratios of additives that can be used to prepare a sheet of dried redispersible NCE. In this specific example, LCST polymer hydroxypropyl methylcellulose (HPMC) was used as the dispersing additive in combination with nanofiberized cellulose (NFC) in a 5:1 NFC:HPMC ratio. The components were combined in an aqueous solution consisting of 1.25 wt% NFC. [Table 1]

[0147] First, 0.25 g of HPMC was added to 58.08 g of water in a beaker while stirring at medium to high speed for approximately 15 minutes. Then, the stirring speed was reduced to its lowest setting, and mixing continued until the bubbles on the surface disappeared. After removing the beaker from the stirring plate, 41.67 g of 3 wt% L NFC (1.25 g of dry weight NFC) was added. These components were then mixed using an overhead stirrer at 250 rpm for 15 minutes. The well-mixed sample was then scooped onto a silicone mat and spread evenly on the mat using a doctor blade set to a thickness of 1.5 mm. The mat with the sample was placed in an oven and dried at 60°C until the sample was completely dry (approximately 2 hours). The dried sheet was slowly removed from the silicone mat. As a result of these procedures, the previously non-dispersible NFC was modified with a drying / dispersing additive so that it could be redispersed when combined with water. Dry sheets containing such redispersible NFC were prepared using these procedures.

[0148] Example 2: Foaming of redispersed NCE material • Valida NCE Methylcellulose (MC), Sigma Aldrich Gumrosin, Sigma Aldrich Ethanol, McMaster Carr Glycerol, Sigma Aldrich • Kraft pulp, General • Pentane, McMaster Carr

[0149] Formulation preparation: The formulation was prepared according to the following protocol. 1. Redispersible NCE sheets were generally prepared using the following ratios of components after the protocol of Example 1: 3:1 MC:NCE and 19:1 MC:glycerol. 2. A 1.94 g dry, redispersible NCE sheet (containing 1.4 g MC, 0.467 g NCE, and 0.074 g glycerol) was subdivided, the subdivided solid was resuspended in 50 mL of water, and the suspension was stirred with a stirrer bar or overhead mixer. 3. 4g of kraft pulp was finely minced in a blender and added to an aqueous slurry of NCE that had been redispersed under medium to high shear force. 4. In a separate beaker, 4 g of gum rosin was thoroughly dissolved in 7.5 g of ethanol. 5. In a separate beaker, a 1:1 mixture containing 10 grams each of ethanol and pentane (20 g total) was prepared. This mixture was added to the aqueous slurry of NCE and pulp. 6. Using high shear force, the rosin-ethanol mixture was slowly poured into the aqueous slurry. 7. Once thoroughly mixed, the sample was placed on a silicone sheet or mold and baked in an oven at 80°C until dry.

[0150] Example 3: Foaming of an NCE composition having oil, fat, and water resistance material ·Redispersibility NCE Methylcellulose, Sigma Aldrich Gumrosin, Sigma Aldrich Ethanol, McMaster Carr • Precipitated calcium carbonate (PCC), Sigma Aldrich • Kraft pulp, Genera • Pentane, McMaster Carr 4% pulp slurry, Dart Capryl glucoside Xanthan gum, Bob's Red Mill

[0151] Formulation preparation: The formulation was prepared according to the following protocol. 1. The redispersible NCE was prepared substantially as described in Example 1. Methylcellulose (MC) was combined with redispersible NCE in an aqueous solution using tap water, a 0.56 g redispersible sheet having a 5:1 NCE:MC ratio, and further MC, resulting in an NCE:MC ratio of 1:3. These components were then combined using an overhead mixer under high shear force to produce a formulation containing the redispersed NCE. 2. Next, pulp derived from the 4% pulp solid slurry was added to the formulation prepared in step 1. The amount of pulp used was 100 g of 4% solid pulp slurry, which was combined with 100 g of aqueous solution prepared in step 1. This step produced a formulation containing pulp and redispersed NCE. 3. 1.2 g of PCC was added to the formulation from step 2; 0.04 g of capryl glucoside was also added. 4. The mixture from step 3 was then combined with the previously mixed 1:1 solution of ethanol and pentane, thereby adding 12 g of ethanol and 12 g of pentane to obtain the final aqueous formulation. 5. In a separate beaker, 20 g of ethanol and 10 g of gum rosin were combined and stirred until fully dissolved to prepare a nonpolar solution, to which the following additional components were added: 2 g of xanthan gum, 0.02 g of capryl glucoside gum, and 8 g of pentane. 6. Next, the nonpolar solution derived from step 5 was added to the final aqueous formulation derived from step 4 with high shear force to obtain a mixture for forming a foamed article. 7. Once sufficiently homogenized, the mixture from step 6 was placed on a perforated silicone sheet or mold and baked in an oven at 80-90°C until dry (approximately 3 hours depending on the size and thickness of the sample). The wet mixture was observed to expand in the expanded foam and then dry / harden. This uncompressible foam was thermoformed into a bowl shape at 200°C for 8 seconds. Through this and other experiments, it was observed that the uncompressible foam prepared as described above is suitable for many applications. For example, it can be used for space-filling articles, such as packing peanuts. It can also be thermoformed into various molded manufactured articles.

[0152] While the present invention is particularly shown and described in relation to its preferred embodiments, it will be understood by those skilled in the art that various variations in form and detail can be made in the present invention without departing from the scope of the invention as encompassed in the appended claims. All U.S. patents and published or unpublished U.S. patent applications cited herein are incorporated by reference. All published foreign patents and patent applications cited herein are incorporated by reference. All other published references, documents, manuscripts and scientific literature cited herein are incorporated by reference. All relevant teachings in all patents, published applications and references cited herein are incorporated by reference in their entirety.

Claims

1. A simple NCE-based material containing a simple NCE-based matrix, A simple NCE matrix comprises a population of redispersible NCEs treated with a drying / dispersing additive containing a low critical solution temperature (LCST) polymer; A simple NCE matrix provides a structural framework for simple NCE materials; The simple NCE-based material further comprises a barrier formulation; Simple NCE-based materials are foamed. Simple NCE-based material.

2. The simple NCE-based material according to claim 1, wherein the barrier formulation comprises a substance selected from the group consisting of cellulose polymers, lipids, proteins, fillers, fatty acids, resin acids, and combinations of resin acids.

3. The simple NCE-based material according to claim 1, wherein the barrier formulation comprises an oleophobic substance selected from the group consisting of MC, HPMC, CMC, NaCMC, CA, CAB, chitosan, rosin, lignin, and plant proteins.

4. The simple NCE-based material according to claim 1, wherein the barrier formulation comprises a hydrophobic substance selected from the group consisting of MC, CA, CAB, chitosan, rosin, hydrophobized starch, lignin, and plant proteins.

5. The simple NCE material according to claim 1, further comprising one or more additive substances selected from the group consisting of bulking agents, reinforcing agents, nucleating agents, plasticizers, thickening agents and appearance modifiers or combinations thereof.

6. The simple NCE-based material according to claim 5, wherein one or more additive substances are fillers.

7. The simple NCE material according to claim 6, wherein the bulking agent comprises pulp or a pulp-based substance.

8. The simple NCE material according to claim 6, wherein the bulking agent includes filler particles.

9. The simple NCE-based material according to claim 8, wherein the filler particles contain a plant-derived organic material.

10. The simple NCE-based material according to claim 5, wherein one or more additive substances are nucleating agents.

11. The simple NCE material according to claim 5, wherein one or more additive substances are plasticizers.

12. The simple NCE-based material according to claim 11, wherein the plasticizer is selected from the group consisting of glycerol, triglycerin, triacetin, triethyl citrate, triethyl acetyl citrate, tributyl citrate, oleic acid, levulinic acid, PEG, and polysorbate.

13. The simple NCE material according to claim 5, wherein one or more additive substances are thickeners.

14. The simple NCE-based material according to claim 13, wherein the thickening agent is selected from the group consisting of xanthan gum, guar gum, agar gum, gellan gum, gellan gum, MC, CMC, and HPMC.

15. The simple NCE material according to claim 1, further comprising a foam-forming material.

16. A manufactured article comprising the simple NCE material described in claim 1.

17. A manufactured article according to claim 16, which is formed into a molded article.

18. The manufactured article according to claim 17, wherein the formed article is shaped into a plate or a bowl.

19. The manufactured article according to claim 17, wherein the formed article is shaped as a floating sheet or floating particles.

20. a. A process for producing a simple NCE system material containing redispersible NC elements, where the simple NCE system material is: i. To provide an initial suspension containing NC elements suspended in a fluid medium; ii. Combining the drying / dispersible additive with the initial suspension to form a suspension of redispersible NCE; and iii. Adding additive substances to a suspension of redispersible NCE to form a simple NCE-based material. It is manufactured by the following sub-processes; b. A step of exposing a simple NCE-based material to the action of a foam-forming material or foam-forming process to form a foamed simple NCE-based material; c. A process of forming or shaping foamed simple NCE-based material into a desired form and providing a foamed article. A method for producing a foamed article containing a simple NCE-based material.

21. The manufacturing method according to claim 20, wherein the step of forming or shaping includes extrusion molding.

22. A foamed composite NCE-containing material containing a composite NCE-containing matrix, The composite NCE-containing matrix comprises a population of redispersible NCEs treated with a drying / dispersing additive containing a low critical solution temperature (LCST) polymer, and the existing matrix; Redispersible NCE is incorporated into an existing matrix, where the existing matrix provides a structural framework for the composite NCE-containing material; The composite NCE-containing material comprises a barrier formulation; at least one of the composite NCE-containing matrix, an existing matrix, or the composite NCE material is exposed to a foam-forming formulation or foam-forming process, thereby converting the composite NCE-containing material into a foamed composite NCE-containing material. Foamed composite NCE-containing material.

23. The foamed composite NCE-containing material according to claim 22, wherein the existing matrix contains a bio-based polymer.

24. The foamed composite NCE-containing material according to claim 23, wherein the bio-based polymer contains a cellulose derivative.

25. The foamed composite NCE-containing material according to claim 22, wherein the existing matrix contains a petroleum-derived polymer.

26. The foamed composite NCE-containing material according to claim 25, wherein the petroleum-derived polymer is derived from recycled plastic material.

27. The foamed composite NCE-containing material according to claim 22, wherein the barrier formulation comprises a substance selected from the group consisting of cellulose polymers, lipids, proteins, fillers, fatty acids, resin acids, and combinations of resin acids.

28. The foamed composite NCE material according to claim 22, wherein the barrier formulation comprises an oleophobic substance selected from the group consisting of MC, HPMC, CMC, NaCMC, CA, CAB, chitosan, rosin, lignin, and plant proteins.

29. The foamed composite NCE-containing material according to claim 22, wherein the barrier formulation comprises a hydrophobic substance selected from the group consisting of MC, CA, CAB, chitosan, rosin, hydrophobic starch, lignin, and plant proteins.

30. The foamed composite NCE-containing material according to claim 22, further comprising one or more additive substances selected from the group consisting of bulking agents, reinforcing agents, nucleating agents, plasticizers, thickening agents and appearance modifiers.

31. The foamed composite NCE-containing material according to claim 30, wherein one or more additive substances are fillers.

32. The foamed composite NCE-containing material according to claim 31, wherein the bulking agent comprises pulp or a pulp-based substance.

33. The foamed composite NCE-containing material according to claim 31, wherein the bulking agent includes filler particles.

34. The foamed composite NCE-containing material according to claim 33, wherein the filler particles contain a plant-derived organic material.

35. The foamed composite NCE-containing material according to claim 30, wherein one or more additive substances are nucleating agents.

36. The foamed composite NCE-containing material according to claim 30, wherein one or more additive substances are plasticizers.

37. The foamed composite NCE-containing material according to claim 36, wherein the plasticizer is selected from the group consisting of glycerol, triglycerin, triacetin, triethyl citrate, triethyl acetyl citrate, tributyl citrate, oleic acid, levulinic acid, PEG, and polysorbate.

38. The foamed composite NCE-containing material according to claim 30, wherein one or more additive substances are thickeners.

39. The foamed composite NCE-containing material according to claim 38, wherein the thickening agent is selected from the group consisting of xanthan gum, guar gum, agar gum, gellan gum, MC, CMC, and HPMC.

40. The foamed composite NCE-containing material according to claim 22, further comprising a foam-forming material.

41. A manufactured article comprising the foamed composite NCE-containing material according to claim 22.

42. A manufactured article according to claim 41, which is formed into a molded article.

43. The manufactured article according to claim 41, wherein the formed article is shaped as a plate or a bowl.

44. The manufactured article according to claim 41, wherein the formed article is shaped as a floating sheet or floating particles.

45. a. A step of providing a composite NCE-containing material containing redispersible NC elements, wherein the composite NCE-containing material is: i. To provide an initial suspension containing NC elements suspended in a fluid medium; ii. Combining the drying / dispersing additive with the initial suspension to form a suspension of redispersible NCE; iii. Incorporating a suspension of redispersible NCE into an existing matrix to form a composite NCE-containing matrix; iv. Adding an additive substance to at least one of the initial suspension, the suspension of redispersible NCE, the existing matrix, and the composite NCE-containing matrix to form a composite NCE-containing material. It is manufactured by the following sub-processes; b. A step of exposing at least one of the initial suspension, the redispersible NCE suspension, the existing matrix, and the composite NCE-containing matrix to a foam-forming formulation or foam-forming process to sufficiently convert the composite NCE-containing material into a foamed composite NCE-containing material; and c. A process of forming or shaping a foamed composite NCE-containing material into a desired form, thereby manufacturing a formed article. A method for producing a molded article containing a foamed composite NCE-containing material.

46. The method according to claim 45, wherein the additive substance is selected from the group consisting of barrier agents, bulking agents, reinforcing agents, nucleating agents, plasticizers, thickening agents and appearance modifiers.

47. The method according to claim 45, wherein step b exposes at least one of the initial suspension, the existing matrix, and the composite NCE-containing matrix to the foaming process.

48. The method according to claim 45, wherein the step of forming or shaping includes extrusion molding.

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