TWI831008B - Biodegradable material and biodegradable food material - Google Patents

Abstract

Embodiments of the invention overcome the shortcomings of prior technologies by infusing nanocellulose in a fibrillated form to enhance the properties of cellulose pulp. These properties may include, for example, the mechanical and barrier properties, i.e., tensile strength, liquid, and gas impermeability such as oxygen, carbon dioxide, and oil, can be improved substantially. Some embodiment of the invention further provide a fibrillated cellulose composite material that includes properties of being a strength-enhancing agent, an oligomer, carboxylic acid, plasticizer, an antimicrobial agent, water repellant, and/or a transparent composite.

Description

Biodegradable materials and biodegradable food materials

Aspects of the invention generally relate to renewable and recyclable materials. More specifically, embodiments of the invention relate to fibrillated cellulose or other natural materials used in the manufacture of consumer products.

Growing concern about the environmental crisis - plastic waste pollution - has led to widespread investigation into sustainable and renewable materials. To avoid the use of petroleum-derived polymers, a natural biopolymer, plant-based cellulose fiber, offers the materials research community an alternative. Cellulose fiber is attracting increasing attention due to its ubiquitous origin, sustainability and renewable nature and, more importantly, the fact that it makes the final product 100% biodegradable in nature.

However, many existing biodegradable products based on cellulose fibers fail to live up to expectations. For example, the cost of producing these cellulosic fiber products does not make economics feasible for large-scale production. Additionally, due to the need to be water-resistant, oil-resistant, or non-stick, many cellulosic fiber products rely heavily on synthetic chemical compositions to achieve these properties or effects. For example, many existing products require a layer of fluorocarbon to be applied to surfaces that will come into contact with food or beverages. Additionally, some of these fluorocarbon-based chemicals, such as perfluorooctane sulfonate (PFOA or C8), can cause long-term negative effects on health and the environment.

Additionally, current approaches do not create two or more layers of fibrillated cellulose material. Conventional practice instead only attempts to produce a single layer from a cellulose pulp solution.

Embodiments of the present invention overcome the shortcomings of the prior art by injecting nanocellulose in a fibrillated form to enhance the properties of cellulose pulp. For example, these properties may include mechanical and barrier properties, namely tensile strength, impermeability to liquids and gases such as oxygen, carbon dioxide and oil, which may be substantially improved.

Some embodiments of the invention further provide fibrillated cellulose composites comprising layers or mixtures of fibrillated cellulose to produce as strength enhancers, oligomers, carboxylic acids, plasticizers, antibacterial agents , waterproofing agents and/or properties of transparent composites. The composite material may further generally contain no chemical additives to enhance the above-described properties. In still other embodiments, the composite may further include a substrate such as slurry or other layers such as fiberized cellulose.

Embodiments may now be described more fully with reference to the accompanying drawings, which form a part hereof, and by which specific exemplary embodiments may be shown as being practiced. These drawings and exemplary embodiments are provided with the understanding that this disclosure is an example of the principles of one or more embodiments and is not intended to be limiting of any embodiment illustrated. The embodiments may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the embodiments The scope is for those with ordinary knowledge in the field. Accordingly, the following detailed description is not to be understood in a limiting sense.

Embodiments of the present invention include a material, such as a Green Composite Material (GCM™), which may include fibrillated cellulose as a core material without any other materials. In one embodiment, the composite material May include pulp and fibrillated cellulose. In some embodiments, the composite material may generally be free of chemical additives or formulations. In still other embodiments, the composite material may be independently derived from plant fibers. In one embodiment, the chemical additive or formulation may be toxic, potentially toxic, natural based, or non-toxic. In some embodiments, the chemical additives or formulations may be manufactured in a laboratory. In some embodiments, these plant fibers may be derived from bagasse, bamboo, abaca, sisal, hemp, flax, hop, jute ), kenaf, palm, coir, corn, cotton, wood and any combination thereof. In other embodiments, the plant fiber may be preprocessed or semi-processed cellulose. In other embodiments, green composite materials with fibrillated cellulose can be obtained by processing plant fibers through a processing procedure, such as a high-pressure homogenizer or a refiner. In a further embodiment, composite materials with fibrillated cellulose (without cellulose-producing microorganisms) are obtained by bacterial strains. In alternative embodiments, materials with fibrillated cellulose may be obtained from marine sources.

In one embodiment, the shape and size of the cellulose may depend on the original source of the fibers or the combination and manufacturing process of the fibers. Nonetheless, fibrillated cellulose generally has diameters and lengths, as discussed below. The fibrillated cellulose, in one embodiment, may have a diameter of about 1 to 5000 nanometers (nm). In still other embodiments, the fibrillated cellulose can have a diameter of about 5 to 150 nanometers or about 100 to 1000 nanometers. In still other embodiments, the fibrillated cellulose can have a diameter of about 5,000 to 10,000 nanometers.

In further embodiments, the materials may have enhanced properties that enhance, enhance, or improve various properties without the need for toxic chemical additives or formulations. In some embodiments, the material has properties suitable for carrying food or liquid items that typically do not contain chemical additives or formulations. For example, as shown in the prior art, various toxic chemical additives or agents are added to or coated on materials during the manufacturing process to provide the desired tensile strength, whether dry tensile strength or wet tensile strength, reinforcement oil barrier, gas and/or liquid impermeability. Instead of adding various toxic chemical additives or agents to the materials, various aspects of the present invention include composite materials with fibrillated cellulose that typically do not contain these additives or agents.

For example, fibrillated cellulose can have a length of about 0.1 to 1000 microns, about 10 to 500 microns, about 1 to 25 microns, or about 0.2 to 100 microns. In some embodiments, materials with fibrillated cellulose of different diameters, for example, have a weight ratio of 1:100. In some embodiments, the fibrillated cellulose can have a weight ratio of 1:50. In further embodiments, materials with mixed fibrillated cellulose can have, for example, improved tensile strength, whether dry or wet, enhanced oil resistance, gas and/or liquid impermeability and cost savings.

In some embodiments, materials having fibrillated cellulose can be characterized by an oxygen transmission rate of about 8,000 cubic centimeters per square meter per 24 hours (cm ³ m ⁻² 24 h ⁻¹ ) or less. In some embodiments, the oxygen transmission rate is about 5,000 cubic centimeters per square meter per 24 hours or less. In other embodiments, the oxygen transmission rate is about 1000 cubic centimeters per square meter per 24 hours or less.

Additionally, in further embodiments, the material may have a water vapor transmission rate of about 3000 grams per square meter per 24 hours (gm ^-2 24 h ^-1 ) or less. Additionally, for other embodiments, the water vapor transmission rate may be about 1500 grams per square meter per 24 hours or less.

In some embodiments, the material may be characterized by a dry tensile strength of about 30 megapascals (MPa) or more. In some embodiments, the dry tensile strength may be about 70 MPa. In other embodiments, the dry tensile strength may be about 100 MPa or higher. In some embodiments, the material may have a dry tensile modulus of about 4 gigapascals (GPa) or greater. In some embodiments, the dry tensile modulus is about 6 GPa or greater.

In some embodiments, the material can have properties of a dry tensile index of about 45 Nmg ^-1 or above. In some embodiments, this property may be about 80 Nm g ^-1 or higher.

In some embodiments, the material may have a wet tensile strength of approximately 5 MPa or higher. In some embodiments, the wet tensile strength may be about 20 MPa or higher.

In some embodiments, the material may have a wet tensile modulus of about 0.4 MPa or higher. In some embodiments, the wet tensile modulus can be about 1.0 MPa or higher.

In some embodiments, the material can have properties of a wet tensile index of about 5 Nm g ^-1 or greater. In some embodiments, the wet tensile index can be about 20 Nmg ^-1 or higher.

In an alternative embodiment, the material may include a binder to enhance dry and/or wet strength. In one embodiment, the adhesive may include a polymer. In other embodiments, the binder may include metal salts. In some embodiments, the binder may include oligomers. In another embodiment, the binder may include carboxylic acid. In yet another alternative embodiment, the adhesive may include a plasticizer. In some embodiments, the weight ratio of fibrillated cellulose to binder in the present invention can be about 33:1 to 1:1.

For example, polymers may include polyester, gelatin, polylactic acid, chitin, sodium alginate, thermoplastic starch, polyethylene, chitosan, chitin glucan, poly vinyl alcohol or polypropylene. In one embodiment, the polymer may include chemical additives that may be applied to composites in aspects of the invention. For example, the chemical additives can be embedded in the material itself or can be sprayed or coated on it.

In still other embodiments, the binder may include a metal salt. For example, metal salts may include potassium zirconium carbonate, potassium aluminum sulphate, calcium carbonate, and calcium phosphate. In some embodiments, the weight ratio of fibrillated cellulose to binder in the present invention can be about 33:1 to 1:1.

In some embodiments, the binder may include oligomers. In one example, oligomers may include oligonucleotides, oligopeptides, and polyethylene glycol. In some embodiments, the weight ratio of fibrillated cellulose to binder in the present invention can be about 33:1 to 1:1.

In yet other embodiments, the binder may include carboxylic acid. For example, carboxylic acids may include citric acid, adipic acid, and glutaric acid. In some embodiments, the weight ratio of fibrillated cellulose to binder in the present invention can be about 33:1 to 1:1.

In embodiments, the adhesive with a plasticizer can reduce the brittleness and gas permeability of the adhered composite material. In some embodiments, the plasticizer may include polyols. In one embodiment, the polyol may include glycerol. In one embodiment, the polyol may include sorbitol. In one embodiment, the polyol may include pentaerythritol. In some embodiments, the polyol may include polyethylene glycol. In some embodiments, the weight ratio of plasticizer to composite material to binder is from about 5:33:1 to about 1:1:1.

In some embodiments, plasticizers may include branched polysaccharides, waxes, fatty acids, fats, and oils.

Aspects of the invention may further include a water repellent as a chemical additive to repel gaseous and/or liquid water. In some embodiments, the waterproofing agent includes animal-based wax, animal-based oil, or animal-based fat. In one embodiment, the water repellent includes petroleum derived wax or petroleum based wax. In other embodiments, the waterproofing agent includes vegetable-based waxes, vegetable-based oils, or vegetable-based fats.

In some embodiments, animal-based water repellents may include beeswax, shellac, and whale oil.

In some embodiments, petroleum-based wax waterproofing agents may include paraffin wax, paraffin oil, and mineral oil.

In some embodiments, plant-based waterproofing agents may include palm wax, soybean oil, palm oil, palm wax, carnauba wax, and coconut oil.

In some embodiments, the waterproofing agent may include binders such as potassium zirconium carbonate, potassium aluminum sulfate, calcium carbonate, and calcium phosphate.

In further embodiments, the material may include fibrillated cellulose and further optionally may include an antimicrobial agent. In some embodiments, the antibacterial agent may include tea polyphenol. In some embodiments, antibacterial agents may include pyrithione salts, parabens, paraben salts, quaternary ammonium salts, imidazolium salts, sorbitol benzoate acid (benzoic acid sorbic acid) and potassium sorbate (potassium sorbate).

Additionally, some embodiments of the present invention may include materials having fibrillated cellulose and further optionally may include transparent composite materials to increase the penetration of light at wavelengths from about 300 nanometers to 800 nanometers. In some embodiments, the material may include branched polysaccharides. In some embodiments, the weight ratio of material to transparent composite ranges from about 99:1 to about 1:99, which may depend on the desired transparency.

In some embodiments, branched polysaccharides may include starch, dextran, xantham gum, and galactomannan. Sources of these branched polysaccharides include, but are not limited to, corn, beans, asparagus, brussels sprouts, legumes, oats, flaxseed, dicots, grasses, coffee Ground and coffee bean film (coffee silverskin).

In some embodiments, polydextrose may include agarose, pullulan, and curdan.

In some aspects, products provided herein are made from materials disclosed herein and are readily formed into specified shapes, for example, whether planar or three-dimensional. For example, an example of a plane may be a planar sheet, where the planar sheet may be used to decompose to form the final product. In another example, the materials may be present in solution ready for use in forming the final product. In other embodiments, the three-dimensional instance may be the final product.

In one aspect, in some embodiments, the final product may include containers for edible or digestible items, such as those shown in Figures 5-7. For example, end products embodying the materials described in this application may include food containers or packaging. By way of example, and not limitation, food containers or packages may include airplane or airline meal containers, disposable cups, ready-to-eat food containers, capsules, ice cream boxes or containers, and chocolate containers. In some embodiments, the product may include a ready-to-eat container, such as instant noodles, ready-to-eat soup, etc., which may further contain flavors. In this case, for consumers to digest or consume items that are edible or digestible in containers embodying various aspects of the invention, the containers may be in contact with water or liquids at high temperatures (e.g., about 100 degrees Celsius). .

In some embodiments, aspects of the invention may be used in airline meal and beverage containers. Currently, airplane meal containers are made of various forms of plastic in order to have characteristics such as light weight, rigidity, and oil resistance. In addition, existing plastic containers can be heated in an oven. Heating may release carcinogens from plastic containers into edible or digestible items. Therefore, this effect is undesirable. The embodiments of the present invention and the above-mentioned characteristics can show characteristics such as waterproofing, high heat resistance, and oil resistance, but do not release carcinogens.

In some embodiments, an example of a capsule may be a capsule for a hot beverage machine. For example, the capsule may contain coffee, tea, herbs, or other beverages. For example, the capsule may be a disposable capsule. In another example, the capsule can be a disposable coffee pod or bag. In this case, the electric beverage machine can deposit or inject water into the capsule at high temperature or pressure to initiate the beverage making process, and the coffee can drip from the capsule or bag into the consumer's cup. Since the capsule or bag includes biodegradable and sustainable materials with one or more of the above-mentioned properties, the capsule or bag body can be easily recycled without burdening the environment.

In one embodiment, the capsule may have sidewalls approximately 500 microns thick. In one embodiment, the capsule may include a top or lid having a thickness of about 500 microns. In yet other embodiments, the capsule may include a base thickness of approximately 300 microns. In yet another embodiment, the capsules may be formed/produced in a single pass from a former (described below) with the top, side walls and bottom having different thicknesses.

In some embodiments, the product may include a filter to separate particles or molecules from the fluid, whether permanently, semi-impermeable, or slightly impermeable. For example, the product may include a mask or filter membrane with solid-liquid separation, liquid-liquid separation or gas-liquid separation effects, etc.

In some embodiments, products may include cosmetic or skin care container products, medical products such as compacts, palettes, protective glass, or medical-grade disposals. In some embodiments, products may include parts of medical devices, automobiles, electronic devices, and construction materials (as reinforced materials).

Generally speaking, in one embodiment, containers embodying the materials of the present invention may be in the form of containers, flat panels, trays, plates, reels, boards, or films. In this embodiment, the width or length of the material may range from about 0.01 mm to 10,000 mm or more. In one embodiment, the width or length may be between approximately 0.01 mm and 1000 mm. In embodiments where the film may be a thin film, its thickness may be about 0.01 to 3.0 mm. In one embodiment, the thickness may be about 0.02 mm to 0.20 mm. In still other embodiments, the product may include food packaging containing an oil to water weight ratio of about 100:1 to about 1:100.

In some embodiments, aspects of the invention may provide methods of manufacturing, producing, or producing materials comprising fibrillated cellulose having the properties described above. Example 1

In addition to the materials described above, aspects of the invention may include cellulose fibrillation processes or methods.

Referring now to Figure 8, a flowchart may illustrate a method for producing such a material according to one embodiment. In one embodiment, the examples shown below generally do not contain toxic chemical additives to improve the mechanical properties of the composite materials. For example, tear cellulose cardboard (approximately 3.0% by weight) into shreds, such as A4 size paper. The chopped pieces are thrown into a pulping machine (not shown in Figure 8). The pulping process can take about 20 minutes. Next, for example, refiner 802 may be used to begin the process. For example, the refiner 802 may be a homogenizer, a grinder, a chemical refining chamber/bath, a combination of mechanical and chemical fiber refining equipment, etc. In an embodiment, in the example of a grinder, the refiner 802 may include two grinding wheels facing each other. The separation or distance between the two grinding wheels can be adjusted depending on the desired end product. In some embodiments, surface grooves or patterns can be tailored to the desired end product. In this manner, the slurry suspension 806 is then fed into the refiner 802, optionally about 1-10 times. In other cases, the slurry suspension 806 may be fed to a refiner (not shown), such as a colloid mill, a double disk grinder, before entering the refiner 802 Before further refining the cellulose pulp.

In one embodiment, Figures 1a to 1d illustrate the state of fibrillated cellulose with increasing number of passes. For example, Figure la may represent an aqueous suspension of cellulosic fibers with 0 cycles or passes. In other words, at the levels of slurry suspension 806 shown in Figure 1a, the slurry does not fibrillate to achieve the quality and performance of aspects of the present invention.

In one embodiment, Figure Ib may show a post-refinement 808 where the slurry suspension 806 has passed through the refiner 802 after 1 pass. For example, mill product 808 may now include an aqueous suspension of fibrillated cellulose fibers. In another example, Figure 1c shows an image of ground material 808 that has passed through refiner 802 after 2 passes or 2 cycles. In one example, the fibrillated cellulose fibers in mill 808 are finer than the fibrillated cellulose fibers shown in Figure 1b. Figure 1d can show an image of the ground product 808 after 3 cycles/passes. In such embodiments, mill 808 may include fibrillated cellulose fibers that are finer than the fibers in Figure 1c.

In one example, different cellulose starting concentrations have been evaluated and tested. For example, the ground product 808 may include fibrillated cellulose and water, with a concentration of fibrillated cellulose of about 2.5 wt.% cellulose (and 97.5% water) and about 3.0 wt.% fiber. Vegetable, approximately 3.6 weight ratio of cellulose, and approximately 4.0 weight ratio of cellulose were tested and used.

For example, a cellulose concentration of about 2.5 weight to cellulose showed insufficient milling and the properties were not tested. In other words, a fibrillated cellulose fiber concentration of about 2.5% by weight, or even a general slurry suspension, is insufficient to achieve the properties of the aspects of the present invention. The fibrillated cellulose having mill product 808 of about 3.0, about 3.6, and about 4.0 weight ratios is designated herein in Figure 5 as L028, L029, and L030, respectively.

In one example, various properties of fibrillated cellulose were tested. For example, in Table 1, the mechanical, water vapor and gas permeability properties are shown. Table 1 fibrillated cellulose Approximate concentration of cellulose pulp Dry tensile strength (MPa) Dry tensile index (Nm/g) Wet tensile strength (MPa) Wet tensile index (Nm/g) Water vapor transmission rate , WVTR (g/m ² .h) Oxygen transmission rate , OTR (cm ³ / m ² 24h) 5%RH 50%RH L028 3.00% 86.89 ± 4.60 102.73 ± 5.70 7.24 ± 0.69 7.78 ± 0.72 918.96 0.0260 0.010 L029 3.60% 90.62± 4.55 95.20 ± 3.39 8.02 ± 2.00 5.54 ± 0.73 924.48 0.0243 0.0345 L030 4.00% 78.00± 5.72 91.63 ± 10.68 8.10 ± 1.62 6.45 ± 1.29 1013.76 1.002 0.350

In one embodiment, FIG. 2 can show a scanning electron microscope (SEM) image of fibrillated cellulose at a concentration of about 3 weight ratio. Example 2

In one example, instead of using the slurry solution obtained directly at mill 808 in Example 1 above, semi-processed cellulosic fibers can be obtained from the market. In this way, semi-processed cellulose fibers (eg, about 3 wt.%) are fed into the colloid grinder and ground for about 1 minute. Alternatively, the fibrillated cellulose fibers may be further processed in refiner 802.

In one example, Figure 3 can show the SEM image of semi-processed fibers after pulverizing them through the interbody for 1 minute. For example Table 2 shows the properties of different fibrillated celluloses from different sources. Table 2 fibrillated cellulose Dry tensile strength (MPa) Wet tensile strength (MPa) Oxygen transmission rate OTR (cc/m ² ·24h) Water vapor transmission rate WVTR (g/m ² .24h) Y 52.09 ± 7.75 6.99 ± 1.91 0.019 (5%RH) 0.011 (50%RH) 864.72 B 30.57 ± 3.64 2.01±0.29 - 1075.68 F 38.97 ± 2.29 3.43 ± 0.20 115.44 (5% RH) 92.98 (50% RH) 1094.4

For example, Figure 3 can show where a-b are SEM images of Y cellulose fibers in Table 2, and c-d are SEM images of B-cellulose fibers in Table 2.

In some embodiments, Figure 4 shows SEM images of semi-processed fibers after mechanical grinding for 1 cycle/time. For example, a-b in Figure 4 are for Y cellulose fibers, and c-d in Figure 4 are for B cellulose fibers.

In one aspect, the mixer 804 can provide a suspension of a slurry 806 of cellulose pulp in water, the suspension comprising a mixture of cellulose pulp in water, wherein the weight ratio of cellulose to water is from about 0.01 to 100. In some embodiments, the weight ratio may be about 0.03 to 0.10. In some embodiments, the grind 808 from the refiner 802 may be retained if it can be used for regrinding in the refiner 802 . For example, as mentioned above, the number of times the grind 808 passes through the refiner 802 may be 1-100. In some embodiments, the number of times or cycles may be further limited to 1-10.

In some embodiments, the weight ratio of fibrillated cellulose to water and/or the number of passes through the refiner 802 may be a function of the desired characteristics of the final product. For example, if the final product requires low water vapor transmission and low oxygen transmission, mill 808 may have a cellulose to water weight ratio of approximately 0.03-0.04, or 3-4% (as evidenced by L28b-L30b) and /or the number of passes may increase. In other embodiments, relatively low water vapor transmission and relatively low oxygen transmission may indicate a long storage life, while relatively high water vapor transmission and relatively high oxygen transmission may indicate a low storage life.

In one embodiment, ground material 808 may be processed through a former 810 . For example, the former 810 may generate an intermediate 818 of a desired material having fibrillated cellulose based on the mill 808 . For example, the weight ratio of fibrillated cellulose to liquid (eg, water) of intermediate 818 can be from about 0.001 to 99. In some embodiments, the ratio may be about 0.001 to 0.10. In one embodiment, the former 810 may include a mesh or a fibrous network. For example, the former 810 may include negative pressure and/or positive pressure, or any combination thereof. In one embodiment, the former 810 may apply pressure to separate the fibrillated cellulose from the liquid in the mill 808 to form the intermediate 818 . Due to the fibrillating nature of the fibrillated cellulose fibers and the process of passing through the refiner 802, as shown in the various SEM images in Figures 2-4 and 7, fibers with different lengths can form intermediate 818.

In some embodiments, a base layer 812 may be used with the mill 808 to form the intermediate 818 . In one embodiment, a GCM™ of aspects of the present invention may include a composite 816 having a substrate layer of slurry (eg, base layer 812) and a layer of fibrillated cellulose (eg, from mill 808). For example, the former 810 may subject the base layer 812 to a mesh, mold, or frame process to form a construct for the intermediate 818 . For example, base layer 812 may first be in the form of a solution or slurry of water and slurry materials. The mud can be in the trough and the net can be in the trough. Water in the tank can be removed or reduced by negative pressure, such as a vacuum, thereby forming a base layer 812 on the mesh.

Then, in one embodiment, the former 810 may include a sprayer or applicator for spraying or applying the mill 808 onto the base layer 812 to form the intermediate 818 . The grind 808 is impregnated with the base layer 812 based on the different sized fibers between the base layer 812 and the grind 808 . In one embodiment, the grind 808 may be applied or sprayed onto the surface of the intermediate 818 carrying the edible items. For example, assuming the final product is a bowl, grind 808 may be applied or sprayed onto the interior surface of the final product.

In one embodiment, the intermediate 818 may display a mesh or fiber network pattern on its outer surface, as shown at 502 or 504 .

In still other embodiments, the former 810 can spray the intermediate 818 onto a flat surface to dry or form in a natural process.

In some embodiments, a dryer 814 may be further provided to dry or dehumidify the intermediate 818. In one embodiment, the dryer 814 can provide drying conditions of 30 degrees Celsius to 200 degrees Celsius. In some embodiments, dryer 814 may include a heated surface, such as infrared heating. In some embodiments, microwave heating or air heating may be used without departing from the spirit and scope of the embodiments. In still other embodiments, dryer 814 may also be assisted by negative pressure and/or positive pressure. Example 3

In one example of a final product that may embody aspects of the present invention, a cellulose-based bowl was successfully produced using a combination of materials and methods previously described. In one embodiment, the functionality of the cellulose-based food container in this example can be used to demonstrate filling a typical edible oil into the container, as shown in Figure 5. In this example, cooking oil and cellulose-based food containers can be microwaved at 800 watts (W) for 4 minutes and observed for 10 days, as shown in Figure 5. In such an illustration, the container in Figure 5 may represent one made from fibrillated cellulose L28b, L29b, L30b and Y. In one embodiment, each example in Figure 5 can hold oil for about 10 days.

In some embodiments, another set of tests was also performed by placing instant noodles (after adding hot water to cook) into a container embodying a composite material according to an embodiment. Observations were recorded the next day. Figure 6A shows an example of a fibrillated cellulose structure in a container, such as a food container. For example, Figure 6A shows a series of images of fibrillated cellulose that was filled with boiling water and left for approximately 5 minutes.

In some embodiments, Figure 6B shows a series of images of fibrillated cellulose loaded with boiling water and microwaved at 800 watts for approximately 2 minutes.

Figure 7 is another image showing an SEM image of the structure of fibrillated cellulose in the food container of Figures 6A and 6B, according to one embodiment. Example 4

Referring now to Figures 9a-9c, images illustrate a film according to Example 4 of the embodiments.

In one embodiment, composite materials according to aspects of the invention may be in a transparent composite film based on fibrillated cellulose. In one example, a membrane can be prepared by dissolving fibrillated cellulose and pullulan powder in water to each produce a solution containing about 1% by weight of solute. In the polytridextrose powder dissolution, the powder can be gradually added to it, and the solution can be heated by a microwave oven at a power of 800W for 1 minute. In one embodiment, this process can be repeated about 4-5 times until a clear solution is formed.

In one embodiment, to produce a composite membrane, the ratio of fibrillated cellulose, such as mill 808, to polytriglycerol can be about 1:1, such as about 250 g of mill 808 (e.g., about 1% of fibrillated cellulose) can be mixed with approximately 250 g of polytrisaccharide solution to produce a solution with approximately 0.5% solute. Then, approximately 100 g of the mixed solution is poured onto a hydrophobic surface such as a silicone surface and allowed to dry at room temperature.

In some embodiments, the ratio of fibrillated cellulose to polytriglycerol can be 2:1, with 250 g of mill 808 (eg, about 2% fibrillated cellulose) and about 250 g of polytriglycerol. The tridextrose solution was mixed to produce a solution with approximately 1% solute. Then, about 100 g of the mixed solution is poured onto a hydrophobic surface such as a silicone surface and dried at 50°C for 12 hours.

As shown, Figures 9a to 9c can show images of cellulose-based films in which the ratios of fibrillated cellulose to polytriglycerol are a.) 0:1, b.) 1:1 and c. )2:1.

In one embodiment, the addition of polytriglycerol can enhance the film-forming process to smooth the surface of the film, in which a film made of fibrillated cellulose (eg, ground material 808), hereafter named L41b, is Highly wrinkled. However, other films with polytriglycerol provided a smoother and more uniform surface. In one embodiment, a membrane having a composite of fibrillated cellulose and polytriglycerol is generally immune to having an uneven surface.

In still other embodiments, the mechanical properties of the transparent composite film are as follows, in which the fibrillated cellulose is denoted as L41b and the polytrisaccharide is denoted as B.

Table 3 Characteristics of fibrillated cellulose membranes added with polytrisaccharide sample 100B L41b:B 1:1 L41b:B 1:1 L41b:B 2:1 L41b:B 1:1, 6% WSA Weight (g) 0.75 1 1g 1 Thickness (mm) 0.025 0.035 0.06 0.05 0.06 Dry tensile strength (MPa) - 33.54 ± 5.49 42.07 ± 11.13 50.055 ± 6.98 60.9 ± 5.17 Dry Young's modulus (MPa) - 1176.01 ± 1469.73 6062.55 ± 886.95 13481.95 ± 13055.80 8203.87 ± 588.09 Dry tensile index (MPa) (Nm/g) - 38.95 ± 5.58 39.94 ± 6.23 51.54 ± 8.07 54.73 ± 6.67 Wet tensile strength (MPa) NA NA NA 4.64 ± 1.11 Wet Young's modulus (MPa) NA NA NA 185.97 ± 228.53 Wet tensile index (Nm/g) NA NA NA 3.98 ± 0.81 OTR (cm ³ _/ m ² 24h) 5%RH 0.055 50%RH 0.137 WVTR (g/m ² h) 103.16 76.57 67.09 69.01 Example 5

Fibrillated cellulose with water repellent

In one embodiment, aspects of the present invention may include fibrillated cellulose with a water repellent. In one example, the mixture may contain the correct proportions of cellulose and water repellent and mixed using a mechanical mixer for 3 minutes. The mixture can be further diluted to 4000 mL and poured onto the former 810. In one aspect, the former 810 may apply negative pressure and/or positive pressure to produce a wet preform with a dryness of 25-35%. The mechanical properties and barrier properties of the mixtures can be shown in Table 4.

Table 4 illustrates the properties of fibrillated cellulose membranes with different waterproofing agents Sample name M055+10% palm wax M055+20% palm wax M055+10% Canola oil Weight (g) 5g GCM™+0.5g wax 5g GCM™+1g wax 5g GCM™+0.5g oil Thickness (mm) 0.156 0.168 0.154 Dry tensile strength (MPa) 78.96 ± 26.68 76.215 ± 14.75 86.47 ± 4.8 Dry Young's modulus (MPa) 7611.49 ± 788.28 7485.75 ± 332.20 8045.41± 742.03 Dry tensile index (Nm/g) 88.85 ± 27.80 86.69 ± 21.71 96.34 ± 2.72 Wet tensile strength (MPa) 11.14 ± 2.48 15.10 ± 2.29 9.03 ± 1.48 Wet Young's modulus (MPa) 1258.27 ± 203.63 1720.10 ± 407.88 949.51 ± 61.29 Wet tensile index (Nm/g) 12.10 ± 2.27 16.82 ± 2.81 9.69 ± 1.52 GTR (cm ³ /m ^{2 ·} 24h · atm) 0%RH 75.88 50%RH 4701.98 OTR (cm ³ /m ^{2 ·} 24h) 5%RH 0.047 0.104 0.009 50%RH 0.044 0.022 0.040 WVTR (g/m ² · 24h) 614.4 411.6 905.52

Overall, aspects of the present invention overcome the shortcomings of existing solutions where toxic chemicals (eg, fluorinated polymers and their derivatives) are added. Various aspects of the present invention also overcome the shortcomings of existing solutions that use slurry as the base layer or multiple layers. It is understood that the diameter of pulp fibers is between 10 and 50 micrometers (µm). However, aspects of the invention have smaller dimensions, such as in the sub-1 µm range.

The above description is illustrative and not restrictive. Many variations of the embodiments may become apparent to those of ordinary skill in the art upon reviewing this disclosure. Therefore, the scope of the embodiments should not be determined with reference to the above description, but should be determined with reference to the full scope or equivalent scope of the claimed patent scope.

One or more features of any embodiment may be used in combination with one or more features of any other embodiment without departing from the scope of the embodiment. The words "a", "an", or "the" are intended to mean "one or more" unless expressly stated to the contrary. The words "and/or" are intended to have the most inclusive meaning of that term, unless expressly stated to the contrary.

While the disclosure may be embodied in many different forms, the drawings and discussion are provided with the understanding that the disclosure is embodying the principles of one or more inventions and are not intended to limit any one embodiment to the illustrated embodiment. Provided.

This disclosure provides a solution to the long-term needs described above. In particular, aspects of the present invention overcome the challenges of existing practices that rely on the use of chemical formulations to provide enhanced properties to cellulosic materials.

Further advantages and modifications of the systems and methods described above will readily occur to those of ordinary skill in the art.

Therefore, the present disclosure in its broader aspects is not limited to the specific details, representative systems and methods, and illustrative examples described above. Various modifications and changes may be made to the above description without departing from the scope or spirit of this disclosure, and this disclosure shall cover all such modifications and changes, provided that these modifications and changes fall within the scope of the following patent applications and their equivalents range.

802: Refining machine 804:Mixer 806: Slurry suspension 808:Grinder 810:former 812: Grassroots 814: Dryer 816:Composite materials 818:Intermediate

Those with ordinary skill in the art will appreciate that the components in the drawings are for simple and clear explanation, so not all connection methods and options may be shown. For example, common but well-known elements that are useful or necessary in a commercially feasible embodiment are often not described in order to present a less obstructed view of the various embodiments of the present disclosure. It will be further understood that certain actions and/or steps may be described or described in a specific order of occurrence, and one of ordinary skill in the art will understand that such specificity with respect to order is not actually required. It is also understood that the terms and expressions used herein are defined with respect to their respective fields of inquiry and study, unless a specific meaning is otherwise specified herein.

Figures 1A-1D show an aqueous suspension of cellulosic fibers according to one embodiment.

Figure 2 is a scanning electron microscope (SEM) image of a material with fibrillated cellulose (3 wt.%) according to one embodiment.

3A to 3D are scanning electron microscope (SEM) images of semi-processed cellulose fibers according to one embodiment, where a-b are SEM images of Y cellulose fibers and c-d are SEM images of B cellulose fibers.

Figures 4A to 4D are SEM images of mechanically grounded semi-processed fibers according to one embodiment, where a-b are Y cellulose fibers and c-d represent B cellulose fibers.

Figure 5 shows images of containers made from fibrillated cellulose L28b, L29b, L30b and Y capable of storing oil for 10 days according to one embodiment.

Figure 6A shows an image of food containing boiling water in the material for approximately 5 minutes, according to one embodiment.

Figure 6B is an image showing food and boiling water heated in a microwave at 800 watts for 2 minutes according to one embodiment.

Figure 7 is another SEM image of a structural material of fibrillated cellulose used in food containers according to one embodiment.

Figure 8 is a flowchart of a method of generating materials according to one embodiment.

Figure 9 depicts three images showing a film according to one embodiment.

802: Refining machine

804:Mixer

806: Slurry suspension

808:Grinder

810:former

812: Grassroots

814: Dryer

816:Composite materials

818:Intermediate

Claims (18)

A biodegradable food material comprising: a composite material containing fibrillated cellulose with independently derived plant fibers, the composite material having dry strength, enhanced oil resistance, gas and/or liquid impermeability , dry tensile modulus, or dry tensile index, and the composite material generally does not contain toxic chemical additives, strength enhancers, oligomers, carboxylic acids, plasticizers, antibacterial agents, waterproofing agents or transparent composite materials to improve Dry strength, enhanced oil resistance, gas and/or liquid impermeability, dry tensile modulus, or dry tensile index; wherein the composite material includes the following dry strength, enhanced oil resistance, gas and/or liquid Properties of impermeability, dry tensile modulus, or dry tensile index: less than about 8000 cubic centimeters per square meter per 24 hours (cm ³ m ^{-2 24h -1 ) oxygen transmission rate; less than about 8000 cubic centimeters per square meter per 24 hours (cm 3 m -2} 24h ^-1 ); less than about A water vapor transmission rate of 3000 grams per square meter per 24 hours (gm ^-2 24h ^-1 ); a dry tensile strength of at least about 30 MPa; a dry tensile modulus of at least about 4 GPa; or a dry tensile modulus of at least about 45 Nm g ^-1 Dry tensile index; wherein the composite material includes fibrillated cellulose having a diameter of about 1 to 10,000 nanometers. The biodegradable food material as claimed in claim 1, wherein the composite material includes fibrillated cellulose with different diameters in a weight ratio of 1:100 or 1:50. The biodegradable food material of claim 1, wherein the composite material includes fibrillated fibers with a length of about 0.1 to 1000 microns, about 10 to 500 microns, about 1 to 25 microns, or about 0.2 to 100 microns. white. The biodegradable food material of claim 1, wherein the composite material further includes the following properties: a wet tensile strength of at least about 5 MPa; a wet tensile modulus of at least about 0.4 MPa; and at least about 5 Nm g ^-1 wet stretch index. The biodegradable food material as claimed in claim 1, wherein the composite material is a flat plate. The biodegradable food material of claim 1, wherein the composite material includes a container for edible items. The biodegradable food material as claimed in claim 1, wherein the composite material includes a fibrillated cellulose mixture. The biodegradable food material of claim 1, wherein the composite material includes a film with a thickness of about 0.01 to 3.0 millimeters (mm). The biodegradable food material as claimed in claim 5, wherein the length of the flat plate is from 0.01 mm to 10,000 mm. A biodegradable material comprising: a composite containing fibrillated cellulose with independently derived plant fibers, the composite having the following wet strength, enhanced oil resistance, gas and/or liquid impermeability, Wet tensile modulus, or wet tensile index, and the composite generally does not contain toxic chemical additives, strength enhancers, oligomers, carboxylic acids, plasticizers, antimicrobials, water repellents or transparent composites to improve wet Tensile strength, enhanced oil resistance, gas and/or liquid impermeability, wet tensile modulus, or wet tensile index; wherein the composite material contains the following wet resistance, enhanced oil resistance, gas and/or liquid Impermeability, wet tensile modulus, or wet tensile index properties: less than about 8000 cubic centimeters per square meter per 24 hours (cm ³ m ^-2 24h ^-1 ) oxygen transmission rate; less than about 3000 A water vapor transmission rate in grams per square meter per 24 hours (gm ^-2 24h ^-1 ); a wet tensile strength of at least about 5 MPa; a wet tensile modulus of at least about 0.4 MPa; or at least about 5 Nm g ^-1 Wet tensile index; wherein the composite material includes fibrillated cellulose having a diameter of about 1 to 10,000 nanometers. The biodegradable material of claim 10, wherein the composite material further includes the following additional properties: a dry tensile strength of at least about 30 MPa; a dry tensile modulus of at least about 4 GPa; or a dry tensile modulus of at least about 45 N mg ^-1 Dry tensile index. The biodegradable material of claim 10, wherein the composite material includes fibrillated cellulose with different diameters in a weight ratio of 1:100 or 1:50. The biodegradable material of claim 10, wherein the composite material includes fibrillated cellulose with a length of about 0.1 to 1000 microns, about 10 to 500 microns, about 1 to 25 microns, or about 0.2 to 100 microns. . The biodegradable material of claim 10, wherein the composite material includes a flat plate. The biodegradable material of claim 14, wherein the length of the flat plate is from 0.01 mm to 10,000 mm. The biodegradable material of claim 10, wherein the composite material includes a fibrillated cellulose mixture. The biodegradable material of claim 10, wherein the composite material includes a film with a thickness of approximately 0.01 to 3.0 millimeters (mm). The biodegradable material of claim 10, wherein the composite material includes a container for edible items.