TW202202694A - Method, apparatus, and system of a fibrillated nanocellulose 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, water, or oil, etc.,) can be improved substantially. Another embodiment of the invention further provide an automated equipment for creating a fibrillated cellulose composite material that include properties of being a strength-enhancing agent, an oligomer, carboxylic acid, plasticizer, an antimicrobial agent, water repellant, and/or a transparent composite.

Description

Method, apparatus and system for fibrillating nanocellulose materials

Aspects of the present invention generally relate to renewable and recyclable materials. More specifically, embodiments of the present invention relate to pure cellulosic materials in relation to consumer products.

Growing concern over the environmental crisis - plastic waste pollution - has sparked a wide-ranging investigation into sustainable and renewable materials. To circumvent petroleum-derived polymers, a natural biopolymer, plant-based cellulose fibers, offers an alternative to the materials research community. Cellulosic fibers are gaining more and more attention due to their ubiquitous origin, sustainable, renewable and, more importantly, it provides 100% ambient biodegradability to the final product.

However, many existing biodegradable products based on cellulose fibers have not lived up to expectations. For example, the cost of producing these cellulosic fiberized products is economically disadvantageous for large-scale production. Additionally, many cellulosic fiber products rely heavily on high proportions of synthetic chemical components to achieve these properties or effects due to the need for water resistance, oil resistance, or non-stick properties. For example, many existing products require a surface coating of a fluorocarbon in the pores of a food or beverage item. Additionally, some of these fluorocarbon-based chemicals, such as perfluorooctane sulfonic acid (PFOA or C8), can cause long-term negative health and environmental effects.

Embodiments of the present invention overcome the shortcomings of the prior art by injecting the form of cellulose fibrillation to improve the properties of the cellulose pulp. For example, these properties may include mechanical and barrier properties, ie tensile strength, liquid (eg water, oil or sauce) and gas (eg oxygen or carbon dioxide) impermeability are greatly improved.

Another embodiment of the present invention further provides fibrillated cellulose composites having properties including reinforcing agents, oligomerizing agents, carbohydrates, plasticizers, antimicrobial agents, water repellants and/or transparent composites.

EMBODIMENTS The accompanying drawings, which form a part hereof, may now be described more fully in the accompanying drawings, by way of which specific exemplary embodiments may be practiced. These drawings and exemplary embodiments may provide an understanding that this disclosure is an exemplification of the principles of one or more embodiments and should not be used to limit any described embodiments. 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 scope of the embodiments to Any techie in art. Therefore, the following detailed description should not be taken in a limiting sense.

Embodiments of the present invention include a material, such as a green composite material (GCM), which may include fibrillated cellulose, typically free of chemical additives or formulations, independently derived from plant fibers. In one embodiment, the chemical augmentation or formulation may be natural based. In another embodiment, the chemical additives or formulations may be laboratory manufactured. In some embodiments, the plant fibers may be derived from bagasse, bamboo, abaca, shisha, hemp, flax, hops, jute, king sword, palm, corn, cotton, wood or agricultural wastes thereof and any of the above combination. In other embodiments, the vegetable fibers may be pre-processed or semi-processed cellulose. In other embodiments, the green composite material with fibrillated cellulose is obtained by processing the plant fibers through a high pressure homogenizer or a mechanical mill. In a further embodiment, the composite material with fibrillated cellulose (cellulose without microorganisms) is obtained by bacterial strains. In alternative embodiments, the fibrous cellulosic material may be obtained from marine sources.

In one implementation, the shape and size of the cellulose may depend on the source of the fibers or the combination of fibers and the manufacturing process. Nonetheless, fibrillated cellulose generally has diameters and lengths, as described below. The fibrillated cellulose, in one embodiment, may have a diameter of about 11 to 5000 micrometers (nm). In another embodiment, the cellulose may have a diameter of about 5 to 150 microns or from about 100 to 1000 microns.

In further implementations, the material may have enhanced properties, enhancing, enhancing or improving various properties without the need for chemical additives or formulations. In another embodiment, materials with various properties are suitable for carrying food or liquid items that are generally free of chemical fats or preparations. For example, as shown in the prior art, various chemicals or additives are used in the manufacturing process or applied to composite materials to provide the desired tensile strength, whether dry or wet, enhanced oil resistance, gas and/or liquid resistance Impermeability. Rather than utilizing various chemical additives or agents added to the material, various aspects of the present invention include a composite material and fibrillated cellulose free from the use of these additives.

For example, the length of the cellulose may be 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, cellulose with cellulose of different diameters, such as materials in a weight ratio of 1:100. In another embodiment, the weight ratio of cellulose is 1:50. In further embodiments, the hybrid cellulosic material may have the advantages of increased tensile strength, dry or wet, enhanced oil resistance, gas and/or liquid impermeability, and cost savings.

In some embodiments, the fiberized cellulosic material may have an oxygen transmission rate of about 8000 cm3 per square foot per 24 hours or less. In another embodiment, the oxygen penetration rate is about equal to or less than 5000 cm3 per square foot per 24 hours. In another embodiment, the oxygen penetration rate is approximately equal to or less than 1000 cm3 per square foot per 24 hours.

Additionally, in some embodiments, the material may have the property of a water vapor transmission rate of about equal to or less than 3000 grams per square foot per 24 hours or less. Additionally, for another embodiment, the water vapor transmission rate may be approximately equal to or less than 1500 grams per square foot per 24 hours.

In some embodiments, the material may have a dry tensile strength of about 30 megapascals (Mpa) or more. In another embodiment, the dry tensile strength can be about 70 MPa. In another embodiment, the dry tensile strength can be about 100 MPa or higher. In some embodiments, the material may be characterized by a dry tensile modulus of about 4 gigaPascals (Gpa) or more. In another embodiment, a dry tensile modulus of about 6 gigaPascals or more.

In some embodiments, the material may have a dry tensile index characteristic of about 45 Nmg ⁻¹ or more. In another embodiment, the characteristic may be about 80 Nm g ^-1 or higher.

In some embodiments, the material may have a wet tensile strength of about 5 MPa or more. In another embodiment, 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 another embodiment, the wet tensile modulus can be about 1.0 MPa or higher.

In some embodiments, the material may have a wet stretch index characteristic of about 5 Nm g ^-1 or higher. In another embodiment, the wet stretch index may be about 20 Nmg ^-1 or higher.

In another embodiment, the material may include a binder to improve dry and/or wet strength. In one embodiment, the adhesive may comprise a polymer. In other embodiments, the binder may include a metal salt. In another embodiment, the binder may include an oligomeric agent. In other embodiments, the binder may include carbohydrate acids. In other embodiments, the adhesive may include a plasticizer. In some embodiments, the weight ratio of cellulose to binder in the present invention may be around 33:1 to 1:1.

For example, the polymer may include polyester, gelatin, polylactic acid, erythrine, sodium alginate, thermoplastic starch, polyethylene, formic acid, formic acid gum, polyvinyl alcohol, or polypropylene.

In another embodiment, the binder may include a metal salt. For example, metal salts may include potassium carbonate, potassium aluminum sulfate, calcium carbonate, and calcium phosphate. In some embodiments, the weight ratio of cellulose to binder in the present invention may be around 33:1 to 1:1.

In another embodiment, the binder may include an oligomeric agent. In one example, oligomers may include oligonucleotides, oligopeptides, and polyethylene glycols. In some embodiments, the weight ratio of cellulose to binder in the present invention may be around 33:1 to 1:1.

In other embodiments, the binder may include carbohydrate acids. For example, carbohydrate acids may include citric acid, sour acid, and glutamic acid. In some embodiments, the weight ratio of cellulose to binder in the present invention may be around 33:1 to 1:1.

In an embodiment, the adhesive using a plasticizer can reduce the brittleness and gas permeability of the adhering composite. In some embodiments, the plasticizer may include a polyalcohol. In one embodiment, the polyol may include glycerol. In one embodiment, the polyol can include sorbitol. In one embodiment, the polyol may include penta alcohol. In some embodiments, the polyalcohol can include polyethylene glycol. In some embodiments, the weight ratio of plasticizer to composite to binder is about 5:33:1 to about 1:1.

In another embodiment, plasticizers may include branched polysaccharides, waxes, fatty acids, fats and oils.

Aspects of the present invention may further include a water repellant as a chemical additive to repel gas and/or liquid water. In some embodiments, the water repellent includes animal wax, animal oil, or animal fat. In one embodiment, the water repellent includes a petroleum derived wax or a petroleum based wax. In other embodiments, the water repellent includes vegetable wax, vegetable oil or vegetable fat.

In some embodiments, animal water repellents may include beeswax, shellfish, and whale oil.

In some embodiments, petroleum-based wax water repellents can include paraffin, paraffin, and mineral oil.

In some embodiments, the vegetable water repellent can include palm wax, soybean oil, palm oil, palm wax, palm wax, and coconut oil.

In some embodiments, the water repellent may include binders such as potassium carbonate, potassium sulfate, calcium carbonate, and calcium phosphate.

In further embodiments, the material may comprise fibrous cellulose further optionally, may comprise an antimicrobial agent. In some embodiments, the antibacterial agent can include tea polyphenols. In some embodiments, the antibacterial agent can include phenylacetonate, para-hydroxybenzoic acid, para-hydroxybenzoic acid, quaternary ammonium salts, acetamide, benzoic acid, and potassium sorbate.

In addition, another embodiment of the present invention may include a material having fibrillated cellulose, which may further optionally include a transparent composite material to increase the transmission of wavelengths of light from about 300 microns to 800 microns. In some embodiments, the material may include branched polysaccharides. In some embodiments, the weight ratio of material to transparent composite varies, which may depend on the desired clarity, for example, from about 99:1 to about 1:99.

In some embodiments, branched polysaccharides can include starch, polysaccharides, and galakmannan.

In some embodiments, a glucan may include Argans, Raoulan, and Jiang Dan.

In certain aspects, the products provided herein are fabricated from the materials disclosed herein and readily form a given shape, eg, planar or three-dimensional. For example, a two-dimensional example could be a flat plate, where the flat plate can be used to break down to form the final product. In another embodiment, the material is soluble in a liquid ready for use in forming the final product. In another embodiment, the three-dimensional embodiment (ie, stereo) may be the final product.

In one aspect, in certain embodiments, the final product may include a container of edible or digestible items, as shown in FIGS. 5-7 . For example, end products embodying the materials described in this embodiment may include food containers or packaging. Food containers or packaging 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 an instant container, such as instant noodles, instant soup, etc., that may further contain flavors. In this case, for the consumer to digest or eat the edible or digestible item placed in the container of various aspects of the present invention, the food may be placed in the case of water or liquid at high temperature (eg, about 100 degrees Celsius). Invented container.

In another embodiment, for products that can use airplane meal and beverage containers. At present, airplane meal containers are made of various forms of plastic, which are lightweight, suitable for hardness, and oil-resistant. In addition, existing plastic containers can be heated by an oven. However, heating may release carcinogens from plastic containers into edible items. Therefore, this should be avoided as much as possible. The embodiments of the present invention and the above-mentioned characteristics can exhibit characteristics such as water resistance, heat resistance, oil resistance, etc., but do not release carcinogens.

In another embodiment, the capsule example may be a coffee capsule. For example, coffee capsules may be disposable capsules. In another example, the coffee capsules may be disposable coffee bags or bags. In this case, the electric coffee maker may deposit or infuse hot water into the capsule at high temperature or pressure in order to initiate the coffee making process, and the coffee may drip from the capsule or bag into the consumer's cup. Since the capsule or pouch comprises a biodegradable and sustainable material having one or more of the above properties, the capsule or pouch body is easy to recycle without burdening the environment.

In one embodiment, the capsule may have sidewalls with a thickness of about 500 microns. In one embodiment, the capsule may include a top or lid with a thickness of about 500 microns. In yet another embodiment, the capsule may include a bottom thickness of about 300 microns. In yet another embodiment, the capsule may be formed with the mold during the mold-forming process (discussed below), and the top, sidewall and bottom thicknesses have different thicknesses.

In some embodiments, the product may include a filter to separate, whether permanent, semi-impermeable, or slightly impermeable to particles or molecules in the fluid. 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, the products may include cosmetic or skin care container products, medical products such as powder cartridges, palettes, protective glass, or medical grade treatments. In some embodiments, products may include medical devices, automobiles, electronic equipment, and building materials (as part of reinforcement materials).

In general, in some embodiments, the container embodying the materials of the present invention may be a container, flat sheet, tray, sheet, reel, sheet, or film. In such embodiments, the width or length of the material may be between about 0.01 millimeters and 10,000 millimeters or more. In one embodiment, the width or length may be between about 0.01 mm and 1000 mm. In embodiments, the film may be a thin layer film having a thickness of about 0.01 to 3.0 millimeters. In one embodiment, the thickness may be around 0.02 mm by 0.20 mm. In other embodiments, the present case may also be a food package, and the product may include an oil-to-water weight ratio of about 100:1 to about 1:100.

In another embodiment, aspects of the present invention may provide materials for the manufacture, generation or manufacture of cellulose having the properties described above. Example 1

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

Referring now to FIG. 8, a flow diagram may illustrate a method for creating such a material according to one embodiment. For example, cellulose cardboard (about 3.0 wt%) is torn into pieces, such as A4 size paper. The chopped pieces are thrown into a pulper (not shown in Figure 8). The pulping process may take about 20 minutes. Next, for example, mechanical grinder 802 may be used to begin the process. For example, mechanical grinder 802 may be a homogenizer. In one embodiment, the mechanical grinder 802 may include two grinding wheels facing each other. The separation or distance between the two grinding wheels can be adjusted according to the desired end product. In another embodiment, the surface grooves or patterns can be adjusted according to the desired end product. As such, the pulp suspension 806 is then fed into a mechanical mill, optionally for about 1-10 times or so. In other cases, the pulp suspension 806 may be fed to a refiner (not shown), eg, a colloid mill, a twin-disc refiner, to further refine the cellulose pulp prior to entering the mechanical mill 802.

In one embodiment, Figures 1a to 1d show the state of fibrillated cellulose with increasing number of passes. For example, Figure 1a may represent an aqueous suspension of cellulosic fibers with 0 cycles or passes. In other words, as shown in Figure 1a, the content of pulp suspension 806 can reach 100%. In Figure 1a, the pulp is unable to form fibrillation to achieve the quality and performance of various aspects of the present invention.

In one embodiment, Figure lb may show a milled product 808, wherein the pulp suspension 806 has passed through the mechanical mill 802 after 1 pass. For example, the milled product 808 may now comprise an aqueous suspension of fibrillated cellulose fibers. In another example, Figure 1c shows an image of the milled product 808 that has passed through the mechanical mill 802 after 2 cycles or 2 cycles. In one example, the fibrillated cellulose fibers in the milled product 808 are thinner than the fibrillated cellulose fibers shown in Figure lb. Figure Id may show an image of the milled product 808 after 3 cycles/pass. In such an embodiment, the milled product 808 may comprise finer fibrillated cellulose fibers than the fibers in Figure 1c.

In other embodiments, at different fibrillated cellulose fiber concentrations, the fibrillated cellulose is about 2.5 weight percent (wt.%), about 3.0 weight percent (wt.%), about 3.6 weight percent (wt.%), About 4.0 weight ratio (wt. %) was tested and used. For example, about 2.5 weight percent (wt. %) of fibrillated cellulose showed insufficient grinding by grinding, so the relevant properties or characteristics were not tested. Whereas L028, L029 and L030 in Figure 5 show that cellulose is referred to as its cellulose at about 3.0 weight ratio (wt.%), about 3.6 weight ratio (wt.%) and about 4.0 weight ratio (wt.%), respectively .

In one example, various properties/properties of cellulose were tested. For example, in Table 1, properties for mechanical, water vapor and gas permeability are shown. Table 1 fibrous cellulose Approx. cellulose pulp concentration 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% 90 ± 5 105 ± 6 10 ± 2 10 ± 3 920 0.1 0.010 L029 3.60% 90±5 100 ± 4 8 ± 2.00 6 ± 2 925 0.1 0.1 L030 4.00% 80±6 95 ± 15 8 ± 2 7 ± 2 1015 1 0.500

Figure 2 additionally illustrates a scanning electron microscope (SEM) image of fibrillated cellulose at a concentration of approximately 3 weight percent (wt. %). Example 2

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

Figure 3 shows a scanning electron microscope (SEM) image of a semi-processed fiber through impact milling for 1 minute in another example. For example Table 2 shows the properties of different fibrillated celluloses from different sources. Table 2 fibrous cellulose Dry Tensile Strength (MPa) Wet tensile strength (MPa) Oxygen transmission rate OTR (cc/m2×24h) Water Vapor Transmission Rate WVTR (g/m2.24h) 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

Figure 3 illustrates that a-b in Table 2 are SEM images of Y-cellulose fibers, and c-d are SEM images of B-cellulose fibers.

In another example, Figure 4 shows an SEM image of a semi-processed fiber after 1 pass grinding with a mechanical grinder. For example, Figures 4a-b are for Y cellulose fibers and Figures 4c-d are for B cellulose fibers.

In one aspect, mixer 804 may provide a suspension of cellulose pulp in water pulp 806 comprising a mixture of cellulose pulp in water with a weight ratio of cellulose to water of about 0.01 to 100. The ratio can be about 0.03 to 0.10. In some embodiments, the milled product 808 from the mechanical grinder 802 may be retained if it can be reused for grinding by the mechanical grinder 802 . For example, as described above, the number of passes through the milled product 808 through the mill 802 may be 1-100. In another embodiment, the number of passes or cycles may be further limited to 1-10.

In another embodiment, the weight ratio of cellulose to water and/or the number of passes through the mechanical grinder 802 may be a function of the desired properties of the final product. For example, if the final product requires low water vapor transmission and low oxygen transmission, the initial mixture 806 may have a weight ratio of cellulose to water close to 0.1 or the number of times may be increased. In another example, relatively low water vapor transmission and relatively low oxygen transmission may indicate a higher shelf life, while relatively high water vapor transmission and relatively high oxygen transmission may indicate a lower shelf life.

In one embodiment, milled product 808 may be processed by shaper 810 . For example, the former 810 may generate the intermediate texture 818 with the desired material of fibrillated cellulose based on the milled product 808 . For example, the weight ratio of fibrillated cellulose to liquid (eg, water) of the intermediate material 818 may be about 0.001 to 99. In another embodiment, the ratio may be about 0.001 to 0.10. In one embodiment, the former 810 may comprise a mesh or fiber web. For example, shaper 810 may include negative 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 milled product 808 to form the intermediate material 818 . Due to the fibrillating nature of the fibrillated cellulose fibers and the process of passing through the mechanical mill 802, fibers having different lengths can form the intermediate material 818, as shown in the various SEM images in FIGS. 2-4 and 7 .

In another embodiment, the base layer 812 may be used to form the intermediate material 818 . In one embodiment, the GCM of aspects of the present invention may include having a pulp layer (eg, base layer 812 ) and a fibrillated cellulose layer (eg, from post-milling 808 ). For example, former 810 may subject base layer 812 to a mesh or frame to form a configuration for intermediate material 818 . For example, the base layer 812 may first be in the form of a solution or syrup of water and pulp material. The mud can be in the trough, and the mesh can also be in the trough. By negative pressure, such as a vacuum, water from the tank can be removed or reduced to form a base layer 812 on the grid.

Subsequently, in one embodiment, the shaper 810 may include a sprayer or applicator for spraying or applying the milled product 808 onto the base layer 812 to form the intermediate material 818 . With fibers of different sizes between the base layers 812 in the after mill 808, the post grinder 808 is injected into the base layer 812. In one embodiment, a milled product 808 may be applied. Or spray on the surface of the intermediate material 818 with edible items. For example, assuming the final product is a bowl, the milled object 808 may be applied or sprayed onto the inner surface of the final product.

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

In another embodiment, the former 810 may apply the intermediate material 818 to a flat surface, formed by a dry or natural process.

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

In one example of a final product that may embody various aspects of the present invention, a cellulose-based bowl was successfully produced using a combination of the previously described materials and methods. In one embodiment, the functionality of the cellulose-based food container in this example can be used to demonstrate filling of a typical edible oil into the container, as shown in FIG. 5 . In this example, edible oil and cellulose food containers can be heated in a microwave oven with 800 watts of electricity for 4 minutes and observed for 10 days, as shown in Figure 5. In such a figure, the container in Figure 5 may be represented by cellulose L28b, L29b, L30b and Y. In one embodiment, each of the embodiments in Figure 5 can carry the oil for about 10 days. In another embodiment, the final product can be heated to a maximum of 260 degrees Celsius in an oven environment, or raw rice can be cooked in a steamer, etc.

In another embodiment, another set of tests was also performed on the composite material according to one embodiment by adding instant noodles (after cooking also with hot water) into a container. The observations were recorded the next day. An example of a cellulosic structure in a container, such as a food container, is shown in Figure 6A. For example, Figure 6A shows a series of images of fibrillated cellulose, allowing the instant noodles themselves to sit in the container for about 5 minutes.

In another example, Figure 6B shows a series of images of cellulose loaded with boiling water and fibrils heated in an 800 watt electric microwave oven, and the instant noodles themselves were left in the container for about 2 minutes.

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

Referring now to Figures 9a to 9c, images show a film of Example 4 according to an embodiment.

In one embodiment, the composite material according to aspects of the present invention may be in a fibrillated cellulose based transparent composite film. In one example, membranes can be prepared by dissolving fibrillated cellulose and pullulan powders in water to produce solutions containing about 1 weight percent (wt. %) of the solute, respectively. In the pullulan powder dissolution, the powder may be gradually added thereto, and the solution may be heated by a microwave oven at 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 film, the ratio of fibrillated cellulose, such as milled 808 to amylopectin can be about 1:1, eg, about 250 g of milled (eg, about 1% of fibrillated cellulose is mixed with about 250 g of amylopectin solution to produce a solution with about 0.5% solute. Then, about 100 g of the mixed solution is poured onto a hydrophobic surface such as a silicone surface and dried at room temperature.

In another embodiment, with a 2:1 ratio of fibrillated cellulose to amylopectin, 250 g of ground product 808 (eg, about 2% fibrillated cellulose) can be mixed with about 250 g of amylopectin The amylose solutions were mixed to produce a solution of about 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 the picture shows. Figures 9a to 9c can show images of cellulose based films with a ratio of fibrillated cellulose to amylopectin. ) 0:1, b. ) 1:1 and c. ) 2:1.

In one embodiment, the addition of amylopectin can enhance the film-forming process to smooth the surface of the film, wherein the film height of a film made of fibrillated cellulose (eg, hereinafter referred to as after-milling 808 ) increases wrinkle. While other films with pullulan provided smoother, more uniform surfaces. In one embodiment, a film having a composite of fibrillated cellulose and amylopectin can generally be free of uneven surfaces.

In another embodiment, the mechanical properties of the transparent composite film are shown below, wherein the fibrillated cellulose is designated as L41b and the amylopectin is designated as B.

Table 3 shows the properties of pullulan-added fibrillated cellulose films. 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 invention may include fibrillated cellulose having water repellency. In one example, the mixture may contain the correct proportions of cellulose and hydrophobic agent and agitated for 3 minutes using a mechanical stirrer. The mixture can be further diluted to 4000 mL and then poured onto mold 810. In one aspect, the former 810 may apply negative and/or positive pressure to produce wet preforms with a dryness of 25-35%. The mechanical properties and barrier properties of the mixtures are shown in Table 4.

Table 4 illustrates the properties of fibrillated cellulose films with different water repellents. sample M055+10% Carnauba wax M055+20% Carnauba 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 (MPa) (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

In addition, the above embodiments can be fabricated using the apparatus shown in FIGS. 10A to 13 . From the schematic diagram of Fig. 10A, the 1000 element can be regarded as a container. After loading the pulp, the vacuum principle is used to absorb the paper fibers on the 1001 from the water tank containing the pulp. For example, 1001 includes a fiber joint or mold, for example, the fiber joint can be a net body, because the paper fibers of the water tank will stay in the net body, and the liquid will pass through the net body. The vacuum principle includes firstly extracting and discharging the water in the water tank, and then allowing the vacuum environment to be densely adsorbed on the 1001 element to make the first material. The product is then rotated 180 degrees and then the vacuum device is used to remove water. .

In another embodiment, the device 1004 can be connected with the 1002 element, and the device 1004 can move its vacuum adsorption function up, down, left and right, and the device can install and configure its 1002 element, and use the 1002 to adsorb the material left on the 1001. As shown in Figures 10A and 10B, elements 1002 and 1004 can be moved to a third element or water removal device. The 1002 has a rotating function that can turn the mold down or up to remove water. In addition, the arrangement of the present invention does not require linear arrangement or alignment of the arrangement elements 1000, 1002, 1004, 1006, and 1008. Since the element 1004 can move in multiple directions, the elements 1000, 1006 or 1008 can be arranged in relative positions such as circle, triangle, above and below. Additionally, the 1004 element may comprise a robotic arm or device for movement. In another embodiment, the element 1004 can be moved manually, by means of mechanical or rail assistance, etc. to 1006 or 1008. 1004 can transfer products in one or more groups.

Single Process: Second material is received through 1002 and 1004, from one embodiment, the second material is effectively added to the first material by elements 1002 and 1004. For example, the second material can be joined to the first material through the 1006 element, and as in the above example, the first and second materials are intimately mixed into a third material. In another embodiment, the third material exhibits different layers of the first material and the second material.

Multi-position process: 1001 and 1000 can accept the first material, 1001 and 1006 can accept the second material, this system can produce two products at the same time, and then use 1002 and 1004 to transfer the material to the next workstation together, thus achieving Continuous production, the production cycle of this method will be shorter than the single process of the previous process.

In another embodiment, the container or workstation where the second material is stored is additionally provided with a source of insulation or heating. For example, the 1002 or 1004 element itself or an additional heating source can perform the function of keeping warm or heating the container, so that the second material can be mixed with the first material or before the second material is mixed with the first material. , up to about 40 degrees Celsius, to get the best and most effective production efficiency. In another embodiment, the heating source can be heated by means of electric heat, steam, liquid or the like.

In one embodiment, after completing the mixing of the first and second materials, as described above, elements 1002 and 1004 are moved to element 1008 to remove water to perform the steps of removing or reducing water. For example, elements 1002 and 1004 move the third material from element 1006 to element 1008 after the process of mixing the first and second materials. In another embodiment, during the mixing process of the third material, the third material is in a vacuum-sealed state during the elements 1002, 1004, 1006, and 1008, and then the element 1008 has positive pressure and compression functions, so that the element is loaded with the combined material. The space pressure of 1002 and 1004 increases, and then the moisture in the combined material is removed. Coupled with the original negative pressure design of 1002 and 1004, the third material is further pumped or the dry humidity of the combined material is reduced. The installation surface of the 1008 positive pressure and compression chamber can be turned up or down and can also be turned over.

Finally, combine the material and enter the shaping stage to make the final product.

In another embodiment, the second material can also directly serve as the main body of the third material, as shown in FIG. 10B . For example, the second material in Figure 10B does not mix with the first material after entering the second element.

The equipment of the present invention can be a piece of automatic equipment, as shown in FIG. 11A , that is, the first element, the second element and the third element are a set of continuous equipment.

In another embodiment of the present invention, as shown in Figures 11B, 11C, and 11D, the third material is detachably and separately arranged.

In addition, Figures 11A-D show that the 1004 element is moved by a track, but people in the related art can easily use other ways to move the 1004 element without departing from the basic principles of the present invention, and the movement need not be limited to a plane movement.

In addition, in one embodiment, the present invention also includes a software system to operate the device of the present invention, including sensors 1000 , 1001 , 1002 , 1004 , 1006 , 1008 etc. to transmit parameter information. The software system also includes different interfaces, whether it is a centralized interface or can be presented on mobile devices through the network. Even as listed in Figures 11B-11D, in various embodiments, separate components may have coherent or separate interfaces and software to communicate and operate the operation of the device. The software system also reports prompts and alerts, providing administrators with efficient management of the production process.

The mold and transfer mold have the function of turning over: The 1001 mold installation equipment has a rotating function. During the molding process, the mold surface can be turned up or down into the 1000 pulp barrel to use vacuum to absorb materials. The 1002 transfer mold equipment also has a rotating function, the mold can be rotated after transferring the product, and the water can be discharged by means of vacuum and gravity.

Grouting: When 1001 and 1002 are closed, there is a casting cavity inside the mold, and 1000 pulp can be used to feed the material into the 1001 mold cavity through a water pump, and then the water in the pulp can be taken out by vacuum to complete the first step. One material, from which the 1006 can also be reused by pouring the second material in the same way. 1000 and 1006 can be installed in any position under or above the equipment in the pouring system.

Figures 12A and B are another embodiment of the apparatus, also a derivative of Figures 10A-11D. For example, the paper-plastic forming process may include: 1. Decompose the cardboard into pulp through the pulping system, and the pulp can be mixed with other materials required for pulp before entering the forming system. 2. Use vacuum or vacuum as power to attach the pulp material to the surface of the mold, and then use the drainage system on the surface of the mold to drain the excess water, so that a thin layer of wet material is formed on the surface of the mold. 3. If there is a lot of moisture on the surface of the product after molding, you can use natural air drying, hot air, air pressure, mold heating to assist hot pressing molding, and other methods to discharge the remaining moisture of the material.

The above description provides several molding processes:

The pulp forming method - the forming method is to use the inside of the mold to make a vacuum cavity. Under the action of the vacuum, the fibers of the pulp can be uniformly layered and attached to the forming net on the surface of the mold. The surface of the mold is upward into the pulp tank. And a lot of moisture will be taken away by vacuum suction. When the product reaches a certain thickness, the product mold will leave the pulp tank, and the wet embryo pulp on the mold surface will be dewatered.

Grouting method - the surface of the mold is facing up, a pulp tank will be made around the mold, the pulp will be connected to the pulp tank by means of pulp pipelines, and the amount of pulp will be quantitatively given according to the thickness of the product, and a vacuum cavity will be made inside the mold Under the action of vacuum, the fibers of the pulp can be uniformly layered and attached to the forming web on the surface of the mold, and a large amount of water will be taken away by vacuum suction, which forms wet embryo pulp on the surface of the mold and then Perform dehydration actions.

Suction back molding - the surface of the mold goes down into the pulp tank, and a large amount of moisture will be taken away by vacuum suction. When the product reaches a certain thickness, the product mold will leave the pulp tank, and the wet embryo pulp on the mold surface will be dewatered.

Because the present invention effectively combines the two materials, through the characteristics of the fiber itself and cellulose, the combination of two or more layers is made more closely when the specific arrangement in the process is used.

Thus, Figures 12A and B illustrate a transverse system, 1204, 1204' and 1204" are clamps, 1202, 1202', 1202" are transfer molds, 1201, 1201' are molds, 1200 is the first layer of paste, and 1206 is the first layer of paste. Two-layer pulp, 1208 is a dewatering or positive press. The characteristics of the equipment are horizontal system or multi-station system, and 1202 or 1201 can be rotated, and 1201' can also be rotated.

Or a vertical system as depicted in Figure 13. The vertical system includes 1304 as a fixture, 1301 as a mold, 1300 as the first layer of pulp, 1306 as the second layer of pulp, 1308 as dehydration, positive pressure, hot air, compression, heating, and other machines. Among them, the 1301 mold can be designed for rotation.

In another embodiment, the systems of Figures 12A and B and Figure 13 may be partially combined.

From the above embodiments, the present invention utilizes the forming method of the pulp barrel 1 and the pulp barrel 2 to include:

In the vertical system, if two molding dies are to be completed at the same time, it needs to cooperate with the rotating action. In the molding station, you can use the injection + suction or the suction + injection. The above rotation actions can be used: 1. The motor drives the mechanism to rotate the mold, 2. The vertical movement of the mold drives the connecting rod, rack or mechanical structure equipment to rotate.

下撈+下撈     分開or同時 下撈+上注 分開   下撈+倒吸  

上注+上注 分開   上注+下撈 分開   上注+倒吸 分開or同時 需要 倒吸+倒吸

  倒吸+下撈     倒吸+上注 分開or同時 需要 In addition, the present invention can make the following combination realize the technology that cannot be realized in the past: forming station Single device (vertical system) Horizontal (can be transferred or linear or rotated by manual or manipulator) Pulp bucket 1 + Pulp bucket 2 1 and 2 order Die rotation

down fishing + down fishing separately or at the same time Fishing + betting separate Fishing down + sucking back

bet + bet separate bet + drop separate bet + suck back separately or at the same time need suck + suck

Suck back + fish down Suck back + bet separately or at the same time need

Therefore, the above table has explained that the equipment of the present invention can have multiple (more than one) pulp barrels mainly in the forming stage, and can make different forming processes to complete other different product requirements:

Thick material to complete products over 2mm

After the forming station is completed, it can be connected or transferred to the 1008 dewatering process. The dewatering equipment of this equipment is equipped with positive pressure and compression devices, which can speed up the time of pulp drainage and forming, and is conducive to forming thick products.

Multilayer transfer stack molding (including composites)

The connection of the first layer of material and the second layer of material can be accomplished at the same time using a linear transfer system or a vertical rotation system. The 1002 and 1004 transfer products can be used to stack two or more or the same materials together to make thick and thin composite materials.

Multi-color molding

The linear transfer system or the vertical rotation system can simultaneously complete the molding of multi-color materials, and complete the blister process with different colors of pulp on a single product.

Dyeing and molding

In the pulp blister molding process, the pulp dyeing needs to be replaced with other colors, which is a very time-consuming work in the cleaning of the pipeline. We can use the multi-pulp drum method to place the pulp dye in a separate molding drum. First, After the layer material is formed, it can be moved to the second layer of dye to absorb the plastic dye, so that the pulp surface adheres to the color, and then transferred to drying. system.

Optimizing Additives

The timing of pulp additives in pulp molding is very important. We can add them and put them in a separate molding barrel. We can choose an appropriate time to add them to increase the ability of additives to combine with pulp fibers. Independent additives can also reduce pulp backwater. The chance of being contaminated by additives in other systems improves the quality of the return water.

Multi-layer material molding

Using this, the forming process of the first layer material and the second layer material can be completed at the same time. The 1002 and 1004 transfer products can be used to stack two or more or the same materials together to make composite materials.

From FIGS. 14A to 14D, because of the process and material toughness of the present invention, the present invention can make special design requirements from the fiber material. For example, as shown in FIG. The incision is pressed in so that the prongs on the edge of the carrier can move into the slit of the incision. Or as shown in FIG. 14B , the edge of the cover is left with a small gap at the height of the fork on the edge of the carrier, so that the fork on the edge of the carrier can be inserted. Or make an arc design from the upper end of the cover to correspond to the support point at the bottom of the carrier, (as shown in Figure 14C), and the support point at the bottom of the carrier can be designed without four feet to raise the bottom exhaust to allow the steam to have space for circulation and maintain the strength of the carrier (Fig. 14D).

In general, aspects of the present invention overcome the shortcomings of prior methods in which toxic chemicals (eg, fluoropolymers and derivatives thereof) were added. Aspects of the present invention also overcome the disadvantages of existing methods of using pulp as one or more base layers. In general understanding, pulp fibers have diameters in the range of 10 to 50 micrometers (μm). Whereas aspects of the present invention are finer in size, eg in the range of 1 μm or less.

Although variable and application dependent, the following are examples of methods of using the devices disclosed herein. Those skilled in the art will recognize that the steps can be performed in any practical order to produce the material for the desired use.

The above description and drawings merely explain and illustrate the present invention, and the present invention is not limited thereto. While the specification has been described with respect to certain implementations or examples, numerous details are set forth for purposes of illustration. Accordingly, the foregoing merely illustrates the principles of the present invention. For example, the present invention may take other specific forms without departing from its spirit or essential characteristics. The described arrangements are illustrative and not restrictive. To those skilled in the art, the invention allows for additional implementations or embodiments, and some of these details described in this application may vary considerably without departing from the underlying principles of the invention. Variety. It should be appreciated that those skilled in the art can devise various arrangements which, although not explicitly described or shown herein, embody the principles of the invention, and are therefore within the scope and spirit thereof.

The above description is illustrative and not restrictive. Many variations of the embodiments may become apparent upon review of the disclosure. Therefore, scope examples should be determined not with reference to the above description, but should instead be determined with reference to the pending claims and their full scope or equivalents.

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 embodiments. References to "a", "single", or "an" are intended to mean "one or more" unless specifically stated to the contrary. Reciting "and/or" is intended to represent the most inclusive sense of the term, unless expressly stated to the contrary.

While this disclosure may be embodied in many different forms, the drawings and discussions are presented with the understanding that this disclosure is an embodiment of one or more inventive principles and is not intended to limit any one embodiment to the described embodiments.

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

Further advantages and modifications of the above systems and methods may readily occur to those skilled in the art.

Therefore, the disclosure in its broader aspects is not limited to the specific details, representative systems and methodologies, and illustrative examples described above. Various modifications and changes may be made to the above specification without departing from the scope or spirit of this disclosure, and this disclosure shall cover all such modifications and changes provided they fall within the scope of the following claims and their equivalents.

802: Abrasives 804: Mixer 806: Mixture 808: After Grinding 810: Shaper 812: Dissolved 814: Drying 816: Final Material 818: Intermediate material

Those skilled in the art may appreciate that elements in the figures are presented for simplicity and clarity of illustration, so not all coherences and selections are presented. For example, common but well-known elements that are useful or necessary in a commercially feasible embodiment often cannot be described so as to be less obstructive to these various embodiments of the present disclosure. It is further understood that certain acts and/or steps may be described or described in a particular order of occurrence, while those skilled in the art may understand that such specificity in sequence is not actually required. It is also to be understood that the terms and expressions used in this case may be defined with respect to their corresponding fields of investigation and research, unless the specific meaning is otherwise specified herein.

1A-1D illustrate the aqueous suspension of cellulosic fibers according to one embodiment.

Figure 2 is a scanning electron microscope (SEM) image for a cellulosic cellulose (3 wt.%) material, according to one embodiment.

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

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

Figure 5 is an image showing containers made of cellulose L28b, L29b, L30b and Y that are capable of holding oil for 10 days, according to one embodiment.

6A is an image showing a food containing boiling water in a material for about 5 minutes, according to one embodiment.

6B is an image showing a food product heated with boiling water and an 800 watt microwave for the next 2 minutes, according to one embodiment.

Figure 7 is another SEM image of a cellulosic structural material used in a food container according to one embodiment.

8 is a flow diagram of a method of generating a material according to one embodiment.

Figure 9 is three images of a film according to one embodiment.

10A-13 are devices applied according to embodiments.

14A-D are drawings of final products made in accordance with embodiments of the present invention.

802: Abrasives

804: Mixer

806: Mixture

808: After Grinding

810: Shaper

812: Dissolved

814: Drying

816: Final Material

818: Intermediate material

Claims (22)

A device for making a biodegradable carrier material, comprising: The first element is loaded with the first material; The first element includes a fiber splicer that carries a portion of the fibers in the first material; The second element adsorbs part of the fibers of the fiber-bonded body; The third element contacts the second material with a portion of the fibers, the second material in turn mixes with the portion of the fibers to form a third material; and A water removal device reduces the moisture of the third material. According to the equipment of claim 1 of the claimed scope, it further comprises a shaping device for shaping the third material after the water has been removed. According to the apparatus of claim 1, the first material comprises pulp. According to the apparatus of claim 1 of the claimed scope, the second material includes the refined material. According to the apparatus of claim 1, the third element further includes a container for carrying the second material. According to the apparatus of claim 5, the third element further includes a heating source. According to the apparatus of claim 6, the heating source preserves the second material above about 40 degrees Celsius. According to the apparatus of claim 6, the heat source causes the second material to reach above about 40 degrees Celsius when in contact with the first material. According to the apparatus of claim 1, the third material is generally free of chemical additives that increase the elongation strength, oil resistance, gas and/or liquid impermeability, tensile modulus, or tensile index of the enhanced material. According to the device of claim 1 of the scope of application, the third material includes the following properties: an oxygen transmission rate of about 8000 cm3 per square foot per 24 hours ( ^{cm3m-224h- 1} ) or less; about 3000 grams per Water vapor transmission rate per square foot per 24 hours (gm ^-2 24 h ^-1 ) or less; dry tensile strength of about 30 MPa or more; dry tensile modulus of about 4 GPa or more; and about 45 Nm A dry stretch index of ^g-1 or higher. According to the apparatus of claim 1, the third material includes the following properties: a wet tensile strength of about 5 MPa or more; a wet tensile modulus of about 0.4 MPa or more; and about 5 Nm ^g-1 or more High wet stretch index. The device according to claim 1, wherein the third material comprises cellulose of different diameters in a weight ratio of 1:100 or 1:50. The apparatus of claim 1, wherein the third material comprises cellulose cellulose having a diameter of about 1-10,000 nanometers. The apparatus according to claim 1, wherein the third material comprises cellulose having a thickness of about 0.1 to 1000 microns, about 10 to 500 microns, about 1 to 25 microns, or about 0.2 to 100 microns. According to the device of claim 1 of the scope of application, wherein the third material is a flat plate. The device according to claim 1, wherein the third material is an edible container. The apparatus according to claim 1, wherein the third material is a fiber mixture. The apparatus of claim 1, wherein the third material comprises a film having a thickness of about 0.01 to 3.0 millimeters (mm). According to the device of claim 1 of the scope of application, the length of the flat plate varies from 0.01 mm to 10000 mm. A device for making a biodegradable carrier material, comprising: The second element adsorbs a second material, the second material comprising a fiber attenuated material; The third element transforms the second material into a third material in a vacuum state; and A water removal device reduces the moisture of the third material. A method of making a biodegradable carrier material comprising: Loading the first material into a mold, the mold carrying some fibers in the first material; Adsorb the part of the fiber; providing a second material in contact with the portion of the fibers, the second material in turn mixes with the portion of the fibers to form a third material; and The moisture of the third material is subtracted. A method of making a biodegradable carrier material comprising: adsorbing the second material and a carrier, the second material including the fiber-reduced material; The empty state turns the second material into the third material; and The moisture of the third material is subtracted.

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