Modified cellulose materials and methods for modifying cellulose material

Abstract

In one aspect, the disclosure relates to a method for modifying or treating a cellulose material, comprising: combining a cellulose feedstock and a first solvent, thereby forming a cellulosic suspension; mixing the cellulosic suspension under high shear; and treating the cellulosic suspension with a reaction treatment comprising: incubation of the cellulosic suspension at a temperature of at least 30°C; microwave irradiation exposure; plasma exposure; ultrasound exposure; grinding; ball-milling; extrusion; a sequence thereof; or any combination thereof. In another aspect, the disclosure relates to compositions produced by the methods disclosed herein. In another aspect, the disclosure relates to filaments, yarns, films, sheets, cast materials, molded materials, articles, and any combination thereof comprising the compositions produced by the methods disclosed herein. In addition, the disclosure provides for compositions, fibers, filaments, yarns, casts, molds, articles, clothing, and the like, that include the modified or treated cellulose.

Description

ATTORNEY DOCKET NO. 331903-2010MODIFIED CELLULOSE MATERIALS AND METHODS FOR MODIFYING CELLULOSE MATERIALCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Provisional Application Serial No. 63 / 690,891, having the title “methods for MODIFYING CELLULOSE MATERIAL” filed September s, 2024, the disclosure of which is incorporated herein in by reference in its entirety.BACKGROUND

[0002] The textile industry is a significant contributor to global carbon dioxide emissions, exceeding those from several other sectors such as international aviation and shipping, due in part, to lengthy supply chains and energy intensive production. Many of the materials utilized in the textile industry are based on petrochemical materials such as polyethers and polyamides, e.g., the use of synthetic fibers has grown exponentially and use of polyester in textiles surpasses cotton as the most widely used fabric in fashion products. Synthetic fibers and yarns have a much greater carbon footprint natural materials such as cotton because they require petroleum-based products as a feedstock. Not surprisingly, the textile industry is under increasing pressure to utilize textile materials that are sustainable and minimally impactful to the environment.

[0003] Moreover, the textile industry, as well as other industries in which products, devices, materials, or systems comprise a coating, decal, label, design, or paint, face concerns of color fading, UV resistance, wear resistance, exfoliation, and photo-oxidation, degradation, and / or underlying material failure.

[0004] Conventionally, organic UV-absorbers, together with radical scavenging compounds may be used to protect coating systems against the aforementioned severe UV irradiation / humid conditions. Such organic UV-absorbers are based on triazine, benzotriazoles, and benzophenones, which may lose their anti-UV performance during service time due to the possibility of UV-absorbent release from the coating. Therefore, organic UV absorbers have been substituted by inorganic UV blocking agents.

[0005] Inorganic UV blocking agents, such as TiC>2, ZnO, and CeC>2 may be able to protect the coating against weathering conditions through UVB (280-315 nm) absorbance, reflection, or scattering mechanisms due to their high refractive index. However, inorganic UV blocking agents may also have some drawbacks, such as improper dispersion in polymeric matrices and also an inadequate ability to absorb hydroxyl groups. For example, to disperse titanium dioxide (TIO2)ATTORNEY DOCKET NO. 331903-2010 into the polymeric matrix of PVC panels, high loading of titanium dioxide is required, which is undesirable from a production point of view due to the high cost. Such drawbacks may lead to loss of coating quality over time.

[0006] Generally, conventional organic and inorganic agents used in coatings, paints, and the like also do not meet current needs for sustainable materials.

[0007] Despite advances in textile research, as well as coatings and paints, there is still a scarcity of materials that meeting the increasing needs for sustainable materials. These needs and other needs are satisfied by the present disclosure.SUMMARY

[0008] The disclosure provides for methods for modifying or treating a cellulose material and compositions, fibers, filaments, yarns, casts, molds, articles, clothing, and the like, that include the modified or treated cellulose.

[0009] In accordance with the purpose(s) of the present disclosure, as embodied and broadly described herein, the disclosure, in one aspect, relate to a method, comprising: combining a cellulose feedstock and a first solvent in a weight ratio of about 1:0.5 to about 1 :200 cellulose feedstock to first solvent, thereby forming a cellulosic suspension; mixing the cellulosic suspension under high shear; and treating the cellulosic suspension with a reaction treatment comprising: incubation of the cellulosic suspension at a temperature of at least 30°C; microwave irradiation exposure; plasma exposure; ultrasound exposure; grinding; ball-milling; extrusion; a sequence thereof; or any combination thereof, thereby forming a treated cellulosic suspension comprising a treated cellulose material; wherein the first solvent comprises a Lewis base and a Lewis acid in an about 10:2 to about 1 :9 molar ratio of Lewis base to Lewis acid.

[0010] In another aspect, the disclosure relates to compositions produced by the methods disclosed herein.

[0011] In another aspect, the disclosure relates to filaments, yarns, films, sheets, cast materials, molded materials, articles, and any combination thereof comprising the compositions produced by the methods disclosed herein

[0012] Other systems, methods, features, and advantages of the present disclosure will be or become apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional systems, methods, features, and advantages be included within this description, be within the scope of the present disclosure, and be protected by the accompanying claims. In addition, all optional and preferred features andATTORNEY DOCKET NO. 331903-2010 modifications of the described embodiments are usable in all aspects of the disclosure taught herein. Furthermore, the individual features of the dependent claims, as well as all optional and preferred features and modifications of the described embodiments are combinable and interchangeable with one another.BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Many aspects of the present disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present disclosure. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views. The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

[0014] FIGS. 1A-1B show representative dynamic light scattering (DLS) size distributions of 0.5 wt% suspensions of a dried (FIG. 1A) and a never-dried (FIG. 1B) seaweed pulp treated with deep eutectic solvents (DESs) after HV-0 mixing (Op) one fluidization step (1 p) or three fluidization steps (3p) A sample of untreated cellulose (dashed lines) is used as a control.

[0015] FIGS. 2A-2B show representative UV-Vis absorbance spectra for a dried (FIG. 2A) and a never-dried (FIG. 2B) seaweed pulp treated with different DESs in the range of 250 nm to 750 nm with a sample suspension having a concentration of 0.5 wt% after HV-0 mixing (Op) one fluidization step (1p) or three fluidization steps (3p).

[0016] FIGS. 3A-3B show representative plots of average absorbance (FIG. 3A) and absorbance at 550 nm (FIG. 3B) of a dried seaweed pulp treated with a DES. A vertical dashed line is placed at an absorbance of 0.1 as a visual guide. Materials below this value can be considered transparent. Samples are compared with controls of sc-pcnf after HV-0 mixing (Op), one fluidization pass (1p), or three fluidization passes (3p).

[0017] FIGS. 4A-4B show representative plots of average absorbance (FIG. 4A) and absorbance at 550 nm (FIG. 4B) of a never-dried seaweed pulp treated with a DES. A vertical dashed line is placed at an absorbance of 0.1 as a visual guide. Materials below this value can be considered transparent. Samples are compared with controls of sc-pcnf after HV-0 mixing (Op), one fluidization pass (1p), or three fluidization passes (3p).

[0018] FIGS. 5A-5B show representative plots of viscosity vs shear rate (with shear rates up to 100 s’1) of a dried (FIG. 5A) or a never-dried (FIG. 5B) seaweed pulp treated with a DES with aATTORNEY DOCKET NO. 331903-2010 sample suspension having a concentration of 0.5 wt% after HV-0 mixing (Op,, one fluidization step (1 p), or three fluidization steps (3p).

[0019] FIG. 6 shows a representative plot of viscosity, at 100 s-1shear rate, of a dried seaweed pulp treated with a DES for functionalized seaweed samples (Sample, sc-oa-d), pristine cellulose nanofibers (Control, sc-pcnf-d), and two reference materials: Mercel and TCNF. Samples, controls, and references underwent high shear mixing (HV-0), with the samples and controls also subjected to one fluidization pass (1p) or three fluidization passes (3p). Viscosity values are presented in logarithmic scale.

[0020] FIG. 7 shows a representative plot of viscosity, at 100 s-1shear rate, of a never-dried seaweed pulp treated with a DES for functionalized seaweed samples (Sample, sc-oa-w), pristine cellulose nanofibers (Control, sc-pcnf-w), and two reference materials: Mercel and TCNF. Samples, controls, and references underwent high shear mixing (HV-0), with the samples and controls also subjected to one fluidization pass (1 p) or three fluidization passes (3p). Viscosity values are presented in logarithmic scale.

[0021] FIGS. 8A-8B show representative DLS size distributions of 0.5 wt% suspensions of a dried (FIG. 8A) and a never-dried (FIG. 8B) seaweed pulp treated with DESs after HV-0 mixing (Op), one fluidization step (1 p) , or three fluidization steps (3p). A sample of untreated cellulose (dashed lines) is used as a control.

[0022] FIGS. 9A-9B show representative UV-Vis absorbance spectra for a dried (FIG. 9A) and a never-dried (FIG. 9B) seaweed pulp treated with different DESs in the range of 250 nm to 750 nm with a sample suspension having a concentration of 0.5 wt% after HV-0 mixing (Op), one fluidization step (1 p), or three fluidization steps (3p).

[0023] FIGS. 10A-10B show representative plots of average absorbance (FIG. 10A) and absorbance at 550 nm (FIG. 10B) of a dried seaweed pulp treated with a DES. A vertical dashed line is placed at an absorbance of 0.1 as a visual guide. Materials below this value can be considered transparent. Samples are compared with controls of sc-pcnf after HV-0 mixing (Op), one fluidization pass (1 p), or three fluidization passes (3p).

[0024] FIGS. 11A-11B show representative plots of average absorbance (FIG. 11 A) and absorbance at 550 nm (FIG. 11 B) of a never-dried seaweed pulp treated with a DES. A vertical dashed line is placed at an absorbance of 0.1 as a visual guide. Materials below this value can be considered transparent. Samples are compared with controls of sc-pcnf after HV-0 mixing (Op), one fluidization pass (1 p), or three fluidization passes (3p).ATTORNEY DOCKET NO. 331903-2010

[0025] FIGS. 12A-12XB show representative plots of viscosity vs shear rate (with shear rates up to 100 s’1) of a dried (FIG. 12A) or a never-dried (FIG. 12B) seaweed pulp treated with a DES with a sample suspension having a concentration of 0.5 wt% after HV-0 mixing (Op), one fluidization step (1 p), or three fluidization steps (3p).

[0026] FIG. 13 shows a representative plot of viscosity, at 100 s-1shear rate, of a dried seaweed pulp treated with a DES for functionalized seaweed samples (Sample, sc-ca-d), pristine cellulose nanofibers (Control, sc-pcnf-d), and two reference materials: Mercel and TCNF. Samples, controls, and references underwent high shear mixing (HV-0), with the samples and controls also subjected to one fluidization pass (1p) or three fluidization passes (3p). Viscosity values are presented in logarithmic scale.

[0027] FIG. 14 shows a representative plot of viscosity, at 100 s’1shear rate, of a never-dried seaweed pulp treated with a DES for functionalized seaweed samples (Sample, sc-ca-w), pristine cellulose nanofibers (Control, sc-pcnf-w), and two reference materials: Mercel and TCNF. Samples, controls, and references underwent high shear mixing (HV-0), with the samples and controls also subjected to one fluidization pass (1 p) or three fluidization passes (3p). Viscosity values are presented in logarithmic scale.

[0028] FIGS. 15A-15B show representative DLS size distributions of 0.5 wt% suspensions of a dried (FIG. 15A) and a never-dried (FIG. 15B) seaweed pulp treated with DESs after HV-0 mixing (Op), one fluidization step (1 p), or three fluidization steps (3p). A sample of untreated cellulose (dashed lines) is used as a control.

[0029] FIGS. 16A-16B show representative UV-Vis absorbance spectra for a dried (FIG. 16A) and a never-dried (FIG. 16B) seaweed pulp treated with different DESs in the range of 250 nm to 750 nm with a sample suspension having a concentration of 0.5 wt% after HV-0 mixing (Op), one fluidization step (1 p), or three fluidization steps (3p).

[0030] FIGS. 17A-17B show representative plots of average absorbance (FIG. 17A) and absorbance at 550 nm (FIG. 17B) of a dried seaweed pulp treated with a DES. A vertical dashed line is placed at an absorbance of 0.1 as a visual guide. Materials below this value can be considered transparent. Samples are compared with controls of sc-pcnf after HV-0 mixing (Op), one fluidization pass (1 p), or three fluidization passes (3p).

[0031] FIGS. 18A-18B show representative plots of average absorbance (FIG. 18A) and absorbance at 550 nm (FIG. 18B) of a never-dried seaweed pulp treated with a DES. A vertical dashed line is placed at an absorbance of 0.1 as a visual guide. Materials below this value canATTORNEY DOCKET NO. 331903-2010 be considered transparent. Samples are compared with controls of sc-pcnf after HV-0 mixing (Op), one fluidization pass (1 p), or three fluidization passes (3p).

[0032] FIGS. 19A-19B show representative plots of viscosity vs shear rate (with shear rates up to 100 s’1) of a dried (FIG. 19A) or a never-dried (FIG. 19B) seaweed pulp treated with a DES with a sample suspension having a concentration of 0.5 wt% after HV-0 mixing (Op), one fluidization step (1 p), or three fluidization steps (3p).

[0033] FIG. 20 shows a representative plot of viscosity, at 100 s-1shear rate, of a dried seaweed pulp treated with a DES for functionalized seaweed samples (Sample, sc-ia-d), pristine cellulose nanofibers (Control, sc-pcnf-d), and two reference materials: Mercel and TCNF. Samples, controls, and references underwent high shear mixing (HV-0), with the samples and controls also subjected to one fluidization pass (1p) or three fluidization passes (3p). Viscosity values are presented in logarithmic scale.

[0034] FIG. 21 shows a representative plot of viscosity, at 100 s’1shear rate, of a never-dried seaweed pulp treated with a DES for functionalized seaweed samples (Sample, sc-ia-w), pristine cellulose nanofibers (Control, sc-pcnf-w), and two reference materials: Mercel and TCNF. Samples, controls, and references underwent high shear mixing (HV-0), with the samples and controls also subjected to one fluidization pass (1 p) or three fluidization passes (3p). Viscosity values are presented in logarithmic scale.

[0035] FIGS. 22A-22B show representative DLS size distributions of 0.5 wt% suspensions of a dried (FIG. 22A) and a never-dried (FIG. 22B) seaweed pulp treated with DESs after HV-0 mixing (Op), one fluidization step (1 p), or three fluidization steps (3p). A sample of untreated cellulose (dashed lines) is used as a control.

[0036] FIGS. 23A-23B show representative UV-Vis absorbance spectra for a dried (FIG. 23A) and a never-dried (FIG. 23B) seaweed pulp treated with different DESs in the range of 250 nm to 750 nm with a sample suspension having a concentration of 0.5 wt% after HV-0 mixing (Op), one fluidization step (1 p), or three fluidization steps (3p).

[0037] FIGS. 24A-24B show representative plots of average absorbance (FIG. 24A) and absorbance at 550 nm (FIG. 24B) of a dried seaweed pulp treated with a DES. A vertical dashed line is placed at an absorbance of 0.1 as a visual guide. Materials below this value can be considered transparent. Samples are compared with controls of sc-pcnf after HV-0 mixing (Op), one fluidization pass (1 p), or three fluidization passes (3p).

[0038] FIGS. 25A-25B show representative plots of average absorbance (FIG. 25A) andATTORNEY DOCKET NO. 331903-2010 absorbance at 550 nm (FIG. 25B) of a never-dried seaweed pulp treated with a DES. A vertical dashed line is placed at an absorbance of 0.1 as a visual guide. Materials below this value can be considered transparent. Samples are compared with controls of sc-pcnf after HV-0 mixing (Op), one fluidization pass (1 p), or three fluidization passes (3p).

[0039] FIGS. 26A-26B show representative plots of viscosity vs shear rate (with shear rates up to 100 s’1) of a dried (FIG. 26A) or a never-dried (FIG. 26B) seaweed pulp treated with a DES with a sample suspension having a concentration of 0.5 wt% after HV-0 mixing (Op), one fluidization step (1 p), or three fluidization steps (3p).

[0040] FIG. 27 shows a representative plot of viscosity, at 100 s’1shear rate, of a dried seaweed pulp treated with a DES for functionalized seaweed samples (Sample, sc-sa-d), pristine cellulose nanofibers (Control, sc-pcnf-d), and two reference materials: Mercel and TCNF. Samples, controls, and references underwent high shear mixing (HV-0), with the samples and controls also subjected to one fluidization pass (1p) or three fluidization passes (3p). Viscosity values are presented in logarithmic scale.

[0041] FIG. 28 shows a representative plot of viscosity, at 100 s’1shear rate, of a never-dried seaweed pulp treated with a DES for functionalized seaweed samples (Sample, sc-sa-w), pristine cellulose nanofibers (Control, sc-pcnf-w), and two reference materials: Mercel and TCNF. Samples, controls, and references underwent high shear mixing (HV-0), with the samples and controls also subjected to one fluidization pass (1 p) or three fluidization passes (3p). Viscosity values are presented in logarithmic scale.

[0042] FIG. 29 shows a representative DLS size distribution of 0.5 wt% suspensions of a never- dried seaweed pulp treated with DESs after HV-0 mixing (Op), one fluidization step (1 p), or three fluidization steps (3p). A sample of untreated cellulose (dashed lines) is used as a control.

[0043] FIG. 30 shows a representative UV-Vis absorbance spectra for a never-dried seaweed pulp treated with different DESs in the range of 250 nm to 750 nm with a sample suspension having a concentration of 0.5 wt% after HV-0 mixing (Op), one fluidization step (1 p), or three fluidization steps (3p).

[0044] FIGS. 31A-31B show representative plots of average absorbance (FIG. 31 A) and absorbance at 550 nm (FIG. 31 B) of a never-dried seaweed pulp treated with a DES. A vertical dashed line is placed at an absorbance of 0.1 as a visual guide. Materials below this value can be considered transparent. Samples are compared with controls of sc-pcnf after HV-0 mixing (Op), one fluidization pass (1 p), or three fluidization passes (3p).ATTORNEY DOCKET NO. 331903-2010

[0045] FIG. 32 shows a representative plots of viscosity vs shear rate (with shear rates up to 100 s-1) of a never-dried seaweed pulp treated with a DES with a sample suspension having a concentration of 0.5 wt% after HV-0 mixing (Op), one fluidization step (1 p), or three fluidization steps (3p).

[0046] FIG. 33 shows a representative plot of viscosity, at 100 s-1shear rate, of a never-dried seaweed pulp treated with a DES for functionalized seaweed samples (Sample, sc-oa-sa-w), pristine cellulose nanofibers (Control, sc-pcnf-w), and two reference materials: Mercel and TCNF. Samples, controls, and references underwent high shear mixing (HV-0), with the samples and controls also subjected to one fluidization pass (1 p) or three fluidization passes (3p). Viscosity values are presented in logarithmic scale.

[0047] FIG. 34 shows a representative DLS size distribution of 0.5 wt% suspensions of a dried seaweed pulp treated with DESs after HV-0 mixing (Op), one fluidization step (1 p), or three fluidization steps (3p). A sample of untreated cellulose (dashed lines) is used as a control.

[0048] FIG. 35 shows a representative UV-Vis absorbance spectra for a dried seaweed pulp treated with different DESs in the range of 250 nm to 750 nm with a sample suspension having a concentration of 0.5 wt% after HV-0 mixing (Op), one fluidization step (1 p), or three fluidization steps (3p).

[0049] FIGS. 36A-36B show representative plots of average absorbance (FIG. 36A) and absorbance at 550 nm (FIG. 36B) of a dried seaweed pulp treated with a DES. A vertical dashed line is placed at an absorbance of 0.1 as a visual guide. Materials below this value can be considered transparent. Samples are compared with controls of sc-pcnf after HV-0 mixing (Op), one fluidization pass (1 p), or three fluidization passes (3p).

[0050] FIG. 37 shows a representative plots of viscosity vs shear rate (with shear rates up to 100 s-1) of a dried seaweed pulp treated with a DES with a sample suspension having a concentration of 0.5 wt% after HV-0 mixing (Op), one fluidization step (1 p), or three fluidization steps (3p).

[0051] FIG. 38 shows a representative plot of viscosity, at 100 s-1shear rate, of a dried seaweed pulp treated with a DES for functionalized seaweed samples (Sample, sc-bet-d), pristine cellulose nanofibers (Control, sc-pcnf-d), and two reference materials: Mercel and TCNF. Samples, controls, and references underwent high shear mixing (HV-0), with the samples and controls also subjected to one fluidization pass (1 p) or three fluidization passes (3p). Viscosity values are presented in logarithmic scale.

[0052] FIGS. 39A-39B show a representative atomic force microscopy (AFM) image (FIG. 39A)ATTORNEY DOCKET NO. 331903-2010 and a representative histogram of fiber height (FIG. 39B) for wet seaweed that has not been subjected to HV-0 mixing (SC-Wet-No HV-0).

[0053] FIGS. 40A-40B show a representative AFM image (FIG. 40A) and a representative histogram of fiber height (FIG. 40B) for wet seaweed that has been subjected to HV-0 mixing (SC-Wet-HV-0).

[0054] FIGS. 41A-41B show a representative AFM image (FIG. 41 A) and a representative histogram of fiber height (FIG. 41 B) for dry seaweed that has not been subjected to HV-0 mixing (SC-Dry-No HV-0).

[0055] FIGS. 42A-42B show a representative AFM image (FIG. 42A) and a representative histogram of fiber height (FIG. 42B) for dry seaweed that has been subjected to HV-0 mixing (SC- Dry-HV-0).

[0056] FIGS. 43A-43B show a representative AFM image (FIG. 43A) and a representative histogram of fiber height (FIG. 43B) for dry seaweed that has been subjected to HV-0 mixing and three fluidization passes (SC-Dry-HV-0-F3P).

[0057] FIG. 44 shows representative variations in fiber height with error bars for dry seaweed that has been subjected to various treatment methods.

[0058] FIGS. 45A-45B show a representative AFM image (FIG. 45A) and a representative histogram of fiber height (FIG. 45B) for dry seaweed that has been treated with an oxalic acid:choline chloride DES and subjected to HV-0 mixing (SC-OA-Dry-HV-0).

[0059] FIGS. 46A-46B show a representative AFM image (FIG. 46A) and a representative histogram of fiber height (FIG. 46B) for dry seaweed that has been treated with an oxalic acid:choline chloride DES and subjected to HV-0 mixing and three fluidization passes (SC-OA- Dry-HV-0-F3P).

[0060] FIGS. 47A-47B show a representative AFM image (FIG. 47A) and a representative histogram of fiber height (FIG. 47B) for dry seaweed that has been treated with a citric acid:choline chloride DES and subjected to HV-0 mixing (SC-CA-Dry-HV-0).

[0061] FIGS. 48A-48B show a representative AFM image (FIG. 48A) and a representative histogram of fiber height (FIG. 48B) for dry seaweed that has been treated with a citric acid:choline chloride DES and subjected to HV-0 mixing and three fluidization passes (SC-CA-Dry-HV-0- F3P).

[0062] FIGS. 49A-49B show a representative AFM image (FIG. 49A) and a representativeATTORNEY DOCKET NO. 331903-2010 histogram of fiber height (FIG. 49B) for dry seaweed that has been treated with a sulphamic acid:choline chloride DES and subjected to HV-0 mixing (SC-SA-Dry-HV-0).

[0063] FIGS. 50A-50B show a representative AFM image (FIG. 50A) and a representative histogram of fiber height (FIG. 50B) for dry seaweed that has been treated with a sulphamic acid:choline chloride DES and subjected to HV-0 mixing and three fluidization passes (SC-SA- Dry-HV-0-F3P).

[0064] FIGS. 51A-51B show a representative AFM image (FIG. 51 A) and a representative histogram of fiber height (FIG. 51 B) for dry seaweed that has been treated with an itaconic acid:choline chloride DES and subjected to HV-0 mixing (SC-IA-Dry-HV-0).

[0065] FIGS. 52A-52B show a representative AFM image (FIG. 52A) and a representative histogram of fiber height (FIG. 52B) for dry seaweed that has been treated with an itaconic acid:choline chloride DES and subjected to HV-0 mixing and three fluidization passes (SC-IA- Dry-HV-0-F3P).

[0066] FIGS. 53A-53B show a representative AFM image (FIG. 53A) and a representative histogram of fiber height (FIG. 53B) for dry seaweed that has been treated with a betaine:choline chloride DES and subjected to HV-0 mixing (SC-Bet-Dry-HV-0).

[0067] FIGS. 54A-54B show a representative AFM image (FIG. 54A) and a representative histogram of fiber height (FIG. 54B) for dry seaweed that has been treated with a betaine:choline chloride DES and subjected to HV-0 mixing and three fluidization passes (SC-Bet-Dry-HV-0- F3P).

[0068] FIG. 55 shows a representative variations in fiber height with error bars for wet and dry seaweeds subjected to HV-0 mixing and, for some of the dry seaweeds, treated with various DESs.

[0069] FIG. 56 shows a representative Fourier transform infrared spectroscopy (FTIR) spectra of never-dried (wet) cellulose and dry cellulose (DMC > 40%,. The inset shows an enlarged fingerprint region.

[0070] FIG. 57 shows a representative FTIR spectra of wet and dry cellulose after choline chloride:oxalic acid (OACC) treatment. The inset shows a new band near 1700 cm-1(dotted circle) present only in dry cellulose.

[0071] FIG. 58 shows a representative FTIR spectra of dry cellulose after citric acid:glycerol (CAGLY) treatment. The inset shows a new carbonyl-related band indicated by arrow.ATTORNEY DOCKET NO. 331903-2010

[0072] FIG. 59 shows a representative FTIR spectra of dry cellulose after betaine:glycerol (BET- GLY) treatment. The inset shows that no new signals were observed.

[0073] FIG. 60 shows a representative FTIR spectra of dry cellulose before and after choline chloride:itaconic acid DES treatment.

[0074] FIG. 61 shows a representative FTIR spectra of wet cellulose before and after two-step OACC + sulphamic acid:glycerol (SAGLY) treatment.

[0075] FIG. 62 shows a representative FTIR spectra of wet cellulose before and after SAGLY treatment. Vertical dotted lines mark expected sulfate absorption regions.

[0076] FIG. 63 shows a representative energy-dispersive X-ray (EDX) spectra of cellulose after OACC and SAGLY treatments. The inset shows an S peak in SAGLY-treated cellulose. Gold originates from sample coating; Ca, Si, and Cl reflect handling impurities.

[0077] FIGS. 64A-64C show representative AFM micrographs of 0.02 wt.% cellulose suspensions deposited on mica substrates. Each image corresponds to a 2.5 x 2.5 pm scan area acquired at 1 Hz. The top row shows cellulose fibers prior to OACC DES treatment, while the bottom row displays the same biomasses after treatment. Samples include Laminaria hyperborea (FIG. 64A), Saccharina latissimi (FIG. 64B), and hemp hurd (FIG. 64C). Dotted circles highlight representative features such as residual bundles or shortened fibrils, illustrating the transition from long cellulose nanofibers (CNFs) to shorter cellulose nanocrystals (CNCs) following OACC DES modification.

[0078] FIG. 65 shows representative AFM micrographs of 0.02 wt.% cellulose suspensions deposited on mica substrates. Each image corresponds to a 2.5 x 2.5 pm scan area acquired at 1 Hz. The panels show cellulose obtained from four different processing routes (Routes 1—4, as described herein), highlighting how distinct combinations of DES treatment and mechanical fibrillation influence fibril morphology

[0079] FIGS. 66A-66D show representative X-ray diffraction (XRD) patterns of cellulose derived from different biomass sources: Laminaria hyperborea (FIG. 66A), Saccharina latissimi (sugar kelp, FIG. 66B), hemp hurd (FIG. 66C), and Sargassum spp. (FIG. 66D). Results are presented for untreated cellulose and OACC DES-treated cellulose. Crystallinity index (Cl) values, calculated using the Segal method, are shown in parentheses. Vertical dotted lines mark crystalline (002) and amorphous regions used in the analysis.

[0080] FIGS. 67A and 67B show representative electrophoretic mobility and zeta potential of cellulose suspensions (0.05 wt%) from Saccharina latissima (FIG. 67A) and hemp hurd (FIG.ATTORNEY DOCKET NO. 331903-201067B). Conditions: untreated cellulose, OACC DES-treated cellulose, and SAGLY DES-treated cellulose. Measurements were performed at 25 °C in deionized water (pH 5-6).

[0081] FIG. 68 shows photographs depicting representative phenoxy resin suspensions (1 wt%) stabilized with cellulose. Left: water control; center: hemp hurd CNCs (0.5 wt%); right: sugar kelp CNCs (0.5 wt%). Rows correspond to Day 0, Day 1 , and Day 7. Dotted circles highlight key stability features.

[0082] FIG. 69 shows photographs depicting representative h-BN suspensions (1 wt%) in water (left), with 1 wt% non-modified sugar kelp cellulose (center), and with 1 wt% OACC DES-modified sugar kelp cellulose (right). Rows correspond to Day 0, Day 1 , and Day 7. Circle insets highlight selected close-up images of suspension drops on glass.

[0083] FIG. 70 shows photographs depicting representative alumina suspensions (1 wt%) in water (left), with 1 wt% non-modified sugar kelp cellulose (center), and with 1 wt% OACC DES- modified sugar kelp cellulose (right). Rows correspond to Day 0, Day 1, and Day 7. Circle insets highlight selected close-up images of suspension drops on glass.

[0084] FIG. 71 shows photographs depicting representative Fe3O4nanoparticle suspensions (1 wt%) in water (left), with 1 wt% non-modified sugar kelp cellulose (center), and with 1 wt% OACC DES-modified sugar kelp cellulose (right). Rows correspond to Day 0, Day 1 , and Day 7. Circle insets highlight selected close-up images of suspension drops on glass.

[0085] FIG. 72 shows a representative DLS spectra of hexagonal boron nitride (HBN) dispersions stabilized with non-modified cellulose and OACC DES-modified cellulose. Both systems contained 0.25 wt% cellulose and 0.07 wt% HBN.

[0086] FIG. 73 shows representative viscosity measurements of hemp hurd cellulose suspensions (1 wt%) treated with OACC DES after one use (fresh DES), two uses (r-DES(1)), and three uses (r-DES(2)). Viscosity is shown as a function of the number of passes through the HV-0 mixer.

[0087] FIG. 74 shows a representative FTIR spectra of dry (DMC > 40%) cellulose after OACC DES treatment at 60 °C and 80 °C. The inset shows a cellulose fingerprint region showing the appearance of new signals at both temperatures.

[0088] FIG. 75 shows a representative FTIR spectra of dry (DMC > 40%) cellulose treated with oxalic acid dihydrate and anhydrous oxalic acid. The inset shows a fingerprint region showing the new signal more clearly with anhydrous oxalic acid.ATTORNEY DOCKET NO. 331903-2010

[0089] Additional advantages of the disclosure will be set forth in part in the description which follows, and in part will be obvious from the description, or can be learned by practice of the disclosure. The advantages of the disclosure will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure, as claimed.DETAILED DESCRIPTION

[0090] The disclosure provides for methods for modifying or treating a cellulose material and compositions, fibers, filaments, yarns, casts, molds, articles, clothing, and the like, that include the modified or treated cellulose.

[0091] Many modifications and other embodiments disclosed herein will come to mind to one skilled in the art to which the disclosed compositions and methods pertain having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the disclosures are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. The skilled artisan will recognize many variants and adaptations of the aspects described herein. These variants and adaptations are intended to be included in the teachings of this disclosure and to be encompassed by the claims herein.

[0092] Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

[0093] As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure.

[0094] Any recited method can be carried out in the order of events recited or in any other order that is logically possible. That is, unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects describedATTORNEY DOCKET NO. 331903-2010 in the specification.

[0095] While aspects of the present disclosure can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only and one of skill in the art will understand that each aspect of the present disclosure can be described and claimed in any statutory class.

[0096] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed compositions and methods belong. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0097] Prior to describing the various aspects of the present disclosure, the following definitions are provided and should be used unless otherwise indicated. Additional terms may be defined elsewhere in the present disclosure.A. DEFINITIONS

[0098] As used herein, “comprising” is to be interpreted as specifying the presence of the stated features, integers, steps, or components as referred to, but does not preclude the presence or addition of one or more features, integers, steps, or components, or groups thereof. Moreover, each of the terms “by”, “comprising,” “comprises”, “comprised of,” “including,” “includes,” “included,” “involving,” “involves,” “involved,” and “such as” are used in their open, non-limiting sense and may be used interchangeably. Further, the term “comprising” is intended to include examples and aspects encompassed by the terms “consisting essentially of” and “consisting of.” Similarly, the term “consisting essentially of” is intended to include examples encompassed by the term “consisting of.

[0099] As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a Lewis acid,” “a Lewis base,” or “a solvent,” including, but not limited to, two or more such Lewis acids, Lewis bases, or solvents, and the like.

[0100] It should be noted that ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format. It will be further understood that the endpoints of each of theATTORNEY DOCKET NO. 331903-2010 ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Ranges can be expressed herein as from “about” one particular value, and / or to “about” another particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further aspect. For example, if the value “about 10” is disclosed, then “10” is also disclosed.

[0101] When a range is expressed, a further aspect includes from the one particular value and / or to the other particular value. For example, where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g., the phrase “x to y” includes the range from ‘x’ to ‘y’ as well as the range greater than ‘x’ and less than ‘y’. The range can also be expressed as an upper limit, e.g., ‘about x, y, z, or less’ and should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘less than x’, less than y’, and ‘less than z’. Likewise, the phrase ‘about x, y, z, or greater’ should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘greater than x’, greater than y’, and ‘greater than z’. In addition, the phrase “about ‘x’ to ‘y’”, where ‘x’ and ‘y’ are numerical values, includes “about ‘x’ to about ‘y’”.

[0102] It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or subranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “about 0.1 % to 5%” should be interpreted to include not only the explicitly recited values of about 0.1 % to about 5%, but also include individual values (e.g., about 1%, about 2%, about 3%, and about 4%) and the sub-ranges (e.g., about 0.5% to about 1.1%; about 5% to about 2.4%; about 0.5% to about 3.2%, and about 0.5% to about 4.4%, and other possible sub-ranges) within the indicated range.

[0103] As used herein, the terms “about,” “approximate,” “at or about,” and “substantially” mean that the amount or value in question can be the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to thoseATTORNEY DOCKET NO. 331903-2010 of skill in the art such that equivalent results or effects are obtained. In some circumstances, the value that provides equivalent results or effects cannot be reasonably determined. In such cases, it is generally understood, as used herein, that “about” and “at or about” mean the nominal value indicated ±10% variation unless otherwise indicated or inferred. In general, an amount, size, formulation, parameter or other quantity or characteristic is “about,” “approximate,” or “at or about” whether or not expressly stated to be such. It is understood that where “about,” “approximate,” or “at or about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0104] As used herein, the term “substituted” is contemplated to include all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents can be one or more and the same or different for appropriate organic compounds. For purposes of this disclosure, the heteroatoms, such as nitrogen, can have hydrogen substituents and / or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms. This disclosure is not intended to be limited in any manner by the permissible substituents of organic compounds. Also, the terms “substitution” or “substituted with” include the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., a compound that does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. It is also contemplated that, in certain aspects, unless expressly indicated to the contrary, individual substituents can be further optionally substituted ( / .e., further substituted or unsubstituted).

[0105] The term “alkyl” as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t- butyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can be cyclic or acyclic. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, aryl, amino, ether, halide, hydroxy, nitro, silyl, sulfooxo, or thiol, as described herein. A “lower alkyl” group is an alkyl group containing from one to six (e.g., from one to four) carbon atoms. The term alkyl group can also be a C1 alkyl, C1-C2 alkyl, C1-C3 alkyl, C1-C4 alkyl, C1-C5 alkyl, C1-C6 alkyl, C1-C7 alkyl, C1-C8 alkyl, C1-C9 alkyl, C1-C10 alkyl, and the like up to and including a C1-C24 alkyl.ATTORNEY DOCKET NO. 331903-2010

[0106] Throughout the specification “alkyl” is generally used to refer to both unsubstituted alkyl groups and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the specific substituent(s) on the alkyl group. For example, the term “halogenated alkyl” or “haloalkyl” specifically refers to an alkyl group that is substituted with one or more halide, e.g., fluorine, chlorine, bromine, or iodine. Alternatively, the term “monohaloalkyl” specifically refers to an alkyl group that is substituted with a single halide, e.g. fluorine, chlorine, bromine, or iodine. The term “polyhaloalkyl” specifically refers to an alkyl group that is independently substituted with two or more halides, i.e. each halide substituent need not be the same halide as another halide substituent, nor do the multiple instances of a halide substituent need to be on the same carbon. The term “alkoxyalkyl” specifically refers to an alkyl group that is substituted with one or more alkoxy groups, as described below. The term “aminoalkyl” specifically refers to an alkyl group that is substituted with one or more amino groups. The term “hydroxyalkyl” specifically refers to an alkyl group that is substituted with one or more hydroxy groups. When “alkyl” is used in one instance and a specific term such as “hydroxyalkyl” is used in another, it is not meant to imply that the term “alkyl” does not also refer to specific terms such as “hydroxyalkyl” and the like.

[0107] The term “alkenyl” as used herein is a hydrocarbon group of from 2 to 24 carbon atoms with a structural formula containing at least one carbon-carbon double bond. Asymmetric structures such as (A1A2)C=C(A3A4) are intended to include both the E and Z isomers. This can be presumed in structural formulae herein wherein an asymmetric alkene is present, or it can be explicitly indicated by the bond symbol C=C. The alkenyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, as described herein.

[0108] The term “aromatic group” as used herein refers to a ring structure having cyclic clouds of delocalized TT electrons above and below the plane of the molecule, where the rr clouds contain (4n+2) TT electrons. A further discussion of aromaticity is found in Morrison and Boyd, Organic Chemistry, (5th Ed., 1987), Chapter 13, entitled “ Aromaticity,” pages 477-497, incorporated herein by reference. The term “aromatic group” is inclusive of both aryl and heteroaryl groups.

[0109] The term “aryl” as used herein is a group that contains any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl, anthracene, and the like. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl,ATTORNEY DOCKET NO. 331903-2010 cycloalkynyl, aryl, heteroaryl, aldehyde, — NH2, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein. The term “biaryl” is a specific type of aryl group and is included in the definition of “aryl.” In addition, the aryl group can be a single ring structure or comprise multiple ring structures that are either fused ring structures or attached via one or more bridging groups such as a carbon-carbon bond. For example, biaryl to two aryl groups that are bound together via a fused ring structure, as in naphthalene, or are attached via one or more carbon-carbon bonds, as in biphenyl.

[0110] The terms “halo,” “halogen” or “halide,” as used herein can be used interchangeably and refer to F, Cl, Br, or I.

[0111] The term “aliphatic” or “aliphatic group,” as used herein, denotes a hydrocarbon moiety that may be straight-chain (i.e. , unbranched), branched, or cyclic (including fused, bridging, and spirofused polycyclic) and may be completely saturated or may contain one or more units of unsaturation, but which is not aromatic. Unless otherwise specified, aliphatic groups contain 1-20 carbon atoms. Aliphatic groups include, but are not limited to, linear or branched, alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.

[0112] The term “carboxylic acid” as used herein refers to an aliphatic group of 1 to 24 carbon atoms that contains at least one functional group represented by the formula — C(O)(OH). The carboxylic acid can be substituted or unsubstituted. Examples of carboxylic acids include, but are not limited to, monocarboxylic acids (e.g., acrylic acid, oleic acid, formic acid, acetic acid, benzoic acid, caffeic acid); dicarboxylic acids (e.g., oxalic acid, pimelic acid, aspartic acid); and tricarboxylic acids (e.g., citric acid, isocitric acid, trimesic acid).

[0113] The term “oligosaccharide” as used herein refers to saccharides, or sugars, comprised of from 3 to about 10 monosaccharide units. Examples of include, but are not limited to, oligosaccharides include maltotriose, raffinose, and cyclodextrins.

[0114] As used herein, “lignocellulosic biomass” refers to a plant or plant-based material that is composed primarily of cellulose, hemicellulose, and lignin.

[0115] As used herein the terms “weight percent,” “wt%,” and “wt. %,” which can be used interchangeably, indicate the percent by weight of a given component based on the total weight of a composition of which it is a component, unless otherwise specified. That is, unless otherwise specified, all wt% values are based on the total weight of the composition. It should be understood that the sum of wt% values for all components in a disclosed composition or formulation are equalATTORNEY DOCKET NO. 331903-2010 to 100. Alternatively, if the wt% value is based on the total weight of a subset of components in a composition, it should be understood that the sum of wt% values the specified components in the disclosed composition or formulation are equal to 100.

[0116] As used herein, the term “effective amount” refers to an amount that is sufficient to achieve the desired modification of a physical property of the composition or material. For example, an “effective amount” of a cooling composition refers to an amount that is sufficient to achieve the desired improvement in the property modulated by the disclosed compositions, e.g., achieving the desired enhancement in flame resistance, thermal conductivity, and / or UV absorption compared to a yarn or fabric without the effective amount of disclosed composition. The specific level in terms of wt% in a composition required as an effective amount will depend upon a variety of factors including the amount and type of polymer and yarn, fabric use, and the like.

[0117] The term “nanoparticle” as used herein comprises a nanoscale deposit of a homogenous or heterogeneous material. Nanoparticles may be regular or irregular in shape and may be formed from a plurality of co-deposited particles that form a composite nanoscale particle. Nanoparticles may be generally spherical in shape or have a composite shape formed from a plurality of codeposited generally spherical particles. Exemplary shapes for the nanoparticles include, but are not limited to, spherical, rod, elliptical, cylindrical, disc, and the like. In some embodiments, the nanoparticles have a substantially spherical shape.

[0118] As used herein, “nanocellulose” refers to a cellulose-based material, in which the median length of particles in at least one dimension is less than about 100 nm. Cellulose refers to a linear polysaccharide material comprising repeating [3-d-glucopyranose molecules having a chemical structure as shown immediately below.

[0119] The term “nanoscale” as used herein comprises a surface having a measurable feature in the range of from about 1 to about 1000 nm.

[0120] As used herein, the term “never-dried” refers to a material (e.g., never-dried cellulose) that has been kept in a moist state and is not subjected to drying processes such as air drying, oven drying, or vacuum drying. The water content of a never-dried material is maintained at a level of more than 50 wt%.ATTORNEY DOCKET NO. 331903-2010

[0121] As used herein, the term “fiber” refers to refers to any slender, elongated structure that can be carded, combed, or otherwise formed into a thread or filament. A fiber can comprise a natural material (e.g., cotton, linen or wool) or an artificial material (e.g., nylon, polyester). A fiber is a material in which the length to diameter ratio is greater than about 10. Fiber is typically classified according to its fineness. Fiber is generally defined as having a fiber fineness greater than about 15 Denier, usually greater than about 30 Denier. Fine Denier fiber generally refers to a fiber having a fineness less than about 15 Denier. Examples of fibers include “staple fibers”, a term that is well-known in the textile art. A reference to “fiber” of “fibers” may mean or include individual fibers or a plurality or bulk of fibers as the situation requires. A plurality of fibers may comprise fibers of different compositions or may be substantially uniform in composition. Thus, by way of illustration, a reference to “natural fiber” or “synthetic fiber” may mean and may include a single fiber of such type or may mean any quantity or plurality of such fibers and they may be comprised in threads, felts, yarns, fabrics materials etc., all as will be apparent from the context.

[0122] The fiber can be a synthetic fiber or a natural or organic fiber. As one of skill in the art is well aware, smoothness of the outer surfaces is significantly varied between different fibers. Accordingly, the outer surface of the fiber can be smooth or rough. By way of example only, manmade fibers, such as polyester fibers, usually have a smooth outer surface. In contrast, natural fibers, such as cotton, usually have a rough outer surface. One consequence of the roughness of the outer surface is that rough surfaces take more fluid to completely cover the surface per unit diameter.

[0123] As used herein, “fiber” refers to any one of the various types of matter that form the basic elements of a textile and that is characterized by a flexible, macroscopically homogeneous body having a high ratio of length to width and being small in cross section, and may include one or more fibrous materials (e.g., fibers or filaments). It is understood that “fiber” includes “filaments.” A fiber can then be texturized directly (which is uncommon), or can be combined with other filaments to form a filament bundle with the resultant filament bundle can then be texturized.

[0124] As used herein, “filament” refers generally to a continuous fiber of extremely long length, whereas a “staple fiber” means a fiber of finite length. A staple fiber can be a natural fiber or a fiber cut from, for example, a filament.

[0125] The term “yarn” refers a structure comprising a plurality of fibers that have been twisted, spun or otherwise joined together to form the yarn and may include spun yarns, continuous filament yarns, and yarns of core spun construction. The strands that that have been twisted, spun or otherwise joined together can be of natural or synthetic material, such as wool, nylon, orATTORNEY DOCKET NO. 331903-2010 polyester, in a form suitable for sewing, knitting, weaving, or otherwise intertwining to form a textile fabric. In general, “yarn” refers to a product obtained when fibers are aligned. Yarns are products of substantial length and relatively small cross-section. Yarns may be single ply yarns, that is, having one yarn strand, or multiple ply yarns, such as 2-ply yarn that comprises two single yarns twisted together or 3-ply yarn that comprises three yarn strands twisted together. In various aspects, the disclosed composite fibers are used to prepare disclosed yarns. The disclosed yarns can be formed using staple fibers, using continuous fibers, or combinations thereof.

[0126] As used herein, “multifilament” means a yarn consisting of many continuous filaments or strands, as opposed to monofilament which is one strand. Most textile filament yarns are multifilament.

[0127] As used herein, the term “filament yarn” refers to a yarn that is composed of more than one fiber filaments that run the whole length of the yarn. Filament yarns can also be referred to as multi-filament yarns. The structure of a filament yarn is influenced by the amount of twist, and in some cases the fiber texturing. The properties of the filament yarn can be influenced by the structure of the yarn, fiber to fiber friction of the constituent fibers, and the properties of the constituent fibers. In some embodiments, the yarn structure and the recombinant protein fiber properties are chosen to impart various characteristics to the resulting yarns. The properties of the yarn can also be influenced by the number of fibers (i.e. , filaments) in the yarn. The filament yarns disclosed herein can be multifilament yarns. Throughout this disclosure “filament yarns” can refer to flat filament yarns, textured filament yarns, drawn filament yarns, undrawn filament yarns, or filament yarns of any structure.

[0128] As used herein, the term “spun yarn” refers to a yarn that is made by twisting staple fibers together to make a cohesive yarn (or thread, or “single”). The structure of a spun yarn is influenced by the spinning methods parameters. The properties of the spun yarn are influenced by the structure of the yarn, as well as the constituent fibers.

[0129] As used herein, the term “blended yarn” refers to a type of yarn comprising various fibers being blended together.

[0130] As used herein, the term “textile” shall mean a fiber, filament, yarn, fabric, or any article comprising fabrics and / or yarns, such as garments, articles of clothing, home goods, including, but not limited to, bed and table linens, linens, draperies and curtains, and upholsteries, and the like.

[0131] The term “articles of clothing” include any article of clothing including, for example,ATTORNEY DOCKET NO. 331903-2010 underwear, t-shirts, shirts, pants, socks, hats, diapers, and jackets.

[0132] As used herein, the term “garment” refers to wearable articles comprising fabrics or cloth to any item that is covers or protects some region of the user's body from weather or other factors in the environment outside the body. Exemplary garments, include, but are not limited to, coats, jackets, pants, hats, gloves, shoes, socks, shirts, blouses, dresses, coats, and the like. It is noted that the term “garment” is intended to cover clothing for human or animal use.

[0133] The term “linen” as used herein, refers to any article routinely washed in a residential or commercial washing machine besides articles of clothing, including, for example, sheets, blankets, towels, drapery, wash cloths, napkins, tablecloths, and pillowcases.

[0134] As used herein, the term “fabric” is to be understood in its widest meaning. The term “fabric” may be used for all structures composed of fibers which have been manufactured according to a surface-forming method. Fabrics include materials where one or more different types of yarns, threads, filaments, or fibers that have been woven, knitted, felted, wrapped, spun, co-mingled, coated, coextruded, braided, entangled, applied or otherwise assembled into a desired material. Generally, the fabric has a structure which comprises a series of meshes or openings and filament bundles which define the mesh boundaries, such as woven, knitted, knotted, interwoven or tufted structures. Without limitations, the term “fabric” is intended to include woven fabrics, yarn sheets, knitted fabrics and non-woven fabrics. Further, the fabrics may be constructed from a combination of fibers, threads or yarns. Fabrics comprising different fibers, threads or yarns are also referred to as fabric blends herein. A knitted fabric may be flat knit, circular knit, warp knit, narrow elastic, and lace. A woven fabric may be of any construction, for example sateen, twill, plain weave, oxford weave, basket weave, and narrow elastic and the like.

[0135] As used herein, the term “cloth” refers to any textile fabric woven, nonwoven, felted, knitted or otherwise formed from any filament or fiber or plurality of filaments or fibers, including but not limited to thread yarn, monofilaments, and ribbons. Further, the term cloth is intended to include within its scope not only woven, knitted, non-woven, and felted materials, but also sheet materials.

[0136] As used herein, the terms “optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0137] As used herein, the term “hornification” refers to a stiffening of the polymer structure that occurs in lignocellulosic materials, such as pulp fibers, upon drying or water removal, as the water- cellulose bonds are replaced by cellulose-cellulose bonds. It involves the irreversible or partiallyATTORNEY DOCKET NO. 331903-2010 reversible formation of hydrogen bonds in the fiber material. Hornification is characterized by a reduction in the ability of fibers to hold water within their cell walls, leading to stiffer and less conformable fibers upon rewetting. This phenomenon is closely associated with changes in fiber morphology, surface characteristics, and suitability for papermaking, including a decrease in flexibility, pore space closure, and damage to fibers.

[0138] As used herein, “deep eutectic solvent” or “DES” refers to a class of solvents that are characterized by their ability to form mixtures with a melting point that is lower than the melting points of the individual components of the mixture. These solvents typically include a Lewis acid, such as a carboxylic acid or a metal halide, and a Lewis base, such as a quaternary ammonium compound. DESs exhibit unique properties such as low toxicity, low volatility, high thermal stability, and tunable polarity, making them attractive alternatives to conventional organic solvents.

[0139] As used herein, “quaternary ammonium compound” or “quaternary ammonium” includes quaternary ammonium compounds such as, for example, salts, halides, sulfates, hydroxides, nitrates, and acetates.

[0140] As used herein, “ambient conditions” refers to reaction conditions including ambient temperatures, where the temperature ranges from about 15 °C to about 30 °C, about 17 °C to about 28 °C, or about 19 °C to about 26 °C, and including ambient pressures, where the pressure ranges from about 0.7 bar to about 1.6 bar, about 0.8 bar to about 1.5 bar, or about 0.9 bar to about 1.4 bar.

[0141] Unless otherwise specified, temperatures referred to herein are based on atmospheric pressure (i.e., one atmosphere).

[0142] Abbreviations used herein throughout are as follows:Abbreviation MeaningAFM Atomic force microscopy-bet or -BET Betaine-ca or -CA Citric acidCBM CarboxymethylcelluloseCNC Cellulose nanocrystalsCNF Cellulose nanofibersATTORNEY DOCKET NO. 331903-2010CNM Cellulose nanomaterial such as a CNC or CNFCM Cellulose material-d Dried seaweed pulpDI Deionized waterDES Deep eutectic solventDLS Dynamic light scatteringGMA glycidyl methacrylateGVL Gammavalerolactone h-BN or HBN hexagonal boron nitrideHV-0 High shear mixing at low pressures-ia or -IA Itaconic acid-oa or -OA Oxalic acid-sa or -SA Sulphamic acid sc or SC Seaweed cellulose sc-pcnf Seaweed pristine cellulose nanofibers-w Never-dried seaweed pulpOp or FOP No fluidization passes1p or F1 P One fluidization pass3p or F3P Three fluidization passesB. INTRODUCTION

[0143] The disclosure provides for methods for modifying or treating a cellulose material as well as compositions, fibers, filaments, yarns, casts, molds, articles, clothing, and the like, that include the modified or treated cellulose. A cellulose material can include CNMs, both exfoliated and pristine, and materials such as CBM or other celluloses. In various aspects, disclosed herein are methods of treating a cellulose material with a solvent (e.g., a DES) comprising a Lewis acid (e.g., a hydrogen bond donor) and a Lewis base (e.g., a hydrogen bond acceptor). In one aspect, the treatment method produces a functionalized cellulose material, such as a functionalized nanocellulose material. Treating a cellulose material with a DES, as opposed to other solvents,ATTORNEY DOCKET NO. 331903-2010 can enable better swelling of the material and more effective functionalization. Furthermore, treating a cellulose material with a compound, such as a carboxylic acid, that is part of the DES can reduce the amount of hydrolysis that the cellulose material may undergo during treatment. In one aspect, more of the treatment compound can be used as part of a DES than if it was included in another solvent, such as water, resulting in more effective functionalization of the cellulose material.

[0144] The term Lewis acid, as used herein, can refer to a compound acting as an electron pair acceptor and / or, in a hydrogen bonding system, a hydrogen bond donor. The term Lewis base, as used herein, can refer to a compound acting as an electron pair donor and / or, in a hydrogen bonding system, a hydrogen bond acceptor. Labeling a given compound as a Lewis acid is not meant to imply that the compound cannot act as a Lewis base. A given compound can act, for example, as a hydrogen bond donor or a hydrogen bond acceptor depending on the identity and the relative acid / base strength of other components present in the solvent. For example, organic acids (e.g., citric acid, sulphamic acid, or oxalic acid), polyols (e.g., glycol), amino acids, and betaine or betaine derivatives are multifunctional species that can interchange roles (Lewis acid / Lewis base) within different solvent formulations.

[0145] The functionalized cellulose material produced by the methods disclosed herein can be used, for example, as a dispersant for (nano)particles, dyes, organic solids, inorganic solids, polymers, liquids, or other chemicals, and / or in coatings, films, fibers, filaments, paints, cosmetics, composites, or drug delivery systems. When using the functionalized cellulose material as a dispersant, the dispersed material can be included in the fibrillation step of the treatment method. A film and / or coating can include the functionalized cellulose material and, optionally, additional materials. The film and / or coating can include the functionalized cellulose material where the functionalized cellulose material acts as a dispersant or carrier for materials such as (nano)particles, dyes, organic solids, inorganic solids, polymers, liquids, or other chemicals. The film and / or coating can further comprise additional materials such as inorganic fibers (e.g., basalt, carbon, or glass), ceramic fibers, synthetic fibers, natural fibers (e.g., flax, hemp, jute, or kenaf), or any combination thereof. For example, the functionalized cellulose material can be a part of a composite layer including the functionalized cellulose material and other fibers. In another aspect, the functionalized cellulose material can be included in a film or a coating applied to a material comprising fibers (e.g., inorganic fibers, ceramic fibers, synthetic fibers, natural fibers, or any combination thereof). In another aspect, the functionalized cellulose material can be included in a film or a coating between two or more layers comprising fibers. For example, the functionalized cellulose material can be used as a binding agent, alone or in combination with other components,ATTORNEY DOCKET NO. 331903-2010 to physically adhere two components together (e.g., physically bind or glue a coloring agent to a fabric). As another example, the functionalized cellulose material can be used as a mordant agent, alone or in combination with other components, to chemically adhere two components together (e.g., chemically connect a coloring agent to a fabric). As another example, the functionalized cellulose material can be used as a sizing agent, along or in combination with other components, to coat a surface of a material (e.g., paper or fabric) and affect the characteristics of the material, such as affecting absorption and / or wear characteristics of the material. In another aspect, the functionalized cellulose material can also act as a carrier of functional materials (e.g., active ingredients) that introduce functional characteristics such as, for example, magnetic properties, electrical properties (e.g., electrically conductive or electrically non-conductive), thermal properties (e.g., thermally conductive), and the like. These functional materials can include organic solids, inorganic solids, polymers, liquids, and the like.

[0146] In one aspect, the method comprises combining a cellulose feedstock and a first solvent in a weight ratio of about 1 :0.5 to about 1 :200 cellulose feedstock to first solvent, thereby forming a cellulosic suspension; mixing the cellulosic suspension under high shear; treating the cellulosic suspension with a reaction treatment comprising: incubation of the cellulosic suspension at a temperature of at least 30°C; microwave irradiation exposure; plasma exposure; ultrasound exposure; grinding; ball-milling; extrusion; a sequence thereof; or any combination thereof, thereby forming a treated cellulosic suspension comprising a treated cellulose material; diluting the treated cellulosic suspension with a second solvent; washing the treated cellulosic suspension with a third solvent, thereby forming a washed cellulosic suspension comprising the treated cellulose material; and draining the washed cellulosic suspension, thereby forming an intermediate cellulosic suspension comprising the treated cellulose material; wherein the first solvent comprises a Lewis base and a Lewis acid in an about 10:2 to about 1:9 molar ratio of Lewis base to Lewis acid; wherein the second solvent is miscible with the first solvent; wherein the third solvent is miscible with the second solvent; and wherein the intermediate cellulosic suspension comprises from about 2 wt% to about 50 wt% of the treated cellulose material.C. COMPOSITIONS

[0147] In various aspects, the disclosed compositions comprise a functionalized cellulose material. In a further aspect, the disclosed compositions comprise a functionalized cellulose nanomaterial, a cellulose material, and combinations thereof. In a still further aspect, the disclosed compositions comprise a cellulose nanomaterial. Exemplary cellulose nanomaterials useful for the disclosed compositions include cellulose nanocrystals, cellulose nanofibers, and mixturesATTORNEY DOCKET NO. 331903-2010 thereof.

[0148] In various aspects, a cellulose material can comprise one or more cellulose materials, including any of the disclosed CNMs, a cellulose material such as CBM, and any of the foregoing cellulose materials as pristine cellulose materials, modified cellulose materials, and / or exfoliated cellulose materials.

[0149] In various aspects, the cellulose feedstock or cellulose material used in the present disclosure can be extracted from softwoods, hardwoods, macro algae, micro algae, bacteria, fungi, and tunicates. In a further aspect, the cellulose material can comprise a variety of morphologies such as those classified as cellulose nanocrystals, cellulose crystallites, cellulose nano whiskers, microcrystalline cellulose, cellulose nanofibrils, and cellulose nanofibers. Cellulose can range in molecular weight from 3 x 104to 2 x 105g mol-1.

[0150] Algal biomass used in the disclosed compositions can be obtained from brown algae (pheophyta) of the genera Macrocystis, Laminaria, Ascophyllum, Alario, Ecklonia, Eisenia, Nercocystis, Sargassum, Cystoseira, and Fucus. The algal biomass can comprise alginate structures composed of linear, unbranched polysaccharide monomers [3-D mannuronic acid blocks and a-L guluronic acid blocks. Insoluble protonated alginate can be readily converted to a soluble salt form, e.g., sodium alginate (SA), calcium alginate, potassium alginate, and / or ammonium alginate, by methods known in the art. In further aspects, the algal biomass used can comprise an ester modified alginate, e.g., propylene glycol alginate, but other ester forms can be used as well. In various aspects, the algal biomass used in the disclosed compositions can possess a viscosity range between 20-400 centipoises when determined using a 1 wt% aqueous solution at 20 °C. In a further aspect, the algal biomass used in the disclosed compositions can possess a viscosity range between 20 mPa«s to 1500 mPa*s when determined using a 1 wt% aqueous solution at 20 °C. The molecular weight of algal biomass used in the final composition can range from 32,000 to 200,000 with a degree of polymerization from 180 to 930.

[0151] In various aspects, the disclosed compositions can further comprise plasticizers, particularly when utilized in forming films, filaments, and molded articles to enhance elasticity of the films, filaments, and molded articles comprising disclosed CNM compositions. Without wishing to be bound by a particular theory, it is believed that hydrogen bonds between water molecules and biopolymers in a disclosed composition can be decreased due to the increased affinity between water and the plasticizer, thereby increasing polymer free volume and thus reducing interchain interactions. In a further aspect, the plasticizer can include, but is not limited to, erythritol, xylitol, sorbitol, maltitol, isomalt, lactitol, hydrogenated starch hydrolysates (HSH),ATTORNEY DOCKET NO. 331903-2010 fructose, mannitol, inulin, arabinogalactan, glucomannan, galactooligosaccharides (GOS), xylooligosaccharides (XOS), cellulose, and glycerol. Plasticizers may also be derived from biobased sources such as but not limited to epoxidized soybean oil, castor oil, cardanol, citrates, succinic acid, and isosorbides (Ref. 10).

[0152] In a further aspect, a film, a filament or a molded article comprising a disclosed composition can comprise a plasticizer in an amount from 0.1% to 250% based on weight of the total dry mass of the film, filament, or molded article to improve % strain from 0 to 40% strain or about 1 to 40% strain. In a further aspect, a film, a filament or a molded article comprising a disclosed composition can comprise a plasticizer in an amount from 0.1% to 50% based on weight of the total dry mass of the film, filament, or molded article to improve % strain from 0 to 40% strain or about 1 to 40% strain. In a further aspect, a film, a filament or a molded article comprising a disclosed composition can comprise a plasticizer in an amount from 0.1% to 250% based on weight of the total dry mass of the film, filament, or molded article to improve % strain from 0 to 210% strain or about 1 to 210% strain. In a further aspect, a film, a filament or a molded article comprising a disclosed composition can comprise a plasticizer in an amount from 0.1 % to 50% based on weight of the total dry mass of the film, filament, or molded article to improve % strain from 0 to 210% strain or about 1 to 210% strain.

[0153] In various aspects, the disclosed compositions can further comprise one or more coagulant such as an acid-based coagulant, an electrolyte coagulant, a cationic polymer, a polyol, or combinations thereof. A suitable acid-based coagulant can be a natural or synthetic mono or polycarboxylate acid, e.g., citric acid or other polycarboxylate acid, particularly a naturally occurring polycarboxylate acid. Citric acid and other acids possess at least one carboxyl groups to crosslink with hydroxyl groups via an esterification reaction. In a further aspect, one or more electrolyte coagulant can be used. In some aspects a coagulant can comprise one or more cationic polymer. A cationic polymer can be utilized to coagulate via in situ polyelectrolyte complexation. In a further aspect, a cationic polymer can comprise a natural cationic polymer such as, but not limited to, a chitosan. In a yet further aspect, a coagulant can comprise a polyol, such as ethylene glycol, glycerol, pentaerythritol, or combinations thereof. In a yet further aspect, a coagulant can comprise in situ coagulation or crosslinking comprising esterification of alginate with one or more polyol in situ using acid catalysis in which the acid catalysis is carried out using a strong acid such as HCI or sulfuric acid (e.g., see Y. Xu, et al. Material. Design (2022) 214:110424).D. DEEP EUTECTIC SOLVENTSATTORNEY DOCKET NO. 331903-2010

[0154] In one aspect, the solvent mixed with the cellulose feedstock (the first solvent) is a DES. The DES can be a natural DES, a synthetic DES, or can include natural and synthetic components. In one aspect, at least one component of the DES has the capacity to react with the cellulose feedstock and alter the chemical structure of the cellulose. The DES can be prepared by mixing a Lewis acid and a Lewis base at a Lewis base:Lewis acid molar ratio of about 10:2 to about 1 :9, about 10:2 to about 1 :7, about 10:3 to about 1 :8, about 10:4 to about 1:9, or about 10:4 to about 1 :7. The mixture can be treated via exposure to heat, optionally under reduced pressure and / or with stirring, exposure to microwave irradiation, exposure to ultrasound, mechanically grinding, a sequence thereof, or a combination thereof. In another aspect, the components of the DES can be mixed (and heated) through extrusion (e.g., twin screw extrusion). In another aspect, the components can be dissolved in a solvent before or after mixing, followed by heating, optionally under reduced pressure and / or with stirring, or followed by freezing and lyophilization. The temperature during the DES preparation process can range from about 20 °C to about 200 °C, about 20 °C to about 165 °C, about 40 °C to about 180 °C, about 60 °C to about 200 °C, or about 60 °C to about 165 °C. The DES can be treated with the selected method until a clear liquid is formed, and the mixing continued at the designated temperature for up to 24 hours. In a further aspect, the mixing can be continued at the designated temperature for about 5 minutes to about 20 hours, about 5 minutes to about 16 hours, about 5 minutes to about 12 hours, about 5 minutes to about 8 hours, about 5 minutes to about 4 hours, about 10 minutes to about 4 hours, or about 10 minutes to about 2 hours.

[0155] During preparation of the DES or after preparation, one or more additional components can be added to the solvent, for example, a reagent or a catalyst used for the cellulose treatment. These additional components can include a metal halide, a metal halide hydrate, an alkali metal chloride, toluenesulfonic acid, or an enzyme, such as endoglucanase, exoglucanase, cellulase, cellobiase, cellobiohydrolase, p-glucosidase, xylanase, mannanase, glucomannanase, or a combination thereof. In a further aspect, the metal halide can be selected from ZnCh, ZnBr2, FeCI3, FeBr3, SnCh, SnBr2, MgCh, MgBr2, CaCh, CaBr2, CrCI3, CrBr3, MnCh, MnBr2, AICI3, AIBr3, CuCI2, CuBr2, and any combination thereof. In another further aspect, the metal halide hydrate can be selected from ZnCh • n H2O; ZnBr2• n H2O; CaCh • 6 H2O; CaBr2• 6 H2O; MgCh • 6 H2O; MgBr2• 6 H2O; CrCI3• 6 H2O; CrBr3• 6 H2O; SnCI2• 2 H2O; SnBr2• 2 H2O; FeCI3• 6 H2O; FeBr3• 6 H2O; MnCh • 4 H2O; MnBr2• 4 H2O; AICI3• 6 H2O; AIBr3• 6 H2O; CuCI2• 2 H2O; CuBr2• 2 H2O; and any combination thereof, wherein n ranges from 1 to 4. In another further aspect, the alkali metal chloride can be selected from LiCI, LiBr, NaCI, NaBr, KCI, KBr, and any combination thereof.ATTORNEY DOCKET NO. 331903-2010

[0156] A supplemental solvent can be added before, during, or after forming the DES and can be included in the cellulosic suspension. In one aspect, the supplemental solvent can be used to help control the viscosity and / or the reaction kinetics during the cellulose treatment method disclosed herein. The supplement solvent can include water, methanol, ethanol, isopropanol, tertbutanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof. Examples of suitable polyols include glycerol, sorbitol, mannitol, maltitol, erythritol, pentaerythritol, xylitol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol), propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and any combination thereof. The supplemental solvent can comprise water in an amount of up to about 70 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent. In a further aspect, the supplemental solvent can comprise water in an amount of from about 5 mol% to about 70 mol%, about 5 mol% to about 60 mol%, or about 10 mol% to about 50 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent. The supplemental solvent can also comprise, in addition to water or in place of water: methanol, ethanol, isopropanol, tert-butanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof in an amount of up to about 50 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent. In another aspect, the supplemental solvent can comprise, in addition to water or in place of water: methanol, ethanol, isopropanol, tert-butanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof in an amount of from about 2 mol% to about 50 mol%, from about 2 mol% to about 40 mol%, or about 4 mol% to about 30 mol%.

[0157] The Lewis base of the first solvent or DES can be a quaternary ammonium compound, carboxylic acid, a polyol, or any combination thereof. The carboxylic acid can be in an acidic (protonated) or a carboxylated (deprotonated) form. In one aspect, the Lewis base can be a monocarboxylic acid (protonated or deprotonated); a dicarboxylic acid (protonated or deprotonated); a tricarboxylic acid (protonated or deprotonated); a polyol; choline halide; an amino acid; tetraalkylammonium halide; benzyltrialkyl ammonium halide; methyltrialkyl ammonium halide; alkyldimethyl(2-hydroxyethyl)ammonium halide; dialkyl-di(2-hydroxyethyl)- ammonium halide; alkyl-tri(2-hydroxyethyl)-ammonium halide; N,N-dialkylethanolammonium halide; 2-(chlorocarbonyloxy)-N,N,N-trialkylethanaminium halide; alkyltriphenylphosphonium halide; alkenyltriphenylphosphonium halide; imidazolium (e.g., 1-ethyl-3-methylimidazolium, 1- butyl-3-methylimidazolium, 1-allyl-3-methylimidazolium); 1 ,5-diazabicyclo[4.3.0]non-5-enium; N- alkenyl-N-methylmorpholinium; sulphamic acid; glycine-betaine; a derivative thereof; or any combination thereof. The amino acid can be selected from alanine, p-alanine, glycine, proline,ATTORNEY DOCKET NO. 331903-2010 histidine, glutamic acid, lysine, ornithine, arginine, citrulline, serine, and any combination thereof. Note that glycine-betaine is also known as trimethylglycine. The polyol can be selected from glycerol, sorbitol, mannitol, maltitol, erythritol, pentaerythritol, xylitol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, poly(ethylene glycol), propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and any combination thereof.

[0158] In a further aspect, the Lewis base can be a saturated monocarboxylic acid (protonated or deprotonated), an unsaturated monocarboxylic acid (protonated or deprotonated), a monocarboxylic acid (protonated or deprotonated) substituted with an aryl group, a dicarboxylic acid (protonated or deprotonated), a tricarboxylic acid (protonated or deprotonated), a polyol, choline halide; acetylcholine halide; an amino acid; a betaine derivative of an amino acid; a betaine hydrochloride derivative of an amino acid; a salt of an amino acid; tetramethylammonium halide; tetraethylammonium halide; tetrapropylammonium halide; tetrabutylammonium halide; benzyltrimethyl ammonium halide; benzyltriethyl ammonium halide; methyltriethyl ammonium halide; ethyldimethyl(2-hydroxyethyl)ammonium halide; benzyldimethyl(2- hydroxyethyl)ammonium halide; dimethyl-di(2-hydroxyethyl)-ammonium halide; methyl-tri(2- hydroxyethyl)-ammonium halide; N,N-dimethylethanolammonium halide; N,N- diethylethanolammonium halide; 2-(chlorocarbonyloxy)-N,N,N-trimethylethanaminium halide; methyltriphenylphosphonium halide; benzyltriphenylphosphonium halide; allyltriphenylphosphonium halide; vinyltriphenylphosphonium halide; imidazolium (e.g., 1-ethyl-3- methylimidazolium, 1-butyl-3-methylimidazolium, 1-allyl-3-methylimidazolium); 1 ,5- diazabicyclo[4.3.0]non-5-enium; N-allyl-N-methylmorpholinium; sulphamic acid; glycine-betaine; a derivative thereof; or any combination thereof.

[0159] The saturated monocarboxylic acid can be selected from formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and any combination thereof. The unsaturated monocarboxylic acid can be selected from acrylic acid, methacrylic acid, oleic acid, linoleic acid, and any combination thereof. The monocarboxylic acid substituted with an aryl group can be selected from benzoic acid, salicylic acid, acetylsalicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, gallic acid, caffeic acid, coumaric acid, cinnamic acid, phenylacetic acid, phenylpropionic acid, and any combination thereof. The dicarboxylic acid can be selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, tartaric acid, itaconic acid, methylsuccinic acid, aspartic acid, glutamic acid, and any combinationATTORNEY DOCKET NO. 331903-2010 thereof. The tricarboxylic acid can be selected from citric acid, isocitric acid, aconitic acid, trimesic acid, tricarbalyllic acid, and any combination thereof.

[0160] The Lewis acid of the first solvent or DES can be a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, a polyol, a monosaccharide (e.g., xylose, mannose, fructose, glucose, ribose), a disaccharide, an oligosaccharide (e.g., cyclodextrin), an amino acid (e.g., lysine, aspartic acid, glutamic acid), an amide (e.g., acetamide, benzamide), an anhydride (e.g., acetic anhydride, succinic anhydride), a dihydrogen phosphate salt, urea, imidazole, ascorbic acid, glucuronic acid, levulinic acid, glycolic acid, p-toluenesulfonic acid, sulphamic acid, glycinebetaine, a derivative thereof, or any combination thereof. The monocarboxylic acid can be a saturated monocarboxylic acid, an unsaturated monocarboxylic acid (optionally with 1 to 7 double bonds), a monocarboxylic acid substituted with an aryl group, or any combination thereof.

[0161] In a further aspect, the Lewis acid can be a saturated monocarboxylic acid, an unsaturated monocarboxylic acid (optionally with 1 to 7 double bonds), a monocarboxylic acid substituted with an aryl group, a dicarboxylic acid, a tricarboxylic acid, a polyol, a monosaccharide (e.g., xylose, mannose, fructose, glucose, ribose), a disaccharide, an oligosaccharide (e.g., cyclodextrin), an amino acid (e.g., lysine, aspartic acid, glutamic acid), an amide (e.g., acetamide, benzamide), an anhydride (e.g., acetic anhydride, succinic anhydride), a dihydrogen phosphate salt, urea, methyl urea, dimethyl urea, thiourea, imidazole, ascorbic acid, glucuronic acid, levulinic acid, glycolic acid, p-toluenesulfonic acid, sulphamic acid, glycine-betaine, a derivative thereof, or any combination thereof.

[0162] The saturated monocarboxylic acid can be selected from formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and any combination thereof. The unsaturated monocarboxylic acid can be selected from acrylic acid, methacrylic acid, oleic acid, linoleic acid, and any combination thereof. The monocarboxylic acid substituted with an aryl group can be selected from benzoic acid, salicylic acid, acetylsalicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, gallic acid, caffeic acid, coumaric acid, cinnamic acid, phenylacetic acid, phenylpropionic acid, and any combination thereof. The dicarboxylic acid can be selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, tartaric acid, itaconic acid, methylsuccinic acid, aspartic acid, glutamic acid, and any combination thereof. The tricarboxylic acid can be selected from citric acid, isocitric acid, aconitic acid, trimesicATTORNEY DOCKET NO. 331903-2010 acid, tricarbalyllic acid, and any combination thereof.

[0163] The Lewis acid polyol can be selected from glycerol, sorbitol, mannitol, maltitol, erythritol, pentaerythritol, xylitol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol), propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and any combination thereof. In another aspect, the Lewis acid can be an organic acid such as sulphamic acid. In another aspect, the Lewis acid can be glycine-betaine.

[0164] In one aspect, the Lewis acid and the Lewis base can be individually selected from a fatty acid, a terpene, or a combination thereof. In a further aspect, the fatty acid can be selected from octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and any combination thereof. In another further aspect, the terpene can be selected from thymol, menthol, carvacrol, and any combination thereof.

[0165] In one aspect, the Lewis base can be an organic salt and the Lewis acid can be a metal halide. The organic salt can be selected from choline chloride, glycine-betaine, and a combination thereof. The metal halide can be selected from ZnCI2, ZnBr2, FeCh, FeBr3, SnCI2, SnBr2, MgCI2, MgBr2, CaCI2, CaBr2, CrCI3, CrBr3, MnCI2, MnBr2, AICI3, AIBr3, CuCI2, CuBr2, and any combination thereof.

[0166] In one aspect, the Lewis base can be an organic salt and the Lewis acid can be a metal halide hydrate. The organic salt can be selected from choline chloride, glycine-betaine, and a combination thereof. The metal halide hydrate can be selected from ZnCI2• n H2O; ZnBr2• n H2O; CaCI2• 6 H2O; CaBr2• 6 H2O; MgCI2• 6 H2O; MgBr2• 6 H2O; CrCI3• 6 H2O; CrBr3• 6 H2O; SnCI2• 2 H2O; SnBr2• 2 H2O; FeCI3• 6 H2O; FeBr3• 6 H2O; MnCI2• 4 H2O; MnBr2• 4 H2O; AICI3• 6 H2O; AIBr3• 6 H2O; CuCI2• 2 H2O; CuBr2• 2 H2O; and any combination thereof, wherein n ranges from 1 to 4.

[0167] In one aspect, the Lewis base can be a metal salt hydrate and the Lewis acid can be urea, a polyol, acetamide, an amino acid, a derivative thereof, or any combination thereof. In a further aspect, the urea or derivative thereof can be selected from urea, methylurea, dimethylurea, thiourea, and any combination thereof. In another further aspect, the polyol can be selected from glycerol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol), propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and any combination thereof. The metal salt hydrate can be selected from ZnCI2• n H2O; FeCI3• 6 H2O; ZrOCI2• 8 H2O; Zn(OAc)2• 2 H2O; Mn(OAc)2• 4 H2O; and any combination thereof, wherein n ranges from 1 to 4.ATTORNEY DOCKET NO. 331903-2010

[0168] A few specific examples of DES are now provided. In one aspect, the DES can comprise choline chloride and a dicarboxylic acid. In a further aspect, the dicarboxylic acid can be oxalic acid and the molar ratio of choline chloride to oxalic acid can be about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1 :7. This choline chloride and oxalic acid DES can be prepared at a temperature of about 40 °C to about 110 °C, about 60 °C to about 80 °C, or about 65 °C to about 75 °C. In another aspect, the dicarboxylic acid can be tartaric acid and the molar ratio of choline chloride to tartaric acid can be about 10:2 to about 10:8, about 10:3 to about 10:7, about 10:4 to about 10:6, about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1 :7. This choline chloride and tartaric acid DES can be prepared at a temperature of about 130 °C to about 165 °C, about 140 °C to about 160 °C, or about 145 °C to about 155 °C. In another aspect, the dicarboxylic acid can be malic acid and the molar ratio of choline chloride to malic acid can be about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1:7. This choline chloride and malic acid DES can be prepared at a temperature of about 130 °C to about 165 °C, about 140 °C to about 160 °C, or about 145 °C to about 155 °C. In another aspect, the dicarboxylic acid can be itaconic acid and the molar ratio of choline chloride to itaconic acid can be about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1 :7. This choline chloride and itaconic acid DES can be prepared at a temperature of about 130 °C to about 165 °C, about 140 °C to about 160 °C, or about 145 °C to about 155 °C. In another aspect, the dicarboxylic acid can be maleic acid and the molar ratio of choline chloride to maleic acid can be about 10:5 to about 1 :9, about 10:6 to about 1:8, or about 10:7 to about 1 :7. This choline chloride and maleic acid DES can be prepared at a temperature of about 130 °C to about 165 °C, about 140 °C to about 160 °C, or about 145 °C to about 155 °C.

[0169] In another aspect, the DES can comprise choline chloride and a tricarboxylic acid. In a further aspect, the tricarboxylic acid can be citric acid and the molar ratio of choline chloride to citric acid can be about 10:5 to about 1 :9, about 10:6 to about 1:8, or about 10:7 to about 1 :7. This choline chloride and citric acid DES can be prepared at a temperature of about 40 °C to about 110 °C, about 60 °C to about 80 °C, or about 65 °C to about 75 °C.

[0170] In another aspect, the DES can comprise citric acid and a polyol. In a further aspect, the polyol can be glycerol and the molar ratio of citric acid to glycerol can be about 10:5 to about 1 :9, about 10:6 to about 1:8, or about 10:7 to about 1 :7. This citric acid and glycerol DES can be prepared at a temperature of about 40 °C to about 110 °C, about 60 °C to about 80 °C, or about 65 °C to about 75 °C.

[0171] In another aspect, the DES can comprise sulphamic acid and a polyol. In a further aspect,ATTORNEY DOCKET NO. 331903-2010 the polyol can be glycerol and the molar ratio of sulphamic acid to glycerol can be about 1 :1 to about 1 :5, about 1 :2 to about 1 :4, or about 1 :2.5 to about 1 :3.5. This sulphamic acid and glycerol DES can be prepared at a temperature of about 110 °C to about 135 °C, about 120 °C to about 130 °C, or about 123 °C to about 127 °C.

[0172] In another aspect, the DES can comprise glycine-betaine (i.e., betaine) or glycine-betaine hydrochloride (i.e., betaine hydrochloride) and a polyol. In a further aspect, the polyol can be glycerol and the molar ratio of betaine or betaine hydrochloride to glycerol can be about 10:5 to about 1:3.5, about 1 : 1 to about 1 :3, or about 1 : 1.5 to about 1 :2.5. This betaine and glycerol DES can be prepared at a temperature of about 110 °C to about 135 °C, about 120 °C to about 130 °C, or about 123 °C to about 127 °C.

[0173] In another aspect, the DES can comprise choline chloride and two or more different dicarboxylic acids. In a further aspect, at least one of the dicarboxylic acids can have five or less carbon atoms (e.g., oxalic, malonic, succinic, glutaric, fumaric, maleic, malic, tartaric, itaconic, methylsuccinic, aspartic, or glutamic acid). In another further aspect, at least one of the dicarboxylic acids can have four or more carbon atoms (e.g., succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, fumaric, maleic, malic, tartaric, itaconic, methylsuccinic, aspartic, or glutamic acid). The molar ratio of choline chloride to the combined dicarboxylic acids can be about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1 :7. When two dicarboxylic acids are present in the DES, the molar ratio of the shorter-chain dicarboxylic acid to the longer- chain dicarboxylic acid can range from about 10:1 to about 1 :10, about 10:2 to about 1:5, or about 10:5 to about 1 :2. This choline chloride and dicarboxylic acid DES can be prepared at a temperature of about 40 °C to about 165 °C, about 60 °C to about 160 °C, or about 65 °C to about 155 °C.

[0174] In another aspect, the DES can comprise choline chloride, a dicarboxylic acid, and a metal or alkali metal halide. In a further aspect, the dicarboxylic acid can be malonic, succinic, adipic, pimelic, suberic, azelaic, sebacic, itaconic, or methylsuccinic acid. In another further aspect, the metal or alkali metal halide can be LiCI, NaCI, ZnCh, FeCh, SnCh, MgCh, CaCh, CrCh, MnCh, or CuCh. The molar ratio of choline chloride to dicarboxylic acid can be about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1 :7. The molar ratio of the combination of choline chloride and dicarboxylic acid to the metal or alkali metal halide can be from about 90:0.1 to about 90:10, about 99:0.1 to about 99:10, about 95:0.3 to about 95:5, about 99.7:0.3 to about 99.7:5, about 97:0.5 to about 97:3, or about 99.5:0.5 to about 99.5:3. This choline chloride and dicarboxylic acid DES with metal or alkali metal halides can be prepared at a temperature of aboutATTORNEY DOCKET NO. 331903-201040 °C to about 165 °C, about 60 °C to about 160 °C, or about 65 °C to about 155 °C.

[0175] In another aspect, the DES can comprise thymol and another terpene or fatty acid. In a further aspect, the additional terpene is carvacrol. The molar ratio of thymol to carvacrol can be about 10:5 to about 1:2, about 10:6 to about 1 :1.7, or about 10:7 to about 1 :1.4. This thymol and carvacrol DES can be prepared at a temperature of about 70 °C to about 110 °C, about 80 °C to about 106 °C, or about 90 °C to about 102 °C.

[0176] In another aspect, the DES can comprise choline chloride and urea. The molar ratio of choline chloride to urea can be about 10:5 to about 1 :3.5, about 1 : 1 to about 1 :3, or about 1:1.5 to about 1 :2.5. This choline chloride and urea DES can be prepared at a temperature of about 70 °C to about 130 °C, about 80 °C to about 120 °C, or about 90 °C to about 110 °C.E. CELLULOSE MATERIAL

[0177] The cellulose material or cellulose feedstock used in the present disclosure can be harvested from nature, agriculture, aquaculture, or forestry; can be obtained as waste or side stream; or can be cultivated biotechnically. In a further aspect, the cellulose feedstock or cellulose material can be extracted from softwoods, hardwoods, macro algae, micro algae, bacteria, fungi, or tunicates. In a further aspect, the cellulose material can comprise a variety of morphologies such as those classified as cellulose nanocrystals, cellulose crystallites, cellulose nano whiskers, microcrystalline cellulose, cellulose nanofibrils, and cellulose nanofibers. Cellulose can range in molecular weight from 3 x 104to 2 x 105g mol-1. In one aspect, the cellulose feedstock can be obtained as side stream from industries such as alginate production, agar-agar production, and paper-making or from the extraction of chemicals such as pharmaceuticals, nutraceuticals, fertilizers, cosmetics ingredients, and pigments. In another aspect, the cellulose feedstock can be obtained as waste stream, such as textile waste, and can include other components, such as waste cotton or waste cotton-polyester blend. In another aspect, the feedstock can include lignocellulosic biomass, such as woody biomass or algal biomass. Woody biomass is derived from trees and woody plants. Examples of woody biomass include biomass obtained from trees including tree limbs, needles, leaves, and other woody plant parts. Woody biomass can include by-products of forest management, including, for example, cleaning that occurs after natural disasters and forest restoration. Examples of woody biomass obtained from woody plants include hemp hurd: the woody, inner-core of a hemp stalk. The cellulose feedstock can also include bacterial cellulose. Bacterial cellulose has relatively high purity, and using a feedstock that comprises primarily or solely bacterial cellulose can reduce or eliminate the need for pretreatment of the feedstock (such as delignification pretreatment) prior to its use in the methods disclosedATTORNEY DOCKET NO. 331903-2010 herein.

[0178] The cellulose feedstock can comprise algal biomass. Many algae species have high cellulose content and relatively low lignin content, and using a feedstock that comprises primarily or solely algal biomass can significantly reduce the need for pretreatment of the feedstock. A cellulose feedstock that comprises woody biomass, for example, can require extensive or intense pretreatment prior to its use in a cellulose treatment and / or functionalization method. Additionally, cellulose exists in thinner units in algal biomass compared to woody biomass. The thinner units of cellulose in an algal biomass-based feedstock can allow for better accessibility for a DES treatment in comparison to a woody biomass-based feedstock. An algal biomass-based feedstock can also require less energy in the defibrillation step after the DES treatment in comparison to a woody biomass-based feedstock.

[0179] Algal biomass used in the disclosed compositions can be obtained from brown algae (Pheophyta), such as brown algae of the genera Macrocystis, Laminaria, Ascophyllum, Alario, Ecklonia, Eisenia, Nercocystis, Sargassum, Cystoseira, Fucus, Saccharina, or any combination thereof. In a further aspect, the algal biomass can be obtained from the species Laminaria hyperborea, Laminaria japonica, Laminaria digitata, Sargassum fluitans, Sargassum natans, Saccharina latissima, or any combination thereof. In another aspect, the algal biomass can be obtained from the species Posidonia oceanica. In another aspect, the algal biomass used in the disclosed compositions can be obtained from green algae (Chlorophyta), such as green algae of the genera Cladophora, Ulva, Valonia, or any combination thereof. In a further aspect, the algal biomass can be obtained from the species Cladophora glomerata, Ulva lactuca, or a combination thereof. In another aspect, the algal biomass used in the disclosed compositions can be obtained from red algae (Rhodophyta), such as red algae of the genera Gelidium. In a further aspect, the algal biomass can be obtained from the species Gelidium elegans. In another aspect, the algal biomass used in the disclosed compositions can be obtained from microalgae, such as the species Nannochloropsis oceanica, Chlorella vulgaris, or a combination thereof. In another aspect, the algal biomass can be a dinoflagellate, a cyanobacteria, or a combination thereof. The algal biomass can include all components or structures of an algae or select components or structures. For example, the algal biomass can include fronds and stems of Laminaria hyperborea or only stems of Laminaria hyperborea. As another example, the algal biomass can include only the fronds of Saccharina latissima.

[0180] The algal biomass can comprise alginate structures composed of linear, unbranched polysaccharide monomers |3-D mannuronic acid blocks and a-L guluronic acid blocks. InsolubleATTORNEY DOCKET NO. 331903-2010 protonated alginate can be readily converted to a soluble salt form, e.g., sodium alginate (SA), calcium alginate, potassium alginate, and / or ammonium alginate, by methods known in the art. In further aspects, the algal biomass used can comprise an ester modified alginate, e.g., propylene glycol alginate, but other ester forms can be used as well. In various aspects, the algal biomass used in the disclosed compositions can possess a viscosity range between 20-400 centipoises when determined using a 1 wt% aqueous solution at 20 °C. In a further aspect, the algal biomass used in the disclosed compositions can possess a viscosity range between 20 mPa*s to 1500 mPa«s when determined using a 1 wt% aqueous solution at 20 °C. The molecular weight of algal biomass used in the final composition can range from 32,000 to 200,000 with a degree of polymerization from 180 to 930.

[0181] In another aspect, the cellulose feedstock can comprise sea squirt biomass or marine organism biomass of the Ascidiacea class. The sea squirt biomass can be obtained from a marine organism of the species Halocynthia roretzi (sea pineapple).

[0182] Prior to its use in the treatment methods of the present disclosure, the cellulose feedstock can undergo pretreatments such as pulping; bleaching; fractionation in a DES, GVL, a supercritical fluid, a similar solvent, or any combination thereof; enzymatic fractionation and / or treatment; microwave fractionation and / or treatment; plasma fractionation and / or treatment; BLN- fractionation; refining; removal of contaminants or additives, e.g., polyester removal with a DES, GVL, supercritical carbon dioxide, or similar solvent; washing; drying; mechanical grinding; any sequence thereof; or any combination thereof.

[0183] In one aspect, the cellulose feedstock is never-dried and is not exposed to drying during or after any pretreatments performed. The feedstock can additionally include water or another solvent. If the feedstock includes water, it may be solvent exchanged to a DES, GVL, ethanol, methanol, a quickly evaporating solvent, or a combination thereof, where the solvent is miscible with the DES used in the methods disclosed herein. In another aspect, the cellulose feedstock is never-dried, includes water, and is used with the water included. In another aspect, the cellulose- rich feedstock is solvent exchanged from water to ethanol. In another embodiment, the cellulose- rich feedstock is solvent exchanged from water to GVL. In another aspect, the feedstock is used as a dry powder.F. METHODS FOR TREATING CELLULOSIC MATERIAL

[0184] In one aspect, the methods disclosed herein comprise combining a cellulose feedstock and a first solvent in a weight ratio of about 1 :0.5 to about 1 :200 cellulose feedstock to first solvent (DES), thereby forming a cellulosic suspension. In another aspect, the weight ratio of celluloseATTORNEY DOCKET NO. 331903-2010 feedstock to first solvent / DES can range from about 1 :0.5 to about 1 :200, about 1:5 to about 1 :200, about 1 :5 to about 1 :150, about 1 :5 to about 1 :100, about 1 :6 to about 1 :150, about 1 :7 to about 1 :200, or about 1:7 to about 1 :100. In one aspect, the cellulose feedstock is dry cellulose feedstock or a never-dried cellulose feedstock. In a further aspect, the weight ratio of dry cellulose feedstock or never-dried cellulose feedstock to first solvent / DES is from about 1 :0.5 to about 1 :100, about 1 :5 to about 1:100, about 1 :5 to about 1 :80, about 1 :5 to about 1 :60, about 1 :5 to about 1:40, about 1 :10 to about 1 :80, about 1 :10 to about 1 :60, about 1 :10 to about 1 :40, about 1 :20 to about 1 :80, about 1 :20 to about 1 :60, or about 1 :20 to about 1 :40. In a further aspect, prior to combining with the feedstock, the first solvent / DES can be heating to a temperature where is has a sufficiently low viscosity for mixing but where none of the components of the DES will degrade. In a further aspect, the DES and cellulose feedstock can be combined at a temperature of about 15 °C to about 170 °C, 15 °C to about 100 °C, about 20 °C to about 165 °C, or about 20 °C to about 150 °C. The cellulosic feedstock and DES can be combined together at a pressure below 1 atm.

[0185] Combining the cellulose feedstock and first solvent / DES can form a cellulosic suspension. The cellulosic suspension can be mixed under high shear (using a high-shear mixer) for about 5 minutes to about 60 minutes, about 5 minutes to about 50 minutes, about 10 minutes to about 50 minutes, about 15 minutes to about 50 minutes, about 20 minutes to about 60 minutes, or about 20 minutes to about 40 minutes.

[0186] After high-shear mixing, the cellulosic suspension can be treated using a reaction treatment method including: incubation of the cellulosic suspension at a temperature of at least 30°C; microwave irradiation exposure; plasma exposure; ultrasound exposure; grinding; ballmilling; extrusion; a sequence thereof; or any combination thereof, thereby forming a treated cellulosic suspension comprising a treated cellulose material. In one aspect, the reaction treatment method includes at least an incubation step. The cellulosic suspension can be incubated (for example, in an oil bath) at a temperature ranging from about 30 °C to about 170 °C, 30 °C to about 150 °C, about 40 °C to about 160 °C, 50 °C to about 170 °C, or about 50 °C to about 150 °C. In a further aspect, the cellulosic suspension can be incubated for about 4 minutes to about 8 hours, about 7 minutes to about 7 hours, about 10 minutes to about 6 hours, about 10 minutes to about 5 hours, or about 10 minutes to about 4 hours. The incubation step and, optionally, any other parts of the treatment method can be performed at a reduced pressure (pressure below 1 atm, preferably 0.001-1 mbar, or more preferably 0.001-0.5 mbar, or more preferably 0.002-0.1 mbar, or most preferably 0.002-0.05 mbar). After incubating and performing any additional treatment methods, the cellulosic suspension, now a treated cellulosic suspensionATTORNEY DOCKET NO. 331903-2010 comprising a treated cellulose material, can be moved to ambient conditions.

[0187] Following treatment, the treated cellulosic suspension can be allowed to cool down (e.g., cool for up to about 30 minutes to about 1 hour). In one aspect, the treated cellulosic suspension can then undergo a defibrillation process, described in further detail below. In another aspect, the treated cellulosic suspension can then be diluted with a second solvent and washed with a third solvent, thereby forming a washed cellulosic suspension comprising the treated cellulose material. The washed cellulosic suspension can then be drained so that the treated cellulose material is from about 2 wt% to about 50 wt%, about 5 wt% to about 50 wt%, about 5 wt% to about 45 wt%, about 5 wt% to about 40 wt%, about 6 wt% to about 45 wt%, about 7 wt% to about 50 wt%, or about 7 wt% to about 40 wt% of the washed cellulosic suspension, thereby forming an intermediate cellulosic suspension (the treated, washed, and drained cellulosic material). In another aspect, the intermediate cellulosic suspension can be comprised of from about 5 wt% to about 50 wt%, about 5 wt% to about 40 wt%, about 6 wt% to about 45 wt%, about 7 wt% to about 50 wt%, or about 7 wt% to about 40 wt% of the treated cellulose material. Washing the treated cellulosic suspension can be done by dialysis against the selected solvent, such as by immersing the treated cellulose material in the selected solvent at a treated cellulose material solids content of about 0.01 wt% to about 20 wt%, about 0.01 wt% to about 10 wt%, about 0.03 wt% to about 15 wt%, about 0.05 wt% to about 20 wt%, or about 0.05 wt% to about 10 wt% for a time period of about 10 min to about 24 hours, about 10 min to about 20 hours, about 10 min to about 16 hours, about 15 min to about 12 hours, about 20 min to about 20 hours, about 20 min to about 16 hours, or about 20 min to about 8 hours. Draining the washed cellulosic material can be done by filtration or centrifugation. The second solvent and the third solvent can be individually comprised of water, methanol, ethanol, isopropanol, tert-butanol, isobutanol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof. After diluting and prior to washing the treated cellulosic suspension, the treated cellulosic suspension can optionally be drained up to a treated cellulose material content of about 5 wt% to about 50 wt%, about 5 wt% to about 40 wt%, about 6 wt% to about 45 wt%, about 7 wt% to about 50 wt%, or about 7 wt% to about 40 wt%, forming an intermediate cellulosic suspension. The intermediate cellulosic suspension can be used as such, dried, or dispersed in a desired solvent (e.g., water) at a desired concentration.

[0188] The intermediate cellulosic suspension can undergo a second DES treatment process, thereby forming a secondary intermediate cellulosic suspension, where the intermediate cellulosic suspension is combined with a new DES, which may be the same, completely different, or comprise some similar components to the first solvent (DES). The second DES treatment process can also include a high shear mixing process akin to the parameters previously described; aATTORNEY DOCKET NO. 331903-2010 treatment process using the treatment methods and parameters previously described; a dilution, washing, and draining process, akin to those previously described; any sequence thereof; or any combination thereof. The pH of the final cellulose material can be adjusted to about 8 to about 11 , about 8.1 to about 10, about 8.2 to about 9 in order to deprotonate any acidic groups, in the case when acidic groups have been introduced. Alternatively, the material may be used as such, dried, or dispersed in a desired solvent at a desired concentration.

[0189] Any one of the treated cellulosic suspension, the intermediate cellulosic suspension, or the secondary intermediate cellulosic suspension can then undergo a defibrillation process to form a nanocellulose material. Optionally, prior to undergoing the defibrillation process, water can be added to the intermediate cellulosic suspension or the secondary intermediate cellulosic suspension to form a diluted cellulosic suspension or a secondary diluted cellulosic suspension, respectively, which can then undergo the defibrillation process. The diluted cellulosic suspension or secondary diluted cellulosic suspension can comprise from about 80% to about 99%, about 85% to about 99%, about 90% to about 99%, about 80% to about 90%, about 98% to about 99.9%, about 98.3% to about 99.7%, about 98.5% to about 99.5%, 98% to 99.9%, 98.3% to 99.7%, or 98.5% to 99.5% water by weight. Additionally, prior to undergoing the defibrillation process, any one of the treated cellulosic suspension, the intermediate cellulosic suspension (or diluted cellulosic suspension), or the secondary intermediate cellulosic suspension (or secondary diluted cellulosic suspension) can be treated with mixing under high shear at low pressures (HV- 0). In one aspect, the suspensions or materials can be treated with mixing under high shear at a pressure of less than about 1000 psi, less than about 500 psi, less than about 100 psi, less than about 80 psi, or less than about 60 psi. In another aspect, the cellulose material can be treated with mixing under high shear at a pressure of at least about 20 psi, at least about 22 psi, or at least about 24 psi. In another aspect, the cellulose material can be treated with mixing under high shear at a pressure ranging from about 20 psi to about 1000 psi, about 20 psi to about 500 psi, about 20 psi to about 100 psi, about 20 psi to about 80 psi, about 20 psi to about 60 psi, about 22 psi to about 100 psi, about 22 psi to about 80 psi, about 24 psi to about 100 psi, about 24 psi to about 80 psi, or about 24 psi to about 60 psi. The nanocellulose material formed can include cellulose nanocrystals, cellulose nanofibers, or a combination thereof. The defibrillation process can be done by suspensions or materials to high shear, ultrasound, or another form of energy that can disintegrate the cellulose fibers, fibrils, and / or crystals into nanoscale fibrils, crystals, and / or aggregates. This can be performed using a high-pressure homogenizer, a microfluidizer, grinding, ball-milling, refining, steam explosion, extrusion, aqueous counter collision, ultrasonication, a sequence thereof, or any combination thereof.ATTORNEY DOCKET NO. 331903-2010

[0190] In another aspect, any one of the treated cellulosic suspension, the treated cellulose material, the intermediate cellulosic suspension, the secondary intermediate cellulosic suspension, or defibrillated suspensions or materials disclosed herein can be used as such for preparation of materials such as films, fibers, filaments, non-wovens, coatings, spheres, or 3D- printed objects. In this case, the prepared shape is immersed in a solvent that is miscible with the DES and solidifies the desired structure. In a further aspect, the shape can be a filament prepared by wet or dry-jet wet spinning the treated cellulose material into an alcohol such as ethanol or isopropanol. In another further aspect, the shape can be a filament prepared by wet or dry-jet wet spinning a cellulosic suspension treated with a DES containing a dicarboxylic acid into an aqueous solution of a divalent salt such as ZnCh, SnCh, MgCh, CaCh, MnCh, or CuCh, or a trivalent salt such as FeCh, CrCH, or any combination thereof. In another aspect, the shape can be a film prepared by extruding or spreading a DES-treated cellulosic suspension while or before immersing the film into an alcohol such as ethanol or isopropanol. In another aspect, the shape can be a film prepared by extruding or spreading a cellulose suspension treated with a DES containing a dicarboxylic acid, while or before immersing the film into an aqueous solution of a divalent salt such as ZnCh, SnCh, MgCh, CaCh, MnCh, or CuCh, or a trivalent salt such as FeCh, CrCh, or any combination thereof. In one aspect, the cellulose material has been treated in a dicarboxylic acid-containing DES, and the prepared object is immersed in a CaCh solution. After the solidification of the material, it can be immersed in another DES with capacity to dissolve cellulose, such as a DES containing 1 ,5-diazabicyclo[4.3.0]non-5-enium, N-allyl-N- methylmorpholinium, or an imidazolium (e.g., 1-ethyl-3-methylimidazolium, 1-butyl-3- methylimidazolium, 1-allyl-3-methylimidazolium). Immersion can be continued for a fixed time to induce partial dissolution of cellulose. Following, the partially dissolved material can be immersed in a non-solvent for cellulose, e.g. water, where the dissolved cellulose solidifies into a regenerated cellulose matrix.G. ONE-STEP EXAMPLES OF TREATING CELLULOSIC MATERIAL

[0191] Disclosed herein are various embodiments of methods for treating cellulosic material comprising at least one primary step of DES treatment. The following embodiments are intended to be purely exemplary of the disclosure and are not intended to limit the scope of what the inventors regard as their disclosure.

[0192] In one aspect, the DES comprises choline chloride and oxalic acid, with a choline chloride:oxalic acid molar ratio ranging from about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1:7. Never-dried feedstock can be added to the DES at a temperature ofATTORNEY DOCKET NO. 331903-2010 about 15 °C to about 110 °C, about 20 °C to about 80 °C, about 40 °C to about 75 °C, or about ambient temperature. The never-dried feedstock can be added to the DES at a feedstock:DES mass ratio ranging from about 1 :0.5 to about 1 :200, about 1 :5 to about 1:200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, or about 1 :7 to about 1 :100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 40 °C to about 100 °C, about 40 °C to about 90 °C, or about 65 °C to about 75 °C, optionally under reduced pressure and / or stirring, for about 30 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient temperature for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1.5% in preparation for fibrillation. The pH of the dispersion may be adjusted to about 8 to about 11 or about 8.1 to about 10, or about 8.2 to about 9 in order to deprotonate the acidic groups. This aspect produces carboxylated cellulose, which has a negative surface charge in neutral conditions, which can improve fibrillation and dispersion in water.

[0193] In another aspect, the DES comprises choline chloride and citric acid, with a choline chloride:citric acid molar ratio ranging from about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1:7. Never-dried feedstock can be added to the DES at a temperature of about 15 °C to about 170 °C, about 20 °C to about 165 °C, about 140 °C to about 160 °C, about 145 °C to about 155 °C, or about ambient temperature. The never-dried feedstock can be added to the DES at a feedstock:DES mass ratio ranging from about 1 :0.5 to about 1 :200, about 1 :5 to about 1 :200, about 1 :5 to about 1 :150, about 1 :6 to about 1:150, or about 1 :7 to about 1 :100. The ratio may be selected depending on the dry matter content of the feedstock, so that the water (or other solvent) comprises about 4 wt% to about 16 wt%, about 6 wt% to about 14 wt%, or about 8 wt% to about 12 wt% of the DES. The feedstock-DES suspension can be mixed under high shear for about 20 to about 40 min. Following mixing, the suspension can be kept at a temperature of about 60 °C to about 165 °C, about 140 °C to about 160 °C, or about 145 °C to about 155 °C, optionally under reduced pressure and / or stirring, for about 30 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1.5% in preparation for fibrillation. The pH of the dispersion may be adjusted to about 8 to about 11 or about 8.1 to about 10, or about 8.2 to about 9 in order to deprotonate the acidic groups. This aspect produces carboxylated cellulose, whichATTORNEY DOCKET NO. 331903-2010 has a negative surface charge in neutral conditions, which can improve fibrillation and dispersion in water.

[0194] In one aspect, the DES comprises citric acid and glycerol, with a citric acid:glycerol molar ratio ranging from about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1 :7. Dried feedstock can be added to the DES at a temperature of about 15 °C to about 110 °C, about 20 °C to about 80 °C, about 40 °C to about 75 °C, or about ambient temperature. The dried feedstock can be added to the DES at a feedstock: DES mass ratio ranging from about 1 :0.5 to about 1 :200, about 1 :0.5 to about 1:100, about 1 :5 to about 1 :100, about 1 :5 to about 1 :60, or about 1 :10 to about 1:40. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 40 °C to about 100 °C, about 40 °C to about 90 °C, or about 65 °C to about 75 °C, optionally under reduced pressure and / or stirring, for about 30 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient temperature for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1.5% in preparation for fibrillation. The pH of the dispersion may be adjusted to about 8 to about 11 or about 8.1 to about 10, or about 8.2 to about 9 in order to deprotonate the acidic groups. This aspect produces carboxylated cellulose, which has a negative surface charge in neutral conditions, which can improve fibrillation and dispersion in water.

[0195] In another aspect, the DES comprises sulphamic acid and glycerol, with a sulphamic acid:glycerol molar ratio ranging from about 1 :1 to about 1 :5, about 1 :2 to about 1 :4, or about 1 :2.5 to about 1 :3.5. Never-dried feedstock can be added to the DES at a temperature of about 15 °C to about 150 °C, about 20 °C to about 140 °C, about 110 °C to about 135 °C, or about ambient temperature. The never-dried feedstock can be added to the DES at a feedstock:DES mass ratio ranging from about 1 :0.5 to about 1 :200, about 1 :5 to about 1:200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, or about 1 :7 to about 1 :100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 70 °C to about 140 °C, about 85 °C to about 135 °C, or about 85 °C to about 130 °C, optionally under reduced pressure and / or stirring, for about 10 minutes to about 4 hours. After the designated time, the suspension can be allowed to cool down at ambient temperature for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to aboutATTORNEY DOCKET NO. 331903-20101.5% in preparation for fibrillation. The pH of the dispersion may be adjusted to about 8 to about 11 or about 8.1 to about 10, or about 8.2 to about 9 in order to deprotonate the acidic groups. This aspect produces sulphonated cellulose, which has a negative surface charge in neutral conditions, which can improve fibrillation and dispersion in water.

[0196] In another aspect, the DES comprises betaine or betaine hydrochloride and glycerol, with betaine:glycerol molar ratio ranging from about 10:5 to about 1 :3.5, about 1 :1 to about 1 :3, or about 1 :1.5 to about 1 :2.5. As used herein, betaine refers to glycine-betaine. Never-dried feedstock can be added to the DES at a temperature of about 15 °C to about 150 °C, about 20 °C to about 140 °C, about 110 °C to about 135 °C, about 120 °C to about 130 °C, or about ambient temperature. The never-dried feedstock can be added to the DES at a feedstock: DES mass ratio ranging from about 1:0.5 to about 1:200, about 1 :5 to about 1:200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, or about 1 :7 to about 1 :100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 70 °C to about 170 °C, about 80 °C to about 160 °C, about 85 °C to about 130 °C, or about 130 °C to about 155 °C, optionally under reduced pressure and / or stirring, for about 10 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient temperature for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns clear or neutral. The washed, DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1.5% in preparation for fibrillation. This aspect produces cationic cellulose, which has a cationic surface charge, which can improve fibrillation and dispersion in water and can introduce the opportunity for complexation with anionic compounds.

[0197] In another aspect, the DES comprises choline chloride and two different dicarboxylic acids; one of them selected from oxalic, malonic, succinic, glutaric, fumaric, maleic, malic, tartaric, itaconic, methylsuccinic, aspartic, and glutamic acid; and the other one selected from succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, fumaric, maleic, malic, tartaric, itaconic, methylsuccinic, aspartic, and glutamic acid; where the molar ratio of the two dicarboxylic acids ranges from about 10:1 to about 1 :10, about 10:2 to about 1 :5, or about 10:5 to about 1 :2; and where the molar ratio of choline chloride:dicarboxylic acids ranges from about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1 :7. Never-dried feedstock can be added to the DES at a temperature of about 15 °C to about 170 °C, about 20 °C to about 165 °C, about 40 °C to about 160 °C, about 65 °C to about 155 °C, or about ambient temperature. The never-dried feedstock can be added to the DES at a feedstock: DES mass ratio ranging from about 1 :0.5 to about 1:200, about 1 :5 to about 1 :200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, orATTORNEY DOCKET NO. 331903-2010 about 1 :7 to about 1 :100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 40 °C to about 165 °C, about 50 °C to about 160 °C, or about 65 °C to about 155 °C, optionally under reduced pressure and / or stirring, for about 30 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1.5% in preparation for fibrillation. The pH of the dispersion may be adjusted to about 8 to about 11 or about 8.1 to about 10, or about 8.2 to about 9 in order to deprotonate the acidic groups. This aspect produces carboxylated cellulose with substituents at two different chain lengths. The resulting cellulosic fibrils may have higher aspect ratio and better dispersibility in water because of the combination of the electrostatic repulsion between the carboxylate groups and the steric effects between the large substituents. The degree of substitution may be higher than by using only the larger dicarboxylic acid, owing to the better mobility of the smaller dicarboxylic acid.

[0198] In another embodiment, the DES comprises choline chloride, a dicarboxylic acid, and a metal or alkalimetal halide. The dicarboxylic acid can be selected from malonic, succinic, adipic, pimelic, suberic, azelaic, sebacic, itaconic, and methylsuccinic acid; and the metal or alkalimetal halide can be selected from LiCI, NaCI, ZnCh, FeCh, SnCh, MgCh, CaCh, CrCh, MnCh, and CuCh. The molar ratio of choline chloride:dicarboxylic acid can range from about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1 :7. The molar ratio of the combination of choline chloride and dicarboxylic acid:metal or alkalimetal halide can range from about 90:0.1 to about 90:10, about 99:0.1 to about 99:10, about 95:0.3 to about 95:5, about 99.7:0.3 to about 99.7:5, about 97:0.5 to about 97:3, or about 99.5:0.5 to about 99.5:3. Never-dried feedstock can be added to the DES at a temperature of about 15 °C to about 170 °C, about 20 °C to about 165 °C, about 40 °C to about 160 °C, about 65 °C to about 155 °C, or about ambient temperature. The never-dried feedstock can be added to the DES at a feedstock: DES mass ratio ranging from about 1 :0.5 to about 1 :200, about 1 :5 to about 1 :200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, or about 1:7 to about 1:100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 40 °C to about 165 °C, about 50 °C to about 160 °C, or about 65 °C to about 155 °C, optionally under reduced pressure and / or stirring, for about 30 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed withATTORNEY DOCKET NO. 331903-2010 deionized water until the filtrate turns neutral. The washed, DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1.5% in preparation for fibrillation. The pH of the dispersion may be adjusted to about 8 to about 11 or about 8.1 to about 10, or about 8.2 to about 9 in order to deprotonate the acidic groups. This aspect produces carboxylated cellulose, where the degree of substitution may be higher and / or the treatment faster and / or the resulting cellulosic fibrils shorter than without using the metal or alkalimetal halide in the DES.

[0199] H. TWO-STEP EXAMPLES OF TREATING CELLULOSE MATERIAL

[0200] Disclosed herein are various embodiments of methods for treating cellulosic material comprising at least two primary steps of DES treatments. In one aspect, a treatment with one DES can be followed by a treatment with a second, optionally different, DES, with the possibility of providing a higher degree of substitution, removal of additives or contaminants, and / or introduction of two or more different functional groups. The following embodiments are intended to be purely exemplary of the disclosure and are not intended to limit the scope of what the inventors regard as their disclosure.

[0201] In one aspect, two DESes can be used: 1) choline chloride - tartaric acid (choline chloride:tartaric acid molar ratio ranging from about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1:7) and 2) sulphamic acid - glycerol (sulphamic acid:glycerol molar ratio ranging from about 1 : 1 to about 1:5, about 1 :2 to about 1 :4, or about 1 :2.5 to about 1 :3.5). Never- dried feedstock can be added first to the choline chloride - tartaric acid DES at a temperature of about 15 °C to about 165 °C, about 20 °C to about 160 °C, about 140 °C to about 160 °C, about 145 °C to about 155 °C, or about ambient temperature. The never-dried feedstock can be added to the DES at a feedstock:DES mass ratio ranging from about 1 :0.5 to about 1 :200, about 1 :5 to about 1 :200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, or about 1:7 to about 1:100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 70 °C to about 165 °C, about 80 °C to about 160 °C, about 85 °C to about 130 °C, or about 130 °C to about 155 °C, optionally under reduced pressure and / or stirring, for about 30 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with ethanol, deionized water, GVL, DMSO, another solvent, a sequence thereof, or a combination thereof until the filtrate turns neutral. After final filtration, the solid fraction can be transferred to the sulphamic acid -ATTORNEY DOCKET NO. 331903-2010 glycerol DES at a temperature of about 15 °C to about 150 °C, about 20 °C to about 140 °C, about 110 °C to about 135 °C, about 120 °C to about 130 °C, or about ambient temperature. The feedstock: DES mass ratio can range from about 1 :0.5 to about 1:200, about 1 :5 to about 1 :200, about 1:5 to about 1 :150, about 1 :6 to about 1 :150, or about 1 :7 to about 1 :100. The feedstock- DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 70 °C to about 140 °C, about 80 °C to about 135 °C, or about 85 °C to about 130 °C, optionally under reduced pressure and / or stirring, for about 10 minutes to about 4 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, twice DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1 .5% in preparation for fibrillation. The pH of the dispersion may be adjusted to about 8 to about 11 or about 8.1 to about 10, or about 8.2 to about 9 in order to deprotonate the acidic groups. This aspect produces carboxylated and sulphonated cellulose. The total degree of substitution may be higher than by using either of the modifications alone.

[0202] In another aspect, two DESes can be used: 1) choline chloride - malic acid (choline chloride:malic acid molar ratio ranging from about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1:7) and 2) sulphamic acid - glycerol (sulphamic acid:glycerol molar ratio ranging from about 1 : 1 to about 1:5, about 1 :2 to about 1 :4, or about 1 :2.5 to about 1 :3.5). Never- dried feedstock can be added first to the choline chloride - malic acid DES at a temperature of about 15 °C to about 165 °C, about 20 °C to about 160 °C, about 140 °C to about 160 °C, about 145 °C to about 155 °C, or about ambient temperature. The never-dried feedstock can be added to the DES at a feedstock:DES mass ratio ranging from about 1 :0.5 to about 1 :200, about 1 :5 to about 1 :200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, or about 1:7 to about 1:100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 70 °C to about 165 °C, about 80 °C to about 160 °C, about 85 °C to about 130 °C, or about 130 °C to about 155 °C, optionally under reduced pressure and / or stirring, for about 30 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with ethanol, deionized water, GVL, DMSO, another solvent, a sequence thereof, or a combination thereof until the filtrate turns neutral. After final filtration, the solid fraction can be transferred to the sulphamic acid - glycerol DES at a temperature of about 15 °C to about 150 °C, about 20 °C to about 140 °C, about 110 °C to about 135 °C, about 120 °C to about 130 °C, or about ambient temperature. TheATTORNEY DOCKET NO. 331903-2010 feedstock: DES mass ratio can range from about 1 :0.5 to about 1:200, about 1 :5 to about 1 :200, about 1:5 to about 1 :150, about 1 :6 to about 1 :150, or about 1 :7 to about 1 :100. The feedstock- DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 70 °C to about 140 °C, about 80 °C to about 135 °C, or about 85 °C to about 130 °C, optionally under reduced pressure and / or stirring, for about 10 minutes to about 4 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, twice DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1 .5% in preparation for fibrillation. The pH of the dispersion may be adjusted to about 8 to about 11 or about 8.1 to about 10, or about 8.2 to about 9 in order to deprotonate the acidic groups. This aspect produces carboxylated and sulphonated cellulose. The total degree of substitution may be higher than by using either of the modifications alone. When malic acid is introduced first, it includes an available hydroxyl group to replace the one it occupied. As such, there is still the original number of hydroxyl groups available for sulphamic acid modification after the initial modification with malic acid.

[0203] In another aspect, two DESes can be used: 1) choline chloride - oxalic acid (choline chloride:oxalic acid molar ratio ranging from about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1:7) and 2) sulphamic acid - glycerol (sulphamic acid:glycerol molar ratio ranging from about 1 : 1 to about 1:5, about 1 :2 to about 1 :4, or about 1 :2.5 to about 1 :3.5). Never- dried feedstock can be added first to the choline chloride - oxalic acid DES at a temperature of about 15 °C to about 110 °C, about 20 °C to about 80 °C, about 40 °C to about 75 °C, about 65 °C to about 75 °C, or about ambient temperature. The never-dried feedstock can be added to the DES at a feedstock:DES mass ratio ranging from about 1 :0.5 to about 1 :200, about 1 :5 to about 1 :200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, or about 1 :7 to about 1 :100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 40 °C to about 75 °C or about 65 °C to about 75 °C, optionally under reduced pressure and / or stirring, for about 30 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with ethanol, deionized water, GVL, DMSO, another solvent, a sequence thereof, or a combination thereof until the filtrate turns neutral. After final filtration, the solid fraction can be transferred to the sulphamic acid - glycerol DES at a temperature of about 15 °C to about 150 °C, about 20 °C to about 140 °C, about 110 °C to about 135 °C, about 120 °C to about 130 °C, orATTORNEY DOCKET NO. 331903-2010 about ambient temperature. The feedstock: DES mass ratio can range from about 1 :0.5 to about 1 :200, about 1 :5 to about 1 :200, about 1:5 to about 1 :150, about 1 :6 to about 1 :150, or about 1:7 to about 1 :100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 70 °C to about 140 °C, about 80 °C to about 135 °C, or about 85 °C to about 130 °C, optionally under reduced pressure and / or stirring, for about 10 minutes to about 4 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, twice DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1.5% in preparation for fibrillation. The pH of the dispersion may be adjusted to about 8 to about 11 or about 8.1 to about 10, or about 8.2 to about 9 in order to deprotonate the acidic groups. This aspect produces carboxylated and sulphonated cellulose. The total degree of substitution may be higher than by using either of the modifications alone.

[0204] In another aspect, two DESes can be used: 1) sulphamic acid - glycerol (sulphamic acid:glycerol molar ratio ranging from about 1 :1 to about 1 :5, about 1 :2 to about 1 :4, or about 1 :2.5 to about 1 :3.5) and 2). choline chloride - oxalic acid (choline chloride:oxalic acid molar ratio ranging from about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1 :7). Never- dried feedstock can be added first to the sulphamic acid - glycerol DES at a temperature of about 15 °C to about 150 °C, about 20 °C to about 140 °C, about 110 °C to about 135 °C, about 120 °C to about 130 °C, or about ambient temperature. The feedstock: DES mass ratio can range from about 1 :0.5 to about 1 :200, about 1 :5 to about 1:200, about 1 :5 to about 1:150, about 1 :6 to about 1 :150, or about 1:7 to about 1:100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 70 °C to about 140 °C, about 80 °C to about 135 °C, or about 85 °C to about 130 °C, optionally under reduced pressure and / or stirring, for about 10 minutes to about 4 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with ethanol, deionized water, GVL, DMSO, another solvent, a sequence thereof, or a combination thereof until the filtrate turns neutral. After final filtration, the solid fraction can be transferred to the choline chloride - oxalic acid DES at a temperature of about 15 °C to about 110 °C, about 20 °C to about 80 °C, about 40 °C to about 75 °C, about 65 °C to about 75 °C, or about ambient temperature. The feedstock:DES mass ratio can range from about 1 :0.5 to about 1 :200, about 1 :5 to about 1 :200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, or about 1 :7 to aboutATTORNEY DOCKET NO. 331903-2010 1 : 100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 40 °C to about 75 °C or about 65 °C to about 75 °C, optionally under reduced pressure and / or stirring, for about 30 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, twice DES- treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1.5% in preparation for fibrillation. The pH of the dispersion may be adjusted to about 8 to about 11 or about 8.1 to about 10, or about 8.2 to about 9 in order to deprotonate the acidic groups. This aspect produces sulphonated and carboxylated cellulose. The total degree of substitution may be higher than by using either of the modifications alone.

[0205] In another aspect, two DESes can be used: 1) thymol - carvacrol (thymol: carvacrol molar ratio ranging from about 10:5 to about 1 :2, about 10:6 to about 1 :1.7, or about 10:7 to about 1 :1.4) and 2). choline chloride - oxalic acid (choline chloride:oxalic acid molar ratio ranging from about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1 :7). The feedstock can be a waste material comprising cellulose and polyester. The feedstock can be immersed first in the thymol - carvacrol DES at a temperature of about 15 °C to about 165 °C, about 20 °C to about 160 °C, about 90 °C to about 155 °C, or about ambient temperature. The feedstock:DES mass ratio can range from about 1 :0.5 to about 1 :200, about 1:5 to about 1 :200, about 1 :5 to about 1 :150, about 1:6 to about 1 :150, or about 1:7 to about 1 :100. Optionally, the feedstock-DES combination can then be mixed under high shear for about 20 minutes to about 40 minutes. Following, the suspension can be kept at a temperature of about 70 °C to about 160 °C, about 80 °C to about 155 °C, or about 90 °C to about 150 °C, optionally under reduced pressure and / or stirring, for about 1 minutes to about 7 hours, about 3 minutes to about 6 hours, or about 5 minutes to about 5 hours. After the designated time, the suspension can be filtered or centrifuged, and the solid residue can be washed with the DES and / or with GVL (optionally twice washed with GVL). In a further aspect, after the designated time, the DES-treated feedstock can also be washed with another solvent, such as water, DMSO, ethanol, a sequence thereof, or a combination thereof. After final washing, the remaining feedstock can be immersed in the choline chloride - oxalic acid DES at a temperature of about 15 °C to about 110 °C, about 20 °C to about 80 °C, about 40 °C to about 75 °C, about 65 °C to about 75 °C, or about ambient temperature. The feedstock: DES mass ratio can range from about 1 :0.5 to about 1:200, about 1 :5 to about 1:200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, or about 1 :7 to about 1 :100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes.ATTORNEY DOCKET NO. 331903-2010 Following mixing, the suspension can be kept at a temperature of about 40 °C to about 75 °C or about 65 °C to about 75 °C, optionally under reduced pressure and / or stirring, for about 30 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, twice DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1.5% in preparation for fibrillation. The pH of the dispersion may be adjusted to about 8 to about 11 or about 8.1 to about 10, or about 8.2 to about 9 in order to deprotonate the acidic groups. This aspect produces carboxylated cellulose, possibly out of a waste material where the cellulose is contaminated in a blend with polyester. This can provide a feasible solution for treating a typical, blended textile waste material into a more valuable form.

[0206] In another aspect, two DESes can be used: 1) thymol - carvacrol (thymol: carvacrol molar ratio ranging from about 10:5 to about 1 :2, about 10:6 to about 1 :1.7, or about 10:8 to about 1 :1.3) and 2). choline chloride - citric acid (choline chloride:citric acid molar ratio ranging from about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1 :7). The feedstock can be a waste material comprising cellulose and polyester. The feedstock can be immersed first in the thymol - carvacrol DES at a temperature of about 15 °C to about 165 °C, about 20 °C to about 160 °C, about 90 °C to about 155 °C, or about ambient temperature. The feedstock:DES mass ratio can range from about 1 :0.5 to about 1 :200, about 1 :5 to about 1 :200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, or about 1 :7 to about 1 :100. Optionally, the feedstock-DES combination can then be mixed under high shear for about 20 minutes to about 40 minutes. Following, the suspension can be kept at a temperature of about 70 °C to about 160 °C, about 80 °C to about 155 °C, or about 90 °C to about 150 °C, optionally under reduced pressure and / or stirring, for about 1 minutes to about 7 hours, about 3 minutes to about 6 hours, or about 5 minutes to about 5 hours. After the designated time, the suspension can be filtered or centrifuged, and the solid residue can be washed with the DES and / or with GVL (optionally twice washed with GVL). In a further aspect, after the designated time, the DES-treated feedstock can also be washed with another solvent, such as water, DMSO, ethanol, a sequence thereof, or a combination thereof. After final washing, the remaining feedstock can be immersed in the choline chloride - citric acid DES at a temperature of about 15 °C to about 110 °C, about 20 °C to about 80 °C, about 40 °C to about 75 °C, about 65 °C to about 75 °C, or about ambient temperature. The feedstock: DES mass ratio can range from about 1 :0.5 to about 1:200, about 1 :5 to about 1:200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, or about 1 :7 to about 1 :100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes.ATTORNEY DOCKET NO. 331903-2010 Following mixing, the suspension can be kept at a temperature of about 40 °C to about 75 °C or about 65 °C to about 75 °C, optionally under reduced pressure and / or stirring, for about 30 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, twice DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1.5% in preparation for fibrillation. The pH of the dispersion may be adjusted to about 8 to about 11 or about 8.1 to about 10, or about 8.2 to about 9 in order to deprotonate the acidic groups. This aspect produces carboxylated cellulose, possibly out of a waste material where the cellulose has been contaminated in a blend with polyester.

[0207] In another aspect, two DESes can be used: 1) thymol - carvacrol (thymol: carvacrol molar ratio ranging from about 10:5 to about 1 :2, about 10:6 to about 1 :1.7, or about 10:8 to about 1 :1.3) and 2). sulphamic acid - glycerol (sulphamic acid:glycerol molar ratio ranging from about 1 :1 to about 1 :5, about 1 :2 to about 1 :4, or about 1 :2.5 to about 1:3.5). The feedstock can be a waste material comprising cellulose and polyester. The feedstock can be immersed first in the thymol - carvacrol DES, optionally at a temperature of about 15 °C to about 165 °C, about 20 °C to about 160 °C, about 90 °C to about 155 °C, or about ambient temperature. The feedstock:DES mass ratio can range from about 1 :0.5 to about 1 :200, about 1:5 to about 1 :200, about 1 :5 to about 1 :150, about 1:6 to about 1 :150, or about 1:7 to about 1 :100. Optionally, the feedstock-DES combination can then be mixed under high shear for about 20 minutes to about 40 minutes. Following, the suspension can be kept at a temperature of about 70 °C to about 160 °C, about 80 °C to about 155 °C, or about 90 °C to about 150 °C, optionally under reduced pressure and / or stirring, for about 1 minutes to about 7 hours, about 3 minutes to about 6 hours, or about 5 minutes to about 5 hours. After the designated time, the suspension can be filtered or centrifuged, and the solid residue can be washed with the DES and / or with GVL (optionally twice washed with GVL). In a further aspect, after the designated time, the DES-treated feedstock can also be washed with another solvent, such as water, DMSO, ethanol, a sequence thereof, or a combination thereof. After final washing, the remaining feedstock can be immersed in the sulphamic acid - glycerol DES at a temperature of about 15 °C to about 150 °C, about 20 °C to about 140 °C, about 110 °C to about 135 °C, about 120 °C to about 130 °C, or about ambient temperature. The feedstock: DES mass ratio can range from about 1 :0.5 to about 1:200, about 1 :5 to about 1 :200, about 1:5 to about 1 :150, about 1 :6 to about 1 :150, or about 1 :7 to about 1 :100. The feedstock- DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 70 °C to about 140 °C,ATTORNEY DOCKET NO. 331903-2010 about 80 °C to about 135 °C, or about 85 °C to about 130 °C, optionally under reduced pressure and / or stirring, for about 10 minutes to about 4 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, twice DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1.5% in preparation for fibrillation. This aspect produces sulphonated cellulose, possibly out of a waste material where the cellulose has been contaminated in a blend with polyester.

[0208] In another aspect, two DESes can be used: 1) thymol - carvacrol (thymol: carvacrol molar ratio ranging from about 10:5 to about 1 :2, about 10:6 to about 1 :1.7, or about 10:8 to about 1 :1.3) and 2). betaine or betaine hydrochloride - glycerol (betaine:glycerol molar ratio ranging from about 10:5 to about 1 :3.5, about 1 :1 to about 1 :3, or about 1 :1.5 to about 1:2.5). The feedstock can be a waste material comprising cellulose and polyester. The feedstock can be immersed first in the thymol - carvacrol DES, optionally at a temperature of about 15 °C to about 165 °C, about 20 °C to about 160 °C, about 90 °C to about 155 °C, or about ambient temperature. The feedstock: DES mass ratio can range from about 1 :0.5 to about 1:200, about 1 :5 to about 1:200, about 1 :5 to about 1 :150, about 1:6 to about 1:150, or about 1 :7 to about 1 :100. Optionally, the feedstock-DES combination can then be mixed under high shear for about 20 minutes to about 40 minutes. Following, the suspension can be kept at a temperature of about 70 °C to about 160 °C, about 80 °C to about 155 °C, or about 90 °C to about 150 °C, optionally under reduced pressure and / or stirring, for about 1 minutes to about 7 hours, about 3 minutes to about 6 hours, or about 5 minutes to about 5 hours. After the designated time, the suspension can be filtered or centrifuged, and the solid residue can be washed with the DES and / or with GVL (optionally twice washed with GVL). In a further aspect, after the designated time, the DES-treated feedstock can also be washed with another solvent, such as water, DMSO, ethanol, a sequence thereof, or a combination thereof. After final washing, the remaining feedstock can be immersed in the betaine or betaine hydrochloride - glycerol DES at a temperature of about 15 °C to about 150 °C, about 20 °C to about 140 °C, about 110 °C to about 135 °C, about 120 °C to about 130 °C, or about ambient temperature. The feedstock:DES mass ratio can range from about 1 :0.5 to about 1 :200, about 1 :5 to about 1 :200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, or about 1:7 to about 1 : 100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 70 °C to about 170 °C, about 80 °C to about 160 °C, about 85 °C to about 130 °C, or about 130 °C to about 155 °C, optionally under reduced pressure and / or stirring, for about 10 minutes to aboutATTORNEY DOCKET NO. 331903-20106 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, twice DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1.5% in preparation for fibrillation. This aspect produces cationic cellulose, possibly out of a waste material where the cellulose has been contaminated in a blend with polyester.

[0209] In another aspect, two DESes can be used: 1) choline chloride - urea (choline chloride:urea molar ratio ranging from about 10:5 to about 1:3.5, about 1 :1 to about 1 :3, or about 1 :1.5 to about 1 :2.5) and 2). choline chloride - oxalic acid (choline chloride:oxalic acid molar ratio ranging from about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1 :7). The feedstock can be a waste material comprising cellulose and polyurethane. The feedstock can be immersed first in the choline chloride - urea DES at a feedstock: DES mass ratio ranging from about 1 :0.5 to about 1 :200, about 1 :5 to about 1:200, about 1 :5 to about 1:150, about 1 :6 to about 1 :150, or about 1:7 to about 1 :100. Optionally, the feedstock-DES combination can then be mixed under high shear for about 20 minutes to about 40 minutes. Following, the suspension can be kept at a temperature of about 100 °C to about 200 °C, about 110 °C to about 190 °C, or about 120 °C to about 180 °C, optionally under reduced pressure and / or stirring, for about 10 minutes to about 10 hours, about 30 minutes to about 9 hours, or about 1 hour to about 8 hours. After the designated time, the suspension can be filtered or centrifuged, and the solid residue can be washed with the DES, acetone (optionally twice washed with acetone), GVL, DMSO, ethanol, deionized water, a sequence thereof, or any combination thereof. After final washing, the remaining feedstock can be immersed in the choline chloride:oxalic acid DES at a temperature of about 15 °C to about 110 °C, about 20 °C to about 80 °C, about 40 °C to about 75 °C, about 65 °C to about 75 °C, or about ambient temperature. The feedstock: DES mass ratio can range from about 1 :0.5 to about 1 :200, about 1 :5 to about 1 :200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, or about 1:7 to about 1:100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 40 °C to about 75 °C or about 65 °C to about 75 °C, optionally under reduced pressure and / or stirring, for about 30 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, twice DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1.5% in preparation for fibrillation. The pH of the dispersion may be adjusted to about 8 to about 11 or about 8.1 to about 10, or about 8.2 to aboutATTORNEY DOCKET NO. 331903-20109 in order to deprotonate the acidic groups. This aspect produces carboxylated cellulose, possibly out of a waste material where the cellulose is contaminated with polyurethane. This can provide a feasible solution for treating a blended waste material into a more valuable form.

[0210] In another aspect, two DESes can be used: 1) choline chloride - urea (choline chloride:urea molar ratio ranging from about 10:5 to about 1:3.5, about 1 :1 to about 1 :3, or about 1 :1.5 to about 1 :2.5) and 2). choline chloride - citric acid (choline chloride:citric acid molar ratio ranging from about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1 :7). The feedstock can be a waste material comprising cellulose and polyurethane. The feedstock can be immersed first in the choline chloride - urea DES at a feedstock: DES mass ratio ranging from about 1 :0.5 to about 1 :200, about 1 :5 to about 1:200, about 1 :5 to about 1:150, about 1 :6 to about 1 :150, or about 1:7 to about 1 :100. Optionally, the feedstock-DES combination can then be mixed under high shear for about 20 minutes to about 40 minutes. Following, the suspension can be kept at a temperature of about 100 °C to about 200 °C, about 110 °C to about 190 °C, or about 120 °C to about 180 °C, optionally under reduced pressure and / or stirring, for about 10 minutes to about 10 hours, about 30 minutes to about 9 hours, or about 1 hour to about 8 hours. After the designated time, the suspension can be filtered or centrifuged, and the solid residue can be washed with the DES, acetone (optionally twice washed with acetone), GVL, DMSO, ethanol, deionized water, a sequence thereof, or any combination thereof. After final washing, the remaining feedstock can be immersed in the choline chloride:citric acid DES at a temperature of about 15 °C to about 170 °C, about 20 °C to about 165 °C, about 140 °C to about 160 °C, about 145 °C to about 155 °C, or about ambient temperature. The feedstock: DES mass ratio can range from about 1 :0.5 to about 1 :200, about 1 :5 to about 1:200, about 1 :5 to about 1 :150, about 1 :6 to about 1:150, or about 1 :7 to about 1 :100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 60 °C to about 165 °C, about 140 °C to about 160 °C, or about 145 °C to about 155 °C, optionally under reduced pressure and / or stirring, for about 30 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, twice DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1.5% in preparation for fibrillation. The pH of the dispersion may be adjusted to about 8 to about 11 or about 8.1 to about 10, or about 8.2 to about 9 in order to deprotonate the acidic groups. This aspect produces carboxylated cellulose, potentially out of a waste material where the celluloseATTORNEY DOCKET NO. 331903-2010 has been contaminated with polyurethane. This can provide a feasible solution for treating a blended waste material into a more valuable form.

[0211] In another aspect, two DESes can be used: 1) choline chloride - urea (choline chloride:urea molar ratio ranging from about 10:5 to about 1:3.5, about 1 :1 to about 1 :3, or about 1 : 1 .5 to about 1 :2.5) and 2). sulphamic acid - glycerol (sulphamic acid:glycerol molar ratio ranging from about 1 :0.5 to about 1 :5, about 1 :1 to about 1 :5, about 1 :2 to about 1:4, or about 1 :2.5 to about 1 :3.5). The feedstock can be a waste material comprising cellulose and polyurethane. The feedstock can be immersed first in the choline chloride - urea DES at a feedstock:DES mass ratio ranging from about 1 :0.5 to about 1 :200, about 1 :0.5 to about 1 :5, about 1 :1 to about 1 :5, about 1 :2 to about 1 :4, or about 1 :2.5 to about 1 :3.5. Optionally, the feedstock-DES combination can then be mixed under high shear for about 20 minutes to about 40 minutes. Following, the suspension can be kept at a temperature of about 100 °C to about 200 °C, about 110 °C to about 190 °C, or about 120 °C to about 180 °C, optionally under reduced pressure and / or stirring, for about 10 minutes to about 10 hours, about 30 minutes to about 9 hours, or about 1 hour to about 8 hours. After the designated time, the suspension can be filtered or centrifuged, and the solid residue can be washed with the DES, acetone (optionally twice washed with acetone), GVL, DMSO, ethanol, deionized water, a sequence thereof, or any combination thereof. After final washing, the remaining feedstock can be immersed in the sulphamic acid - glycerol DES at a temperature of about 15 °C to about 150 °C, about 20 °C to about 140 °C, about 110 °C to about 135 °C, about 120 °C to about 130 °C, or about ambient temperature. The feedstock: DES mass ratio can range from about 1 :0.5 to about 1 :200, about 1:5 to about 1 :200, about 1:5 to about 1 :150, about 1 :6 to about 1 :150, or about 1 :7 to about 1 :100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 70 °C to about 140 °C, about 80 °C to about 135 °C, or about 85 °C to about 130 °C, optionally under reduced pressure and / or stirring, for about 10 minutes to about 4 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, twice DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1 .5% in preparation for fibrillation. This aspect produces sulphonated cellulose, potentially out of a waste material where the cellulose has been contaminated with polyurethane. This can provide a feasible solution for treating a blended waste material into a more valuable form.

[0212] In another aspect, two DESes can be used: 1) choline chloride - urea (choline chloride:urea molar ratio ranging from about 10:5 to about 1:3.5, about 1 :1 to about 1 :3, or aboutATTORNEY DOCKET NO. 331903-2010 1 :1.5 to about 1 :2.5) and 2). betaine or betaine hydrochloride - glycerol (betaine:glycerol molar ratio ranging from about 10:5 to about 1 :3.5, about 1 :1 to about 1 :3, or about 1 :1.5 to about 1 :2.5). The feedstock can be a waste material comprising cellulose and polyurethane. The feedstock can be immersed first in the choline chloride - urea DES at a feedstock:DES mass ratio ranging from about 1 :0.5 to about 1 :200, about 1 :5 to about 1:200, about 1 :5 to about 1:150, about 1 :6 to about 1 :150, or about 1:7 to about 1 :100. Optionally, the feedstock-DES combination can then be mixed under high shear for about 20 minutes to about 40 minutes. Following, the suspension can be kept at a temperature of about 100 °C to about 200 °C, about 110 °C to about 190 °C, or about 120 °C to about 180 °C, optionally under reduced pressure and / or stirring, for about 10 minutes to about 10 hours, about 30 minutes to about 9 hours, or about 1 hour to about 8 hours. After the designated time, the suspension can be filtered or centrifuged, and the solid residue can be washed with the DES, acetone (optionally twice washed with acetone), GVL, DMSO, ethanol, deionized water, a sequence thereof, or any combination thereof. After final washing, the remaining feedstock can be immersed in the betaine or betaine hydrochloride - glycerol DES at a temperature of about 15 °C to about 150 °C, about 20 °C to about 140 °C, about 110 °C to about 135 °C, about 120 °C to about 130 °C, or about ambient temperature. The feedstock: DES mass ratio can range from about 1 :0.5 to about 1 :200, about 1:5 to about 1 :200, about 1:5 to about 1 :150, about 1 :6 to about 1 :150, or about 1 :7 to about 1 :100. The feedstock-DES suspension can then be mixed under high shear for about 20 minutes to about 40 minutes. Following mixing, the suspension can be kept at a temperature of about 70 °C to about 170 °C, about 80 °C to about 160 °C, about 85 °C to about 130 °C, or about 130 °C to about 155 °C, optionally under reduced pressure and / or stirring, for about 10 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to about 30 minutes; diluted with deionized water; filtered; and washed with deionized water until the filtrate turns neutral. The washed, twice DES-treated cellulosic material can be dispersed in deionized water at a consistency of about 0.5% to about 1.5% in preparation for fibrillation. This aspect produces sulphonated cellulose, possibly out of a waste material where the cellulose has been contaminated with polyurethane. This can provide a feasible solution for treating a blended waste material into a more valuable form.I. THREE OR MORE STEP EXAMPLES OF TREATING CELLULOSE MATERIAL

[0213] Disclosed herein are various embodiments of methods for treating cellulosic material comprising at least three primary steps of DES treatments. In one aspect, a feedstock can be first exposed to two steps of DES treatment as detailed above. After the second step, the twice DES- treated cellulose can be washed (instead of being dispersed in deionized water), followed byATTORNEY DOCKET NO. 331903-2010 dispersion into another DES. The treatment in this DES can be carried out as described in the corresponding aspect above. Treatment in new DESs can be repeated 1 to 12 times, 1 to 9 times, 1 to 6 times, or 1 to 3 times. The following embodiments are intended to be purely exemplary of the disclosure and are not intended to limit the scope of what the inventors regard as their disclosure.J. EXAMPLES OF TREATING CELLULOSE MATERIAL COMPRISING A MATERIAL PREPARATION STEP

[0214] In one aspect, the feedstock can be first treated with one or more DES according to one of the aspects detailed above. After the final DES treatment step, the feedstock-DES suspension can be fibrillated via exposure to high shear or ultrasound through, for example, a high-pressure homogenizer, microfluidizer, grinding, ball milling, aqueous counter collision, or ultrasonication, or a sequence or combination thereof. Following, the suspension can be formed into a desired shape, such as film, fiber, filament, non-woven, coating, sphere, or 3D-printed object. Without, before, during or after the formation, the suspension can be exposed to a solvent that is miscible with the DES and solidifies the desired structure. After the solidification, the solvent may be fully or partly washed or evaporated away from the structure.

[0215] In one aspect, the DES comprises choline chloride and itaconic acid, with a choline chloride:itaconic acid molar ratio ranging from about 10:5 to about 1:9, about 10:6 to about 1 :8, or about 10:7 to about 1 :7. Never-dried feedstock can be added to the DES at a temperature of about 15 °C to about 170 °C, about 20 °C to about 165 °C, about 140 °C to about 160 °C, about 145 °C to about 155 °C, or about ambient temperature. The never-dried feedstock can be added to the DES at a feedstock:DES mass ratio ranging from about 1 :0.5 to about 1 :200, about 1 :5 to about 1 :200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, or about 1:7 to about 1:100. The feedstock-DES suspension can be mixed under high shear for about 20 to about 40 min. Following mixing, the suspension can be kept at a temperature of about 60 °C to about 165 °C, about 140 °C to about 160 °C, or about 145 °C to about 155 °C, optionally under reduced pressure and / or stirring, for about 30 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to 2 hours. Following, the DES-treated cellulose still immersed in the DES can be fibrillated via exposure to high shear or ultrasound through, e.g., a high-pressure homogenizer, microfluidizer, grinding, ball milling, aqueous counter collision, ultrasonication, a sequence thereof, or any combination thereof. Optionally, the resulting DES suspension of nano- or microfibri Hated cellulose can be mixed with GMA, with the GMA comprising about 20 wt% to about 60 wt%, about 30 wt% to about 50 wt%, or about 35 wt% to about 45 wt% of DES. If GMA is used, the suspension can be heated to a temperature of aboutATTORNEY DOCKET NO. 331903-2010 80 °C to about 120 °C, about 90 °C to about 110 °C, or about 95 °C to about 105 °C for about 0.5 hours to 2.5 hours or about 1 hour to about 2 hours. A polymerization initiator, such as ammonium persulfate, can be dissolved in a small amount of water and added to the suspension, where the polymerization initiator comprises a percent molar fraction of the itaconic acid present in the suspension that ranges from about 2% to about 10%, about 3% to about 9%, or about 4% to about 8%. Additionally, a crosslinking agent, such as polyethylene glycol diacrylate or N,N’- methylenebisacrylamide, can be added to the suspension, where the crosslinking agent comprises about 0.5 wt% to about 70 wt% of the GMA or the itaconic acid. The suspension can be formed into a desired shape, such as film, fiber, filament, non-woven, coating, sphere, or 3D- printed object. Without, before, during or after the formation, the suspension can be heated at a temperature of about 40 °C to about 90 °C, about 50 °C to about 80 °C, or about 60 °C to about 70 °C for up to about 24 hours to induce polymerization. The polymerized material can be washed until the washing liquid turns neutral. The material formation and the first washing step can take place simultaneously, if the formation is done in water under heating. This aspect produces a crosslinked network of cellulose and itaconic acid-based polymer. As an alternative to adding ammonium persulfate and heating, a photoinitiator, such as 2-hydroxy-4-(2-hydroxyethyl)-2- methylpropiophenone can be added before the possible material formation. The photoinitiator can comprise about 0.5 wt% to about 1.5 wt% of the GMA or itaconic acid. When using a photoinitiator, the material can be irradiated with about 200 nm to about 400 nm, about 330 nm to about 385 nm, about 360 nm to about 370 nm UV light for several seconds, during or after the washing.

[0216] In another aspect, the DES comprises choline chloride and maleic acid, with a choline chloride:maleic acid molar ratio ranging from about 10:5 to about 1 :9, about 10:6 to about 1 :8, or about 10:7 to about 1:7. Never-dried feedstock can be added to the DES at a temperature of about 15 °C to about 170 °C, about 20 °C to about 165 °C, about 140 °C to about 160 °C, about 145 °C to about 155 °C, or about ambient temperature. The never-dried feedstock can be added to the DES at a feedstock:DES mass ratio ranging from about 1 :0.5 to about 1 :200, about 1 :5 to about 1 :200, about 1 :5 to about 1 :150, about 1 :6 to about 1 :150, or about 1:7 to about 1:100. The feedstock-DES suspension can be mixed under high shear for about 20 to about 40 min. Following mixing, the suspension can be kept at a temperature of about 60 °C to about 165 °C, about 140 °C to about 160 °C, or about 145 °C to about 155 °C, optionally under reduced pressure and / or stirring, for about 30 minutes to about 6 hours. After the designated time, the suspension can be allowed to cool down at ambient conditions for up to 2 hours. Following, the DES-treated cellulose still immersed in the DES can be fibrillated via exposure to high shear or ultrasound through, e.g., a high-pressure homogenizer, microfluidizer, grinding, ball milling, aqueous counter collision,ATTORNEY DOCKET NO. 331903-2010 ultrasonication, a sequence thereof, or any combination thereof. Optionally, the resulting DES suspension of nano- or microfibri Hated cellulose can be mixed with GMA, with the GMA comprising about 20 wt% to about 60 wt%, about 30 wt% to about 50 wt%, or about 35 wt% to about 45 wt% of the DES. If GMA is used, the suspension can be heated to a temperature of about 80 °C to about 120 °C, about 90 °C to about 110 °C, or about 95 °C to about 105 °C for about 0.5 hours to 2.5 hours or about 1 hour to about 2 hours. Following the heating, a crosslinking agent, such as polyethylene glycol diacrylate or / V, / V’-methylenebisacrylamide, can be added to the suspension, where the crosslinking agent comprises about 0.5 wt% to about 1.5 wt% of the GMA. Additionally a photoinitiator, such as 2-hydroxy-4-(2-hydroxyethyl)-2-methylpropiophenone (0.5-1.5wt% out of GMA or itaconic acid) can be added to the suspension. The photoinitiator can comprise about 0.5 wt% to about 1.5 wt% of the GMA. The suspension can be formed into a desired shape, such as film, fiber, filament, non-woven, coating, sphere, or 3D-printed object. Without, before, during or after the formation, the suspension can be irradiated with about 200 nm to about 400 nm, about 330 nm to about 385 nm, about 360 nm to about 370 nm UV light for several seconds. The polymerized material can be washed until the washing liquid turns neutral. The material formation and the first washing step can take place simultaneously, if the formation is done in water under UV irradiation. This embodiment produces a crosslinked network of cellulose and maleic acid -based polymer. As an alternative to adding a photoinitiator and UV irradiation, another initiator, such as ammonium persulfate can be added before the possible material formation. The alternative initiator can comprise a percent molar fraction of the GMA present in the suspension that ranges from about 2% to about 10%, about 3% to about 9%, or about 4% to about 8%. When using this initiator, the material can be heated to a temperature of about 40 °C to about 90 °C, about 50 °C to about 80 °C, or about 60 °C to about 70 °C for up to about 24 hours to induce polymerization.K. ALTERNATIVE PREPARATION OF RAW FEEDSTOCK MATERIALS

[0217] In one aspect, the feedstock can be dried before the DES treatment. In this case, all or part of the dry raw material can be ground into a granular or powder form prior to its treatment. The dry feedstock can be mixed with a DES, as described herein. Any remaining steps (e.g., mixing, treatment, washing, diluting, etc.) can be carried out using the methods described herein. This aspect can provide for functionalized cellulose out of a dry raw material, which is relatively easy to transport.

[0218] In another aspect, a never-dried feedstock can be first solvent exchanged into a DES. This can be done by immersing the feedstock in an excess of the DES for about 5 minutes to about 24ATTORNEY DOCKET NO. 331903-2010 hours, about 10 minutes to about 12 hours, about 15 minutes to about 8 hours, about 20 minutes to about 4, or about 5 minutes to about 4 hours. Following immersion, the solid feedstock can be separated by filtration or centrifugation, a sequence thereof, or a combination thereof. An immersion to a fresh DES and a separation step can be repeated 1 to 9 times, 2 to 7 times, or 3 to 5 times. After the final repetition, the solvent exchanged feedstock can be immersed in a DES intended for use in any one of the treatment methods disclosed herein. The rest of the treatment method (e.g., mixing, treatment, washing, diluting, etc.) can carried out as described herein.L. FILAMENTS, FILMS, AND MOLDED MATERIALS

[0219] In various aspects, a disclosed composition as a stable solution comprising CNM can be used to make a filament, film, or a molded material.

[0220] In a further aspect, the disclosed compositions can be used to form filaments in a spinning process such as a wet spinning process. For example, in some aspects, the disclosed compositions can be formed into filaments by use of the wet spinning process comprising extrusion of the disclosed composition into a coagulation bath comprising one or more divalent cations including, but not limited, to Ca2+, Mg2+, Mn2+, Zn2+, Fe2+, Co2+, Sn2+, through a spinneret with 80 to 1000 micron holes. Without wishing to be bound by a particular theory, the G-blocks of alginate can participate in intermolecular cross-linking through exchange of its sodium ion with divalent ions. In order to form a stable fiber comprising nanocellulose and hexagonal boron nitride, filaments can be drawn through a washing bath of, but not limited to, deionized water, acetone, or ethanol in order to remove excess calcium. After washing, the filaments can then be dried under heat, e.g., radiant or convection heat, in order to collect onto a take up. Filaments drawn in this manner can have tensile strengths of from 140 mPa to 1040 mPa.

[0221] In a further aspect, electric-field assisted wet spinning processes can be utilized, e.g., used to align polymer chains by applying an alternating current voltage to improve the Young's modulus, tensile strength, yield strength, strain-at-break, and toughness. In an exemplary aspect, this can be carried out by placing the metal cathode and anode, from an arbitrary waveform and high-voltage function generator, on the wet-spinning spinneret and / or in the coagulation bath respectively. Applied voltages could range from 0.1 V to 10,000 V.

[0222] In a further aspect, a disclosed composition as a stable solution comprising CNM as described above and in the examples, can be used for cast or form a film. Following casting, evaporation of water can yield a desired film.ATTORNEY DOCKET NO. 331903-2010

[0223] In a further aspect, a disclosed composition as a stable solution comprising CNM can be injected or extruded into a suitable mold to form molded articles of desired geometries, shapes, thicknesses and the like comprising a disclosed composition. In a still further aspect, the disclosed composition can be subjected to evaporative dehydration in situ in the mold using a suitable method such as radiant or convective heating.M. YARNS

[0224] In various aspects, the present disclosure pertains to a yarn comprising a disclosed composition. The yarn can be a blended yarn or composite yarn comprising fibers or filaments comprising the disclosed composition and one or more additional fibers or filaments, including natural fibers and / or synthetic fibers or filaments. In a further aspect, a disclosed yarn can be flat. In a still further aspect, or other aspects, a disclosed yarn can be texturized, e.g., via a draw texturizing process.

[0225] In a further aspect, the blended yarn or composite yarn can comprise one or more additional fibers or filaments comprising a polyamide, including, but not limited to, a nylon 6, nylon 4 / 6, nylon 6 / 6, nylon 6 / 10, nylon 6 / 12, nylon 11 , nylon 12, or combinations thereof. In a further aspect, the polyamide can comprise a nylon 6 / 6. In a still further aspect, the polyamide is a polyamide co-polymer comprising nylon 6, nylon 4 / 6, nylon 6 / 6, nylon 6 / 10, nylon 6 / 12, nylon 11 , nylon 12, or combinations thereof. In a yet further aspect, the polyamide is a polyamide copolymer comprising nylon 6 / 6.

[0226] In a further aspect, a disclosed yarn has a linear mass density of about 50d / 20f to about 130d / 90f; about 105d / 20f to about 130d / 40f; about 110d / 20f to about 130d / 40f; about 115d / 20f to about 130d / 40f; about 105d / 20f to about 130d / 35f; about 110d / 35f to about 130d / 35f; about 115d / 20f to about 130d / 35f; about 105d / 20f to about 130d / 30f; about 110d / 20f to about 130d / 30f ; about 115d / 20f to about 130d / 30f; about 105d / 20f to about 130d / 40f; about 115d / 25f to about 135d / 35f; a sub-range within any of the foregoing ranges; or any set of values utilizing values within any of the foregoing ranges. It is understood in the foregoing values that "d" indicates Denier for the yarn and "f1indicates number of filaments in a yarn fiber. Thus, a disclosed yarn having a weight of 75d / 72f would be a yarn have a linear mass density of 75 Denier with 72 filaments per yarn fiber.

[0227] In a further aspect, a disclosed yarn has a linear mass density of about 120d / 20f ± 10%; about 120d / 20f ± 5%; about 120d / 20f ± 3%; 121 d / 20f ± 10%; about 121 d / 20f ± 5%; about 121 d / 20f ± 3%; 122d / 20f ± 10%; about 122d / 20f ± 5%; about 122d / 20f ± 3%; 123d / 20f ± 10%; about 123d / 20f ± 5%; about 123d / 20f ± 3%; 124d / 20f ± 10%; about 124d / 20f ± 5%; about 124d / 20f ±ATTORNEY DOCKET NO. 331903-2010 3%; 125d / 20f ± 10%; about 125d / 20f ± 5%; about 125d / 20f ± 3%; 126d / 20f ± 10%; about 126d / 20f ± 5%; about 126d / 20f ± 3%; 127d / 20f ± 10%; about 127d / 20f ± 5%; about 127d / 20f ± 3%; 128d / 20f ± 10%; about 128d / 20f ± 5%; about 128d / 20f ± 3%; 129d / 20f ± 10%; about 129d / 20f ± 5%; about 129d / 20f ± 3%; 130d / 20f ± 10%; about 130d / 20f ± 5%; about 130d / 20f ± 3%; about 120d / 25f ± 10%; about 120d / 25f ± 5%; about 120d / 25f ± 3%; 121d / 25f ± 10%; about 121 d / 25f ± 5%; about 121 d / 25f ± 3%; 122d / 25f ± 10%; about 122d / 25f ± 5%; about 122d / 25f ± 3%; 123d / 25f ± 10%; about 123d / 25f ± 5%; about 123d / 25f ± 3%; 124d / 25f ± 10%; about 124d / 25f ± 5%; about 124d / 25f ± 3%; 125d / 25f ± 10%; about 125d / 25f ± 5%; about 125d / 25f ± 3%; 126d / 25f ± 10%; about 126d / 25f ± 5%; about 126d / 25f ± 3%; 127d / 25f ± 10%; about 127d / 25f ± 5%; about 127d / 25f ± 3%; 128d / 25f ± 10%; about 128d / 25f ± 5%; about 128d / 25f ± 3%; 129d / 25f ± 10%; about 129d / 25f ± 5%; about 129d / 25f ± 3%; 130d / 25f ± 10%; about 130d / 25f ± 5%; about 130d / 25f ± 3%; about 120d / 30f ± 10%; about 120d / 30f ± 5%; about 120d / 30f ± 3%; 121 d / 30f ± 10%; about 121 d / 30f ± 5%; about 121 d / 30f ± 3%; 122d / 30f ± 10%; about 122d / 30f ± 5%; about 122d / 30f ± 3%; 123d / 30f ± 10%; about 123d / 30f ± 5%; about 123d / 30f ± 3%; 124d / 30f ± 10%; about 124d / 30f ± 5%; about 124d / 30f ± 3%; 125d / 30f ± 10%; about 125d / 30f ± 5%; about 125d / 30f ± 3%; 126d / 30f ± 10%; about 126d / 30f ± 5%; about 126d / 30f ± 3%; 127d / 30f ± 10%; about 127d / 30f ± 5%; about 127d / 30f ± 3%; 128d / 30f ± 10%; about 128d / 30f ± 5%; about 128d / 30f ± 3%; 129d / 30f ± 10%; about 129d / 30f ± 5%; about 129d / 30f ± 3%; 130d / 30f ± 10%; about 130d / 30f ± 5%; about 130d / 30f ± 3%; about 120d / 35f ± 10%; about 120d / 35f ± 5%; about 120d / 35f ± 3%; 121 d / 35f ± 10%; about 121 d / 35f ± 5%; about 121 d / 35f ± 3%; 122d / 35f ± 10%; about 122d / 35f ± 5%; about 122d / 35f ± 3%; 123d / 35f ± 10%; about 123d / 35f ± 5%; about 123d / 35f ± 3%; 124d / 35f ± 10%; about 124d / 35f ± 5%; about 124d / 35f ± 3%; 125d / 35f ± 10%; about 125d / 35f ± 5%; about 125d / 35f ± 3%; 126d / 35f ± 10%; about 126d / 35f ± 5%; about 126d / 35f ± 3%; 127d / 35f ± 10%; about 127d / 35f ± 5%; about 127d / 35f ± 3%; 128d / 35f ± 10%; about 128d / 35f ± 5%; about 128d / 35f ± 3%; 129d / 35f ± 10%; about 129d / 35f ± 5%; about 129d / 35f ± 3%; 130d / 35f ± 10%; about 130d / 35f ± 5%; about 130d / 35f ± 3%; about 120d / 40f ± 10%; about 120d / 40f ± 5%; about 120d / 40f ± 3%; 121 d / 40f ± 10%; about 121 d / 40f ± 5%; about 121 d / 40f ± 3%; 122d / 40f ± 10%; about 122d / 40f ± 5%; about 122d / 40f ± 3%; 123d / 40f ± 10%; about 123d / 40f ± 5%; about 123d / 40f ± 3%; 124d / 40f ± 10%; about 124d / 40f ± 5%; about 124d / 40f ± 3%; 125d / 40f ± 10%; about 125d / 40f ± 5%; about 125d / 40f ± 3%; 126d / 40f ± 10%; about 126d / 40f ± 5%; about 126d / 40f ± 3%; 127d / 40f ± 10%; about 127d / 40f ± 5%; about 127d / 40f ± 3%; 128d / 40f ± 10%; about 128d / 40f ± 5%; about 128d / 40f ± 3%; 129d / 40f ± 10%; about 129d / 40f ± 5%; about 129d / 40f ± 3%; 130d / 40f ± 10%; about 130d / 40f ± 5%; about 130d / 40f ± 3%; a range encompassing any of the foregoing value; or any combination of the foregoing values.ATTORNEY DOCKET NO. 331903-2010

[0228] In a further aspect, a disclosed yarn has a linear mass density of about 70d / 70f ± 10%; about 70d / 70f ± 5%; about 70d / 70f ± 3%; 71d / 70f ± 10%; about 71d / 70f ± 5%; about 71d / 70f ± 3%; 72d / 70f ± 10%; about 72d / 70f ± 5%; about 72d / 70f ± 3%; 73d / 70f ± 10%; about 73d / 70f ± 5%; about 73d / 70f ± 3%; 74d / 70f ± 10%; about 74d / 70f ± 5%; about 74d / 70f ± 3%; 75d / 70f ± 10%; about 75d / 70f ± 5%; about 75d / 70f ± 3%; 76d / 70f ± 10%; about 76d / 70f ± 5%; about 76d / 70f ± 3%; 77d / 70f ± 10%; about 77d / 70f ± 5%; about 77d / 70f ± 3%; 78d / 70f ± 10%; about 78d / 70f ± 5%; about 78d / 70f ± 3%; 79d / 70f ± 10%; about 79d / 70f ± 5%; about 79d / 70f ± 3%; 80d / 70f ± 10%; about 80d / 70f ± 5%; about 80d / 70f ± 3%; about 70d / 75f ± 10%; about 70d / 75f ± 5%; about 70d / 75f ± 3%; 71d / 75f ± 10%; about 71d / 75f ± 5%; about 71 d / 75f ± 3%; 72d / 75f ± 10%; about 72d / 75f ± 5%; about 72d / 75f ± 3%; 73d / 75f ± 10%; about 73d / 75f ± 5%; about 73d / 75f ± 3%; 74d / 75f ± 10%; about 74d / 75f ± 5%; about 74d / 75f ± 3%; 75d / 75f ± 10%; about 75d / 75f ± 5%; about 75d / 75f ± 3%; 76d / 75f ± 10%; about 76d / 75f ± 5%; about 76d / 75f ± 3%; 77d / 75f ± 10%; about 77d / 75f ± 5%; about 77d / 75f ± 3%; 78d / 75f ± 10%; about 78d / 75f ± 5%; about 78d / 75f ± 3%; 79d / 75f ± 10%; about 79d / 75f ± 5%; about 79d / 75f ± 3%; 80d / 75f ± 10%; about 80d / 75f ± 5%; about 80d / 75f ± 3%; about 70d / 80f ± 10%; about 70d / 80f ± 5%; about 70d / 80f ± 3%; 71d / 80f ± 10%; about 71d / 80f ± 5%; about 71d / 80f ± 3%; 72d / 80f ± 10%; about 72d / 80f ± 5%; about 72d / 80f ± 3%; 73d / 80f ± 10%; about 73d / 80f ± 5%; about 73d / 80f ± 3%; 74d / 80f ± 10%; about 74d / 80f ± 5%; about 74d / 80f ± 3%; 75d / 80f ± 10%; about 75d / 80f ± 5%; about 75d / 80f ± 3%; 76d / 80f ± 10%; about 76d / 80f ± 5%; about 76d / 80f ± 3%; 77d / 80f ± 10%; about 77d / 80f ± 5%; about 77d / 80f ± 3%; 78d / 80f ± 10%; about 78d / 80f ± 5%; about 78d / 80f ± 3%; 79d / 80f ± 10%; about 79d / 80f ± 5%; about 79d / 80f ± 3%; 80d / 80f ± 10%; about 80d / 80f ± 5%; about 80d / 80f ± 3%; about 70d / 85f ± 10%; about 70d / 85f ± 5%; about 70d / 85f ± 3%; 71d / 85f ± 10%; about 71 d / 85f ± 5%; about 71d / 85f ± 3%; 72d / 85f ± 10%; about 72d / 85f ± 5%; about 72d / 85f ± 3%; 73d / 85f ± 10%; about 73d / 85f ± 5%; about 73d / 85f ± 3%; 74d / 85f ± 10%; about 74d / 85f ± 5%; about 74d / 85f ± 3%; 75d / 85f ± 10%; about 75d / 85f ± 5%; about 75d / 85f ± 3%; 76d / 85f ± 10%; about 76d / 85f ± 5%; about 76d / 85f ± 3%; 77d / 85f ± 10%; about 77d / 85f ± 5%; about 77d / 85f ± 3%; 78d / 85f ± 10%; about 78d / 85f ± 5%; about 78d / 85f ± 3%; 79d / 85f ± 10%; about 79d / 85f ± 5%; about 79d / 85f ± 3%; 80d / 85f ± 10%; about 80d / 85f ± 5%; about 80d / 85f ± 3%; about 70d / 90f ± 10%; about 70d / 90f ± 5%; about 70d / 90f ± 3%; 71d / 90f ± 10%; about 71d / 90f ± 5%; about 71d / 90f ± 3%; 72d / 90f ± 10%; about 72d / 90f ± 5%; about 72d / 90f ± 3%; 73d / 90f ± 10%; about 73d / 90f ± 5%; about 73d / 90f ± 3%; 74d / 90f ± 10%; about 74d / 90f ± 5%; about 74d / 90f ± 3%; 75d / 90f ± 10%; about 75d / 90f ± 5%; about 75d / 90f ± 3%; 76d / 90f ± 10%; about 76d / 90f ± 5%; about 76d / 90f ± 3%; 77d / 90f ± 10%; about 77d / 90f ± 5%; about 77d / 90f ± 3%; 78d / 90f ± 10%; about 78d / 90f ± 5%; about 78d / 90f ± 3%; 79d / 90f ± 10%;ATTORNEY DOCKET NO. 331903-2010 about 79d / 90f ± 5%; about 79d / 90f ± 3%; 80d / 90f ± 10%; about 80d / 90f ± 5%; about 80d / 90f ± 3%; a range encompassing any of the foregoing value; or any combination of the foregoing values.

[0229] In various aspects, a disclosed yarn has a linear mass density of about 250 Denier to about 370 Denier; about 260 Denier to about 370 Denier; about 270 Denier to about 370 Denier; about 280 Denier to about 370 Denier; about 290 Denier to about 370 Denier; about 300 Denier to about 370 Denier; about 310 Denier to about 370 Denier; about 320 Denier to about 370 Denier; about 330 Denier to about 370 Denier; about 340 Denier to about 370 Denier; about 350 Denier to about 370 Denier; about 355 Denier to about 370 Denier; about 360 Denier to about 370 Denier; about 250 Denier to about 360 Denier; about 260 Denier to about 360 Denier; about 270 Denier to about 360 Denier; about 280 Denier to about 360 Denier; about 290 Denier to about 360 Denier; about 300 Denier to about 360 Denier; about 310 Denier to about 360 Denier; about 320 Denier to about 360 Denier; about 330 Denier to about 360 Denier; about 340 Denier to about 360 Denier; about 350 Denier to about 360 Denier; about 250 Denier to about 350 Denier; about 260 Denier to about 350 Denier; about 270 Denier to about 350 Denier; about 280 Denier to about 350 Denier; about 290 Denier to about 350 Denier; about 300 Denier to about 350 Denier; about 310 Denier to about 350 Denier; about 320 Denier to about 350 Denier; about 330 Denier to about 350 Denier; about 340 Denier to about 350 Denier; about 250 Denier to about 340 Denier; about 260 Denier to about 340 Denier; about 270 Denier to about 340 Denier; about 280 Denier to about 340 Denier; about 290 Denier to about 340 Denier; about 300 Denier to about 340 Denier; about 310 Denier to about 340 Denier; about 320 Denier to about 340 Denier; about 330 Denier to about 340 Denier; about 250 Denier to about 330 Denier; about 260 Denier to about 330 Denier; about 270 Denier to about 330 Denier; about 280 Denier to about 330 Denier; about 285 Denier to about 330 Denier; about 290 Denier to about 330 Denier; about 300 Denier to about 330 Denier; about 310 Denier to about 330 Denier; about 320 Denier to about 330 Denier; about 250 Denier to about 320 Denier; about 260 Denier to about 320 Denier; about 270 Denier to about 320 Denier; about 280 Denier to about 320 Denier; about 290 Denier to about 320 Denier; about 300 Denier to about 320 Denier; about 310 Denier to about 320 Denier; about 250 Denier to about 310 Denier; about 260 Denier to about 310 Denier; about 270 Denier to about 310 Denier; about 280 Denier to about 310 Denier; about 290 Denier to about 310 Denier; about 300 Denier to about 310 Denier; about 250 Denier to about 300 Denier; about 260 Denier to about 300 Denier; about 270 Denier to about 300 Denier; about 280 Denier to about 300 Denier; about 290 Denier to about 300 Denier; about 250 Denier to about 350 Denier; about 270 Denier to about 330 Denier; about 280 Denier to about 320 Denier; about 285 Denier to about 310 Denier; about 250 Denier to about 360 Denier; about 270 Denier to about 360 Denier; about 280 Denier to about 360 Denier; about 285 Denier to about 360 Denier;ATTORNEY DOCKET NO. 331903-2010 a sub-range within any of the foregoing ranges; or any set of values utilizing values within any of the foregoing ranges.

[0230] In a further aspect, a disclosed yarn has a linear mass density of about 270 Denier ± 10%; 270 Denier ± 5%; about 270 Denier ± 3%; about 271 Denier ± 10%; 271 Denier ± 5%; about 271 Denier ± 3%; about 272 Denier ± 10%; 272 Denier ± 5%; about 272 Denier ± 3%; about 273 Denier ± 10%; 273 Denier ± 5%; about 273 Denier ± 3%; about 274 Denier ± 10%; 274 Denier ± 5%; about 274 Denier ± 3%; about 275 Denier ± 10%; 275 Denier ± 5%; about 275 Denier ± 3%; about 276 Denier ± 10%; 276 Denier ± 5%; about 276 Denier ± 3%; about 277 Denier ± 10%; 277 Denier ± 5%; about 277 Denier ± 3%; about 278 Denier ± 10%; 278 Denier ± 5%; about 278 Denier ± 3%; about 279 Denier ± 10%; 279 Denier ± 5%; about 279 Denier ± 3%; about 280 Denier ± 10%; 280 Denier ± 5%; about 280 Denier ± 3%; about 281 Denier ± 10%; 281 Denier ± 5%; about 281 Denier ± 3%; about 282 Denier ± 10%; 282 Denier ± 5%; about 282 Denier ± 3%; about 283 Denier ± 10%; 283 Denier ± 5%; about 283 Denier ± 3%; about 284 Denier ± 10%; 284 Denier ± 5%; about 284 Denier ± 3%; about 285 Denier ± 10%; 285 Denier ± 5%; about 285 Denier ± 3%; about 286 Denier ± 10%; 286 Denier ± 5%; about 286 Denier ± 3%; about 287 Denier ± 10%; 287 Denier ± 5%; about 287 Denier ± 3%; about 288 Denier ± 10%; 288 Denier ± 5%; about 288 Denier ± 3%; about 289 Denier ± 10%; 289 Denier ± 5%; about 289 Denier ± 3%; about 290 Denier ± 10%; 290 Denier ± 5%; about 290 Denier ± 3%; about 291 Denier ± 10%; 291 Denier ± 5%; about 291 Denier ± 3%; about 292 Denier ± 10%; 292 Denier ± 5%; about 292 Denier ± 3%; about 293 Denier ± 10%; 293 Denier ± 5%; about 293 Denier ± 3%; about 294 Denier ± 10%; 294 Denier ± 5%; about 294 Denier ± 3%; about 295 Denier ± 10%; 295 Denier ± 5%; about 295 Denier ± 3%; about 296 Denier ± 10%; 296 Denier ± 5%; about 296 Denier ± 3%; about 297 Denier ± 10%; 297 Denier ± 5%; about 297 Denier ± 3%; about 298 Denier ± 10%; 298 Denier ± 5%; about 298 Denier ± 3%; about 299 Denier ± 10%; 299 Denier ± 5%; about 299 Denier ± 3%; about 300 Denier ± 10%; 300 Denier ± 5%; about 300 Denier ± 3%; about 301 Denier ± 10%; 301 Denier ± 5%; about 301 Denier ± 3%; about 302 Denier ± 10%; 302 Denier ± 5%; about 302 Denier ± 3%; about 303 Denier ± 10%; 303 Denier ± 5%; about 303 Denier ± 3%; about 304 Denier ± 10%; 304 Denier ± 5%; about 304 Denier ± 3%; about 305 Denier ± 10%; 305 Denier ± 5%; about 305 Denier ± 3%; about 306 Denier ± 10%; 306 Denier ± 5%; about 306 Denier ± 3%; about 307 Denier ± 10%; 307 Denier ± 5%; about 307 Denier ± 3%; about 308 Denier ± 10%; 308 Denier ± 5%; about 308 Denier ± 3%; about 309 Denier ± 10%; 309 Denier ± 5%; about 309 Denier ± 3%; about 310 Denier ± 10%; 310 Denier ± 5%; about 310 Denier ± 3%; about 311 Denier ± 10%; 311 Denier ± 5%; about 311 Denier ± 3%; about 312 Denier ± 10%; 312 Denier ± 5%; about 312 Denier ± 3%; about 313 Denier ± 10%; 313 Denier ± 5%; about 313ATTORNEY DOCKET NO. 331903-2010Denier ± 3%; about 314 Denier ± 10%; 314 Denier ± 5%; about 314 Denier ± 3%; about 315 Denier ± 10%; 315 Denier ± 5%; about 315 Denier ± 3%; about 316 Denier ± 10%; 316 Denier ± 5%; about 316 Denier ± 3%; about 317 Denier ± 10%; 317 Denier ± 5%; about 317 Denier ± 3%; about 318 Denier ± 10%; 318 Denier ± 5%; about 318 Denier ± 3%; about 319 Denier ± 10%; 319 Denier ± 5%; about 319 Denier ± 3%; about 320 Denier ± 10%; 320 Denier ± 5%; about 320 Denier ± 3%; about 321 Denier ± 10%; 321 Denier ± 5%; about 321 Denier ± 3%; about 322 Denier ± 10%; 322 Denier ± 5%; about 322 Denier ± 3%; about 323 Denier ± 10%; 323 Denier ± 5%; about 323 Denier ± 3%; about 324 Denier ± 10%; 324 Denier ± 5%; about 324 Denier ± 3%; about 325 Denier ± 10%; 325 Denier ± 5%; about 325 Denier ± 3%; about 326 Denier ± 10%; 326 Denier ± 5%; about 326 Denier ± 3%; about 327 Denier ± 10%; 327 Denier ± 5%; about 327 Denier ± 3%; about 328 Denier ± 10%; 328 Denier ± 5%; about 328 Denier ± 3%; about 329 Denier ± 10%; 329 Denier ± 5%; about 329 Denier ± 3%; about 330 Denier ± 10%; 330 Denier ± 5%; about 330 Denier ± 3%; about 331 Denier ± 10%; 331 Denier ± 5%; about 331 Denier ± 3%; about 332 Denier ± 10%; 332 Denier ± 5%; about 332 Denier ± 3%; about 333 Denier ± 10%; 333 Denier ± 5%; about 333 Denier ± 3%; about 334 Denier ± 10%; 334 Denier ± 5%; about 334 Denier ± 3%; about 335 Denier ± 10%; 335 Denier ± 5%; about 335 Denier ± 3%; about 336 Denier ± 10%; 336 Denier ± 5%; about 336 Denier ± 3%; about 337 Denier ± 10%; 337 Denier ± 5%; about 337 Denier ± 3%; about 338 Denier ± 10%; 338 Denier ± 5%; about 338 Denier ± 3%; about 339 Denier ± 10%; 339 Denier ± 5%; about 339 Denier ± 3%; about 340 Denier ± 10%; 340 Denier ± 5%; about 340 Denier ± 3%; about 341 Denier ± 10%; 341 Denier ± 5%; about 341 Denier ± 3%; about 342 Denier ± 10%; 342 Denier ± 5%; about 342 Denier ± 3%; about 343 Denier ± 10%; 343 Denier ± 5%; about 343 Denier ± 3%; about 344 Denier ± 10%; 344 Denier ± 5%; about 344 Denier ± 3%; about 345 Denier ± 10%; 345 Denier ± 5%; about 345 Denier ± 3%; about 346 Denier ± 10%; 346 Denier ± 5%; about 346 Denier ± 3%; about 347 Denier ± 10%; 347 Denier ± 5%; about 347 Denier ± 3%; about 348 Denier ± 10%; 348 Denier ± 5%; about 348 Denier ± 3%; about 349 Denier ± 10%; 349 Denier ± 5%; about 349 Denier ± 3%; about 350 Denier ± 10%; 350 Denier ± 5%; about 350 Denier ± 3%; about 351 Denier ± 10%; 351 Denier ± 5%; about 351 Denier ± 3%; about 352 Denier ± 10%; 352 Denier ± 5%; about 352 Denier ± 3%; about 353 Denier ± 10%; 353 Denier ± 5%; about 353 Denier ± 3%; about 354 Denier ± 10%; 354 Denier ± 5%; about 354 Denier ± 3%; about 355 Denier ± 10%; 355 Denier ± 5%; about 355 Denier ± 3%; about 356 Denier ± 10%; 356 Denier ± 5%; about 356 Denier ± 3%; about 357 Denier ± 10%; 357 Denier ± 5%; about 357 Denier ± 3%; about 358 Denier ± 10%; 358 Denier ± 5%; about 358 Denier ± 3%; about 359 Denier ± 10%; 359 Denier ± 5%; about 359 Denier ± 3%; about 360 Denier ± 10%; 360 Denier ± 5%; about 360 Denier ± 3%; about 361 Denier ± 10%; 361ATTORNEY DOCKET NO. 331903-2010Denier ± 5%; about 361 Denier ± 3%; about 362 Denier ± 10%; 362 Denier ± 5%; about 362 Denier ± 3%; about 363 Denier ± 10%; 363 Denier ± 5%; about 363 Denier ± 3%; about 364 Denier ± 10%; 364 Denier ± 5%; about 364 Denier ± 3%; about 365 Denier ± 10%; 365 Denier ± 5%; about 365 Denier ± 3%; about 366 Denier ± 10%; 366 Denier ± 5%; about 366 Denier ± 3%; about 367 Denier ± 10%; 367 Denier ± 5%; about 367 Denier ± 3%; about 368 Denier ± 10%; 368 Denier ± 5%; about 368 Denier ± 3%; about 369 Denier ± 10%; about 369 Denier ± 5%; about 369 Denier ± 3%; about 370 Denier ± 10%; 370 Denier ± 5%; about 370 Denier ± 3%; about 371 Denier ± 10%; 371 Denier ± 5%; about 371 Denier ± 3%; about 372 Denier ± 10%; 372 Denier ± 5%; about 372 Denier ± 3%; about 373 Denier ± 10%; 373 Denier ± 5%; about 373 Denier ± 3%; about 374 Denier ± 10%; 374 Denier ± 5%; about 374 Denier ± 3%; about 375 Denier ± 10%; 375 Denier ± 5%; about 375 Denier ± 3%; about 376 Denier ± 10%; 376 Denier ± 5%; about 376 Denier ± 3%; about 377 Denier ± 10%; 377 Denier ± 5%; about 377 Denier ± 3%; about 378 Denier ± 10%; 378 Denier ± 5%; about 378 Denier ± 3%; about 379 Denier ± 10%; about 379 Denier ± 5%; about 379 Denier ± 3%; about 380 Denier ± 10%; about 380 Denier ± 5%; about 380 Denier ± 3%; a range encompassing any of the foregoing values; or any combination of the foregoing values.

[0231] In various aspects, a disclosed yarn has a linear mass density of about 50 Denier to about 170 Denier; about 60 Denier to about 170 Denier; about 70 Denier to about 170 Denier; about 80 Denier to about 170 Denier; about 90 Denier to about 170 Denier; about 100 Denier to about 170 Denier; about 110 Denier to about 170 Denier; about 120 Denier to about 170 Denier; about 130 Denier to about 170 Denier; about 140 Denier to about 170 Denier; about 150 Denier to about 170 Denier; about 155 Denier to about 170 Denier; about 160 Denier to about 170 Denier; about 50 Denier to about 160 Denier; about 60 Denier to about 160 Denier; about 70 Denier to about 160 Denier; about 80 Denier to about 160 Denier; about 90 Denier to about 160 Denier; about 100 Denier to about 160 Denier; about 110 Denier to about 160 Denier; about 120 Denier to about 160 Denier; about 130 Denier to about 160 Denier; about 140 Denier to about 160 Denier; about 150 Denier to about 160 Denier; about 50 Denier to about 150 Denier; about 60 Denier to about 150 Denier; about 70 Denier to about 150 Denier; about 80 Denier to about 150 Denier; about 90 Denier to about 150 Denier; about 100 Denier to about 150 Denier; about 110 Denier to about 150 Denier; about 120 Denier to about 150 Denier; about 130 Denier to about 150 Denier; about 140 Denier to about 150 Denier; about 50 Denier to about 140 Denier; about 60 Denier to about 140 Denier; about 70 Denier to about 140 Denier; about 80 Denier to about 140 Denier; about 90 Denier to about 140 Denier; about 100 Denier to about 140 Denier; about 110 Denier to about 140 Denier; about 120 Denier to about 140 Denier; about 130 Denier to about 140 Denier; aboutATTORNEY DOCKET NO. 331903-2010 50 Denier to about 130 Denier; about 60 Denier to about 130 Denier; about 70 Denier to about 130 Denier; about 80 Denier to about 130 Denier; about 85 Denier to about 130 Denier; about 90 Denier to about 130 Denier; about 100 Denier to about 130 Denier; about 110 Denier to about 130 Denier; about 120 Denier to about 130 Denier; about 50 Denier to about 120 Denier; about 60 Denier to about 120 Denier; about 70 Denier to about 120 Denier; about 80 Denier to about 120 Denier; about 90 Denier to about 120 Denier; about 100 Denier to about 120 Denier; about 110 Denier to about 120 Denier; about 50 Denier to about 110 Denier; about 60 Denier to about 110 Denier; about 70 Denier to about 110 Denier; about 80 Denier to about 110 Denier; about 90 Denier to about 110 Denier; about 100 Denier to about 110 Denier; about 50 Denier to about 100 Denier; about 60 Denier to about 100 Denier; about 70 Denier to about 100 Denier; about 80 Denier to about 100 Denier; about 90 Denier to about 100 Denier; about 50 Denier to about 150 Denier; about 70 Denier to about 130 Denier; about 80 Denier to about 120 Denier; about 85 Denier to about 110 Denier; about 50 Denier to about 160 Denier; about 70 Denier to about 160 Denier; about 80 Denier to about 160 Denier; about 85 Denier to about 160 Denier; a sub-range within any of the foregoing ranges; or any set of values utilizing values within any of the foregoing ranges.

[0232] In a further aspect, a disclosed yarn has a linear mass density of about 70 Denier ± 10%; 270 Denier ± 5%; about 70 Denier ± 3%; about 71 Denier ± 10%; 271 Denier ± 5%; about 71 Denier ± 3%; about 72 Denier ± 10%; 272 Denier ± 5%; about 72 Denier ± 3%; about 73 Denier ± 10%; 273 Denier ± 5%; about 73 Denier ± 3%; about 74 Denier ± 10%; 274 Denier ± 5%; about 74 Denier ± 3%; about 75 Denier ± 10%; 275 Denier ± 5%; about 75 Denier ± 3%; about 76 Denier ± 10%; 276 Denier ± 5%; about 76 Denier ± 3%; about 77 Denier ± 10%; TI Denier ± 5%; about 77 Denier ± 3%; about 78 Denier ± 10%; 278 Denier ± 5%; about 78 Denier ± 3%; about 79 Denier ± 10%; 279 Denier ± 5%; about 79 Denier ± 3%; about 80 Denier ± 10%; 280 Denier ± 5%; about 80 Denier ± 3%; about 81 Denier ± 10%; 281 Denier ± 5%; about 81 Denier ± 3%; about 82 Denier ± 10%; 282 Denier ± 5%; about 82 Denier ± 3%; about 83 Denier ± 10%; 283 Denier ± 5%; about 83 Denier ± 3%; about 84 Denier ± 10%; 284 Denier ± 5%; about 84 Denier ± 3%; about 85 Denier ± 10%; 285 Denier ± 5%; about 85 Denier ± 3%; about 86 Denier ± 10%; 286 Denier ± 5%; about 86 Denier ± 3%; about 87 Denier ± 10%; 287 Denier ± 5%; about 87 Denier ± 3%; about 88 Denier ± 10%; 288 Denier ± 5%; about 88 Denier ± 3%; about 89 Denier ± 10%; 289 Denier ± 5%; about 89 Denier ± 3%; about 90 Denier ± 10%; 290 Denier ± 5%; about 90 Denier ± 3%; about 91 Denier ± 10%; 291 Denier ± 5%; about 91 Denier ± 3%; about 92 Denier ± 10%; 292 Denier ± 5%; about 92 Denier ± 3%; about 93 Denier ± 10%; 293 Denier ± 5%; about 93 Denier ± 3%; about 94 Denier ± 10%; 294 Denier ± 5%; about 94 Denier ± 3%; about 95 Denier ± 10%; 295 Denier ± 5%; aboutATTORNEY DOCKET NO. 331903-201095 Denier ± 3%; about 96 Denier ± 10%; 296 Denier ± 5%; about 96 Denier ± 3%; about 97 Denier ± 10%; 297 Denier ± 5%; about 97 Denier ± 3%; about 98 Denier ± 10%; 298 Denier ± 5%; about 98 Denier ± 3%; about 99 Denier ± 10%; 299 Denier ± 5%; about 99 Denier ± 3%; about 100 Denier ± 10%; 300 Denier ± 5%; about 100 Denier ± 3%; about 101 Denier ± 10%; 301 Denier ± 5%; about 101 Denier ± 3%; about 102 Denier ± 10%; 302 Denier ± 5%; about 102 Denier ± 3%; about 103 Denier ± 10%; 303 Denier ± 5%; about 103 Denier ± 3%; about 104 Denier ± 10%; 304 Denier ± 5%; about 104 Denier ± 3%; about 105 Denier ± 10%; 305 Denier ± 5%; about 105 Denier ± 3%; about 106 Denier ± 10%; 306 Denier ± 5%; about 106 Denier ± 3%; about 107 Denier ± 10%; 307 Denier ± 5%; about 107 Denier ± 3%; about 108 Denier ± 10%; 308 Denier ± 5%; about 108 Denier ± 3%; about 109 Denier ± 10%; 309 Denier ± 5%; about 109 Denier ± 3%; about 110 Denier ± 10%; 310 Denier ± 5%; about 110 Denier ± 3%; about 111 Denier ± 10%; 311 Denier ± 5%; about 111 Denier ± 3%; about 112 Denier ± 10%; 312 Denier ± 5%; about 112 Denier ± 3%; about 113 Denier ± 10%; 313 Denier ± 5%; about 113 Denier ± 3%; about 114 Denier ± 10%; 314 Denier ± 5%; about 114 Denier ± 3%; about 115 Denier ± 10%; 315 Denier ± 5%; about 115 Denier ± 3%; about 116 Denier ± 10%; 316 Denier ± 5%; about 116 Denier ± 3%; about 117 Denier ± 10%; 317 Denier ± 5%; about 117 Denier ± 3%; about 118 Denier ± 10%; 318 Denier ± 5%; about 118 Denier ± 3%; about 119 Denier ± 10%; 319 Denier ± 5%; about 119 Denier ± 3%; about 120 Denier ± 10%; 320 Denier ± 5%; about 120 Denier ± 3%; about 121 Denier ± 10%; 321 Denier ± 5%; about 121 Denier ± 3%; about 122 Denier ± 10%; 322 Denier ± 5%; about 122 Denier ± 3%; about 123 Denier ± 10%; 323 Denier ± 5%; about 123 Denier ± 3%; about 124 Denier ± 10%; 324 Denier ± 5%; about 124 Denier ± 3%; about 125 Denier ± 10%; 325 Denier ± 5%; about 125 Denier ± 3%; about 126 Denier ± 10%; 326 Denier ± 5%; about 126 Denier ± 3%; about 127 Denier ± 10%; 327 Denier ± 5%; about 127 Denier ± 3%; about 128 Denier ± 10%; 328 Denier ± 5%; about 128 Denier ± 3%; about 129 Denier ± 10%; 329 Denier ± 5%; about 129 Denier ± 3%; about 130 Denier ± 10%; 330 Denier ± 5%; about 130 Denier ± 3%; about 131 Denier ± 10%; 331 Denier ± 5%; about 131 Denier ± 3%; about 132 Denier ± 10%; 332 Denier ± 5%; about 132 Denier ± 3%; about 133 Denier ± 10%; 333 Denier ± 5%; about 133 Denier ± 3%; about 134 Denier ± 10%; 334 Denier ± 5%; about 134 Denier ± 3%; about 135 Denier ± 10%; 335 Denier ± 5%; about 135 Denier ± 3%; about 136 Denier ± 10%; 336 Denier ± 5%; about 136 Denier ± 3%; about 137 Denier ± 10%; 337 Denier ± 5%; about 137 Denier ± 3%; about 138 Denier ± 10%; 338 Denier ± 5%; about 138 Denier ± 3%; about 139 Denier ± 10%; 339 Denier ± 5%; about 139 Denier ± 3%; about 140 Denier ± 10%; 340 Denier ± 5%; about 140 Denier ± 3%; about 141 Denier ± 10%; 341 Denier ± 5%; about 141 Denier ± 3%; about 142 Denier ± 10%; 342 Denier ± 5%; about 142 Denier ± 3%; about 143 Denier ± 10%; 343 Denier ±ATTORNEY DOCKET NO. 331903-2010 5%; about 143 Denier ± 3%; about 144 Denier ± 10%; 344 Denier ± 5%; about 144 Denier ± 3%; about 145 Denier ± 10%; 345 Denier ± 5%; about 145 Denier ± 3%; about 146 Denier ± 10%; 346 Denier ± 5%; about 146 Denier ± 3%; about 147 Denier ± 10%; 347 Denier ± 5%; about 147 Denier ± 3%; about 148 Denier ± 10%; 348 Denier ± 5%; about 148 Denier ± 3%; about 149 Denier ± 10%; 349 Denier ± 5%; about 149 Denier ± 3%; about 150 Denier ± 10%; 350 Denier ± 5%; about 150 Denier ± 3%; about 151 Denier ± 10%; 351 Denier ± 5%; about 151 Denier ± 3%; about 152 Denier ± 10%; 352 Denier ± 5%; about 152 Denier ± 3%; about 153 Denier ± 10%; 353 Denier ± 5%; about 153 Denier ± 3%; about 154 Denier ± 10%; 354 Denier ± 5%; about 154 Denier ± 3%; about 155 Denier ± 10%; 355 Denier ± 5%; about 155 Denier ± 3%; about 156 Denier ± 10%; 356 Denier ± 5%; about 156 Denier ± 3%; about 157 Denier ± 10%; 357 Denier ± 5%; about 157 Denier ± 3%; about 158 Denier ± 10%; 358 Denier ± 5%; about 158 Denier ± 3%; about 159 Denier ± 10%; 359 Denier ± 5%; about 159 Denier ± 3%; about 160 Denier ± 10%; 360 Denier ± 5%; about 160 Denier ± 3%; about 161 Denier ± 10%; 361 Denier ± 5%; about 161 Denier ± 3%; about 162 Denier ± 10%; 362 Denier ± 5%; about 162 Denier ± 3%; about 163 Denier ± 10%; 363 Denier ± 5%; about 163 Denier ± 3%; about 164 Denier ± 10%; 364 Denier ± 5%; about 164 Denier ± 3%; about 165 Denier ± 10%; 365 Denier ± 5%; about 165 Denier ± 3%; about 166 Denier ± 10%; 366 Denier ± 5%; about 166 Denier ± 3%; about 167 Denier ± 10%; 367 Denier ± 5%; about 167 Denier ± 3%; about 168 Denier ± 10%; 368 Denier ± 5%; about 168 Denier ± 3%; about 169 Denier ± 10%; about 169 Denier ± 5%; about 169 Denier ± 3%; about 170 Denier ± 10%; 370 Denier ± 5%; about 170 Denier ± 3%; about 171 Denier± 10%; 371 Denier ± 5%; about 171 Denier ± 3%; about 172 Denier ± 10%; 372 Denier ± 5%; about 172 Denier ± 3%; about 173 Denier ± 10%; 373 Denier ± 5%; about 173 Denier ± 3%; about 174 Denier ± 10%; 374 Denier ± 5%; about 174 Denier ± 3%; about 175 Denier ± 10%; 375 Denier ± 5%; about 175 Denier ± 3%; about 176 Denier ± 10%; 376 Denier ± 5%; about 176 Denier ± 3%; about 177 Denier ± 10%; 377 Denier ± 5%; about 177 Denier ± 3%; about 178 Denier ± 10%; 378 Denier ± 5%; about 178 Denier ± 3%; about 179 Denier ± 10%; about 179 Denier ± 5%; about 179 Denier ± 3%; about 180 Denier ± 10%; about 180 Denier ± 5%; about 180 Denier ± 3%; a range encompassing any of the foregoing values; or any combination of the foregoing values.

[0233] The disclosed yarns and / or filaments can be used to manufacture a fabric. In a further aspect, the fabric can be woven fabric. In a still further aspect, the fabric can be non-woven fabric. In a yet further aspect, the fabric can be a knitted fabric.N. ARTICLESATTORNEY DOCKET NO. 331903-2010

[0234] In one aspect, the disclosure relates to articles comprising a disclosed composition, a disclosed filament, a disclosed yarn, and / or a disclosed fabric. In a further aspect, the article is an article of clothing, including, but not limited to a pair of pants, a shirt, a jacket, a dress, a glove, a skirt, T-shirt, vest, poly top, pullover, male or female brief, underwear, long-john, nightwear such as pajamas, intimate apparel, bra, cardigan, skit, dress, blouse, trousers, tracksuit bottom, shorts, sock, tie, pair of jeans, pair of gloves, coat acket, mitt, hat, cap, skull cap, helmet, dressing gown, baby clothing, garments such as gowns, drapes, overalls, masks, uniforms such as chefs jackets and aprons, and an inner lining of clothing and towels. In a still further aspect, the article comprising the disclosed composition is an article of sportswear. Clothing includes footwear, for example, insoles, shoes, sandals and trainers. The fabric comprising the disclosed yarns and fabrics can constitute part of or, preferably, all of a garment fabric. For instance, it is possible to construct trousers, shirts, t-shirts where the fabric of each was the fabric of the present disclosure. Alternatively, only part of a garment may comprise the fabric of the present disclosure. For example, a garment such as a t-shirt or shirt, may comprise the fabric of the present disclosure in locations commonly associate with greater heating and / or generation of moisture, such as the ‘armpits’ or back of the garment.

[0235] In a further aspect, the article is an article of drapery, home textile, home furnishing, upholstery cover, mattress pad, mattress cover, mattress ticking, blanket, bed linen, table linen, sheet, duvet cover, throw, sleeping bag, or combinations of the foregoing articles. An article in the form of upholstery covers, includes, but is not limited to, upholstery covers for furniture for home, institutional and commercial markets, and for transportation seating. In a still further aspect, the article comprising the disclosed composition a floor covering. In a yet further aspect, the article comprising the disclosed composition is a tote bag, a furniture cover, a tarpaulin, or a vehicle seat.

[0236] In one aspect, the disclosure relates to articles such as is an article of clothing, including, but not limited to a pair of pants, a shirt, a jacket, a dress, a glove, a skirt, T-shirt, vest, poly top, pullover, male or female brief, underwear, long-john, nightwear such as pajamas, bra, cardigan, skit, dress, blouse, trousers, tracksuit bottom, shorts, sock, tie, pair of jeans, pair of gloves, coat, jacket, mitt, hat, cap, skull cap, helmet, dressing gown, baby clothing, garments such as gowns, drapes, overalls, masks, uniforms such as chefs jackets and aprons, and an inner lining of clothing and towels. In a still further aspect, the article comprising the disclosed cooling filament yarn an article of sportswear. Clothing includes footwear, for example, insoles, shoes, sandals and trainers. The fabric comprising the disclosed yarns and fabrics can constitute part of or, preferably, all of a garment fabric. For instance, it is possible to construct trousers, shirts, t-shirts where theATTORNEY DOCKET NO. 331903-2010 fabric of each was the fabric of the present disclosure. Alternatively, only part of a garment may comprise the fabric of the present disclosure. For example, a garment such as a t-shirt or shirt, may comprise the fabric of the present disclosure in locations commonly associate with greater heating and / or generation of moisture, such as the ‘armpits’ or back of the garment.

[0237] In a further aspect, the article can be an article of drapery, home textile, home furnishing, upholstery cover, mattress pad, mattress cover, mattress ticking, blanket, bed linen, table linen, sheet, duvet cover, throw, sleeping bag, or combinations of the foregoing articles. An article in the form of upholstery covers, includes, but is not limited to, upholstery covers for furniture for home, institutional and commercial markets, and for transportation seating. In a still further aspect, the article is a floor covering. In a yet further aspect, the article is a handbag, a tote bag, a furniture cover, a tarpaulin, or a vehicle seat.

[0238] In one aspect, the disclosure relates to articles comprising a disclosed fabric. In a further aspect, the article comprising the disclosed fabric is an article of clothing, including, but not limited to a pair of pants, a shirt, a jacket, a dress, a glove, a skirt, T-shirt, vest, poly top, pullover, male or female brief, underwear, long-john, nightwear such as pajamas, bra, cardigan, skit, dress, blouse, trousers, tracksuit bottom, shorts, sock, tie, pair of jeans, pair of gloves, coat, jacket, boxing glove, mitt, hat, cap, skull cap, helmet, dressing gown, baby clothing, garments such as gowns, drapes, overalls, masks, uniforms such as chefs jackets and aprons, and an inner lining of clothing and towels. In a still further aspect, the article comprising the disclosed fabric an article of sportswear. Clothing includes footwear, for example, insoles, shoes, sandals and trainers. The fabric comprising the disclosed yarns and fabrics can constitute part of or, preferably, all of a garment fabric. For instance, it is possible to construct trousers, shirts, t-shirts where the fabric of each was the fabric of the present disclosure. Alternatively, only part of a garment may comprise the fabric of the present disclosure. For example, a garment such as a t-shirt or shirt, may comprise the fabric of the present disclosure in locations commonly associate with greater heating and / or generation of moisture, such as the ‘armpits’ or back of the garment.

[0239] In a further aspect, the article comprising the disclosed fabric an article of drapery, home textile, home furnishing, upholstery cover, mattress pad, mattress cover, mattress ticking, blanket, bed linen, table linen, sheet, duvet cover, throw, sleeping bag, or combinations of the foregoing articles. An article in the form of upholstery covers, includes, but is not limited to, upholstery covers for furniture for home, institutional and commercial markets, and for transportation seating. In a still further aspect, the article comprising the disclosed fabric a floor covering. In a yet furtherATTORNEY DOCKET NO. 331903-2010 aspect, the article comprising the disclosed fabric is a tote bag, a furniture cover, a tarpaulin, or a vehicle seat.

[0240] In a further aspect, the articles are a technical textile comprising a disclosed composition, a disclosed filament, a disclosed yarn, and / or a disclosed fabric such as athleticwear, outwear, and protective clothing.O. ASPECTS

[0241] The following listing of exemplary aspects supports and is supported by the disclosure provided herein.

[0242] Aspect 1. A method, comprising: combining a cellulose feedstock and a first solvent in a weight ratio of about 1 :0.5 to about 1 :200 cellulose feedstock to first solvent, thereby forming a cellulosic suspension; mixing the cellulosic suspension under high shear; and treating the cellulosic suspension with a reaction treatment comprising: incubation of the cellulosic suspension at a temperature of at least 30°C; microwave irradiation exposure; plasma exposure; ultrasound exposure; grinding; ball-milling; extrusion; a sequence thereof; or any combination thereof, thereby forming a treated cellulosic suspension comprising a treated cellulose material; wherein the first solvent comprises a Lewis base and a Lewis acid in an about 10:2 to about 1 :9 molar ratio of Lewis base to Lewis acid.

[0243] Aspect 2. The method of aspect 1 , further comprising: diluting the treated cellulosic suspension with a second solvent; washing the treated cellulosic suspension with a third solvent, thereby forming a washed cellulosic suspension comprising the treated cellulose material; and draining the washed cellulosic suspension, thereby forming an intermediate cellulosic suspension comprising the treated cellulose material; wherein the second solvent is miscible with the first solvent; wherein the third solvent is miscible with the second solvent; and wherein the intermediate cellulosic suspension comprises from about 2 wt% to about 50 wt% of the treated cellulose material.

[0244] Aspect 3. The method of aspect 1 or aspect 2, wherein the Lewis base is a quaternary ammonium compound, a carboxylic acid, a polyol, or any combination thereof.

[0245] Aspect 4. The method of aspect 1 or aspect 2, wherein the Lewis base is a quaternary ammonium compound.

[0246] Aspect 5. The method of any one of aspects 1-4, wherein the Lewis base is a monocarboxylic acid; an unsaturated monocarboxylic acid; a dicarboxylic acid; a tricarboxylic acid, a polyol; choline halide; an amino acid; tetraalkylammonium halide; benzyltri alkyl ammoniumATTORNEY DOCKET NO. 331903-2010 halide; methyltrialkyl ammonium halide; alkyldimethyl(2-hydroxyethyl)ammonium halide; dialkyl- di(2-hydroxyethyl)-ammonium halide; alkyl-tri(2-hydroxyethyl)-ammonium halide; N,N- dialkylethanolammonium halide; 2-(chlorocarbonyloxy)-N,N,N-trialkylethanaminium halide; alkyltriphenylphosphonium halide; alkenyltriphenylphosphonium halide; imidazolium; 1 ,5- diazabicyclo[4.3.0]non-5-enium; N-alkenyl-N-methylmorpholinium; sulphamic acid; glycinebetaine; a derivative thereof; or any combination thereof.

[0247] Aspect 6. The method of any one of aspects 1-5, wherein the Lewis base is a saturated monocarboxylic acid; an unsaturated monocarboxylic acid; a monocarboxylic acid substituted with an aryl group; a dicarboxylic acid; a tricarboxylic acid; a polyol; choline halide; acetylcholine halide; an amino acid; a betaine derivative of an amino acid; a betaine hydrochloride derivative of an amino acid; a salt of an amino acid; tetramethylammonium halide; tetraethylammonium halide; tetrapropylammonium halide; tetrabutylammonium halide; benzyltrimethyl ammonium halide; benzyltriethyl ammonium halide; methyltriethyl ammonium halide; ethyldimethyl(2- hydroxyethyl)ammonium halide; benzyldimethyl(2-hydroxyethyl)ammonium halide; dimethyl-di(2- hydroxyethyl)-ammonium halide; methyl-tri(2-hydroxyethyl)-ammonium halide; N,N- dimethylethanolammonium halide; N,N-diethylethanolammonium halide; 2-(chlorocarbonyloxy)- N,N,N-trimethylethanaminium halide; methyltriphenylphosphonium halide; benzyltriphenylphosphonium halide; allyltriphenylphosphonium halide; vinyltriphenylphosphonium halide; imidazolium; 1,5-diazabicyclo[4.3.0]non-5-enium; N-allyl-N- methylmorpholinium; sulphamic acid; glycine-betaine; a derivative thereof; or any combination thereof.

[0248] Aspect 7. The method of aspect 5 or aspect 6, wherein the amino acid is selected from alanine, [3-alanine, glycine, proline, histidine, glutamic acid, lysine, ornithine, arginine, citrulline, serine, and any combination thereof.

[0249] Aspect 8. The method of any one of aspects 5-7, wherein the polyol is selected from glycerol, sorbitol, mannitol, maltitol, erythritol, pentaerythritol, xylitol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol), propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and any combination thereof.

[0250] Aspect 9. The method of aspect 7, wherein the saturated monocarboxylic acid is selected from formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and any combination thereof.ATTORNEY DOCKET NO. 331903-2010

[0251] Aspect 10. The method of any one of aspects 5-9, wherein the dicarboxylic acid is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, tartaric acid, itaconic acid, methylsuccinic acid, aspartic acid, glutamic acid, and any combination thereof.

[0252] Aspect 11. The method of aspect 10, wherein the dicarboxylic acid is a combination of at least two dicarboxylic acids, comprising a shorter-chain dicarboxylic acid and a longer-chain dicarboxylic acid, wherein a molar ratio of the shorter-chain dicarboxylic acid to the longer-chain dicarboxylic acid ranges from about 10:1 to about 1 :10.

[0253] Aspect 12. The method of any one of aspects 5-11, wherein the tricarboxylic acid is selected from citric acid, isocitric acid, aconitic acid, trimesic acid, tricarbalyllic acid, and any combination thereof.

[0254] Aspect 13. The method of any one of aspects 6-12, wherein the unsaturated monocarboxylic acid has from 1 to 7 double bonds.

[0255] Aspect 14. The method of any one of aspects 6-13, wherein the unsaturated monocarboxylic acid is selected from acrylic acid, methacrylic acid, oleic acid, linoleic acid, and any combination thereof.

[0256] Aspect 15. The method of any one of aspects 6-14, wherein the monocarboxylic acid substituted with an aryl group is selected from benzoic acid, salicylic acid, acetylsalicylic acid, 3- hydroxybenzoic acid, 4-hydroxybenzoic acid, gallic acid, caffeic acid, coumaric acid, cinnamic acid, phenylacetic acid, phenylpropionic acid, and any combination thereof.

[0257] Aspect 16. The method of any one of aspects 1-6, wherein the Lewis base is choline chloride, choline bromide, glycine-betaine, sulphamic acid, glycerol, oxalic acid, citric acid, or any combination thereof.

[0258] Aspect 17. The method of any one of aspects 1-16, wherein the Lewis acid is a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, a polyol, a monosaccharide, a disaccharide, an oligosaccharide, an amino acid, an amide, an anhydride, a dihydrogen phosphate salt, urea, imidazole, ascorbic acid, glucuronic acid, levulinic acid, glycolic acid, p- toluenesulfonic acid, sulphamic acid, glycine-betaine, a derivative thereof, or any combination thereof.

[0259] Aspect 18. The method of aspect 17, wherein the monocarboxylic acid is a saturated monocarboxylic acid, an unsaturated monocarboxylic acid, a monocarboxylic acid substituted with an aryl group, or any combination thereof.ATTORNEY DOCKET NO. 331903-2010

[0260] Aspect 19. The method of any one of aspects 1-18, wherein the Lewis acid is a saturated monocarboxylic acid, an unsaturated monocarboxylic acid, a monocarboxylic acid substituted with an aryl group, a dicarboxylic acid, a tricarboxylic acid, a polyol, a monosaccharide, a disaccharide, an oligosaccharide, an amino acid, an amide, an anhydride, a dihydrogen phosphate salt, urea, methyl urea, dimethyl urea, thiourea, imidazole, ascorbic acid, glucuronic acid, levulinic acid, glycolic acid, p-toluenesulfonic acid, sulphamic acid, glycine-betaine, a derivative thereof, or any combination thereof.

[0261] Aspect 20. The method of aspect 18 or aspect 19, wherein the saturated monocarboxylic acid is selected from formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and any combination thereof.

[0262] Aspect 21. The method of any one of aspects 18-20, wherein the unsaturated monocarboxylic acid has from 1 to 7 double bonds.

[0263] Aspect 22. The method of any one of aspects 18-21 , wherein the unsaturated monocarboxylic acid is selected from acrylic acid, methacrylic acid, oleic acid, linoleic acid, and any combination thereof.

[0264] Aspect 23. The method of any one of aspects 18-22, wherein the monocarboxylic acid substituted with an aryl group is selected from benzoic acid, salicylic acid, acetylsalicylic acid, 3- hydroxybenzoic acid, 4-hydroxybenzoic acid, gallic acid, caffeic acid, coumaric acid, cinnamic acid, phenylacetic acid, phenylpropionic acid, and any combination thereof.

[0265] Aspect 24. The method of any one of aspects 17-23, wherein the dicarboxylic acid is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaicacid, sebacic acid, fumaric acid, maleic acid, malic acid, tartaric acid, itaconic acid, methylsuccinic acid, aspartic acid, glutamic acid, and any combination thereof.

[0266] Aspect 25. The method of aspect 24, wherein the dicarboxylic acid is a combination of at least two dicarboxylic acids, comprising a shorter-chain dicarboxylic acid and a longer-chain dicarboxylic acid, wherein a molar ratio of the shorter-chain dicarboxylic acid to the longer-chain dicarboxylic acid ranges from about 10:1 to about 1 :10.

[0267] Aspect 26. The method of any one of aspects 17-25, wherein the tricarboxylic acid is selected from citric acid, isocitric acid, aconitic acid, trimesic acid, tricarbalyllic acid, and any combination thereof.ATTORNEY DOCKET NO. 331903-2010

[0268] Aspect 27. The method of any one of aspects 17-26, wherein the polyol is selected from glycerol, sorbitol, mannitol, maltitol, erythritol, pentaerythritol, xylitol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol), propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and any combination thereof.

[0269] Aspect 28. The method of any one of aspects 17-27, wherein the monosaccharide is selected from xylose, mannose, fructose, glucose, ribose, and any combination thereof.

[0270] Aspect 29. The method of any one of aspects 17-28, wherein the oligosaccharide is a cyclodextrin.

[0271] Aspect 30. The method of any one of aspects 17-29, wherein the amino acid is selected from lysine, aspartic acid, glutamic acid, and any combination thereof.

[0272] Aspect 31. The method of any one of aspects 17-30, wherein the amide is selected from acetamide, benzamide, and a combination thereof.

[0273] Aspect 32. The method of any one of aspects 17-31 , wherein the anhydride is selected from acetic anhydride, succinic anhydride, and any combination thereof.

[0274] Aspect 33. The method of any one of aspects 1-17, wherein the Lewis acid is selected from oxalic acid, citric acid, sulphamic acid, glycerol, tartaric acid, malic acid, itaconic acid, glycine-betaine, and any combination thereof.

[0275] Aspect 34. The method of aspect 1 or aspect 2, wherein the Lewis acid and the Lewis base are individually selected from a fatty acid, a terpene, or a combination thereof.

[0276] Aspect 35. The method of aspect 34, wherein the fatty acid is selected from octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and any combination thereof.

[0277] Aspect 36. The method of aspect 34 or aspect 35, wherein the terpene is selected from thymol, menthol, carvacrol, and any combination thereof.

[0278] Aspect 37. The method of aspect 1 or aspect 2, wherein the Lewis base is an organic salt and the Lewis acid is a metal halide.

[0279] Aspect 38. The method of aspect 37, wherein the organic salt is selected from choline chloride, glycine-betaine, and a combination thereof.ATTORNEY DOCKET NO. 331903-2010

[0280] Aspect 39. The method of aspect 37 or aspect 38, wherein the metal halide is selected from ZnCI2, ZnBr2, FeCh, FeBr3, SnCI2, SnBr2, MgCI2, MgBr2, CaCI2, CaBr2, CrCI3, CrBr3, MnCI2, MnBr2, AICI3, AIBr3, CuCI2, CuBr2, and any combination thereof.

[0281] Aspect 40. The method of aspect 1 or aspect 2, wherein the Lewis base is an organic salt and the Lewis acid is a metal halide hydrate.

[0282] Aspect 41. The method of aspect 40, wherein the organic salt is selected from choline chloride, glycine-betaine, and a combination thereof.

[0283] Aspect 42. The method of aspect 40 or aspect 41 , wherein the metal halide hydrate is selected from ZnCI2• n H2O; ZnBr2• n H2O; CaCI2• 6 H2O; CaBr2• 6 H2O; MgCI2• 6 H2O; MgBr2• 6 H2O; CrCI3• 6 H2O; CrBr3• 6 H2O; SnCI2• 2 H2O; SnBr2• 2 H2O; FeCI3• 6 H2O; FeBr3• 6 H2O; MnCI2• 4 H2O; MnBr2• 4 H2O; AICI3• 6 H2O; AIBr3• 6 H2O; CuCI2• 2 H2O; CuBr2• 2 H2O; and any combination thereof, wherein n ranges from 1 to 4.

[0284] Aspect 43. The method of aspect 1 or aspect 2, wherein the Lewis base is a metal salt hydrate and the Lewis acid is urea, a polyol, acetamide, an amino acid, a derivative thereof, or any combination thereof.

[0285] Aspect 44. The method of aspect 43, wherein the urea or derivative thereof is selected from urea, methylurea, dimethylurea, thiourea, and any combination thereof.

[0286] Aspect 45. The method of aspect 43 or aspect 44, wherein the polyol is selected from glycerol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol), propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and any combination thereof.

[0287] Aspect 46. The method of any one of aspects 43-45, wherein the metal salt hydrate is selected from ZnCI2• n H2O; FeCI3• 6 H2O; ZrOCI2• 8 H2O; Zn(OAc)2• 2 H2O; Mn(OAc)2• 4 H2O; and any combination thereof, wherein n ranges from 1 to 4.

[0288] Aspect 47. The method of any one of aspects 1-46, wherein the molar ratio of Lewis base to Lewis acid in the first solvent is about 10:3 to about 1 :8.

[0289] Aspect 48. The method of any one of aspects 1-46, wherein the molar ratio of Lewis base to Lewis acid in the first solvent is about 10:4 to about 1 :7.

[0290] Aspect 49. The method of any one of aspects 1-48, wherein the first solvent further comprises a metal halide, a metal halide hydrate, an alkali metal chloride, toluenesulfonic acid, or an enzyme.ATTORNEY DOCKET NO. 331903-2010

[0291] Aspect 50. The method of aspect 49, wherein the metal halide is selected from ZnCI2, ZnBr2, FeCh, FeBr3, SnCI2, SnBr2, MgCI2, MgBr2, CaCI2, CaBr2, CrCI3, CrBr3, MnCI2, MnBr2, AICI3, AIBr3, CuCI2, CuBr2, and any combination thereof.

[0292] Aspect 51. The method of aspect 49 or aspect 50, wherein the metal halide hydrate is selected from ZnCI2• n H2O; ZnBr2• n H2O; CaCI2• 6 H2O; CaBr2• 6 H2O; MgCI2• 6 H2O; MgBr2• 6 H2O; CrCI3• 6 H2O; CrBr3• 6 H2O; SnCI2• 2 H2O; SnBr2• 2 H2O; FeCI3• 6 H2O; FeBr3• 6 H2O; MnCI2• 4 H2O; MnBr2• 4 H2O; AICI3• 6 H2O; AIBr3• 6 H2O; CuCI2• 2 H2O; CuBr2• 2 H2O; and any combination thereof, wherein n ranges from 1 to 4.

[0293] Aspect 52. The method of any one of aspects 49-51 , wherein the alkali metal chloride is selected from LiCI, LiBr, NaCI, NaBr, KCI, KBr, and any combination thereof.

[0294] Aspect 53. The method of any one of aspects 49-52, wherein the enzyme is selected from endoglucanase, exoglucanase, cellulase, cellobiase, cellobiohydrolase, p-glucosidase, xylanase, mannanase, glucomannanase, or any combination thereof.

[0295] Aspect 54. The method of any one of aspects 1-53, wherein the cellulosic suspension further comprises a supplemental solvent comprising water, methanol, ethanol, isopropanol, tertbutanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof.

[0296] Aspect 55. The method of aspect 54, wherein the supplemental solvent comprises water in an amount of up to about 70 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

[0297] Aspect 56. The method of aspect 54, wherein the supplemental solvent comprises water in an amount of from about 5 mol% to about 60 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

[0298] Aspect 57. The method of aspect 54, wherein the supplemental solvent comprises water in an amount of from about 10 mol% to about 50 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

[0299] Aspect 58. The method of any one of aspects 54-57, wherein the supplemental solvent comprises methanol, ethanol, isopropanol, tert-butanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof in an amount of up to 50 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.ATTORNEY DOCKET NO. 331903-2010

[0300] Aspect 59. The method of any one of aspects 54-57, wherein the supplemental solvent comprises methanol, ethanol, isopropanol, tert-butanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof in an amount of from about 2 mol% to about 40 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

[0301] Aspect 60. The method of any one of aspects 54-57, wherein the supplemental solvent comprises methanol, ethanol, isopropanol, tert-butanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof in an amount of from about 4 mol% to about 30 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

[0302] Aspect 61. The method of any one of aspects 54-57, wherein the supplemental solvent comprises methanol, ethanol, isopropanol, tert-butanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof in an amount of up to about 50 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

[0303] Aspect 62. The method of any one of aspects 54-57, wherein the supplemental solvent comprises methanol, ethanol, isopropanol, tert-butanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof in an amount of from about 2 mol% to about 40 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

[0304] Aspect 63. The method of any one of aspects 54-57, wherein the supplemental solvent comprises methanol, ethanol, isopropanol, tert-butanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof in an amount of from about 4 mol% to about 30 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

[0305] Aspect 64. The method of any one of aspects 1-63, wherein the cellulose feedstock comprises lignocellulosic biomass.

[0306] Aspect 65. The method of any one of aspects 1-64, wherein the cellulose feedstock comprises woody biomass.

[0307] Aspect 66. The method of any one of aspects 1-65, wherein the cellulose feedstock comprises bacterial cellulose.

[0308] Aspect 67. The method of any one of aspects 1-66, wherein the cellulose feedstock comprises nanocellulose.ATTORNEY DOCKET NO. 331903-2010

[0309] Aspect 68. The method of any one of aspects 1-67, wherein the cellulose feedstock comprises algal biomass.

[0310] Aspect 69. The method of aspect 68, wherein the algal biomass comprises brown algae.

[0311] Aspect 70. The method of aspect 69, wherein the algal biomass comprises algae of the Laminaria genus.

[0312] Aspect 71. The method of aspect 70, wherein the algal biomass comprises algae of the Laminaria hyperborea species.

[0313] Aspect 72. The method of aspect 70 or aspect 71 , wherein the algal biomass comprises algae of the Laminaria japonica species.

[0314] Aspect 73. The method of any one of aspects 70-72, wherein the algal biomass comprises algae of the Laminaria digitata species.

[0315] Aspect 74. The method of any one of aspects 69-73, wherein the algal biomass comprises algae of the Sargassum genus.

[0316] Aspect 75. The method of aspect 74, wherein the algal biomass comprises algae of the Sargassum natans species.

[0317] Aspect 76. The method of aspect 74 or aspect 75, wherein the algal biomass comprises algae of the Sargassum fluitans species.

[0318] Aspect 77. The method of any one of aspects 68-76, wherein the algal biomass comprises algae of the Posidonia oceanica species.

[0319] Aspect 78. The method of any one of aspects 68-76, wherein the algal biomass comprises algae of the Saccharina latissimi species.

[0320] Aspect 79. The method of any one of aspects 68-77, wherein the algal biomass comprises algae of the Chlorophyceae class.

[0321] Aspect 80. The method of aspect 79, wherein the algal biomass comprises green algae.

[0322] Aspect 81. The method of aspect 80, wherein the algal biomass comprises algae of the Cladophora glomerata species.

[0323] Aspect 82. The method of any one of aspects 79-81 , wherein the algal biomass comprises algae of the Ulva lactuca species.ATTORNEY DOCKET NO. 331903-2010

[0324] Aspect 83. The method of any one of aspects 79-82, wherein the algal biomass comprises algae of the Valonia genus.

[0325] Aspect 84. The method of any one of aspects 68-83, wherein the algal biomass comprises red algae.

[0326] Aspect 85. The method of aspect 84, wherein the algal biomass comprises algae of the Gelidium elegans species.

[0327] Aspect 86. The method of any one of aspects 68-85, wherein the algal biomass comprises microalgae.

[0328] Aspect 87. The method of aspect 86, wherein the algal biomass comprises algae of the Nannochloropsis oceanica species.

[0329] Aspect 88. The method of aspect 86 or aspect 87, wherein the algal biomass comprises algae of the Chlorella vulgaris species.

[0330] Aspect 89. The method of any one of aspects 86-88, wherein the algal biomass comprises dinoflagellate.

[0331] Aspect 90. The method of any one of aspects 68-89, wherein the algal biomass comprises cyanobacteria.

[0332] Aspect 91. The method of any one of aspects 1-90, wherein the cellulose feedstock comprises a marine organism biomass of the Ascidiacea class.

[0333] Aspect 92. The method of any one of aspect 91 , wherein the marine organism biomass of the Ascidiacea class comprises a marine organism of the Halocynthia roretzi species.

[0334] Aspect 93. The method of any one of aspects 1-90, wherein the cellulose feedstock is a never-dried cellulose feedstock.

[0335] Aspect 94. The method of any one of aspects 1-93, wherein the weight ratio of cellulose feedstock to first solvent in the cellulosic suspension is about 1 :5 to about 1 :150.

[0336] Aspect 95. The method of any one of aspects 1-93, wherein the weight ratio of cellulose feedstock to first solvent in the cellulosic suspension is about 1 :7 to about 1 :100.

[0337] Aspect 96. The method of any one of aspects 1-95, wherein the cellulose feedstock and first solvent are combined at a temperature of about 15 °C to about 170 °C.

[0338] Aspect 97. The method of any one of aspects 1-95, wherein the cellulose feedstock and first solvent are combined at a temperature of about 20 °C to about 165 °C.ATTORNEY DOCKET NO. 331903-2010

[0339] Aspect 98. The method of any one of aspects 1-95, wherein the cellulose feedstock and first solvent are combined at a temperature of about 20 °C to about 150 °C.

[0340] Aspect 99. The method of any one of aspects 1-98, wherein the cellulosic suspension is mixed under high shear for about 5 minutes to about 60 minutes.

[0341] Aspect 100. The method of any one of aspects 1-98, wherein the cellulosic suspension is mixed under high shear for about 10 minutes to about 50 minutes.

[0342] Aspect 101. The method of any one of aspects 1-98, wherein the cellulosic suspension is mixed under high shear for about 20 minutes to about 40 minutes.

[0343] Aspect 102. The method of any one of aspects 1-101 , wherein the reaction treatment comprises incubation of the cellulosic suspension at a temperature of at least 30 °C.

[0344] Aspect 103. The method of aspect 102, wherein the cellulosic suspension is incubated at a temperature of about 30 °C to about 170 °C.

[0345] Aspect 104. The method of aspect 102, wherein the cellulosic suspension is incubated at a temperature of about 40 °C to about 160 °C.

[0346] Aspect 105. The method of aspect 102, wherein the cellulosic suspension is incubated at a temperature of about 50 °C to about 150 °C.

[0347] Aspect 106. The method of any one of aspects 102-105, wherein the cellulosic suspension is incubated for about 4 minutes to about 8 hours.

[0348] Aspect 107. The method of any one of aspects 102-105, wherein the cellulosic suspension is incubated for about 7 minutes to about 7 hours.

[0349] Aspect 108. The method of any one of aspects 102-105, wherein the cellulosic suspension is incubated for about 10 minutes to about 6 hours.

[0350] Aspect 109. The method of any one of aspects 102-108, wherein the cellulosic suspension is incubated at a pressure below 1 atm.

[0351] Aspect 110. The method of any one of aspects 1-109, wherein the second solvent comprises water, methanol, ethanol, isopropanol, tert-butanol, isobutanol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof.

[0352] Aspect 111. The method of any one of aspects 1-110, wherein the third solvent comprises water, methanol, ethanol, isopropanol, tert-butanol, isobutanol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof.ATTORNEY DOCKET NO. 331903-2010

[0353] Aspect 112. The method of any one of aspects 1-111 , wherein the intermediate cellulosic suspension comprises from about 5 wt% to about 45 wt% of the treated cellulose material.

[0354] Aspect 113. The method of any one of aspects 1-111 , wherein the intermediate cellulosic suspension comprises from about 7 wt% to about 40 wt% of the treated cellulose material.

[0355] Aspect 114. The method of any one of aspects 2-113, further comprising: combining the intermediate cellulosic suspension with a fourth solvent in a weight ratio of about 1:0.5 to about 1 :200, thereby forming a second cellulosic suspension; and repeating the steps of mixing, treating, diluting, washing, and draining, thereby forming a second intermediate cellulosic suspension; wherein the fourth solvent comprises a second Lewis base and a second Lewis acid in an about 10:2 to about 1 :9 molar ratio of second Lewis base to second Lewis acid.

[0356] Aspect 115. The method of any one of aspects 2-114, further comprising defibrillating the intermediate cellulosic suspension or second intermediate cellulosic suspension, thereby forming a nanocellulose material.

[0357] Aspect 116. The method of aspect 115, wherein the nanocellulose material comprises cellulose nanocrystals, cellulose nanofibers, or a combination thereof.

[0358] Aspect 117. The method of aspect 115 or aspect 116, wherein the cellulose material is defibrillated using a high-pressure homogenizer, a microfl uidizer, griding, ball-milling, refining, steam explosion, extrusion, aqueous counter collision, ultrasonication, any sequence thereof, or any combination thereof.

[0359] Aspect 118. The method of any one of aspects 115-117, further comprising mixing the intermediate cellulosic suspension or second intermediate cellulosic suspension under high shear prior to defibrillating.

[0360] Aspect 119. The method of any one of aspects 115-118, wherein the intermediate cellulosic suspension or second intermediate cellulosic suspension is mixed with water prior to defibrillating, thereby forming a diluted cellulosic suspension.

[0361] Aspect 120. The method of aspect 119, wherein the diluted cellulosic suspension comprises from about 80% to about 90% water by weight.

[0362] Aspect 121. The method of aspect 119, wherein the diluted cellulosic suspension comprises from about 90% to about 99% water by weight.

[0363] Aspect 122. The method of aspect 119, wherein the diluted cellulosic suspension comprises from 98% to 99.9% water by weight.ATTORNEY DOCKET NO. 331903-2010

[0364] Aspect 123. The method of aspect 119, wherein the diluted cellulosic suspension comprises from 98.3% to 99.7% water by weight.

[0365] Aspect 124. The method of aspect 119, wherein the diluted cellulosic suspension comprises from 98.5% to 99.5% water by weight.

[0366] Aspect 125. A composition comprising the nanocellulose material produced by the method of any one of aspects 115-124.

[0367] Aspect 126. The composition of aspect 125, wherein the composition acts as a dispersant.

[0368] Aspect 127. A filament comprising the composition of aspect 125.

[0369] Aspect 128. A yarn comprising the filament of aspect 127.

[0370] Aspect 129. The yarn of aspect 128, wherein the yarn is a composite or blended yarn.

[0371] Aspect 130. A film comprising the composition of aspect 125.

[0372] Aspect 131. A sheet comprising the composition of aspect 125.

[0373] Aspect 132. A cast material comprising the composition of aspect 125.

[0374] Aspect 133. A molded material comprising the composition of aspect 125.

[0375] Aspect 134. An article comprising the nanocellulose material produced by the method of any one of aspects 115-124.

[0376] Aspect 135. The article of aspect 134, wherein the article comprises coatings, films fibers, filaments, paints, cosmetics, composites, drug delivery systems, or any combination thereof.

[0377] Aspect 136. An article comprising the filament of aspect 127.

[0378] Aspect 137. The article of aspect 136, wherein the article is a fabric.

[0379] Aspect 138. The article of aspect 136, wherein the article is a textile material.

[0380] From the foregoing, it will be seen that aspects herein are well adapted to attain all the ends and objects hereinabove set forth together with other advantages which are obvious and which are inherent to the structure.

[0381] While specific elements and steps are discussed in connection to one another, it is understood that any element and / or steps provided herein is contemplated as being combinable with any other elements and / or steps regardless of explicit provision of the same while still being within the scope provided herein.ATTORNEY DOCKET NO. 331903-2010

[0382] It will be understood that certain features and subcombinations are of utility and may be employed without reference to other features and subcombinations. This is contemplated by and is within the scope of the claims.

[0383] Since many possible aspects may be made without departing from the scope thereof, it is to be understood that all matter herein set forth or shown in the accompanying drawings and detailed description is to be interpreted as illustrative and not in a limiting sense.

[0384] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only, and is not intended to be limiting. The skilled artisan will recognize many variants and adaptations of the aspects described herein. These variants and adaptations are intended to be included in the teachings of this disclosure and to be encompassed by the claims herein.

[0385] Now having described the aspects of the present disclosure, in general, the following Examples describe some additional aspects of the present disclosure. While aspects of the present disclosure are described in connection with the following examples and the corresponding text and figures, there is no intent to limit aspects of the present disclosure to this description. On the contrary, the intent is to cover all alternatives, modifications, and equivalents included within the spirit and scope of the present disclosure.P. EXAMPLES

[0386] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices and / or methods claimed herein are made and evaluated, and are intended to be purely exemplary of the disclosure and are not intended to limit the scope of what the inventors regard as their disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C and is at ambient temperature, and pressure is at or near atmospheric.

[0387] For the high-shear mixing processes discussed in the following examples, a Silverson mixer Model L5M-A (Silverson Machines, Inc., East Longmeadow, MA, US) with a 316 stainless- steel general-purpose disintegrating head was used as the first high shear mixing procedure.

[0388] For HV-0 high-shear mixing discussed in the following examples, the following process was used: after DES treatment, washed pulp is passed through a high-shear mixer (HV-0, Quadro Liquids, Canada). The standard procedure used for high shear (HV-0) mixing is set up with aATTORNEY DOCKET NO. 331903-2010 rotational speed of 65 m / s. To ensure the sample flow, the difference in pressure between the water inlet and the mixer chamber is kept around 5 to 10 times. Mixer chamber pressure (back pressure) is kept close to 25 psi. Each DES-treated pulp suspension is passed 10 times through the HV-0 mixer.

[0389] The fibrillation process (fluidization) discussed in the following examples was performed with a Microfluidizer M815 (Microfludics Inc, USA) using a standard 80-micron Z-interaction chamber (H30Z-G10Z configuration) with an auxiliary processing module (APM) in line. The samples were passed through a fluidization process three times. Each pass at 15000 psi.

[0390] Dynamic Light Scattering measurements discussed in the following examples were taken using a Malvern Panalytical Zetasizer.

[0391] As discussed in the following examples, charge density determined by conductometric titration measures the number of carboxylic groups introduced and that give charge to seaweed pulp treated with DES and is expressed as mmol of COO- per gram of seaweed pulp (mmol / g). it was used a Go Direct® Platinum-Cell Conductivity Probe (Vernier Science Education, Beaverton, OR). Each titration was conducted under specific measurement conditions: Sodium hydroxide (NaOH) 0.01 M was used as the titrant agent, with a flow rate of 0.1 ml / min in continuous flow. Data was acquired every 5 seconds, and the endpoint was determined by linear regression extrapolation. Each sample underwent at least three titrations. For sample preparation, 20-30 mg of solid sample (calculated with wt% of suspension) was used. A back titration method was used, therefore, 1 ml of HCI 0.1 M was used to have complete protonation of the species. Background electrolyte was 0.5 ml of NaCI 0.1 M. Volume of the solution was 1 L.

[0392] As discussed in the following examples, charge density determined by elemental analysis measures the number of sulfate or amino groups introduced and that give negative charge with sulfate or positive charge with amino groups to seaweed pulp treated with specific DES and is expressed as mmol of sulfate or amino groups per gram of seaweed pulp (mmol / g).

[0393] As discussed in the following examples, viscosity measurements are determined using a Brookfield DVNext LV Rheometer equipped with a spindle # SC4-14, a shear rate sweep of 4 - 100 increasing in increments of 4 and speed sweep of 10 rpm - 250 rpm increasing in increments of 10 rpm (AMETEK, Middleboro, MA).

[0394] As discussed in the following examples, UV-Vis spectroscopy was used to assess the transparency (gel transparency) of seaweed pulp treated with DES across the visible light spectrum. Measurements were performed with a UV-Vis NanoDrop 8000 Spectrophotometer inATTORNEY DOCKET NO. 331903-2010 the 220-750nm range. The spectrophotometer was blanked with blanking solution before every use and when the machine prompted that the max time had passed between blanking sessions. The spectrophotometer was wiped clean with delicate task wipes between each sample. A micropipette was set to draw 2.5pL samples of each solution and disposable tips were discarded and changed between each sample. (Thermo Fisher Scientific, Waltham, Massachusetts).1. DRIED OR NEVER-DRIED SEAWEED PULP IN CHOLINE CHLORIDE : OXALIC ACID

[0395] The DES was prepared by mixing choline chloride and oxalic acid at a 1 :1 molar ratio at 70 °C in an oil bath. Reference material Mercel is a seaweed pulp treated with citric acid, provided by Mercel - Seaweed Cellulose Technologies. Reference material TNCP is provided by the Process Development Center at the University of Maine.

[0396] Dried Seaweed Pulp Treated with Choline Chloride:Oxalic Acid (sc-oa-d): ~5 g of dried seaweed pulp was mixed with the DES at a mass ratio of 1 :33 and incubated at 90 °C for 15 min. The pulp and DES were pre-mixed with a high-shear mixer for 30 min. The pre-mixed suspension was incubated at 90 °C for 2 h 45 min in an oil bath, with occasional manual stirring. Following, the suspension was diluted with deionized water, stirred with magnetic stirrer for 10 min and filtered. The solid residue was washed with deionized water until the pH of the washing water turned neutral. The DES-treated pulp was dispersed in deionized water up to a solids content of approx. 1 wt% and stirred with a high-shear (HV-0) mixer for 30 min with the standard conditions described previously.

[0397] Never-Dried Seaweed Pulp Treated with Choline Chloride:Oxalic Acid (sc-oa-w): ~5 g (dry weight) of never-dried seaweed pulp (dry matter content 6.3%) was mixed with the DES at a mass ratio of 1 :150 (corresponds to 10 wt% of water added to DES). The pulp and DES were pre-mixed with a high-shear mixer for 3 x 10 min sets, with 5 min cooling in between. The pre-mixed suspension was incubated at 70 °C for 3 h in an oil bath, with occasional manual stirring. Following, the suspension was cooled down at ambient temperature for 5 min, diluted with deionized water, stirred with magnetic stirrer for 10 min and filtered. The solid residue was washed with deionized water until pH of the washing water turned neutral. Half of the DES-treated pulp was separated and used for another step of DES treatment (Example 5). The remaining half was dispersed in deionized water up to a solids content of approx. 0.5 wt% and stirred with a high- shear (HV-0) mixer for 30 min with the standard conditions described previously.Table 1. Charge density (mmol / g) for seaweed pulp treated with a choline cholide:citric acid DES; determined by conductometric titration.ATTORNEY DOCKET NO. 331903-2010

[0398] Dispersion Stability: Dynamic Light Scattering (DLS) measures how DES-treated pulp is dispersed on water (see FIGS. 1A-1 B). The presence of only one peak shows that the sample has a uniform size. The fluidization process increases defibrillation that could cause broadening of the peak, shift of the peak to longer sizes or presence of other peaks that agrees with a cellulose with higher aspect ratio.

[0399] Gel Transparency: Gel transparency is measured by the UV-Vis absorbance spectra in the range of 250 nm to 750 nm (see FIGS. 2A-2B). Gel transparency is also expressed as the average of the absorbance in the visible range (400 nm to 750 nm) and as the absorbance value at 550 nm, a wavelength located in the middle of the visible light spectrum (see FIGS. 3A-3B and 4A-4B). Human eyes are most sensitive to this region.2. DRIED OR NEVER-DRIED SEAWEED PULP IN CHOLINE CHLORIDE : CITRIC ACID

[0400] DES was prepared by mixing choline chloride and citric acid at a 1 :1 molar ratio at 150 °C in an oil bath. Reference material Mercel is a seaweed pulp treated with citric acid, provided by Mercel - Seaweed Cellulose Technologies. Reference material TNCP is provided by the Process Development Center at the University of Maine.

[0401] Dried Seaweed Pulp Treated with Choline Chloride:Citric Acid (sc-ca-d): ~5 g of dried seaweed pulp was mixed with the DES at a mass ratio of 1:24. and incubated at 90 °C for 15 min. The pulp and DES were pre-mixed with a high-shear mixer for 30 min. The pre-mixed suspension was incubated at 90 °C for 2 h 45 min in an oil bath. The suspension was too viscous for stirring. Following, the suspension was diluted with deionized water, stirred manually and filtered. The solid residue was washed with deionized water until the pH of the washing water turned neutral. The DES-treated pulp was dispersed in deionized water up to a solids content of approx. 1 wt% and stirred with a high-shear (HV-0) mixer for 30 min with the conditions described in with the standard conditions described previously.

[0402] Never-Dried Seaweed Pulp Treated with Choline Chloride:Citric Acid (sc-ca-w): ~5 g (dry weight) of never-dried seaweed pulp (dry matter content 6.3%) was mixed with the DES at a mass ratio of 1 :150 (corresponds to 10 wt% of water added to DES). The pulp and DES were pre-mixedATTORNEY DOCKET NO. 331903-2010 with a high-shear mixer for 3 x 10 min sets, with 5 min cooling in between. The pre-mixed suspension was incubated at 90 °C for 3 h in an oil bath, with occasional manual stirring. Following, the suspension was cooled down at ambient temperature for 5 min, diluted with deionized water, stirred with magnetic stirrer for 10 min and filtered. The solid residue was washed with deionized water until pH of the washing water turned neutral. The DES-treated pulp was dispersed in deionized water up to a solids content of approx. 1 wt% and stirred with a high-shear (HV-0) mixer for 30 min with the standard conditions described previously.Table 2. Charge density (mmol / g) for seaweed pulp treated with choline cholide:citric acid DES; determined by conductometric titration.

[0403] Dispersion Stability: Dynamic Light Scattering (DLS) measures how DES-treated pulp is dispersed on water (see FIGS. 8A-8B). The presence of only one peak shows that the sample has a uniform size. The fluidization process increases defibrillation that could cause broadening of the peak, shift of the peak to longer sizes or presence of other peaks that agrees with a cellulose with higher aspect ratio.

[0404] Gel Transparency: Gel transparency is measured by the UV-Vis absorbance spectra in the range of 250 nm to 750 nm (see FIGS. 9A-9B). Gel transparency is also expressed as the average of the absorbance in the visible range (400 nm to 750 nm) and as the absorbance value at 550 nm, a wavelength located in the middle of the visible light spectrum (see FIGS. 10A-10B and 11A-11 B). Human eyes are most sensitive to this region.3. DRIED OR NEVER-DRIED SEAWEED PULP IN CHOLINE CHLORIDE : ITACONIC ACID

[0405] DES was prepared by mixing choline chloride and itaconic acid at a 1 :1 molar ratio at 150 °C in an oil bath. Reference material Mercel is a seaweed pulp treated with citric acid, provided by Mercel - Seaweed Cellulose Technologies. Reference material TNCP is provided by the Process Development Center at the University of Maine.

[0406] Dried Seaweed Pulp Treated with Choline Chloride: Itaconic Acid (sc-ia-d): ~5 g of dried seaweed pulp was mixed with the DES at a mass ratio of 1:33. and incubated at 90 °C for 15 min.ATTORNEY DOCKET NO. 331903-2010The pulp and DES were pre-mixed with a high-shear mixer for 30 min. The pre-mixed suspension was incubated at 90 °C for 2 h 45 min in an oil bath, with occasional manual stirring. Following, the suspension was diluted with deionized water, stirred manually and filtered. The solid residue was washed with deionized water until the pH of the washing water turned neutral. The DES- treated pulp was dispersed in deionized water up to a solids content of approx. 1 wt% and stirred with a high-shear (HV-0) mixer for 30 min with the conditions described in our standard procedure.

[0407] Never-Dried Seaweed Pulp Treated with Choline ltaconic:Citric Acid (sc-ia-w): ~5 g (dry weight) of never-dried seaweed pulp was solvent exchanged to ethanol by mixing the pulp in excess ethanol with an overhead mixer for 30 min, filtering and repeating two more times with fresh ethanol. The ethanol-containing pulp (dry matter content ~8%) was mixed with the DES at ratio of 1 :100 (dry pulp mass: DES mass). The pulp and DES were pre-mixed with a high-shear mixer for 3 x 10 min sets, with 5 min cooling in between. The pre-mixed suspension was incubated at 90 °C for 3 h in an oil bath, with occasional manual stirring. Following, the suspension was cooled down at ambient temperature for 5 min, diluted with deionized water, stirred with magnetic stirrer for 10 min and filtered. The solid residue was washed with deionized water until the pH of the washing water turned neutral. The DES-treated pulp was dispersed in deionized water up to a solids content of approx. 1 wt% and stirred with a high-shear (HV-0) mixer for 30 min with the conditions described in our standard procedure.Table 3. Charge density (mmol / g) for seaweed pulp treated with choline cholide: itaconic acid DES; determined by conductometric titration.

[0408] Dispersion Stability: Dynamic Light Scattering (DLS) measures how DES-treated pulp is dispersed on water (see FIGS. 15A-15B). The presence of only one peak shows that the sample has a uniform size. The fluidization process increases defibrillation that could cause broadening of the peak, shift of the peak to longer sizes or presence of other peaks that agrees with a cellulose with higher aspect ratio.

[0409] Gel Transparency: Gel transparency is measured by the UV-Vis absorbance spectra in the range of 250 nm to 750 nm (see FIGS. 16A-16B). Gel transparency is also expressed as theATTORNEY DOCKET NO. 331903-2010 average of the absorbance in the visible range (400 nm to 750 nm) and as the absorbance value at 550 nm, a wavelength located in the middle of the visible light spectrum (see FIGS. 17A-17B and 18A-18B). Human eyes are most sensitive to this region.4. DRIED OR NEVER-DRIED SEAWEED PULP IN SULPHAMIC ACID : GLYCEROL

[0410] DES was prepared by mixing sulphamic acid and glycerol at a 1 :3 molar ratio (1 :3.2 molar ratio) at 125 °C in an oil bath. Reference material Mercel is a seaweed pulp treated with citric acid, provided by Mercel - Seaweed Cellulose Technologies. Reference material TNCP is provided by the Process Development Center at the University of Maine.

[0411] Dried Seaweed Pulp Treated with Sulphamic Acid:Glycerol (sc-sa-d): ~6 g of dried seaweed pulp was mixed with the DES at a mass ratio of 1:33. and incubated at 90 °C for 15 min. The pulp and DES were pre-mixed with a high-shear mixer for 30 min. The pre-mixed suspension was incubated at 90 °C for 1 h 15 min in an oil bath, with occasional manual stirring. Following, the suspension was diluted with deionized water, stirred manually and filtered. The solid residue was washed with deionized water until the pH of the washing water turned neutral. The DES- treated pulp was dispersed in deionized water up to a solids content of approx. 1 wt% and stirred with a high-shear (HV-0) mixer for 30 min with the conditions described in our standard procedure.

[0412] Never-Dried Seaweed Pulp Treated with Sulphamic Acid:Glycerol (sc-sa-w): ~5 g (dry weight) of never-dried seaweed pulp was solvent exchanged to ethanol by mixing the pulp in excess ethanol with an overhead mixer for 30 min, filtering and repeating two more times with fresh ethanol. The ethanol-containing pulp (dry matter content ~8%) was mixed with the DES at a ratio of 1 :100 (dry pulp mass: DES mass). The pulp and DES were pre-mixed with a high-shear mixer for 3 x 10 min sets, with 5 min cooling in between. The pre-mixed suspension was incubated at 90 °C for 1.5 h in an oil bath, with occasional manual stirring. Following, the suspension was cooled down at ambient temperature for 5 min, diluted with deionized water, stirred with magnetic stirrer for 10 min and filtered. The solid residue was washed with deionized water until pH of the washing water turned neutral. The DES-treated pulp was dispersed in deionized water up to a solids content of approx. 1 wt% and stirred with a high-shear (HV-0) mixer for 30 min with the conditions described in our standard procedure.Table 4. Charge density (mmol / g) for seaweed pulp treated with sulphamic acid:glycerol DES; determined by elemental analysis.ATTORNEY DOCKET NO. 331903-2010

[0413] Dispersion Stability: Dynamic Light Scattering (DLS) measures how DES-treated pulp is dispersed on water (see FIGS. 22A-22B). The presence of only one peak shows that the sample has a uniform size. The fluidization process increases defibrillation that could cause broadening of the peak, shift of the peak to longer sizes or presence of other peaks that agrees with a cellulose with higher aspect ratio.

[0414] Gel Transparency: Gel transparency is measured by the UV-Vis absorbance spectra in the range of 250 nm to 750 nm (see FIGS. 23A-23B). Gel transparency is also expressed as the average of the absorbance in the visible range (400 nm to 750 nm) and as the absorbance value at 550 nm, a wavelength located in the middle of the visible light spectrum (see FIGS. 24A-24B and 25A-25B). Human eyes are most sensitive to this region.5. NEVER-DRIED SEAWEED PULP TREATED IN TWO STEPS: 1) CHOLI E CHLORIDE : OXALIC ACID; 2) SULPHAMIC ACID : GLYCEROL

[0415] DES-1 was prepared by mixing choline chloride and oxalic acid at a 1 :1 molar ratio at 70 °C in an oil bath. DES-2 was prepared by mixing sulphamic acid and glycerol at a 1:3 mass ratio (1 :3.2 molar ratio) at 125 °C in an oil bath. Reference material Mercel is a seaweed pulp treated with citric acid, provided by Mercel - Seaweed Cellulose Technologies. Reference material TNCP is provided by the Process Development Center at the University of Maine.

[0416] Never-Dried Seaweed Pulp Treatment with Choline Chloride:Oxalic Acid and Sulphamic Acid:Glycerol (sc-oa-sa-w): ~5 g (dry weight) of never-dried seaweed pulp (dry matter content 6.3%) was mixed with DES-1 at a mass ratio of 1:150 (corresponds to 10 wt% of water added to DES). The pulp and DES-1 were pre-mixed with a high-shear mixer for 3 x 10 min sets, with 5 min cooling in between. The pre-mixed suspension was incubated at 70 °C for 3 h in an oil bath, with occasional manual stirring. Following, the suspension was cooled down at ambient temperature for 5 min, diluted with deionized water, stirred with magnetic stirrer for 10 min and filtered. The solid residue was washed with deionized water until pH of the washing water turned neutral. Half of the DES-treated pulp was separated and dispersed (Example 1).

[0417] The remaining half was solvent exchanged to ethanol by mixing the pulp in excess ethanol with an overhead mixer for 30 min, filtering and repeating two more times with fresh ethanol. TheATTORNEY DOCKET NO. 331903-2010 ethanol-containing pulp was mixed with the DES at a ratio of 1:100 (dry pulp mass:DES mass). The pulp and DES were pre-mixed with a high-shear mixer for 3 x 10 min sets, with 5 min cooling in between. The pre-mixed suspension was incubated at 90 °C for 1.5 h in an oil bath, with occasional manual stirring. Following, the suspension was cooled down at ambient temperature for 5 min, diluted with deionized water, stirred manually and filtered. The solid residue was washed with deionized water until the pH of the washing water turned neutral.

[0418] The twice DES-treated pulp was dispersed in deionized water up to a solids content of approx. 0.5 wt% and stirred with a high-shear (HV-0) mixer for 30 min with the standard conditions described previously.Table 5. Charge density (mmol / g) for seaweed pulp treated with a two-step process of oxalic acid:choline chloride and sulphamic acid:glycerol DES. sulphamic acid:glycerol DES; determined by elemental analysis or conductimetric titration.

[0419] Dispersion Stability: Dynamic Light Scattering (DLS) measures how DES-treated pulp is dispersed on water (see FIG. 29). The presence of only one peak shows that the sample has a uniform size. The fluidization process increases defibrillation that could cause broadening of the peak, shift of the peak to longer sizes or presence of other peaks that agrees with a cellulose with higher aspect ratio.

[0420] Gel Transparency: Gel transparency is measured by the UV-Vis absorbance spectra in the range of 250 nm to 750 nm (see FIG. 30). Gel transparency is also expressed as the average of the absorbance in the visible range (400 nm to 750 nm) and as the absorbance value at 550 nm, a wavelength located in the middle of the visible light spectrum (see FIG. 31A-31 B). Human eyes are most sensitive to this region.6. DRIED OR NEVER-DRIED SEAWEED PULP IN BETAINE : GLYCEROL

[0421] DES was prepared by mixing betaine and glycerol at a 1 :2 molar ratio at 125 °C in an oil bath.ATTORNEY DOCKET NO. 331903-2010

[0422] Dried Seaweed Pulp Treated with Betaine:Glvcerol (sc-bet-d): ~5 g of dried seaweed pulp is mixed with the DES at a mass ratio of 1:100. The pulp and DES are pre-mixed with a high- shear mixer for 3 x 10 min sets, with 5 min cooling in between. The pre-mixed suspension is incubated at 125 °C for 2 h in an oil bath, with occasional manual stirring. Following, the suspension is cooled down at ambient temperature for 5 min, diluted with deionized water, stirred with magnetic stirrer for 10 min and filtered. The solid residue is washed with deionized water until the washing water turns clear. The DES-treated pulp is dispersed in deionized water up to a solids content of approx. 1 wt% and stirred with a high-shear (HV-0) mixer for 30 min with the conditions described in our standard procedure.

[0423] Never-Dried Seaweed Pulp Treated with Betaine:Glycerol (sc-bet-w): ~5 g (dry weight) of never-dried seaweed pulp is solvent exchanged to ethanol by mixing the pulp in excess ethanol with an overhead mixer for 30 min, filtering and repeating two more times with fresh ethanol. The ethanol-containing pulp is mixed with the DES at a ratio of 1 :100 (dry pulp mass : DES mass). The pulp and DES are pre-mixed with a high-shear mixer for 3 x 10 min sets, with 5 min cooling in between. The pre-mixed suspension is incubated at 125 °C for 2 h in an oil bath, with occasional manual stirring. Following, the suspension is cooled down at ambient temperature for 5 min, diluted with deionized water, stirred with magnetic stirrer for 10 min and filtered. The solid residue is washed with deionized water until the washing water turns clear. The DES-treated pulp is dispersed in deionized water up to a solids content of approx. 1 wt% and stirred with a high-shear (HV-0) mixer for 30 min with the conditions described in our standard procedure.Table 4. Charge density (mmol / g) for seaweed pulp treated with betaine:glycerol DES; determined by elemental analysis.

[0424] Dispersion Stability: Dynamic Light Scattering (DLS) measures how DES-treated pulp is dispersed on water (see FIG. 34). The presence of only one peak shows that the sample has a uniform size. The fluidization process increases defibrillation that could cause broadening of the peak, shift of the peak to longer sizes or presence of other peaks that agrees with a cellulose with higher aspect ratio.ATTORNEY DOCKET NO. 331903-2010

[0425] Gel Transparency: Gel transparency is measured by the UV-Vis absorbance spectra in the range of 250 nm to 750 nm (see FIG. 35). Gel transparency is also expressed as the average of the absorbance in the visible range (400 nm to 750 nm) and as the absorbance value at 550 nm, a wavelength located in the middle of the visible light spectrum (see FIGS. 36A-36B). Human eyes are most sensitive to this region.7. PRE-MIXING OF DRIED OR NEVER-DRIED SEAWEED PULP

[0426] DES is prepared by mixing choline chloride and oxalic acid at a 1 :1 molar ratio at 70 °C in an oil bath.

[0427] ~5 g (dry weight) of dried or never-dried seaweed pulp is mixed with the DES at a mass ratio of 1 :100 (dry pulp mass: DES mass). The pulp and DES are pre-mixed with one of the following methods:

[0428] High shear mixing for 30 min

[0429] High shear mixing for 30 min under cooling

[0430] Ball milling for 30 min

[0431] The different pre-mixed suspensions are stirred at 70 °C for 2 h under vacuum. In the case of never-dried pulp, time starts when most of the water has evaporated. Following, the suspensions are cooled down at ambient conditions for 5 min, diluted with deionized water, stirred with magnetic stirrer for 10 min and filtered. The solid residues are washed with deionized water until the pH of the washing water turns neutral. The DES-treated pulps are dispersed in deionized water up to a solids content of approx. 1 wt% and stirred with a high-shear (HV-0) mixer for 30 min with the conditions described in our standard procedure.8. DRIED OR NEVER-DRIED SEAWEED PULP IN DES WITH GAMMAVALEROLACTONE (GVL)

[0432] A DES with oxalic acid (DES-OA is prepared by mixing choline chloride and oxalic acid at a 1 :1 molar ratio at 70 °C in an oil bath. A DES with citric acid (DES-CA) is prepared by mixing choline chloride and citric acid at a 1 :1 molar ratio at 150 °C in an oil bath. 0 wt%, 10 wt% or 20 wt% of GVL is added to each DES. Thus, six different DESs are obtained: GVLO-DES-OA and GVL0-DES-CA with no GVL, GVL10-DES-OA and GVL10-DES-CA with 10% GVL, as well as GVL20-DES-OA and GVL20-DES-CA with 20% GVL.

[0433] -10 g (dry weight) of dried or never-dried seaweed pulp is mixed with the GVLO-DES-OA, GVL0-DES-CA, GVL10-DES-OA, GVL10-DES-CA, GVL20-DES-OA, or GVL20-DES-CA at a mass ratio of 1:10, 1 :24, 1 :50, or 1 :100 (dry pulp mass: DES mass). The different combinationsATTORNEY DOCKET NO. 331903-2010 of pulp and GVL-DES are pre-mixed with the preferred method selected based on Example 7. The pre-mixed suspensions are stirred at 70 °C or 100 °C for 2 h, 3 h or 4 h under vacuum. In the case of never-dried pulp, time starts when most of the water has evaporated. Following, the suspensions are cooled down at ambient conditions for 5 min, diluted with deionized water, stirred with magnetic stirrer for 10 min and filtered. The solid residues are washed with deionized water until the pH of the washing water turns neutral. The GVL-DES-treated pulps are dispersed in deionized water up to a solids content of approx. 1 wt% and stirred with a high-shear (HV-0) mixer for 30 min with the standard conditions described previously.9. TREATMENT OF ALGAL, WOOD-BASED, AND BACTERIAL CELLULOSE

[0434] DES is prepared like DES-OA or DES-CA with optional GVL in Example 8, selecting the preferred formulation based on Example 8.

[0435] Dried or never-dried seaweed pulp, wood pulp, or bacterial cellulose is mixed with the DES at the preferred mass ratio selected based on Example 8. The different feedstock and DES combinations are pre-mixed with the preferred method selected based on Example 7. The premixed suspensions are stirred at the preferred temperature for the preferred time selected based on Example 8 under vacuum. In the case of never-dried feedstock, the time starts when most of the water has evaporated. Following, the suspensions are cooled down at ambient conditions for 5 min, diluted with deionized water, stirred with magnetic stirrer for 10 min and filtered. The solid residues are washed with deionized water until the pH of the washing water turns neutral. The DES-treated celluloses are dispersed in deionized water up to a solids content of approx. 1 wt% and stirred with a high-shear (HV-0) mixer for 30 min with the standard conditions described previously.10. DRIED OR NEVER-DRIED SEAWEED PULP IN DES WITH TWO DICARBOXYLIC ACIDS

[0436] DES is prepared by mixing choline chloride, oxalic acid and sebacic acid at a 2:1 :1 molar ratio at 70 °C in an oil bath. GVL may be added if preferred based on Example 8.

[0437] ~5 g (dry weight) of dried or never-dried seaweed pulp is mixed with the DES at a mass ratio of 1 :100 (dry pulp mass: DES mass). The pulp and DES are pre-mixed with the preferred method selected based on Example 7. The suspension is stirred at 70 °C for 2 h under vacuum. In the case of never-dried pulp, time starts when most of the water has evaporated. Following, the suspensions are cooled down at ambient conditions for 5 min, diluted with deionized water, stirred with magnetic stirrer for 10 min and filtered. The solid residues are washed with deionized water until the pH of the washing water turns neutral. The DES-treated pulps are dispersed inATTORNEY DOCKET NO. 331903-2010 deionized water up to a solids content of approx. 1 wt% and stirred with a high-shear (HV-0) mixer for 30 min with the standard conditions described previously.11. DRIED OR NEVER-DRIED SEAWEED PULP IN DES WITH SALT

[0438] DES is prepared like DES-OA or DES-CA with optional GVL in Example 8, selecting the preferred formulation based on Example 8. ZnCh, MgCh, MnCh, or LiCI is added in salt: DES molar ratio of 1 :99 or 2:98.

[0439] Dried or never-dried seaweed pulp is mixed with the different DESs at the preferred mass ratio selected based on Example 8. The DES combinations are pre-mixed with the preferred method selected based on Example 7. The pre-mixed suspensions are stirred at the preferred temperature for the preferred time selected based on Example 8 under vacuum. In the case of never-dried pulp, time starts when most of the water has evaporated. Following, the suspensions are cooled down at ambient conditions for 5 min, diluted with deionized water, stirred with magnetic stirrer for 10 min and filtered. The solid residues are washed with deionized water until the pH of the washing water turns neutral. The DES-treated pulps are dispersed in deionized water up to a solids content of approx. 1 wt% and stirred with a high-shear (HV-0) mixer for 30 min with the standard conditions described previously.12. AFM ANALYSIS

[0440] FIGS. 39A-43B show AFM images and histograms of fiber height for dry and wet seaweed cellulose samples that have not undergone high shear mixing (HV-0), have undergone HV-0 mixing, or have undergone both HV-0 mixing and a fluidization treatment with three fluidization passes (F3P). FIGS. 45A-54B show AFM images and histograms of fiber height for dry seaweed cellulose samples that have been treated with various DESs and have undergone high shear mixing (HV-0) or both HV-0 mixing and a fluidization treatment with three fluidization passes (F3P). FIGS. 44 and 55 show the range of fiber height in the various dry and wet seaweed cellulose samples treated using different methods and, in some cases, DESs. AFM fiber height refers to the thickness of individual fibers. High shear mixing treatments such as HV-0 and fluidization can decrease the thickness of the fibers. DES treatments can reverse the hornification process in dry seaweed cellulose, giving fiber thickness similar to wet seaweed cellulose. Depending on the type of DES, the morphology and length of the fibers can be modified, allowing for tuning properties such as crosslinking capacity and viscosity, among others.13. ADDITIONAL SAMPLE PREPARATION AND CHARACTERIZATIONATTORNEY DOCKET NO. 331903-2010

[0441] Sample Preparation and Characterization Methods - Gravimetric Analysis’. Dry matter content (DMC) was determined by oven drying under controlled conditions. Mass loss was used to estimate the cellulose content in suspensions and to monitor consistency during processing.

[0442] Sample Preparation and Characterization Methods - Masuko High-Shear Mixing: Hemp hurd pulp modified with OACC DES was refined using a Masuko grinder (1750 rpm on Redmed, 2000 rpm on SMC). The plate gap was adjusted to maintain motor load below 80% and to prevent plate contact. Solids content was optimized to avoid clogging and to ensure efficient fibrillation. Fiber length distribution shifted from 80% < 0.325 mm before refining to 99% < 0.252 mm after refining.

[0443] Sample Preparation and Characterization Methods - Fourier Transform Infrared Spectroscopy (FTIR): Bond vibrations and chemical modifications in cellulose were analyzed using an FT-IR Spectrometer (Shimadzu IRSpirit with QATR-S AT).

[0444] Sample Preparation and Characterization Methods - Energy-Dispersive X-rav Spectroscopy (EDX): Elemental composition of cellulose films was evaluated with a benchtop SEM equipped with EDS (ThermoFisher Scientific Phenom G6 ProX). Films were dried, mounted on aluminum holders, and gold-coated prior to analysis.

[0445] Sample Preparation and Characterization Methods - Atomic Force Microscopy (AFM): Nanoscale morphology and fibril thickness distribution were measured using AFM (Park NX10), providing high-resolution images of cellulose surface topography.

[0446] Sample Preparation and Characterization Methods - Viscosity: Single-point viscosity was measured with a spindle #14 at 250 rpm (shear rate = 100 Hz) using a DVNext Rheometer.

[0447] Biomass Sources - Laminaria hyperborea (stems pulp): The stems of Laminaria hyperborea are rich in structural polysaccharides, including cellulose and alginates. Compared to the fronds, the stems provide a higher dry matter content, making them an excellent source for biopolymer extraction.

[0448] Biomass Sources - Saccharina latissima (Sugar kelp): The dried and processed fronds of Saccharina latissima, commonly known as sugar kelp, yield cellulose that is widely used in cosmetic formulations and as a renewable biomass feedstock.

[0449] Biomass Sources - Sargassum spp. (Brown algae): Sargassum often accumulates in large quantities along coastal areas, where it can become an environmental burden. Its biomass contains a complex composition of cellulose, alginates, and phenolic compounds, offering a promising resource for sustainable biopolymer production.ATTORNEY DOCKET NO. 331903-2010

[0450] Biomass Sources - Hemp hurd: Hemp hurd, the woody inner core of the hemp stalk, is a lignocellulosic material left after removal of the bast fibers. It is fast-growing, renewable, and provides a high cellulose yield, making it an attractive raw material for sustainable materials development.

[0451] DES Treatments - Choline Chloride:Oxalic Acid (OACC) DES - Wet vs. Dry Cellulose:• Preparation: Choline chloride and anhydrous or dihydrated oxalic acid, 1 :1 molar ratio, mixed at 70 °C.• Treatment: ~5 g never-dried (wet) or dried pulp mixed with DES at 1 :30 (dry mass:DES). Pre-mixed with high-shear mixing (30 min), incubated at 90 °C (15 min + 2 h 45 min, occasional stirring). The suspension was diluted with deionized water, stirred (10 min, magnetic), filtered, washed to neutral pH, and dispersed in deionized water (~1 wt. % solids). Fibrillation performed with HV-0 mixer.

[0452] DES Treatments - Citric Acid:Glycerol (CAGLY) DES - Dried Pulp:• Preparation: Glycerol and citric acid mixed 1 :4 molar ratio at 120 °C.• Treatment: ~5 g dried pulp mixed with DES at 1:30 (dry mass:DES). Pre-mixed with high-shear mixer (30 min), incubated at 90 °C (15 min + 2 h 45 min, highly viscous suspension). Diluted, stirred manually, filtered, washed to neutral pH, and dispersed (~1 wt. % solids). Fibrillated with HV-0 mixer.

[0453] DES Treatments - Betaine:Glycerol (BET-GLY) DES - Dried Pulp:• Preparation: Betaine and glycerol mixed 1 :2 molar ratio at 125 °C.• Treatment: ~5 g dried pulp mixed with DES at 1 :100 (dry mass:DES). Pre-mixed (3 x 10 min with 5 min cooling intervals), incubated at 125 °C for 2 h (occasional manual stirring). After cooling, diluted, stirred, filtered, and washed until clear. Dispersed in deionized water (~1 wt. % solids) and fibrillated with HV-0 mixer.

[0454] DES Treatments - Choline Chloride: Itaconic Acid DES - Dried Pulp:• Preparation: Choline chloride and itaconic acid, 1 :1 molar ratio, mixed at 150 °C.• Treatment: ~5 g dried pulp mixed with DES at 1 :33 (dry mass:DES). Pre-mixed (30 min), incubated at 90 °C (15 min + 2 h 45 min, occasional stirring). Diluted, stirred manually, filtered, washed to neutral pH. Dispersed (~1 wt. % solids) and fibrillated with HV-0 mixer.ATTORNEY DOCKET NO. 331903-2010

[0455] DES Treatments - Two-Step DES (OACC + SAGLY) - Wet Pulp:• Step 1 : OACC (Choline chloride:Oxalic acid 1 :1 molar) prepared at 70 °C. Never-dried pulp (-5 g dry basis; 6.3 % solids) mixed at 1 :150 (dry mass:DES, -10 wt. % water in DES). Pre-mixed (3 * 10 min sets, 5 min cooling intervals) and incubated at 70 °C for 3 h. Diluted, filtered, washed.• Step 2: SAGLY (Sulphamic acid:Glycerol, 1:3 mass; 1 :3.2 molar) prepared at 125 °C. The OACC-treated pulp was ethanol-exchanged (3 cycles) and mixed with SAGLY at 1 :100 (dry mass:DES). Pre-mixed (3 x 10 min sets, 5 min cooling intervals) and incubated at 90 °C for 1.5 h. Diluted, filtered, washed. Final suspension: ~0.5 wt. % solids and fibrillated with HV-0 mixer.

[0456] DES Treatments - Sulphamic Acid: Glycerol (SAGLY) DES - Wet Pulp:• Preparation: Sulphamic acid and glycerol mixed at 1 :3 mass ratio (1 :3.2 molar) at 125 °C.• Treatment: -5 g never-dried pulp, pre-mixed (3 x 10 min sets, 5 min cooling intervals). Incubated at 90 °C for 1.5 h. Diluted, filtered, washed to neutral pH. Dispersed (-1 wt. % solids) and fibrillated with HV-0 mixer.

[0457] Chemical modifications (FTIR measurements): For control samples, never-dried (wet) and dry cellulose suspensions were prepared to obtain films for FTIR analysis. Despite the difference in water content, the FTIR spectra (FIG. 56) of both types were very similar. This can be explained by the fact that even "dry" cellulose retains significant bound water, as seen in the broad O-H stretching band between 3000 and 3600 cm1. The fingerprint region showed the same cellulose I signals in both cases, confirming no detectable differences under these conditions.

[0458] FTIR characterization was also done for a choline chloride:oxalic acid DES treatment of never-dried (wet) and dried cellulose pulp. After OACC treatment, both wet and dry cellulose retained the general cellulose spectral features (FIG. 57). However, in the dry cellulose samples, a new absorption band appeared near 1700 cm-1, suggesting the formation of additional carbonyl- related bonds. This signal was absent in the wet cellulose, indicating that only dry cellulose with a DMC above 40% undergoes detectable chemical modification under these conditions.

[0459] FTIR characterization was also done for a citric acid-glycerol DES treatment of dried seaweed pulp. FTIR spectra of dry cellulose after CAGLY treatment showed a distinct new bandATTORNEY DOCKET NO. 331903-2010 near 1700 cm-1(FIG. 58), again attributed to carbonyl bond formation. This supports the conclusion that CAGLY induces chemical modification of cellulose when processed in its dry form.

[0460] FTIR characterization was also done for a betaine:glycerol DES treatment of dried seaweed pulp. The betaine:glycerol DES did not produce detectable new FTIR signals in dry cellulose (FIG. 59). The fingerprint and carbonyl regions remained unchanged, suggesting either minimal chemical modification or modifications below the detection sensitivity of FTIR.

[0461] FTIR characterization was also done for a choline chloride: itaconic Acid DES treatment of dried seaweed pulp. Treatment with choline chloride:itaconic acid DES did not result in new detectable FTIR signals (FIG. 60). The cellulose spectra before and after treatment were essentially identical, suggesting no significant chemical modification within FTIR’s sensitivity.

[0462] FTIR characterization was also done for a two-step DES treatment of never-dried seaweed pulp. Sequential treatment of never-dried cellulose with OACC followed by SAGLY did not show detectable new FTIR signals (FIG. 61). The absence of observable changes in the fingerprint and carbonyl regions suggests that either chemical modifications did not occur or were masked by overlapping cellulose bands.

[0463] FTIR characterization was also done for a sulphamic acid:glycerol DES treatment of never-dried seaweed pulp. FTIR analysis of wet cellulose treated with SAGLY also did not reveal clear new signals (FIG. 62). Without wishing to be bound by theory, it is possible that this is due to overlap between potential S-0 vibrational modes and the strong cellulose background bands, which can mask the subtle contributions from sulfate groups.

[0464] To resolve this limitation for the sulphamic acid:glycerol DES treatment, EDX analysis was carried out. The spectra revealed a measurable sulfur signal corresponding to ~0.8 wt. % S, confirming incorporation of sulfate groups into the cellulose structure (FIG. 63). This suggests that SAGLY treatment successfully modifies cellulose, even if FTIR is unable to directly detect it.

[0465] Overall, the FTIR and EDX analyses highlight distinct outcomes for different DES systems. Clear chemical modifications were detected for OACC and CAGLY treatments, evidenced by the emergence of carbonyl-related bands near 1700 cm-1. SAGLY treatment also modified cellulose, although the effect was masked in FTIR by overlapping signals; instead, EDX confirmed sulfur incorporation (-0.8 wt.%). In contrast, betaine:glycerol and choline chloride: itaconic acid treatments did not yield new FTIR signals, though this absence does not necessarily exclude chemical modification.ATTORNEY DOCKET NO. 331903-2010

[0466] For betaine:glycerol DES, FTIR did not show detectable new signals and EDX could not confirm nitrogen incorporation. However, the treated cellulose exhibited distinct physical changes compared to the untreated material, suggesting that some degree of modification or structural rearrangement could have occurred. Because betaine introduces nitrogen groups, its effect may be subtle or below the sensitivity limits of FTIR and EDX. Taken together, the combination of physical evidence and the known reactivity of betaine-based systems support the possibility of modification having occurred. Itaconic acid and other carboxylic DES lack distinctive elemental markers for EDX. Their modifications may therefore be subtle, present at levels below FTIR detection, or limited to structural rearrangements that require more sensitive methods to confirm. These results demonstrate that DES treatments do modify cellulose, with FTIR revealing clear changes in some systems and EDX analysis confirming modifications in others, together providing evidence of effective functionalization.

[0467] Cellulose Nanofibers (CNFs) to Cellulose nanocrystals (CNCs): This Example demonstrates that DES treatments, particularly anhydrous oxalic acid-choline chloride, citric acid-glycerol, and sulphamic acid-glycerol, can chemically modify dry cellulose (DMC > 40%). FTIR confirmed chemical modifications in OACC- and CAGLY-treated samples, while EDX analysis verified sulfur incorporation in SAGLY-treated cellulose. These chemical changes highlight the versatility of DES in tailoring cellulose at the molecular level.

[0468] Beyond chemical modification, DES can also enable structural tailoring, shortening fiber length and converting cellulose nanofibers (CNFs, several microns in length) into cellulose nanocrystals (CNCs, sub-micron length). Atomic Force Microscopy (AFM) provided direct evidence of these morphological changes (FIGS. 64A-64C). Cellulose from Laminaria hyperborea, Saccharina latissima, and hemp hurd showed long fibers before DES treatment but yielded shorter CNCs (~500 nm) after OACC modification. Average fiber thickness decreased to ~4 nm post HV-0 high-shear mixing process. On hemp hurd, some bundles (>12 nm) persisted after extended HV-0 shearing, underscoring the importance of mechanical post- processing and type of initial biomass.

[0469] To systematically evaluate processing routes, different DES-mechanical combinations were applied on hemp hurd (FIG. 65). Route 1 : hemp hurd treated with oxalic acid and subsequently processed with the HV-0 high-shear mixer yielded cellulose nanocrystals (CNCs) with an average length of ~500 nm and a thickness of 9.8 ± 3.9 nm. Route 2: replacing the HV-0 with a Masuko grinder after oxalic acid treatment produced shorter CNCs, with lengths ranging between 200-300 nm and a reduced thickness of 5.6 ± 1.3 nm. Route 3: based solely on a 1.5 hATTORNEY DOCKET NO. 331903-2010 treatment with sulphamic acid: glycerol DES, generated cellulose nanofibers (CNFs) with lengths exceeding 1 pm, confirming that without mechanical post-processing the fibers remain longer. Route 4: extends the sulphamic acid:glycerol DES treatment to 3 h and following with HV-0 high- shear mixing converted the material back into CNCs with an average length of -500 nm and a finer thickness of 4.8 ± 2.8 nm. High-shear mixing methods such as extrusion, HV-0, fluidization, or Masuko milling can promote defibrillation of cellulose, reducing fiber thickness and converting thick cellulose fibers into m icrofi bri Hated cellulose or nanofibril lated cellulose. These methods may also reduce fiber length to some extent. In contrast, treatment with DESs enables shortening of the fibers, enabling the conversion of microfibril lated cellulose or nanofibrillated cellulose further into CNC at specific conditions.

[0470] These results demonstrate that DES chemistry combined with controlled mechanical treatment provides a tunable pathway to transform CNFs into CNCs. By adjusting solvent type, treatment time, and fibrillation method, cellulose morphology can be precisely tailored to fit application-specific requirements.

[0471] Cellulose length and crystallinity (X-Ray Diffraction): Treatment with OACC DES not only decreases cellulose fiber length, producing CNCs, but can at the same time decrease the amorphous regions, modifying the crystalline structure of the material. These changes can be effectively tracked by X-ray diffraction (XRD), which provides direct insight into crystalline and amorphous regions of cellulose.

[0472] XRD analyses were performed on cellulose from Laminaria hyperborea, Saccharina latissima, Sargassum spp., and hemp hurd before and after OACC DES treatment (FIGS. 66A- 66D). Each sample was dewatered and cast into thin films (2-5 nm) for measurement.

[0473] The characteristic diffraction peaks of cellulose I (20 ~ 14.5° and 22.4°) were retained after DES treatment, confirming preservation of the native cellulose crystalline structure. At the same time, a decrease in the amorphous background and an increase in diffraction peak intensity were consistently observed, indicating that OACC DES enhances crystallinity.

[0474] Quantification of this effect was achieved using the Segal method (Eq. 1), where the crystallinity index (Cl) is calculated by comparing the intensity of the main (002) diffraction peak at 22.4° with the intensity of the amorphous region at 18.5°.ATTORNEY DOCKET NO. 331903-2010

[0475] These results demonstrate that OACC DES treatment increases cellulose crystallinity across all biomass sources tested by selectively reducing the amorphous fraction of the fibers.

[0476] Cellulose stability and dispersion enhancement: Surface charge and colloidal stability of DES-treated cellulose suspensions were evaluated by zeta potential measurements. In the Zetasizer Nano system, electrophoretic mobility is determined using Laser Doppler Velocimetry (LDV) and converted to zeta potential via the Henry equation. A higher absolute corresponds to stronger electrostatic repulsion and therefore greater suspension stability. Negative values indicate net negative surface charge.

[0477] Cellulose suspensions (0.05 wt%) were tested in deionized water (pH 5-6, conductivity 0.007-0.026 mS / cm) at 25 °C for two biomass sources: Saccharina latissima and hemp hurd. For each, three conditions were analyzed: untreated cellulose, OACC DES-treated cellulose, and SAGLY DES-treated cellulose. SAGLY treatment consistently yielded the most negative indicating strong electrostatic stabilization. OACC DES samples showed intermediate values, while untreated cellulose was close to neutral and near the lower limit for electrostatic stabilization under low ionic strength conditions. Results are depicted in FIGS. 67A and 67B.

[0478] These findings demonstrate that DES chemistry not only modifies cellulose structure but also tunes its surface charge, with SAGLY imparting the strongest electrostatic stabilization....

Claims

ATTORNEY DOCKET NO. 331903-2010CLAIMSWhat is claimed is:

1. A method, comprising: combining a cellulose feedstock and a first solvent in a weight ratio of about 1 :0.5 to about 1 :200 cellulose feedstock to first solvent, thereby forming a cellulosic suspension; mixing the cellulosic suspension under high shear; and treating the cellulosic suspension with a reaction treatment comprising: incubation of the cellulosic suspension at a temperature of at least 30°C; microwave irradiation exposure; plasma exposure; ultrasound exposure; grinding; ball-milling; extrusion; a sequence thereof; or any combination thereof, thereby forming a treated cellulosic suspension comprising a treated cellulose material; wherein the first solvent comprises a Lewis base and a Lewis acid in an about 10:2 to about 1 :9 molar ratio of Lewis base to Lewis acid.

2. The method of claim 1 , further comprising: diluting the treated cellulosic suspension with a second solvent; washing the treated cellulosic suspension with a third solvent, thereby forming a washed cellulosic suspension comprising the treated cellulose material; and draining the washed cellulosic suspension, thereby forming an intermediate cellulosic suspension comprising the treated cellulose material; wherein the second solvent is miscible with the first solvent; wherein the third solvent is miscible with the second solvent; and wherein the intermediate cellulosic suspension comprises from about 2 wt% to about 50 wt% of the treated cellulose material.

3. The method of claim Error! Reference source not found, or claim 2, wherein the Lewis base is a quaternary ammonium compound, a carboxylic acid, a polyol, or any combination thereof.

4. The method of claim Error! Reference source not found, or claim 2, wherein the Lewis base is a quaternary ammonium compound.

5. The method of any one of claims Error! Reference source not found. -4, wherein the Lewis base is a monocarboxylic acid; an unsaturated monocarboxylic acid; a dicarboxylic acid; a tricarboxylic acid, a polyol; choline halide; an amino acid; tetraalkylammonium halide; benzyltrialkyl ammonium halide; methyltrialkyl ammonium halide; alkyldimethyl(2- hydroxyethyl)ammonium halide; dialkyl-di(2-hydroxyethyl)-ammonium halide; alkyl-tri(2-ATTORNEY DOCKET NO. 331903-2010 hydroxyethyl)-ammonium halide; N,N-dialkylethanolammonium halide; 2- (chlorocarbonyloxy)-N,N,N-trialkylethanaminium halide; alkyltriphenylphosphonium halide; alkenyltriphenylphosphonium halide; imidazolium; 1,5-diazabicyclo[4.3.0]non-5-enium; N- alkenyl-N-methylmorpholinium; sulphamic acid; glycine-betaine; a derivative thereof; or any combination thereof.

6. The method of any one of claims Error! Reference source not found. -5, wherein the Lewis base is a saturated monocarboxylic acid; an unsaturated monocarboxylic acid; a monocarboxylic acid substituted with an aryl group; a dicarboxylic acid; a tricarboxylic acid; a polyol; choline halide; acetylcholine halide; an amino acid; a betaine derivative of an amino acid; a betaine hydrochloride derivative of an amino acid; a salt of an amino acid; tetramethylammonium halide; tetraethylammonium halide; tetrapropylammonium halide; tetrabutylammonium halide; benzyltrimethyl ammonium halide; benzyltriethyl ammonium halide; methyltriethyl ammonium halide; ethyldimethyl(2-hydroxyethyl)ammonium halide; benzyldimethyl(2-hydroxyethyl)ammonium halide; dimethyl-di(2-hydroxyethyl)-ammonium halide; methyl-tri(2-hydroxyethyl)-ammonium halide; N,N-dimethylethanolammonium halide; N,N-diethylethanolammonium halide; 2-(chlorocarbonyloxy)-N,N,N-trimethylethanaminium halide; methyltriphenylphosphonium halide; benzyltriphenylphosphonium halide; allyltriphenylphosphonium halide; vinyltriphenylphosphonium halide; imidazolium; 1 ,5- diazabicyclo[4.3.0]non-5-enium; N-allyl-N-methylmorpholinium; sulphamic acid; glycinebetaine; a derivative thereof; or any combination thereof.

7. The method of claim 5 or claim 6, wherein the amino acid is selected from alanine, p-alanine, glycine, proline, histidine, glutamic acid, lysine, ornithine, arginine, citrulline, serine, and any combination thereof.

8. The method of any one of claims 5-7, wherein the polyol is selected from glycerol, sorbitol, mannitol, maltitol, erythritol, pentaerythritol, xylitol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol), propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and any combination thereof.

9. The method of claim 7, wherein the saturated monocarboxylic acid is selected from formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and any combination thereof.ATTORNEY DOCKET NO. 331903-201010. The method of any one of claims 5-9, wherein the dicarboxylic acid is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, tartaric acid, itaconic acid, methylsuccinic acid, aspartic acid, glutamic acid, and any combination thereof.

11. The method of claim 10, wherein the dicarboxylic acid is a combination of at least two dicarboxylic acids, comprising a shorter-chain dicarboxylic acid and a longer-chain dicarboxylic acid, wherein a molar ratio of the shorter-chain dicarboxylic acid to the longer- chain dicarboxylic acid ranges from about 10:1 to about 1 :10.

12. The method of any one of claims 5-11 , wherein the tricarboxylic acid is selected from citric acid, isocitric acid, aconitic acid, trimesic acid, tricarbalyllic acid, and any combination thereof.

13. The method of any one of claims 6-12, wherein the unsaturated monocarboxylic acid has from 1 to 7 double bonds.

14. The method of any one of claims 6-13, wherein the unsaturated monocarboxylic acid is selected from acrylic acid, methacrylic acid, oleic acid, linoleic acid, and any combination thereof.

15. The method of any one of claims 6-14, wherein the monocarboxylic acid substituted with an aryl group is selected from benzoic acid, salicylic acid, acetylsalicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, gallic acid, caffeic acid, coumaric acid, cinnamic acid, phenylacetic acid, phenylpropionic acid, and any combination thereof.

16. The method of any one of claims Error! Reference source not found. -6, wherein the Lewis base is choline chloride, choline bromide, glycine-betaine, sulphamic acid, glycerol, oxalic acid, citric acid, or any combination thereof.

17. The method of any one of claims Error! Reference source not found.- 16, wherein the Lewis acid is a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, a polyol, a monosaccharide, a disaccharide, an oligosaccharide, an amino acid, an amide, an anhydride, a dihydrogen phosphate salt, urea, imidazole, ascorbic acid, glucuronic acid, levulinic acid, glycolic acid, p-toluenesulfonic acid, sulphamic acid, glycine-betaine, a derivative thereof, or any combination thereof.

18. The method of claim 17, wherein the monocarboxylic acid is a saturated monocarboxylic acid, an unsaturated monocarboxylic acid, a monocarboxylic acid substituted with an aryl group, or any combination thereof.ATTORNEY DOCKET NO. 331903-201019. The method of any one of claims Error! Reference source not found.- 18, wherein the Lewis acid is a saturated monocarboxylic acid, an unsaturated monocarboxylic acid, a monocarboxylic acid substituted with an aryl group, a dicarboxylic acid, a tricarboxylic acid, a polyol, a monosaccharide, a disaccharide, an oligosaccharide, an amino acid, an amide, an anhydride, a dihydrogen phosphate salt, urea, methyl urea, dimethyl urea, thiourea, imidazole, ascorbic acid, glucuronic acid, levulinic acid, glycolic acid, p-toluenesulfonic acid, sulphamic acid, glycine-betaine, a derivative thereof, or any combination thereof.

20. The method of claim 18 or claim 19, wherein the saturated monocarboxylic acid is selected from formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and any combination thereof.

21. The method of any one of claims 18-20, wherein the unsaturated monocarboxylic acid has from 1 to 7 double bonds.

22. The method of any one of claims 18-21 , wherein the unsaturated monocarboxylic acid is selected from acrylic acid, methacrylic acid, oleic acid, linoleic acid, and any combination thereof.

23. The method of any one of claims 18-22, wherein the monocarboxylic acid substituted with an aryl group is selected from benzoic acid, salicylic acid, acetylsalicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, gallic acid, caffeic acid, coumaric acid, cinnamic acid, phenylacetic acid, phenylpropionic acid, and any combination thereof.

24. The method of any one of claims 17-23, wherein the dicarboxylic acid is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, tartaric acid, itaconic acid, methylsuccinic acid, aspartic acid, glutamic acid, and any combination thereof.

25. The method of claim 24, wherein the dicarboxylic acid is a combination of at least two dicarboxylic acids, comprising a shorter-chain dicarboxylic acid and a longer-chain dicarboxylic acid, wherein a molar ratio of the shorter-chain dicarboxylic acid to the longer- chain dicarboxylic acid ranges from about 10:1 to about 1 :10.

26. The method of any one of claims 17-25, wherein the tricarboxylic acid is selected from citric acid, isocitric acid, aconitic acid, trimesic acid, tricarbalyllic acid, and any combination thereof.ATTORNEY DOCKET NO. 331903-201027. The method of any one of claims 17-26, wherein the polyol is selected from glycerol, sorbitol, mannitol, maltitol, erythritol, pentaerythritol, xylitol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol), propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and any combination thereof.

28. The method of any one of claims 17-27, wherein the monosaccharide is selected from xylose, mannose, fructose, glucose, ribose, and any combination thereof.

29. The method of any one of claims 17-28, wherein the oligosaccharide is a cyclodextrin.

30. The method of any one of claims 17-29, wherein the amino acid is selected from lysine, aspartic acid, glutamic acid, and any combination thereof.

31. The method of any one of claims 17-30, wherein the amide is selected from acetamide, benzamide, and a combination thereof.

32. The method of any one of claims 17-31 , wherein the anhydride is selected from acetic anhydride, succinic anhydride, and any combination thereof.

33. The method of any one of claims 1-17, wherein the Lewis acid is selected from oxalic acid, citric acid, sulphamic acid, glycerol, tartaric acid, malic acid, itaconic acid, glycine-betaine, and any combination thereof.

34. The method of claim 1 or claim 2, wherein the Lewis acid and the Lewis base are individually selected from a fatty acid, a terpene, or a combination thereof.

35. The method of claim 34, wherein the fatty acid is selected from octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and any combination thereof.

36. The method of claim 34 or claim 35, wherein the terpene is selected from thymol, menthol, carvacrol, and any combination thereof.

37. The method of claim 1 or claim 2, wherein the Lewis base is an organic salt and the Lewis acid is a metal halide.

38. The method of claim 37, wherein the organic salt is selected from choline chloride, glycinebetaine, and a combination thereof.

39. The method of claim 37 or claim 38, wherein the metal halide is selected from ZnCI2, ZnBr2, FeCI3, FeBr3, SnCI2, SnBr2, MgCI2, MgBr2, CaCI2, CaBr2, CrCI3, CrBr3, MnCI2, MnBr2, AICI3,ATTORNEY DOCKET NO. 331903-2010AIBrs, C11CI2, CuBr2, and any combination thereof.

40. The method of claim Error! Reference source not found, or claim 2, wherein the Lewis base is an organic salt and the Lewis acid is a metal halide hydrate.

41. The method of claim 40, wherein the organic salt is selected from choline chloride, glycinebetaine, and a combination thereof.

42. The method of claim 40 or claim 41 , wherein the metal halide hydrate is selected from ZnCh• n H2O; ZnBr2• n H2O; CaCI2• 6 H2O; CaBr2• 6 H2O; MgCI2• 6 H2O; MgBr2• 6 H2O; CrCI3• 6 H2O; CrBr3• 6 H2O; SnCI2• 2 H2O; SnBr2• 2 H2O; FeCI3• 6 H2O; FeBr3• 6 H2O; MnCI2• 4 H2O; MnBr2• 4 H2O; AICI3• 6 H2O; AIBr3• 6 H2O; CuCI2• 2 H2O; CuBr2• 2 H2O; and any combination thereof, wherein n ranges from 1 to 4.

43. The method of claim 1 or claim 2, wherein the Lewis base is a metal salt hydrate and the Lewis acid is urea, a polyol, acetamide, an amino acid, a derivative thereof, or any combination thereof.

44. The method of claim 43, wherein the urea or derivative thereof is selected from urea, methylurea, dimethylurea, thiourea, and any combination thereof.

45. The method of claim 43 or claim 44, wherein the polyol is selected from glycerol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, poly(ethylene glycol), propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and any combination thereof.

46. The method of any one of claims 43-45, wherein the metal salt hydrate is selected from ZnCh• n H2O; FeCI3• 6 H2O; ZrOCI2• 8 H2O; Zn(OAc)2• 2 H2O; Mn(OAc)2• 4 H2O; and any combination thereof, wherein n ranges from 1 to 4.

47. The method of any one of claims 1-46, wherein the molar ratio of Lewis base to Lewis acid in the first solvent is about 10:3 to about 1 :8.

48. The method of any one of claims 1-46, wherein the molar ratio of Lewis base to Lewis acid in the first solvent is about 10:4 to about 1 :7.

49. The method of any one of claims 1-48, wherein the first solvent further comprises a metal halide, a metal halide hydrate, an alkali metal chloride, toluenesulfonic acid, or an enzyme.

50. The method of claim 49, wherein the metal halide is selected from ZnCI2, ZnBr2, FeCI3, FeBr3, SnCL, SnBr2, MgCh, MgBr2, CaCh, CaBr2, CrCI3, CrBr3, MnCL, MnBr2, AICI3, AIBr3, CuCL, CuBr2, and any combination thereof.ATTORNEY DOCKET NO. 331903-201051. The method of claim 49 or claim 50, wherein the metal halide hydrate is selected from ZnCh • n H2O; ZnBr2• n H2O; CaCI2• 6 H2O; CaBr2• 6 H2O; MgCI2• 6 H2O; MgBr2• 6 H2O; CrCI3• 6 H2O; CrBr3• 6 H2O; SnCI2• 2 H2O; SnBr2• 2 H2O; FeCI3• 6 H2O; FeBr3• 6 H2O; MnCI2• 4 H2O; MnBr2• 4 H2O; AICI3• 6 H2O; AIBr3• 6 H2O; CuCI2• 2 H2O; CuBr2• 2 H2O; and any combination thereof, wherein n ranges from 1 to 4.

52. The method of any one of claims 49-51 , wherein the alkali metal chloride is selected from LiCI, LiBr, NaCI, NaBr, KCI, KBr, and any combination thereof.

53. The method of any one of claims 49-52, wherein the enzyme is selected from endoglucanase, exoglucanase, cellulase, cellobiase, cellobiohydrolase, p-glucosidase, xylanase, mannanase, glucomannanase, or any combination thereof.

54. The method of any one of claims 1-53, wherein the cellulosic suspension further comprises a supplemental solvent comprising water, methanol, ethanol, isopropanol, tert-butanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof.

55. The method of claim 54, wherein the supplemental solvent comprises water in an amount of up to about 70 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

56. The method of claim 54, wherein the supplemental solvent comprises water in an amount of from about 5 mol% to about 60 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

57. The method of claim 54, wherein the supplemental solvent comprises water in an amount of from about 10 mol% to about 50 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

58. The method of any one of claims 54-57, wherein the supplemental solvent comprises methanol, ethanol, isopropanol, tert-butanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof in an amount of up to 50 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

59. The method of any one of claims 54-57, wherein the supplemental solvent comprises methanol, ethanol, isopropanol, tert-butanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof in an amount of from about 2 mol% to about 40 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

60. The method of any one of claims 54-57, wherein the supplemental solvent comprisesATTORNEY DOCKET NO. 331903-2010 methanol, ethanol, isopropanol, tert-butanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof in an amount of from about 4 mol% to about 30 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

61. The method of any one of claims 54-57, wherein the supplemental solvent comprises methanol, ethanol, isopropanol, tert-butanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof in an amount of up to about 50 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

62. The method of any one of claims 54-57, wherein the supplemental solvent comprises methanol, ethanol, isopropanol, tert-butanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof in an amount of from about 2 mol% to about 40 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

63. The method of any one of claims 54-57, wherein the supplemental solvent comprises methanol, ethanol, isopropanol, tert-butanol, isobutanol, a polyol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof in an amount of from about 4 mol% to about 30 mol% of the combined amount of Lewis acid and Lewis base present in the first solvent.

64. The method of any one of claims 1-63, wherein the cellulose feedstock comprises lignocellulosic biomass.

65. The method of any one of claims 1-64, wherein the cellulose feedstock comprises woody biomass.

66. The method of any one of claims 1-65, wherein the cellulose feedstock comprises bacterial cellulose.

67. The method of any one of claims 1-66, wherein the cellulose feedstock comprises nanocellulose.

68. The method of any one of claims 1-67, wherein the cellulose feedstock comprises algal biomass.

69. The method of claim 68, wherein the algal biomass comprises brown algae.

70. The method of claim 69, wherein the algal biomass comprises algae of the Laminaria genus.

71. The method of claim 70, wherein the algal biomass comprises algae of the Laminaria hyperborea species.

72. The method of claim 70 or claim 71 , wherein the algal biomass comprises algae of theATTORNEY DOCKET NO. 331903-2010Laminaria japonica species.

73. The method of any one of claims 70-72, wherein the algal biomass comprises algae of the Laminaria digitata species.

74. The method of any one of claims 69-73, wherein the algal biomass comprises algae of the Sargassum genus.

75. The method of claim 74, wherein the algal biomass comprises algae of the Sargassum natans species.

76. The method of claim 74 or claim 75, wherein the algal biomass comprises algae of the Sargassum fluitans species.

77. The method of any one of claims 68-76, wherein the algal biomass comprises algae of the Posidonia oceanica species.

78. The method of any one of claims 68-76, wherein the algal biomass comprises algae of the Saccharina latissimi species.

79. The method of any one of claims 68-77, wherein the algal biomass comprises algae of the Chlorophyceae class.

80. The method of claim 79, wherein the algal biomass comprises green algae.

81. The method of claim 80, wherein the algal biomass comprises algae of the Cladophora glomerata species.

82. The method of any one of claims 79-81 , wherein the algal biomass comprises algae of the Ulva lactuca species.

83. The method of any one of claims 79-82, wherein the algal biomass comprises algae of the Valonia genus.

84. The method of any one of claims 68-83, wherein the algal biomass comprises red algae.

85. The method of claim 84, wherein the algal biomass comprises algae of the Gelidium elegans species.

86. The method of any one of claims 68-85, wherein the algal biomass comprises microalgae.

87. The method of claim 86, wherein the algal biomass comprises algae of the Nannochloropsis oceanica species.

88. The method of claim 86 or claim 87, wherein the algal biomass comprises algae of theATTORNEY DOCKET NO. 331903-2010Chlorella vulgaris species.

89. The method of any one of claims 86-88, wherein the algal biomass comprises dinoflagellate.

90. The method of any one of claims 68-89, wherein the algal biomass comprises cyanobacteria.

91. The method of any one of claims 1-90, wherein the cellulose feedstock comprises a marine organism biomass of the Ascidiacea class.

92. The method of any one of claim 91 , wherein the marine organism biomass of the Ascidiacea class comprises a marine organism of the Halocynthia roretzi species.

93. The method of any one of claims 1-90, wherein the cellulose feedstock is a never-dried cellulose feedstock.

94. The method of any one of claims 1-93, wherein the weight ratio of cellulose feedstock to first solvent in the cellulosic suspension is about 1:5 to about 1:150.

95. The method of any one of claims 1-93, wherein the weight ratio of cellulose feedstock to first solvent in the cellulosic suspension is about 1:7 to about 1:100.

96. The method of any one of claims 1-95, wherein the cellulose feedstock and first solvent are combined at a temperature of about 15 °C to about 170 °C.

97. The method of any one of claims 1-95, wherein the cellulose feedstock and first solvent are combined at a temperature of about 20 °C to about 165 °C.

98. The method of any one of claims 1-95, wherein the cellulose feedstock and first solvent are combined at a temperature of about 20 °C to about 150 °C.

99. The method of any one of claims 1-98, wherein the cellulosic suspension is mixed under high shear for about 5 minutes to about 60 minutes.

100. The method of any one of claims 1-98, wherein the cellulosic suspension is mixed under high shear for about 10 minutes to about 50 minutes.

101. The method of any one of claims 1-98, wherein the cellulosic suspension is mixed under high shear for about 20 minutes to about 40 minutes.

102. The method of any one of claims 1-101 , wherein the reaction treatment comprises incubation of the cellulosic suspension at a temperature of at least 30 °C.

103. The method of claim 102, wherein the cellulosic suspension is incubated at a temperature of about 30 °C to about 170 °C.ATTORNEY DOCKET NO. 331903-2010104. The method of claim 102, wherein the cellulosic suspension is incubated at a temperature of about 40 °C to about 160 °C.

105. The method of claim 102, wherein the cellulosic suspension is incubated at a temperature of about 50 °C to about 150 °C.

106. The method of any one of claims 102-105, wherein the cellulosic suspension is incubated for about 4 minutes to about 8 hours.

107. The method of any one of claims 102-105, wherein the cellulosic suspension is incubated for about 7 minutes to about 7 hours.

108. The method of any one of claims 102-105, wherein the cellulosic suspension is incubated for about 10 minutes to about 6 hours.

109. The method of any one of claims 102-108, wherein the cellulosic suspension is incubated at a pressure below 1 atm.

110. The method of any one of claims 1-109, wherein the second solvent comprises water, methanol, ethanol, isopropanol, tert-butanol, isobutanol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof.

111. The method of any one of claims 1-110, wherein the third solvent comprises water, methanol, ethanol, isopropanol, tert-butanol, isobutanol, gammavalerolactone, dimethyl sulfoxide, or any combination thereof.

112. The method of any one of claims 1-111 , wherein the intermediate cellulosic suspension comprises from about 5 wt% to about 45 wt% of the treated cellulose material.

113. The method of any one of claims 1-111 , wherein the intermediate cellulosic suspension comprises from about 7 wt% to about 40 wt% of the treated cellulose material.

114. The method of any one of claims 2-113, further comprising: combining the intermediate cellulosic suspension with a fourth solvent in a weight ratio of about 1 :0.5 to about 1 :200, thereby forming a second cellulosic suspension; and repeating the steps of mixing, treating, diluting, washing, and draining, thereby forming a second intermediate cellulosic suspension; wherein the fourth solvent comprises a second Lewis base and a second Lewis acid in an about 10:2 to about 1 :9 molar ratio of second Lewis base to second Lewis acid.

115. The method of any one of claims 2-114, further comprising defibril lating the intermediate cellulosic suspension or second intermediate cellulosic suspension, thereby forming aATTORNEY DOCKET NO. 331903-2010 nanocellulose material.

116. The method of claim 115, wherein the nanocellulose material comprises cellulose nanocrystals, cellulose nanofibers, or a combination thereof.

117. The method of claim 115 or claim 116, wherein the cellulose material is defibrillated using a high-pressure homogenizer, a microfluidizer, griding, ball-milling, refining, steam explosion, extrusion, aqueous counter collision, ultrasonication, any sequence thereof, or any combination thereof.

118. The method of any one of claims 115-117, further comprising mixing the intermediate cellulosic suspension or second intermediate cellulosic suspension under high shear prior to defibrillating.

119. The method of any one of claims 115-118, wherein the intermediate cellulosic suspension or second intermediate cellulosic suspension is mixed with water prior to defibrillating, thereby forming a diluted cellulosic suspension.

120. The method of claim 119, wherein the diluted cellulosic suspension comprises from about 80% to about 90% water by weight.

121. The method of claim 119, wherein the diluted cellulosic suspension comprises from about 90% to about 99% water by weight.

122. The method of claim 119, wherein the diluted cellulosic suspension comprises from 98% to 99.9% water by weight.

123. The method of claim 119, wherein the diluted cellulosic suspension comprises from 98.3% to 99.7% water by weight.

124. The method of claim 119, wherein the diluted cellulosic suspension comprises from 98.5% to 99.5% water by weight.

125. A composition comprising the nanocellulose material produced by the method of any one of claims 115-124.

126. The composition of claim 125, wherein the composition acts as a dispersant.

127. A filament comprising the composition of claim 125.

128. A yarn comprising the filament of claim 127.

129. The yarn of claim 128, wherein the yarn is a composite or blended yarn.ATTORNEY DOCKET NO. 331903-2010130. A film comprising the composition of claim 125.

131. A sheet comprising the composition of claim 125.

132. A cast material comprising the composition of claim 125.

133. A molded material comprising the composition of claim 125.

134. An article comprising the nanocellulose material produced by the method of any one of claims 115-124.

135. The article of claim 134, wherein the article comprises coatings, films fibers, filaments, paints, cosmetics, composites, drug delivery systems, or any combination thereof.

136. An article comprising the filament of claim 127.

137. The article of claim 136, wherein the article is a fabric.

138. The article of claim 136, wherein the article is a textile material.

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