Aqueous nanocellulose dispersion of plant and tunicate derived cellulose

Abstract

The present application relates to aqueous nanocellulose dispersions of plant and tunicate derived cellulose, methods of making and uses thereof. In particular, the present application relates the use of the dispersions in additive manufacturing to achieve high-performance, bio-derived polymer nanocomposites by, for example, improving the rheology of the ink.

Description

1 AQUEOUS NANOCELLULOSE DISPERSION OF PLANT AND TUNICATE DERIVED CELLULOSE FIELD

[0001] The present application relates to aqueous nanocellulose dispersions of plant and tunicate derived cellulose, methods of making and uses thereof. BACKGROUND

[0002] Cellulose nanocrystals (CNCs), carbon nanotubes (CNTs), hydroxyapatite (HA), and graphene particles are widely used fillers for additive manufacturing (AM) of nanocomposites [1]. CNCs have a high surface area, high on-axis stiffness (Young’s modulus of 100 to 143 GPa), and tensile strength in the range of 7.5–7.7 GPa [2–4], and can be used as nanofiller materials for polymer matrix nanocomposites. In comparison to other nanofillers, such as CNTs [5], carbon nanofibers [6,7], and graphene [8], CNCs have several advantages, including green processing, sustainability, renewability, and low production cost. Moreover, CNCs offer carbohydrate-based surface chemistry, which can readily be modified with desired functional groups. Furthermore, due to the isolation process, wood-CNCs (W-CNC)s have a wide range of aspect ratio distributions that create inconsistencies in W-CNC-based nanocomposites

[12] . It has been suggested that the higher aspect ratio of tunicate-CNCs (T-CNC)s may enhance the stress transfer in composites and improve the mechanical properties

[13] . For example, nematic films with increased mechanical properties were prepared by assembling W-CNC with T-CNC

[14] . Such mixtures have shown increased stiffness in polymer matrix composites compared to either individual CNC source

[15] .

[0003] Masked stereolithography (mSLA) is a high-resolution additive manufacturing process where light-sensitive liquid resin is solidified (cured) via selective exposure to light, for example ultraviolet (UV), in a layer-by-layer process.

[0004] Traditional mSLA-printed bio-derived thermoset polymer matrices are highly crosslinked and thus generally brittle

[18] . They also feature low glass transition temperatures, which causes them to soften at moderate temperatures. Their unbalanced stiffness / toughness / heat stability profile limits their application, especially in rapid prototyping applications

[19] . Improvement of the mechanical and physical properties can be achieved by the addition of filler particles such as glass fibers, silica, and others. However, it has been challenging to maintain a CA 3302214 Date reçue / Received date 2026-02-18 2 high level of transparency and high resolution in the mSLA printing process as the filler particles tend to absorb and / or scatter light. The use of nanoscale fillers is a viable solution to that issue.

[0005] However, the dispersion of CNCs into various media as reinforcement is a technological challenge

[20] . They tend to form agglomerates due to their surface charge and polarity. The presence of negatively charged sulfate ester moieties on the CNC surfaces may help with dispersion in polar aprotic solvents

[21] , but the individual particle dispersion in nonpolar solvents is limited. The higher aspect ratio also affects the formation of more agglomerates. Lack of dispersion and resulting agglomerations of nano-scale reinforcements result in stress concentrations, degrading mechanical performance, especially strength, rather than achieving the theoretical improvements expected due to the mechanical properties of the filler and the high surface-to-volume ratios. Dispersion and mechanical properties depend on the compatibility of the filler with the resin, i.e. the interfacial interactions / bonding.

[0006] The polarity of the CNC particles is often different from the 3D printable polymer resins. Previous works demonstrated that nanoscale uniform dispersion of CNCs and interfacial bonding between hydrophilic CNC and hydrophilic / hydrophobic resin matrices were attained through effective surface modification to improve compatibility [22–25].

[0007] Tunicate CNCs (T-CNCs), derived from an invasive marine species of tunicates, have a higher aspect ratio (~50–100) and crystallinity (>90%) than W-CNCs [9–11]. Therefore, there is a need to explore the properties of the tunicate derived cellulose (T-CNC) and applications thereof. SUMMARY

[0008] The present application relates to nanocellulose dispersed resin compositions containing tunicate derived cellulose nanocrystals (T-CNC), which may optionally be surface modified. Suitable resins for these compositions include, for example, photopolymer resins. The nanocellulose dispersed resin compositions can be used for example in additive manufacturing of polymer nanocomposites. Additionally, the present application relates to ink compositions containing nanofiller dispersed in a photopolymer resin and a that is dispersed in the resin and includes T-CNC. The ink can be used for example in additive manufacturing.

[0009] The incorporation of T-CNC yields superior resin and ink properties relative to plant derived cellulose establishing it as a high-performance alternative to commercially available plant derived cellulose. CA 3302214 Date reçue / Received date 2026-02-18 3

[0010] The present application relates to aqueous nanocellulose dispersion comprising a mixture of a plant derived nanocellulose (P-CNC) and a tunicate derived nanocellulose (T-CNC) in water, wherein the P-CNC and T-CNC are optionally surface modified with a surface modifier. This dispersion is compatible with hydrophobic and hydrophilic media and can be used, for example, in additive manufacturing to achieve high-performance, bio-derived polymer nanocomposites by, for example, improving the rheology of the ink. The present application also relates to bio-derived polymer resin matrices, as green alternatives to nonrenewable petroleumbased materials, to fabricate mechanically superior (high strength, high fracture toughness) nanocomposites thereby improving the strength, stiffness, and toughness of bio-derived thermoset polymer matrices. The present application demonstrates that T-CNC may complement or outperform commercially available W-CNCs in the growing global demand.

[0011] Accordingly, the present application discloses an aqueous nanocellulose dispersion comprising: a mixture of a plant derived nanocellulose (P-CNC) and a tunicate derived nanocellulose (T-CNC) in water, wherein the P-CNC and T-CNC are optionally surface modified with a surface modifier.

[0012] In some embodiments, the P-CNC is a wood derived nanocellulose (W-CNC).

[0013] The mixture of the P-CNC and T-CNC is typically a hybrid mixture. It is hybrid because it is from two different sources, a plant-derived source and a tunicate derived cellulose.

[0014] In some embodiments, both the P-CNC and T-CNC are surface modified with a surface modifier.

[0015] The present application also discloses a nanocellulose dispersed resin composition comprising: a resin; and a mixture of a plant derived cellulose nanocrystals (P-CNC) and a tunicate derived cellulose nanocrystals (T-CNC), wherein the P-CNC and T-CNC are optionally surface modified with a surface modifier, and wherein the mixture of the P-CNC and T-CNC is dispersed in the resin thereby forming the nanocellulose dispersed resin composition.

[0016] In some embodiments, the P-CNC is a wood derived nanocellulose (W-CNC).

[0017] In some embodiments, the mixture of the P-CNC and T-CNC is a hybrid mixture. CA 3302214 Date reçue / Received date 2026-02-18 4

[0018] In some embodiments, both the P-CNC and T-CNC are surface modified with a hydrophobic surface modifier.

[0019] The present application also discloses use of the nanocellulose dispersed resin composition of the application in additive manufacturing of polymer nanocomposites.

[0020] The present application discloses an ink composition for additive manufacturing comprising: a photopolymer resin; and a nanofiller, wherein the nanofiller is a mixture of a plant derived cellulose nanocrystals (P-CNC) and tunicate derived cellulose nanocrystals (T-CNC), wherein the P-CNC and T-CNC are optionally surface modified with a surface modifier, and wherein said nanofiller is dispersed in the photopolymer resin.

[0021] In some embodiments, the photopolymer resin is a bio-based photopolymer resin.

[0022] In some embodiments, the bio-based photopolymer resin comprises soybean oil.

[0023] In some embodiments, the bio-based photopolymer resin comprises a methacrylated epoxidized soybean oil (mAESO).

[0024] In some embodiments, the P-CNC is a wood derived nanocellulose (W-CNC).

[0025] In some embodiments, the mixture of the P-CNC and T-CNC is a hybrid mixture.

[0026] In some embodiments, both of the P-CNC and T-CNC are surface modified with a hydrophobic surface modifier.

[0027] The present application also includes a polymer nanocomposite manufactured via additive manufacturing by curing the ink composition of the present application.

[0028] The present application also includes a method of printing 3D object via additive manufacturing comprising using an ink composition of the present application.

[0029] The present application includes a method of making the aqueous nanocellulose dispersion and the nanocellulose dispersed resin of the present application.

[0030] The present application also includes a nanocellulose dispersed resin composition comprising: a resin; and CA 3302214 Date reçue / Received date 2026-02-18 5 a tunicate derived cellulose nanocrystals (T-CNC), optionally surface modified with a surface modifier, and wherein the T-CNC is dispersed in the resin thereby forming the nanocellulose dispersed resin composition.

[0031] The present application also includes an ink composition for additive manufacturing comprising: a photopolymer resin; and a nanofiller, wherein the nanofiller comprises tunicate derived cellulose nanocrystals (T-CNC), wherein the T-CNC are optionally surface modified with a surface modifier, and wherein said nanofiller is dispersed in the photopolymer resin.

[0032] Other features and advantages of the present application will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating embodiments of the application, are given by way of illustration only and the scope of the claims should not be limited by these embodiments but should be given the broadest interpretation consistent with the description as a whole. DRAWINGS

[0033] Certain embodiments of the application will now be described in greater detail with reference to the attached drawings in which:

[0034] Figure 1. Schematic of the reaction between CNC and methacrylic anhydride (MAA) in exemplary embodiments of the application.

[0035] Figure 2. Schematic of the reaction between CNC and glycidyl methacrylate (GMA) in exemplary embodiments of the application.

[0036] Figure 3. 3D printed tensile and fracture testing specimens of the exemplary 1wt% W-CNC / mAESO / HEMA nanocomposite of the application.

[0037] Figure 4: FTIR spectra of raw and modified wood-cellulose nanocrystals (W-CNC) using methacrylic anhydride (CelMA), oleic acid (Cel-Oacid), and oleylamine (cel-OAmine) at the range of 500 – 4000 cm-1 in exemplary embodiments of the application. The curves are as follows (from top to bottom): cel-OAmine, cel-Oacid, celMA and W-CNC. CA 3302214 Date reçue / Received date 2026-02-18 6

[0038] Figure 5. FTIR spectra of raw and modified W-CNC using methacrylic anhydride (CelMA), oleic acid (Cel- Oacid), and oleylamine (cel-OAmine) at the range of 750 – 850 cm-1 in exemplary embodiments of the application.

[0039] Figure 6. FTIR spectra of raw (W-wood and T-tunicate) and GMA-modified WCNCs (WM) and T-CNCs (TM) at the range of 500 – 4000 cm-1 in exemplary embodiments of the application. The curves are as follows (from top to bottom): TM, T, WM and W.

[0040] Figure 7. FTIR spectra of raw (W-wood and T-tunicate) and GMA-modified WCNCs (WM) and T-CNCs (TM) at the range of 1650 – 1800 cm-1 in exemplary embodiments of the application.

[0041] Figure 8. FTIR spectra of raw (W-wood and T-tunicate) and GMA-modified WCNCs (WM) and T-CNCs (TM) at the range of 790 – 830 cm-1 in exemplary embodiments of the application.

[0042] Figure 9. FTIR spectra of raw (W-wood and T-tunicate) and GMA-modified WCNCs (WM) and T-CNCs (TM) at the range of 1600 – 1680 cm-1 in exemplary embodiments of the application.

[0043] Figure 10. Light scattering in W (W-CNC), WM (modified W-CNC), T (T-CNC), and TM (modified T-CNC) at a 1 wt% in water (n=3) in exemplary embodiments of the application.

[0044] Figure 11. Light scattering in W (W-CNC), WM (modified W-CNC), T (T-CNC), and TM (modified T-CNC) at a 0.1 wt% in resin (n=3) in exemplary embodiments of the application.

[0045] Figure 12. Representative plots of shear stress (a) and viscosity (b) vs shear rate of W-CNC and WM-CNC based inks in exemplary embodiments of the application.

[0046] Figure 13. Representative plots of shear stress (a) and viscosity (b) vs shear rate of T- CNC and TM-CNC based inks in exemplary embodiments of the application.

[0047] Figure 14. Representative true stress vs true strain curves from tensile mechanical testing of the mSLA- printed 3 wt% and 5 wt% W-CNC and WM-CNC nanocomposites in exemplary embodiments of the application.

[0048] Figure 15. Representative true stress vs true strain curves from tensile mechanical testing of the mSLA- printed 0.1, 0.25, and 0.5 wt% W-CNC and WM-CNC nanocomposites in exemplary embodiments of the application. CA 3302214 Date reçue / Received date 2026-02-18 7

[0049] Figure 16. Representative true stress vs true strain curves from tensile mechanical testing of the mSLA- printed 0.1, 0.25, and 0.5 wt% T-CNC and TM-CNC nanocomposites in exemplary embodiments of the application.

[0050] Figure 17. Representative true stress vs true strain curves from tensile mechanical testing of the mSLA- printed 0.5 wt% W-CNC, WM-CNC, T-CNC, and TM-CNC nanocomposites in exemplary embodiments of the application.

[0051] Figure 18. SEM images of fracture surfaces of the W-CNC and WM-CNC nanocomposites after tensile testing (low magnification) in exemplary embodiments of the application.

[0052] Figure 19. SEM images of fracture surfaces of the T-CNC and TM-CNC nanocomposite after tensile testing (low magnification) in exemplary embodiments of the application.

[0053] Figure 20. SEM images of fracture surfaces of the W-CNC and WM-CNC nanocomposite after tensile testing (high magnification) in exemplary embodiments of the application.

[0054] Figure 21. SEM images of fracture surfaces of the T-CNC and TM-CNC nanocomposite after tensile testing (high magnification) in exemplary embodiments of the application.

[0055] Figure 22. Representative load versus load-line deflection curves resulting from fracture toughness testing of 3wt% W-CNC and WM-CNC nanocomposites in exemplary embodiments of the application.

[0056] Figure 23. Representative load versus load-line deflection curves for W-CNC and WM-CNC nanocomposites with 0.1, 0.25 and 0.5 wt% loading in exemplary embodiments of the application.

[0057] Figure 24. Representative load versus load-line deflection curves from fracture toughness testing of T-CNC and TM-CNC nanocomposites with 0.1-0.5 wt% loading in exemplary embodiments of the application.

[0058] Figure 25. Representative plots of shear stress (a) and viscosity (b) vs shear rate of T:W hybrids (1 wt% in water) in exemplary embodiments of the application. CA 3302214 Date reçue / Received date 2026-02-18 8

[0059] Figure 26. Representative plots of shear stress (a) and viscosity (b) vs shear rate of T:W hybrids (0.1 wt% in resin) in exemplary embodiments of the application.

[0060] Figure 27. Representative plots of shear stress (a) and viscosity (b) vs shear rate of TM:WM hybrids (0.1 wt% in resin) in exemplary embodiments of the application.

[0061] Other features and advantages of the present disclosure will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating embodiments of the disclosure, are given by way of illustration only and the scope of the claims should not be limited by these embodiments, but should be given the broadest interpretation consistent with the description as a whole. DETAILED DESCRIPTION Definitions

[0062] Unless otherwise indicated, the definitions and embodiments described in this and other sections are intended to be applicable to all embodiments and aspects of the present application herein described for which they are suitable as would be understood by a person skilled in the art.

[0063] The terms "about", “substantially” and “approximately” as used herein mean a reasonable amount of deviation of the modified term such that the end result is not significantly changed. These terms of degree should be construed as including a deviation of at least ±5% of the modified term if this deviation would not negate the meaning of the word it modifies or unless the context suggests otherwise to a person skilled in the art.

[0064] The term “nanocellulose” as used herein refers to cellulose nanofibers and / or cellulose nanocrystals with at least one dimension in the nanoscale, typically the diameter.

[0065] The term “aqueous nanocellulose dispersion of the application” and variations thereof refers to the aqueous nanocellulose dispersion comprising a mixture of optionally surface modified P-CNC and T-CNC as defined in the application.

[0066] The term “nanocellulose dispersed resin composition of the application” and variations thereof refers to the resin comprising a mixture of optionally surface modified P-CNC and T-CNC as defined in the application. CA 3302214 Date reçue / Received date 2026-02-18 9 Compositions of the Application

[0067] The present application relates to nanocellulose dispersed resin compositions with tunicate derived cellulose nanocrystals (T-CNC), which is optionally surface modified. The resins in the compositions can be for example photopolymer resins and said nanocellulose dispersed resin compositions can be used for example in additive manufacturing of polymer nanocomposites. The present application also relates to ink compositions that include photopolymer resins and a nanofiller that is dispersed in the resin and includes T-CNC. The ink can be used for example in additive manufacturing.

[0068] The incorporation of T-CNC yields superior resin and ink properties relative to plant derived cellulose establishing it as a high-performance alternative to commercially available plant derived cellulose.

[0069] The present application includes an aqueous nanocellulose dispersion comprising: a mixture of a plant derived nanocellulose (P-CNC) and a tunicate derived nanocellulose (T-CNC) in water, wherein the P-CNC and T-CNC are optionally surface modified with a surface modifier.

[0070] In some embodiments, plant derived nanocellulose includes but is not limited to natural cellulose obtained from a natural plant raw material such as wood, plant and plant residue. Exemplary plants include but are not limited to grass such as Poaceae, Asteraceae, Orchidaceae, Fabaceae and Rubiaceae, ramie, cotton such as Rosids, jute, hemp such as Cannabaceae, and flax. Exemplary plant residue includes but is not limited to bagasse, potato peel waste, oil palm biomass, cereal straws and the like. Wood includes hardwood such as Angiosperm and includes Oak, Teak, Sapele, Iroko, Meranti, bamboo, kenaf, blue gum, and acacia and softwood such as Gymnosperm and includes pine, cedar, spruce Plant derived nanocellulose can include nanocellulose derived from one or two or more plant nanocellulose sources. The plant nanocellulose can be obtained by any method known in the art.

[0071] In some embodiments, the P-CNC is a wood derived nanocellulose (W-CNC).

[0072] In some embodiments, the tunicate derived nanocellulose is optionally a nanofibrillated cellulose, a nanocrystalline cellulose or a combination thereof. Nanofibrillated cellulose contains both amorphous and crystalline regions, and by substantially removing amorphous regions, for example by acid hydrolysis, nanocrystalline cellulose can be obtained. In some embodiments, the tunicate derived nanocellulose is a nanocrystalline cellulose. CA 3302214 Date reçue / Received date 2026-02-18 10 Tunicate cellulose can be obtained from any known species, such as for example Ascidians. In some embodiments, tunicate derived cellulose is obtained from ciona intestinalis and / or styela clava. Tunicate cellulose can be prepared from tunicate by any known method, for example by a method published by M. J. Dunlop [9].

[0073] T-CNCs have a higher aspect ratio (~50–100) and crystallinity (>90%), compared to P-CNCs which have an aspect ratio of 10–20 and crystallinity (60–80%). In some embodiments, the mixture of the P-CNC and T-CNC is a hybrid mixture. The hybrid mixture is a mixture of plant and tunicate derived cellulose forming a hybrid cellulose having one or more functional and / or a structural properties that are different from that of the individual components. In some embodiments, the hybrid mixture has different rheology, viscosity, average aspect ratio, crystallinity and optical properties when compared to the individual components. In some embodiments, the hybrid mixture has a mixed aspect ratio (low aspect ratio plant derived CNCs and high aspect ratio tunicate derived CNCs).

[0074] In some embodiments, the aspect ratio and the crystallinity of the hybrid mixture is higher than that of the P-CNC alone. In some embodiments, the average aspect ratio of the hybrid mixture is from about 50 to about 70, or about 50. In some embodiments, the average crystallinity of the hybrid mixture is above 80%, or from about 80% to about 95%.

[0075] Properties of the hybrid mixture can be tailored by using various ratios of the PCNC and T-CNC in the hybrid mixture. For example, hybrid mixture of 50:50 ratio of T-CNC to P-CNC results in the CNC having average crystallinity of >80% and average aspect ratio of about 50. The ability to tailor the properties of the hybrid mixture of the present application for the system of interest provides an advantage to the hybrid mixture as it can be incorporated in various systems, such as a polymer matrix and others.

[0076] In some embodiments, high aspect ratio allows to increase the viscosity of the hybrid mixture. In some embodiments, high aspect ratio of the hybrid mixture allows to reach percolation (the ideal loading level for performance enhancement) at lower CNC content then smaller aspect ratio CNCs. In some embodiments, the increased crystallinity produces high tensile modulus / strength of the system of interest when said hybrid mixture is incorporated in said system.

[0077] In some embodiments, the aqueous nanocellulose dispersion of the application is free from polyvinyl alcohol. CA 3302214 Date reçue / Received date 2026-02-18 11

[0078] In some embodiments, the aqueous nanocellulose dispersion of the application is consisting essentially of the P-CNC and T-CNC mixture.

[0079] In some embodiments, the aqueous nanocellulose dispersion of the application is consisting of the P-CNC and T-CNC mixture.

[0080] In some embodiments, the P-CNC and T-CNC are non-surface modified (the surface of the P-CNC and T-CNC is unmodified). The non-surface modified P-CNC and T-CNC are dispersed in water.

[0081] In some embodiments, at least one of the P-CNC and T-CNC is surface modified with a surface modifier. In some embodiments, one of the P-CNC and T-CNC is surface modified with a surface modifier. In some embodiments, both the P-CNC and T-CNC are surface modified with a surface modifier.

[0082] The surface modifier can include a hydrophilic or a hydrophobic functional group and thus the surface modifier can be a hydrophilic or a hydrophobic surface modifier. In some embodiments, hydroxyl groups present on the surface of the cellulose are modified by reacting the cellulose with the surface modifier. Adding suitable functional groups to the surface of the CNCs improves compatibility of the cellulose with hydrophilic or hydrophobic medium and reduces the size of agglomerates in the medium.

[0083] In some embodiments, at least one of the P-CNC and T-CNC is surface modified with a hydrophobic surface modifier. In some embodiments, when at least of the P-CNC and TCNC is surface modified with a hydrophobic surface modifier, the resulting mixture of the P-CNC and T-CNC is dispersible in a hydrophobic medium. Thus, in some embodiments, surface modification of the at least one of the P-CNC and T-CNC with hydrophobic surface modifier enhances the compatibility of the mixture of the P-CNC and T-CNC with a hydrophobic medium. In some embodiments, the hydrophobic medium is a hydrophobic polymer. In some embodiments, the hydrophobic polymer is a resin.

[0084] In some embodiments, at least one of the P-CNC and T-CNC is surface modified with a hydrophilic surface modifier. Any hydrophilic surface modifier which can form covalent bonds with the surface hydroxyl groups present in cellulose can be used. For example, oils, surfactants and polymers which can form covalent bonds with the surface hydroxyl groups by esterification, grafting, sulfonation, silylation, transesterification and adsorption can be used as hydrophilic surface modifiers. Exemplary hydrophilic surface modifiers include, but are not limited to silanes, methacrylates, folic acid, cyclodextrin, octenyl succinic anhydride, poly(lactic CA 3302214 Date reçue / Received date 2026-02-18 12 acid), poly(dl-lactide-co-glycolide), chitosan, cetyltrimethylammonium bromide, rarasaponins and the like.

[0085] In some embodiments, the mixture of the P-CNC and T-CNC is dispersible in a hydrophilic medium.

[0086] In some embodiments, the surface modifier comprises an oleate group, such as for example oleic acid or oleylamine.

[0087] In some embodiments, the surface modifier comprises a methacrylate group. In some embodiments, the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA). In some embodiments, the surface modifier is GMA.

[0088] In some embodiments, P-CNC is W-CNC and W-CNC is non-surface modified and T-CNC is surface modified with GMA. In some embodiments, P-CNC is W-CNC and both WCNC and T-CNC are surface modified with GMA.

[0089] In some embodiments, the mixture of the P-CNC and T-CNC is present in the aqueous nanocellulose dispersion in an amount of about 0.1 wt% to about 10 wt% based on the total weight of the dispersion. In some embodiments, the mixture of the P-CNC and T-CNC is present in the aqueous nanocellulose dispersion in an amount of about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 3 wt%, about 5 wt%, about 8 wt% and values therebetween, based on the total weight of the dispersion.

[0090] In some embodiments, the ratio of the P-CNC to the T-CNC in the aqueous nanocellulose dispersion is about 9:1 to about 1:9 weight ratio. In some embodiments, the ratio of the P-CNC to the T-CNC in the aqueous nanocellulose dispersion is about 3:1, about 1:1, about 1:3 weight ratio and values therebetween.

[0091] In some embodiments, the ratio of the P-CNC to the T-CNC in the aqueous nanocellulose dispersion is greater than 1.5. In some embodiments, the ratio of the P-CNC to the T-CNC in the aqueous nanocellulose dispersion is about 3:2, about 4:1, about 9:1 weight ratio and values therebetween.

[0092] In some embodiments, the T-CNC is included in the aqueous nanocellulose dispersion as a dispersion of the T-CNC in water (the CNC is included in the dispersion in a wet form). The T-CNC is included in the aqueous nanocellulose dispersion in a wet form to avoid irreversible aggregation of cellulose particles (hornification). In some embodiments, the T-CNC is present in said dispersion (dispersion of the T-CNC in water) in an amount of about 0.1 wt% CA 3302214 Date reçue / Received date 2026-02-18 13 to about 8 wt% based on the total weight of the water dispersion (dispersion of the T-CNC in water). In some embodiments, the T-CNC is present in the dispersion (dispersion of the T-CNC in water) in an amount of about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 5 wt%, or values therebetween based on the total weight of the water dispersion (dispersion of the T-CNC in water).

[0093] In some embodiments, the P-CNC is included in the aqueous nanocellulose dispersion as a dispersion of the P-CNC in water. In some embodiments, the P-CNC is present in said dispersion (dispersion of the P-CNC in water) in an amount of about 1 wt% to about 15 wt% based on the total weight of the water dispersion (dispersion of the P-CNC in water). In some embodiments, the P-CNC is present in the dispersion (dispersion of the P-CNC in water) in an amount of about 1 wt%, about 5 wt%, about 10 wt% or values therebetween based on the total weight of the water dispersion (dispersion of the P-CNC in water).

[0094] In some embodiments, the rheological behavior of the aqueous nanocellulose dispersion of the present application fits Herschel-Bulkley model with yield shear stress at low shear rates and shear thinning trend with increasing shear rates. In some embodiments, viscosity values of the dispersion decrease as the shear rates increase. Thus, in some embodiments, the aqueous nanocellulose dispersion of the present application is a Herschel- Bulkley fluid. In some embodiments, the aqueous nanocellulose dispersion of the present application has a shear yield strength of below 15000mPa. In some embodiments, the aqueous nanocellulose dispersion of the present application has a shear yield strength between about 5 mPa and about 10000 mPa, about 6000mPa, about 4000mPa, about 1500mPa, about 100mPa, about 500mPa, about 100mPa, about 20mPa and values therebetween. In some embodiments, the aqueous nanocellulose dispersion of the present application has a shear yield strength of below 15000mPa, and the P-CNC and T-CNC are non-surface modified. In some embodiments, the shear yield strength is below 15000mPa or below 10000 mPa for aqueous nanocellulose dispersion containing 0.5 to 2% hybrid mixture, or about 1% hybrid mixture and the P-CNC and T-CNC are non-surface modified. In some embodiments, the shear yield strength is below 500, or below 100 mPa for aqueous nanocellulose dispersion containing P-CNC to the T-CNC ratio of greater than 1.5. In some embodiments, the shear yield strength is below 500, or below 100 mPa for aqueous nanocellulose dispersion containing 0.5 to 2% hybrid mixture, or about 1% hybrid mixture. The shear yield strength was measured using a rheometer. Measurements were conducted at room temperature under shear strain rates from 0.01 s−1 and 100 s−1. CA 3302214 Date reçue / Received date 2026-02-18 14

[0095] In some embodiments, increased amount of the P-CNC in the mixture decreases the yield shear stress and the viscosity of the aqueous nanocellulose dispersion of the present application. Thus, the hybrid mixture of the P-CNC and T-CNC reduces the yield shear stress and the viscosity of the aqueous nanocellulose dispersion of the present application. In some embodiments, the hybrid mixture of the application has a nonlinear correlation between the ratios of P-CNC and T-CNC in the mixture and the sheer stress. This is surprising, as a linear relationship between the hybrid CNC ratio and the sheer stress was expected. An advantage of the hybrid mixture of the application is the tailorable sheer stress of the hybrid mixture compared to the two CNC sources individually.

[0096] The present application includes an aqueous nanocellulose dispersion consisting essentially of a mixture of a plant derived nanocellulose (P-CNC) and a tunicate derived nanocellulose (T-CNC) in water, wherein the P-CNC and T-CNC are optionally surface modified with a surface modifier.

[0097] The present application also includes an aqueous nanocellulose dispersion consisting of a mixture of a plant derived nanocellulose (P-CNC) and a tunicate derived nanocellulose (T-CNC) in water, wherein the P-CNC and T-CNC are optionally surface modified with a surface modifier.

[0098] The present application also includes a nanocellulose dispersed resin composition comprising: a resin; and a mixture of a plant derived cellulose nanocrystals (P-CNC) and a tunicate derived cellulose nanocrystals (T-CNC), wherein the P-CNC and T-CNC are optionally surface modified with a surface modifier, and wherein the mixture of the P-CNC and T-CNC is dispersed in the resin thereby forming the nanocellulose dispersed resin composition.

[0099] In some embodiments, the P-CNC is a wood derived nanocellulose (W-CNC).

[00100] In some embodiments, the mixture of the P-CNC and T-CNC is a hybrid mixture.

[00101] In some embodiments, the P-CNC and T-CNC are non-surface modified (the surface is unmodified).

[00102] In some embodiments, at least one of the P-CNC and T-CNC is surface modified with a hydrophobic surface modifier. In some embodiments, one of the P-CNC and T-CNC is surface modified with a hydrophobic surface modifier. In some embodiments, both of the P-CNC CA 3302214 Date reçue / Received date 2026-02-18 15 and T-CNC are surface modified with a hydrophobic surface modifier. In some embodiments, the resulting mixture of the P-CNC and T-CNC is dispersible in the resin. Thus, in some embodiments, surface modification of the at least one of the P-CNC and T-CNC with hydrophobic surface modifier enhances the compatibility of the mixture of the P-CNC and TCNC with the resin.

[00103] Hydrophobic surface modifier can be any hydrophobic surface modifier which can form covalent bonds with the surface hydroxyl groups present in cellulose. Exemplary hydrophobic surface modifiers include but are not limited to methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, glycidyl methacrylate and the like.

[00104] In some embodiments, the surface modifier comprises a methacrylate group. In some embodiments, the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA). In some embodiments, the surface modifier is GMA.

[00105] In some embodiments, P-CNC is W-CNC and both W-CNC and T-CNC are surface modified. In said embodiments, both W-CNC and T-CNC are surface modified with GMA.

[00106] In some embodiments, the mixture of the P-CNC and T-CNC is present in the nanocellulose dispersed resin in an amount of about 0.1 wt% to about 10 wt% based on the total weight of the nanocellulose dispersed resin composition. In some embodiments, the mixture of the P-CNC and T-CNC is present in the nanocellulose dispersed resin in an amount of about 0.1 wt%, about 0.25 wt%, about 0.5 wt%, about 1 wt%, about 3 wt%, about 5 wt%, about 8 wt% and values therebetween, based on the total weight of the nanocellulose dispersed resin composition.

[00107] In some embodiments, the ratio of the P-CNC to the T-CNC in the resin is about 9:1 to about 1:9 weight ratio. In some embodiments, the ratio of the P-CNC to the T-CNC in the resin is about 3:1, about 1:1, about 1:3 weight ratio and values therebetween.

[00108] In some embodiments, the ratio of the P-CNC to the T-CNC in the resin is greater than 1.5. In some embodiments, the ratio of the P-CNC to the T-CNC in the resin is about 3:2, about 4:1, about 9:1 weight ratio and values therebetween.

[00109] In some embodiments, the T-CNC is included in the resin as a dispersion of the TCNC in water (in a wet form). The T-CNC is included in the resin in a wet form to avoid irreversible aggregation of cellulose particles (hornification). In some embodiments, the T-CNC is present in said dispersion (dispersion of the T-CNC in water) in an amount of about 0.1 wt% CA 3302214 Date reçue / Received date 2026-02-18 16 to about 8 wt% based on the total weight of the water dispersion (dispersion of the T-CNC in water). In some embodiments, the T-CNC is present in the dispersion (dispersion of the T-CNC in water) in an amount of about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 5 wt%, or values therebetween based on the total weight of the water dispersion (dispersion of the T-CNC in water).

[00110] In some embodiments, the P-CNC is included in the resin as a dispersion of the P-CNC in water. In some embodiments, the P-CNC is present in said dispersion (dispersion of the P-CNC in water) in an amount of about 1 wt% to about 15 wt% based on the total weight of the water dispersion (dispersion of the P-CNC in water). In some embodiments, the P-CNC is present in the dispersion (dispersion of the P-CNC in water) in an amount of about 1 wt%, about 5 wt%, about 10 wt% or values therebetween based on the total weight of the water dispersion (dispersion of the P-CNC in water).

[00111] In some embodiments, the resin is a photopolymer resin. In some embodiments, the resin is a bio-based resin.

[00112] In some embodiments, the mixture of the P-CNC and T-CNC is dispersed in the resin, thereby forming a homogenous nanocellulose dispersed resin composition.

[00113] In some embodiments, the rheological behavior of the nanocellulose dispersed resin composition of the present application fits Herschel-Bulkley model with yield shear stress at low shear rates and shear thinning trend with increasing shear rates. In some embodiments, viscosity values of the composition decrease as the shear rates increase. Thus, in some embodiments, the nanocellulose dispersed resin composition of the present application is a Herschel-Bulkley fluid. In some embodiments, the nanocellulose dispersed resin composition of the present application has a shear yield strength of below 18000mPa. In some embodiments, the nanocellulose dispersed resin composition of the present application has a shear yield strength between about 500mPa and 15000mPa, about 500 mPa and about 3000 mPa, about 15000mPa, about 12000mPa, about 8000mPa, about 4000mPa, about 2500mPa, about 2000mPa, about 1500mPa, about 1000mPa, about 500mPa and values therebetween. In some embodiments, the shear yield strength is below 2000 mPa or below 8000mPa for dispersion containing P-CNC to the T-CNC ratio of greater than 1.5. In some embodiments, the shear yield strength is below 2000 mPa or below 8000mPa for dispersion containing 0.1 to 5 % hybrid mixture or about 0.1% hybrid mixture. In some embodiments, the shear yield strength is below 3000 mPa, the P-CNC and the T-CNC are surface modified and optionally the dispersion CA 3302214 Date reçue / Received date 2026-02-18 17 comprises 0.1 to 5 % hybrid mixture or about 0.1% hybrid mixture. In some embodiments, the shear yield strength is below 2000 mPa for dispersion containing P-CNC to the T-CNC ratio of greater than 1.5, the P-CNC and the T-CNC are surface modified and optionally the dispersion comprises 0.01 % hybrid mixture. In some embodiments, the shear yield strength is below 15000 mPa, the P-CNC and the T-CNC are non-surface modified and optionally the dispersion comprises 0.1 to 5 % hybrid mixture or about 0.1% hybrid mixture. In some embodiments, the shear yield strength is below 5000 mPa for dispersion containing P-CNC to the T-CNC ratio of greater than 1.5, the P-CNC and the T-CNC are non-surface modified and optionally the dispersion comprises 0.1 to 5 % hybrid mixture or about 0.1% hybrid mixture.

[00114] In some embodiments, increased amount of the P-CNC in the mixture decreases the yield shear stress and the viscosity of the nanocellulose dispersed resin composition of the present application. Thus, the hybrid mixture of the P-CNC and T-CNC reduces the yield shear stress and the viscosity of the nanocellulose dispersed resin composition of the present application. In some embodiments, the hybrid mixture of the application has a nonlinear correlation between the ratios of P-CNC and T-CNC in the mixture and the sheer stress. This is surprising, as a linear relationship between the hybrid CNC ratio and the sheer stress was expected. An advantage of the hybrid mixture of the application is the tailorable sheer stress of the hybrid mixture compared to the two CNC sources individually.

[00115] In some embodiments, the nanocellulose dispersed resin composition of the application is for use in additive manufacturing of polymer nanocomposites.

[00116] The present application also includes an ink composition for additive manufacturing comprising: a photopolymer resin; and a nanofiller, wherein the nanofiller is a mixture of a plant derived cellulose nanocrystals (PCNC) and tunicate derived cellulose nanocrystals (T-CNC), wherein the P-CNC and T-CNC are optionally surface modified with a surface modifier, and wherein said nanofiller is dispersed in the photopolymer resin.

[00117] In some embodiments, the photopolymer resin is a bio-based photopolymer resin.

[00118] In some embodiments, the bio-based photopolymer resin comprises a plant oil. Exemplary plant oils include but are not limited to linseed oil, castor oil, soybean oil, olive oil, cottonseed oil, grape seed oil, palm oil, sunflower seed oil, coconut oil, rapeseed oil and mixtures CA 3302214 Date reçue / Received date 2026-02-18 18 thereof. In some embodiments, the plant oil comprises epoxidized oil oligomers. In some embodiments, the plant oil comprises acrylated epoxidized oil oligomers. In some embodiments, the plant oil comprises methacrylated epoxidized oil oligomers.

[00119] In some embodiments, the bio-based resin comprises soybean oil. In some embodiments, the bio-based resin comprises a methacrylated epoxidized soybean oil (mAESO).

[00120] In some embodiments, the bio-based resin further comprises an additional photocurable monomer. In some embodiments, the photocurable monomer is an acrylate monomer. Exemplary photocurable monomers include but are not limited to hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate and a combination thereof. In some embodiments, the photocurable monomer is 2-hydroxyethyl methacrylate (HEMA).

[00121] In some embodiments, volume ratio of the mAESO to HEMA in the ink composition is about 85:15 to about 98:2 volume ratio. In some embodiments, volume ratio of the mAESO to HEMA in the composition is about 95:5 volume ratio.

[00122] In some embodiments, the ink composition further comprises a photo-initiator. Exemplary photo initiators that can be used in the ink composition of the present application include but are not limited to Irgacure 819, 360, 379, 1800, 1850 and 1870 or a combination thereof. In some embodiments, the photo-initiator is Irgacure 819.

[00123] In some embodiments, the photo-initiator is present in the ink composition in an amount of about 0.05 vol% to about 5 vol% based on the total volume of the photopolymer resin. In some embodiments, the photo-initiator is present in the ink composition in an amount of about 0.05 vol%, about 0.1 vol%, about 0.5 vol%, about 1 vol%, about 3 vol% and values therebetween based on the total volume of the photopolymer resin. In some embodiments, the photo-initiator is present in the ink composition in an amount of about 1 vol% based on the total volume of the photopolymer resin.

[00124] In some embodiments, the ink composition further comprises one or more additives including colorants, such as dyes or pigments or the mixture of pigments and dyes. These colorants can be dispersed or dissolved in the ink composition.

[00125] In some embodiments, the P-CNC is a wood derived nanocellulose (W-CNC).

[00126] In some embodiments, the mixture of the P-CNC and T-CNC is a hybrid mixture. CA 3302214 Date reçue / Received date 2026-02-18 19

[00127] In some embodiments, at least one of the P-CNC and T-CNC is surface modified with a hydrophobic surface modifier. In some embodiments, one of the P-CNC and T-CNC is surface modified with a hydrophobic surface modifier. In some embodiments, both of the P-CNC and T-CNC are surface modified with a hydrophobic surface modifier. In some embodiments, surface modification of the at least one of the P-CNC and T-CNC with hydrophobic surface modifier improves dispersibility of the P-CNC and T-CNC in the resin, thus enhancing the compatibility of the mixture of the P-CNC and T-CNC with the resin.

[00128] In some embodiments, the at least one of the P-CNC and T-CNC is surface modified with a hydrophobic surface modifier containing a chemical group which is similar to the chemical group present in the monomers forming the photopolymer resin. For example, if photopolymer resin is comprised of methacrylate monomers, then methacrylate surface modified CNC surfaces will have good compatibility with said resin.

[00129] In some embodiments, the surface modifier comprises a methacrylate group. In some embodiments, the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA). In some embodiments, the surface modifier is GMA.

[00130] In some embodiments, P-CNC is W-CNC and both W-CNC and T-CNC are surface modified. In said embodiments, both W-CNC and T-CNC are surface modified with GMA.

[00131] In some embodiments, the mixture of the P-CNC and T-CNC is present in the composition in an amount of about 0.1 wt% to about 10 wt% based on the total weight of the composition. In some embodiments, the mixture of the P-CNC and T-CNC is present in the composition in an amount of about 0.1 wt%, about 0.25 wt%, about 0.5 wt%, about 1 wt%, about 3 wt%, about 5 wt%, about 8 wt% and values therebetween, based on the total weight of the composition.

[00132] In some embodiments, the ratio of the P-CNC to the T-CNC in the composition is about 9:1 to about 1:9 weight ratio. In some embodiments, the ratio of the P-CNC to the T-CNC in the resin is about 3:1, about 1:1, about 1:3 weight ratio and values therebetween.

[00133] In some embodiments, the ratio of the P-CNC to the T-CNC in the composition is greater than 1.5. In some embodiments, the ratio of the P-CNC to the T-CNC in the composition is about 3:2, about 4:1, about 9:1 weight ratio and values therebetween.

[00134] In some embodiments, the nanofiller is dispersed in the resin, thereby forming a homogenous ink composition. Homogeneous ink composition provides excellent bonding within CA 3302214 Date reçue / Received date 2026-02-18 20 the resin and between the cellulose and the resin. The bio-derived nanofiller of the present application provides an excellent approach to sustainable and green additive manufacturing of high-performance nanocomposites.

[00135] In some embodiments, the ink composition is a liquid pre-polymer mixture, which is solidified to form a polymer nanocomposite by using for example UV or visible light radiation. In some embodiments, the photopolymer resin is UV curable.

[00136] In some embodiments, the additive manufacturing is masked stereolithography (mSLA).

[00137] In some embodiments, the rheological behavior of the ink composition of the present application fits Herschel-Bulkley model with yield shear stress at low shear rates and shear thinning trend with increasing shear rates. In some embodiments, viscosity values of the ink composition decrease as the shear rates increase. Thus, in some embodiments, the ink composition of the present application is a Herschel-Bulkley fluid. In some embodiments, the ink composition of the present application has a shear yield strength of below 18000mPa. In some embodiments, the ink composition of the present application has a shear yield strength between about 500mPa and 15000mPa, about 500 mPa and about 3000 mPa, about 15000mPa, about 12000mPa, about 8000mPa, about 4000mPa, about 2500mPa, about 2000mPa, about 1500mPa, about 1000mPa, about 500mPa and values therebetween. In some embodiments, the shear yield strength is below 2000 mPa or below 8000mPa for ink composition containing P-CNC to the T-CNC ratio of greater than 1.5. In some embodiments, the shear yield strength is below 2000 mPa or below 8000mPa for ink composition containing 0.1 to 5 % hybrid mixture or about 0.1% hybrid mixture. In some embodiments, the shear yield strength is below 3000 mPa, the P-CNC and the T-CNC are surface modified and optionally the ink composition comprises 0.1 to 5 % hybrid mixture or about 0.1% hybrid mixture. In some embodiments, the shear yield strength is below 2000 mPa for ink composition containing P-CNC to the T-CNC ratio of greater than 1.5, the P-CNC and the T-CNC are surface modified and optionally the ink composition comprises 0.01 % hybrid mixture. In some embodiments, the shear yield strength is below 15000 mPa, the P-CNC and the T-CNC are non-surface modified and optionally the ink composition comprises 0.1 to 5 % hybrid mixture or about 0.1% hybrid mixture. In some embodiments, the shear yield strength is below 5000 mPa for ink composition containing P-CNC to the T-CNC ratio of greater than 1.5, the P-CNC and the T-CNC are non-surface modified and optionally the ink composition comprises 0.1 to 5 % hybrid mixture or about 0.1% hybrid mixture. CA 3302214 Date reçue / Received date 2026-02-18 21

[00138] In some embodiments, increased amount of the P-CNC in the mixture decreases the yield shear stress and the viscosity of the ink composition of the present application. Thus, the hybrid mixture of the P-CNC and T-CNC reduces the yield shear stress and the viscosity of the ink composition of the present application. In some embodiments, the hybrid mixture of the application has a nonlinear correlation between the ratios of P-CNC and T-CNC in the mixture and the sheer stress. This is surprising, as a linear relationship between the hybrid CNC ratio and the sheer stress was expected. An advantage of the hybrid mixture of the application is the tailorable sheer stress of the hybrid mixture compared to the two CNC sources individually.

[00139] In some embodiments, the present application includes a polymer nanocomposite manufactured via additive manufacturing by curing the ink composition of the present application. In some embodiments, the ink composition is cured by using UV radiation.

[00140] In some embodiments, the additive manufacturing is masked stereolithography (mSLA).

[00141] In some embodiments, the present application includes a nanocellulose dispersed resin composition comprising: a resin; and a tunicate derived cellulose nanocrystals (T-CNC), optionally surface modified with a surface modifier, and wherein the T-CNC is dispersed in the resin thereby forming the nanocellulose dispersed resin composition.

[00142] In some embodiments, the composition further comprises plant derived cellulose nanocrystals (P-CNC). In some embodiments, the P-CNC is a wood derived nanocellulose (WCNC). In some embodiments, the P-CNC and T-CNC is a hybrid mixture.

[00143] In some embodiments, the P-CNC and T-CNC are non-surface modified.

[00144] In some embodiments, at least one of the P-CNC and T-CNC is surface modified with a surface modifier. In some embodiments, both the P-CNC and T-CNC are surface modified with a surface modifier. In some embodiments, the surface modifier is hydrophobic surface modifier. In some embodiments, the surface modifier comprises a methacrylate group. In some embodiments, the surface modifier comprises a methacrylate group. In some embodiments, the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA).

[00145] In some embodiments, the composition is free from plant derived cellulose nanocrystals (P-CNC). In some embodiments, the T-CNC is surface modified with a surface CA 3302214 Date reçue / Received date 2026-02-18 22 modifier. In some embodiments, the surface modifier is hydrophobic surface modifier. In some embodiments, the surface modifier comprises a methacrylate group. In some embodiments, the surface modifier comprises a methacrylate group. In some embodiments, the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA).

[00146] In some embodiments, the T-CNC is included in the aqueous nanocellulose dispersion as a dispersion of the T-CNC in water.

[00147] In some embodiments, the resin is a photopolymer resin. In some embodiments, the resin is a bio-based resin.

[00148] In some embodiments, the rheological behavior of the nanocellulose dispersed resin composition of the present application fits Herschel-Bulkley model with yield shear stress at low shear rates and shear thinning trend with increasing shear rates. In some embodiments, viscosity values of the composition decrease as the shear rates increase. Thus, in some embodiments, the nanocellulose dispersed resin composition of the present application is a Herschel-Bulkley fluid.

[00149] In some embodiments, the nanocellulose dispersed resin composition of the application is for use in additive manufacturing of polymer nanocomposites.

[00150] An ink composition for additive manufacturing comprising: a photopolymer resin; and a nanofiller, wherein the nanofiller comprises tunicate derived cellulose nanocrystals (T-CNC), wherein the T-CNC are optionally surface modified with a surface modifier, and wherein said nanofiller is dispersed in the photopolymer resin.

[00151] In some embodiments, the photopolymer resin is a bio-based photopolymer resin. In some embodiments, the bio-based resin comprises soybean oil. In some embodiments, the bio-based resin comprises a methacrylated epoxidized soybean oil (mAESO).

[00152] In some embodiments, the bio-based resin further comprises an additional photocurable monomer. In some embodiments, the photocurable monomer is an acrylate monomer. Exemplary photocurable monomers include but are not limited to hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate and a combination thereof. In some embodiments, the photocurable monomer is 2-hydroxyethyl methacrylate (HEMA). CA 3302214 Date reçue / Received date 2026-02-18 23

[00153] In some embodiments, volume ratio of the mAESO to HEMA in the ink composition is about 85:15 to about 98:2 volume ratio. In some embodiments, volume ratio of the mAESO to HEMA in the composition is about 95:5 volume ratio.

[00154] In some embodiments, the ink composition further comprises a photo-initiator. Exemplary photo initiators that can be used in the ink composition of the present application include but are not limited to Irgacure 819, 360, 379, 1800, 1850 and 1870 or a combination thereof. In some embodiments, the photo-initiator is Irgacure 819.

[00155] In some embodiments, the photo-initiator is present in the ink composition in an amount of about 0.05 vol% to about 5 vol% based on the total volume of the photopolymer resin. In some embodiments, the photo-initiator is present in the ink composition in an amount of about 0.05 vol%, about 0.1 vol%, about 0.5 vol%, about 1 vol%, about 3 vol% and values therebetween based on the total volume of the photopolymer resin. In some embodiments, the photo-initiator is present in the ink composition in an amount of about 1 vol% based on the total volume of the photopolymer resin.

[00156] In some embodiments, the ink composition further comprises one or more additives including colorants, such as dyes or pigments or the mixture of pigments and dyes. These colorants can be dispersed or dissolved in the ink composition.

[00157] In some embodiments, the composition further comprises plant derived cellulose nanocrystals (P-CNC). In some embodiments, the P-CNC is a wood derived nanocellulose (WCNC). In some embodiments, the mixture of the P-CNC and T-CNC is a hybrid mixture.

[00158] In some embodiments, at least one of the P-CNC and T-CNC is surface modified with a surface modifier. In some embodiments, both of the P-CNC and T-CNC are surface modified with a surface modifier. In some embodiments, the surface modifier is hydrophobic surface modifier. In some embodiments, the surface modifier comprises a methacrylate group. In some embodiments, the surface modifier comprises a methacrylate group. In some embodiments, the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA).

[00159] In some embodiments, the composition is free from plant derived cellulose nanocrystals (P-CNC). In some embodiments, the T-CNC is surface modified with a surface modifier. In some embodiments, the surface modifier is hydrophobic surface modifier. In some embodiments, the surface modifier comprises a methacrylate group. In some embodiments, the CA 3302214 Date reçue / Received date 2026-02-18 24 surface modifier comprises a methacrylate group. In some embodiments, the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA).

[00160] In some embodiments, the nanofiller is dispersed in the resin, thereby forming a homogenous ink composition. Homogeneous ink composition provides excellent bonding within the resin and between the cellulose and the resin. The bio-derived nanofiller of the present application provides an excellent approach to sustainable and green additive manufacturing of high-performance nanocomposites.

[00161] In some embodiments, the ink composition is a liquid pre-polymer mixture, which is solidified to form a polymer nanocomposite by using for example UV or visible light radiation. In some embodiments, the photopolymer resin is UV curable.

[00162] In some embodiments, the additive manufacturing is masked stereolithography (mSLA).

[00163] In some embodiments, the rheological behavior of the ink composition of the present application fits Herschel-Bulkley model with yield shear stress at low shear rates and shear thinning trend with increasing shear rates. In some embodiments, viscosity values of the ink composition decrease as the shear rates increase. Thus, in some embodiments, the ink composition of the present application is a Herschel-Bulkley fluid.

[00164] In some embodiments, the present application includes a polymer nanocomposite manufactured via additive manufacturing by curing the ink composition of the present application. In some embodiments, the ink composition is cured by using UV radiation.

[00165] In some embodiments, the additive manufacturing is masked stereolithography (mSLA). Methods of Preparing the Compositions of the Application

[00166] The present application includes a method of making an aqueous nanocellulose dispersion comprising: combining a plant derived nanocellulose (P-CNC) and a tunicate derived nanocellulose (T-CNC) in water to produce the aqueous nanocellulose dispersion of P-CNC and T-CNC; and optionally modifying a surface of the P-CNC and T-CNC with a surface modifier.

[00167] In some embodiments, the P-CNC is a wood derived nanocellulose (W-CNC). CA 3302214 Date reçue / Received date 2026-02-18 25

[00168] In some embodiments, the P-CNC and T-CNC are non-surface modified (the surface is unmodified).

[00169] In some embodiments, at least one of the P-CNC and T-CNC is surface modified with a surface modifier. In some embodiments, one of the P-CNC and T-CNC is surface modified with a surface modifier. In some embodiments, both the P-CNC and T-CNC are surface modified with a surface modifier.

[00170] In some embodiments, the surface modifier is a hydrophilic or a hydrophobic surface modifier.

[00171] In some embodiments, at least one of the P-CNC and T-CNC is surface modified with a hydrophobic surface modifier.

[00172] In some embodiments, the surface modifier comprises a methacrylate group. In some embodiments, the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA). In some embodiments, the surface modifier is GMA.

[00173] In some embodiments, P-CNC is W-CNC and both W-CNC and T-CNC are surface modified with GMA. In some embodiments, P-CNC is W-CNC and W-CNC is non-surface modified and T-CNC is surface modified with GMA.

[00174] In some embodiments, the mixture of the P-CNC and T-CNC is present in the aqueous nanocellulose dispersion in an amount of about 0.1 wt% to about 10 wt% based on the total weight of the dispersion. In some embodiments, the mixture of the P-CNC and T-CNC is present in the aqueous nanocellulose dispersion in an amount of about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 3 wt%, about 5 wt%, about 8 wt% and values therebetween, based on the total weight of the dispersion.

[00175] In some embodiments, the ratio of the P-CNC to the T-CNC in the dispersion is about 9:1 to about 1:9 weight ratio. In some embodiments, the ratio of the P-CNC to the T-CNC in the dispersion is about 3:1, about 1:1, about 1:3 weight ratio and values therebetween.

[00176] In some embodiments, the ratio of the P-CNC to the T-CNC in the dispersion is greater than 1.5. In some embodiments, the ratio of the P-CNC to the T-CNC in the dispersion is about 3:2, about 4:1, about 9:1 weight ratio and values therebetween.

[00177] In some embodiments, the T-CNC is included in the aqueous nanocellulose dispersion as a dispersion of the T-CNC in water. In some embodiments, the T-CNC is present in said dispersion (dispersion of the T-CNC in water) in an amount of about 0.1 wt% to about 8 CA 3302214 Date reçue / Received date 2026-02-18 26 wt% based on the total weight of the water dispersion (dispersion of the T-CNC in water). In some embodiments, the T-CNC is present in the dispersion (dispersion of the T-CNC in water) in an amount of about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 5 wt%, or values therebetween based on the total weight of the water dispersion (dispersion of the T-CNC in water).

[00178] In some embodiments, the P-CNC is included in the aqueous nanocellulose dispersion as a dispersion of the P-CNC in water. In some embodiments, the P-CNC is present in said dispersion (dispersion of the P-CNC in water) in an amount of about 1 wt% to about 15 wt% based on the total weight of the water dispersion (dispersion of the P-CNC in water). In some embodiments, the P-CNC is present in the dispersion (dispersion of the P-CNC in water) in an amount of about 1 wt%, about 5 wt%, about 10 wt% or values therebetween based on the total weight of the water dispersion (dispersion of the P-CNC in water).

[00179] In some embodiments, the modifying the surface of the at least one of the P-CNCs and T-CNC with the surface modifier comprises reacting the at least one of the P-CNCs and TCNC with the surface modifier.

[00180] In some embodiments, the surface modifier is added to the cellulose in a dry form. In some embodiments, the surface modifier is added to the cellulose as a solution containing the surface modifier in a suitable solvent.

[00181] In some embodiments, surface modification reaction is carried out by mixing the cellulose with the surface modifier under suitable elevated temperature to obtain the surface modified cellulose. In some embodiments, the cellulose is mixed with the surface modifier under a temperature of about 40 °C to about 90 °C. In some embodiments, the cellulose is mixed with the surface modifier under a temperature of about 40 °C, about 50 °C, about 60 °C, about 70 °C or values therebetween. In some embodiments, the surface modification reaction takes about 1h to about 24h. The precipitate formed in the mixture can be isolated from the mixture by any method known in the art. In some embodiments, the precipitate is isolated from the mixture by dialysis or centrifugation, and optional washing.

[00182] In some embodiments, the modified cellulose is dried, optionally in a freeze dryer. In some embodiments, the freeze drying is carried out for about 3 days. Other drying techniques may also be used. CA 3302214 Date reçue / Received date 2026-02-18 27

[00183] In some embodiments, the method comprises reacting the least one of the P-CNC and T-CNC with the surface modifier in the presence of a suitable catalyst, such as for example DMAP catalyst.

[00184] In some embodiments, prior to modifying the surface of the at least one of the PCNCs and T-CNC with the surface modifier, the method comprises functionalizing the surface of the cellulose with hydroxyl groups. Thus, in some embodiments, prior to modifying the surface of the at least one of the P-CNCs and T-CNC with the surface modifier, the method comprises reacting functionalizing agent containing hydroxyl groups with the cellulose.

[00185] In some embodiments, the functionalizing agent is NaOH. In some embodiments, the NaOH is added to the cellulose as a solution, such as an NaOH / ethanol solution. In some embodiments, the functionalizing agent containing hydroxyl groups is mixed with the cellulose for a suitable time, such as for about 10 minutes, optionally under ultrasonic homogenizer.

[00186] The precipitate formed in the mixture can be isolated from the mixture by any method known in the art. In some embodiments, the precipitate is isolated from the mixture by centrifugation and optional washing.

[00187] The present application includes a method of making a nanocellulose dispersed resin comprising: combining a plant derived nanocellulose (P-CNC), a tunicate derived nanocellulose (TCNC) and a resin to produce a nanocellulose dispersed resin; and optionally modifying a surface of the P-CNC and T-CNC with a surface modifier.

[00188] In some embodiments, the P-CNC is a wood derived nanocellulose (W-CNC).

[00189] In some embodiments, the P-CNC and T-CNC are non-surface modified (the surface is unmodified).

[00190] In some embodiments, at least one of the P-CNC and T-CNC is surface modified with a surface modifier with hydrophobic surface modifier. In some embodiments, one of the PCNC and T-CNC is surface modified with a hydrophobic surface modifier. In some embodiments, both of the P-CNC and T-CNC are surface modified with a hydrophobic surface modifier.

[00191] In some embodiments, the surface modifier comprises a methacrylate group. In some embodiments, the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA). In some embodiments, the surface modifier is GMA. CA 3302214 Date reçue / Received date 2026-02-18 28

[00192] In some embodiments, P-CNC is W-CNC and both W-CNC and T-CNC are surface modified with GMA.

[00193] In some embodiments, the mixture of the P-CNC and T-CNC is present in the nanocellulose dispersed resin in an amount of about 0.1 wt% to about 10 wt% based on the total weight of the nanocellulose dispersed resin. In some embodiments, the mixture of the P-CNC and T-CNC is present in the nanocellulose dispersed resin in an amount of about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 3 wt%, about 5 wt%, about 8 wt% and values therebetween, based on the total weight of the nanocellulose dispersed resin.

[00194] In some embodiments, the ratio of the P-CNC to the T-CNC in the resin is about 9:1 to about 1:9 weight ratio. In some embodiments, the ratio of the P-CNC to the T-CNC in the resin is about 3:1, about 1:1, about 1:3 weight ratio and values therebetween.

[00195] In some embodiments, the ratio of the P-CNC to the T-CNC in the resin is greater than 1.5. In some embodiments, the ratio of the P-CNC to the T-CNC in the resin is about 3:2, about 4:1, about 9:1 weight ratio and values therebetween.

[00196] In some embodiments, the T-CNC is included in the nanocellulose dispersed resin as a dispersion of the T-CNC in water. In some embodiments, the T-CNC is present in said dispersion (dispersion of the T-CNC in water) in an amount of about 0.1 wt% to about 8 wt% based on the total weight of the water dispersion (dispersion of the T-CNC in water). In some embodiments, the T-CNC is present in the dispersion (dispersion of the T-CNC in water) in an amount of about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 5 wt%, or values therebetween based on the total weight of the water dispersion (dispersion of the T-CNC in water).

[00197] In some embodiments, the P-CNC is included in the nanocellulose dispersed resin as a dispersion of the P-CNC in water. In some embodiments, the P-CNC is present in said dispersion (dispersion of the P-CNC in water) in an amount of about 1 wt% to about 15 wt% based on the total weight of the water dispersion (dispersion of the P-CNC in water). In some embodiments, the P-CNC is present in the dispersion (dispersion of the P-CNC in water) in an amount of about 1 wt%, about 5 wt%, about 10 wt% or values therebetween based on the total weight of the water dispersion (dispersion of the P-CNC in water).

[00198] In some embodiments, the resin is a photopolymer resin. In some embodiments, the resin is a bio-based resin. CA 3302214 Date reçue / Received date 2026-02-18 29

[00199] In some embodiments, the P-CNC and T-CNC are mixed with the resin to produce the nanocellulose dispersed resin.

[00200] In some embodiments, when at least one of the P-CNC and T-CNC are surface modified, said surface modified cellulose is prepared by mixing the cellulose with the surface modifier in the presence of the resin. Thus, in some embodiments, the surface modifier is added to the cellulose and then the resin is added to the mixture of the surface modifier with the cellulose.

[00201] In some embodiments, when one of the P-CNC and T-CNC is surface modified, said surface modified cellulose is prepared separately by mixing the cellulose, the surface modifier and the resin and then combined with the other cellulose.

[00202] In some embodiments, when both the P-CNC and the T-CNC are surface modified, then each one of the modified cellulose can be prepared separately in the presence of a surface modifier and the resin and then the modified cellulose is combined to prepare the nanocellulose dispersed resin. In some embodiments, when both the P-CNC and the T-CNC are surface modified, then the nanocellulose dispersed resin can be prepared by mixing the P-CNC and TCNC with the surface modifier and adding the resin.

[00203] In some embodiments, the surface modifier is added to the cellulose in a dry form. In some embodiments, the surface modifier is added to the cellulose as a solution containing the surface modifier in a suitable solvent.

[00204] In some embodiments, the nanocellulose dispersed resin is prepared by mixing the cellulose with the surface modifier and the resin under suitable elevated temperature. In some embodiments, the temperature is about 40 °C to about 90 °C. In some embodiments, the temperature is about 40 °C, about 50 °C, about 60 °C, about 70 °C or values therebetween. In some embodiments, the reaction may take about 1h to about 24h.

[00205] In some embodiments, the resulting mixture is dried, optionally in a fume hood to remove water. In some embodiments, the drying is carried out for about 7 days. In some embodiments, the method further comprises optional drying in a desiccator chamber at reduced pressure to remove any remaining water. Other drying techniques such as for example rotary evaporator or inert gas chamber may also be used. CA 3302214 Date reçue / Received date 2026-02-18 30

[00206] In some embodiments, the method comprises reacting the least one of the P-CNC and T-CNC with the surface modifier in the presence of a suitable catalyst, such as for example DMAP catalyst.

[00207] In some embodiments, prior to modifying the surface of the at least one of the PCNCs and T-CNC with the surface modifier, the method comprises functionalizing the surface of the cellulose with hydroxyl groups. Thus, in some embodiments, prior to modifying the surface of the at least one of the P-CNCs and T-CNC with the surface modifier, the method comprises mixing functionalizing agent containing hydroxyl groups with the cellulose.

[00208] In some embodiments, the functionalizing agent is NaOH. In some embodiments, the NaOH is added to the cellulose as a solution, such as an NaOH / ethanol solution. In some embodiments, the functionalizing agent containing hydroxyl groups is mixed with the cellulose for a suitable time, such as for about 10 minutes, optionally under ultrasonic homogenizer.

[00209] The precipitate formed in the mixture can be isolated from the mixture by any method known in the art. In some embodiments, the precipitate is isolated from the mixture by centrifugation and optional washing.

[00210] The present application includes a method of printing 3D object via additive manufacturing comprising using an ink composition of the present application.

[00211] In some embodiments, the method comprising exposing the ink composition of the application to UV or visible light radiation. In some embodiments, the ink composition of the application is exposed to UV radiation.

[00212] In some embodiments, the 3D object undergoes slicing using a suitable software, such as Phrozen slicer software.

[00213] In some embodiments, exposure to the UV light can be carried out for a period ranging from 0.1 second to 1 minute. In some embodiments, each layer of the specimen is exposed to UV for about 10s, except for the first six layers, which are cured for 15 seconds to ensure good build plate adhesion.

[00214] In some embodiments, the 3D objects are optionally rinsed with a suitable solvent, such as ethanol.

[00215] The present application also include the following embodiments: 1. An aqueous nanocellulose dispersion comprising: CA 3302214 Date reçue / Received date 2026-02-18 31 a mixture of a plant derived nanocellulose (P-CNC) and a tunicate derived nanocellulose (TCNC) in water, wherein the P-CNC and T-CNC are optionally surface modified with a surface modifier. 2. The aqueous nanocellulose dispersion of embodiment 1, wherein the P-CNC is a wood derived nanocellulose (W-CNC). 3. The aqueous nanocellulose dispersion of embodiment 1 or embodiment 2, wherein the mixture of the P-CNC and T-CNC is a hybrid mixture. 4. The aqueous nanocellulose dispersion of any one of embodiments 1 to 3, wherein the PCNC and T-CNC are non-surface modified. 5. The aqueous nanocellulose dispersion of any one of embodiments 1 to 3, wherein at least one of the P-CNC and T-CNC is surface modified with a surface modifier. 6. The aqueous nanocellulose dispersion of any one of embodiments 1 to 3, wherein both the P-CNC and T-CNC are surface modified with a surface modifier. 7. The aqueous nanocellulose dispersion of any one of embodiments 1 to 3, wherein at least one of the P-CNC and T-CNC is surface modified with a hydrophobic surface modifier. 8. The aqueous nanocellulose dispersion of embodiment 7, wherein the mixture of the PCNC and T-CNC is dispersible in a hydrophobic medium. 9. The aqueous nanocellulose dispersion of any one of embodiments 1 to 3 and 5 to 8, wherein the surface modifier comprises a methacrylate group. 10. The aqueous nanocellulose dispersion of embodiment 9, wherein the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA). 11. The aqueous nanocellulose dispersion of embodiment 10, wherein the surface modifier is GMA. 12. The aqueous nanocellulose dispersion of embodiment 10, wherein P-CNC is W-CNC and both W-CNC and T-CNC are surface modified with GMA. 13. The aqueous nanocellulose dispersion of any one of embodiments 1 to 12, wherein the mixture of the P-CNC and T-CNC is present in the aqueous nanocellulose dispersion in an amount of about 0.1 wt% to about 10 wt% based on the total weight of the dispersion. CA 3302214 Date reçue / Received date 2026-02-18 32 14. The aqueous nanocellulose dispersion of any one of embodiments 1 to 13, wherein the ratio of the P-CNC to the T-CNC in the aqueous nanocellulose dispersion is about 9:1 to about 1:9 weight ratio. 15. The aqueous nanocellulose dispersion of any one of embodiments 1 to 13, wherein the ratio of the P-CNC to the T-CNC in the aqueous nanocellulose dispersion is greater than 1.5. 16. The aqueous nanocellulose dispersion of any one of embodiments 1 to 15, wherein the T-CNC is included in the aqueous nanocellulose dispersion as a dispersion of the T-CNC in water. 17. The aqueous nanocellulose dispersion of any one of embodiments 1 to 15, wherein the aqueous nanocellulose dispersion is a Herschel-Bulkley fluid. 18. The aqueous nanocellulose dispersion of embodiment 17, wherein the aqueous nanocellulose dispersion has a shear yield strength between about 5mPa and about 10000mPa. 19. A nanocellulose dispersed resin composition comprising: a resin; and a mixture of a plant derived cellulose nanocrystals (P-CNC) and a tunicate derived cellulose nanocrystals (T-CNC), wherein the P-CNC and T-CNC are optionally surface modified with a surface modifier, and wherein the mixture of the P-CNC and T-CNC is dispersed in the resin thereby forming the nanocellulose dispersed resin composition. 20. The nanocellulose dispersed resin composition of embodiment 19, wherein the P-CNC is a wood derived nanocellulose (W-CNC). 21. The nanocellulose dispersed resin composition of embodiment 19 or embodiment 20, wherein the mixture of the P-CNC and T-CNC is a hybrid mixture. 22. The nanocellulose dispersed resin composition of any one of embodiments 19 to 21, wherein at least one of the P-CNC and T-CNC is surface modified with a hydrophobic surface modifier. 23. The nanocellulose dispersed resin composition of any one of embodiments 19 to 21, wherein both of the P-CNC and T-CNC are surface modified with a hydrophobic surface modifier. CA 3302214 Date reçue / Received date 2026-02-18 33 24. The nanocellulose dispersed resin composition of any one of embodiments 19 to 23, wherein the surface modifier comprises a methacrylate group. 25. The nanocellulose dispersed resin composition of embodiment 24, wherein the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA). 26. The nanocellulose dispersed resin composition of embodiment 25, wherein the surface modifier is GMA. 27. The nanocellulose dispersed resin composition of embodiment 24, wherein P-CNC is WCNC and both W-CNC and T-CNC are surface modified with GMA. 28. The nanocellulose dispersed resin composition of any one of embodiments 19 to 27, wherein the mixture of the P-CNC and T-CNC is present in the nanocellulose dispersed resin in an amount of about 0.1 wt% to about 10 wt% based on the total weight of the nanocellulose dispersed resin composition. 29. The nanocellulose dispersed resin composition of any one of embodiments 19 to 28, wherein the ratio of the P-CNC to the T-CNC in the nanocellulose dispersed resin composition is about 9:1 to about 1:9 weight ratio. 30. The nanocellulose dispersed resin composition of any one of embodiments 19 to 28, wherein the ratio of the P-CNC to the T-CNC in the nanocellulose dispersed resin composition is greater than 1.5. 31. The nanocellulose dispersed resin composition of any one of embodiments 19 to 30, wherein the T-CNC is included in the composition as a dispersion of the T-CNC in water. 32. The nanocellulose dispersed resin composition of any one of embodiments 19 to 31, wherein the resin is a photopolymer resin. 33. The nanocellulose dispersed resin composition of any one of embodiments 19 to 32, wherein the nanocellulose dispersed resin composition is a Herschel-Bulkley fluid. 34. The nanocellulose dispersed resin composition of any one of embodiments 19 to 33, wherein the nanocellulose dispersed resin composition has a shear yield strength between about 500mPa and about 15000mPa. 35. The nanocellulose dispersed resin composition of any one of embodiments 19 to 34 for use in additive manufacturing of polymer nanocomposites. CA 3302214 Date reçue / Received date 2026-02-18 34 36. Use of the nanocellulose dispersed resin composition of any one of embodiments 19 to 34 in additive manufacturing of polymer nanocomposites. 37. The use of embodiment 36, wherein the additive manufacturing is masked stereolithography (mSLA). 38. An ink composition for additive manufacturing comprising: a photopolymer resin; and a nanofiller, wherein the nanofiller is a mixture of a plant derived cellulose nanocrystals (P-CNC) and tunicate derived cellulose nanocrystals (T-CNC), wherein the P-CNC and T-CNC are optionally surface modified with a surface modifier, and wherein said nanofiller is dispersed in the photopolymer resin. 39. The ink composition of embodiment 38, wherein the photopolymer resin is a bio-based photopolymer resin. 40. The ink composition of embodiment 39, wherein the bio-based photopolymer resin comprises a plant oil. 41. The ink composition of embodiment 40, wherein the bio-based photopolymer resin comprises soybean oil. 42. The ink composition of embodiment 41, wherein the bio-based photopolymer resin comprises a methacrylated epoxidized soybean oil (mAESO). 43. The ink composition of embodiment 42, wherein the bio-based photopolymer resin further comprises an additional photocurable monomer. 44. The ink composition of embodiment 43, wherein the photocurable monomer is 2- hydroxyethyl methacrylate (HEMA). 45. The ink composition of embodiment 44, wherein volume ratio of the mAESO to HEMA in the composition is about 85:15 to about 98:2 volume ratio. 46. The ink composition of any one of embodiments 38 to 45, wherein the ink composition further comprises a photo-initiator. 47. The ink composition of embodiment 46, wherein the photo-initiator is present in the ink composition in an amount of about 0.05 vol% to about 5 vol% based on the total volume of the photopolymer resin. CA 3302214 Date reçue / Received date 2026-02-18 35 48. The ink composition of any one of embodiments 38 to 47, wherein the P-CNC is a wood derived nanocellulose (W-CNC). 49. The ink composition of any one of embodiments 38 to 48, wherein the mixture of the PCNC and T-CNC is a hybrid mixture. 50. The ink composition of any one of embodiment 38 to 49, wherein both of the P-CNC and T-CNC are surface modified with a hydrophobic surface modifier. 51. The ink composition of embodiment 50, wherein the surface modifier comprises a methacrylate group. 52. The ink composition of embodiment 51, wherein the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA). 53. The ink composition of embodiment 52, wherein the surface modifier is GMA. 54. The ink composition of embodiment 52, wherein P-CNC is W-CNC and both W-CNC and T-CNC are surface modified with GMA. 55. The ink composition of any one of embodiments 38 to 54, wherein the mixture of the PCNC and T-CNC is present in the composition in an amount of about 0.1 wt% to about 10 wt% based on the total weight of the composition. 56. The ink composition of any one of embodiments 38 to 55, wherein the ratio of the W-CNC to the T-CNC in the resin is about 9:1 to about 1:9 weight ratio. 57. The ink composition of any one of embodiments 38 to 56, wherein the ratio of the W-CNC to the T-CNC in the resin is greater than 1.5. 58. The ink composition of any one of embodiments 38 to 57, wherein the photopolymer resin is UV curable. 59. The ink composition of any one of embodiments 38 to 58, wherein the additive manufacturing is masked stereolithography (mSLA). 60. The ink composition of any one of embodiments 38 to 59, wherein the ink composition is a Herschel-Bulkley fluid. 61. The ink composition of any one of embodiments 38 to 60, wherein the ink composition has a shear yield strength between about 500mPa and about 15000mPa. CA 3302214 Date reçue / Received date 2026-02-18 36 62. A polymer nanocomposite formed by additive manufacturing and curing the ink composition as defined in any one of embodiments 38 to 61. 63. A method of making an aqueous nanocellulose dispersion comprising: combining a plant derived nanocellulose (P-CNC) and a tunicate derived nanocellulose (T-CNC) in water to produce the aqueous nanocellulose dispersion of P-CNC and T-CNC; and optionally modifying a surface of the P-CNC and T-CNC with a surface modifier. 64. The method of embodiment 63, wherein the surface modifier comprising a methacrylate group. 65. The method of embodiment 64, wherein the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA). 66. The method of embodiment 65, wherein P-CNC is W-CNC and both W-CNC and T-CNC are surface modified with GMA. 67. The method of any one of embodiments 63 to 66, wherein the mixture of the P-CNC and T-CNC is present in the aqueous nanocellulose dispersion in an amount of about 0.1 wt% to about 10 wt% based on the total weight of the dispersion. 68. The method of any one of embodiments 63 to 67, wherein the ratio of the W-CNC to the T-CNC in the resin is about 9:1 to about 1:9 weight ratio. 69. The method of any one of embodiments 63 to 67, wherein the ratio of the W-CNC to the T-CNC in the resin is greater than 1.5. 70. The method of any one of embodiments 63 to 69, wherein the T-CNC is included in the aqueous nanocellulose dispersion as a dispersion of the T-CNC in water. 71. The method of any one of embodiments 63 to 70, wherein prior to modifying the surface of the at least one of the P-CNCs and T-CNC with the surface modifier, the method comprises functionalizing the surface of the cellulose with hydroxyl groups. 72. An aqueous nanocellulose dispersion prepared by the method of any one of embodiments 63 to 71. 73. A method of making a nanocellulose dispersed resin comprising: combining a plant derived nanocellulose (P-CNC), a tunicate derived nanocellulose (TCNC) and a resin to produce a nanocellulose dispersed resin; and optionally modifying a surface of the P-CNC and T-CNC with a surface modifier. CA 3302214 Date reçue / Received date 2026-02-18 37 74. The method of embodiment 73, wherein the surface modifier comprising a methacrylate group. 75. The method of embodiment 74, wherein the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA). 76. The method of embodiment 75, wherein P-CNC is W-CNC and both W-CNC and T-CNC are surface modified with GMA. 77. The method of any one of embodiments 73 to 76, wherein the mixture of the P-CNC and T-CNC is present in the nanocellulose dispersed resin in an amount of about 0.1 wt% to about 10 wt% based on the total weight of the nanocellulose dispersed resin. 78. The method of any one of embodiments 73 to 77, wherein the ratio of the W-CNC to the T-CNC in the resin is about 9:1 to about 1:9 weight ratio. 79. The method of any one of embodiments 73 to 77, wherein the ratio of the W-CNC to the T-CNC in the resin is greater than 1.5. 80. The method of any one of embodiments 73 to 79, the T-CNC is included in the nanocellulose dispersed resin as a dispersion of the T-CNC in water. 81. The method of any one of embodiments 73 to 80, wherein the resin is a photopolymer resin. 82. The method of any one of embodiments 73 to 81, wherein prior to modifying the surface of the at least one of the P-CNCs and T-CNC with the surface modifier, the method comprises functionalizing the surface of the cellulose with hydroxyl groups. 83. A nanocellulose dispersed resin prepared by the method of any one of claims 73 to 81. 84. A method of printing a 3D object via additive manufacturing comprising exposing an ink composition as defined in any one of embodiments 38 to 61 to UV light radiation. 85. The method of embodiment 84, wherein exposure to the UV light is carried out for a period ranging from 0.1 second to 1 minute. The following non-limiting examples are illustrative of the present application: EXAMPLES Materials and methods CA 3302214 Date reçue / Received date 2026-02-18 38 Materials:

[00216] Wood (W-CNC) and Tunicate (T-CNC) derived nanocellulose crystals (supplied as 10 wt% and 0.5 wt% in water, respectively) were provided by Tunistrong Technologies Inc. Methacrylic Anhydride (MAA) (Sigma Aldrich, CAS No. 760-93-0), 4-(Dimethyl Amino)pyridine (DMAP) (Alfa Aesar, CAS No. 1122-58-3), Oleic acid (OA) (Sigma Aldrich, CAS No. 112-80-1), Sodium Hydroxide (NaOH) (Sigma Aldrich, CAS No. 1310-73-2), Oleylamine (OLA) (Sigma Aldrich, CAS No. 112-90-3), Glycidyl Methacrylate (GMA) (Sigma Aldrich, CAS No. 106-91-2), phenylbis (2,4,6-trimethylbenzoyl)phosphine oxide (Irgacure 819) (Sigma Aldrich, CAS No. 162881-26-7), Acrylated Epoxidized Soybean Oil (AESO) (Sigma Aldrich, CAS No. 91722-144), and 2-Hydroxyethyl Methacrylate (HEMA) (Sigma Aldrich, CAS No. 868-77-9) were used without purification. Anhydrous ethanol was purchased from the University of Waterloo Chemical Stores. Functionalization of CNCs using methacrylic anhydride

[00217] Cellulose nanocrystals (CNC)s were grafted with methacrylate groups using methacrylic anhydride (MAA) (Figure 1). Inside the fume hood, 14.5 ml of MAA (15 g) was weighed and poured into a 250 ml beaker. The beaker was placed on a hot / stir plate. 0.2 g of 4- (dimethyl amino)pyridine (DMAP) was weighed inside the fume hood, added to MAA, and dissolved by stirring at 500 rpm. This MAA and DMAP mixture was then added to a 250 ml glass beaker containing 3 ml of W-CNC-water solution (0.3 g dry W-CNC equivalent) or 60 ml of TCNC- Water solution (0.3 g dry T-CNC equivalent). The beaker was then placed on the hot / stir plate with a water bath and a thermometer and set the temperature at 60 °C with continuous stirring at 500 rpm for 24 hours. After 24 hours, the reaction was terminated by turning off the heat. The mixture was added to 100 ml of anhydrous ethanol and centrifuged at 1000 relative centrifugal field (rcf) for 10 minutes to precipitate the modified W-CNC or modified T-CNC. The supernatant was discarded, and precipitated CNC was dispersed by adding 100 ml of fresh anhydrous ethanol and homogenizing using an ultrasonic homogenizer for 2 minutes. The centrifugation step was repeated. The supernatant was discarded, and 30 ml of de-ionized water was added to CNC and homogenized using ultrasonic homogenizer for 2 minutes. The modified CNCs were dried in the freeze dryer for 3 days.

[00218] The presence of methacrylate groups on functionalized CNC was evaluated by conducting an Fourier transform infrared spectroscopy (FTIR) study on the dry CNC powder. FTIR spectra were obtained using a Nicolet 6700 FT-IR Spectrometer (Thermo Scientific, USA) at a resolution of 4 cm−1 with a sample scan of 32. CA 3302214 Date reçue / Received date 2026-02-18 39 Functionalization of CNCs using glycidyl methacrylate

[00219] CNCs were functionalized with methacrylate groups using glycidyl methacrylate (GMA) (Figure 2). Before the addition of methacrylate to the CNC particles, the -SO4H groups in CNCs were replaced by -OH to increase the grafting sites. 5 g dry NaOH was added to 200 ml anhydrous ethanol in a 500 ml glass beaker and dissolved by stirring at 500 rpm in a stir plate. This NaOH / ethanol solution was added to 3 ml of W-CNC / water solution (0.3 g dry W-CNC equivalent), or 60 ml of T-CNC-Water solution (0.3 g dry T-CNC equivalent) and homogenized thoroughly for 10 minutes using the ultrasonic homogenizer. The mixture was then transferred to a 50 ml centrifuge tube and centrifuged at 1000 rcf for 10 minutes. The supernatant was discarded, fresh deionized water was added, and CNC was re-homogenized using the ultrasonic homogenizer. The centrifugation and re-homogenization were repeated once.

[00220] Next, 14.4 ml of GMA (15 g) was weighed and mixed with the CNC-water solution in a 250 ml beaker. The beaker was placed on a hot / stir plate with a water bath and a thermometer and set the temperature at 60 °C with continuous stirring at 500 rpm for 3 hours. After 3 hours, the reaction was terminated by turning off the heat and allowing to cool to room temperature. The mixture was collected in a dialysis tube (Sigma Aldrich Co., molecular weight cut-off = 14,000), and submerged in water for 24 hours at room temperature to wash off the unreacted GMA. After 24 hours, the functionalized CNC-water mixture was poured into 50 ml centrifuge tubes and dried in a freeze-dryer for 3 days.

[00221] Dried powders of the modified CNCs were characterized using FTIR. FTIR spectra were obtained using a Nicolet 6700 FT-IR Spectrometer (Thermo Scientific, USA) at a resolution of 4 cm−1 with a sample scan of 32. Functionalization of CNCs using oleylamine

[00222] 15 g oleylamine (OLA) was separately dissolved in 200 ml ethanol by mixing in the stir plate at 500 rpm for 10 minutes and added to the 3 ml CNC / water solution (0.3 g dry CNC equivalent) or 60 ml of T-CNC-Water solution (0.3 g dry T-CNC equivalent). The CNC / OLA mixture was placed in a water bath on top of the hot / stir plate and the temperature was set at 80 °C. The reaction was continued for 7 h, stirring at 300 rpm. After 7 hours, the heat was turned off and the beaker was left inside the fume hood until the mixture cooled down to room temperature. The mixture was transferred to 50 ml centrifuge tubes and centrifuged at 3000 rcf for 15 minutes. The supernatant was discarded, and 30 ml ethanol was added to the precipitate CA 3302214 Date reçue / Received date 2026-02-18 40 and re-homogenized using the ultrasonic homogenizer. The centrifuge process and rehomogenizing were repeated once. Ink preparation

[00223] The CNC / mAESO / HEMA inks were prepared with modified (functionalized) and unmodified (raw) W-CNC and T-CNC. During ink preparation, the CNCs were functionalized in the presence of methacrylated epoxidized soybean oil (mAESO) / 2-hydroxyethyl methacrylate (HEMA), to avoid phase separation during the drying process. The functionalization was carried out as described in sections as described above, except the mAESO and HEMA were added before the reaction was started. The functionalized CNCs were not washed / purified as they were dispersed in mAESO / HEMA / water mixture. The raw (unmodified) CNC–based inks were prepared similarly without the addition of functionalizing agents (such as GMA). Table 1: Nomenclature example of the nanocomposite inks. Wt% WCNC WCNC-MA TCNC TCNC-MA 0.1 0.1W 0.1WM 0.1T 0.1TM 0.25 0.25W 0.25WM 0.25T 0.25TM 0.5 0.5W 0.5WM 0.5T 0.5TM MA = methacrylate

[00224] For example, to prepare 60 ml of 0.25wt% TCNC-MA (0.25TM) ink, 0.15g raw TCNC (30 ml of 0.5wt% TCNC / water solution, Tunistrong Technologies Inc.) was functionalized using 7.2 ml of GMA as described above. 56.7 ml mAESO and 2.7 ml HEMA were added to the mixture just after adding the GMA. After the functionalization, the ink and water mixture were left in the fume hood for 7 days to dry off the water and finally placed in a desiccator chamber at reduced pressure. The drying process was monitored by measuring the weight and assumed dry when the total mass was not changed for two consecutive days. After removing the water from the ink, 0.6 ml Irgacure 819 (1 vol% of mAESO / HEMA) was weighed and added to the ink. The volume ratio of mAESO: HEMA was set to 95:5 and kept constant in this study. The ink was homogenized using a mechanical homogenizer for 3 minutes and an ultrasonic homogenizer for 5 minutes. Rheology of the Inks CA 3302214 Date reçue / Received date 2026-02-18 41

[00225] Viscosity and shear yield strength of the nanocomposite inks were measured using a Bohlin CS Rheometer with a cone and plate assembly (CP 4 / 40, with 150 μm gap). Nanocomposite inks were prepared without adding the photo-initiator Irgacure 819. This was done to avoid any curing during the experiment caused by normal lighting in the lab. All measurements were conducted at room temperature under shear strain rates from 0.01 s−1 and 100 s−1 (n = 3). At each shear strain rate, the viscosity and shear stress were recorded at 10s intervals. The viscosities of the nanocomposite inks were calculated by measuring the slopes of the linear portion of the shear stress vs shear rate plots at higher shear rates. Dispersion of CNCs in the mAESO / HEMA ink

[00226] 100 μl of CNC / mAESO / HEMA ink was poured into each well of a 96-well plate. The same amount of resin and water was poured into other wells as control. The plate was mounted in a plate reader (SpectraMax Plus 384 Microplate Reader) and absorbance was measured using 490 nm wavelength. The absorbed light due to the presence of CNC was calculated by subtracting the light absorbed by the resin. The 490 nm wavelength was used to detect the light absorbance / scattering caused by agglomerates / particles larger than 490 nm. 3D printing

[00227] mSLA-based 3D printing was performed using a Phrozen Sonic XL 4 K (Phrozen Technology, Taiwan). Initially, 3D stereolithographic (.stl) files were sliced using the Phrozen slicer software. All specimens were printed with a layer height of 50 μm. Each layer was exposed to UV for 10s, except for the first six layers, which were cured for 15 seconds to ensure good build plate adhesion. After completion of 3D printing, the specimens were carefully removed from the print bed using a metal spatula, thoroughly rinsed with ethanol using an ultrasonic homogenizer for 5 min, and then wiped thoroughly. To avoid uncured ink residue on the surfaces of the specimens, they were exposed to additional UV in a post-print curing chamber (CureZone MKII, Creative CADWORKS, Canada) for 10 min on each side (Figure 3). Tensile testing

[00228] Dogbone-shaped test specimens (overall length = 30 mm, gauge length = 10 mm, gauge length width = 2.5 mm, and thickness = 2 mm; based on ASTM D3039 test method, were printed using the mSLA 3D printer. The Phrozen Slicer software was used to set the orientation and for the addition of necessary supports. Support material of six support fixtures per specimen was added in the grip areas only, not along the gauge length, to avoid defects and damage to the specimens’ gauge lengths during printing and removal from the print bed. CA 3302214 Date reçue / Received date 2026-02-18 42

[00229] All mechanical testing was conducted using a Psylotech μTS mechanical testing machine (Psylotech Inc., Evanston, IL, United States) equipped with a 1.6 kN windowing load cell. Strain measurement was conducted using microscope-enabled digital image correlation (DIC; Vic 2D 6, Correlated Solutions Inc., USA). A microscope (BXFM, Olympus Corp., Center Valley, PA, USA) with a digital camera (Point Grey, 5 MP, 2 / 3” detector) was mounted over the test system to take magnified images of the gauge length during the test. A 2.5x magnification objective lens (Olympus Corp., Center Valley, PA, USA) was used. The resulting spatial resolution was 360 pixels mm-1.

[00230] The specimens (n=5 per group) were sprayed with high-resolution toner powder (Xerox Phaser 6000) using an atomizer jar to create speckle patterns, enabling digital Image correlation (DIC) deformation measurement and strain calculations. These particles were 4–5 μm in diameter. In displacement control mode, specimens were first preconditioned at 1 Hz for 100 cycles. The extension was applied at a rate of 16 μm / s speed (average strain rate of 0.0016 s−1). All testing was carried out at room temperature. Data were acquired at 5 Hz. The average engineering strains over the entire gauge length were measured from the DIC using a line extensometer tool. The engineering stress was calculated by dividing the applied load by the initial cross-sectional area. True strain (εt) was also calculated, using the formula,

[00231] 𝜀𝑡 = ln ( 𝑙 𝑙0 )

[00232] Both the current length (l) and original length (l0) were obtained from the extensometer tool. The transverse strain (y-axis) was calculated using the extensometer tool. It was assumed the z-axis strain would be the same as the transverse strain; therefore, it was possible to calculate the true cross-sectional area for each data point. Therefore, the true stress was calculated by dividing the applied load by the true cross-sectional area. Young’s modulus was determined from the slope of the initial linear elastic portion (0-0.3% strain) of the stressstrain curve. Yield strength was calculated using a conventional 0.2% offset from the linear portion of the curve. Toughness values were obtained as the area under the stress-strain curves up to the point of fracture. Fracture testing

[00233] Single-point fracture toughness (K1c) of each of the mSLA-printed nanocomposites was measured using the same testing frame but equipped with a 3-point bending fixture and performed according to ASTM D5045-14 test method. Single edge notch bending (SENB) test specimens with a length of 50 mm (gauge length of 40 mm), thickness (B) CA 3302214 Date reçue / Received date 2026-02-18 43 of 5 mm, and a width (W) of 10 mm were 3D printed with the same settings as for the tensile testing specimens. A 4.5 mm notch was cut into the width using an IsoMettm low-speed metallurgical saw (Buehler Ltd., IL, USA) and then a starter crack was created by gently tapping a sharp razor blade placed in the notch. The initial crack lengths (𝑎0) fell within the 0.45 < a / W < 0.55 specification. All testing (n=5) was conducted at room temperature and in displacement control mode with a crosshead speed of 3.3 μm / s. Data were acquired at 5 Hz. Stress intensity factor based plane strain fracture toughness was calculated using the standard equation,

[00234] 𝐾𝑄 = ( 𝑃𝑄 𝐵𝑊0.5) [6𝑥0.5 [1.99− 𝑎 𝑊(1− 𝑎 𝑊)(2.15−3.93 𝑎 𝑊+2.7 𝑎2 𝑊2)] (1+2 𝑎 𝑊)(1− 𝑎 𝑊) 1.5 ]

[00235] KQ was considered as K1c if 2.5 (𝐾𝑄 𝜎𝑦 ) < 𝐵, 𝑎, 𝑎𝑛𝑑 (𝑊 − 𝑎)

[00236] In those cases where yield strength (σy) was not detectable due to the absence of a yield point, tensile fracture strength (σmax) was used instead of σy. Scanning Electron Microscope (SEM) imaging

[00237] SEM images of the fracture surfaces after tensile and fracture testing were acquired by mounting the fractured specimens on SEM stubs and without further treatment. Imaging was conducted using a Quanta FEG 250 (ThermoFisher Scientific, USA) in low vacuum mode using Secondary Electron (SE) mode. Low vacuum SEM was used to avoid charging and burning on the rough fracture surfaces. Rheology of the functionalized and raw CNCs and their hybrid mixtures in water and resin

[00238] Functionalized and raw CNCs were suspended in water and freeze-dried for 3 days. The dry Wand T-CNC particles were mixed in either water or mAESO / HEMA resin (without the Irgacure 819) using weight ratios of 100:0, 75:25, 50:50, 25:75, and 0:100. The mixture was homogenized using a mechanical homogenizer for 3 minutes and ultrasonic homogenizer for 5 minutes. The rheological properties were measured as described above. Results and discussion Functionalization of CNCs using methacrylic anhydride, oleic acid, and oleylamine:

[00239] In the first attempt to graft methacrylate groups to W-CNC, methacrylic anhydride was used as the functionalizing agent with DMAP as the catalyst. Figure 4 represents the FTIR spectra of raw and modified W-CNC after grafting with methacrylate and oleate. CA 3302214 Date reçue / Received date 2026-02-18 44

[00240] Distinctive peaks of C=O from ester groups (methacrylate) and carboxylic acid (oleic acid) at the range of 1700-1760 cm-1 are visible in the CelMA and Cel-Oacid spectra. Asymmetric peaks for C=C are visible in the spectra at the range of 750-850 cm-1 in all modified spectra (Figure 5).

[00241] The W-CNC was successfully grafted with methacrylate and oleate groups. However, the processing of W-CNC-methacrylate using MAA involved the use of DMAP, a toxic catalyst, and the duration of the reaction was 24 hours. Therefore, it has been decided to proceed with the use of GMA as the functionalizing agent as the reaction does not require any catalysts and the reaction takes only 3 hours. The presence of oleate groups in the CNCs would not help in the dispersion and caused phase separation of modified CNCs from the resin. Therefore, the functionalization of CNCs with oleates was not pursued. In the next steps, surface grafting of CNCs with methacrylates using the GMA was used. Functionalization of CNCs using GMA

[00242] FTIR spectra of the raw and GMA-functionalized W- and T-CNCs are plotted in Figure 6. The functionalized wood (WM) and tunicate (TM) had a strong peak at 1700 cm−1 associated with C=O groups from the grafted ester (Figure 7). Strong peaks at 1630 cm−1 (associated with stretching vibration for C=C) and at 806 cm−1 (for asymmetric vibration of outof- plane vinyl groups) in the WM and TM spectra indicate successful functionalization of WM and TM with methacrylate groups (Figure 8 and Figure 9 respectively). Dispersion of raw and functionalized CNCs in water and resin:

[00243] The dispersion of raw and functionalized CNCs in both water and resin was studied by quantifying the absorbed / scattered light using a plate reader. While 490 nm wavelength light was used, the scattered light was directly proportional to the suspended agglomerates larger than 500 nm. W-CNCs are very soluble in water and there was no light absorbance (Figure 10). However, the greater absorbance of WM compared to W revealed the presence of agglomerations, presumably due to the relatively hydrophobic nature of the methacrylated WM. Both T and TM absorbed light when suspended in water. When suspended in resin at 0.1 wt%, the WM absorbed less light compared to W, indicating greater compatibility of WM within the resin than W (Figure 11). T and TM showed the same trend but with greater absorption, presumably due to their greater length. Rheology of the nanocomposite inks CA 3302214 Date reçue / Received date 2026-02-18 45

[00244] The rheological behavior of the nanocomposite inks is shown in Figure 12 and Figure 13. The inks demonstrated non-Newtonian behavior at low shear rates. The inks followed the Herschel-Bulkley model with the presence of yield shear stress at low shear rates and showing shear-thinning behavior as shear rates increased. All WM-containing nanocomposite inks demonstrated lower shear yield strength than the raw W-containing inks. Viscosity values decreased as the shear rates increased, showing distinct shear-thinning behavior at lower shear strain rates. Consistent viscosity values appeared for shear rates exceeding 20 s−1. The highrate viscosity and shear yield strength values were calculated from the slopes and the y-axis intercept values of the shear stress vs shear rate curves and summarized in Table 2 below. The higher aspect ratio of the TCNCs compared to WCNCs presumably leads to greater viscosity and shear yield strength for the T and TM inks. For example, the mean (n=3) viscosity values of 0.25T and 0.25W are 3.29±0.03 Pa.s and 1.58±0.03 Pa.s respectively, and the mean shear yield strength values of 0.25T and 0.25W are 3.81±0.59 Pa and 1.97±.03 Pa, respectively. The viscosity of the 0.1 wt% TM ink was found to be below the printable range (viscosity < 5 Pa.s) but the shear yield strength was too high for the ink to flow freely during the repositioning of the build plate, which is one of the parameters for mSLA printing. Table 2. Rheological properties of the nanocomposite inks (n=3) Nanocomposite Ink (%wt) Shear Yield Strength (Pa) Viscosity (Pa.s) Resin mSH0 4.12 ± 0.77 3.29 ± 0.03 W-CNC 0.1W 1.37 ± 0.05 1.47 ± 0.01 0.1WM 0.16 ± 0.04 1.64 ± 0.01 0.25W 1.97 ± 0.05 1.56 ± 0.02 0.25WM 0.13 ± 0.01 1.58 ± 0.03 0.5W 2.47 ± 0.34 2.79 ± 0.04 0.5WM 0.38 ± 0.21 2.82 ± 0.04 T-CNC 0.1T 12.51 ± 3.57 5.91 ± 0.16 0.1TM 3.44 ± 1.95 3.51 ± 0.08 0.25T 3.81 ± 0.59 3.29 ± 0.03 0.25TM 3.16 ± 0.53 3.18 ± 0.04 0.5T 8.11 ± 0.98 6.65 ± 0.09 0.5TM 25.18 ± 3.33 4.62 ± 0.03 Tensile mechanical properties of the 3d printed nanocomposites CA 3302214 Date reçue / Received date 2026-02-18 46

[00245] The tensile mechanical properties of 3D printed nanocomposites were measured by using 3D printed dogbone-shaped specimens following the ASTM D3039 standard test method.

[00246] WM-containing nanocomposites had higher tensile fracture strengths than Wcontaining nanocomposites (Figure 14). Tensile strength and modulus values for 5WM were 26.4 ± 3.2 MPa and 1464.2 ± 112.1 MPa, respectively. This equated to a 3- and 4.5-fold increase in properties from 5W, respectively. Grafting methacrylate groups onto the CNCs significantly improved the tensile fracture strength and modulus but decreased the fracture strain as a person skilled in the art might expect. Table 3. Tensile mechanical properties of WCNC nanocomposites (n=5). Material (n=5) Tensile fracture strength (MPa) Young’s modulus (MPa) Tensile fracture strain (%) Resin 6.7 ± 1.2 277.1 ± 86.1 7.3 ± 1.2 3W 9.3 ± 0.9 491.4 ± 204.6 4.4 ± 0.9 3WM 23.3 ± 3.2 1369.5 ± 15.2 1.2 ± 0.4 5W 8.9 ± 0.5 324.1 ± 73.8 5.6 ± 1.5 5WM 26.4 ± 3.2 1464.2 ± 112.1 1.7 ± 0.2

[00247] Tensile fracture strength, Young's modulus, and fracture strain of nanocomposites containing lower amounts of W- and WM -containing nanocomposites are summarized in Table 3, and the representative curves are shown in Figure 15. The tensile fracture strength and modulus were not different between the 0.1, 0.25, and 0.5 wt% W-CNC groups, in contrast to the 3 and 5 wt% of W and WM. Incorporation of WM into the mAESO / HEMA resin did not improve the tensile fracture strength and modulus but increased the strain-at-fracture. 0.1, 0.25 and 0.5 wt% WM nanocomposites demonstrated similar fracture strengths and improved ductility and toughness compared to their unmodified counterparts (Table 4). Table 4. Tensile mechanical properties of low weight% W and WM containing nanocomposites (n=5) Nanocomposites (n=5) Fracture Strength (MPa) Young's Modulus (MPa) Fracture Strain (%) Resin 6.65 ± 1.17 277.07 ± 86.09 7.29 ± 1.21 0.1W 14.03 ± 0.17 704.23 ± 65.14 2.34 ± 0.07 0.25W 15.53 ± 0.21 745.79 ± 99.69 2.16 ± 0.18 0.5W 15.18 ± 1.49 927.92 ± 33.98 1.73 ± 0.23 0.1WM 15.41 ± 1.18 587.64 ± 35.31 5.21 ±1.27 0.25WM 12.62 ± 2.03 569.35 ± 33.51 3.17 ± 1.21 CA 3302214 Date reçue / Received date 2026-02-18 47 0.5WM 15.85 ± 0.65 574.04 ± 15.71 5.63 ± 0.55

[00248]

[00249] T- and TM-CNC-containing nanocomposites displayed trends like those of the Wand WM-CNC-containing nanocomposites. The fracture strength and modulus did not vary detectable between T and TM and the ductility (measured in terms of fracture strain) improved with the incorporation of TM (Figures 16-17). The 3WM had shown brittle fracture compared to 3W, but the 0.5W was brittle and 0.5WM had shown ductility (Figures 15-17). The increased brittleness in higher WM-containing nanocomposites (3WM and 5WM) may be due to the higher amount of residual non-reacted GMA during functionalization causing increased crosslinking during 3D printing. The 0.1 to 0.5 wt% WM-containing nanocomposites have less crosslinking than 3WM which contribute to interfacial debonding upon tensile loading. Table 5. Tensile mechanical properties of nanocomposites containing T and TM CNCs at 0.1, 0.25 and 0.5 wt% (n=3). Nanocomposites (n=5) Fracture Strength (MPa) Young's Modulus (MPa) Fracture Strain (%) Resin 6.65 ± 1.17 277.07 ± 86.09 7.29 ± 1.21 0.1T 32.13 ± 2.45 1580.17 ± 75.21 2.54 ± 0.47 0.25T 38.45 ± 3.98 1702.08 ± 110.45 2.46 ± 0.22 0.5T 29.02 ± 2.92 2010.13 ± 93.76 1.45 ± 0.12 0.1TM 30.85 ± 7.19 1653.74 ± 321.71 1.69 ± 0.56 0.25TM 24.12 ± 2.81 2150.23 ±184.75 1.11 ± 0.16 0.5TM 35.03 ±2.77 1681.36 ± 302.79 3.77 ± 0.57

[00250] The representative curves of 0.5 wt% W, WM, T, and TM are re-plotted in Figure 17. Both 0.5T and 0.5TM had increased tensile strength, fracture strain, and modulus compared to that of 0.5W and 0.5WM. The raw W and T -based composites were brittle whereas WM and TM based nanocomposites were relatively ductile. The surface modification improves the dispersion of CNCs in the resin matrix due to the increased miscibility. The improved nanoscale dispersion of CNCs in WM and TM nanocomposites with interfacial crosslinking required more energy to de-bond and that might lead to the increased ductility.

[00251] The fracture surfaces of all nanocomposites after tensile testing were observed by SEM imaging (See Figure 18, Figure 19, Figure 20, Figure 21). The absence of voids or entrapped bubbles in modified WM and TM nanocomposites indicates excellent processing and printing of these nanocomposites. T- and TM-containing nanocomposites had much rougher fracture surfaces than W and WM after tensile testing. Large agglomerates are visible in high- CA 3302214 Date reçue / Received date 2026-02-18 48 magnification images of W-based nanocomposites (black arrows) (Figure 20). The WM-based nanocomposites had no visible agglomerates which indicates the improved dispersion of WM compared to W in the resin. The T and TM nanocomposites have no visible agglomerates either. Plain Strain Fracture Toughness of the 3D Printed Nanocomposites:

[00252] The fracture behavior of the 3D printed nanocomposites was evaluated by conducting single-edge notch bending (SENB) tests in three-point bending following the ASTM D5045 standard test method. Representative load versus load-line deflection curves of the fracture tests are plotted in Figures 22-24. Stable tearing was observed for 3W, presumably due to a lack of methacrylate crosslinking within the resin and between the CNCs and the resin. The functionalized WM nanocomposites were brittle and demonstrated unstable fracture. All W- and T-based nanocomposites in the 0.1 to 0.5 %wt groups demonstrated brittle fracture with fast unstable crack growth, consistent with the tensile testing results. The mean Mode-I plane strain fracture toughness values (KIc) for the nanocomposites are summarized in Tables 6-7. The fracture toughnesses of all T-CNC containing nanocomposites was greater than those of the W and WM-based nanocomposites. The challenge associated with printing SENB beams of TMbased nanocomposites limited the SENB testing only to 0.1TM (n=2). The 3D printed beams of 0.25TM and 0.5TM nanocomposites had defects and were not eligible for testing.

[00253] Lack of notable differences in fracture toughness, KIc, between the functionalized and unfunctionalized groups in either W and WM or T and TM may be the result of A) a more dominate hydrostatic pressure effect over any toughening mechanism due to the functionalization of the CNCs. This is commonly observed in polymers because failure of polymers is sensitive to hydrostatic pressure. B) The choice of a stress bases analysis, calculating stress intensity factor, KIc, rather than GIc, the energy release rate. Table 6. Plane-strain fracture toughness (K1c) values of the nanocomposites (n=5). Nanocomposite (n=5) KIc (MPa.m0.5) 3W 0.253 ± 0.021 3WM 0.616 ± 0.099 Table 7. Plane-strain fracture toughness (KIc) values of the nanocomposites tested in this project (n=2-5). Nanocomposites (n=5) KIc (MPa.m0.5) 0.1W 0.27 ± 0.01 0.1WM 0.27 ± 0.03 CA 3302214 Date reçue / Received date 2026-02-18 49 0.25W 0.39 ± 0.14 0.25WM 0.31 ± 0.02 0.5W 0.32 ± 0.04 0.5WM 0.28 ± 0.02 0.1T 0.65 ± 0.09 0.1TM (n=2) 0.53 ± 0.04 0.25T 0.63 ± 0.09 0.5T 0.59 ± 0.04 Rheology of the hybrid mixtures of W- and T-CNCs in Water and Resin

[00254] The rheology of hybrid mixtures of raw and modified W and T-CNC in water and resin were studied and plotted in Figures 25-27, and the values were summarized in Table 8. The raw TCNC in water had shown higher yield shear stress and the values were decreased with the increase of WCNC in the mixture. The rheological behavior of the hybrids fits with Herschel-Bulkley fluid with yield shear stress and shear thinning trend with increasing shear rates (Figure 25). The raw WCNC in water fits with the Newtonian fluid with zero yield shear stress. The rheology plots of modified hybrids in water are not shown here as these hybrids had non-dispersed agglomerates which precipitated rapidly (Table 8).

[00255] The hybrids behave similarly in the resins. The yield shear stress values were higher with greater raw or modified TCNC content. The amount of WCNC decreased the yield shear stress and viscosity values. Compared to the raw CNC hybrids with modified CNC hybrids, modification of CNCs using methacrylates decreased the yield shear stress and viscosity values due to their increased miscibility in the hydrophobic resin (Table 8) Table 8: Rheological properties of the hybrids (n=3) Media CNC Wt% of hybrid T / W ratio Shear Yield Strength (mPa) Viscosity (mPa.s) Water Unmodified 1 100 / 0 15834.2 ± 1895.6 57.2 ± 12.3 75 / 25 5722.3 ± 240.9 26.4 ± 1.6 50 / 50 1378.4 ± 165.5 7.9 ± 1.8 25 / 75 19.0 ± 15.5 3.4 ± 0.9 0 / 100 0 2.1 ± 0.5 Unmodified 0.1 100 / 0 0 2.6 ± 0.7 75 / 25 0 1.6 ± 0.5 50 / 50 0 2.6 ± 0.2 25 / 75 0 2.2 ± 0.4 0 / 100 0 2.0 ± 0.4 100 / 0 0 3.1 ± 0.4 75 / 25 0 3.1 ± 0.3 50 / 50 0 2.9 ± 0.3 CA 3302214 Date reçue / Received date 2026-02-18 50 Modified 0.1 25 / 75 0 3.0 ± 0.3 0 / 100 0 2.6 ± 0.2 Resin (mSH0) Unmodified 0.1 100 / 0 18235.0 ± 4361.9 5822.4 ± 128.8 75 / 25 14617.8 ± 2367.1 5139.5 ± 269.3 50 / 50 11887.9 ± 3683.5 5135.1 ± 64.6 25 / 75 3769.9 ± 720.6 4499.4 ± 27.7 0 / 100 579.3 ± 102.0 3345.4 ± 68.9 Modified 0.1 100 / 0 3105.8 ± 225.7 3466.6 ± 87.8 75 / 25 2482.5 ± 317.5 3865.3 ± 118.6 50 / 50 2395.2 ± 682.4 3648.3 ± 133.8 25 / 75 1411.1 ± 330.1 3522.2 ± 72.6 0 / 100 518.6 ± 92.3 3341.7 ± 114.8 Conclusion

[00256] Both T-CNCs and W-CNCs were successfully functionalized with methacrylate groups using glycidyl methacrylate (GMA). Raw W and T CNCs were soluble in water; but after grafting with methacrylate groups, their miscibility in the water decreased drastically. The miscibility of WM and TM in the resin was improved compared to that in water. The improved miscibility in resin helped to lower the yield shear stress of functionalized W-CNC inks. Although 0.1 wt% T-CNC ink followed the trend, the higher 0.25 and 0.5 wt% functionalized T-CNCs demonstrated increased shear yield strength values, which might be the result of residual water in the ink. Due to the higher aspect ratio of TCNC compared to the WCNC, TCNC particles have a higher surface area-to-volume ratio that can cause increased affinity to the residual water through H-bonding. The entrapped water can effectively increase the yield shear stress and lower the 3D printability of high TCNC-loaded inks.

[00257] The tensile fracture strength and modulus of functionalized WCNC nanocomposites were improved greatly upon 3 and 5 wt% of loading. The tensile fracture strength improved 2.5-fold for 3WM and 5WM whereas the modulus was increased 4-fold. However, their ductility decreased drastically, presumably due to an increase in crosslinking due to the methacrylate groups on the CNCs but also possibly due to extra crosslinking provided by residual GMA. The tensile strength and modulus were not improved for low (0.1-0.5 wt%) loading of WM, but the ductility did increase. Overall, the WM-based nanocomposites demonstrated increased tensile fracture strain and ductility, translating to greater toughness. The 0.5TM nanocomposite demonstrated similar behavior. The tensile fracture strength and modulus of 0.5TM were 35.03 ±2.77 MPa and 1681.36 ± 302.79 MPa, respectively, whereas the tensile fracture strength and modulus of the 0.5WM were 15.85 ± 0.65 MPa and 574.04 ± 15.71 MPa, CA 3302214 Date reçue / Received date 2026-02-18 51 respectively. The increased tensile properties of TM-based nanocomposites indicate the potential of these nanocomposites and the advantages of tunicate CNCs over wood CNCs. The mode-I plain strain fracture toughness (KIc) test indicated the same trend for TCNC-based nanocomposites. The KIc values of TCNC nanocomposites were two times greater than those of the WCNC nanocomposites. No effect of functionalization on KIc was detected in either the wood (W vs WM) or tunicate (T vs TM) groups. FULL CITATIONS FOR DOCUMENTS REFERRED TO IN THE APPLICATION [1] M. Shah, A. Ullah, K. Azher, A. U. Rehman, W. Juan, N. Aktürk, C. S. Tüfekci, M. U. Salamci, RSC Adv. 2023, 13, 1456. [2] M. A. S. Azizi Samir, F. Alloin, A. Dufresne, Biomacromolecules 2005, 6, 612. [3] L. Tang, C. Weder, ACS Appl. Mater. Interfaces 2010, 2, 1073. [4] N. Lin, J. Huang, A. Dufresne, Nanoscale 2012, 4, 3274. [5] M. R. Ayatollahi, S. Shadlou, M. M. Shokrieh, M. Chitsazzadeh, Polym. Test. 2011, 30, 548. [6] J. Zhu, S. Wei, J. Ryu, M. Budhathoki, G. Liang, Z. Guo, J. Mater. Chem. 2010, 20, 4937. [7] Y.-K. Choi, K. Sugimoto, S.-M. Song, Y. Gotoh, Y. Ohkoshi, M. Endo, Carbon N. Y. 2005, 43, 2199. [8] I. Zaman, T. T. Phan, H.-C. Kuan, Q. Meng, L. T. Bao La, L. Luong, O. Youssf, J. Ma, Polymer (Guildf). 2011, 52, 1603. [9] M. J. Dunlop, B. Acharya, R. Bissessur, J. Environ. Chem. Eng. 2018, 6, 4408.

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Claims

53 CLAIMS:

1. An aqueous nanocellulose dispersion comprising: a mixture of a plant derived nanocellulose (P-CNC) and a tunicate derived nanocellulose (T-CNC) in water, wherein the P-CNC and T-CNC are optionally surface modified with a surface modifier.

2. The aqueous nanocellulose dispersion of claim 1, wherein the P-CNC is a wood derived nanocellulose (W-CNC).

3. The aqueous nanocellulose dispersion of claim 1, wherein the mixture of the P-CNC and T-CNC is a hybrid mixture.

4. The aqueous nanocellulose dispersion of claim 1, wherein at least one of the P-CNC and T-CNC is surface modified with a hydrophobic surface modifier.

5. The aqueous nanocellulose dispersion of claim 4, wherein the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA).

6. The aqueous nanocellulose dispersion of claim 1, wherein the aqueous nanocellulose dispersion is a Herschel-Bulkley fluid and / or the aqueous nanocellulose dispersion has a shear yield strength between about 5mPa and about 10000mPa.

7. A nanocellulose dispersed resin composition comprising: a resin; and a tunicate derived cellulose nanocrystals (T-CNC), optionally surface modified with a surface modifier, and wherein the T-CNC is dispersed in the resin thereby forming the nanocellulose dispersed resin composition.

8. The nanocellulose dispersed resin composition of claim 7, wherein the composition further comprises plant derived cellulose nanocrystals (P-CNC), optionally a wood derived nanocellulose (W-CNC) and wherein the P-CNC and T-CNC is a hybrid mixture. CA 3302214 Date reçue / Received date 2026-02-18 54 9. The nanocellulose dispersed resin composition of claim 8, wherein at least one of the PCNC and T-CNC is surface modified with a hydrophobic surface modifier, optionally wherein the surface modifier comprises a methacrylate group.

10. The nanocellulose dispersed resin composition of claim 7, wherein the surface modifier comprises a methacrylate group, optionally wherein the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA).

11. The nanocellulose dispersed resin composition of claim 7, wherein the resin is a photopolymer resin.

12. The nanocellulose dispersed resin composition of claim 7, wherein the nanocellulose dispersed resin composition is a Herschel-Bulkley fluid.

13. An ink composition for additive manufacturing comprising: a photopolymer resin; and a nanofiller, wherein the nanofiller comprises tunicate derived cellulose nanocrystals (TCNC), wherein the T-CNC are optionally surface modified with a surface modifier, and wherein said nanofiller is dispersed in the photopolymer resin.

14. The ink composition of claim 13, wherein the photopolymer resin is a bio-based photopolymer resin, optionally a plant oil and wherein the photopolymer resin is UV curable.

15. The ink composition of claim 14, wherein the bio-based photopolymer resin comprises soybean oil, optionally a methacrylated epoxidized soybean oil (mAESO).

16. The ink composition of claim 13, wherein the composition further comprises plant derived cellulose nanocrystals (P-CNC), optionally a wood derived nanocellulose (W-CNC), and the mixture of the P-CNC and T-CNC is a hybrid mixture.

17. The ink composition of claim 16, wherein both of the P-CNC and T-CNC are surface modified with a hydrophobic surface modifier, optionally wherein the surface modifier comprises a methacrylate group.

18. The ink composition of claim 13, wherein the surface modifier is methacrylic anhydride (MAA) or glycidyl methacrylate (GMA). CA 3302214 Date reçue / Received date 2026-02-18 55 19. The ink composition of claim 13, wherein the additive manufacturing is masked stereolithography (mSLA) and / or wherein the ink composition is a Herschel-Bulkley fluid.

20. A polymer nanocomposite formed by additive manufacturing and curing the ink composition as defined in claim 13. CA 3302214 Date reçue / Received date 2026-02-18