Chemically Cross-Linked Cellulose Nanocrystal Aerogels with Shape Recovery and Superabsorbent Properties

Cellulose nanocrystals (CNCs) are entering the marketplace as new high-strength nanoadditives from renewable resources. These high aspect ratio particles have potential applications as rheological modifiers, reinforcing agents in composites, coatings, and porous materials. In this work, chemically cross-linked CNC aerogels were prepared based on hydrazone cross-linking of hydrazide and aldehyde-functionalized CNCs. The resulting aerogels were ultralightweight (5.6 mg/cm³) and highly porous (99.6%) with a bimodal pore distribution (mesopores <50 nm and macropores >1 μm). Chemically cross-linked CNC aerogels showed enhanced mechanical properties and shape recovery ability, particularly in water, compared to previous reports of physically cross-linked CNC aerogels. Specifically, the aerogel shape recovered more than 85% after 80% compression, even after 20 compress and release cycles. These CNC aerogels can absorb significant amounts of both water (160 ± 10 g/g of aerogel) and dodecane (72 ± 5 g/g of aerogel) with cyclic absorption capacity. We demonstrate that CNC aerogels can be used as superabsorbents and for oil/water separations and they may also find application as insulating or shock-absorbing materials. The cross-linking technology developed here presents new ways to design CNC networked structures and suggests an alternate route to incorporate CNCs into matrix materials, such as epoxies and foams

Benchmarking Cellulose Nanocrystals: From the Laboratory to Industrial Production

The renewability, biocompatibility, and mechanical properties of cellulose nanocrystals (CNCs) have made them an attractive material for numerous composite, biomedical, and rheological applications. However, for CNCs to shift from a laboratory curiosity to commercial applications, researchers must transition from CNCs extracted on the bench scale to material produced on an industrial scale. There are a number of companies currently producing kilogram to ton per day quantities of sulfuric acid-hydrolyzed CNCs as well as other nanocelluloses, as described herein. With the recent intensification of industrially produced CNCs and the variety of cellulose sources, hydrolysis methods, and purification procedures, the characterization of these materials becomes critical. This has further been justified by the past two decades of research that demonstrate that the CNC stability and behavior are highly dependent on the surface chemistry, surface charge density, and particle size. This work outlines key test methods that should be employed to characterize these properties to ensure a “known” starting material and consistent performance. Of the sulfuric acid-extracted CNCs examined, industrially produced material compared well with laboratory-made CNCs, exhibiting similar charge density, colloidal and thermal stability, crystallinity, morphology, and self-assembly behavior. In addition, it was observed that further purification of CNCs using Soxhlet extraction in ethanol had minimal impact on the nanoparticle properties and is unlikely to be necessary for many applications. Overall, the current standing of industrially produced CNCs is positive, suggesting that the evolution to commercial-scale applications will not be hindered by CNC production

Supporting Information from Optimization of cellulose nanocrystal length and surface charge density through phosphoric acid hydrolysis

Cellulose nanocrystals (CNCs) are emerging nanomaterials with a large range of potential applications. CNCs are typically produced through acid hydrolysis with sulfuric acid; however, phosphoric acid has the advantage of generating CNCs with higher thermal stability. This paper presents a design of experiments approach to optimize the hydrolysis of CNCs from cotton with phosphoric acid. Hydrolysis time, temperature and acid concentration were varied across nine experiments and a linear least-squares regression analysis was applied to understand the effects of these parameters on CNC properties. In all but one case, rod-shaped nanoparticles with a high degree of crystallinity and thermal stability were produced. A statistical model was generated to predict CNC length, and trends in phosphate content and zeta potential were elucidated. The CNC length could be tuned over a relatively large range (238–475 nm) and the polydispersity could be narrowed most effectively by increasing the hydrolysis temperature and acid concentration. The CNC phosphate content was most affected by hydrolysis temperature and time; however, the charge density and colloidal stability was considered low compared with sulfuric acid hydrolysed CNCs. This study provides insight into weak acid hydrolysis and proposes ‘design rules’ for CNCs with improved size uniformity and charge density.This article is part of a discussion meeting issue ‘New horizons for cellulose nanotechnology’

Injectable Polysaccharide Hydrogels Reinforced with Cellulose Nanocrystals: Morphology, Rheology, Degradation, and Cytotoxicity

Injectable hydrogels based on carboxymethyl cellulose and dextran, reinforced with rigid rod-like cellulose nanocrystals (CNCs) and aldehyde-functionalized CNCs (CHO–CNCs), were prepared and characterized. The mechanical properties, internal morphology, and swelling of injectable hydrogels with unmodified and modified CNCs at various loadings were examined. In all cases, gelation occurred within seconds as the hydrogel components were extruded from a double-barrel syringe, and the CNCs were evenly distributed throughout the composite, as observed by scanning and transmission electron microscopy. When immersed in purified water or 10 mM PBS, all CNC-reinforced hydrogels maintained their original shape for more than 60 days. The maximum storage modulus was observed in hydrogels with 0.250 wt % of unmodified CNCs and 0.375 wt % of CHO–CNCs. CHO–CNCs acted as both a filler and a chemical cross-linker, making the CHO–CNC-reinforced hydrogels more elastic, more dimensionally stable, and capable of facilitating higher nanoparticle loadings compared to hydrogels with unmodified CNCs, without sacrificing mechanical strength. No significant cytotoxicity to NIH 3T3 fibroblast cells was observed for the hydrogels or their individual components. These properties make CNC-reinforced injectable hydrogels of potential interest for various biomedical applications such as drug delivery vehicles or tissue engineering matrices

Synergistic Stabilization of Emulsions and Emulsion Gels with Water-Soluble Polymers and Cellulose Nanocrystals

The effect of water-soluble polymers on the properties of Pickering emulsions stabilized by cellulose nanocrystals (CNCs) was investigated. Pretreatment of CNCs with excess adsorbing polymer, hydroxyethyl cellulose (HEC) or methyl cellulose (MC), gave smaller and more stable dodecane-in-water emulsion droplets compared to either polymer or CNCs alone, i.e., synergistic stabilization. By contrast, dextran, which does not adsorb on CNCs, gave unstable emulsions, with or without CNCs. CNCs with HEC or MC produced emulsions that showed no significant creaming or phase separation over several months. Interfacial tension, quartz crystal microbalance and confocal laser scanning microscopy measurements indicate that both HEC and MC are surface active and adsorb onto CNCs. 75% of the oil–water interface is covered by CNC particles coated with HEC or MC and the remaining interface is stabilized by HEC or MC chains not bound to cellulose. Viscoelastic emulsion gels were also produced by adding excess MC to the CNC-HEC emulsions and heating above 70 °C. The thermogelation was reversible, and multiple cycles of heating/cooling did not lead to coalescence of the emulsion. This work points to broad application of CNCs with water-soluble polymers as promising green emulsion stabilizers for food, pharmaceutical, and cosmetic products

Stable Aqueous Foams from Cellulose Nanocrystals and Methyl Cellulose

The addition of cellulose nanocrystals (CNC) greatly enhanced the properties of methylcellulose (MC) stabilized aqueous foams. CNC addition decreased air bubble size, initial foam densities and drainage rates. Mixtures of 2 wt % CNC + 0.5 wt % MC gave the lowest density foams. This composition sits near the onset of nematic phase formation and also near the overlap concentration of methylcellulose. More than 94% of the added CNC particles remained in the foam phase, not leaving with the draining water. We propose that the nanoscale CNC particles bind to the larger MC coils both in solution and with MC at the air/water interface, forming weak gels that stabilize air bubbles. Wet CNC-MC foams were sufficiently robust to withstand high temperature (70 °C for 6 h) polymerization of water-soluble monomers giving macroporous CNC composite hydrogels based on acrylamide (AM), 2-hydroxyethyl methacrylate (HEMA), or polyethylene glycol diacrylate (PEGDA). At high temperatures, the MC was present as a fibrillar gel phase reinforced by CNC particles, explaining the very high foam stability. Finally, our CNC-MC foams are based on commercially available forms of CNC and MC, already approved for many applications. This is a “shovel-ready” technology

Tuning Cellulose Nanocrystal Gelation with Polysaccharides and Surfactants

Gelation of cellulose nanocrystal (CNC) dispersions was measured as a function of the presence of four nonionic polysaccharides. Addition of hydroxyethyl cellulose (HEC), hydroxypropyl guar (HPG), or locust bean gum (LBG) to CNC dispersions induced the gelation of dilute CNC dispersions, whereas dextran (DEX) did not. These behaviors correlated with adsorption tendencies; HEC, HPG, and LBG adsorbed onto CNC-coated quartz crystal microbalance sensors, whereas DEX did not adsorb. We propose that the adsorbing polysaccharides greatly increased the effective volume fraction of dilute CNC dispersions, driving more of the nanocrystals into anisotropic domains. SDS and Triton X-100 addition disrupted HEC–CNC gels whereas CTAB did not. Surface plasmon resonance measurements with CNC-coated sensors showed that SDS and Triton X-100 partially removed adsorbed HEC, whereas CTAB did not. These behaviors illustrate the complexities associated with including CNC dispersions in formulated products: low CNC contents can induce spectacular changes in rheology; however, surfactants and soluble polymers may promote gel formation or induce CNC coagulation

Polymer-Grafted Cellulose Nanocrystals as pH-Responsive Reversible Flocculants

Cellulose nanocrystals (CNCs) are a sustainable nanomaterial with applications spanning composites, coatings, gels, and foams. Surface modification routes to optimize CNC interfacial compatibility and functionality are required to exploit the full potential of this material in the design of new products. In this work, CNCs have been rendered pH-responsive by surface-initiated graft polymerization of 4-vinylpyridine with the initiator ceric­(IV) ammonium nitrate. The polymerization is a one-pot, water-based synthesis carried out under sonication, which ensures even dispersion of the cellulose nanocrystals during the reaction. The resultant suspensions of poly­(4-vinylpyridine)-grafted cellulose nanocrystals (P4VP-<i>g</i>-CNCs) show reversible flocculation and sedimentation with changes in pH; the loss of colloidal stability is visible by eye even at concentrations as low as 0.004 wt %. The presence of grafted polymer and the ability to tune the hydrophilic/hydrophobic properties of P4VP-<i>g</i>-CNCs were characterized by Fourier transform infrared spectroscopy, elemental analysis, electrophoretic mobility, mass spectrometry, transmittance spectroscopy, contact-angle measurements, thermal analysis, and various microscopies. Atomic force microscopy showed no observable changes in the CNC dimensions or degree of aggregation after polymer grafting, and a liquid crystalline nematic phase of the modified CNCs was detected by polarized light microscopy. Controlled stability and wettability of P4VP-<i>g</i>-CNCs is advantageous both in composite design, where cellulose nanocrystals generally have limited dispersibility in nonpolar matrices, and as biodegradable flocculants. The responsive nature of these novel nanoparticles may offer new applications for CNCs in biomedical devices, as clarifying agents, and in industrial separation processes

DNA Stickers Promote Polymer Adsorption onto Cellulose

Adsorption of oligonucleotides onto model cellulose surfaces was investigated by comparing the Boese and Breaker’s cellulose binding oligonucleotide (CBO) with a nonspecific oligonucleotide control (NSO). Measurements using the quartz crystal microbalance with dissipation technique confirmed that CBO adsorbed onto cellulose more than NSO, particularly at high ionic strengths (100 mM CaCl₂). CBO showed a higher maximum adsorption on nanofibrillated and nanocrystalline cellulose than on regenerated cellulose, indicating a preference for the native cellulose I crystal structure under conditions that favored specific adsorption over calcium-mediated electrostatically driven adsorption. In addition, an anionic polyacrylamide (A-PAM) with grafted CBO also adsorbed onto the surface of cellulose in CaCl₂, whereas the unmodified A-PAM did not. This work shows that CBO performs as a “sticker”, facilitating the adsorption of polyacrylamide onto cellulose, even under high ionic strength conditions where the adsorption of conventional polyelectrolytes is inhibited