Short cellulose nanofibrils as reinforcement in polyvinyl alcohol fiber

Short cellulose nanofibrils (SCNF) were investigated as reinforcement for polyvinyl alcohol (PVA) fibers. SCNF were mechanically isolated from hard wood pulp after enzymatic pretreatment. Various levels of SCNF were added to an aqueous PVA solution, which was gel-spun into continuous fibers. The molecular orientation of PVA was affected by a combination of wet drawing during gel spinning and post-hot-drawing at a high temperature after drying. A maximum total draw ratio of 27 was achieved with various SCNF contents investigated. The PVA crystal orientation increased when small amounts of SCNF were added, but decreased again as the SCNF content was increased above about 2 or 3 %, likely due to SCNF percolation resulting in network formation that inhibited alignment. SCNF fillers were effective in improving PVA fiber tensile properties (i.e., ultimate strength and elastic modulus). For example, the ultimate strength and modulus of PVA/SCNF composite fiber with a SCNF weight ratio of 6 were nearly 60 and 220 % higher than that of neat PVA. Shifts in the Raman peak at ~1,095 cm^?1, which were associated with the C–O–C glycosidic bond of SCNF, indicated good stress-transfer between the SCNF and the PVA matrix due to strong interfacial hydrogen bonding. Cryogenic fractured scanning electron microscopy images of filled and unfilled PVA fibers showed uniform SCNF dispersion.     

Water redispersible cellulose nanofibrils adsorbed with carboxymethyl cellulose

Cellulose nanofibrils (CNFs) are difficult to redisperse in water after they have been completely dried due to the irreversible agglomeration of cellulose during drying. Here, we have developed a simple process to prepare water-redispersible dried CNFs by the adsorption of small amounts of carboxymethyl cellulose (CMC) and oven drying. The adsorption of CMC onto CNFs in water suspensions at 22 and 121 °C was studied, and the adsorbed amount of CMC was measured via conductimetric titration. The water-redispersibility of dried CNFs adsorbed with different amounts of CMC was characterized by sedimentation test. Above a critical threshold of CMC adsorption, i.e. 2.3 wt%, the oven dried CNF–CMC sample was fully redispersible in water. The morphology, rheological, and mechanical properties of water-redispersed CNF–CMC samples were investigated by field emission scanning electron microscopy, viscosity measurement, and tensile test, respectively. The water-redispersed CNFs preserved the original properties of never dried CNFs. This new method will facilitate the production, transportation and storage, and large-scale industrial applications of CNFs.     

Interactions between inorganic nanoparticles and cellulose nanofibrils

Nanofibrillated cellulose (NFC) is increasingly utilized in materials and biomedical applications consequently increasing interest in the modification of its surface properties. Besides modification using polyelectrolytes and polysaccharides, NFC can be combined with solid particles enabling formation of fibril network loaded with particles. Use of particles enabling easy functionalization could be beneficial for the development of hybrid structures, and lead to preparation of nanocomposites and functional materials. In order to explore interactions related to preparation of such structures, the interactions between nanosized precipitated calcium carbonate (nanoPCC) and nanoclay particles and NFC were examined by observing adsorption of the particles on NFC substrate using a quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM) imaging. By a treatment with carboxymethylated cellulose (CMC), the anionicity of the NFC substrate could be increased, providing an additional tool to affect the interplay between NFC and the inorganic particles. For slightly cationic nanoPCC particles an increase in the anionicity of the NFC by the CMC treatment increased the affinity, while the opposite was true for anionic nanoclay. Additionally, for interactions between nanoclay and NFC, dispersion stability was an important factor. QCM-D was successfully used to examine the adsorption characteristics of nanoparticles although the technique is commonly used to study the adsorption of thin polymer layers. Distinct adsorption characteristics were observed depending on the nanoparticle used; nanoclay particles deposited as a thin layer, whereas nanoPCC particles formed clusters.     

Dewatering of cellulose nanofibrils using ultrasound

Although cellulose nanomaterials have promising properties and performance in a wide application space, one hinderance to their wide scale industrial application has been associated with their economics of dewatering and drying and the ability to redisperse them back into suspension without introducing agglomerates or lose of yield. The present work investigates the dewatering of aqueous suspensions of cellulose nanofibrils (CNFs) using ultrasound as a potentially low-cost, non-thermal, and scalable alternative to traditional heat-based drying methods such as spray drying. Specifically, we use vibrating mesh transducers to develop a direct-contact mode ultrasonic dewatering platform to remove water from CNF suspensions in a continuous manner. We demonstrate that the degree of dewatering is modulated by the number of transducers, their spatial configuration, and the flow rate of the CNF suspension. Water removal of up to 72 wt.% is achieved, corresponding to a final CNF concentration of 11 wt.% in 30 min using a two-transducer configuration. To evaluate the redispersibility of the dewatered CNF material, we use a microscopic analysis to quantify the morphology of the redispersed CNF suspension. By developing a custom software pipeline to automate image analysis, we compare the histograms of the dimensions of the redispersed dewatered fibrils with the original CNF samples and observe no significant difference, suggesting that no agglomeration is induced due to ultrasonic dewatering. We also perform SEM analysis to evaluate the nanoscale morphology of these fibrils showing a width range of 20 nm–4 um. We estimate that this ultrasound dewatering technique is also energy-efficient, consuming up to 36% less energy than the enthalpy of evaporation per kilogram of water. Together with the inexpensive cost of transducers (<?$1), the potential for scaling up in parallel flow configurations, and excellent redispersion of the dewatered CNFs, our work offers a proof-of-concept of a sustainable CNF dewatering system, that addresses the shortcomings of existing techniques.

     

Aerogel microspheres based on cellulose nanofibrils as potential cell culture scaffolds

Crosslinked poly(vinyl alcohol) (PVA)/cellulose nanofibril (CNF) hybrid aerogel micro-spheres with two different particle sizes were fabricated via a combination of the water-in-oil (W/O) emulsification process and the freeze-drying process. The aerogel micro-spheres were highly porous with a bulk density as low as 0.0047 g/cm³ for the large microspheres. The pore size of the microspheres ranged from nano- to micro-meters. Preliminary biocompatibility assays of the aerogel microspheres were investigated with NIH 3T3 cells to explore their potential application as cell culture scaffolds. The highly crosslinked aerogel microspheres were robust and were able to maintain their shape during the cell culture process. The live/dead assay showed that the cells could be seeded, attached, and proliferated on the surface of PVA/CNF aerogel microspheres. The fluorescence images showed that some of the cells migrated into the inner pores of the microspheres. Moreover, the large microspheres with larger average pore sizes had a higher cell count than that of the small microspheres. This study confirms that the PVA/CNF aerogel microspheres fabricated in this work are nontoxic and biocompatible. Furthermore, the interconnected, highly porous nanofibrous structure of the microspheres can successfully facilitate cell attachment, differentiation, and proliferation.     

Nanocomposites of natural rubber and polyaniline-modified cellulose nanofibrils

Cellulose nanofibrils (CNF) were isolated from cotton microfibrils (CM) by acid hydrolysis and coated with polyaniline (PANI) by in situ polymerization of aniline onto CNF in the presence of hydrochloride acid and ammonium peroxydisulfate to produce CNF/PANI. Nanocomposites of natural rubber (NR) reinforced with CNF and CNF/PANI were obtained by casting/evaporation method. TG analyses showed that coating CNF with PANI resulted in a material with better thermal stability since PANI acted as a protective barrier against cellulose degradation. Nanocomposites and natural rubber showed the same thermal profiles to 200 °C, partly due to the relatively lower amount of CNF/PANI added as compared to conventional composites. On the other hand, mechanical properties of natural rubber were significantly improved with nanofibrils incorporation, i.e., Young’s modulus and tensile strength were higher for NR/CNF than NR/CNF/PANI nanocomposites. The electrical conductivity of natural rubber increased five orders of magnitude for NR with the addition of 10 mass% CNF/PANI. A partial PANI dedoping might be responsible for the low electrical conductivity of the nanocomposites.     

Length-controlled cellulose nanofibrils produced using enzyme pretreatment and grinding

The length of cellulose nanofibrils (CNFs) is a significant parameter for various applications. The goal of this research was to employ a fabrication method to produce length-controlled CNFs; the chosen technique was enzy-grinding (enzyme pretreatment followed by mechanical grinding). Here, we presented the results of the optimization of the diameter and length, the characterization of the properties of CNFs and nanofilms prepared using these fibrils. The cellulose morphology, crystallinity index (CrI), chemical structure, and thermal stability were investigated as functions of the enzyme loading and hydrolysis time. The results showed that enzy-grinding could effectively reduce the diameter and length of cellulose fibrils. The average diameter was about 8.6 ± 3.6 nm, and the length could be controlled over the range from 0.76 ± 0.38 μm to ≥ 4 μm (i.e. aspect ratios from 43 to ≥ 328). After the grinding process, the CNFs maintained high thermal stability and no change in the chemical structure compared to the original pulp. The transmittance and mechanical properties of the CNF films were strongly dependent on the fibril length. The fabrication of length-controlled CNFs using the enzy-grinding process is meaningful and significant research which could be relevant to the optimization of such materials for various applications.     

Chemically modified nylons as supports for enzyme immobilization

An isocyanide derivative of nylon, polyisonitrile-nylon (1,2), was used as a starting material whereby, through a series of modification reactions, different chemically reactive functional groups could be introduced on the polyamide backbone. The chemistry employed allowed for considerable flexibility in the choice of procedures for covalent fixation of proteins, all starting from the same chemically reactive parent polymer, polyisonitrile-nylon. Thus, polyisonitrilenylon could be used directly for the immobilization of enzymes via fourcomponent condensation reactions. The isocyanide functional groups of the parent polymer could be transformed, by treatment with bromine, into the strongly electrophilic dibromoisocyanide (—N=CBr^b2) groups. The selectivity of the —N=CBr^b2 group toward the various functional groups present in proteins could be regulated by appropriate control of the pH of the coupling reaction. Dibromoisocyanide-nylon was also further modified into other types of chemically reactive nylon derivatives.     

Production of cellulose nanofibrils via an eco-friendly approach

Cellulose - Swelling of cellulose fibers facilitates the fibrillation process by mechanical treatment. In this study, potassium hydroxide (KOH)-urea (KUr) solution was investigated to swell fibers...     

Intrinsic viscosity of aqueous suspensions of cellulose nanofibrils

Cellulose nanofibrils (CNF) from wood fibers are of increasing interest to industry because they are from renewable sources and are biodegradable. Owing to their high aspect ratio, they produce viscous suspensions and stiff gels that are strengthened by interfibrillar hydrogen bonds. In this study, the viscosity of aqueous CNF suspensions, at dilute concentrations ( \(nL^{3}<1\) ), was measured at various pH values by addition of HCl, and at various ionic strengths by addition of NaCl and \(\hbox {CaCl}_{2}\) . The results show that the primary electroviscous effect significantly increases the intrinsic viscosity. The intrinsic viscosity under conditions where the surface charge of nanofibrils is fully screened is in good agreement with the predictions of classical theory for dispersions of rodlike particles at low shear rates. Increasing the ionic strength up to \(\kappa d\approx 1\) decreases the intrinsic viscosity; at \(\kappa d>1\) , the intrinsic viscosity increases because of fibril aggregation and increase of the effective volume fraction.     

Wood cellulose nanofibrils prepared by TEMPO electro-mediated oxidation

A softwood bleached kraft pulp (SBKP) was subjected to electro-mediated oxidation in water with TEMPO or 4-acetamido-TEMPO without any chlorine-containing oxidant. Solid recovery ratios of water-insoluble fractions of the oxidized SBKPs were more than 80%, and C6-carboxylate contents increased up to approximately 1 mmol g⁻¹ after oxidation for 48 h. Significant amounts of C6-aldehyde groups (0.17–0.38 mmol g⁻¹) were also formed in the oxidized SBKPs. The degree of polymerization decreased from 2,200 to 520 and 1,400 by the oxidation for 48 h with TEMPO at pH 10 and 4-acetamido-TEMPO at pH 6.8, respectively. The original cellulose I crystal structure and crystallinity of SBKP were maintained after the oxidation, indicating that all C6-oxidized groups were selectively formed on crystalline cellulose microfibril surfaces. The oxidized SBKPs with carboxylate contents of more than 0.9 mmol g⁻¹ were convertible to individual cellulose nanofibrils in yields of more than 80% by disintegration in water.     

Chemically modified opals as thin permselective nanoporous membranes

Thin-film opals comprising three layers of 440 nm diameter SiO2 spheres were assembled on Pt electrodes and modified with amino groups on the silica surface. Diffusion of anionic, cationic, and neutral redox species through the opals was studied by cyclic voltammetry. The chemically modified opal membranes demonstrate high molecular throughput and, at low pH, selectively block transport of a cationic redox species relative to that of anionic and neutral redox species. This permselective behavior is attributed to the electrostatic interactions that are enhanced by the tortuous pathway within the opal and by the high surface area of the chemically modified spheres.     

Degradation of TEMPO-oxidized cellulose fibers and nanofibrils by crude cellulase

The biodegradation behavior of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized cellulose fibers (TOCs) suspended in water and TEMPO-oxidized cellulose nanofibrils (TOCNs) dispersed in water by a commercial crude cellulase was studied. Products crude cellulase-treated for 0–7 days were separated into water/ethanol-insoluble and -soluble fractions. Weight recovery ratios and viscosity-average degrees of polymerization of the water/ethanol-insoluble fractions clearly decreased with crude cellulase-treatment time, showing that both TOCs and TOCNs have biodegradability. Water/ethanol-soluble fractions were subjected to size-exclusion chromatography (SEC) with photodiode array (PDA) detection to obtain SEC elution patterns detected by reflective index and UV spectra of each SEC pattern elution slice. SEC–PDA and ¹³C-NMR analyses showed that glucuronosyl unit-containing molecules present on microfibril surfaces in TOCs and TOCNs were primarily cleaved by hydrolyzing enzymes present as contaminants in the crude cellulase to form glucuronic acid as one of the major water-soluble degradation compounds. After the glucuronosyl units in TOCs and TOCNs were degraded and removed from microfibril surfaces by the hydrolyzing enzymes, cellulose chains newly exposed on the microfibril surfaces were rapidly hydrolyzed by cellulases predominantly present in the crude cellulase to form cellobiose. Both TOCs and TOCNs having sodium carboxyl groups are thus biodegradable, but TOCN having free carboxyl groups had clearly low biodegradability by the crude cellulase. Thus, biodegradation behavior may be controllable by controlling the structure of carboxyl group counter ions in TOCs and TOCNs.     

DFT study of metal cation-induced hydrogelation of cellulose nanofibrils

We report a density functional theory study of cation-induced bonding between carboxylated cellulose nanofibrils (CNFs). We describe a methodology of using cleaved cellulose crystal unit cells to develop simple surface and molecular models of charged CNFs. We compare bond lengths, binding energies, and displaced solvation volumes for interfibril models intercalated with alkali, alkaline earth, main group, or transition metal cations, surrounded by an implicit solvent. We characterize the type of bonding interactions that occur between metal cations, Mⁿ⁺ and carboxylated CNF surfaces by calculating the electronic density of states and Mayer bond orders. We find that Mⁿ⁺–O interactions for alkaline earth metal systems are predominantly electrostatic whereas transition metal cations form stronger, more covalent bonds with enhanced valence orbital overlap. Our results show that multivalent—as opposed to monovalent—ions can create CNF networks by effectively crosslinking multiple fibrils through surface carboxylate anions. Our computational results agree with empirical models of metal–carboxylate binding, while also providing a deeper understanding of the bonding mechanisms for different cations. Our findings help to explain trends in recent CNF hydrogelation experiments, and we also predict the existence of two new hydrogels—CNF-Mg²⁺ and CNF-Zr⁴⁺.     

Dispersion stability and aggregation behavior of TEMPO-oxidized cellulose nanofibrils in water as a function of salt addition

Dispersion stability of TEMPO-oxidized cellulose nanofibrils (TOCNs) in water was investigated through both experimental and theoretical analyses to elucidate the critical aggregation concentration of different salts. The 0.1 wt% TOCN/water dispersions with various NaCl concentrations were evaluated by measuring light transmittance, viscosity under steady-shear flow, and the weight fraction of TOCN that had aggregated. Homogeneous TOCN/water dispersion turned to gel as the NaCl concentration increased. The TOCN dispersion maintained its homogeneous state up to 50 mM NaCl, but aggregated gel particles were formed at 100 mM NaCl. The mixture became separated into two phases (gel and supernatant) at ≥200 mM NaCl. Theoretical analysis using ζ-potentials of TOCN elements in the dispersions revealed that the aggregation behavior upon NaCl addition could be explained well in terms of the interaction potential energy between two cylindrical rods based on the Derjaguin–Landau–Verwey–Overbeek theory. The experiments were extended to analyze critical aggregation concentrations of MgCl₂ and CaCl₂ for the 0.1 wt% TOCN dispersion. In the case of divalent electrolytes, TOCN elements began to form aggregated gel particles at salt concentrations of 2–4 mM, corresponding to the critical aggregation concentration predicted by the empirical Schultz-Hardy rule.     

Comparison of multilayer formation between different cellulose nanofibrils and cationic polymers

The multilayer formation between polyelectrolytes of opposite charge offers possibility for creating new tailored materials. Exchanging one or both components for charged nanofibrillated cellulose (NFC) further increases the variety of achievable properties. We explored this by introducing unmodified, low charged NFC and high charged TEMPO-oxidized NFC. Systematic evaluation of the effect of both NFC charge and properties of cationic polyelectrolytes on the structure of the multilayers was performed. As the cationic component cationic NFC was compared with two different cationic polyelectrolytes, poly(dimethyldiallylammoniumchloride) and cationic starch. Quartz crystal microbalance with dissipation (QCM-D) was used to monitor the multilayer formation and AFM colloidal probe microscopy (CPM) was further applied to probe surface interactions in order to gain information about fundamental interactions and layer properties. Generally, the results verified the characteristic multilayer formation between NFC of different charge and how the properties of formed multilayers can be tuned. However, the strong nonelectrostatic affinity between cellulosic fibrils was observed. CPM measurements revealed monotonically repulsive forces, which were in good correspondence with the QCM-D observations. Significant increase in adhesive forces was detected between the swollen high charged NFC.     

Enzymatic hydrolysis of native cellulose nanofibrils and other cellulose model films: effect of surface structure

Model films of native cellulose nanofibrils, which contain both crystalline cellulose I and amorphous domains, were used to investigate the dynamics and activities of cellulase enzymes. The enzyme binding and degradation of nanofibril films were compared with those for other films of cellulose, namely, Langmuir-Schaefer and spin-coated regenerated cellulose, as well as cellulose nanocrystal cast films. Quartz crystal microbalance with dissipation (QCM-D) was used to monitor the changes in frequency and energy dissipation during incubation at varying enzyme concentrations and experimental temperatures. Structural and morphological changes of the cellulose films upon incubation with enzymes were evaluated by using atomic force microscopy. The QCM-D results revealed that the rate of enzymatic degradation of the nanofibril films was much faster compared to the other types of cellulosic films. Higher enzyme loads did not dramatically increase the already fast degradation rate. Real-time measurements of the coupled contributions of enzyme binding and hydrolytic reactions were fitted to an empirical model that closely described the cellulase activities. The hydrolytic potential of the cellulase mixture was found to be considerably affected by the nature of the substrates, especially their crystallinity and morphology. The implications of these observations are discussed in this report.