The influence of cellulose crystallinity on mechanical properties of cellulose nano-fibrils (CNF) was investigated. Degree of crystallinity (DoC) was modified using liquid anhydrous ammonia. Such treatment changes crystal allomorph from cellulose I to cellulose III, a change which was reversed by subsequent boiling in water. DoC was measured using solid state nuclear magnetic resonance (NMR). Crystalline index (CI) was also measured using wide angle X-ray scattering (WAXS). Cotton linters were used as the raw material. The cotton linter was ammonia treated prior to fibrillation. Reduced DoC is seen to associate with an increased yield point and decreased Young modulus. Young modulus is here defined as the maximal slope of the stress-strain curves. The association between DoC and Young modulus or DoC and yield point are both statistically significant. We cannot conclude there has been an effect on strainability. While mechanical properties were affected, we found no indication that ammonia treatment affected degree of fibrillation. CNF was also studied in air and liquid using atomic force microscopy (AFM). Swelling of the nanofibers was observed, with a mean diameter increase of 48.9%.

Noncrystalline cellulose-based gel beads were used as a model material to investigate the effect of osmotic stress on a cellulosic network. The gel beads were exposed to osmotic stress by immersion in solutions with different concentrations of high molecular mass dextran and the equilibrium dimensional change of the gel beads was studied using optical microscopy. The volume fraction of cellulose was calculated from the volume of the gel beads in dextran solutions and their dry content and the relation between the cellulose volume fraction and the total osmotic pressure was thus obtained. The results show that the contribution to the osmotic pressure from counterions increases the water-retaining capacity of the beads at high osmotic pressures but also that the main factor controlling the gel bead collapse at high osmotic strains is the resistance to the deformation of the polymer chain network within the beads. Furthermore, the osmotic pressure associated with the deformation of the polymer network, which counteracts the deswelling of the beads, could be fitted to the Wall model indicating that the response of the cellulose polymer networks was independent of the charge of the cellulose. The best fit to the Wall model was obtained when the Flory-Huggins interaction parameter () of the cellulose-water system was set to 0.55-0.60, in agreement with the well-established insolubility of high molecular mass β-(1,4)-d-glucan polymers in water.

Macroscopic beads of water-based gels consisting of uncharged and partially charged beta-(1,4)-D-glucan polymers were developed to be used as a novel model material for studying the water induced swelling of the delignified plant fiber walls. The gel beads were prepared by drop-wise precipitation of solutions of dissolving grade fibers carboxymethylated to different degrees. The internal structure was analyzed using Solid State Cross-Polarization Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance and Small Angle X-ray Scattering showing that the internal structure could be considered a homogeneous, non-crystalline and molecularly dispersed polymer network. When beads with different charge densities were equilibrated with aqueous solutions of different ionic strengths and/or pH, the change in water uptake followed the trends expected for weak polyelectrolyte gels and the trends found for cellulose-rich fibers. When dried and subsequently immersed in water the beads also showed an irreversible loss of swelling depending on the charge and type of counter-ion which is commonly also found for cellulose-rich fibers. Taken all these results together it is clear that the model cellulose-based beads constitute an excellent tool for studying the fundamentals of swelling of cellulose rich plant fibers, aiding in the elucidation of the different molecular and supramolecular contributions to the swelling.

Nanoscale building blocks of many materials exhibit extraordinary mechanical properties due to their defect-free molecular structure. Translation of these high mechanical properties to macroscopic materials represents a difficult materials engineering challenge due to the necessity to organize these building blocks into multiscale patterns and mitigate defects emerging at larger scales. Cellulose nanofibrils (CNFs), the most abundant structural element in living systems, has impressively high strength and stiffness, but natural or artificial cellulose composites are 3-15 times weaker than the CNFs. Here, we report the flow-assisted organization of CNFs into macroscale fibers with nearly perfect unidirectional alignment. Efficient stress transfer from macroscale to individual CNF due to cross-linking and high degree of order enables their Young's modulus to reach up to 86 GPa and a tensile strength of 1.57 GPa, exceeding the mechanical properties of known natural or synthetic biopolymeric materials. The specific strength of our CNF fibers engineered at multiscale also exceeds that of metals, alloys, and glass fibers, enhancing the potential of sustainable lightweight high-performance materials with multiscale self-organization.

Herein, we present a route to obtain bi-functional cellulose nanofibrils (CNF) by a one-pot approach using an already established functionalisation route, carboxymethylation, to which a subsequent functionalisation step, allylation or alkynation, has been added in the same reaction pot, eliminating the need of solvent exchange procedures. The total charge of the fibres and the total surface charge of the nanofibrils were determined by conductometric and polyelectrolyte titration, respectively. Furthermore, the allyl and alkyne functionalised cellulose were reacted with methyl 3-mercaptopropionate and azide-functionalised disperse red, respectively, to estimate the degree of functionalisation. The samples were further assessed by XPS and FT-IR. Physical characteristics were evaluated by CP/MAS C-13-NMR, XRD, AFM and DLS. This new approach of obtaining bi-functionalised CNF allows for a facile and rapid functionalisation of CNF where chemical handles can easily be attached and used for further modification of the fibrils.

Poly(epsilon-caprolactone) (PCL) is a ductile thermoplastic, which is biodegradable in the marine environment. Limitations include low strength, petroleum-based origin, and comparably high cost. Cellulose fiber reinforcement is therefore of interest although uniform fiber dispersion is a challenge. In this study, a one-step wet compounding is proposed to validate a sustainable and feasible method to improve the dispersion of the cellulose fibers in hydrophobic polymer matrix as PCL, which showed to be insensitive to the presence of the water during the processing. A comparison between unmodified and acetylated cellulosic wood fibers is made to further assess the net effect of the wet feeding and chemical modification on the biocomposites properties, and the influence of acetylation on fiber structure is reported (ATR-FTIR, XRD). Effects of processing on nano fibrillation, shortening, and dispersion of the cellulose fibers are assessed as well as on PCL molar mass. Mechanical testing, dynamic mechanical thermal analysis, FE-SEM, and X-ray tomography is used to characterize composites. With the addition of 20 wt % cellulosic fibers, the Young's modulus increased from 240 MPa (neat PCL) to 1850 MPa for the biocomposites produced by using the wet feeding strategy, compared to 690 MPa showed for the biocomposites produced using dry feeling. A wet feeding of acetylated cellulosic fibers allowed even a greater increase, with an additional 46% and 248% increase of the ultimate strength and Young's modulus, when compared to wet feeding of the unmodified pulp, respectively.

By combining H-2-NMRD and CP/MAS C-13-NMR measurements of water-based cellulose gels and of water swollen pulps it was possible to estimate the nature of the interior structure of cellulose fibril aggregates. A set of samples with high cellulose purity and low charge was used. The interpretation of data was based on a relaxation model describing the exchange dynamics for deuterium exchange between water molecules and cellulose hydroxyl groups. The theoretical model used made it possible to calculate cellulose surface-to-volume ratios (q-values) from both H-2-NMRD and CP/MAS C-13-NMR data. Good consistency between H-2-NMRD and CP/MAS C-13-NMR data was found. In all investigated samples the cellulose fibril aggregates showed a different degree of "openness" interpreted as the presence of interstitial water inside fibril aggregates. One result also showed that an increased degree of fibril aggregate openness results from the TEMPO-oxidation. Common to all samples was that in the water swollen state water molecules could access part of the fibril aggregate interior.

By combining H-2-NMRD and CP/MAS C-13-NMR measurements of water-based cellulose gels and of water swollen pulps it was possible to estimate the nature of the interior structure of cellulose fibril aggregates. A set of samples with high cellulose purity and low charge was used. The interpretation of data was based on a relaxation model describing the exchange dynamics for deuterium exchange between water molecules and cellulose hydroxyl groups. The theoretical model used made it possible to calculate cellulose surface-to-volume ratios (q-values) from both H-2-NMRD and CP/MAS C-13-NMR data. Good consistency between H-2-NMRD and CP/MAS C-13-NMR data was found. In all investigated samples the cellulose fibril aggregates showed a different degree of "openness" interpreted as the presence of interstitial water inside fibril aggregates. One result also showed that an increased degree of fibril aggregate openness results from the TEMPO-oxidation. Common to all samples was that in the water swollen state water molecules could access part of the fibril aggregate interior.

Background: The efficiency of enzymatic hydrolysis is reduced by the structural properties of cellulose. Although efforts have been made to explain the mechanism of enzymatic hydrolysis of cellulose by considering the interaction of cellulolytic enzymes with cellulose or the changes in the structure of cellulose during enzymatic hydrolysis, the process of cellulose hydrolysis is not yet fully understood. We have analysed the characteristics of the complex supramolecular structure of cellulose on the nanometre scale in terms of the spatial distribution of fibrils and fibril aggregates, the accessible surface area and the crystallinity during enzymatic hydrolysis. Influence of the porosity of the substrates and the hydrolysability was also investigated. All cellulosic substrates used in this study contained more than 96% cellulose. Results: Conversion yields of six cellulosic substrates were as follows, in descending order: nano-crystalline cellulose produced from never-dried soda pulp (NCC-OPHS-ND) > never-dried soda pulp (OPHS-ND) > dried soda pulp (OPHS-D) > Avicel > cotton treated with sodium hydroxide (cotton + NaOH) > cotton. Conclusions: No significant correlations were observed between the yield of conversion and supramolecular characteristics, such as specific surface area (SSA) and lateral fibril dimensions (LFD). A strong correlation was found between the average pore size of the starting material and the enzymatic conversion yield. The degree of crystallinity was maintained during enzymatic hydrolysis of the cellulosic substrates, contradicting previous explanations of the increasing crystallinity of cellulose during enzymatic hydrolysis. Both acid and enzymatic hydrolysis can increase the LFD, but no plausible mechanisms could be identified. The sample with the highest initial degree of crystallinity, NCC-OPHS-ND, exhibited the highest conversion yield, but this was not accompanied by any change in LFD, indicating that the hydrolysis mechanism is not based on lateral erosion.