This paper summarizes chemical technologies aimed at making bulking fibres, a technology mainly practiced in the area of tissue and hygiene products but also highly relevant for board products made by sheet stratification containing bulking layers in the middle of the board in order to improve the bending stiffness of the board. There is a long history of different ways to make bulking fibres albeit the fact that such technologies have scarcely been used for commercial stratified board (apart from a variety of different pulp types), but more in tissue and hygiene products. The objective is to review the very different approaches that may be used for the purpose of making bulking fibres.

Cellulose nanofibrils (CNF) are mixed with plasticizers; sorbitol and glycerol, through high-pressure homogenization to prepare multifunctional biohybrid films. The resulting plasticized films obtained after solvent evaporation are strong, flexible and demonstrate superior toughness and optical transparency. The oxygen barrier properties of the biohybrid films outperform commercial packaging materials. The sorbitol-plasticized CNF films possess excellent oxygen barrier properties, 0.34 cm3·μm/m2·day·kPa at 50 % relative humidity, while significantly enhancing the toughness and fracture strength of the films. CNF films plasticized by 20 wt.% of sorbitol and glycerol could before rupture, be strained to about 9 % and 12 %, respectively. The toughness of the plasticized films increased by ca. 300 % compared to the pristine CNF film. Furthermore, the water vapor barrier properties of the biohybrid films were also preserved by the addition of sorbitol. CNF films plasticized with sorbitol was demonstrated to simultaneously enhance fracture toughness, work of fracture, softening behavior while preserving gas barrier properties. Highly favorable thermomechanical characteristics were found with CNF/sorbitol combinations and motivate further work on this material system, for instance as a thermoformable matrix in biocomposite materials. The unique combination of excellent oxygen barrier behavior, formability and optical transparency suggest the potential of these CNF-based films as an alternative in flexible packaging of oxygen sensitive devices like thin-film transistors or organic light-emitting diode displays, gas storage applications and as barrier coatings/laminations in packaging applications, including free-standing films as aluminium-replacement in liquid board and primary packaging, as replacement for polyethylene (PE) in wrapping paper, e. g. sweats and confectionary.

Unbleached wood fibers and nanofibers are environmentally friendly bio-based candidates for material production, in particular, as reinforcements in polymer matrix biocomposites due to their low density and potential as carbon sink during the materials production phase. However, producing high reinforcement content biocomposites with degradable or chemically recyclable matrices is troublesome. Here, we address this issue with a new concept for facile and scalable in-situ polymerization of polyester matrices based on functionally balanced oligomers in pre-formed lignocellulosic networks. The idea enabled us to create high reinforcement biocomposites with well-dispersed mechanically undamaged fibers or nanocellulose. These degradable biocomposites have much higher mechanical properties than analogs in the literature. Reinforcement geometry (fibers at 30 µm or fibrils at 10-1000 nm diameter) influenced the polymerization and degradation of the polyester matrix. Overall, this work opens up new pathways toward environmentally benign materials in the context of a circular bioeconomy. © 2022. The Author(s).

This paper deals with the details of preparation of three principal routes for bulking of cellulose fibres. One route is dry cross-linking/hornification using aluminium ions and other salts followed by drying/curing. The mechanisms of these reactions still remain unknown. A second route is physical grafting of fibres using carboxymethylcellulose and bringing the acidic groups into their aluminium form before forming a sheet of paper/board. Hence, curing is not necessary, and this constitutes a unique wet bulking methodology. The mechanism behind this method is believed to be an increase in the surface friction of fibres, when the electrostatic double layer is shielded together with electrostatic cross-linking with aluminium ions. The higher friction between fibres partly prevents the sheet consolidation during drying. A third route is physical grafting of fibres using carboxymethyl cellulose and ion-exchanging the acidic groups with aluminium salts before drying and curing of the fibres. A most interesting factor is that all the thermal treatment methods do not form fibre nodules due to interfibre crosslinking during the heat treatment, a commonly observed phenomena when dealing with chemical crosslinking of fibres. All routes investigated are water-based and should be fairly simple to implement in commercial operations. An inherent advantage is that the bulking is associated with lower water retention values, which should be advantageous for a higher solids content after pressing and, hence, beneficial for paper machine productivity. Bulking is, however, also associated with a loss in bond strength, which in most cases must be alleviated using various additives such as starches and microfibrillated cellulose and it has also been demonstrated in the project how the strength properties (such as z-strength) could be restored at a higher bulk.

Cellulose-rich never-dried acetate grade Eucalyptus dissolving pulp was used to study the effects on the supramolecular structure of cellulose due to the addition of AlCl3 during drying from acidic conditions (pH 3.5). CP/MAS 13C-NMR was the analytical technique used for taking measures of the cellulose supramolecular structure. In this study AlCl3 was used as source of Al3+, but Al2(SO4)3 has been shown to give the same effect and it is believed that any salt of Al3+ will give the same effect. The presence of AlCl3 increased the average lateral fibril aggregate dimensions some 25% above that reached by the pulp dried without addition of AlCl3. The observed changes in cellulose supramolecular structure due to the addition of AlCl3 are large considering the low AlCl3 concentration that was used. No change in degree of crystallinity was observed as the result of drying, either with or without AlCl3 addition. Although the mechanism of action for AlCl3, causing the observed effects on the cellulose supramolecular structure, is currently not fully understood, the interpretation made was that the presence of AlCl3 increased the agglomeration of the cellulose that always take place during the first drying of cellulosic fibres. This can be seen as an increased degree of physical cross-linking in the cellulose network. 

Unbleached lignocellulosic wood fiber materials of low porosity are of great interest as eco-friendly load-bearing materials because their yield is much higher than that for “pure” wood cellulosics. The difference between comparable materials based on lignocellulose fibers or nanocellulose is investigated. The structure, surface area, mechanical properties, moisture sorption, and optical properties of films based on fibers or microfibrillated lignocellulose (MFLC) were characterized as a function of lignin content, and the environmental impact was compared. The modulus and tensile strength of comparable fiber and MFLC films (≈25% porosity) increased up to an optimum lignin content (11−17%) and then decreased at a very high lignin content. Hot-pressed MFLC films with little porosity showed excellent properties, 230−260 MPa strength, 17−20 GPa modulus, and 81 MPa wet strength. The mechanical property values of hot-pressed wood fibers with 25% porosity were also as high as 154 MPa strength and 13.2 GPa modulus, which are higher than those of comparable materials reported in the literature. Because hot-pressed lignocellulose fibers can be readily recycled and show low cumulative energy demand, they are candidates for semistructural engineering materials. MFLC is of great interest for coatings, films, adhesives, and as additives or in high-technology applications. 

Microfibrillated cellulose (MFC) is an important industrial nanocellulose product and material component. New MFC grades can widen the materials property range and improve product tailoring. Microfibrillated lignocellulose (MFLC) is investigated, with the hypothesis that there is an optimum in lignin content of unbleached wood pulp fibre with respect to nanofibril yield. A series of kraft fibres with falling Kappa numbers (lower lignin content) was prepared. Fibres were beaten and fibrillated into MFLC by high-pressure microfluidization. Nano-sized fractions of fibrils were separated using centrifugation. Lignin content and carbohydrate analysis, total charge, FE-SEM, TEM microscopy and suspension rheology characterization were carried out. Fibres with Kappa number 65 (11% lignin) combined high lignin content with ease of fibrillation. This confirms an optimum in nanofibril yield as a function of lignin content, and mechanisms are discussed. MFLC from these fibres contained a 40-60 wt% fraction of nano-sized fibrils with widths in the range of 2.5-70 nm. Despite the large size distribution, data for modulus and tensile strength of MFLC films with 11% lignin were as high as 14 GPa and 240 MPa. MFLC films showed improved water contact angle of 84-88 degrees, compared to neat MFC films (< 50 degrees). All MFLC films showed substantial optical transmittance, and the fraction of haze scattering strongly correlated with defect content in the form of coarse fibrils. [GRAPHICS]

Fiber length and fiber-to-fiber bonding effects on tensile strength and fracture toughness of kraft paper have experimentally been investigated. Laboratory sheets were made from kraft pulp, each with a distinct set of fiber lengths. Additionally, the fiber–fiber bond strength was improved by carboxymethyl (CMC) grafting. The tensile strength and work of fracture toughness results were compared to predictions from a shear-lag model which considers the fiber–fiber bond shear strength, the fiber tensile strength and fiber pull-out work. The tensile strength and fracture work for papers with weak fiber–fiber bonds increased with fiber length consistent with the shear-lag model. CMC-treated fibers provided strong fiber–fiber bonds. Papers made from such fibers displayed high strength and work of fracture independent of fiber length which indicates that the failure process is governed by fiber failures rather than bond failures. The fracture toughness, expressed as the critical value of the J-integral, increased strongly with fiber length for both untreated and CMC-treated papers. The results show that long fibers and CMC addition are extremely beneficial for improving the fracture toughness. © 2017, Springer Science+Business Media, LLC.

Nanocelluloses are natural materials with at least one dimension in the nano-scale. They combine important cellulose properties with the features of nanomaterials and open new horizons for materials science and its applications. The field of nanocellulose materials is subdivided into three domains: biotechnologically produced bacterial nanocellulose hydrogels, mechanically delaminated cellulose nanofibers, and hydrolytically extracted cellulose nanocrystals. This review article describes today's state regarding the production, structural details, physicochemical properties, and innovative applications of these nanocelluloses. Promising technical applications including gels/foams, thickeners/stabilizers as well as reinforcing agents have been proposed and research from last five years indicates new potential for groundbreaking innovations in the areas of cosmetic products, wound dressings, drug carriers, medical implants, tissue engineering, food and composites. The current state of worldwide commercialization and the challenge of reducing nanocellulose production costs are also discussed.