Previous efforts to acetylate fibers and cellulose nanofibers (CNFs) are methodologically demanding and usually based on organic solvents catalyzed by acids. Hence, the purpose of this study was to introduce an improved method to acetylate unbleached (2 % and 5 % lignin) and bleached fibers (<1% lignin), and the corresponding CNFs, using a one-pot strategy in an aqueous alkaline medium. The lignin content in the pulp fibers (5 %) influenced the morphology of the corresponding fibrillated materials, i.e., increased secondary fines (92 %) and mean fibril area (36 %). Additionally, the pulps and CNFs (0 % and 5 % lignin content) were acetylated and compounded with high-density poly(ethylene) (HDPE). Acetylation improved the mechanical strength from 19 MPa (HDPE) to 30–40 MPa (when including acetylated fibers or CNFs). Finally, acetylation revealed a positive effect on melt-flow-index and elongation at break, and the water absorption of injection molded specimens was reduced to roughly 0.6 % after 10 days of testing. 

Cellulose nanofibrils (CNFs) have been proposed as reinforcement for thermoplastic polymers due to their potentially superior mechanical properties. However, it seems still uncertain how the reinforcement ability of CNFs compares to cheaper pulp fibres, and how the suspected potential of CNFs can be fully utilized in biocomposites. Therefore, this study presents a direct comparative investigation of kraft pulp fibres and their fibrillated materials as reinforcement of high- or low-density polyethylene. Besides the experimental investigations, the tensile properties of the corresponding biocomposites were predicted by using micromechanical analysis. It was shown that considering the same fraction of fibrous materials (pulp fibres vs CNFs), the experimental and modelling results revealed that the highest tensile strength was obtained from the pulp fibre-reinforced biocomposites. Regarding the CNFs-reinforced biocomposites, the compatibilizer content had to be up to 20 wt% to experimentally achieve the tensile strength predicted by the model. © 2023 The Author(s)

Three-dimensional (3D) printing is a useful technique that allows the creation of objects with complex structures by deposition of successive layers of material. These materials are often from fossil origin. However, efforts are being made to produce environmentally friendly materials for 3D printing. The addition of lignocellulosic fibres to a polymer matrix is one of the alternatives to replace, for instance, glass fibres in composites as reinforcing materials. The fields of biocomposites and 3D printing open innovative application areas for pulp fibres from the pulp and paper industry. In this work, biocomposites of poly(lactic acid) (PLA), poly(hydroxyalkanoate) (PHA) and kraft pulp fibres were prepared in order to find a suitable formulation for filaments for 3D printing. The effect of two different types of kraft fibres (bleached (B) and unbleached (U)) and of PHA on the mechanical and thermal properties of the biocomposites was assessed. The addition of 30% kraft fibres to PLA resulted in an increase of the tensile modulus from 3074 to ∼4800 MPa. In the case of biocomposites containing PHA (50% PLA/20% PHA/30% kraft) the increase in modulus was more moderate (PLA+PHA+U: 3838 MPa, and PLA+PHA+B: 3312 MPa). The tensile strength of PLA (66 MPa) increased to 77 MPa in PLA+kraft biocomposites, while a reduction in strength was observed for PLA+PHA+U (43 MPa) and PLA+PHA+B (32 MPa). Filaments prepared with PLA, PHA and bleached and unbleached pulp fibres showed similar printability of complex geometries, demonstrating that unbleached pulp fibres could also be utilized in the preparation of biocomposites with good mechanical performance and 3D printing properties. © 2022 The Author(s)

This review is the first part of a comprehensive review of hydrophobisation of lignocellulosic materials. The purpose of this review has been to compare physical hydrophobisation methods of lignocellulosic materials. We have compared molecular physical adsorption with plasma etching and grafting. Adsorption methods are facile and rely upon the simple mixing or coating of the substrate with the hydrophobing agent. However, none of the surfactant-based methods reviewed here reach contact angles above 90°, making them unsuitable for applications where a high degree of hydrophobisation is required. Nevertheless, surfactant based methods are well suited for compatibilising the lignocellulosic material with a hydrophobic matrix/polymer in cases where only a slight decrease in the hydrophilicity of the lignocellulosic substrate is required. On the other hand, wax- and lignin-based coatings can provide high hydrophobicity to the substrates. Plasma etching requires a more complex set-up but is relatively cheap. By physically etching the surface with or without the deposition of a hydrophobic coating, the material is rendered hydrophobic, reaching contact angles well above 120°. A major drawback of this method is the need for a plasma etching set-up, and some researchers co-deposit fluorine-based layers, which have a negative environmental impact. An alternative is plasma grafting, where single molecules are grafted on, initiated by radicals formed in the plasma. This method also requires a plasma set-up, but the vast majority of hydrophobic species can be grafted on. Examples include fatty acids, silanes and alkanes. Contact angles well above 110° are achieved by this method, and both fluorine and non-toxic species may be used for grafting. Graphical abstract: [Figure not available: see fulltext.]. © 2022, The Author(s).

Lignocellulosic materials with hydrophobic properties are of great interest for developing sustainable products that can be used in various applications such as packaging, water-repellent and self-cleaning materials, oil and water separation or as reinforcements in biocomposite materials. The hydroxyl functional groups present in cellulose provide the possibility to perform various chemical modifications to the cellulosic substrates that can increase their hydrophobicity. This review is the second part of a comprehensive review on hydrophobization of lignocellulosic materials and summarizes the recent advances in the chemical modification of such substrates. The methods described in this review can provide changes in the hydrophilicity of the materials that range from a small decrease in the initial hydrophilicity of the substrate (contact angles below 90°) to superhydrophobic properties (contact angles above 150°). Additional attention has been paid to whether the modification is limited to the surface of the substrate or if it occurs in the bulk of the material. We also discuss hydrophobized cellulose material applications in packing and oil/water purification. Graphical abstract: [Figure not available: see fulltext.] © 2022, The Author(s).

This review is the third part of a series of reviews on hydrophobization of lignocellulosic materials, a relevant topic nowadays, due to the need to replace fossil fuel-based materials. The review provides an overview of the hydrophobization of lignocellulosic materials by polymer adsorption, and both chemical and radiation-induced grafting of polymers. While adsorbed polymers are only attached to the surfaces by physical interactions, grafted polymers are chemically bonded to the materials. Radiation-induced grafting is typically the most environmentally friendly grafting technique, even though it provides little control on the polymer synthesis. On the other hand, controlled radical polymerization reactions are more complex but allow for the synthesis of polymers with elaborated architectures and well-defined properties. Overall, a wide range of contact angles can be obtained by polymer adsorption and grafting, from a slight increase in hydrophobicity to superhydrophobic properties. The choice of modification technique depends on the end-use of the modified material, but there is a clear trend towards the use of more environmentally friendly chemicals and processes and the grafting of polymers with complex structures. Graphical abstract: [Figure not available: see fulltext.]. © 2022, The Author(s).

Thermomechanical pulp (TMP) fibres can serve as renewable, cost-efficient and lightweight reinforcement for thermoplastic polymers such as poly(lactic acid) (PLA). The reinforcing ability of TMP fibres can be reduced due to various factors, e.g., insufficient dispersion of the fibres in the matrix material, fibre shortening under processing and poor surface interaction between fibres and matrix. A two-level factorial design was created and PLA together with TMP fibres and an industrial and recyclable side stream were processed in a twin-screw microcompounder accordingly. From the obtained biocomposites, dogbone specimens were injection-moulded. These specimens were tensile tested, and the compounding parameters statistically evaluated. Additionally, the analysis included the melt flow index (MFI), a dynamic mechanical analysis (DMA), scanning electron microscopy (SEM) and three-dimensional X-ray micro tomography (X- (Formula presented.) CT). The assessment provided insight into the microstructure that could affect the mechanical performance of the biocomposites. The temperature turned out to be the major influence factor on tensile strength and elongation, while no significant difference was quantified for the tensile modulus. A temperature of 180 °C, screw speed of 50 rpm and compounding time of 1 min turned out to be the optimal settings. © 2022 by the authors.

Wood fibres are hygroscopic and swell when immersed in water. This effect can be used to create shape-changing structures in 3D printing. Hence, wood fibre reinforced filaments have the potential to be used in four-dimensional (4D) printing. In this work, biocomposites based on granulated or milled thermomechanical pulp (TMP) fibres and poly(lactic acid) (PLA) were prepared and evaluated based on their tensile properties. Poly(hydroxyalkanoates) (PHA) or poly(butylene-adipate-terephthalate) (PBAT) were included in the biocomposite recipes to assess their effect on the melt flow index (MFI) and tensile properties. Clear effects of the TMP fibre morphology on MFI were quantified. Biocomposites containing 20 wt% PBAT turned out to be stronger and tougher than the ones containing PHA. Based on that, filaments for 3D and 4D printing were manufactured. Interestingly, the tensile strength of 3D printed specimens containing milled TMP (TMPm) fibres was about 33% higher compared to those containing TMP fibre granulate (TMPg). Using hot water as the stimulus, the 3D printed specimens containing TMPg showed a greater reactivity and shape change compared to TMPm specimens. © 2022 The Authors

Side streams were collected from three locations in a flooring factory and their suitability in biocomposite formulations was assessed. The side stream (S3) that contained mainly residues from high-density fibreboards (HDF) was selected for further material testing. The effect of different fractions of S3, thermomechanical pulp (TMP) fibres and polylactic acid (PLA) were assessed in terms of their mechanical, melt flow and thermal properties. A biocomposite made from PLA, 20 wt% TMP fibres and 10 wt% S3 revealed a significant increase in modulus (5800 MPa), compared to the neat PLA (3598 MPa), and a similar melt-flow index (MFI = 4.5). The tensile strength was however somewhat reduced from 66 to 58 MPa. Importantly, numerical modelling and simulations were applied to demonstrate that building a model chair out of biocomposite can potentially reduce the material volume by 12% while maintaining similar load bearing capacity, compared to neat PLA. © 2021 The Author(s)

We have in this paper investigated how water sorbs to cellulose. We found that both cellulose nanofibril (CNF) and cellulose nanocrystal (CNC) films swell similarly, as they are both mainly composed of cellulose. CNF/CNC films subjected to water at 0.018 kg/m3 at 25 °C and 39 °C, showed a decrease in swelling from ~ 8 to 2%. This deswelling increased the tensile index of CNF-films by ~ 13%. By molecular modeling of fibril swelling, we found that water sorbed to cellulose exhibits a decreased diffusion constant compared to bulk water. We quantified this change and showed that diffusion of sorbed water displays less dependency on swelling temperature compared to bulk water diffusion. To our knowledge, this has not previously been demonstrated by molecular modeling. The difference between bulk water diffusion (DWW) and diffusion of water sorbed to cellulose (DCC) increased from DWW − DCC ~ 3 × 10–5 cm/s2 at 25 °C to DWW − DCC ~ 8.3 × 10–5 cm/s2 at 100 °C. Moreover, water molecules spent less successive time sorbed to a fibril at higher temperatures. © 2022, The Author(s).