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To expand the application of transparent wood (TW) in the field of photoluminescence, lignin-based carbon quantum dots (CDs) were impregnated into wood cellulose template (CT) as a fluorescent functional material, the photoluminescent transparent wood (PTW) with light conversion was prepared. The results showed that FTW with different wavelength emissions could be obtained by controlling the CDs' conjugated size and surface functional groups. The loading of CDs does not affect the excellent transmittance (86.1%) and optical haze (73%) of TW. Compared to the original wood, the tensile properties of PTW have been enhanced from 368 MPa to 422 MPa. By controlling the content of different CDs, a PTW for white light conversion was prepared with the CIE color coordinates of (0.29, 0.34). This study is a new attempt to apply CDs to TW, providing a broad prospect for uniform light conversion and color display.

The isolation of lignin containing micro- and nanofibrillated cellulose (L-MNFC) requires a multistep process. In this study, beech wood was pre-treated by steam explosion (SE), refined or pre-treated by 3 SE and grinded until gel formation. A conventional cooking in an autoclave (SC) was applied in order to get a control sample. The effect of bleaching of a SE pulp was also studied. The chemical composition of the pulps was assessed as well as fiber morphology to compare the effect of the different processes. Quality index and energy consumption during the production process were studied. Results showed that SE can replace SC for the production of pulps with higher lignin content: 8-12% wt. and 3% wt., respectively. Gels contain micro and nanofibrillated cellulose and residual fibers with a dispersion of lignin nanoparticles and some nanocrystals. Optimization of the ultrafine grinding step was required to minimize the energy consumption.

Funding Information: The authors thank Aalto University staff for their supporting, especially Ms. Rita Hataka for her support with the chromatographic analysis. The authors also wish to acknowledge Professor Alistair King from Helsinki University to provide part of IL used in this research. This work was a part of the Academy of Finland's Flagship Programme under Project Nos. 318890 and 318891 (Competence Center for Materials Bioeconomy, FinnCERES). We would like to thank Dr. Eero Hiltunen and Professor Thad Maloney for their advices on the analyses of the paper-making properties analysis of our pulps. Publisher Copyright: © 2022 Elsevier Ltd This study presents an environmentally friendly process to produce high-purity cellulose (dissolving pulp) from birch wood by combining γ-valerolactone (GVL)/water fractionation and ionic liquid treatment of pulp, IONCELL-P (IP). A paper grade pulp was produced from optimal GVL cook with a similar composition to birch kraft pulp and was bleached with ECF sequence before the hemicelluloses were removed using the IONCELL-P process. The purity of the GVL-IP pulp significantly exceeded that of commercial prehydrolysis kraft (PHK) and prehydrolysis soda-anthraquinone (PH-Soda-AQ) pulps. IONCELL-P extraction removed more than 90% of the hemicelluloses, resulting in a dissolving pulp with a purity of 96% and a high molecular mass fraction, 2.3 times higher than that of a conventional PHK pulp. GVL-IP pulps are suitable not only for regenerated cellulose fibers or films, but also for high-purity, high-viscosity cellulose acetate and ethers, which cannot be produced in an environmentally friendly way by conventional processes.

The impact of various degrees of acetylation on improving the thermal stability of xylan isolated from different botanical source has been studied; methylglucuronoxylan from birch and eucalyptus, arabinoglucuronoxylan from spruce and glucuronoarabinoxylan from sugarcane bagasse and straw. The lower molecular weight of nonacetylated methylglucuronoxylan (17.7-23.7 kDa) and arabinoglucuronoxylan (16.8 kDa) meant that they were more soluble in water than glucuronoarabinoxylan (43.0-47.0 kDa). The temperature at the onset of degradation increased by 17-61 degrees C and by 75-145 degrees C for low and high acetylated xylans respectively, as a result of acetylation. A glass transition temperature in the range of 121-132 degrees C was observed for the samples non-acetylated and acetylated at low degree of acetylation (0.0-0.6). The acetylation to higher degrees (1.4-1.8) increased the glass transition temperature of the samples to 189-206 degrees C. Acetylation proved to be an efficient method for functionalization of the xylan to increase the thermal stability.

Masson pine undergoes rapid degradation by brown-rot fungi, but how the fungus alters the microstructure of Masson pine cell wall is still unclear. In this study, Masson pine samples were incubated with Gloeophyllum trabeum to aid in characterizing changes in the crystalline structure of cellulose and chemical composition of wood in brown-rot decay. Fungal action resulted in an initial increase in wood cellulose crystallinity and crystallite width because of early removal of the more amorphous celluloses, followed by a decrease in crystallinity and crystallite size. All data suggest that hemicellulose, amorphous cellulose and crystalline cellulose are sequentially depolymerized via a non-enzymatic pathway, concurrent with early-stage changes in the rearrangement of cellulose chains and the diffusion of depolymerized less-crystalline polysaccharides out of the cell wall. Our work provides insight into the role of a non-enzymatic system in brown-rot decay as well as its potential application in lignocellulose preservation and biorefineries.

Wood is one of the most abundant materials in nature, with excellent mechanical properties and anisotropy. Its main component, cellulose has excellent dispersion properties and biocompatibility after nano-treatment, which has aroused the interest of researchers. Therefore, this study prepared a thermoelectric aerogel based on carboxylated nanocellulose fiber and carbon nanotube, and made it have a wood-like anisotropic structure through directional freezing technology. The aerogel exhibited excellent mechanical properties and had the stress of up to 152 kPa when compressed at 90%. It also exhibited low thermal conductivity (0.03-0.08 W/mK) and density (7.5 mg/cm

The present review explores the recent developments of cellulose nanocrystals, a class of captivating nanomaterials in variety of applications. CNCs are made by acid hydrolysing cellulosic materials like wood, cotton, tunicate, flax fibers by sonochemistry. It has many desirable properties, including a high tensile strength, wide surface area, stiffness, exceptional colloidal stability, and the ability to be modified. CNCs are colloidally stable, hydrophilic, and rigid rod-shaped bio-based nanomaterials in the form of rigid rods with high strength and surface area that has a diverse set of applications and properties. The intriguing features emerging from numerous fibers studies, such as renewable character and biodegradability, piqued the curiosity of many researchers who worked on lowering the size of these fibers. Physicochemical properties such as rheological, mechanical, thermal, lipid crystalline, swelling capacity, microstructural properties result in affecting surface-area to volume ratio and crystallinity of cellulose nanocrystals. The present article highlights the fundamentals of cellulose nanocrystals such as sources, isolation, fabrication, properties and surface modification with an emphasis on plethora of biomedical applications. Selected nanocellulose studies with significant findings on cellular labelling and bioimaging, tissue engineering, biosensors, gene delivery, anti-viral property, anti-bacterial property, ocular delivery, modified drug release, anti-cancer activity and enzyme immobilization are emphasized.

Optimization of the rheological properties of the matrix is ​​critical for high-fidelity matrix-assisted 3D printing (MAP), which enables the free-form fabrication of fluidic soft materials. This report describes the generic criteria observable in the printing process of cellulose nanofiber (CNF) hydrogels: the sharpness of an angled line, the cross-sectional ratio of a feature, the surface roughness of features, and the completeness of multi-line writing. The concentration and physical properties of the CNF affects the printing fidelity by changing the values of the four criteria, which are closely related to the rheological properties of the matrix. The printing fidelity can be enhanced by the optimal combination of the inks and the CNF matrix. Hydrophilic and hydrophobic inks are printed in the CNF matrix demonstrating as a universal matrix for free-form fabrication with liquid inks.

Hydrogels are an attractive system for a myriad of applications. While most hydrogels are usually formed from synthetic materials, lignocellulosic biomass appears as a sustainable alternative for hydrogel development. The valorization of biomass, especially the non-woody biomass to meet the growing demand of the substitution of synthetics and to leverage its benefits for cellulose hydrogel fabrication is attractive. This review aims to present an overview of advances in hydrogel development from non-woody biomass, especially using native cellulose. The review will cover the overall process from cellulose depolymerization, dissolution to crosslinking reaction and the related mechanisms where known. Hydrogel design is heavily affected by the cellulose solubility, crosslinking method and the related processing conditions apart from biomass type and cellulose purity. Hence, the important parameters for rational designs of hydrogels with desired properties, particularly porosity, transparency and swelling characteristics will be discussed. Current challenges and future perspectives will also be highlighted.

Transparent-wood (TW) is an emerging research topic that can be applied to biobased products. However, it is necessary to fill pores in TW with natural substances to prepare all-biobased TW. This paper reports an all-biobased TW by infiltrating cellulose nanofiber (CNF) and chitosan (CTS) suspensions into the bleached wood. CNF was isolated by combining the chemical and physical methods, and CTS was dissolved in acetic acid, and they were infiltrated into the pores of the bleached Fir veneer wood using a vacuum jar. The CNF and chitosan effects on the mechanical properties of the TW were studied, and the morphologies, crystallinity index, water contact angle, antioxidant, thermal degradation, and UV-shielding properties were investigated. The prepared TW showed 80 % total transmittance and 30–60 % haze, suitable for solar cell application. The all-biobased TW showed good thermal stability up to 315 °C and excellent UV shielding property for UV-B and UV-C. The antioxidant property of the CTS-TW significantly increased as compared to the original wood. The CNF-TW showed considerable tensile strength and yield strength of more than 200 % improved from the original wood. The potential for environment-friendly packaging applications was demonstrated by making a bag, medicine packaging, and straw for a drink.

A direct production route of cellulose nanofibers (TOCN-D) from raw wood particles of paulownia using simultaneous bleaching and TEMPO oxidation process was specifically investigated and introduced. For comparison, we prepared cellulose nanofibers (TOCN-C) through a common route of TEMPO oxidation of cellulose fibers, and cellulose nanofibers with disk grinding (GCNF). FE-SEM analysis showed that the average diameter of TOCN-D (5 ± 3 nm) was similar to that of TOCN-C (6 ± 3 nm). XRD results confirmed that the crystal properties of TOCN-D and that of TOCN-C were almost the same. TOCN-D and TOCN-C showed similar chemical, thermal and optical properties in FTIR, TGA and transparency tests, respectively. The nanopaper made from TOCN-D showed high Young's modulus (13.8 GPa) and tensile strength (233 MPa), which were similar to those of TOCN-C nanopaper. Owing the aforementioned similarities, it is concluded that the TOCN-D produced through direct route is a technically, environmental-friendly and economically valuable product.

Cellulose nanocrystals are hydrophilic nanomaterials, which limits their applications as interfacial compounds. Herein, we propose using modified wood-based cellulose nanocrystals as Pickering emulsion stabilizer. Wood cellulose was consecutively oxidized and modified with phenyltrimethylammonium chloride to create hydrophobic domains comprised of phenyl groups. These modified oxidized cellulose nanocrystals (m-O-CNCs) were homogeneous/electrostatically stable in water and they can stabilize O/W Pickering emulsions. The dispersed phase volume fraction (DPVF) of the Pickering emulsion was 0.7 at around 1.5g/L, whereas the tween-20 control needed a 13-fold greater concentration to have a similar DPVR. In addition, these m-O-CNC stabilized Pickering emulsions also showed good mechanical and thermal stability against centrifugation and heat, as well as size controllability. In terms of stability, size controllability, surfactant-free status, these m-O-CNCs possess superior and enhanced emulsifying properties. Future research for these new interfacial materials have potential in applications, for personal care, cosmetic and pharmaceutic industries.

Herein we propose a versatile method for the surface tailoring of cellulose nanocrystals (CNCs) based on the reactivity of vinyl ester molecules toward the accessible hydroxyl groups located at the surface of the nanoparticles. CNCs produced from wood pulp were acylated in various conditions, with potassium carbonate as catalyst and under microwave activation. The impact of solvent, temperature and reagent concentration on the reaction efficiency and kinetics was then investigated, using vinyl acetate as a model vinyl ester. Results indicated that the chemical reactivity was significantly influenced by the quality of the CNCs dispersion in the solvent of reaction, the ratio of reagent relative to the CNCs surface OH groups, the diffusion of reagent and catalyst within the CNCs aggregates, and the different nucleophilic strengths of the surface hydroxyl groups. The versatility of the method was verified by extending the reaction to a selection of vinyl esters bearing various functionalities.

Xylooligosaccharides (XOS) are emerging prebiotics which can be produced from lignocellulosic biomass including agro-residues and hardwood. In this study, we report the production of XOS from thermal-alkali pretreated hardwood such as mahogany and mango by using a purified xylanase from Clostridium strain BOH3. In the first approach, pure xylan is extracted from mahogany and mango hardwood and then the pure xylan is hydrolyzed by using the xylanase. In this case, 572 and 504 mg XOS/g pure xylan were obtained from mahogany and mango woods, respectively. In the second approach, the same xylanase is employed to hydrolyze sawdust of hardwood after different types of pretreatments. After a thermal (121 °C for 15 min) pretreatment under a mild alkaline (0.05N NaOH) condition, the pretreated mahogany and mango sawdust can be utilized directly to produce 89.5 and 67.6 mg XOS/g pretreated sawdust, respectively. XOS produced from the pretreated sawdust show strong prebiotic effects on Bifidobacteria and Lactobacilli. This report shows the possibility of producing XOS from pretreated woody wastes without using pure xylan as a substrate.

To help understand factors controlling the recalcitrance of lignocellulosic biomass to deconstruction to sugars, poplar was pretreated with liquid hot water (LHW) and extremely dilute acid (EDA) at 140 °C and 180 °C in batch and flowthrough reactors. The resulting solids were then subjected to enzymatic hydrolysis by eight combinations of cellulase, xylanase, and bovine serum albumin (BSA). Co-addition of xylanase to cellulase resulted in up to 11 percentage points higher overall sugar yield than their sequential addition. In general, supplementation of BSA to enzymes had a larger impact on flowthrough solids with reduced lignin content than batch solids with high lignin content. BSA did not affect xylan yields and while it had low impact on LHW solids, it caused large increases in sugar yields from EDA solids. Flowthrough pretreatment produced less recalcitrant solids than did batch operation, but using very dilute acid reduced recalcitrance even more.

In this work, TEMPO-oxidized cellulose nanofibers (TOCNs) were investigated as a green additive to the waterborne polyurethane (WPU) based coating, for improving its mechanical properties. The structure, morphology, mechanical properties and performances of the WPU/TOCNs coating were determined. Results showed that TOCNs had good compatibility to the WPU coating, and significantly enhanced the mechanical properties of the coating. The Halpin-Tsai and Ouali models were used to fit for the Young’s modulus of the resulting coating, and good agreements were found between the Ouali model and experimental results when the TOCNs content exceeded the critical percolation threshold (0.7 vol% or 1.0 wt%). It was also found that the pencil hardness of the coating was improved with the addition of TOCNs. However, AFM and pull-off test revealed the negative effects of the TOCNs addition on the surface roughness and adhesion strength of the coating to the wood surface.

In this study, we report a novel, facile, and green method that was used for creating a new all-cellulose composite (ACC) based on inorganic molten salt solvent. Three representatively native fibers from softwood (Pinus kesiya), hardwood (Eucalyptus globulus), and agricultural straw (Zea mays) were selected to verify the effect of the method. The welded sheets were thoroughly characterized and compared. Cellulose sheets from the pine exhibited excellent mechanical properties (σb 16.94 MPa) and thermal stability (Tmax 265 °C) after the welding process, while the corn stalk sheets displayed more robust and thermostable features than the eucalyptus. The welding technique using inorganic metal salt hydrate provides a promising and convenient route to obtain firm sheet-materials with micro- or nano-structures from nature fibers.

Aminated cellulose nanofibers (A-CNF) with high thermostability (>350 ℃), high crystallinity (81.25 %), and high dispersion stability were extracted from “biological grinding” biomass through one-pot microwave-hydrothermal synthesis. Worm-eaten wood powder (WWP) as the product of “biological grinding” by borers is a desirable lignocellulose for fabricating A-CNF in a green and cost-effective way since it is a well-milled fine powder with dimension of dozens of microns, which can be used directly, saving energy and labor. Generated A-CNF proved to be an excellent reinforcing and curing agent for constructing high performance epoxy nanocomposites. The nanocomposites exhibited a thermal conductivity enhancement of about 120 %, coefficient of thermal expansion reduction of 78 %, and Young’s modulus increase of 108 % at a low A-CNF loading of 1 wt.%, demonstrating their remarkable reinforcing potential and effective stress transfer behavior. The process proposed herein might help to bridge a closed-loop carbon cycle in the whole production-utilization of biomass.

This study aims to understand the effect of micro- and nanofibrillated cellulose (MNFC) on the tensile index, softness, and water absorbency of tissue paper. MNFC was produced from four different fiber sources. The results show that MNFC acts as an effective strength enhancer at the expense of a reduced water absorbency and softness. The impact of the fiber source on MNFC manufacturing cost and the trade-off with performance was also investigated. MNFCs produced from southern bleached hardwood kraft, northern bleached softwood kraft, and deinked pulp exhibited similar performance trends with the MNFC from the deinked pulp having a significantly lower cost. This suggests that MNFCs with similar degrees of fibrillation may be used interchangeably regardless of the fiber source, revealing the possibility to minimize MNFC manufacturing costs based on fiber selection. MNFC produced from bleached Eucalyptus kraft showed the lowest degree of fibrillation and the lowest strength improvements among the MNFCs evaluated.

Electromagnetic-interference (EMI) shielding materials that are green, lightweight, and with high mechanical properties need to be urgently developed to address increasingly severe radiation pollution. However, limited EMI shielding materials are successfully used in practical applications, due to the intensive energy consumption or the absence of sufficient strength. Herein, an environmentally friendly and effective method was proved to fabricate wood-based composites with high mechanical robustness and EMI shielding performance by a MXene/cellulose scaffold assembly strategy. The lignocellulose composites with a millimeter-thick mimic the "mortar-brick" layered structure, resulting in excellent mechanical properties that can achieve the compressive strength of 288 MPa and EMI shielding effectiveness of 39.3 dB. This "top-down" method provides an alternative for the efficient production of robust and sustainable EMI shielding materials that can be used in the fields of structural materials for next-generation communications and electronic devices.

This study aims to investigate the relationship between lignin content, morphology, and rheology of lignin containing cellulose nanofibers (LCNFs). The morphology and rheology of LCNFs were dominated by lignin content. Lignin content had two-sides on mechanical fibrillation. At high lignin content (23.79 %), reduced efficiency of defibrillation resulted in large LCNFs connecting with lignin patches. LCNF suspensions exhibited low viscosity, weak gel behavior due to infirm fibril network. Small yield stress of 1.14 Pa suggested that fibril network was easily disrupted. At residual lignin of 6.52 %, fibril bundles were sensitive to defibrillation, producing long and flexible LCNFs with high capacity of entanglement. The entangled fibril network had high viscosity and strong gel like behavior. Creep compliance of 0.09 Pa−1 and large yield stress of 4.25 Pa indicated excellent resistance to deformation. The desired rheology can be tailored by lignin content, providing practical guidance on novel rheology-dependent LCNF based materials.

Cellulose–lignin composite carbon fibers have shown to be a potential environmentally benign alternative to the traditional polyacrylonitrile precursor. With the associated cost reduction, cellulose–lignin carbon fibers are an attractive light-weight material for, e.g. wind power and automobile manufacturing. The carbon fiber tenacity, tensile modulus and creep resistance is in part determined by the carbon content and the molecular orientation distribution of the precursor. This work disassociates the molecular orientation of different components in cellulose–lignin composite fibers using rotor-synchronized solid-state nuclear magnetic resonance spectroscopy and X-ray scattering. Our results show that lignin is completely disordered, in a mechanically stretched cellulose–lignin composite fiber, while the cellulose is ordered. In contrast, the native spruce wood raw material displays both oriented lignin and cellulose. The current processes for fabricating a cellulose–lignin composite fiber cannot regain the oriented lignin as observed from the native wood.

Deep eutectic solvents (DESs), as emerging green solvents, provide a new opportunity for the biorefinement of biomass, component extraction, and cellulose nanofibrillation. Herein, different carboxylic acid-based DESs were applied for preparation of cellulose nanofibers (CNFs) from cellulose raw materials accompanied by simultaneous esterification modifications of CNFs. The results showed that pretreatment of DESs combined with mechanical treatment can swell and esterify the cellulose materials, producing CNFs with widths less than 100 nm. The DES pretreatment temperature played important roles in the esterification modifications and nanofibrillation of cellulose. The esterification modifications of cellulose prevented the over-hydrolysis and dissolution of cellulose during the DES pretreatment, guaranteeing CNFs with high yields of 72 %-88 % and maintaining the cellulose I crystal structure. Moreover, the esterified CNFs were used as a reinforcement to prepare CNF-strengthened polylactic acid (PLA) composites. The surface esterification of the CNFs improved their dispersibility and interfacial compatibility with PLA, thereby achieving the mechanical enhancement of CNF/PLA composites.

Nanocellulose is a promising material but its isolation generally requires unrecyclable hazardous chemicals and high energy consumption and its overall yield is low due to the use of high purity cellulose as precursor. In order to overcome these shortcomings, in this study, thermomechanical pulp (TMP) was investigated as a precursor for isolating lignin containing nanocellulose (LNC) using an environmentally friendly acidic deep eutectic solvent (DES) pre-treatment. Flat "ribbon" like LNCs (around 7.1 nm wide, 3.7 nm thick) with uniformly distributed lignin nanoparticles of 20-50 nm in diameter were successfully obtained at 57 % yield under optimum pre-treatment conditions (90 °C, 6 h, 1:1 oxalic acid dihydrate to choline chloride ratio). The LNCs exhibit cellulose Iβ structure, high lignin content (32.6 %), and high thermal stability (Tmax of 358 °C). In general, green acidic DES pre-treatment has shown high efficiency in converting high lignin content biomass into value-added LNC, which benefits both lignocellulose utilization and environmental protection.

The upturn of viscose fiber market has triggered an augmented dissolving pulp usage over the last decade. Dissolving pulp is feasible to obtain from kraft pulp after two essential steps including hemicellulose removal and subsequent pulp activation. Prerequisite of conversion being hemicellulose reduction can be gently done by using xylanase treatment prior to alkali extraction. Herein, the significance of xylanase treatment and the optimum xylanase dose required in conjunction with subsequent alkali extraction was investigated. An increase in xylanase dose prior to alkali extraction had no significant effect on pentosans while the Fock reactivity and viscosity both improved at the dose of 50AXU/g. Also, alkali extraction without xylanase pretreatment resulted in decreased Fock reactivity, alpha cellulose, brightness and viscosity of paper grade pulp. A moderate dose of xylanase prior to alkali extraction can thus be used to facilitate the hemicellulose removal while simultaneously protecting the native structure of cellulose.

The effect of the degradation induced by the solvents for cellulose cuoxam and cadoxen and its dependency on the nature of the carbonyls in oxidatively-damaged cellulosics was investigated by combining a novel approach of sample regeneration and gel permeation chromatography coupled with carbonyl-selective labelling for reliable molecular characterization. The type of cellulosic pulp, degree and mode of oxidation and dissolution time were considered. Results show that the main discriminating factors in determining the degradation of oxidatively-damaged celluloses in alkaline dissolving media are: (1) the type of pulp, i.e. hemicellulose-containing pulps are more severely compromised; (2) of particular relevance, the prior oxidation mechanism, meaning not only the amount of oxidized moieties (greater oxidation, greater solvent-induced damage) but also their position on the chains (i.e. peroxide-oxidized cellulose is more unstable than hypochlorite-oxidized cellulose).

Cellulose nanocrystals (CNCs), a biomaterial with high added value, were obtained from pure cellulose, Eucalyptus holocellulose, unbleached Kraft pulp, and sugarcane bagasse, by fibrillating these biomass substrates using wet disk milling (WDM) followed by enzymatic hydrolysis using endoglucanase/β-glucosidase. The hydrolysis experiments were conducted using the commercial enzyme OptimashBG or a blend of Pyrococcus horikoshii endoglucanase and Pyrococcus furiosus β-glucosidase. The fibrillated materials and CNCs were analyzed by X-ray diffraction, atomic force microscopy, scanning electron microscopy, and the specific surface area (SSA) was measured. WDM resulted in the formation of long and twisted microfibers of 1000-5000 nm in length and 4-35 nm in diameter, which were hydrolyzed into shorter and straighter CNCs of 500-1500 nm in length and 4-12 nm in diameter, with high cellulose crystallinity. Therefore, the CNC's aspect ratio was successfully adjusted by endoglucanases under mild reaction conditions, relative to the reported acidic hydrolysis method.

An in vitro system was used to determine if the addition of insoluble or soluble fibre to aqueous suspensions of gelatinised starch affected the rate at which the starch was digested. Pre-gelatinised potato or corn starch suspensions were digested with porcine pancreatic amylase in the presence of either finely milled insoluble fibres from various sources or with guar gum. In vitro digestion was conducted at 37°C in a rheometer at a low and constant shear rate of 10s(-1) and the quantity of glucose released measured. The rates of starch digestion and suspension viscosity declined asymptotically and were unaffected by the addition of wheat fibre, but were considerably reduced by the addition of wood and AllBran(®) fibre and to a much greater extent (60%) by the addition of guar. The latter effect may be due to inhibition of amylase activity by non starch polysaccharide sequences.

Eucalyptus was sequentially extracted with 70% ethanol containing 0.4, 1.0, 2.0, 3.0, and 5.0% NaOH for 2 h at 80 °C. The chemical composition and structural features of the hemicellulosic fractions obtained were comparatively characterized by the combination of high-performance anion-exchange chromatography, gel permeation chromatography, Fourier transform infrared, and nuclear magnetic resonance spectroscopies. Furthermore, the main component distribution and their changes in cell wall were investigated by confocal Raman microscopy. Based on the Fourier transform infrared and nuclear magnetic resonance analyses, the hemicelluloses extracted from Eucalyptus mainly have a linear backbone of (1 → 4)-linked-β- d -xylopyranosyl residues decorated with branch at O -2 of 4- O -methyl-α-glucuronic acid unit. Raman analysis revealed that the dissolution of hemicelluloses was different in the morphological regions, and the hemicelluloses released mainly originated from the secondary wall. The information obtained from the study conducted by combining chemical characterization with ultrastructure provides important basis for studying the mechanism of the alkali treatment.

The analysis of native wood components by size-exclusion chromatography (SEC) is challenging. Isolation, derivatization and solubilization of wood polymers is required prior to the analysis. The present approach allowed the determination of molecular weight distributions of the carbohydrates and of lignin in native and processed woods, without preparative component isolation steps. For the first time a component selective SEC analysis of sawdust preparations was made possible by the combination of two selective derivatization methods, namely; ionic liquid assisted benzoylation of the carbohydrate fraction and acetobromination of the lignin in acetic acid media. These were optimized for wood samples. The developed method was thus used to examine changes in softwood samples after degradative mechanical and/or chemical treatments, such as ball milling, steam explosion, green liquor pulping, and chemical oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). The methodology can also be applied to examine changes in molecular weight and lignin-carbohydrate linkages that occur during wood-based biorefinery operations, such as pretreatments, and enzymatic saccharification.

The effects of compression combined with steam treatment (CS-treatment), i.e. a hygro-mechanical steam treatment on Spruce wood were studied on a cell-structure level to understand the chemical and physical changes of the secondary cell wall occurring under such conditions. Specially, imaging FT-IR microscopy, nanoindentation and dynamic vapour absorption were used to track changes in the chemical structure, in micromechanical and hygroscopic properties. It was shown that CS-treatment resulted in different changes in morphological, chemical and physical properties of the cell wall, in comparison with those under pure steam treatment. After CS-treatment, the cellular structure displayed significant deformations, and the biopolymer components, e.g. hemicellulose and lignin, were degraded, resulting in decreased hygroscopicity and increased mechanical properties of the wood compared to both untreated and steam treated wood. Moreover, CS-treatment resulted in a higher degree of degradation especially in earlywood compared to a more uniform behaviour of wood treated only by steam.

Wood flour (WF) based natural polymer biocomposites were produced using the equal channel angular pressing (ECAP) technique. The wood particle structures were disrupted and the cellulose crystallinity was decreased while bulk materials were formed with continuous phase structures by the severe shear-deformation during ECAP. The mechanical properties of the processed WF materials were enhanced when the processing temperature was increased due to enhanced intermolecular interactions and thermal crosslinking reactions among WF components. The processing capability was improved by using wheat gluten (WG) as additives, leading to significantly reduced processing temperature. Effective chain penetration and strong intermolecular interactions in conjunction with chemical crosslinking occurred between WG and the amorphous components in WF. However, the thermal decomposition of the WG component also occurred at increased temperatures, resulting in a decrease in the mechanical strength of the WF/WG composites. The result has demonstrated that ECAP is a promising methodology to produce renewable and degradable biocomposites from wood waste.

This study involved a detailed investigation of a novel approach to reducing naturally occurring cellulose fibers into nanofibers solely by the use of aqueous counter collision (ACC) without any chemical modification. In this process, equivalent aqueous suspensions of cellulose are ejected from dual nozzles and collide at high speed and pressure. Even a few repetitions of the collision process are sufficient to produce nano-sized fibers dispersed in water. This work compared the ACC nano-pulverization of stable Iβ-rich and meta-stable Iα-rich cellulose samples. The ACC method is applicable to various kinds of polymeric materials with hierarchical structures, either natural or synthetic, as a means of preparing aqueous dispersions of nano-sized structures.

Self-assembly is a technique of preparing functional materials based on targeted intermolecular interactions involving different macromolecules. In this work, hardwood xylan was disassembled from wood and birch bleached kraft pulp using pressurized hot water extraction (HWX) and cold alkali extraction (CAX), respectively. The extracted biopolymers were characterized using gas chromatography (GC), size exclusion chromatography (SEC) and Fourier transform infrared spectroscopy (FTIR), and subsequently added into an oxygen delignification reactor containing pine kraft pulp. The assembly of xylan-pulp fiber was characterized using advanced time-of-flight secondary ion mass spectrometry (ToF-SIMS) and imaging. The xylan-pine pulp assembly was not significantly removed during the whole elemental chlorine free bleaching sequence or during low consistency refining. Modified fibers had superior mechanical properties compared to the reference pulp. Our concept can be easily applied in the pulp and paper industry, and it opens new possibilities for the utilization of fully bio-based fibers in new materials.

After cotton fabric (CF) and hinoki lumber (HL) were dipped in 1-butyl-3-methylimidazolium chloride (BMIMCl) at 100 °C, the BMIMCl-impregnated CF and HL were hot-pressed to give CF-BMIMCl and HL-BMIMCl composites, respectively. The BMIMCl contained in the composites was removed by Soxhlet extraction, and subsequently annealed to produce all-cellulose and all-wood composites (CF-A and HL-A). The SEM analyses revealed that cellulose fibers combined together for CF-A and the surface of HL-A became smooth, respectively. The XRD measurements indicated that the crystallinity index of cellulose component decreased by the hot press, increased by the extraction, and further increased by the annealing for both the composites. The tensile modulus of CF-A increased with increasing pressure of hot-press. Although tensile strength of HL-A was a little lower than that of original HL, tensile modulus of the former was much higher than that of the latter.

The objective of this study was to extract cellulose nanofibrils (CNFs) from dry softwood pulp through a simple and environmentally friendly physical method of refining pretreatment coupled with high shear homogenization. An optical microscopy (OM) clearly showed the morphological development from the cellulose fibers to CNFs under repeated shear forces. The morphology, structure and properties of the obtained CNFs were comprehensively investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transformed infrared (FTIR) spectra, X-ray diffraction (XRD) and thermogravimetric (TG) analysis. The results indicated that the CNFs had diameters mainly ranged from 16 to 28 nm. Compared with the pulp fibers, the CNFs exhibited a slightly higher crystallinity and a lower thermal stability. Moreover, a novel nanopaper with high optical transparency was prepared from the obtained CNFs, and a possible mechanism for the high optical transparency was discussed.

Wood chips, macerated wood chips and coarse wood fibers were compressed and allowed to decompress in enzyme solutions prior to mechanical refining. Electrical consumption in refining was monitored in order to investigate potential energy savings during refining. Wood treated with Celluclast® 1.5 L showed a reduction in refining energy up to a 36%. Canadian Standard Freeness was used to track degree of refining. Decompressing in the enzyme solution gave a 15% reduction in energy consumption compared to having the already decompressed substrate treated with enzymes. This indicated that improving the transportation of enzymes into wood chips would further enhance the enzyme effect on refining. In this study, confocal laser scanning microscopy (CLSM) was used to track a dyed dextran of 70k molecular weight (the size of some of the larger enzymes) which was used as molecular probe to investigate the potential added penetration of enzymes induced by compression/decompression in the selected chip sizes.

In this study two imidazole-based ionic liquids (ILs), namely 1-butyl-3-methyl-1-imidazolium chloride ([BMIM]Cl) and 1,3-methyl imidazolium dimethyl sulfate ([DiMIM][MeSO4]), were used to dissolve ball-milled poplar wood (PW), chemi-mechanical pulp (CMP), and cotton linter (CEL). A set of comparative experiments was carried out, and physical and mechanical properties of the composite films from three different raw materials were determined by means of optical transparency (OT), scanning electron microscopy (SEM), water absorption (WA), thickness swelling (TS), water vapor permeability (WVP), and tensile strength (σb). The overall evaluation indicates the inability of [DiMIM][MeSO4] in complete dissolution of lignocellulosic materials, and sample treatment with this solvent did not lead to water soluble degradation products. However, dissolution trials using [BMIM]Cl were able to dissolve all used lignocellulosic materials by destroying inter and intramolecular hydrogen bonds between lignocelluloses. The OT, WA, TS, and σb of regenerated CEL films were much higher than those of CMP and PW composites. In addition, CEL film showed the lowest WVP compared to WF and CMP composite films. This work demonstrated a promising route for the preparation of biodegradable green cellulose composite films.

International audience; Direct fluorination was applied to wood flour in order to improve its compatibility with polymers and thus enhance the properties of wood-polymer composites. Fourier-transform infrared spectra and 19F solidstate nuclear magnetic resonance results underlined a successful covalent grafting of fluorine atoms onto the wood chemical structure. No physical damage of the wood particles was observed during scanning electron microscopy analysis. The thermal behaviour of the wood flour was also studied by thermogravimetric analysis. The hydrophilic property changes of wood flour were examined by evaluating the water content and the rate of water uptake of samples under different relative humidity conditions. A decrease in the wood flour water content was noted after fluorination. All these studies tend to prove the efficiency of this treatment on wood hydrophilia

The emerging biobased economy is causing shifts from mineral fossil oil based resources towards renewable resources. Because of market mechanisms, current and new industries utilising renewable commodities, will attempt to secure their supply of resources. Cellulose is among these commodities, where large scale competition can be expected and already is observed for the traditional industries such as the paper industry. Cellulose and lignocellulosic raw materials (like wood and non-wood fibre crops) are being utilised in many industrial sectors. Due to the initiated transition towards biobased economy, these raw materials are intensively investigated also for new applications such as 2nd generation biofuels and 'green' chemicals and materials production (Clark, 2007; Lange, 2007; Petrus & Noordermeer, 2006; Ragauskas et al., 2006; Regalbuto, 2009). As lignocellulosic raw materials are available in variable quantities and qualities, unnecessary competition can be avoided via the choice of suitable raw materials for a target application. For example, utilisation of cellulose as carbohydrate source for ethanol production (Kabir Kazi et al., 2010) avoids the discussed competition with easier digestible carbohydrates (sugars, starch) deprived from the food supply chain. Also for cellulose use as a biopolymer several different competing markets can be distinguished. It is clear that these applications and markets will be influenced by large volume shifts. The world will have to reckon with the increase of competition and feedstock shortage (land use/biodiversity) (van Dam, de Klerk-Engels, Struik, & Rabbinge, 2005). It is of interest - in the context of sustainable development of the bioeconomy - to categorize the already available and emerging lignocellulosic resources in a matrix structure. When composing such "cellulose resource matrix" attention should be given to the quality aspects as well as to the available quantities and practical possibilities of processing the feedstock and the performance in the end-application. The cellulose resource matrix should become a practical tool for stakeholders to make choices regarding raw materials, process or market. Although there is a vast amount of scientific and economic information available on cellulose and lignocellulosic resources, the accessibility for the interested layman or entrepreneur is very difficult and the relevance of the numerous details in the larger context is limited. Translation of science to practical accessible information with modern data management and data integration tools is a challenge. Therefore, a detailed matrix structure was composed in which the different elements or entries of the matrix were identified and a tentative rough set up was made. The inventory includes current commodities and new cellulose containing and raw materials as well as exotic sources and specialties. Important chemical and physical properties of the different raw materials were identified for the use in processes and products. When available, the market data such as price and availability were recorded. Established and innovative cellulose extraction and refining processes were reviewed. The demands on the raw material for suitable processing were collected. Processing parameters known to affect the cellulose properties were listed. Current and expected emerging markets were surveyed as well as their different demands on cellulose raw materials and processes. The setting up of the cellulose matrix as a practical tool requires two steps Firstly, the reduction of the needed data by clustering of the characteristics of raw materials, processes and markets and secondly, the building of a database that can provide the answers to the questions from stakeholders with an indicative character. This paper describes the steps taken to achieve the defined clusters of most relevant and characteristic properties. These data can be expanded where required. More detailed specification can be obtained from the background literature and handbooks. Where gaps of information are identified, the research questions can be defined that will require further investigation. (C) 2012 Elsevier Ltd. All rights reserved.

Various mechanical disintegration conditions in water were applied to 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose to prepare TEMPO-oxidized cellulose nanofibrils (TOCNs) of uniform widths ∼4 nm but with three different average lengths, 200, 680, and 1100 nm. The viscosity average degrees of polymerization of the TOCNs were 250, 350, and 400, respectively. Self-standing TOCN and TOCN-coated poly(ethylene terephthalate) (PET) and poly(lactic acid) (PLA) films were prepared, and the optical, mechanical and gas-barrier properties of the films were evaluated in terms of nanofibril length. Only small differences in density, water content, and elastic modulus of the films were observed but TOCN films prepared from longer nanofibrils clearly showed higher tensile strengths, elongations at break and crystallinity indices. The oxygen barrier properties of the TOCN-coated PET and PLA films increased with increasing nanofibril length. In contrast, nanofibril length had almost no influence on water vapor-barrier properties.

In this paper we describe the effect of enzyme treatments on the production of polymeric xylan, oligosaccharides and hemicellulose lean pulp by alkaline extraction of bleached hardwood kraft pulp. Enzyme treatments were carried out before one or in between two subsequent alkaline extractions by purified Trichoderma reesei xylanase and endoglucanase II (Cel 5a) as well as by a commercial monocomponent endoglucanase (FibreCareR). Without enzyme pre-treatment 61% and 7% of the pulp xylan was extracted in high purity in the first and second alkaline stage, respectively. Higher molecular mass xylan was obtained in the second than in the first alkaline extraction. Xylanase treatment before alkaline extraction hydrolyzed up to 12% of xylan to xylooligosaccharides. According to our results, preparation of polymeric xylan, and/or oligosaccharides as well as hemicellulose lean pulp with cellulose content of 93-94%, is possible by enzyme-aided alkaline extraction process.

In this work, the adsorption of lignocelluloses of pre-hydrolysis liquor (PHL) on precipitated calcium carbonate (PCC) was studied in the presence of poly diallyldimethylammonium chloride (PDADMAC) or cationic polyacrylamide (CPAM). The results revealed that adding PCC to PHL and subsequently adding cationic polymers to PHL/PCC systems was more effective than adding cationic polymers to PHL and then adding PCC to the cationic polymer/PHL systems. At the same dosage applied, PDADMAC resulted in a higher adsorption of lignocelluloses on PCC than CPAM did due to its higher charge density. The adsorption of lignocelluloses on PCC reached its maximum in 3 h, and a high temperature reduced the adsorption level as the adsorption was an exothermic process. The maximum adsorptions of 530 mg/g oligo-sugars, 203 mg/g lignin and 58 mg/g furfural on PCC were achieved via adding 0.8 mg/g PDADMAC2 (i.e. higher MW PDADMAC) to PCC/PHL system.

PLA biocomposites were prepared using three corn cob fractions and a wood fiber as reference. The composites were characterized by tensile testing, scanning electron microscopy (SEM) and polarization optical microscopy (POM). Micromechanical deformation processes were followed by acoustic emission measurements. The different strength of the components was proved by direct measurements. Two consecutive micromechanical deformation processes were detected in composites containing the heavy fraction of corncob, which were assigned to the fracture of soft and hard particles, respectively. The fracture of soft particles does not result in the failure of the composites that is initiated either by the fracture of hard particles or by matrix cracking. Very large particles debond easily from the matrix resulting in catastrophic failure at very low stresses. At sufficiently large shear stresses large particles break easily during compounding, thus reinforcement depending on interfacial adhesion was practically the same in all composites irrespectively of initial fiber characteristics.

International audience; Two types of ionic liquids, 1-ethyl-3-methylimidazolim acetate and 1-ethyl-3-methylimidazolium lactate, were employed for the direct processing of pine wood into microfibers. The concentration of 5 wt.% of wood in ionic liquids was rated as the most appropriate for electrospinning. The fibers were electrospun into the collector water bath. The final structure varied from individual microfibers to fiber bundles. It was demonstrated that 1-ethyl-3-methylimidazolium lactate is a powerful solvent and provides the direct transformation of pristine pine wood into the non-wovens.

Dilute oxalic acid pretreatment was applied to maple wood to improve compatibility with downstream operations, and its performance in pretreatment and subsequent enzymatic hydrolysis was compared to results for hydrothermal and dilute hydrochloric and sulfuric acid pretreatments. The highest total xylose yield of ∼84% of the theoretical maximum was for both 0.5% oxalic and sulfuric acid pretreatment at 160 °C, compared to ∼81% yield for hydrothermal pretreatment at 200 °C and for 0.5% hydrochloric acid pretreatment at 140 °C. The xylooligomer fraction from dilute oxalic acid pretreatment was only 6.3% of the total xylose in solution, similar to results with dilute hydrochloric and sulfuric acids but much lower than the ∼70% value for hydrothermal pretreatment. Combining any of the four pretreatments with enzymatic hydrolysis with 60 FPU cellulase/g of glucan plus xylan in the pretreated maple wood resulted in virtually the same total glucose plus xylose yields of ∼85% of the maximum possible.

The accuracy of commercial α- d -glucopyranosyl uronic acid (GlcA) as a calibration standard for the determination of the 4-O-methyl-α- d -glucopyranosyl uronic acid (meGlcA) content in plant materials was studied. A batch of meGlcA standard was purified from commercial birch xylan and quantified using nuclear magnetic resonance spectroscopy. Both commercial GlcA and the purified meGlcA were used as standards for the quantitation of meGlcA in Arabidopsis thaliana stems, as well as wood and wheat straw samples using acid methanolysis and gas chromatography (GC). The GlcA standard was partially lactonized during acid methanolysis, thus yielding six glycoside peaks in GC. If all six GlcA-derived peaks were included in the GlcA calibration curve, the calculated meGlcA content was underestimated by 30% compared with that obtained using the purified meGlcA as a standard. The meGlcA content was best estimated by including either the two main GlcA peaks or only peaks corresponding to pyranosides and furanosides of GlcA in the calibration curve.

The sorption of copper ions onto natural bamboo sawdust with cellulose-lignin polymeric structure strongly depends on pH. The adsorption capacity for copper ions increases as increasing pH and copper loadings. The fitting of copper pH boundary curve by NEM surface complexation models shows that: three-sites model including the ion exchange reaction of permanent charge fits better than two-sites model. The incorporation of the hydrated ion reaction gives better fitting results. XAFS study shows that: copper ions mainly form inner complexation with sawdust, but there is no obvious evidence on the complexation of carboxylic acid groups with copper ions. EXAFS fitting result shows that: as pH rises, the spatial configuration of copper ions shifts from tetrahedron to octahedron. Meanwhile the increase in the coordination number indicates that hydrated copper ions participate in the adsorption. Both XANES and EXFAS spectrum offer a similar explanation for copper adsorption in the range of experimental and fitting errors.