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1-Alkyl-3-methylimidazolium ionic liquids are common cellulose solvents and biomass pretreatment agents, while beta-irradiation ("e-beaming") is often used to decrease the recalcitrance of biomass towards hydrolysis or saccharification. Aiming at the general goal of elucidating the interaction between lignocellulosics, imidazolium-based ionic liquids, and beta-irradiation, we studied the effect of beta-irradiation on the pure ILs 1-ethyl-3-methylimidazolium and 1-butyl-3-methylimidazolium, both as chloride and acetate. Contrary to the expectation of inertness, irradiation caused degradation of the ILs, which was proportional to irradiation dosage, i.e., to irradiation time and intensity. At a dosage of 2400 kGy, 0.2% (2000 ppm) of the IL were chemically altered. The main degradation pathway is the formation of imidazole and N-methylimidazole with concomitant dealkylation. The cleaved-off alkyl groups, apparently in cationic form, react with the anions present, accounting for the formation of alkyl chlorides and alkyl acetates from the chloride ILs and acetate ILs, respectively. A second, minor pathway comprises the degradation of the imidazole ring under conversion of the C2-unit from the former C4-C5 moiety into ethylenediamine and reaction of the C1-unit from the former C2 with the IL anions. Because of the non-neglible byproduct formation, the degradation of the ILs upon beta-irradiation and possible side reactions of the resulting byproducts need to be kept in mind for all setups that involve beta-irradiation and imidazolium ILs simultaneously. [ABSTRACT FROM AUTHOR]

Hypochlorous acid bleaching under amine catalysis (Hcat bleaching stage) is an optimized bleaching stage variant that is characterized by working at weakly acidic, near-neutral pH, having high bleaching efficiency, and discharging only very small amounts of chloro-organics. This study addressed the chemical fate of the used 1,4-diazabicyclo[2.2.2]octane (DABCO) catalyst. While literature proposed either homolytic or heterolytic breakage of one ethylene bridge and subsequent release of the resulting fragments as two molecules of formaldehyde, we demonstrated the degradation to proceed by ionic elimination of one ethylene bridge starting from mono-N-chlorinated DABCO. The resulting N-vinyl (enamine) derivative adds water under the release of acetaldehyde and formation of piperazine. The generation of acetaldehyde was experimentally confirmed by 2,4-dinitrophenylhydrazine trapping, directly from the processing liquid. The experimental findings agreed superbly with computations which showed the "acetaldehyde mechanism" to be much favored over the previously proposed pathways under C–C bond cleavage and release of formaldehyde. The results of this study add to a better understanding of the novel Hcat bleaching system. [ABSTRACT FROM AUTHOR]

Pretreatment of pulp is a critical step in the fibrillation process to improve the quality and efficiency for cellulose nanofibril (CNF) production. This work employed a straightforward and entirely aqueous methacrylation and subsequent grafting-through polymerization technique to modify bleached softwood kraft pulp (BSKP). Specifically, methacrylate groups, poly(acrylamide) (PAM), and poly(methyl methacrylate) (PMMA) were chemically affixed to the surface of BSKP fibers, which was confirmed using FTIR spectroscopy. Bench-scale experiments were scaled up to pilot scale to prepare the modified BSKP samples, these were subjected to fibrillation using a Supermasscolloider (SMC), and the net cumulative energy (NCE) expended was monitored during the fibrillation process. Notably, the modified BSKP samples exhibited a substantial reduction in NCE, with the methacrylate modified BSKP sample achieving a 68% reduction in NCE expenditure to attain 90% fines as compared to the fibrillation of unmodified BSKP and producing methacrylate modified cellulose nanofibrils (Met-CNFs). Furthermore, we delved into the impact of polymeric surface modifications, both pre-and post-fibrillation, on fiber and fibril behavior, including the water retention value (WRV), hard-to-remove water (HR-Water), and rheological behavior. The attached polymer's hydrophilicity and hydrophobicity influenced the physical properties of the CNFs. Additionally, we executed a post-grafting polymerization process on the produced Met-CNFs. This additional step allowed us to modify nanofibril surfaces, yielding increased surface functionalization and producing modified CNFs that could be used for composite applications. [ABSTRACT FROM AUTHOR]

The main aim of this work was to study the role of the acetylation process of wheat straw pulp on its ability to rheologically modify two of the most important non-polar engineering fluid: bitumen and oil. Pulp was produced by a pilot-scale kraft pulping process from local wheat straw. Pulp was functionalized with acetic anhydride and sulfuric acid as a catalyst by modifying (temperature, pulp/acetic anhydride mass ratio, and reaction time. Further, chemical, morphological and thermal changes induced by the acetylation process were properly assessed. Acetylated wheat straw pulp dispersions in oil showed gel-like behaviour, with a mechanical spectrum characterized by higher values of the storage modulus (G′) and a minimum in the loss modulus (G″) at intermediate frequencies. The complex modulus (G*) for bitumen dispersions formulated with acetylated samples was up to 4 times higher than neat bitumen, and the phase angle (δ) indicated an enhancement in the elastic behavior parameters. The rheological response of these systems was associated with the microstructural network formed by pulp fibers and the balance between the physical and chemical changes of wheat straw fibers. According to the experimental results obtained, it can be concluded that acetylation is a relevant chemical treatment to modulate the rheological properties of wheat straw pulp dispersions in non-polar fluids, improving the compatibility between pulp fibers and these engineering fluids. Accordingly, this study provides valuable insights into the development of sustainable multiphasic materials (bitumen binders and semi-solid lubricants) for industrial applications. [ABSTRACT FROM AUTHOR]

Kraft pulp is the most common and economically advantageous raw material for making cellulose nanofibers (CNFs). However, it is revealed that high temperatures and pressures during kraft cooking cause the aggregation of cellulose microfibrils, which reduces the nanofibrillation capability of kraft pulp. Herein, we studied the optimum kraft cooking conditions required to obtain uniform CNFs by preventing aggregation. The fibrillation ability was compared with that of undried pulp treated with purification method only. Suspensions of undried pulps were mechanically fibrillated for various durations. The degree of fibrillation was evaluated by sedimentation, morphology, and water retention values. Kraft pulp cooking at a H-factor of approximately 650 for 140 °C, 160 °C and 170 °C resulted in less fibrillation than in the Wise-based pulp, even at low temperatures such as 140 °C. In contrast to expectations, high matrix substances with lignin contents of 30% did not prevent aggregation of the cellulose microfibrils. The production of CNFs requires a pulping technique for extracting cellulose without aggregation. [ABSTRACT FROM AUTHOR]

In recent years, the search for alternatives to petroleum derived products, such as plastic films, has become a priority due to the growing depletion of fossil reserves and the pollution of water resources by microplastics, microscopically small plastic particles which are harmful to ocean and aquatic life. Cellulose-based films, e.g., cellophane and cuprophane, have been on the market for almost a century. Despite being a more ecological option compared to plastic films, the manufacture of these cellulose films involves high production costs and the use of harmful chemicals. As an alternative, a sustainable and eco-friendly process based on the Lyocell-type Ioncell® technology is presented to produce cellulose films. Regenerated cellulose films are created by continuous extrusion via dry-jet wet spinning of an ionic liquid–cellulose solutions. The influence of the polymer concentration (8–13 wt%) and processing temperature (50–100 °C) on the properties of the films were studied by the determination of the thickness, mechanical properties, physical appearance, morphology, chemical composition, and hydrophobicity. The obtained films are thin (12–21 μm), transparent (transmittance = 91%) and of homogeneous structure. Moreover, they exhibit excellent mechanical properties: stress values up to 210 MPa and elongations up to 19% in machine (longitudinal) direction. These values clearly outperform commercial cellophane, which presents stress values of 125 MPa and elongations of 22%. The films presented herein hold great potential to become an eco-friendly and sustainable option to commercial films. [ABSTRACT FROM AUTHOR]

β-Irradiation ("e-beaming") as well as swelling in ionic liquids, each process by itself, are common pretreatments in biorefinery scenarios. A combination of both, such as occurs with β-irradiation of biomass that was insufficiently washed and still contains traces of ionic liquids, causes covalent derivatization of the contained cellulose and incorporation of nitrogen. The nitrogen uptake occurred only in the presence of the ionic liquid and correlated linearly with both the irradiation dose and the concentration of the contained ionic liquid. The presence of other wood constituents during β-irradiation decreased nitrogen uptake, but did not prevent it. The derivatization of cellulose did not depend on the degree of crystallinity, but appeared to depend on the content of oxidized groups (carbonyl functionalities), also with a linear correlation. Future work must now clarify the mechanism of this reaction and the influence of other wood constituents, and address the possible potential of e-beaming in the presence of imidazolium ionic liquids for cellulose chemistry. [ABSTRACT FROM AUTHOR]

In this study, a strategy of corncob valorization was proposed. Corncob was first pretreated with a recyclable acid hydrotrope (p-TsOH, aqueous solution) to selectively remove lignin and hemicelluloses. After pretreatment, the collected liquid phase was diluted with deionized water to precipitate lignin. The hemicelluloses degradation products, mainly pentose, in the resulting acid liquor were converted into furfural with a yield of 53.65% without adding any catalyst. The collected lignin was depolymerized to phenolic monomers with a yield of 68.00% via a hydrodeoxygenation process. The pretreated cellulose-rich solid was subjected to 10 s ultrasonic treatment to form pulp and subsequently used for papermaking by blending it with commercial softwood pulp. With a corncob pulp addition of 20%, the tensile index and ring crush index of hand sheets increased by 10.62% and 5.05%, respectively, compared with those containing 100% softwood pulp. Therefore, this study provided a strategy for corncob valorization toward multipurpose fractionation: furfural, phenolic monomers, and pulp, reaching a comprehensive utilization of corncob. [ABSTRACT FROM AUTHOR]

In this work, we produced composites of mesoporous silica synthesized in-situ on never-dried bleached eucalyptus kraft pulp fibers with the aim of providing cost-effective depth filters, having high flux, and adsorptivity. The mesoporous silica loading for the produced samples was in the range of 12–35 wt%. The performance of double-layer membranes was studied for the adsorption of charged molecules. The best nanofibrillated cellulose-pulp-mesoporous silica membrane adsorbed 1160 mg/m2 of methylene blue and had a flux of 10 L m−2 h−1 bar−1. The nanofibrillated cellulose layer supported the pulp-mesoporous silica layer and improved the adsorptivity of the pulp-mesoporous silica depth filter layer by controlling flux. The membranes showed non-linear-pseudo-first-order adsorption kinetics and non-linear Freundlich isotherm for methylene blue adsorption. The nanofibrillated cellulose-pulp-mesoporous silica membrane was modified for metanil yellow adsorption by adding polyamide amine-epichlorohydrin resin. The best metanil yellow saturated adsorption capacity was 9400 mg/m2. The nanofibrillated cellulose-pulp-mesoporous silica depth filter without modification with a polyelectrolyte also had 92% and 94% heavy metal removal of 20 mg of Cu2+ and Pb2+ ions, respectively. The novel pulp-mesoporous silica composite membrane, with high adsorption capacity and manufactured by lower embodied energy of cellulose fiber, can significantly lower large-scale depth filter production costs due to the elimination of cellulose pre-treatment for the depth filter layer. The reusability performance in the fifth cycle, after four cycles of metanil yellow adsorption and desorption, was 5.2 mg/g, which was stabilized from the 3rd to 5th cycles. This suggests the suitability of these membranes for industrial applications. [ABSTRACT FROM AUTHOR]

Correctness and reliability of molar mass data by viscometry in organometallic solvents (cuen, cuoxam, cadoxen) are compromised by the alkalinity of these solvents which causes immediate depolymerization especially in the case of pulps with higher carbonyl content (oxidative damage). The viscosity values thus correspond to the molar mass after the beta-elimination reactions that underly these degradative processes, which is sometimes significantly smaller than the molar mass determined by gel permeation chromatography (GPC) in the non-degrading solvent system DMAc/LiCl. Despite this well-known drawback, viscosity measurements have become a standard approach for molar mass measurements due to their ease and fastness, especially in the pulp and paper industries. A potential way to reduce the inherent error of these molar mass determinations via viscosity measurements is a reductive treatment prior to dissolution of the pulp in the organometallic solvents, which converts the labile, alkali-sensitive carbonyl structures back to the respective alcohols. Using sodium borohydride (NaBH4) on different types of cellulosic pulps, we demonstrate the beneficial effects of such a reduction step on the determined degree of polymerization (DP) for all three common solvents: cuen, cuoxam and cadoxen. Molar mass distributions and profiles of carbonyl groups were determined by GPC and by carbonyl selective fluorescence labeling ("CCOA method"). Such a reductive treatment was especially valuable for hemicellulose-containing pulps. While the decreased measurement error according to the new protocol is beyond doubt, an immediate acceptance in the pulp and paper industries is at least questionable, because the new, more correct data would not agree with the old – wrong, but consistent – numbers accumulated over years and decades. In the long run, however, the new, improved protocol will prevail here as well due to its lower error rate. [ABSTRACT FROM AUTHOR]

The dry pulp direct kneading method is an industrially viable, low-energy process for manufacturing cellulose nanofiber (CNF)-reinforced polymer composites, where the chemically modified pulps are nanofibrillated and uniformly dispersed in the polymer matrix during melt compounding. In the present study, cellulose fibers of various sizes ranging from surface-fibrillated pulps (20 μm in width) to fine CNFs (20 nm in width) were prepared from softwood bleached kraft pulps using a refiner and a high-pressure homogenizer. These cellulose fibers were modified with alkenyl succinic anhydride and dried. The dried fibers were used as a feed material for melt compounding in the dry pulp direct kneading method to fabricate CNF-reinforced high-density polyethylene (HDPE). When surface-fibrillated pulps were employed as a feed material, the pulps were nanofibrillated and dispersed uniformly in the HDPE matrix during melt compounding. The resulting composites had much better properties—i.e., much higher tensile modulus and strength values, and much lower coefficient of thermal expansion values—than the composites produced using pulps without pre-fibrillation. However, when CNFs were used as a feed material, they were shortened and agglomerated during melt compounding, and the properties of the composites consequently deteriorated. The study concludes that surface-fibrillated pulp, which can be produced cost-effectively using a refiner on an industrial scale, is more suitable as a feed material than CNFs for melt compounding in the dry pulp direct kneading method. This finding enables the elimination of a preliminary step in the preparation of CNFs from pulps, which is a time-consuming and energy-intensive process. [ABSTRACT FROM AUTHOR]

Owing to the rapid development of biotechnology, enzymes are being used more frequently in the manufacturing industry, especially in the pulp and paper industry. Compared with traditional pulping, biopulping has the advantage of requiring mild reaction conditions, which makes it more eco-friendly and faster than other methods. When enzymes are combined with other pulping technologies, maximum pulping efficiency can be ensured and pollution could be reduced. However, to maximize pulping efficiency, control pulping costs, and achieve the best quality paper, enzymatic methods are often combined with other pulping technologies. Therefore, enzyme production costs for papermaking remains a problem to be addressed in future research. [ABSTRACT FROM AUTHOR]

With an annual production of more than 400 million tons, paper is the main product of the largest biorefinery process industrially implemented. Enzymes have been used for pulp refining to dramatically reduce energy consumption. However, exact mechanisms related to the individual enzymes are hardly understood. Yet, this knowledge would be important to predict enzyme performance in industrial processes. Three commercial refining enzyme formulations showed different endoglucanase (1.25 nkat mg−1–13.7 nkat mg−1), β-glucosidase (0.57 nkat mg−1–1.34 nkat mg−1) and xylanase activities (1.78 nkat ml−1–62.1 nkat mg−1) on model substrates. Additionally, distinct amounts of reducing sugars from hardwood sulfate pulp were released. Endoglucases were purified from each formulation by using hydrophobic interaction and anion exchange chromatography and showed molecular weights from 20 to 55 kDa and specific activities ranging between 3.11 and 26.3 nkat mg−1 according to endoglucanase specific derivatized cellopentaose (CellG5). Refining trials of hardwood sulfate pulp were conducted using a PFI laboratory mill and fiber properties such as degree of refining or fiber length and properties of formed sheets like tensile index were monitored. Thereby, enzymes were dosed based on identical endoglucanase activity on CellG5. Enzyme formulations and purified endoglucanases led to an increase of the degree of refining of up to 47.9 [°SR] at 6000 PFI revolutions while the tensile index was improved by up to 76.0 Nm g−1. In summary, refining effects can be primarily attributed to endoglucanases indicating activity on CellG5 being a suitable parameter for enzyme dosing. [ABSTRACT FROM AUTHOR]

TEMPO-oxidised cellulose fibres are often explored as nano-reinforcement for polymers. However, it is unclear whether micrometre-sized TEMPO-oxidised cellulose fibres also possess similar reinforcing potential. In this work, we report the mechanical response of polypropylene (PP) composites reinforced with TEMPO-oxidised cellulose (TOC) of different fibre widths. Micrometre-sized TOC fibres (TOCF) containing sodium carboxylate (TOCF-Na) and free hydroxyl (TOCF-H) groups, as well as nano-sized TOC nanofibrils (TOCN) were produced from dissolving pulp and incorporated into PP matrix via melt-extrusion. It was found that model PP composites containing micrometre-sized TOCF-Na and TOCF-H possessed the highest tensile modulus of up to 2.5 GPa; 40% improvement over neat PP and 30% increase over PP/TOCN composite. No significant differences in the tensile strength of PP/TOCF-Na and PP/TOCF-H composites were observed when compared to neat PP. The incorporation of nano-sized TOCN into PP however, led to a 6% decrease in tensile strength. Single-edge notched beam fracture toughness test further showed that PP/TOCN composite possessed the lowest fracture toughness of 2.52 MPa m1/2; a decrease of 18% over PP reinforced with micrometre-sized TOCF-Na and TOCF-H. Our study shows that micrometre-sized TOCFs serve as better reinforcement for polymers compared to nano-sized TOCN. This is attributed to the better dispersion of TOCF in the PP matrix. Furthermore, the presence of surface microfibrillation on TOCFs also enhanced the quality of the TOCF-PP interface through mechanical interlocking and local stiffening of the PP matrix. [ABSTRACT FROM AUTHOR]

Properties of cellulose nanocrystals (CNCs) depend upon their supramolecular structures, which are important to understand in order to optimize their applications. In this investigation, the structures of CNCs produced upon 48–64% H2SO4 hydrolysis of hydrothermally-treated poplar, bleached kraft pulp, cotton microcrystalline cellulose, bacterial cellulose, tunicin, and cladophora cellulose were comparatively analyzed. TEM provided information on the morphological aspects. Raman, MAS-NMR, and XRD provided information on one aspect of the supramolecular organization, namely, crystallinity (CrI). Other characteristics of supramolecular structure were analyzed by various Raman methods, namely, accessibility to water, exocyclic CH2OH conformation ratio, and chain conformation disorder (CCONDIS)—the last method was developed in the present study. In general, CNCs retained the crystallinity of the starting material irrespective of the measurement method of CrI. Additionally, it was found that crystallite size and supramolecular organization influenced CrI as well. These analyses further indicated that poplar- and pulp-CNCs had significantly higher water accessibility as compared with CNCs from cladophora, bacterial, tunicin, and cotton MCC CNCs, implying higher molecular disorder, which was also reflected in measurements of CH2OH conformation ratio and CCONDIS. The findings indicate that significant differences among the CNCs seem to arise largely from differences between the starting materials. Additionally, considering that CNCs can have very different morphologies and structural properties depending upon how they are produced, the analyses carried out here can characterize such CNCs and estimate their applications. [ABSTRACT FROM AUTHOR]

Along with the emergence of micro and nanofibrillated celluloses and their application in papermaking, the influence of the so called fines fraction of pulps on both process and product properties has received increasing research interest in recent years. Several researchers have experimented with primary and/or secondary pulp fines to assess their effects on paper properties with not always consistent results. Our work focuses on the targeted application of the primary fines fraction of an unbleached softwood kraft pulp. The primary fines are separated from the pulp to be subsequently added to achieve blends of 5 % , 9 % and 12 % primary fines content. These blends were then refined in a PFI mill to evaluate the effect of the primary fines on refining as well as on paper properties of hand sheets prepared from these pulps. It is shown that the addition of primary fines enhances tensile strength in the unrefined and slightly refined state, while the maximum tensile strength of the highly refined reference pulp is not increased. A slightly increased dewatering resistance (Schopper Riegler) at comparable air permeability (Gurley) for a given tensile strength was also observed. The linear relationship between tensile index and apparent sheet density seems to be affected in the unrefined and slightly refined state where the breaking length of the fines enriched samples is higher for a given apparent density. [ABSTRACT FROM AUTHOR]

Hornification of cellulose is a well-known phenomenon that takes place during the drying process. Hornification involves a structural change in the cellulose that restricts the enzyme's ability to access and saccharify the cellulose. We observed never-dried (ND), pressed (PR), and oven-dried (OD) softwood pulp during saccharification catalyzed by fluorescent labelled cellulase from Trichoderma reesei by confocal laser scanning microscopy. Initially cellulases were observed on outer surfaces and dislocations of all the ND, PR, and OD pulp fibers. It was clearly observed that over time that cellulases penetrated the cell walls of the ND pulp fiber from the outer surface, inner surface and cracks and remained in the cell walls. In contrast, they did not penetrate the cell walls of the OD pulp fiber and instead stayed on the cracks and ends of the shortened fibers. Mannan and xylan were found at dislocations of ND and OD fibers by immunolabelling microscopy. The results suggested that hemicellulose plays an important role in hornification at dislocations. [ABSTRACT FROM AUTHOR]

Bacterial nanocellulose (BNC) is a unique natural nanomaterial that shares very few similarities with other natural or industrially produced nanomaterials. BNC can be produced by a variety of bacteria, as a survival aid in different ecological niches. BNC is traditionally produced by static or shaking culture methods, and the 'mother vinegar', or biofilm, is a typical example of this product after static vinegar fermentation. BNC has great potential in biomedicine, and recent studies have also demonstrated its use in the papermaking industry. It has nanoscale fiber size and large numbers of free hydroxyl groups, which ensure high inter-fiber hydrogen bonding. Thus, BNC has great potential as a reinforcing material, and is especially applicable for recycled paper and for paper made of nonwoody cellulose fiber. As well as enhancing the strength and durability of paper, modified BNC shows great potential for production of fire resistant and specialized papers. However, the biotechnological aspects of BNC need to be improved to minimize the cost of its production, and to thus make this process economically feasible. [ABSTRACT FROM AUTHOR]

This study examines the effect of pulp type on the formability and elongation of paperboard, which are of key importance when producing 3D packages. Material performance was studied with a press-forming machine using laboratory handsheets as substrates. The handsheets were prepared from bleached softwood and hardwood kraft pulps, chemi-thermomechanical pulp, recycled newsprint, and mixtures of birch kraft and other pulps. The effect of microfibrillated cellulose (MFC) on substrate properties and material formability was also investigated. The 3D elongation of MFC-free handsheets varied between 1.2 and 5.5%. Depending on the pulp type and sheet composition, three essential sheet properties were recognized. These properties were bulk, elastic modulus and bending stiffness, the first two of which affect material bending stiffness. Sheets made from softwood fibers were superior to other samples, but their low bending stiffness resulted in distortion of formed trays. A partial replacement of birch kraft with recycled newsprint did not lead to a loss of sheet extensibility, which suggests that the interactions between the converting tools and the substrate have a great effect on material convertibility. Scanning electron micrographs showed that the pulp type affects the mechanism behind fracture initiation. The ability of MFC to increase extensibility was limited to mechanical pulps, indicating the important role of the main pulp component in defining tensile properties. [ABSTRACT FROM AUTHOR]

Abstract: The chemistry of cellulosic key chromophores is challenging because of the usually very low concentration of the colored compounds in real-world cellulosic matrices. It offers many surprises and positive outcomes; unfortunately there are also pitfalls and disappointments. This report discusses eight examples or surprising chemistry out of the realm of cellulosic key chromophores. The reactions have either taken unforeseen paths or provided unexpected products. The reaction mechanisms of the "strange" processes are described and the products are comprehensively analytically characterized. Given that the seemingly obvious approaches have failed, alternatives for obtaining the desired products are provided, wherever possible. Graphical abstract: [ABSTRACT FROM AUTHOR]

Abstract: Dynamic vapor sorption (DVS) coupled with deuterium exchange was applied in determining the amount of hydroxyl (OH) groups accessible for deuteration in pulps and pure cellulose quantitatively. The samples studied with the method were different types of chemical pulps as well as microcrystalline and amorphous cellulose powders. The measurement sequence consisted of drying the samples first until the change in sample mass was less than 0.0005% min−1 followed by rewetting the sample with deuterium oxide (D2O) vapor at set relative humidity (RH) of 95% for 600 min and then drying the sample again the same way as the initial drying was done. The method allows determination of the absolute amount of OH groups accessible to deuterium exchange in the samples fully automatically within 1 day. In addition, the equilibrium moisture contents (EMC) of the samples were measured at RH 95% without prior drying enabling the assessment of the EMC of the samples in as-received state without the need to assess the effect of drying. The accessibilities of chemical pulps were found to vary between 54 and 61% of the theoretical maximum, whereas the accessibilities of microcrystalline cellulose and amorphous cellulose were 51 and 63%, respectively. Interestingly, it was found that the accessible OH group content and the EMC of the samples in mol kg−1 correlated with each other and that, in fact, their ratio was close to one.Graphical abstract: [ABSTRACT FROM AUTHOR]

Cellulosic materials are highly sensitive towards environmental changes such as temperature and especially towards humidity. Besides morphological changes like swelling and/or shrinking, the mechanical properties of pulp fibres and fibre to fibre joints change as well. The current study sets to elucidate the changes and the extent to which elevated or decreased relative humidity (RH) influences the load bearing capacity of individual hardwood and softwood fibres and joints. The device used for the measurements is a micro bond tester with a custombuilt humidity chamber in which the humidity can be controlled in a range from 25 to 95% RH. Individual fibres and joints have been tested at 30, 50 and 80% RH after equilibration time of 120 min. The breaking load of individual softwood fibres and joints displayed a maximum breaking load at 50% RH, with the values showing a decreasing trend towards higher or lower RH. In case of hardwoods, no change in the breaking load of either individual fibres or fibre to fibre joints has been observed at different RH. [ABSTRACT FROM AUTHOR]

A deep eutectic solvent composed of choline chloride (ChCl) and urea has been recently introduced as a promising cellulose compatible medium that enables e.g. fibre spinning. This paper clarifies the influence of such a solvent system on the structure and chemical composition of the cellulosic pulp fibres. Special emphasis was placed on the probable alterations of the chemical composition due to the dissolution of the fibre components and/or due to the chemical derivatisation taking place during the DES treatment. Possible changes in fibre morphology were studied with atomic force microscopy and scanning electron microscopy. Chemical compositions of pulp fibres were determined from the carbohydrate content, and by analysing the elemental content. Detailed structural characterisation of the fibres was carried out using spectroscopic methods; namely X-Ray Photoelectron Spectroscopy, solid state Nuclear Magnetic Resonance and Raman Spectroscopy. No changes with respect to fibre morphology were revealed and negligible changes in the carbohydrate composition were noted. The most significant change was related to the nitrogen content of the pulp after the DES treatment. Comprehensive examination using spectroscopic methods revealed that the nitrogen originated from strongly bound ChCl residuals that could not be removed with a mild ethanol washing procedure. According to Raman spectroscopic data and methylene blue adsorption tests, the cationic groups of ChCl seems to be attached to the anionic groups of pulp by electrostatic forces. These findings will facilitate the efficient utilisation of DES as a cellulose compatible medium without significantly affecting the native fibre structure. [ABSTRACT FROM AUTHOR]

As worldwide agricultural production rises, agro-industrial biomass becomes an abundant raw source for uses in energy and materials production. In Colombia fique plants ( Furcraea spp.) are traditionally used to extract hard cellulosic fibers using mechanical decortication. Juice, pulp and tow, the by-products of this process, represent almost 95% of the fique leaf weight and are produced in large quantities. Data on these materials is scarce and greatly needed to guide and fuel fique agro-industrial development in Colombia. In this contribution we study the physicochemical properties of fique fibers and by-products (tow and pulp), before and after alkaline hydrogen peroxide treatment (AHP), using spectroscopic and microscopic techniques. Raw/clean fique tow is similar in structure and composition to fique fibers with average cellulose, hemicellulose and lignin contents of 52.3, 23.8 and 23.9%; in this by-product cellulose exists as a highly ordered structure with crystallinity index of 57%. Raw/clean fique pulp, composed of cellulose filaments from secondary cell walls and leaf epidermis, has average cellulose, hemicellulose and lignin contents of 30.5, 29.7 and 9.6%, with cellulose exhibiting an amorphous structure with a crystallinity index of 35%. The AHP treatment of these by-products effectively removed non-cellulosic compounds such as hemicellulose and lignin. After AHP lignin content in fique tow decreases to 2.8% while cellulose crystallinity increases up to 73%, Likewise, fique pulp shows a reduction in lignin to 2.1% and an increase in cellulose crystallinity up to 47%. IR spectroscopic analysis, after AHP, show a decrease of signals attributed to hemicellulose and lignin and FESEM images show a disruption of the lamellar structure in the macro fiber by the removal of hemicellulose, lignin and ground tissue, leaving cellulose fibrils exposed. As the first in-depth report on fique by-products characterization, our results indicate that pulp and tow are interesting lignocellulosic materials due to their significant content of crystalline and amorphous cellulose. [ABSTRACT FROM AUTHOR]

Hexeneuronic acid (HexA) is formed under pulping conditions from 4- O-methyl-glucuronic acid residues in xylans by methanol elimination. It is usually removed by an acidic washing treatment (A-stage) within the pulp bleaching sequence. Hexeneuronic acid has long been recognized as a source of color generation in pulps, but the chemical structure of the actual chromophoric compounds remained elusive. We report the synthesis of isotopically (C) labeled HexA model units carrying a label at any of the six carbon atoms. Confirming pertinent literature accounts, it is shown that HexA forms three primary degradation intermediates, 2-furancarboxylic acid, 5-formyl-2-furancarboxylic acid, and formic acid, under mildly acidic conditions, and their formation mechanism is discussed. 2-Furancarboxylic acid is demonstrated to be deformylation product of 5-formyl-2-furancarboxylic acid. The three primary intermediates are colorless and do not represent chromophores themselves. Their mixture, upon thermal or acidic treatment, gives rise to the same chromophores that are also directly formed from HexA. [ABSTRACT FROM AUTHOR]

Hexeneuronic acids (HexA) have long been known as triggers for discoloration processes in glucuronoxylan-containing cellulosic pulps. They are formed under the conditions of pulping from 4- O-methylglucuronic acid residues, and are removed in an 'A stage' along the bleaching sequences, which mainly comprises acidic washing treatments. The chemical structures of HexA-derived chromophoric compounds 4- 8, which make up 90% of the HexA-derived chromophores, are reported here for the first time. The compounds are ladder-type, mixed quinoid-aromatic oligomers of the bis(furano)-[1,4]benzoquinone and bis(benzofurano)-[1,4]benzoquinone type. The same chromophoric compounds are generated independently of the starting material, which can be either a) HexA in pulp, b) the HexA model compound methyl 1-C-4-deoxy-β-L- threo-hex-4-enopyranosiduronic acid ( 1) or c) a mixture of the primary degradation intermediates of 1, namely 5-formyl-furancarboxylic acid ( 2) and 2-furancarboxylic acid ( 3). Isotopic labeling (C) in combination with NMR spectroscopy and mass spectrometry served for structure elucidation, and final confirmation was provided by X-ray structure analysis. C-Isotopic labeling was also used to establish the formation mechanisms, showing all the compounds to be composed of condensed, but otherwise largely intact, 2-carbonylfuran and 2-carbonylfuran-5-carboxylic acid moieties. These results disprove the frequent assumption that HexA-derived or furfural-derived chromophores are linear furanoid polymers, and might have a direct bearing on structure elucidation studies of 'humins', which are formed as dark-colored byproducts in depolymerization of pentosans and hexosans in different biorefinery scenarios. [ABSTRACT FROM AUTHOR]

Hexeneuronic acids (HexA) are a major cause of discoloration (yellowing/brightness reversion) in pulps from xylan-containing wood, being generated from the xylan's 4- O-methylglucuronic acid residues. The HexA-derived chromophores, whose identification and structure confirmation have been described in the previous part of this series (Rosenau et al. in Cellulose, 2017), were subject to conditions of peroxide bleaching, i.e. treatment with hydrogen peroxide in alkaline medium. These chromophores, ladder-type oligomers of mixed aromatic-quinoid and mixed furanoid-benzoid character, are degraded relatively quickly to one major product, 2,5-dihydroxy-[1,4]-benzoquinone (DHBQ), and a minor component, 2,5-dihydroxyacetophenone (DHA). These two compounds, which have already been identified as two of the three key chromophores (besides 5,8-dihydroxy-[1,4]-naphthoquinone, DHNQ) in aged cellulosics, are potent chromophores themselves and are subsequently more slowly degraded to non-colored degradation products, according to pathways already described in previous parts of this series. The occurrence of DHBQ and DHA in the bleaching treatment of the HexA-derived chromophores establishes the link between HexA chemistry and the key chromophore classes of residual chromophores found in aged cellulosic materials. [ABSTRACT FROM AUTHOR]

The rheological behaviour of homogenised fibres originally having different lengths was evaluated. For this purpose, mixtures of pulp fibres and fines were fibrillated mechanically without pre-treatment and characterised with regard to morphology and viscosity. It was found that, for all samples, a similar number of homogenisation passes was needed to reach a viscosity plateau. However, the value of the final viscosity differed significantly: homogenised suspensions derived from fines achieved only about 60 % of the viscosity of suspensions derived from pulp. Already after a few homogenisation cycles, no differences between the samples could be measured using optical devices, indicating that fibrillation on the nanometre scale was responsible for the distinct rheological behaviours. Atomic force microscopy measurements indicated significantly reduced fibril lengths for the suspensions derived from fines, which explains their reduced viscosity. [ABSTRACT FROM AUTHOR]

The direct acylation of cellulose and different pulps with various acid chlorides was systematically screened. The syntheses were started in a heterogeneous solid-liquid reaction medium in hot pyridine with aliphatic and aromatic acid chlorides. After a few hours, depending on the reagent used, a homogenous solution was obtained. The obtained cellulose esters usually show a high degree of substitution (DS) and polymerization and are soluble in organic solvents. Esterification of softwood dissolving pulp, hardwood kraft pulp and hardwood kraft pulp-hemicellulose poor were also studied. The results show that almost identical DS were obtained for pulp derivatives compared to esters of microcrystalline cellulose. Thermogravimetric analysis and differential scanning calorimetry of the synthesized materials showed an improved thermal stability and various discrete thermal transitions compared to the original cellulose. The scanning electron microscopy images of derivatives showed a relatively flat and smooth surface with an absence of fibrous structure. The reactive dissolution of cellulose or pulp in pyridine is a straightforward and easy route to obtain long-chain aliphatic and aromatic cellulose esters. [ABSTRACT FROM AUTHOR]

Cellulose nanofibers have a bright future ahead as components of nano-engineered materials, as they are an abundant, renewable and sustainable resource with outstanding mechanical properties. However, before considering real-world applications, an efficient and energetically friendly production process needs to be developed that overcomes the extensive energy consumption of shear-based existing processes. This paper analyses how the charge content influences the mechanical energy that is needed to disintegrate a cellulose fiber. The introduction of charge groups (carboxylate) is achieved through periodate oxidation followed by chlorite oxidation reactions, carried out to different extents. Modified samples are then subjected to different levels of controlled mechanical energy and the yields of three different fractions, separated by size, are obtained. The process produces highly functionalized cellulose nanofibers based almost exclusively on chemical reactions, thus avoiding the use of intensive mechanical energy in the process and consequently reducing drastically the energy consumption. [ABSTRACT FROM AUTHOR]

Solid-state 13C NMR spectroscopy was used to determine the degree of cellulose crystallinity (Crl) in kraft, flow-through kraft and polysulphide anthraquinone (PS-AQ) pulps of pine and birch containing various amounts of hemicelluloses. The applicability of acid hydrolysis and the purely spectroscopic proton spin-relaxation based spectral edition (PSRE) method to remove the interfering hemicellulose signals prior to the determination of Crl were also compared. For softwood pulps, the spectroscopic removal of hemicelluloses by PSRE was found to be more efficient than the removal of hemicelluloses by acid hydrolysis, in addition to that, the PSRE method also provides information on the associations between cellulose and hemicelluloses. On the basis of the incomplete removal of xylan from the cellulose subspectra by PSRE, the deposition of xylan on cellulose fibrils and therefore an ordered ultrastructure of xylan in birch pulps was suggested. The ordered structure of xylan in birch pulps was also supported by the observed change of xylan conformation after regeneration. Similarly, glucomannan in pine pulps may have an ordered structure. According to the 13C CPMAS measurements conducted after acid hydrolysis, the degree of cellulose crystallinity was found to be slightly lower in birch pulps than in the pine pulps. Any significant differences in cellulose crystallinity were not found between the pulps obtained by the various pulping methods. Only in pine PS-AQ pulp, the degree of cellulose crystallinity may be slightly lower than in the kraft pulps containing less hemicelluloses. [ABSTRACT FROM AUTHOR]