Carbon fibre reinforced composites are used to provide high-strength light-weight materials that are sought after in mobility applications to reduce weight and consequently fuel or energy consumption of the transportation vehicle. Cost and environmental considerations have resurged research on biobased precursors for carbon fibres (CFs) with cellulose being one of the most prominent examples. In this study we shed light on the purity requirements of the cellulose substrate. Thus far, most reports on lignocellulose-based CFs implement highly refined dissolving-grade pulp. To reduce the cost of the precursor fibres and their environmental footprint even further, less refined cellulose sources are desirable. The role of xylan on the properties of the precursor fibres and the carbonization behaviour of holocellulosic precursor fibres were studied. It was found that natively present hemicelluloses in paper-grade kraft pulp can be incorporated homogeneously into the cellulose matrix without impairing the fibre properties, and even showing a beneficial effect on the final carbon yield.

Cellulose is synthesized at the plasma membrane by the cellulose synthase complex, a structure that contains three distinct isoforms of the catalytic subunit, cellulose synthase A (CESA). The division into three subunits appears early in land plant evolution and is highly conserved, particularly for the secondary cell wall. However, what if any unique roles each isoform plays in the complex remain unclear. Here, we assessed the contributions of specific isoforms to microfibril synthesis. First, we expressed CESA isoforms of the primary cell wall or the moss Physcomitrium patens in Arabidopsis thaliana backgrounds missing a secondary cell wall CESA. While the primary cell wall isoforms rescued the cesa knockout phenotype with partial isoform specificity, those from the moss rescued with fewer restrictions. Then, we recreated various CESA missense mutations in all three of the secondary cell wall isoforms; while results are consistent with isoform specificity, they are difficult to interpret further without molecular structures. Finally, we show that catalytically inactive CESA isoforms restore growth and cellulose content in the corresponding knockout in an isoform-specific manner; along with partial rescue of the growth and cellulose content of the inflorescence stem, the replacement lines have fiber cells with partially disorganized microfibrils and secondary cell wall cellulose with narrow crystal width. Generally, effects were more pronounced in lines where CESA8 was inactivated compared with inactivating CESA4 or 7, which tended to have similar phenotypes to each other. We account for these results with a model for cellulose synthase structure with the isoforms assigned specific localization within the cellulose synthase complex.

The chemical recycling of cotton towels via the Ioncell (R) technique is demonstrated. Cotton is the most common natural fiber. The season's value jumped 31% to 54.3 billion US$ in 2020/2021, and annually the average value in quota-free periods accounts to 46.3 billion US$. Consequently, enormous amounts of cotton wastes are emerging. Especially, European countries are forced by the new legislation of the union to develop new recycling strategies. Due to uncountable cotton applications, various types of garments exist, which require different recycling strategies. The recycling of an additional cotton waste side stream of Lindstrom Oy white pre and dyed and white postconsumer cotton roll towels was pursued. The mechanical properties of the fibers and yarns have been evaluated. Thereby, the following elongations and tenacities of conditioned fibers produced at DR11 have been achieved: 10.4%/59.5 cN/tex for preconsumer and 10.6%/60.4 cN/tex for postconsumer white cotton, 10.4%/60.0 cN/tex for postconsumer blue cotton. The achieved elongations at break are close to values reported in literature (7%-14%), however, the tenacities exceed reported values (40-58 cN/tex). Highly oriented fibers of high quality have been produced and with regards to the mechanical properties, a technique to perform fiber-to-fiber upcycling is illustrated.

The Ioncell process is capable of producing high-quality regenerated cellulose fibers from dissolving pulps with a wide range of intrinsic viscosity and different molecular mass distributions.

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.

The chemical recycling of hemp fabric into high-tenacity man-made cellulose fibers was demonstrated. The fabric was laundered 25 and 50 times to mimic the wear cycles of post-consumer textile waste. Despite the launderings, the molar mass of the material was still too high for recycling via dry-jet-wet spinning. Thus, the fabrics were treated with an aqueous sulfuric acid solution to adjust the intrinsic viscosity to the targeted level of 400–500 ml/g. The acid hydrolyzed sample was dissolved in 1,5-diazabicyclo[4.3.0]non-5-enium acetate and man-made cellulose fibers were regenerated by dry-jet-wet spinning. The properties of hemp and regenerated fibers were determined by tensile testing, birefringence measurements, and X-ray diffraction. Regenerated fibers were spun into yarn and knitted into a fabric. The tensile properties of the yarn and the abrasion and pilling resistance of the fabric were determined. Regenerated fibers showed a higher modulus of toughness (55.9 MPa) compared with hemp fibers (28.7 MPa). The fineness and staple length uniformity of regenerated fibers resulted in a high yarn structure evenness, a yarn tenacity of 28.1 cN/tex, and an elongation at break of 7.5%. Due to the even fabric structure, the fabric from regenerated fibers showed higher abrasion resistance than the hemp fabric.

One main challenge to utilize cellulose-based fibers as the precursor for carbon fibers is their inherently low carbon yield. This study aims to evaluate the use of keratin in chicken feathers, a byproduct of the poultry industry generated in large quantities, as a natural charring agent to improve the yield of cellulose-derived carbon fibers. Keratin-cellulose composite fibers are prepared through direct dissolution of the pulp and feather keratin in the ionic liquid 1,5-diazabicyclo[4.3.0]non-5-enium acetate ([DBNH]OAc) and subsequent dry jet wet spinning (so-called Ioncell process). Thermogravimetric analysis reveals that there is an increase in the carbon yield by ∼53 wt % with 30 wt % keratin incorporation. This increase is comparable to the one observed for lignin-cellulose composite fibers, in which lignin acts as a carbon booster due to its higher carbon content. Keratin, however, reduces the mechanical properties of cellulose precursor fibers to a lesser extent than lignin. Keratin introduces nitrogen and induces the formation of pores in the precursor fibers and the resulting carbon fibers. Carbon materials derived from the keratin-cellulose composite fiber show potential for applications where nitrogen doping and pores or voids in the carbon are desirable, for example, for low-cost bio-based carbons for energy harvest or storage.

The performance of biobased carbon fiber (CF) can potentially be improved to a new level by enhancing its graphitization by including graphitic additives as structural templates in the precursor. Mixing these additives in the precursor spinning solution can influence the solution rheology and thus its spinning process and ensuing carbonization, though these effects are not well understood. Herein, we analyze the influence of carbon nanotube (CNT) and graphene oxide (GO) additives on the rheology of cellulose solutions in ionic liquid as well as the subsequent precursor and CF preparation. Addition of GO both thickened the solution and clearly increased its elastic (solid-like) nature in comparison to pure cellulose solution in ionic liquid, while CNT only made the solution moderately more elastic. Still, solutions with both additives were spinnable into continuous precursor fibers, though the inclusion of GO somewhat disturbed cellulose alignment in the fiber, as observed through X-ray diffraction. In addition, GO induced structural order development, observed as a decrease in the intensity and ratio between the Raman peaks at similar to 1300 cm(-1) (related to disorder) and , similar to 1600 cm(-1) (related to sp2-hybridized carbon in general).

Naturally occurring plant cellulose, our most abundant renewable resource, consists of fibers of long polymer chains that are tightly packed in parallel arrays in either of two crystal phases collectively referred to as cellulose I. During mercerization, a process that involves treatment with sodium hydroxide, cellulose goes through a conversion to another crystal form called cellulose II, within which every other chain has remarkably changed direction. We designed a neutron diffraction experiment with deuterium labelling in order to understand how this change of cellulose chain direction is possible. Here we show that during mercerization of bacterial cellulose, chains fold back on themselves in a zigzag pattern to form crystalline anti-parallel domains. This result provides a molecular level understanding of one of the most widely used industrial processes for improving cellulosic materials.

All-cellulose composites (ACCs) were prepared from filter paper via partial dissolution in the ionic liquid 1-ethyl-3-methylimidazolium acetate, and material tensile properties were investigated using various approaches. One is based on data directly taken from a tensile testing machine, and the other uses two-cameras stereovision with digital image correlation (DIC) technique. In the latter case, virtual extensometer with different locations on the sample and averaging over sample surface were tested. Nominal and true stress–strain dependences were built and Young's modulus, tensile strength, elongation at maximal stress and toughness were evaluated as a function of ACC density. A minor difference was observed for the stress–strain dependences derived from different approaches which use the DIC technique, most probably because of low ACC deformation. However, the results reveal that the nominal stress–strain curve from DIC is significantly different from that which is directly derived from the data provided by machine sensors thus strongly impacting Young’s modulus and elongation at break values. This study provides an insight into the evaluation of the mechanical properties of ACCs.

The manufacturing of man-made cellulose fibers starts with the dissolution of wood pulp fibers. Pulps can dissolve at different rates and leave different amounts of undissolved particles. Thus, their properties can be modified to achieve better dissolution. Enzymatic treatments are an effective means of enhancing pulp dissolution, and this study compares the effect of endoglucanase (TrCel45A) and lytic polysaccharide monooxygenase (LPMO, TrAA9A) on bleached softwood Kraft pulp at 20 % solids content. The enzymes were applied individually and in combination. Both enzymes increased fibrillation, fines content, porosity, water retention value, crystallinity index and crystallite size, but the largest changes were achieved with the enzyme mixture. For example, fiber saturation point and water retention value increased by 64 and 37 % with TrCel45A, by 27 and 25 % with TrAA9A, and by 73 and 52 % with both TrCel45A and TrAA9A. Pulp reactivity was indirectly assessed by measuring the dissolution time in cupriethylenediamine. The average dissolution time of the reference pulp measured 642 s, while those of the pulps treated with TrCel45A, TrAA9A and their mixture were 399, 473 and 298 s, respectively. The decrease in dissolution time correlated with the increase in fines, fibrillation, porosity, and water retention value.

We report on the physicochemical changes of infant formula (IF) powder and its macronutrients (lactose, fat, and proteins) under given storage conditions. Colloidal (particle size distribution, emulsion stability and sedimentation), morphological (scanning electron microscopy), thermal (differential scanning calorimetry), structural (synchrotron X-ray diffraction) as well as surface and chemical (X-ray photoelectron and Fourier transform infrared spectroscopies) data were used to elucidate the main cause-effect relationships for microstructural, functional, and other properties of the IF powder. The wetting behavior of the powder was found to be significantly affected by water activity (a(w)) during storage (a(w) in the range between 0.24 and 0.42). At the highest a(w) (a(w) = 0.42), lactose crystallization and fat migration took place, leading to changes on the surface of the particles that reduced powder wettability. We propose possible mechanisms to explain the observations, associated with changes in protein conformation. Interestingly, no major changes in the pH and colloidal characteristics, including particle size and distribution, stability, and sedimentation were observed in the reconstituted IF powder upon storage for 6 weeks. The results indicated a negligible contribution from possible Maillard reactions. We propose leading microstructural and wetting characterization to troubleshoot changes in the quality of IF powder, most relevant from the perspective of reconstitution after storage. (C) 2020 Elsevier Inc. All rights reserved.

The cellulosic fiber-based sustainable textile industry needs greener alternatives to the existing hydrophobization approaches—which are essentially based on nonrenewable and expensive hydrophobizi...

Prehydrolysis kraft (PHK) pulps account for more than half of the global market of dissolving pulp. Characterized by high reactivity toward dissolution, their performances can still be improved by activation treatments. This study compares the dissolution kinetics in cupriethylenediamine of a hardwood and a softwood PHK pulps before and after their activation by high-solid-content mechano-enzymatic treatments. Three enzyme combinations were tested: endoglucanase (E), xylanase and mannanase (XM), and endoglucanase, xylanase, and mannanase (EXM). Xylanase and mannanase reduced the hemicellulose content of only hardwood (by max. 2.4%). Mixing and carbohydrate depolymerization decreased the dissolution time of hardwood and softwood pulps by a maximum of 63 and 30% with E, 37 and 16% with XM, and 44 and 30% with EXM, respectively. The shortening of the dissolution time was partially hindered by hornification, which increased with hemicellulose degradation. Interestingly, XM accelerated the dissolution while preserving a high weight-average molecular mass.

A novel, small-volume vertically arranged spin bath was successfully developed for an air gap lyocell-type spinning process. A maximum regeneration bath length with a minimum free volume characterizes the concept of the new spin bath. Using the ionic liquid (IL) 1,5-diazabicyclo[4.3.0]non-5-enium acetate [DBNH][OAc], the spin bath showed very good spinning performances of IL-cellulose dopes at high draw ratios and spinning duration for single filament spinning experiments. Using this new device, it was possible to get a step further in the optimization of the Ioncell (R) process and simulate a process closed loop operation by performing single filament spinning in IL/H2O mixtures. Good dope spinnability and preserved fibers mechanical properties were achieved in a coagulation bath containing up to 30 wt% IL. It is only at 45 wt% of IL in the bath that the spinnability and fibers mechanical properties started to deteriorate. The fibers fibrillar structure was less pronounced in IL-containing spinning bath in comparison to a pure water bath. However, their crystallinity after washing was preserved regardless of the spinning bath composition. The results presented in this work have a high relevance to the upscaling of emerging IL-based cellulose dissolution and spinning processes.

A new type of polysaccharide (hemicellulose) nanocrystal, bearing the shape of an anisotropic nanoflake, emerged from a dimethyl sulfoxide (DMSO) dispersion of wood-based xylan through heat-induced crystallization. The dimensions of these xylan nanocrystals were controlled by the crystallization conditions. Sharp signals in solid-state NMR indicated a well-ordered crystal structure. The unit cell is constituted of two asymmetric xylose residues, and DMSO molecules resided in a host-guest type of arrangement with more than one local environment. This corroborates with the identical 1H NMR relaxation time between DMSO and xylan, indicative of intimate mixing of the two at the tens of nanometer length scale. X-ray and electron diffraction indicated a 2-fold helical helix along the chain in a monoclinic unit cell with an antiparallel arrangement, with chains placed on the 2-fold helix axes: at the corner and at the center. The 2-fold helical structure is unique for xylan for which only a 3-fold helical form has been reported. The DMSO molecules participated in the crystallization, and they were shown to be vital in stabilizing the crystalline structure. The manipulation of temperature, concentration, and incubation time of the xylan/DMSO dispersion provided pathways for the crystallization to form size-adjustable nanocrystals. As 20-30% of biomass consists of hemicelluloses, this work will serve as a starting point to understand the controlled assembly of hemicelluloses to discover their full application potential.

The nanometric internal structure of polymeric fibres is fundamental for their mechanical properties. Two-dimensional small angle neutron scattering patterns were collected to obtain structural parameters of the elementary fibrils in regenerated cellulose fibres prepared by various fibre spinning technologies. Scattering features were fitted to model functions to derive parameters such as elementary fibril radius, long period of the repeating units of crystal and amorphous phase along the fibre axis, degree of orientation, and ellipticity. The correlation between structural parameters and the mechanical properties was studied for the fibres of different existing spinning processes and for the high-strength fibres. Former group showed high correlation with mechanical properties. The latter group showed generally lower correlation, but showed relatively high correlation with the long period. These structural parameters provide a basis for understanding the structure-property relationship of regenerated cellulose fibres as function of spinning types and conditions for further optimization.

The production of sustainable and high-performance fabrics requires high mechanical strength of the individual (staple) fibers. Although Ioncell fibers already exhibit higher fiber strength than commercial man-made cellulose fibers or cotton fibers, we further aimed to increase both strength and toughness to gradually approach synthetic fibers in these properties. Decisive factors for the achievable mechanical properties of the fibers were the pulp purity, the cellulose concentration in the spinning solution and length-to-diameter (L/D) ratio of the cylindrical part of the spinneret. The absence of low molecular weight fractions in combination with an increased average molecular weight had the highest impact on the achievement of both high strength and toughness. Using a spinneret with a high L/D ratio, it was possible to spin Ioncell fibers with a tensile strength of 925 MPa (61.5 cN/tex) and a modulus of toughness of 83.3 MPa (55.5 J/g). According to a fluid dynamic simulation, uniformly longer molecular cellulose chains in combination with a longer cylindrical capillary promoted an effective alignment of the cellulose molecules inside the spinneret capillary before entering the airgap, thus creating the conditions for a simultaneous increase in tensile strength and elongation i.e. toughness of the fiber. Mechanistically, high fiber toughness is caused by the structural parameters in longitudinal direction, in particular by a higher tilt angle, a longer periodicity of the lamellar plane and lower micro void orientation. In summary, we have developed lyocell-type fibers with high strength and toughness, which can potentially be used as a surrogate for synthetic fibers. Graphic abstract

Chitosan-cellulose composite fibers spun using a Lyocell technology are characterized by a homogeneous distribution and a close packing of the two biopolymers inside the fibrous matrix. Due to the intimate contact of cellulose and chitosan, synergistic effects can be observed during the pyrolysis of the composite fibers. In this study, the catalytic role of chitosan in altering the cellulose pyrolysis pathway in the composite fibers at moderate treatment temperatures up to 900 degrees C is confirmed. Analyses of the evolved gases during pyrolysis revealed that chitosan promoted cellulose dehydration and substantially decreased the formation of levoglucosan, explaining the higher char yield. The enhanced dehydration reaction is associated with the formation of intermolecular crosslinks due to the incorporation of nitrogen from chitosan in the resulting carbon structures. Nitrogen could also contribute to the in-plane disorder in the aromatic clusters when the pyrolysis is carried out at 500-700 degrees C, although the in-plane disorder is less noticeable from 700 to 900 degrees C. Nevertheless, the size of the aromatic cluster continues to grow when the composite fibers are pyrolyzed in a temperature range of 500-900 degrees C. (C) 2021 The Author(s). Published by Elsevier Ltd.

Cellulose-lignin composite fibres were spun from ionic liquid (IL) solutions by dry-jet wet spinning. Birch pre-hydrolysed Kraft (PHK) pulp and organosolv beech (BL) or spruce lignin (SL) were dissolved in the IL 1,5-diazabicyclo[4.3.0]non-5-enium acetate ([DBNH]OAc) to prepare spinning dopes. Fibres with lignin concentrations of up to 50 % were spun successfully. The fibres were analysed focusing on important properties for the production of carbon fibres (CF). Due to the higher molar mass of the SL compared to the BL, SL showed higher stability in the spinning process, giving higher lignin content in the final fibres. The CF yield after carbonization increased with increasing lignin content. The higher carbon content of SL compared to BL, resulted in moderately higher CF yield of the SL fibres, compared to fibres with BL. Overall, the produced cellulose-lignin composite fibres show great potential as precursors for CF production.