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Unbleached lignocellulosic wood fiber materials of low porosity are of great interest as eco-friendly load-bearing materials because their yield is much higher than that for “pure” wood cellulosics...

Organic polymer thermoelectrics (TE) as well as transition metal (TM) silicides are two thermoelectric class of materials of interest because they are composed of atomic elements of high abundatice; which is a prerequisite for mass implementation of thermoelectric (TE) solutions for solar and waste heat recovery. But both materials have drawbacks when it comes to finding low-cost manufacturing. The metal silicide needs high temperature (amp;gt;1000 degrees C) for creating TE legs in a device from solid powder, but it is easy to achieve long TE legs in this case. On the contrary, organic TEs are synthesized at low temperature from solution. However, it is difficult to form long legs or thick films because of their low solubility. In this work, we propose a novel method for the room temperature synthesis of TE composite containing the microparticles of chromium disilicide; CrSi2 (inorganic filler) in an organic matrix of nanofibrillated cellulose-poly(3,4-ethyelenedioxythiophene)-polystyrene sulfonate (NFC-PEDOT:PSS). With this method, it is easy to create long TE legs in a room temperature process. The originality of the approach is the use of conducting polymer aerogel microparticles mixed with CrSi2 microparticles to obtain a composite solid at room temperature under pressure. We foresee that the method can be scaled up to fabricate and pattern TE modules. The composite has an electrical conductivity (sigma) of 5.4 +/- 0.5 S/cm and the Seebeck coefficient (a) of 88 +/- 9 mu V/K, power factor (alpha(2)sigma) of 4 +/- 1 mu Wm(-1) K-2 at room temperature. At a temperature difference of 32 degrees C, the output power/unit area drawn across the load, with the resistance same as the internal resistance of the device is 0.6 +/- 0.1 mu W/cm(2). (C) 2017 Elsevier B.V. All rights reserved. Funding Agencies|European Research Council [307596]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; "the Power Papers project" - Knut and Alice Wallenberg foundation; RISE - the Research Institutes of Sweden; University Grants Commission, India

Composites formed from wood fibers and man-made cellulosic fibers in PLA (polylactic acid) matrix, manufactured using sheet forming technique and hot pressing, are studied. The composites have very low density (due to high porosity) and rather good elastic modulus and tensile strength. As expected, these properties for the four types of wood fiber composites studied here improve with increasing weight fraction of fibers, even if porosity is also increasing. On the contrary, for man-made cellulosic fiber composites with circular fiber cross-section, the increasing fiber weight fraction (accompanied by increasing void content) has detrimental effect on stiffness and strength. The differences in behavior are discussed attributing them to fiber/ fiber interaction in wood fiber composites which does not happen in man-made fiber composites, and by rather weak fiber/matrix interface for man-made fibers leading to macro-crack formation in large porosity regions. peerReviewed

Ecofriendly materials based on well-preserved and nanostructured wood cellulose fibers are investigated for the purpose of load-bearing applications, where optical transmittance may be advantageous. Wood fibers are subjected to mild delignification, flow orientation, and hot-pressing to form an oriented material of low porosity. The biopolymer composition of the fibers is determined. Their morphology is studied by scanning electron microscopy, cellulose orientation is quantified by X-ray diffraction, and the effect of beating is investigated. Hot-pressed networks are impregnated by a methyl methacrylate monomer and polymerized to form thermoplastic wood fiber/poly(methyl methacrylate) biocomposites. Tensile tests are performed, as well as optical transmittance measurements. Structure-property relationships are discussed. High-density molded fibers from holocellulose have mechanical properties comparable with nanocellulose materials and are recyclable. The thermoplastic matrix biocomposites showed superior mechanical properties (Young's modulus of 20 GPa and ultimate strength of 310 MPa) at a fiber volume fraction of 52%, with high optical transmittance of 90%. The study presents a scalable approach for strong, stiff, and transparent molded fibers/biocomposites.

CNFs (cellulose nanofibers) based on holocellulose have a pure cellulose fibril core, with a hemicellulose coating. The diameter is only around 6–8 nm and the hemicellulose surface coating has anio ...

Poly(lactic acid) (PLA)/kraft pulp fiber (30 wt%) composites were prepared with and without a coupling agent (epoxidized linseed oil, ELO, 1.5 wt%) by injection molding. The non-annealed composite samples, along with lean PLA, were exposed to two hydro-thermal conditions: cyclic 50% RH/90% RH at 23 and 50°C, both up to 42 days. The aging effects were observed by size exclusion chromatography, differential scanning calorimetry, dynamic and tensile mechanical analysis, and fracture surface imaging. ELO temporarily accelerated the material's internal transition from viscous to an increasingly elastic response during the aging at 50°C. ELO also slowed down the tensile strength reduction of the composites at 50°C. These observations were explained with the hydrophobic ELO molecules' coupling and plasticizing effects at fiber/matrix interfaces. No effects were observed at 23°C. CODEN: JAPNA; Funding details: Teknologian Tutkimuskeskus VTT; Funding text 1: The authors would like to thank Mr. Upi Anttila (VTT) and Mr. Eino Sivonen (VTT) for the preparation of the composite samples, and a number people at RISE Bioeconomy; Dr. Kristoffer Segerholm, Dr. Prashanth Srinivasa, Mr. Henrik Pettersson, Mr. Jens Haraldsson, Ms. Anna Östberg, Ms. Erika Back, for their help executing the experimental work in Stockholm in the spring 2019. The authors gratefully acknowledge the funding from VTT and RISE.

To expand the use of renewable materials, paper products with superior mechanical and optical properties are needed. Although beating, bleaching, and additives are known to improve industrially produced Kraft pulp papers, properties are limited by the quality of the fibers. While the use of nanocellulose has been shown to significantly increase paper properties, the current cost associated with their production has limited their industrial relevance. Here, using a simple mild peracetic acid (PAA) delignification process on spruce, we produce hemicellulose-rich holocellulose fibers (28.8 wt %) with high intrinsic strength (1200 MPa for fibers with microfibrillar angle smaller than 10°). We show that PAA treatment causes less cellulose/hemicellulose degradation and better preserves cellulose nanostructure in comparison to conventional Kraft pulping. High-density holocellulose papers with superior mechanical properties (Young's modulus of 18 GPa and ultimate strength of 195 MPa) are manufactured using a water-based hot-pressing process, without the use of beating or additives. We propose that the preserved hemicelluloses act as "glue" in the interfiber region, improving both mechanical and optical properties of papers. Holocellulose fibers may be affordable and applicable candidates for making special paper/composites where high mechanical performance and/or optical transmittance are of interest.

Certain xylanases from family GH10 are highly expressed during secondary wall deposition, but their function is unknown. We carried out functional analyses of the secondary-wall specific PtxtXyn10A in hybrid aspen (Populus tremula × tremuloides). PtxtXyn10A function was analysed by expression studies, overexpression in Arabidopsis protoplasts and by downregulation in aspen. PtxtXyn10A overexpression in Arabidopsis protoplasts resulted in increased xylan endotransglycosylation rather than hydrolysis. In aspen, the enzyme was found to be proteolytically processed to a 68 kDa peptide and residing in cell walls. Its downregulation resulted in a corresponding decrease in xylan endotransglycosylase activity and no change in xylanase activity. This did not alter xylan molecular weight or its branching pattern but affected the cellulose-microfibril angle in wood fibres, increased primary growth (stem elongation, leaf formation and enlargement) and reduced the tendency to form tension wood. Transcriptomes of transgenic plants showed downregulation of tension wood related genes and changes in stress-responsive genes. The data indicate that PtxtXyn10A acts as a xylan endotransglycosylase and its main function is to release tensional stresses arising during secondary wall deposition. Furthermore, they suggest that regulation of stresses in secondary walls plays a vital role in plant development.

Nanocomposites, reinforced by different types of cellulose fibrils, have gained increased interest the last years due to the promising mechanical properties. There is a lack of knowledge about the mechanical properties of the cellulose fibrils, and their contribution to the often claimed potential of the impressive mechanical performance of the nanocomposites. This paper investigates the contribution from different types of cellulose nanofibril to the overall elastic properties of composites. A multiscale model is proposed, that allows back-calculation of the elastic properties of the fibril from the macroscopic elastic properties of the composites. The different types of fibrils used were nanofibrillated cellulose from wood, bacterial cellulose nano-whiskers and microcrystalline cellulose. Based on the overall properties of the composite with an unaged polylactide matrix, the effective longitudinal Young’s modulus of the fibrils was estimated to 65 GPa for the nanofibrillated cellulose, 61 GPa for the nano whiskers and only 38 GPa for the microcrystalline cellulose. The ranking and absolute values are in accordance with other studies on nanoscale morphology and stiffness estimates. Electron microscopy revealed that in the melt-processed cellulose nanofibril reinforced thermoplastics, the fibrils tended to agglomerate and form micrometer scale platelets, effectively forming a microcomposite and not a nanocomposite. This dispersion effect has to be addressed when developing models describing the structure–property relations for cellulose nanofibril composites.

Wood fiber-reinforced polylactic acid composite foams have been successfully produced using supercritical carbon dioxide. The addition of fibers had a strong effect on microstructure of the foams. An increase in wood fiber content implied smaller average cell size and higher average cell wall thickness as estimated from image analysis of scanning electron microscopy micrographs. Addition of 10 wt% wood fibers seemed to be a limit to obtain foams, with the used processing conditions. The stiffness properties of the foams in compression improved upon addition of wood fibers. A significant increase of specific stiffness was achieved by adding 5–10 wt% wood fibers. It was shown that the stiffness was about 50% higher in the transverse direction for reinforced foams. The strength in the transverse direction increased for foams with unmodified wood fibers but decreased for foams with two types of treated wood fibers as compared with the strength of the pure polylactic acid foam of similar density. A butyl tetracarboxylic acid treatment followed by an additional surfactant treatment results in reduced wood fiber network-forming ability and reduced fiber–matrix adhesion. This contributes to the inferior observed strength properties in this study. The experimental stiffness was comparable with a superposed micromechanical model for a three-phase fiber-reinforced foam. The model shows that increasing the relative density, that is, the ratio of the density of the foam to the density of the composite material, by adding wood fibers results in a noteworthy increase in the transverse compression stiffness of the foams but only at relative density values above 0.2 for the used processing conditions in this study. The key factor for reinforcement is the relation between foam relative density and fiber volume fraction in the preform. The foaming conditions have to be adapted for each wood fiber content to obtain foams with the desired relative density.

Composites with cellulose reinforcements are steadily gaining increased use. The stress transfer ability between reinforcement and polymer matrix has a strong influence on mechanical properties like strength and fracture toughness. This work presents a method to assess the stress transfer ability between cellulose and polymer matrix from a model material with cellulose spheres embedded in a polymer matrix. Such a material show smaller variability compared with composites based on natural cellulose fibres, and is less cumbersome than single fibre tests with regard to interfacial characterization. Measured elastic moduli of particulate composites is compared with predicted values from a micromechanical model based on a composite sphere assembly in a self-consistent scheme with only a spring constant of an imperfect interface as fitting parameter expressed in Pa/m. This interface parameter is identified through inverse modelling and used to quantify stress-transfer ability of cellulose/polylactide and cellulose/polystyrene composite interfaces. A higher degree of interfacial interaction was found for the former. This ranking was corroborated by adhesive force measurements using a micrometre sized cellulose sphere attached to the end of a cantilever in an atomic force microscope. With the model microstructure of a cellulose-sphere composite, an interfacial efficiency parameter can be backed out from stiffness measurements to be used in e.g. ranking of different fibre surface treatments and choice of matrix in the development of stronger natural-fibre composites.

Effects of butantetracarboxylic acid (BTCA) modification, choice of matrix, and fiber volume fraction on hygroexpansion of wood fiber composites have been investigated. Untreated reference wood fib ...

Wood cellulose nanofibers (CNFs) based on bleached pulp are different from the cellulose microfibrils in the plant cell wall in terms of larger diameter, lower cellulose molar mass, and modified cellulose topochemistry. Also, CNF isolation often requires high-energy mechanical disintegration. Here, a new type of CNFs is reported based on a mild peracetic acid delignification process for spruce and aspen fibers, followed by low-energy mechanical disintegration. Resulting CNFs are characterized with respect to geometry (AFM, TEM), molar mass (SEC), and polysaccharide composition. Cellulose nanopaper films are prepared by filtration and characterized by UV–vis spectrometry for optical transparency and uniaxial tensile tests. These CNFs are unique in terms of high molar mass and cellulose–hemicellulose core–shell structure. Furthermore, the corresponding nanopaper structures exhibit exceptionally high optical transparency and the highest mechanical properties reported for comparable CNF nanopaper structures.

Wood pulp fibers can serve as useful reinforcement of plastics for increased stiffness. To assess the potential of various wood fibers as reinforcement, a method has been developed to determine the contribution of the fibers to the elastic properties of the composite. A micromechanical composite model and classical laminate mechanics are used to relate the elastic properties of the fibers to the elastic properties of the composite. A large variety of composites made of various wood pulp fibers in an epoxy vinyl ester matrix was manufactured. From the tensile test results of the composites, the contributing Young’s moduli of the fibers in the longitudinal direction are back-calculated and summarized. One finding is that there is an optimum in fiber stiffness as a function of lignin content. It is also found that industrially pulped hardwood fibers have higher stiffness than the corresponding softwood fibers. One example is kraft-cooked Norway spruce fiber, for which a Young’s modulus of 40 GPa is found. The effects of hornification, prehydrolysis, and sulfite processing are also investigated. The results indicate that mild defibration process should be used, that does not damage the cell wall structure so that the inherent high stiffness of the native fibers can be retained. It can be concluded that the proposed method works well to rank the wood fiber candidates in terms of their contribution to the composite stiffness.

Three kraft pulps in the kappa number range between 50 and 20 and the same pulps oxygen-delignified to similar lignin contents (kappa approximately 6) were analyzed for lignin-carbohydrate complexes (LCC) by a method based on selective enzymatic hydrolysis of the cellulose, and quantitative fractionation of the LCC. Between 85 and 90% of residual lignin in the unbleached kraft pulp and all residual lignin in the oxygen-delignified pulps were isolated as LCC. Three types of complexes were found; viz., xylan-lignin, glucomannan-lignin-xylan and glucanlignin complexes. After pulping to a high kappa number, most of the residual lignin was linked to xylan. Different delignification rates were observed so that most of the residual lignin was linked to glucomannan when the pulping was extended to a low kappa number. With increasing degree of oxygen delignification, a similar trend in the delignification rates of LCC was observed so that the residual lignin was increasingly linked to glucomannan. Complex LCC network structures seemed to be degraded into simpler structures during delignification. The differences in delignification rates are discussed with reference to the solubility properties and structural differences of LCC, and to morphological aspects of the pulp.

A method for the characterization of the molar mass distributions (MMDs) of softwood kraft pulps dissolved in 0.5% lithium chloride (LiCl)/N,N-dimethylacetamide (DMAc) by size exclusion chromatogra ...

The potential of pulp fiber-reinforced thermoplastics is currently not fully explored in composites. One of the main reasons is that pulp fibers are extracted for the use in papermaking and are thu ...

Multi-angle laser light scattering (MALLS) was used to characterize birch kraft pulps with respect to their absolute molecular mass distributions (MMDs). The pulps were dissolved in lithium chloride/N,N-dimethylacetamide and separated by size exclusion chromatography (SEC). The weight-average and number-average molecular masses of the cellulose fractions of the pulps obtained from the absolute MALLS measurements were compared with the molar masses obtained by direct-standard-calibration relative pullulan standards. Discrepancies between the two detection methods were found, and two ways of correlating the relative pullulan molar masses to the absolute molar masses were examined. In the first method, the correlation was made over a large range of molecular masses. The second method correlated the molecular masses of the standards to the molecular masses of samples by the calculation of fictitious, cellulose-equivalent molar masses of the standards. With the preferred second method, a more correct MMD of kraft pulp samples could, therefore, be obtained from an SEC system calibrated with narrow standards. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1170–1179, 2003

The alkaline degradation of birch and Norway spruce during kraft pulping was studied on a laboratory scale by two degradation strategies, by varying the pulping time using the same initial alkali level and by varying the initial alkali concentration using a constant time. The degradation at the molecular level was monitored by determining the carbohydrate composition, intrinsic viscosity and molecular mass distribution (MMD). The influence of the degradation on fibre strength was studied as zero-span tensile index. The alkaline degradation was to a large extent homogeneous on a molecular level. However, some significant differences in degradation patterns were found. In the case of birch, the two different degradation strategies (increased alkali level and increased pulping time) caused differences in MMD and fibre strength (comparisons made at a given intrinsic viscosity or M w ). For spruce pulps, the decrease in fibre strength and the shift in MMD were the same in both series, regardless of degradation strategy.

The molecular weight distribution (MWD) of hardwood kraft pulps and softwood kraft pulps dissolved in lithium chloride/N,N-dimethylacetamide (LiCl/DMAc) have a different shape. Two fairly well separated distributions of hardwood kraft pulps are obtained by size exclusion chromatography whereas the MWDs of softwood kraft pulp is more complex. Since these two pulps contain different types of hemicelluloses, the neutral carbohydrate composition of different cuts of the MWDs was examined. The results indicate that the two distributions observed for hardwood kraft pulps originate from cellulose and xylan, respectively. In contrast, the hemicellulose of softwood kraft pulps elute over the entire molecular weight range. The carbohydrate analysis of the collected fractions shows that glucose is the major component in all fractions. The relative concentration of mannose decreases during elution, i.e. with decreasing molecular weight (M) whereas galactose, xylose and arabinose increases during elution, i.e. with decreasing M. The coelution of cellulose and glucomannan may be due to association properties, which gradually decrease with increasing amount of galactose substituents. The difference in elution behaviour between hardwood and softwood kraft pulp xylans may be due to different amounts of glucuronic acid groups and/or how these groups are distributed along the main chain. It is thus more difficult to interpret differences in the MWDs of softwood kraft pulps than of hardwood kraft pulps.

The degradation of guaiacylglycerol-β-guaiacyl ether by HS - and polysulphide was studied at various alkalinities between 0.025 M and 1.1 M OH- at 130°C. Polysulphide strongly suppressed the reverse aldol pathway and thereby the formation of enol ether over the whole [OH - ] interval investigated. We therefore conclude that polysulphide increases the fragmentation step and probably also acts as a stronger nucleophile than HS - towards intermediate quinone methide structures during the alkaline treatment of guaiacylglycerol-β-guaiacyl ether. At alkalinities above 0.2M OH - , polysulphide tended to degrade the tested β-model faster than HS - .

Coniferyl alcohol was found to be a minor degradation product when guaiacylglycerol-β-guaiacyl ether reacted with 0.2M NaHS at alkalinities between 0.025 and 1,1 M NaOH at 130°C. During similar treatments with 0.2M S 0 as polysulphide, coniferyl alcohol was released in yields varying with NaOH concentration, suggesting different mechanisms for the formation of degradation products by HS and by polysulphide. The formation of polysulphide and thiosulphate was found to be negligible under comparable, kraft-pulping-like conditions, which supports the conclusion that coniferyl alcohol is not formed during HS treatment of guaiacylglycerol-β-guaiacyl ether at temperatures below 130°C.

The mechanical properties of composites in the fibre direction are mainly attributed to the fibre slenderness, or aspect ratio. A trade-off between performance and processability is usually required, and dependent on the intended application. If the fibre length could be retained or not severely degraded during various processing steps towards the injection-moulded component, a stiffer and stronger composite product could be obtained. The processing steps for injection moulded wood-fibre composites here include: Pulping, commingling, extrusion, pelletizing, and injection moulding. To tune the processing parameters systematically for retained fibre length, it would be useful to investigate the degradation of the original fibre length distribution throughout the processing chain. The fibre length degradation has been monitored by X-ray micro-computed tomography through the processing steps in wood pulp- fibre reinforced polylactide. A significant fibre-length degradation was found, in particular, the extrusion step was found to result in a drastic fibre length reduction. peerReviewed