One way to protect timber in service against basidiomycete deterioration is by means of acetylation via reaction with acetic anhydride. The reason why acetylated wood (WAc) is resistant against decay fungi is still not exactly understood. The aim of this study was to contribute to this field of science, and Postia placenta colonisation after 4, 12, 20, 28 and 36 weeks was observed at three acetylation levels of Pinus spp. sapwood. Mass loss (ML) and wood moisture content (MC) data reflected the acetylation levels. The initial equilibrium MC (EMC) proved to be a good indicator of subsequent ML. Genomic DNA quantification showed P. placenta colonisation in all samples, also in samples where no ML were detectable. The number of expressed gene transcripts was limited, but the findings supported the results of previous studies: WAc seems to have some resistance against oxidative mechanisms, which are part of the metabolism of P. placenta. This leads to a delay in decay initiation, a delay in expression of genes involved in enzymatic depolymerisation, and a slower decay rate. The magnitudes of these effects are presented for each acetylation level. The data also imply that there is no absolute decay threshold at high acetylation levels, but instead a significant delay of decay initiation and a slower decay rate.

The dissolution of a softwood dissolving pulp in a NaOH/ZnO system was improved by means of a three-stage pretreatment with an initial xylanase treatment, followed by an alkaline extraction, and finally an endoglucanase stage. The solubility of the pulp increased from 29% to 81%, although the crystallinity and the specific surface area of the pulp did not change during the enzymatic treatment.

To meet the demand for carbon-fibre-reinforced composites in lightweight applications, cost-efficient processing and new raw materials are sought for. Cellulose and kraft lignin are each interesting renewables for this purpose due to their high availability. The molecular order of cellulose is an excellent property, as is the high carbon content of lignin. By co-processing cellulose and lignin, the advantages of these macromolecules are synergistic for producing carbon fibre (CF) of commercial grade in high yields. CFs were prepared from precursor fibres (PFs) made from 70:30 blends of softwood kraft lignin (SW-KL) and cellulose by dry-jet wet spinning with the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([EMIm][OAc]) as a solvent. In focus was the impact of the molecular mass of lignin and the type of cellulose source on the CF yield and properties, while membrane-filtrated kraft lignin and cellulose from dissolving kraft pulp and fully bleached paper-grade SW-KP (kraft pulp) served as sources. Under the investigated conditions, the yield increased from around 22% for CF from neat cellulose to about 40% in the presence of lignin, irrespective of the type of SW-KL. The yield increment was also higher relative to the theoretical one for CF made from blends (69%) compared to those made from neat celluloses (48-51%). No difference in the mechanical properties of the produced CF was observed.

In this paper, bending creep test results from high-temperature (HT) dried Norway Spruce timber are presented. The results are compared with creep tests of conventional low-temperature (LT) dried timber. The HT drying was performed at 115°C and the LT drying was performed at 70°C. The creep tests were performed in a varying climate with 20°C and 30–90% relative humidity. A total number of 24 specimens, 45 × 70 × 1100 mm, were loaded in bending during approximately 240 days. Both the HT-dried and the LT-dried material were cut from the same four trees to have as equal raw material as possible for the two drying methods. The results show smaller bending creep deformations of HT-dried timber (approximately 30%) as compared to the LT-dried timber. The variation in magnitude of creep for HT-dried timber was equal to or smaller than for LT-dried timber. Additionally, the variation in deformation between the moisture cycles was smaller for HT-dried timber. These observations indicate a less pronounced mechano-sorptive effect for HT-dried timber. The free shrinkage in the grain direction was significantly smaller for the HT-dried material than for the LT-dried material.

Adhesion of fibers within a spun tow, including carbon fibers and precursors, is undesirable as it may interrupt the manufacturing process and entail inferior fiber properties. In this work, softwood kraft lignin was used together with a dissolving pulp to spin carbon fiber precursors. Lignin-cellulose precursors have previously been found to be prone to fiber fusion, both post-spinning and during carbon fiber conversion. In this study, the efficiency of applying different kinds of spin finishes, with respect to rendering separable precursors and carbon fibers, has been investigated. It was found that applying a cationic surfactant, and to a similar extent a nonionic surfactant, resulted in well separated lignin-cellulose precursor tows. Furthermore, the fiber separability after carbon fiber conversion was evaluated, and notably, precursors treated with a silicone-based spin finish generated the most well-separated carbon fibers. The underlying mechanism of fiber fusion post-spinning and converted carbon fibers is discussed. 

Lignin, a substance considered as a residue in biomass and ethanol production, has been identified as a renewable resource suitable for making inexpensive carbon fibers (CFs), which would widen the range of possible applications for light-weight CFs reinforced composites. Wet spinning of lignin-cellulose ionic liquid solutions is a promising method for producing lignin-based CFs precursors. However, wet-spinning solutions containing lignin pose technical challenges that have to be solved to enable industrialization. One of these issues is that a part of the lignin leaches into the coagulation liquid, which reduces yield and might complicate solvent recovery. In this work, the mass transport during coagulation is studied in depth using a model system and trends are confirmed with spinning trials. It was discovered that during coagulation, efflux of ionic liquid is not hindered by lignin concentration in solution and the formed cellulose network will enclose soluble lignin. Consequently, a high total concentration of lignin and cellulose in solution is advantageous to maximize yield. This work provides a fundamental understanding on mass transport during coagulation of lignin-cellulose solutions, crucial information when designing new solution-based fiber forming processes.

With the aim of investigating kraft lignin as a raw material for carbon fibre production, different lignins have been stabilised in air at conditions varied according to a full factorial experimental design. The lignins under examination were purified kraft lignin powders originating from birch, spruce/pine and Eucalyptus globules, as well as lignin fibres originating from birch with 5 poly(ethylene oxide) (PEO) added as a plasticiser. The influence of temperature, time and heating rate on yield and glass-transition temperature (Tg) was investigated. The highest yield was achieved after stabilisation at 280°C during 2h with a heating rate of 0.2°C min -1. The Tg of all lignin powders was increased when stabilisation occurred under harsher conditions. X-ray photoelectron spectroscopy analysis (XPS) of both the outer surface and the cleaved cross-section of individual lignin/PEO fibres showed a clear gradient in the degree of chemical modification, with the major change occurring on the surface resulting in the appearance of a skin-core structure after stabilisation. The behaviour of the lignin fibres during stabilisation is similar to that of pitch-based fibres, indicating good possibilities for lignin as raw material for carbon fibre production.

The use of technical lignins as feedstock for chemical products will require improvements in purity, molecular mass distribution, and thermal behavior. Therefore, industrial black liquors from kraft pulping of softwood (spruce/pine) and hardwood (birch and Eucalyptus globulus) have been subjected to fractionation according to molecular mass by ceramic membranes. After acidification and isolation of the lignin fractions, a variety of analytical methods have been applied to help understand their structure - property relationships. From all types of lignin, the chemical and polymeric properties of fractions isolated from the membrane permeates were more homogeneous. This demonstrates that technical kraft lignins, irrespective of origin, may constitute an interesting feedstock for products, such as carbon fibers, adhesives, and phenol-based polymers.

The main objective of this work was to study the chemical composition of surfaces and ageing effects on acetylated pine (Pinus sylvestris), heat treated spruce (Picea abies), and furfurylated radiata pine (Pinus radiata) in comparison to unmodified wood. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were the instruments of choice. Observation with a low-vacuum scanning electron microscope (LV-SEM) complemented the study. The spectroscopic information was also linked to a parallel wettability study on matched wood samples by the Wilhelmy method. The results show that XPS and ToF-SIMS are two powerful tools that in combination give complementary information, both quantitative and qualitative, and are well suited for observation of the ageing process of different wood surfaces. The hydrophobization process as a result of migration of extractives during ageing was well quantified by the XPS measurements and the results correlated well with wetting results. Several specific hydrophobic substances could be identified by ToF-SIMS measurements.

The main objective of this work was to apply contact angle analysis to predict work of adhesion (Wa) between some modified wood materials and certain thermoplastics and adhesives. Wetting properties, i.e., contact angles, were measured by the Wilhelmy method on both freshly prepared and aged veneer samples of unmodified and acetylated Scots pine, furfurylated radiata pine, and heat treated Norway spruce. The sessile drop method was used to measure contact angles on a phenol resorcinol formaldehyde, an emulsion polymer isocyanate, and a one-component polyurethane adhesive. Contact angle data were also collected from the literature on polyethylene, polyvinyl chloride, polymethyl methacrylate, polystyrene, and Nylon 6. Contact angle analysis based on the Chang-Qin-Chen model was then applied to determine so-called acid-base interaction parameters and Wa between the wood samples and the selected thermoplastics and adhesives. Results show that the ageing process led to an increased hydrophobic character of unmodified, heat treated, and furfurylated wood samples. The freshly prepared acetylated wood samples had a pronounced hydrophobic character which remained approximately constant after ageing. The predicted Wa between the wood and the adhesives was considerably higher than that between the wood and the thermoplastics. Furthermore, the predicted Wa between the acetylated wood and both the thermoplastics and water was approximately unchanged when comparing the fresh and aged samples. In contrast, the ageing of all other wood samples resulted in a dramatic decrease of the wood-water Wa and a moderate decrease of the wood-thermoplastics Wa. The wood-adhesives Wa, however, was unchanged for the unmodified and furfurylated wood when comparing the fresh and aged samples and even increased for heat treated and acetylated wood samples.

Pulp yield can be improved by a more homogeneous delignification of the chips, achieved by improved impregnation prior to the cooking stage. Complete and efficient impregnation is obtained by increasing the diffusion rate by means of an impregnation liquor with a high initial effective alkali concentration (HIEAC). In the present study, the effect of HIEAC in the impregnation was evaluated and compared to a reference impregnation procedure and a prolonged impregnation. After the various impregnation scenarios, the alkali concentration was always adjusted to the same level in the beginning of the cooking stage. Impregnation with a HIEAC resulted in yield improvements by 1-1.5% units, due to a higher cellulose yield and possibly also to higher yield of glucomannan. The HIEAC with an even alkali distribution within the chips prior to the cooking stage resulted in a more uniform delignification carbohydrate degradation. Yield increase obtained by uniform delignification is due to both decreased shives content as well as less secondary peeling.

A pulp yield increase up to 2% can be achieved by impregnation with a liquor containing 2 M effective alkali (EA) concentration instead of 1 M. The yield increase is due to higher cellulose and glucomannan contents in the pulp, which can be rationalized by less yield loss by peeling, as impregnation is more effective at an elevated EA level. A rapid loading of chips with alkali can be realized due to a high diffusion rate. When the temperature becomes higher in the cooking stage, enough alkali is available for delignification reactions without the risk of alkali depletion in the chip core, so that the delignification is more homogeneous.

The purpose of the impregnation stage is to ensure that cooking chemicals reach all parts of the chips. However, as alkali comes into contact with wood, reactions take place, which alter the paths available for ionic transport and dissolve wood components. The aim of the present study is to establish the most favorable impregnation conditions, which result in an even alkali concentration profile through the chip at a sufficiently high level without extensive yield losses due to peeling. Softwood chips were subjected to different impregnation conditions. The progress of impregnation was assessed by analyzing the concentration of hydroxide ions in the bound liquor inside wood chips and the release of acetic acid. The extent of undesired reactions was measured as the amount of carbohydrate degradation products formed and amount of wood dissolved. Increased temperature and time lead to more degradation of the carbohydrates during impregnation. At high temperature, the concentration of alkali in the bound liquor was lower due to higher alkali consumption in degradation reactions. The most favorable process is to perform impregnation at an elevated initial effective alkali (EA) for a short time. This resulted in an increased alkali concentration in the bound liquor within the chip without extensive carbohydrate degradation.

Specific enzymes hydrolyzing pulp carbohydrates can be used for characterization of pulp fibres. By combining enzymatic peeling of fibre hemicelluloses with novel techniques of surface analysis, such as ESCA, new information can be obtained on the location of different components, i.e. xylan, glucomannan and lignin on the fibre surfaces. In this work unbleached kraft pulps were selectively peeled with purified Trichoderna reesi xylanase and mannanase and the structural modifications caused by the removal of the hemicelluloses were analyzed with ESCA. The removal of the accessible portion of the pine kraft xylan increased the amount of surface lignin, whereas mannan removal had no effect on the amount of lignin on the surface. In the case of birch kraft pulp the removal of accessible xylan did not enhance the amount of lignin on the surface. However, in birch kraft pulp the removal of xylan decreased the amount of extractives covering the surface.

Presteaming is a well-established technique in pulp mills, which improves cooking liquor impregnation by removing air from within and between chips. The aim of the study was to investigate how conditions during steaming affect the subsequent kraft cook and properties of the obtained pulp. It was found that higher pressure and temperature during chip presteaming led to increased degradation and dissolution of hemicelluloses. Lower refinability and tensile index was obtained for pulps cooked after presteaming at high pressure and for a long time.

Fines are an essential component in the papermaking process because they have a profound influence on the behaviour of the wet web and on the mechanical properties of the final sheet. Primary fines are present in the pulp prior to refining, and secondary fines are produced during refining. In the present investigation, two commercially manufactured unbleached pulps with kappa numbers of 45 and 90 were studied in terms of how they responded to refining with respect to the quality of fibre and fines. Primary and secondary fines were collected and characterised and their impact on sheet strength was evaluated by addition of known amounts to a refined and decrilled pulp. All the measured paper strength properties improved when primary and secondary fines were added. The strength improvement was generally somewhat higher in the second case. The effect was more pronounced at a higher level of addition. We attribute the main strength improvements associated with fines to improved consolidation by the creation of capillary forces between the surfaces.

Fiber (tracheid) length is an important trait targeted for genetic and silvicultural improvement. Such studies require large-scale non-destructive sampling, and accurate length determination. The standard procedure for non-destructive sampling is to collect increment cores, singularize their cells by maceration, measure them with optical analyzer and apply various corrections to suppress influence of non-fiber particles and cut fibers, as fibers are cut by the corer. The recently developed expectation-maximization method (EM) not only addresses the problem of non-fibers and cut fibers, but also corrects for the sampling bias. Here, the performance of the EM method has been evaluated by comparing it with length-weighing and squared length-weighing, both implemented in fiber analyzers, and with microscopy data for intact fibers, corrected for sampling bias, as the reference. This was done for 12-mm increment cores from 16 Norway spruce (Picea abies (L.) Karst) trees on fibers from rings 8-11 (counted from pith), representing juvenile wood of interest in breeding programs. The EM-estimates provided mean-fiber-lengths with bias of only +2.7% and low scatter. Length-weighing and length2-weighing gave biases of-7.3% and +9.3%, respectively, and larger scatter. The suggested EM approach constitutes a more accurate non-destructive method for fiber length (FL) determination, expected to be applicable also to other conifers.

Changes in supramolecular properties of cellulose I, namely its lateral fibril aggregate dimension (LFAD), in bleached hardwood acid bisulphite pulp during drying was studied using cross-polarization/magic angle spinning carbon-13 nuclear magnetic resonance (CP/MAS 13C-NMR) in combination with spectral fitting. A significant change in aggregate dimensions was noticed when each of the pulp grades were oven dried. The effect of drying was further investigated with pulp samples subjected to different drying methods. A comparison of a harsh oven drying, mild and rapid air drying, and a very mild and slow condition drying showed that the LFAD of the material decreases in the following order: oven drying > air drying > condition drying. The correlation between the total extractable material S10 (%) and LFAD and also the LFAD increment (ΔLFAD in %) are presented and shown to be intimately related. This means that the method of drying influences the size of the fibril aggregate dimensions and depends on the presence of extractable material within the fibre cell wall. Reactivity studies were carried out based on the acetylation of cotton linters and commercial 96α pulp. Results indicate that the initial reaction rate is proportional to the specific surface area of the two cellulose pulp samples. Accordingly, the specific surface area is directly related to initial reactivity of the performed acetylation. We demonstrated that it is possible to control the LFAD and hence specific surface area in laboratory-produced pulps 91α, 92α, and 96α by the drying method. Thus controlling LFAD can probably be one viable route for controlling the initial reactivity of dissolving pulp towards acetylation.

The wood in the 17th century Swedish warship Vasa is weak. A depolymerization of the wood's cellulose has been linked to the weakening, but the chemical mechanisms are yet unclear. The objective of this study was to analyze the lignin and tannin moieties of the wood to clarify whether the depolymerization of cellulose via ongoing oxidative mechanisms is indeed the main reason for weakening the wood in the Vasa. Lignin was analyzed by solid-state nuclear magnetic resonance [cross-polarization/magic-angle spinning (CP/MAS) 13C NMR] and by means of wet chemical degradation (thioacidolysis) followed by gas chromatography-mass spectrometry (GC-MS) of the products. No differences could be observed between the Vasa samples and the reference samples that could have been ascribed to extensive lignin degradation. Wood extracts (tannins) were analyzed by matrix-assisted laser desorption ionization (MALDI) combined with time-of-flight (TOF) MS and 13C NMR spectroscopy. The wood of the Vasa contained no discernible amounts of tannins, whereas still-waterlogged Vasa wood contained ellagic acid and traces of castalagin/vescalagin and grandinin. The results indicate that the condition of lignin in the Vasa wood is similar to fresh oak and that potentially harmful tannins are not present in high amounts. Thus, oxidative degradation mechanisms are not supported as a primary route to cellulose depolymerization.

The interaction between moisture and the macromolecular wood tissue is of critical importance to wood properties. In this context, magnetic resonance imaging (MRI) is very promising as this method could deliver molecular information on the submillimeter scale (i.e., along concentration gradients) about both free and adsorbed water and the cell wall polymers. In the present study, it is demonstrated for the first time that wood containing adsorbed heavy water (2H2O) can be studied by MRI based on separated images due to water (2H MRI) and cell wall polymers (1H MRI). Data confirm that in specimens equilibrated at controlled humidity there is a direct correlation between bound water content and relative density of the polymers in wood tissue; there is a strong variation across annual rings.

Furfurylation is one of the wood modification techniques via catalytic polymerization of the monomeric furfuryl alcohol (FA) in the impregnated cell wall. Little is known about the topochemistry of this process. Brown rot degradation begins with lignin modification and therefore, the reactions between FA and lignin was one focus of this research. Furfurylated radiata pine (Pinus radiata) with three different weight percent gains (WPGs of 57%, 60% and 70%) after FA uptake was observed by cellular ultraviolet microspectrophotometry (UMSP) to analyze chemical alterations of the individual cell wall layers. Moreover, light microscopy (LM) and scanning electron microscopy (SEM) analyses were performed. The ultraviolet (UV) absorbance of the modified samples increased significantly compared to the untreated controls, indicating a strong polymerization of the aromatic compounds. Highest UV absorbances were found in areas with the highest lignin concentration. The UMSP images of individual cell wall layers support the hypothesis concerning condensation reactions between lignin and FA.

The time-dependent mechanical behaviour (TDMB) of wood is important when using the material for structural purposes. Recently, a new method for predicting the TDMB by numerical modelling was established based on the assumption that TDMB is caused by the sliding of the microfibrils past each other. In this study, the TDMB is examined via creep experiments on small specimens of Norway spruce latewood. The results of these are compared with results from numerical modelling. The experiments include results at two levels of moisture content and three levels of temperature, enabling an investigation of these two climatic factors on TDMB of wood. It was found that the mechanical response of wood tissue is the sum of responses from both tracheids and middle lamella, with only the previous being reversible. The effect of moisture and temperature differed in that the latter affected the elastic and time-dependent responses equally. Moisture, on the other hand, reduced both the elastic properties and the activation energy barrier for sliding of the microfibrils, but furthermore changed the microfibril angle of the sample as a result of swelling. Hereby, moisture had a larger effect on the time-dependent response than the elastic. All of these effects were predicted by numerical modelling.

Different methods for estimation of the surface coverage by extractives and lignin were critically compared. For data collection, four state-of-the-art X-ray photoelectron spectroscopy (XPS) instruments located in four different laboratories were used. Hand sheets of one mechanical and two chemical pulp samples were prepared in one laboratory and distributed among the other participants. The XPS results based on O/C ratios and curve fitting of the C 1s peak had very good intra- and interlaboratory variation for extracted and non-extracted pulp samples. The estimations of surface coverage by extractives and lignin also had acceptable intra- and interlaboratory variation. However, significant differences were observed between the results for the various methods. Estimation of surface coverage by extractives based on O/C ratios was much higher than that based on the C1 component analysis in the case of mechanical and unbleached chemical pulp. The surface coverage by lignin of mechanical pulp was reproducibly detected based on O/C ratios, C1 component analysis and by labelling with mercury acetate. The same data were, however, rather scattered if they were collected with these three methods for bleached and unbleached chemical pulp. In spite of the differences, similar trends regarding the pulp type could be observed. We interpret the results as indicating that the surface coverage for both extractives and lignin should not be considered as absolute “true” values, but rather as relative values, which are reliable only for comparison of samples for the same instrument. Even for relative comparisons, we recommend the selection of a strict experimental set-up for spectral acquisition and data treatment when applying any of the instruments and calculation models currently available.

Wood chips from a novel type of drum chipper were compared to wood chips from a conventional disc chipper in an evaluation based on demonstration-scale and industrial-scale machinery. The evaluation was performed as the wood chippers were used as production machines in a kraft pulp mill using softwood. The average bulk density of the wood chips from the disc chipper and the drum chipper was similar and within the range of 138-140 kg/m 3 . The size distribution of the wood chips was investigated using a conventional screening method, and by using an automatized image-analysis system based on laser scanning. The average length was set to be the same, but the wood chips from the drum chipper had a more uniform length. The average thickness was similar, but the drum chipper generated slightly more thinner wood chips. Compared to the disc chipper and using the screening method, the drum chipper generated a similar fraction of oversized and overthick wood chips, 51% more large accept chips, 11% more total accept chips, and 74% less pin chips and fines. Image analysis resulted in similar data. The results indicate that drum chippers warrant further attention as an alternative to conventional industrial-scale disc chippers. ©2019 Jessica Gard Timmerfors et al.

Capillary zone electrophoresis (CZE) in an alkaline glycine buffer is suggested for the quantification of lignin content in black liquors (BL). The method was first tested by an external calibration with LignoBoost lignins. Then, the lignin content in BL was determined by means of a multivariate calibration with the application of a standard normal variate filter and partial least squares approach based on five principal components. The results are in agreement with those obtained by sulfuric acid lignin precipitation combined with ultraviolet measurement of the lignin in solution. The advantage of the CZE method is its independence from the knowledge of the exact absorptivity coefficient, which is needed for direct spectrophotometric lignin determination. Moreover, interfering substances and degradation products could be recognized and excluded from lignin determination; thus, the selectivity was increased significantly.

For producing wood products without fractures based on thermo-hygro-mechanical (THM) treatments, it is essential to understand how steaming and compression change the wood softening and cell wall components. In this paper, the effects of compression combined with steam treatment (CS) on the viscoelasticity of the in-situ lignin of Chinese fir has been investigated through dynamic mechanical analysis (DMA) under fully saturated conditions. Several variations were studied, such as the softening temperature (Tg) and apparent activation energy (ΔHa) of the softening process in response to CS treatment conditions (such as steam temperature and compression ratio) under separate consideration of earlywood (EW) and latewood (LW). No difference between EW and LW with respect to the viscoelasticity was noted. Tg and ΔHa of the lignin softening were nearly unaffected by the compression ratio, but were highly influenced by the steam temperature. The Tg decreased significantly with CS treatments at or above 160oC, but showed no appreciable change, compared to the native wood, at the lower steaming temperature of 140oC. ΔHa increased at higher steam temperatures, while ΔHa showed a decreasing tendency with decreasing Tg. This indicates that lignin undergoes a simultaneous depolymerization as well as a condensation during CS treatment.

Three different XPS methods based on the O/C atomic ratio, C1 carbon content, and Hg amount are compared in this study to quantify the surface coverage of various pulp fiber surfaces by lignin and extractives. The sensitivity of the methods to drying technique and the stability of organically bound mercury when subjected to X-ray irradiation were also investigated. Results reveal that the surfaces of all pulp fibers have a higher content of lignin and extractives than the bulk of the fibers. Similar lignin surface coverage was obtained for thermomechanical pulp fibers using the Hg, O/C, and C1 carbon methods, while the Hg method gave lower values for kraft pulp fibers than the O/C and C1 carbon methods. The O/C and C1 carbon methods are sensitive to the drying technique, i.e., air-dried samples showed a higher amount of lignin on the fiber surface than freeze-dried samples, while no or only minor differences in results were obtained using the Hg method. The Hg method was more reproducible than the other methods. Special care must be exercised during XPS analysis to minimize mercury degradation.

The chemistry of thermomechanical pulp bleaching and brightness reversion was studied. First, UV-Vis reflectance spectroscopy was used to obtain information on the reactive structures in pulp. Based on these data, a Raman excitation wavelength was chosen close to the absorption bands of the chromophores formed to take advantage of the resonance enhancement (resonance Raman spectroscopy). Fluorescence was rejected with a picosecond Kerr gate. The results revealed that coniferyl aldehyde structures were partly removed by alkaline peroxide bleaching and these structures were further degraded during light exposure. However, this reaction was obviously not responsible for chromophore formation in the pulp. On the other hand, based on the resonance Raman spectra, formation of quinonoid structures, possibly para-quinones, was a more prominent explanation for the brightness reversion

The effect of extractives removal on liquid sorption, swelling and surface energy properties of unmodified wood (UW) and thermally modified Scots pine heartwood (hW) (TMW) was studied. The extraction was performed by a Soxtec procedure with a series of solvents and the results were observed by the multicycle Wilhelmy plate method, inverse gas chromatography (IGC) and Fourier transform infrared (FTIR) spectroscopy. A significantly lower rate of water uptake was found for the extracted UW, compared with the unextracted one. This is due to a contamination effect in the latter case from water-soluble extractives increasing the capillary flow into the wood voids, proven by the decreased water surface tension. The swelling in water increased after extraction 1.7 and 3 times in the cases of UW and TMW, respectively. The dispersive part of the surface energy was lower for the extracted TMW compared to the other sample groups, indicating an almost complete removal of the extractives. The FTIR spectra of the extracts showed the presence of phenolic compounds but also resin acids and aliphatic compounds.

The industrially produced chemical pulps have lower strength properties than those obtained under laboratory conditions, and this difference is referred to as the strength delivery (SD) problem. In this study, the hypothesis was put forward that the SD could, at least in part, be accounted for by the supramolecular structure of the cellulose microfibrils of the fiber wall. To test the hypothesis, two bleached softwood kraft pulps (BSKP) were manufactured from the same starting material with different degrees of cellulose aggregation, but the pulps were otherwise as similar as possible in other controllable respects. The chemical and physical properties, including the pulp strength, were tested. A selective increase of the degree of cellulose microfibril aggregation resulted in a pulp with a decreased tear index (TI) at a specified tensile index, and this decrease was similar in magnitude to what is typically encountered in SD. Accordingly, the current experimental study succeeded in mimicking the SD problem. The lateral fibril aggregate dimensions (LFAD) seem to play a pivotal role and it can be safely concluded in general that the supramolecular structure of cellulose in the fibers may be an important factor contributing to the SD problem.

X-ray tomography and densitometry (XRT and XRD) were applied to characterise wood fibre based insulation materials, which were produced by the foam forming technology. XRT is a high resolution approach with long measurement times of around 29 h, while XRD measurement needs only a few minutes. The determination of density distribution of boards in the thickness direction was the focus of this study. Both approaches visualised well the impact of raw materials and manufacturing processes on the structure of the panels. The density profiles were dependent on the pulp applied for panel production, and the processing conditions were also influential. Air flow resistance correlated with the maximum density measured inside the board. Both XRT and XRD revealed similar trends, which are useful for the characterisation of insulation materials.

Suberin is a natural hydrophobic material that could be used to improve the water repellency of cellulose surfaces. It is also abundant in the outer bark of birch (Betula verrucosa); birch bark is a side-stream product in Scandinavia from the forest industry, which is generally burned for energy production. A suberin monomer, cis-9,10-epoxy-18-hydroxyoctadecanoic acid, was isolated from birch outer bark and polymerized via lipase (immobilized Candida antarctica lipase B). The resulting epoxy-activated polyester was characterized by nuclear magnetic resonance (NMR) imaging, matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry, and size exclusion chromatography. Then the polyester was cured with tartaric or oxalic acid, and the crosslinked polyesters were characterized by Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry. Hydrophobic materials were prepared by compression molding of polyester-impregnated cellulose sheets, and the final products were characterized by FTIR, cross-polarization magic angle spinning 13C NMR, and field-emission scanning electron microscopy. The water contact angle was significantly increased from 0° for the original cellulose sheets to over 100° for the produced hydrophobic materials.

A rather extensive degradation of cellulose and hemicelluloses was found in waterlogged oak wood samples from the ancient warship Vasa by size exclusion chromatography with the solvent system lithium chloride/N,N-dimethylacetamide (LiCl/DMAc). The degradation has mainly occurred after salvage of the wreck, probably as a consequence of keeping iron contaminated wood in contact with air. The most likely explanation is Fenton type of reactions degrading the wood polymers and oxidising reduced sulphur forms to sulphuric acid. An increased degradation rate of the Vasa wood can be anticipated in the future if the sulphuric acid cannot be neutralised and the oxidative reactions cannot be quenched.

The aim of cell wall modification is to keep wood moisture content (MC) below favorable conditions for decay organisms. However, thermally modified, furfurylated, and acetylated woods partly show higher MCs than untreated wood in outdoor exposure. The open question is to which extent decay is influenced by the presence of liquid water in cell lumens. The present paper contributes to this topic and reports on physiological threshold values for wood decay fungi with respect to modified wood. In total, 4200 specimens made from acetylated, furfurylated, and thermally modified beech wood (Fagus sylvatica L.) and Scots pine sapwood (sW) (Pinus sylvestris L.) were exposed to Coniophora puteana and Trametes versicolor. Piles consisting of 50 small specimens were incubated above malt agar in Erlenmeyer flasks for 16 weeks. In general, pile upward mass loss (ML) and MC decreased. Threshold values for fungal growth and decay (ML≥2%) were determined. In summary, the minimum MC for fungal decay was slightly below fiber saturation point of the majority of the untreated and differently modified materials. Surprisingly, T. versicolor was able to degrade untreated beech wood at a minimum of 15% MC, and growth was possible at 13% MC. By contrast, untreated pine sW was not decayed by C. puteana at less than 29% MC.

Wood modification with furfuryl alcohol is a non-toxic alternative to conventional preservation treatments. A process in which furfuryl alcohol polymerises in situ was previously proposed for chemical modification of wood. In the present work, liquid model systems were investigated using compounds that resemble repeating units of lignin to verify whether chemical bonds form between the furfuryl alcohol polymer and wood. Using different NMR spectroscopic techniques we confirmed that these model compounds do form covalent bonds with the polymerising polymer. The results indicate that the furan polymer grafts to lignin, supporting observations in similar studies performed with genuine wood materials.

Lignin-based carbon fibers (LCFs) from the renewable resource softwood kraft lignin were synthesized via oxidative thermostabilization of pure melt-spun lignin and carbonization at different temperatures from 1000°C to 1700°C. The resulting LCFs were characterized by tensile testing, scanning electron microscopy (SEM), X-ray diffraction (XRD) and confocal Raman spectroscopy. The microstructure is mainly amorphous carbon with some nanocrystalline domains. The strength and stiffness are inversely proportional to the carbonization temperature, while the LCFs carbonized at 1000°C exhibit a strength of 628 MPa and a stiffness of 37 GPa. Furthermore, the application potential of LCFs was evaluated as negative electrodes in a lithium-ion battery (LIB) by electrochemical cycling at different current rates in a half-cell setup. The capacity drops with the carbonization temperature and the LCFs carbonized at 1000°C have a capacity of 335 mAh g-1. All LCFs showed good cycling stability. Because of the mechanical integrity and conductivity of the LCFs, there is no need to apply current collectors, conductive additives or binders. The advantage is an increased gravimetric energy density compared to graphite, which is the most common negative electrode material. LCFs show a promising multifunctional behavior, including good mechanical integrity, conductivity and an ability to intercalate lithium for LIBs.

A styrene-butadiene-styrene (SBS) block copolymer has been used as a compatibilizer in a low density polyethylene/wood flour (LDPE/WF) composite system. Dynamic mechanical thermal analysis (DMTA) and a transmission electron microscopy (TEM) were used to investigate the interfacial properties in the composites. A high resolution study of the composite microstructure, and especially of the interfaces between the wood particles and LDPE matrix, indicated that the SBS compatibilizer was located at the interface region between the wood particles and LDPE matrix and partially covered the wood particle surfaces. The SBS was also found in the LDPE matrix. The unsaturated part of the copolymer was stained with osmium(VIII)tetraoxide (OsO4) to enhance contrast and to allow it to be detectable in TEM. Dynamic mechanical measurements confirmed interaction between polystyrene (PS) and wood in the PE/PS/WF system. The tan d peak of PS was shifted about 10°C to a higher temperature and also broadened when wood flour was added in the LDPE/PS blend.

A part of kraft lignin (KL) can be used as a value-added product without detracting the chemical recovery and the energy balance of the kraft mill. The focus of this study is the production of light-weight carbon fibres (CFS) from KL obtained by the LignoBoost process. For this purpose, crude KL and various cellulose products from kraft pulping of hardwood (HW) and softwood (SW) were dissolved in 1-ethyl-3-methylimidazolium acetate ([EMIm][OAc]) and submitted to dry-jet wet-spun to obtain precursor fibres containing 70% KL and 30% cellulose, which were thermally stabilised and further converted by thermal treatments into CF. The initial and final products were characterised with respect to, e.g. mole mass distribution, thermal properties, tensile strength and tensile modulus determination. The optimised precursor fibres are smooth and flexible with similar mechanical properties as commercial textile fibres. The best CFS made had a tensile strength of 780 MPa and a tensile modulus of 68 GPa and are thus stronger and stiffer than those produced by melt-spinning of SW-based lignins alone. The new CFS based on dry-jet wet-spun precursors still have a high potential for further improvements.

To achieve efficient utilization of compression wood (CW), a deeper insight into the molecular interactions is necessary. In particular, the role of lignin in the wood needs to be better understood, especially concerning how lignin contributes to its mechanical properties. For this reason, the properties of CW and normal wood (NW) from Chinese fir (Cunninghamia lanceolata) have been studied on a molecular scale by means of polarized Fourier transform infrared (FTIR) spectroscopy, under both static and dynamic loading conditions. Under static tensile loading, only molecular deformations of cellulose were observed in both CW and NW. No participation of lignin could be detected. In relation to the macroscopic strain, the molecular deformation of the cellulose C-O-C bond was greater in NW than in CW as a reflection of the higher microfibril angle and the lower load taken up by CW. Under dynamic deformation, a larger contribution of the lignin to stress transfer was detected in CW; the molecular deformation of the lignin being highly related to the amplitude of the applied stress. Correlation analysis indicated that there was a direct coupling between lignin and cellulose in CW, but there was no evidence of such a direct coupling in NW. 

Traditional wood preservatives based on biocides are effective against wood-deteriorating organisms because of their toxicity. By contrast, modified woods are non-toxic by definition. To investigate the efficiency of various wood modifications, quantitative real-time polymerase chain reaction (qPCR) was used to profile the DNA amounts of the white-rot fungus Trametes versicolor (L.) [Lloyd strain CTB 863 A] during an 8-week-long growth period in treated Pinus sylvestris (L.) sapwood. The studied wood was modified by acetylation, furfurylation, and thermal treatment. The traditional wood preservatives bis-(N-cyclohexyldiazeniumdioxy)-copper (Cu-HDO) and chromated copper arsenate (CCA) were used as references, whereas untreated P. sylvestris (L.) sapwood served as a control. The maximum levels of fungal DNA in native wood occurred at the end of the experiment. For all wood treatments, the maximum fungal DNA level was recorded after an incubation period of 2 weeks, followed by a decline until the end of the trial. For the preservative-treated woods, Cu-HDO showed the lowest level of fungal DNA throughout the experiment, indicating that exploratory hyphal growth is limited owing to the phytotoxicity of the treatment. The other treatments did not inhibit the exploratory hyphal growth phase. We conclude that qPCR studies of hyphal growth patterns within wood should provide a powerful tool for evaluating and further optimizing new wood protection systems.