The influence of different aspects of alkali profiling in the kraft cook on QPQP bleachability of oxygen-delignified birch pulp was investigated. The use of a levelled-out alkali profile was compared to a conventional, and different modifications to the levelled-out alkali profile, like alkali charge, degree of delignification and amount of dissolved organic substance and ionic strength in the cooking liquor were studied. The alkali profile itself was found to have a significant effect where a levelled-out alkali profile showed a superior bleachability compared to a conventional one. The bleachability improved with an increased alkali charge towards the end of the cook, a high kappa number after cooking or by a cooking liquor exchange in order to decrease the amount of dissolved organic substance and the ionic strength towards the end of the cook. When a levelled-out alkali profile was used, the bleachability correlated well with the light-absorption of the lignin in the unbleached pulp, where a pulp with a brighter lignin consumed less peroxide in the QPQP sequence, for the pulp to reach 89% brightness.
The main objective of this investigation was to study how the alkali charge and the temperature in the kraft cook influence the QPQP bleachability of oxygen-delignified birch pulp. The bleachability was evaluated as the normalised consumption of bleaching chemicals required to reach a certain light absorption coefficient of the pulp. All the pulps had a kappa number of about 17 after the cook and a kappa number of about 10 after oxygen delignification. The alkali charge significantly affected the bleachability and the best bleachability was obtained for an intermediate level alkali charge ([HO-](initial)=1,35 mol/L, corresponding to an effective alkali charge of 21.6% on wood). An increase in cooking temperature gave only a slight increase in bleachability. The contributions to the kappa number of lignin, hexenuronic acids (HexA) and other non-lignin structures were also investigated. Lignin contributed to about 60% of the kappa number in pulps after the cook, to about 40% in pulps after the oxygen delignification, and to about 30% after QPQP bleaching. Hexenuronic acids contributed between 3.7 to 4.7 kappa number units in all pulps, which makes them the largest contributors to the kappa number in oxygen-delignified and QPQP bleached pulps. Other non-lignin structures, were contributing about 3 kappa number units in pulps after the cook, but decreased to less than I kappa number unit after QPQP bleaching. No great differences in the composition of the kappa number could be seen between pulps produced under different pulping conditions, except that there was a somewhat lower hexenuronic acid content in the pulps produced with the highest alkali charge or at the highest cooking temperature.
The performance of biocomposites of poly(hydroxybutyrate-co-valerate) (PHBV) and sisal fibre subjected to hydrothermal tests at different temperatures above the glass transition of PHBV (T-H = 26, 36 and 46 degrees C) was evaluated in this study. The influences of both the fibre content and presence of coupling agent were focused. The water absorption capability and water diffusion rate were considered for a statistical factorial analysis. Afterwards, the physico-chemical properties of water-saturated biocomposites were assessed by Fourier-Transform Infrared Analysis, Size Exclusion Chromatography, Differential Scanning Calorimetry and Scanning Electron Microscopy. It was found that the water diffusion rate increased with both temperature and percentage of fibre, whereas the amount of absorbed water was only influenced by fibre content. The use of coupling agent was only relevant at the initial stages of the hydrothermal test, giving an increase in the diffusion rate. Although the chemical structure and thermal properties of water-saturated biocomposites remained practically intact, the physical performance was considerably affected, due to the swelling of fibres, which internally blew-up the PHBV matrix, provoking cracks and fibre detachment.
The dielectric properties of virgin polylactide (PLA) and its reinforced composites with different weight amounts of sisal fibres were assessed at broad temperature (from −130 °C to 130 °C) and frequency ranges (from 10−2–107 Hz), before and after being subjected to accelerated hydrothermal ageing. The synergetic effects of both the loading of sisal and hydrothermal ageing were analysed by means of dielectric relaxation spectra. The relaxation time functions were evaluated by the Havriliak-Negami model, substracting the ohmic contribution of conductivity. The intramolecular and intermolecular relaxations were respectively analysed by means of Arrhenius and Vogel-Fulcher-Tammann-Hesse thermal activation models. The addition of fibre increased the number of hydrogen bonds, which incremented the dielectric permittivity and mainly hindered the non-cooperative relaxations of the biocomposites by increasing the activation energy. Hydrothermal ageing enhanced the formation of the crystalline phase at the so-called transcrystalline region along sisal. This fact hindered the movement of the amorphous PLA fraction, and consequently decreased the dielectric permittivity and increased the dynamic fragility.
The eco-design considers the factors to prepare biocomposites under an end-of-life scenario. PLA/sisal biocomposites were obtained from amorphous polylactide and sisal loadings of 10, 20 and 30 wt% with and without coupling agent, and subjected to biodegradation in soil according to standard ISO846. Mass-loss, differential scanning calorimetry and size-exclusion chromatography were used for monitoring biodegradation. A statistical factorial analysis based on the molar mass Mn and crystallinity degree XC pointed out the relevance and interaction of amount of fibre and use of coupling agent with the time of burial in soil. During the preparation of biocomposites, chain scission provoked a similar reduction of Mn for coupled and non-coupled biocomposites. The amount of fibre was relevant for the increase of XC due to the increase of nucleation sites. The coupling agent accelerated the evolution of both factors: reduction of Mn and the consequent increase of XC, mainly during biodegradation in soil. Both factors should be balanced to facilitate microbial assimilation of polymer segments, since bacterial digestion is enhanced by chain scission but blocked by the promotion of crystalline fractions.
Carbon fibers (CFs) are gaining increasing importance in lightweight composites, but their high price and reliance on fossil-based raw materials stress the need for renewable and cost-efficient alternatives. Kraft lignin and cellulose are renewable macromolecules available in high quantities, making them interesting candidates for CF production. Dry-jet wet spun precursor fibers (PFs) from a 70/30 w/w blend of softwood kraft lignin (SKL) and fully bleached softwood kraft pulp (KP) were converted into CFs under fixation. The focus was to investigate the effect of carbonization temperature and time on the CF structure and properties. Reducing the carbonization time from 708 to 24 min had no significant impact on the tensile properties. Increasing the carbonization temperature from 600 to 800 °C resulted in a large increase in the carbon content and tensile properties, suggesting that this is a critical region during carbonization of SKL:KP PFs. The highest Young's modulus (77 GPa) was obtained after carbonization at 1600 °C, explained by the gradual transition from amorphous to nanocrystalline graphite observed by Raman spectroscopy. On the other hand, the highest tensile strength (1050 MPa) was achieved at 1000 °C, a decrease being observed thereafter, which may be explained by an increase in radial heterogeneity.
In recent years, there has been extensive research into the development of cheaper and more sustainable carbon fiber (CF) precursors, and air-gap-spun cellulose-lignin precursors have gained considerable attention where ionic liquids have been used for the co-dissolution of cellulose and lignin. However, ionic liquids are expensive and difficult to recycle. In the present work, an aqueous solvent system, cold alkali, was used to prepare cellulose-lignin CF precursors by wet spinning solutions containing co-dissolved dissolving-grade kraft pulp and softwood kraft lignin. Precursors containing up to 30 wt% lignin were successfully spun using two different coagulation bath compositions, where one of them introduced a flame retardant into the precursor to increase the CF conversion yield. The precursors were converted to CFs via batchwise and continuous conversion. The precursor and conversion conditions had a significant effect on the conversion yield (12-44 wt%), the Young's modulus (33-77 GPa), and the tensile strength (0.48-1.17 GPa), while the precursor morphology was preserved. Structural characterization of the precursors and CFs showed that a more oriented and crystalline precursor gave a more ordered CF structure with higher tensile properties. The continuous conversion trials highlighted the importance of tension control to increase the mechanical properties of the CFs.
The brightness reversion of kraft pulps is caused by the presence of residual lignin, chlorinated extractives, or oxidized carbohydrates. The effect of hemicellulose content, i.e., xylan (I) and glucomannan (II), on the thermal stability of modern bleached kraft pulps was investigated. Different O-delignified hard- and softwood kraft pulps were bleached with different bleaching sequences contg. ClO2, H2O2, or O3. Hemicellulose-degrading enzymes, i.e., xylanase or mannanase, were used for selective removal of the resp. hemicellulose from the pulps, and the role of partially removed I and II on the brightness stability of these pulps was studied. Because of the structure of kraft I, enzymic removal of I also resulted in a decreased carboxyl group content in the pulps, whereas II removal did not affect the carboxyl group content. By decreasing the carboxyl groups in the pulps in conjunction with I removal, the thermal aging of the pulps was significantly decreased. The role of II was less significant. Thus, the uronic acids present in the pulp participate in the brightness reversion of kraft pulps.
The effects of xylan and glucomannan on the thermal stability of unbleached, partially bleached, and fully bleached pine and birch kraft pulps were studied. The choice of bleaching chems. strongly affected the brightness reversion. Compared with hydrogen peroxide or chlorine dioxide, bleaching with ozone reduced the amt. of carboxyl groups and subsequently the pc-nos. of oxygen-delignified pulps. Xylan removal reduced also the amt. of carboxyl groups in the pulps and this was reflected in improved brightness stability whereas glucomannan removal had no effect. Thus, the uronic acids bound to pulp xylan were found to participate in the brightness reversion of kraft pulps.
Pulping and bleaching have a profound effect on the carbohydrate chem. of kraft pulps. The chem. structure of xylan is modified due to the conversion of methylglucuronic acid side groups to hexenuronic acid side groups. Pulping conditions strongly affect the amt. of hexenuronic acid present in the pulp and subsequently modified kraft pulps have different carboxyl group profiles as compared with conventionally cooked pulps. Due to its reactivity, hexenuronic acid is readily degraded when chlorine dioxide or ozone are used as bleaching chems. However, TCF-pulps bleached with peroxide and oxygen contain high amts. of hexenuronic acid. Thus, depending on the pulping and bleaching method, the quality and quantity of carboxylic acids in different types of pulps varies significantly. The differences in the uronic acid content are in turn reflected in the macroscale properties of the pulps, such as brightness stability.
Biocidal multilayered system, characterized in that it comprises at least the following layers: - an anionic or cationic carrier, preferably cellulose as anionic carrier, - on this carrier alternating polymeric cationic and anionic layers starting with a layer having a charge opposite to that of the carrier, - wherein at least one layer is hydrophobically modified.
Earlier studies have shown that 3-layer-modified cellulose fibers with poly(acrylic acid) (PAA) as the middle layer between two cationic polyelectrolyte polyvinylamine (PVAm) layers have strong antibacterial efficacy in terms of both bacteria adsorption and bacterial growth inhibition. In the present work, the fossil-based PAA middle layer was replaced by sustainable wood-based cellulose nano-fibrils (CNF), i. e., the fibers were modified by a 3-layer PVAm/CNF/PVAm system. Interestingly, the antibacterial efficacy of this system was greater than that of the previous PVAm/PAA/PVAm system. A higher salt concentration and lower assembly pH in the multilayer build-up resulted in better bacterial reduction. As the surface of a cellulose fiber is heterogeneous, making it difficult to characterize and visualize at high resolution, more homogeneous cellulose model surfaces were prepared by spin coating the dissolved cellulose fiber onto a silica surface to model the fiber surface. With increasing ionic strength, more aggregated and heterogeneous structures can be observed on the PVAm/CNF/PVAm modified model surfaces. The adsorbed bacteria distributed on the structured surfaces were clearly seen under fluorescence microscopy. Adsorbed amounts of bacteria on either aggregate or flat regions were quantified by scanning electron microscopy (SEM). More adsorbed bacteria were clearly seen on aggregates than on the flat regions at the surfaces. Degrees of bacteria deformation and cell damage were also seen under SEM. The surface roughness of the modified model surfaces was examined by atomic force microscopy (AFM), and a positive correlation was found between the surface roughness and the bacterial adhesion. Thus, an additional factor that controls adhesion, in addition to the surface charge, which is probably the most dominant factor affecting the bacteria adhesion, is the surface structures, such as roughness.
Antimicrobial surfaces are important in medical, clinical, and industrial applications, where bacterial infection and biofouling may constitute a serious threat to human health. Conventional approaches against bacteria involve coating the surface with antibiotics, cytotoxic polymers, or metal particles. However, these types of functionalization have a limited lifetime and pose concerns in terms of leaching and degradation of the coating. Thus, there is a great interest in developing long-lasting and non-leaching bactericidal surfaces. To obtain a bactericidal surface, we combine micro and nanoscale patterning of borosilicate glass surfaces by ultrashort pulsed laser irradiation and a non-leaching layer-by-layer polyelectrolyte modification of the surface. The combination of surface structure and surface charge results in an enhanced bactericidal effect against both Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli bacteria. The laser patterning and the layer-by-layer modification are environmentally friendly processes that are applicable to a wide variety of materials, which makes this method uniquely suited for fundamental studies of bacteria-surface interactions and paves the way for its applications in a variety of fields, such as in hygiene products and medical devices.
Contact-active surfaces have been created by means of the layer-by-layer (LbL) modification technique, which is based on previous observations that cellulose fibers treated with polyelectrolyte multilayers with polyvinylamine (PVAm) are perfectly protected against bacteria. Several different cationic polyelectrolytes were applied, including PVAm, two different poly(diallyl dimethyl ammonium chloride) polymers and two different poly(allylamine hydrochloride) polymers. The polyelectrolytes were self-organized in one or three layers on cellulosic fibers in combination with polyacrylic acid by the LbL method, and their antibacterial activities were evaluated. The modified cellulose fibers showed remarkable bacterial removal activities and inhibited bacterial growth. It was shown that the interaction between bacteria and modified fibers is not merely a charge interaction because a certain degree of bacterial cell deformation was observed on the modified fiber surfaces. Charge properties of the modified fibers were determined based on polyelectrolyte titration and zeta potential measurements, and a correlation between high charge density and antibacterial efficiency was observed for the PVAm and PDADMAC samples. It was demonstrated that it is possible to achieve antibacterial effects by the surface modification of cellulosic fibers via the LbL technique with different cationic polyelectrolytes.
A contact-active antibacterial approach based on the physical adsorption of a cationic polyelectrolyte onto the surface of a cellulose material is today regarded as an environment-friendly way of creating antibacterial surfaces and materials. In this approach, the electrostatic charge of the treated surfaces is considered to be an important factor for the level of bacteria adsorption and deactivation/killing of the bacteria. In order to clarify the influence of surface charge density of the cellulose on bacteria adsorption as well as on their viability, bacteria were adsorbed onto cellulose model surfaces, which were modified by physically adsorbed cationic polyelectrolytes to create surfaces with different positive charge densities. The surface charge was altered by the layer-by-layer (LbL) assembly of cationic polyvinylamine (PVAm)/anionic cellulose nanofibril/PVAm onto the initially differently charged cellulose model surfaces. After exposing the LbL-treated surfaces to Escherichia coli in aqueous media, a positive correlation was found between the adsorption of bacteria as well as the ratio of nonviable/viable bacteria and the surface charge of the LbL-modified cellulose. By careful colloidal probe atomic force microscopy measurements, it was estimated, due to the difference in surface charges, that interaction forces at least 50 nN between the treated surfaces and a bacterium could be achieved for the surfaces with the highest surface charge, and it is suggested that these considerable interaction forces are sufficient to disrupt the bacterial cell wall and hence kill the bacteria.
An ionization difference UV-Vis method (Delta epsilon-spectrum method) is the most potentially simple method for fast quantitation of phenolic hydroxyl groups (ph-OH) in lignin. However, the underestimated results were calculated from the conventional Delta epsilon-spectrum method using one- or two-point wavelengths measurement. In this study, a modified Delta epsilon-spectrum method using multi-point wavelengths measurement was developed and the negative absorbance was also considered. Four main typical lignin models, e.g. vanilla alcohol, 5-5 biphenyl, stilbenoid and vanillin, were applied as the guaiacyl-type (G-type) phenolic models for the determination of ph-OH by the modified Delta epsilon-spectrum method. The 2-methoxyethanol/water/acetic acid = 8/2/0.2 (V/V/V) was used as the acidic solvent system and the 2-methoxyethanol/0.2 M NaOH solution = 1/9 (V/V) was used as the alkaline solvent system. The ph-OH contents in the spruce milled wood lignin (SMWL) and the spruce Kraft lignin (SKL) were respectively quantified by the modified Delta epsilon-spectrum method as 1.078 and 4.348 mmol/g, which were comparable to the counterparts determined by P-31 Nuclear Magnetic Resonance Spectroscopy (P-31 NMR). The results revealed that the modified Delta epsilon-spectrum method can provide more accurate and reliable results compared to the conventional method.
The oak timbers of the Swedish warship Vasa are deteriorating. High amounts of oxalic acid have been found along with a low pH and low molecular weight cellulose deep in the wood timbers. The iron-rich surface wood differs from the interior wood in that it displays higher pH and cellulose with higher molecular weight. The objective of this study was to determine why there is a difference in cellulose degradation, pH, and oxalic acid amount between the surface region and the interior of the Vasa timbers. Analysis of cellulose weight average molecular weight by size exclusion chromatography was performed, as well as quantification of oxalic acid and iron by high-performance anion exchange chromatography and atomic emission spectroscopy, respectively. It was found that a decrease in iron content coincides with an increase in oxalic acid concentration and a drop in pH at a certain depth from the wood surface. When iron-rich surface wood samples from the Vasa were mixed with an aqueous solution of oxalic acid, a fast increase of pH over time was observed. Neither interior wood poor in iron nor the fresh oak reference showed the same neutralizing effect during the time of measurement. This indicates that the presence of iron (rust) causes a neutralization of the wood, through the formation of iron(III) oxalato complexes, thus protecting the wood from oxalic acid hydrolysis. This effect was not observed to the same extent for other acids observed in Vasa wood (sulfuric, formic, glycolic, and acetic acids).
In order to map the source of oxalic acid in the interior wood of the Vasa ship, an analysis of wood extractives (tannins) was conducted. Samples used for analysis were PEG-impregnated dry Vasa wood, waterlogged Vasa wood and a reference material (fresh oak). The wood material was ground and extracted with an acetone/water-mixture. In the reference sample, several types of tannins were found such as the isomers castalagin/vescalagin and grandinin and their dimmers roburin A/D and roburin B/C respectively. The results have been confirmed by NMR spectroscopy and MALDI-TOF. The interior of the waterlogged Vasa wood contained small amounts of monomers, whereas the dry, PEG treated Vasa revealed no discernible amounts of hydrolysable tannins or other easily soluble compounds. Furthermore, an analysis of lignin was made by means of chemical degradation (thioacidolysis). A decrease in the amount of β-O-4 bonds in the lignin structure would imply a formation of easily oxidized free phenolics. The products were analyzed by GC-MS, which revealed no dramatic differences between the Vasa samples and the reference. The results were confirmed by CP/MAS NMR by analyzing the differences in the aromatic region (150∼160 ppm) as well as the carbonyl region (190∼200 ppm).
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) C-13 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 C-13 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.
WOBAMA - Wood Based Materials and Fuels is a biorefinery oriented scientific research project supported by Wood Wisdom-Net Research Programme and ERA-NET Bioenergy. In this project, the wood based raw materials were converted to a range of value added products through unconventional techniques. So far, many demonstrators have been prepared, such as the dissolving pulps with high cellulose content, the regenerated cellulose films with high tenacity, the hydrophobic materials based on cellulose and birch bark suberin, as well as the adhesives based on polysaccharides.
In modern pulp mills with prodn. of bleached chem. pulp the increased closure of the bleach plant effluent water system will lead to increased concns. of a variety of dissolved org. substances. Among these oxalic acid is one of the most detrimental due to the facile formation of insol. calcium oxalate once the pH-value is low enough to liberate calcium ions from the pulp. The ppt. may cause severe prodn. problems. Therefore, the formation of oxalic acid from the bleaching of kraft pulps with a variety of bleaching agents have been analyzed. Two methods of anal. have been employed, viz. ion chromatog. and enzymic oxidn. to hydrogen peroxide. The former is a std. method requiring a certain sample treatment whereas the latter may be used on line. Anal. of the aq. phase after each bleaching stage in a O D EO D sequence reveals that oxalic acid can be formed in all stages with the oxygen stage being the predominant contributor. A comparison between different bleaching agents applied to the same pulp again reveals oxygen as a major producer of oxalic acid. The oxalic acid can be formed from both lignin and polysaccharides but expts. with isolated lignin indicates that the predominant part of the oxalic acid is formed from carbohydrates.
The production of forestry products is based on a complex chain of knowledge in which the biological material wood with all its natural variability is converted into a variety of fiber-based products, each one with its detailed and specific quality requirements. This four volume set covers the entire spectrum of pulp and paper chemistry and technology from starting material to processes and products including market demands. Supported by a grant from the Ljungberg Foundation, the Editors at the Royal Institute of Technology, Stockholm, Sweden coordinated over 30 authors from university and industry to create this comprehensive overview. This work is essential for all students of wood science and a useful reference for those working in the pulp and paper industry or on the chemistry of renewable resources.
Cellulose is the most abundant biorenewable material, constitutes an important polymer since it is used as raw material for several products, e.g. Paper and board but also cellulose-based products which have many important applications in the pharmaceutical, textile, food and paint industries. A raw material with high cellulose content and low content of hemicelluloses, residual lignin, extractives and minerals is required for the prodn. of these products, e.g. Cotton and dissolving grade pulp are used. However, the high cost prodn. of dissolving grade pulps has aroused the possibility of upgrading paper grade pulps into dissolving pulps by selective removal of hemicelluloses and subsequent activation of the pulps. This study reports the feasibility to produce dissolving grade pulps from different pulps, i.e. Non-wood paper grade pulps and conventional hardwood kraft pulps, employing enzymic and chem. pretreatments. A monocomponent endoglucanase and a xylanase followed by alk. extn. were tested in order to increase the accessibility and reactivity of the cellulose pulp and decrease the hemicellulose content, resp. An optimization of these treatments in terms of enzyme dosage, incubation time and a possible combination of them was investigated. The treatment effects on reactivity according to Fock's method, viscosity, hemicellulose content and mol. wt. distribution, using size exclusion chromatog. (SEC), were analyzed. The characterization of cellulose structure after the enzymic and chem. treatments was investigated by different techniques.
Bacterial growth is a risk of infection. Antibiotics did long time seem to be a soln. to the problem, but now the consequences are seen, as antibiotic-resistant strains are evolving. The substances are also eventually released into the environment, where they often are harmful to living organisms. Antibacterial surfaces state another option. However, a majority of the now existing surfaces are of leaching type i.e. assocd. with the same problems as the antibiotics. The non-leaching are a safer option, but until now the fabrication has been a problem with use of e.g. org. solvents. We present a sustainable way of forming an antibacterial material onto cellulose by using the polyelectrolyte multilayer technique. By step-wise adsorbing oppositely charged polyelectrolytes in an aq. soln. contg. fibers, at room-temp., the surface of the fibers are modified. The result is a non-leaching material with bacteria inhibiting properties. Also the fabrication is quite safe, as polymers have shown lower toxicity to humans than their monomeric counterparts. Cellulose is an excellent substrate for antibacterial surfaces. It is easy to modify with the present technique and is in itself a sustainable materials, with multiple applications. Combined this gives us in total a new, antibacterial material which also opens up for sustainable cellulose-based products.