A comparison of softwood and birch kraft pulp fibers as raw materials for production of TEMPO-oxidized pulp, MFC and superabsorbent foam

This study compares the suitability of using birch kraft pulp or softwood kraft pulp in the preparation of TEMPO-oxidized pulp, MFC and superabsorbent foam. TEMPO oxidation was performed using five different dosages of primary oxidant. The time of disintegration treatment was varied to study its influence on the properties of the produced MFCs and foams. Both the birch and the softwood pulps could be used for producing superabsorbent foams, depending on the process conditions, the absorption capacities were about the same for the two pulps and varied between 25 and 55 g saline solution/g absorbent. The foams based on birch pulp had, however, on average, 30 % higher retention capacity than the foams based on softwood pulp. The maximum retention capacity obtained was 16.6 g saline solution/g absorbent. The greater retention capacity of birch-based foams is not fully understood, but a smaller pore size may be the reason, which in turn would generate greater capillary forces. In addition to this, it was found that birch pulps, contrary to softwood pulps, had a substantial amount of fibers that were relatively unaffected by the disintegration treatment. These oxidized fibers are likely to reinforce the foam, thereby making the foam more resistant to external pressures, which is in accordance with earlier findings.     

Sorption of spruce O-acetylated galactoglucomannans onto different pulp fibres

Sorption of spruce acetylated galactoglucomannans (GGM) onto different pulps, among which unbleached and peroxide-bleached mechanical pulps, and unbleached and bleached kraft (BK) pulps, was studied as a means of understanding the retention of acetylated GGMs in mechanical pulping and papermaking. The fibre surface coverage of lignin and carbohydrates was estimated by X-ray photoelectron spectroscopy (XPS) or electron spectroscopy for chemical analysis (ESCA). GGM sorption was clearly favoured on kraft pulps. Hardly any differences in sorption were, however, observed between unbleached and BK pulps, even if the surface coverage of lignin was lower on the bleached pulp. Neither thermomechanical pulp (TMP) nor chemithermomechanical pulp (CTMP) manufactured from spruce sorbed any acetylated GGMs. Peroxide bleaching of the pulp did not increase sorption. Only CTMP produced from aspen sorbed some GGMs. The anionic charge of neither chemical nor mechanical pulps influenced GGM sorption.     

Saccharification of Brazilian sisal pulp: evaluating the impact of mercerization on non-hydrolyzed pulp and hydrolysis products

Cultivation of sisal, a plant with a short growth cycle, is highly productive in Brazil. This work is part of extensive research in which sisal is valued. In these studies, sisal fibers are used in the preparation of bio-based composites and in the derivatization of the pulp, including posterior preparation of films. This study aimed to examine the use of sisal pulp in the production of bioethanol, which can potentially be a high efficiency process because of the cellulose content of this fiber. A previous paper addressed the hydrolysis of sisal pulp using sulfuric acid as a catalyst. In the present study, the influence of the mercerization process on the acid hydrolysis of sisal pulp was evaluated. Mercerization was achieved in a 20% wt NaOH solution, and the cellulosic pulp was suspended and vigorously mixed for 1, 2 and 3 h, at 50 °C. The previously characterized mercerized pulps were hydrolyzed (100 °C, 30% H₂SO₄, v/v), and the results are compared with those obtained for unmercerized pulp (described in a companion paper). The starting sample was characterized by viscometry, α-cellulose content, crystallinity index and scanning electron microscopy. During the reactions, aliquots were withdrawn, and the liquor was analyzed by HPLC. The residual pulps (non-hydrolyzed) were also characterized by the techniques described for the initial sample. The results revealed that pretreatment decreases the polyoses content as well as causes a decrease of up to 23% in the crystallinity and up to 21% in the average molar mass of cellulose after 3 h of mercerization. The mercerization process proved to be very important to achieve the final target. Under the same reaction conditions (30% and 100 °C, 6 h), the hydrolysis of mercerized pulp generated yields of up to 50% more glucose. The results of this paper will be compared with the results of subsequent studies obtained using other acids, and enzymes, as catalysts.     

Accessibility of hydroxyl groups in birch kraft pulps quantified by deuterium exchange in D2O vapor

Deuterium exchange in a deuterium oxide (D₂O) atmosphere (95 % relative humidity), quantified by a dynamic vapor sorption (DVS) apparatus, was applied for assessing the accessibility of hydroxyl groups in birch kraft pulps. Achieving the maximum deuteration level exhibited slower kinetics than was earlier reported for experiments with ground wood and bacterial cellulose. The deuterium exchange process followed two parallel phenomena. Applying multiple drying and rewetting cycles gave kinetic information also on the hornification phenomenon occurring during these cycles. Dry birch pulps treated with sodium hydroxide solution of varying alkalinities at elevated temperatures were assessed for their accessible hydroxyl groups by DVS with deuterium exchange. This method was evaluated against deuteration combined with Fourier transform infra-red spectroscopy and water retention value (WRV). DVS measurements were in correlation with WRV and both the methods indicated that an alkaline treatment of dry birch pulp improves cellulose accessibility. The level of irreversible deuteration also decreased as the alkalinity was increased. DVS was shown to provide quantitative information on the accessibility but to be a time-consuming method for the pulp samples. A potential means to decrease the duration of the measurement is increased D₂O exposure by excluding the drying phases.     

Compression molded wood pulp biocomposites: a study of hemicellulose influence on cellulose supramolecular structure and material properties

In this study, the importance of hemicellulose content and structure in chemical pulps on the property relationships in compression molded wood pulp biocomposites is examined. Three different softwood pulps are compared; an acid sulfite dissolving grade pulp with high cellulose purity, an acid sulfite paper grade pulp and a paper grade kraft pulp, the latter two both containing higher amounts of hemicelluloses. Biocomposites based the acid sulfite pulps exhibit twice as high Young’s modulus as the composite based on paper grade kraft pulp, 11–12 and 6 GPa, respectively, and the explanation is most likely the difference in beating response of the pulps. Also the water retention value (WRV) is similarly low for the two molded sulfite pulps (0.5 g/g) as compared to the molded kraft pulp (0.9 g/g). The carbohydrate composition is determined by neutral sugar analysis and average molar masses by SEC. The cellulose supramolecular structure (cellulose fibril aggregation) is studied by solid state CP/MAS ¹³C-NMR and two forms of hemicellulose are assigned. During compression molding, cellulose fibril aggregation occurs to higher extent in the acid sulfite pulps as compared to the kraft pulp. In conclusion, the most important observation from this study is that the difference in hemicellulose content and structure seems to affect the aggregation behaviour and WRV of the investigated biocomposites.     

Cellulose crystallinity and ordering of hemicelluloses in pine and birch pulps as revealed by solid-state NMR spectroscopic methods

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

Determination of nonylphenol and nonylphenol ethoxylates in pulp samples by Py-GC/MS

We have developed a method for ascertaining the presence of nonylphenol (NP) and nonylphenol ethoxylates (NPEs) in pulp samples at very low levels. The method entails pre-concentration of the compounds and their detection by Py-GC/MS. Solvent extraction of the compounds from pulps with acetone gives better recoveries than desorption of the compounds from the pulps by gas stripping. The detection limit for NPEs with our technique is as low as 0.003 ppm in pulp sheets.     

Purification of cellulosic pulp by hot water extraction

Hot water extraction (HWE) of pulp in a flow-through reactor was evaluated as a method to purify paper-grade pulps. About 50–80 % of the xylan and up to 50 % of the lignin in unbleached birch Kraft pulp was extracted by the HWE without losses in cellulose yield. The residual xylan content in the extracted pulps was predominantly too high for dissolving-grade applications, but some of the pulps with a xylan content of 5–7 % might still be suitable as rayon-grade pulps. Increasing extraction temperature lowered the xylan content at which cellulose yield started to decrease. Furthermore, at any given xylan content, increasing extraction temperature resulted in cellulosic pulp with higher degree of polymerization. The extracted xylan was recovered almost quantitatively as xylo-oligosaccharides. The results suggest that HWEs at elevated temperatures may be applied to purify cellulosic pulps, preferably containing a low xylan content, and to recover the extracted sugars.     

Determination of zeta potential and cationic demand in ECF and TCF bleached pulp from eucalyptus and flax. Influence of measuring conditions

The electrical nature of cellulose fibres is known to govern flocculation, retention and drainage mechanisms during the papermaking process. Zeta (ζ) potential provides useful information towards better control of wet-end chemistry in respects such as the dosaging of chemical aids. The purpose of this work was to study two electrokinetic properties (ζ potential and cationic demand) in ECF (elementary chlorine free) and TCF (totally chlorine free) bleached pulps from eucalyptus and flax, and examine the influence of pH and conductivity on measurements of such properties made with various methods based on the streaming potential, electrophoresis, polyelectrolyte titration and colloidal titration. Measurements of the electrokinetic properties made at high conductivities (C > 0.1 mS/cm) afforded no discrimination between pulp types in terms of electric charge. In fact, the conductivity used had a strong influence on measurements and shifted ζ potential to less negative values at high levels and to more negative values at low levels. The streaming potential technique proved to be more sensitive to changes in the properties (pH and conductivity) of the fibre suspension than did electrophoresis. Conductivity also influenced polyelectrolyte adsorption in the determination of cationic demand. The study also involved assessing the effect of low conductivities (0.01 < C < 0.1 mS/cm), which allowed fibre types and bleaching processes to be easily distinguished. Based on the results, accurately characterizing and identifying not only pulp types, but also the effects of mechanical, chemical and biochemical treatments on fibres, requires measuring the electrokinetic properties at a fixed pH and low conductivity.     

On the accessibility and structure of xylan in birch kraft pulp

The structure of -(14)-xylan, both in isolated form and as a component of bleached birch kraft pulp, was studied employing CP/MAS ¹³C NMR spectroscopy. Bleached birch kraft pulp was treated with xylanases or alkali in order to distinguish between accessible and inaccessible xylan. In xylan which was alkali-extracted from bleached birch kraft pulp, the relative contents of xylose and 4-O-methylglucuronic acid were 99.4 and 0.6 weight %, respectively, and the degree of polymerization was 70. The supermolecular structure of xylan is very sensitive to the surrounding environment. All extracted xylan chains were accessible to water and methanol and the solvent molecules easily exchanged. In bleached birch kraft pulp, cellulose fibrils interact with xylan chains, causing these to adopt a conformation similar to one of the configurations observed for dry xylan. In birch pulp, about 1/3 of the xylan was found to be accessible to digestion by xylanases or extraction with 5% w/w potassium hydroxide (aq). A signal at 81.7ppm in the C-4 region of the CP/MAS ¹³C NMR spectrum of bleached birch kraft pulp originated from xylan at the accessible fibril surfaces. A portion of a broad signal at 83.5ppm reflected inaccessible xylan, which is probably present as co-aggregates with cellulose fibril aggregates.     

Dissolving-grade birch pulps produced under various prehydrolysis intensities: quality,structure and applications

Aqueous-phase prehydrolysis followed by alkaline pulping is a viable process to produce wood-based dissolving pulps. However, detailed characterisation of the achievable pulp quality, performance and cellulose structure is yet lacking. In this study, the production of hemicellulose-lean birch soda-anthraquinone pulps after prehydrolysis under various intensities was investigated. Increasing prehydrolysis intensity resulted in pulps of higher purity but lower cellulose yield and degree of polymerisation. Higher cellulose yield by using sodium borohydride during pulping was achieved at the expense of reducing pulp purity. Cellulose crystallinity was similar in all pulps indicating simultaneous degradation of both crystalline and amorphous cellulose regions. Reinforced prehydrolysis seemingly increased the cellulose crystal size and the interfibrillar distances. Moderate intensity prehydrolysis (170 °C) resulted in a pulp well suited for viscose application, whereas reinforced prehydrolysis favoured the production of acceptable cellulose triacetate dope. The performance of the pulps in viscose and acetate applications was strongly related to the chemical and structural properties.     

Preparation of electrically conducting cellulose fibres utilizing polyelectrolyte multilayers of poly(3,4-ethylenedioxythiophene):poly(styrene sulphonate) and poly(allyl amine)

The primary goal with this work is to create electrically conductive cellulose fibres, this has been done to explore possible new applications for fibre based material. This research uses various methods to create polyelectrolyte multilayers (PEMs) on bleached softwood fibres and on SiO₂ model surfaces, by sequentially treating these materials with poly(3,4-ethylenedioxythiophene):poly(styrene sulphonate) (PEDOT:PSS) and poly(allyl amine) (PAH). Paper sheets were then produced from the PEM-modified pulp and evaluated in terms of tensile strength, adsorbed amount of polymer, and electrical conductivity. To evaluate the influence of fibre charge on the measured paper properties, pulps of two different initial fibre charge densities were prepared via carboxymethylation. Because of the bluish colour of PEDOT:PSS, the build-up of PEM could be easily followed, since the fibres grew increasingly darker blue throughout the modification sequence. The conductivity of the fibre network increased by 2−3 orders of magnitude when the pulp of a higher fibre charge density was used. This suggests that it is more important to create a fibrous network with a high fibre-fibre joint strength and a large total joined area in the sheet rather than to maximize the adsorbed amount of PEDOT:PSS. A difference in conductivity could also be noted depending on the polyelectrolyte adsorbed in the outer layer, PAH lowered the conductivity compared to PEDOT:PSS. Evaluating the mechanical properties revealed that the use of PEDOT:PSS reduces the tensile strength of the paper. When five double layers had been adsorbed onto the carboxymethylated sample in which PEDOT:PSS formed the outer layer, calculations indicated a 25% decrease in tensile strength compared to that of reference material without PEMs. ESEM studies indicate that PEM treatment produces a significantly changed and somewhat smoother fibre surface.     

Diepoxide treatment of softwood kraft pulp: influence on absorption properties of fibre networks

Many different approaches to the introduction of intra-fibre cross-links in fibres for use in absorption products are described in the patent literature, but relatively little has been done in terms of academic research. In this study, the long fibre fraction of a Scandinavian softwood kraft pulp has been cross-linked with the diepoxide 1,4-butanediol diglycidyl ether (BDDE). The fibre properties and the performance of the pulp in low density fibre networks were analyzed. In experiments, the cross-linking agent (BDDE) was dissolved in acetone and then mixed with the pulp. It was shown that a prior wash with NaOH (0.1 M) activates the polysaccharides and increases the extent of cross-linking, detected as a decrease in the water retention value. Chemical analysis of modified fibres also gave a clear indication of that cross-linking reactions actually occurred. The pulp properties could furthermore be influenced by varying time, temperature and the amount of BDDE in the reaction. It was also shown that it is possible to use water as a solvent for the cross-linking agent, even though the reactivity of water towards diepoxide must be considered to be high. The cross-linked pulps showed wet bulk under load comparable to that of the mechanical pulps and enhanced properties than unmodified Scandinavian softwood kraft pulp. It was also observed that fibre network test pads of the cross-linked pulp fibres, after being tested in the wet state, regained a substantially large part of their low-density structure when air-dried.     

Surface selective removal of xylan from refined never-dried birch kraft pulp

In this study, the effect of enzyme treatment on refined, never-dried bleached birch kraft pulp was investigated, using an endo-1,4-β-xylanase, that is substantially free from cellulase activity. The xylanase treatment of refined never-dried pulp revealed a rapid initial hydrolysis rate with a time-dependent saturation level in the amount of hydrolyzed pulp carbohydrates. Surprisingly short xylanase treatment times were found to have an impact on the fiber surface structure and on the physicochemical properties of kraft pulp fibers. Xylanase treatment led to mild microscopic differences in the ultrastructure of a never-dried fiber, whereas local topographical differences were distinguishable with atomic force microscopy. Results from the analysis of dissolved carbohydrates and the interfacial properties of the xylanase-treated never-dried fibers thus confirm a selective removal of xylan from the fiber surfaces. The zeta-potential charge and dewatering properties of the pulp slurry, fiber morphology, and strength properties of the paper were affected, which is a concomitant of xylanase treatment. However, the papermaking properties of the fibers were mainly preserved with simultaneous improvement in the dewatering rate of the pulp. Thus, optimized xylanase treatment of refined bleached kraft pulp provides a fiber for papermaking or fiber modification purposes with a selectively modified chemical composition of the fiber surface layer.     

Improving Accessibility and Reactivity of Celluloses of Annual Plants for the Synthesis of Methylcellulose

Pretreatments (water-soaking, pre-mercerization, mercerization under a pressure of 15 bars and steam explosion) were used to improve the accessibilities and reactivities of celluloses of bleached flax, hemp, sisal, abaca and jute pulps for the synthesis of methylcellulose. Degrees of crystallinity were determined by X-ray Diffraction (XRD) spectra. The iodine adsorption accessibilities of pulps were low and accessible fractions ranged from 1.3 to 5.2%. Accessible fractions in amorphous cellulose were calculated in the 5–18% range. The accessibilities of these pulps were hemp pulp > flax pulp > sisal pulp > jute pulp > abaca pulp. Fourier Transform Infrared (FTIR) spectra showed that mean hydrogen bond strengths were weakened and relative crystallinity indexes were decreased by pretreatments. The accessibility and reactivity of the abaca pulp were improved by water soaking, mercerization under 15 bars pressure, steam explosion and preliminary mercerization, of which steam explosion and pre-mercerization were the best treatments. Species was the main factor for the accessibility and reactivity.     

The Degree of Disorder in Hardwood Kraft Pulps Studied by Means of LODP

The amount of disordered material in two types of hardwood kraft pulps was estimated by determining the weight loss at the point where the levelling-off degree of polymerisation (LODP) was reached. The pulps used were commercial pulps viz (1)one conventional birch kraft and (2)one mixed hardwood (MHW) kraft pulp that had been prehydrolysed prior to cooking. The results indicated that the hemicellulose xylan is closely associated with the cellulose in commercial birch pulps. It is therefore only possible to use LODP as a measure of the crystallite length of hardwood cellulose in highly purified pulps, such as prehydrolysed kraft pulp. A model explaining the LODP-results is proposed.     

Upgrading of paper-grade pulps to dissolving pulps by nitren extraction: properties of nitren extracted xylans in comparison to NaOH and KOH extracted xylans

Different paper-grade pulps were extracted with nitren, NaOH and KOH in order to produce dissolving pulps and polymeric xylan. The yield and structure of the isolated nitren and alkali xylans were investigated by carbohydrate analysis, HPSEC and ¹H-NMR spectroscopy. In addition the effect of washing stages on the residual nickel content of the nitren xylans was investigated. By nitren extraction up to 98% of the xylan could be extracted out of the fully bleached eucalyptus and birch kraft pulps. The nitren extracted kraft xylans had DP values between 95 (birch) and 111 (eucalyptus). At most 5 mol% of the xylose units were substituted. In the case of pulps with low mannan content only marginally differences between the nitren and alkaline (KOH, NaOH) extractions occurred. The extraction of the relatively “mannnan rich” pulps of this study like softwood kraft and beech sulfite pulps revealed that the dissolution effect regarding mannans increased in the following order: nitren < KOH < NaOH. In general the nitren extractions required a lower chemical charge compared to the alkaline extractions, in order to yield similar amounts of xylans. On the other side the necessity of an effective nickel removal is a disadvantage of the nitren extractions.     

Pyrolysis-GC/MS and TG/MS study of mediated laccase biodelignification of Eucalyptus globulus kraft pulp

Biobleaching studies using laccase mediator system (LMS) were carried out, under optimized conditions, on two unbleached Eucalyptus globulus kraft pulps, one produced by conventional way, with kappa number of 16.1, and another with kappa number of 14.5, obtained by modified kraft procedure with a high liquor/wood ratio and with black liquor replacement in the middle of the cooking. The pulp properties before and after LMS and alkaline extraction were evaluated in terms of kappa number, hexeneuronic acid content, viscosity, brightness and acid insoluble lignin content.The original milled wood sample and the kraft pulps were characterized by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and thermogravimetry/mass spectrometry (TG/MS). Eucalypt wood lignin produces guaiacol and syringol derivatives during pyrolysis. These lignin products can be detected with high sensitivity using the selected ion chromatograms even in the bleached pulp of low lignin content (about 0.5%). Py-GC/MS revealed that the lignin moieties were similarly altered during biobleaching as during pulping, which is exemplified by the preferential removal of aldehyde groups from the alkyl side groups. Semi-quantitative analysis of the pyrograms indicates that the lignin content of the biobleached pulps is reduced by about half in comparison with the unbleached pulps. The TG/MS results show that the hemicellulose content of wood was strongly modified during pulping resulting in higher thermal stability.     

Pre-fibrillation of pulps to manufacture cellulose nanofiber-reinforced high-density polyethylene using the dry pulp direct kneading method

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

Graphical abstract

     

Effect of pulp composition on the characteristics of residuals in CMC made from such pulps

Four different spruce sulphite pulp samples were used for the preparation of carboxymethylcellulose (CMC). The characteristics of the unreacted fibre and particle residuals obtained in the CMC-preparation were used to establish a correlation between the hemicellulose in the pulp and the intrinsic viscosity, i.e.,␣cellulose chain length and the occurence of unreacted residuals. It was shown that the residual particles in the CMC consisted of fibres, fibre fractions and gel particles of different degrees of substitution. The results suggested that pulps with long cellulose chains, i.e., pulps with high intrinsic viscosities, resulted in particles that were more substituted and more swollen. These pulps also resulted in more substituted hemicelluloses in the CMC and more substituted residuals. It was also suggested that galactoglucomannan in the cellulose pulps is favourable for the swelling which results in more substituted hemicelluloses in the CMC and more swollen residuals. The amount of residuals was influenced mainly by the characteristics of the cellulose in the pulp. It is therefore believed that a combination of high viscosity and a suitable combination of hemicelluloses is the most favourable way of eliminating the occurrence of undissolved residuals in CMC.