Carboxymethyl cellulose on a fiber substrate: the interactions with cationic polyelectrolytes

High and low molecular weight (M_w) carboxymethyl celluloses (CMC) were adsorbed on a well-characterized fiber substrate (long fibers of a commercial bleached birch kraft pulp with the carboxylic acid groups in Na-form) to increase the charge of the fibers in a controlled fashion. The M_w played a role in the utilization of CMCs as a strength additive in paper sheets nearly doubling the tensile strength with the high M_w CMC. Swelling properties of the CMC treated fibers were measured with water retention value (WRV). The WRV increased more with the high M_w CMC. The swelling was further tuned by two highly cationic polyelectrolytes; high M_w poly(diallyldimethyl ammonium chloride) (PDADMAC) and low M_w polybrene (hexadimethrine bromide, [3,6]-ionene). They were chosen because of their known ability to neutralize the anionic charge either exclusively on the surface or in the whole fiber, respectively. Adsorption of PDADMAC could reduce WRV of the CMC pre-treated fibers to the level of the untreated reference, while polybrene adsorbed pulps with 3–10 times more cationic polyelectrolyte deswelled the fibers only slightly more than the surface neutralized fibers. These results indicated surface conformation differences with low and high M_w CMCs. While the conformation did play a role after physical alteration (drying and rewetting) of the fibers, the paper sheets produced from these fibers showed remarkable differences. In extreme cases, the strength of the paper could be retained after drying (low M_w CMC + PDADMAC) or paper, resistant to disintegration, could be achieved (CMC + polybrene).     

Ionic liquid extraction method for upgrading eucalyptus kraft pulp to high purity dissolving pulp

High purity cellulose from wood is an important raw material for many applications such as cellulosic fibers, films or the manufacture of various cellulose acetate products. Hitherto, multi-step refining processes are needed for an efficient hemicellulose removal, most of them suffering from severe cellulose losses. Recently, a novel method for producing high purity cellulose from bleached paper grade birch kraft pulp was presented. In this so called IONCELL process, hemicelluloses are extracted by an ionic liquid–water mixture and both fractions can be recovered without yield losses or polymer degradation. Herein, it is demonstrated that bleached Eucalyptus urograndis kraft pulp can be refined to high purity acetate grade pulp via the IONCELL process. The hemicellulose content could be reduced from initial 16.6 to 2.4 wt% while persevering the cellulose I crystal form by using an optimized 1-ethyl-3-methylimidazolium dimethylphosphate-water mixture as the extraction medium. The degree of polymerization was then reduced by a sulfuric acid treatment for subsequent acetylation of the pulp, resulting in a final hemicellulose content of 2.2 wt%. When pre-treating the pulp enzymatically with endoxylanase, the final hemicellulose content could be reduced even to 1.7 wt%. For comparison, the eucalyptus kraft pulp was also subjected to cold caustic extraction and the same subsequent acid treatment which led to 3.9 wt% of residual hemicelluloses. The performance in acetylation of all produced pulps was tested and compared to commercial acetate grade pulp. The endoxylanase-IONCELL-treated pulp showed superior properties. Thus, an ecologically and economically efficient alternative for the production of highest value cellulose pulp is presented.     

Residual lignin inhibits thermal degradation of cellulosic fiber sheets

The market for cellulosic fiber based food packaging applications is growing together with the importance of improving the thermal durability of these fibers. To shed light on this, we investigated the role of residual lignin in pulp on the thermal stability of refined pulp sheets. The unbleached, oxygen delignified, and fully bleached pulp sheets were studied after four separate refining degrees. Comparison by Gurley air resistance, Bendtsen porosity, and the oxygen transmission rate tests showed that lignin containing sheets had better air and oxygen barrier properties than fully bleached sheets. Sheet density and light scattering coefficient measurements further confirmed that the lignin containing pulps underwent more intense fibrillation upon refining that changed the barrier properties of the sheets. Thermal treatments (at 225 °C, 20 and 60 min, in water vapor atmospheres of 1 and 75 v/v %) were applied to determine the thermal durability of the sheets. The results revealed that the residual lignin in pulps improved the thermal stability of the pulp sheets in the hot humid conditions. This effect was systematically studied by tensile strength, brightness, and light absorption coefficient measurements. The intrinsic viscosity results support the findings and suggest that lignin is able to hinder the thermal degradation of pulp polysaccharides. In spite of the fact that lignin is known to enhance the thermal yellowing of paper, no significant discoloration of the pulp sheets containing residual lignin was observed in the hot humid conditions (75 v/v %). Our results support the idea of lignin strengthening the thermal durability of paper.     

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.     

Investigation of the effect of drying and refining on the fiber–fiber shear bond strength measured using tensile fracture line analysis of sheets weakened by acid gas exposure

No reliable method exists for measuring the cellulose fiber–fiber shear bond strength in paper. This paper reports a simple method for measuring the fiber–fiber shear bond strength by weakening the fibers independently of the bonds in a sheet of paper, using acid vapor, until all the fibers break across the fracture line. The bond strength is then calculated from the fiber strength, as measured by the zero span test, at the point where the fibers first are weakened such that they all break. The method was used to calculate the average bond strength of handsheets made out of two different pulps. The first pulp was a never dried, 60% yield, unbleached radiata pine. The bond strength was 25.0 ± 3.3 MPa. Drying the fibers before reslushing and making sheets reduced the bond strength by up to 33%, with the reduction depending on the severity of the drying treatment. The second pulp was a bleached dried softwood kraft and was used to investigate the effect of low consistency refining on bond strength. The bond strength increased from 13.7 ± 1.0 MPa for the sheets made from the unrefined pulp to 37.0 ± 1.0 MPa, for the sheets made from the most heavily refined pulp. The bond strength measurements are considerably higher than previous literature estimates for the shear bond strength. The causes for the discrepancy include stress concentrations in tests of single fiber–fiber bonds.     

Properties and treatments of pulps from recycled paper. Part II. Surface properties and crystallinity of fibers and fines

Surface properties of bleached kraft pulps were evaluated before and after recycling, and after a series of chemical treatments designed to improve and/or modify the pulp characteristics. The surface free energy characteristics of the pulps were determined using the Wilhelmy technique, and ESCA and ATR-FTIR methods were used to evaluate the chemical composition of the surfaces of the pulp fibers. In general rather small changes were noted at the fiber surfaces with recycling and chemical treatment. Recycling tended to increase the acid component and decrease the base component of the surface free energy of the pulps. This could result from exposure of carboxyl groups from hemicelluloses and/or from oxidized layers from the bleaching process. ESCA analyses also indicated increased carboxyl concentration at the surfaces of the recycled fibers. Although treatment with aqueous bases and organic solvents tended to increase the hydroxyl content on the surface of recycled pulps, the chemical treatments were not beneficial to pulp quality. AFM and SEM of fiber and fine surfaces of kraft pulps revealed that the fines fraction was altered to a much greater extent with recycling. Although recycled fibers appeared to have improved wettability, these small changes in the surface characteristics do not appear to play the dominant role in the characteristics of recycled pulps. Recycling did not change the crystallinity of whole pulps, but it increased the crystallinity of the fines fraction. The increase in the crystallinity of the fines fraction and the reduction in the water retention value (WRV) and the bulk carboxyl content (xylan) of the recycled pulps, as noted in Part I of this paper, appear to play the predominant role in determining the characteristics of recycled pulps. It appears that the loss of the hemicelluloses in the bulk of the fiber with recycling is much more important for internal fibrillation than the apparent small increase of hemicelluloses at the surface of recycled fibers.     

Development of continuous process enabling nanofibrillation of pulp and melt compounding

Microfibrillated cellulose (MFC), a mechanically fibrillated pulp mostly consisting of nanofibrils, is a very attractive material because of its high elastic modulus and strength. Although much research has been done on composites of MFC and polypropylene (PP), it has been difficult to produce such composites at an industrial level because of the difficulties in using MFC in such composites are not only connected to the polarity (that can be improved with compatibilizers), but also with the challenge to make a homogeneous blend of the components, and also the low temperature stability of cellulose that could cause problems during processing. We developed a new processing method which enables continuous microfibrillation of pulp and its melt compounding with PP. Never-dried kraft pulp and powdered PP were used as raw materials to obtain MFC by kneading via a twin-screw extruder. Scanning electron microscopy showed nano to submicron wide fibers entangled in the powdered PP. MFC did not aggregate during the melt compounding process, during which the water content was evaporated. Maleic anhydride polypropylene (MAPP) was used as a compatibilizer to reinforce interfacial adhesion between the polar hydroxyl groups of MFC and non-polar PP. We investigated the effect of MAPP content on the mechanical properties of the composite, which were drastically improved by MAPP addition. Needle-leaf unbleached kraft pulp (NUKP)-derived MFC composites had better mechanical properties than needle-leaf bleached kraft pulp (NBKP)-derived MFC composites. Injection molded NUKP-derived MFC composites had good mechanical and thermal properties. The tensile modulus of 50 wt% MFC composite was two times, and the tensile strength 1.5 times higher than that of neat PP. The heat distortion temperature of 50 wt% MFC content composite under 1.82 MPa flexural load was increased by 53 °C, from 69 to 122 °C. This newly developed continuous process using powder resin has the potential for application at an industrial level.     

Some Properties of Polyelectrolyte-G rafted Cellulose

Anionic and cationic polyelectrolytes were grafted on a bleached kraft pulp. Grafting an anionic polyelectrolyte (sodium poly-acrylate-polyacrylamide copolymer) resulted in modified fibers possessing outstanding affinity for water and saline solutions in the pH range where the polymer is ionized. Swelling is the result of both the grafting operation itself and of the presence of the ionized polyelectrolyte.

The swollen grafted fibers could be disintegrated under intense shear to give a colloidal solution exhibiting pseudoplastic thixo-tropic behavior. Electron microscopic examination revealed that during the shearing process the fiber had been disintegrated into its constitutive elements, long rodlike protofibrils, which are believed to be mainly responsible for the high viscosities observed.

Grafting a cationic polyelectrolyte (polydimethylamino ethyl methacrylate hydrochloride) produced fibers with lower but significant water swelling. The influence of pH on swelling was similar, although reversed, to that observed with the anionic grafted fibers. The presence of a large number of cationic groups in the porous cellulose fiber gel points to applications in ion-exchange and adsorption processes.     

The effect of eucalypt pulp xylan content on its bleachability,refinability and drainability

Currently, bleached eucalypt pulps are largely used for printing and writing (P&W) and sanitary (tissue) paper grades. Among the many pulp quality requirements for P&W and tissue paper production the xylan content is one of the most significant. For P&W papers, increasing xylans improve pulp refinability and strength properties but negatively affect bulk and drainability. For tissue paper, xylans are purportedly advantageous during paper drying in the Yankee cylinder but negatively affect paper bulk and may increase dusting during paper manufacture. On the other hand, bleachability is a very important parameter for both P&W and tissue grade pulps since bleaching cost is the second most significant in eucalypt bleached kraft pulp production. The aim of this study was evaluating the influence of eucalyptus pulp xylan content on its bleachability, refinability and drainability. A sample of industrial unbleached eucalyptus kraft pulp containing 15.6?% xylans was treated with various alkali charges at room temperature in order to obtain materials with different xylan contents. The pulps were bleached to 90 % ISO brightness with the O–D_HT–(EP)–D sequence and evaluated for their refinability and drainability. By increasing the alkali concentration in the range of 10–70 g/L pulps of 14.5–5.9 % xylans were produced with no significant impact on cellulose crystallinity. The decrease of xylan content significantly decreased pulp bleaching chemical demand, water retention value and refinability and increased pulp drainability.     

In situ generated cellulose nanoparticles to enhance the hydrophobicity of paper

Handsheets with in situ generated cellulose nanoparticles were made from oxidized pulp fibers prepared by 2,2,6,6-tetramethylpiperidinyl-1-oxyl-mediated oxidation of kraft fiber with sodium hypochlorite and sodium bromide. The oxidized pulp fibers were blended prior to handsheet formation for short times (1–3 min). From gravimetric analysis of the supernatant, yield of cellulose nanoparticles generated from this blending process were up to 9.5 dry wt%. Scanning electron microscopy showed that the handsheets fabricated in a wetlay process had increased smoothness with increased blending time. A significant decrease in water vapor transmission rate for the sheets supported the hypothesis that cellulose nanoparticles fill the empty spaces between pulp fibers throughout the handsheet affording a more dense structure. Oxidation significantly enhanced the tensile index of the handsheets and this value was further improved by blending for 2 min. The handsheets were treated with a solution of octadecylamine (ODA) modifying the surface chemistry of the paper. Irreversibly adsorbed ODA on the oxidized cellulose surfaces after extensive extraction was confirmed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Sessile drop contact angle tests for modified handsheets illustrated its enhanced hydrophobicity with contact angles over 90°. Overall the study developed a novel route to make paper with enhanced functionality without the need to separately deposit nanocellulose onto the paper surface.     

Effect of Bacillus circulans D1 thermostable xylanase on biobleaching of eucalyptus kraft pulp

The alkalophilic Bacillus circulans D1 was isolated from decayed wood. It produced high levels of extracellular cellulase-free xylanase. The enzyme was thermally stable up to 60°C, with an optimal hydrolysis temperature of 70°C. It was stable over a wide pH range (5.5—10.5), with an optimum pH at 5.5 and 80% of its activity at pH 9.0. This cellulase-free xylanase preparation was used to biobleach kraft pulp. Enzymatic treatment of kraft pulp decreased chlorine dioxide use by 23 and 37% to obtain the same kappa number (κ number) and brightness, respectively. Separation on Sephadex G-50 isolated three fractions with xylanase activity with distinct molecular weights.     

Photoyellowing inhibition of bleached high yield pulps using novel water-soluble UV screens

To address the deficiencies of benzophenone UV screens for preventing brightness reversion in high yield mechanical papers, we synthesized a new series of such materials with enhanced water solubility and compatibility with the lignocellulosic substrate. A series of 2,4-dihydroxybenzophenones (DHB) were synthesized containing various Mannich bases at the C3 position of one of its rings. They possess the UV-screening ability of o-hydroxylbenzophenones, and they also contain tertiary nitrogen atoms that may function as radical scavengers. Aqueous solutions of the hydrochloride salt of 3-(dimethylaminomethylene)-2,4-dihydroxylbenzophenone (1), when applied on bleached chemithermomechanical pulp (CTMP) sheets, were significantly more efficient in preventing photoyellowing than the original DHB applied on the sheets from ethanol-water solutions. This confirmed our original hypothesis that increasing the compatibility of the UV screen with the lignocellulosic matrix would increase its efficiency in preventing photoyellowing. Compound 1, however, was found to be somewhat more effective than its hydrochloride salt toward preventing photoyellowing. This was attributed to the synergistic action of the free tertiary aminic center attached on the molecule with its UV-screening ability. To comprehend further the various parameters that influence the photoyellowing inhibition performance of these compounds and DHB with bleached CTMP pulp fibers, a series of handsheets were prepared at different pH. The interactions of the protonated compound 1 with pulp fibers were then evaluated by studying their kinetics of absorption and desorption to and from the fiber matrix. This part of our study found that the adsorption of protonated Mannich derivatives of DHB onto pulp is most likely governed by a cation-exchange mechanism involving the cationic amine group with the sulfonic and carboxylic acid groups located on the surface of the fibers. The pH the paper sheet was made from was also found to affect profoundly the adsorption and retention characteristics of these compounds onto the lignocellulosic matrix.     

NMR cryoporometry to study the fiber wall structure and the effect of drying

NMR cryoporometry has been used for investigating the porosity changes of bleached wood pulp upon drying. This NMR method follows the same principles as thermoporosimetry, which has been used for the same purpose during the last decade and makes it possible to investigate porous material in the water-swollen state. In this study bleached softwood kraft pulp was exposed to a series of drying procedures where the decrease in porosity within the fiber cell wall could be characterized for pore radii below 100 nm. This decrease in porosity is called hornification, which is an irreversible collapse of the fiber wall structure during drying and results in decreased uptake of water and reduced swelling of the fiber upon rewetting. Our results have been compared to the traditionally used water retention value (WRV) and correlates well with these. Furthermore, this NMR method could show the reduction of hornification when adsorbing the hemicellulose glucuronoxylan to the fiber.     

Fiber properties of eucalyptus kraft pulp with different carboxyl group contents

Fiber properties (fiber swelling ability, crystal structure of cellulose, fiber surface morphology, and etc.) of eucalyptus kraft pulp with different contents of carboxyl group in Na-form were studied. There was a direct proportional relationship between water retention value and carboxyl content of pulp. When the carboxyl content increased from 35.6 to 315.7 mmol/kg, tensile index and burst index increased by 56.1 and 117.8 %, respectively, and crystallinity of cellulose decreased by 11.8 %. Environmental scanning electron microscope showed that more fibrillation was observed on the carboxymethylated fiber surface, compared with the control sample. The results from Fourier transform infrared spectra analysis suggested that the relative intensity of the band at 1,633/cm was increased after carboxymethylation treatment, which showed that the carboxyl content increased. The increase in the carboxyl content not only could increase the fiber strength properties, but also could increase the recycling times of the fiber.     

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.     

Analysis of the topochemical effects of dielectric-barrier discharge on cellulosic fibers

This study investigates the fundamental topochemical effects of dielectric-barrier discharge treatment on bleached chemical pulp and unbleached mechanical pulp fiber surfaces. Fibers were treated with various levels of dielectric-barrier discharge treatment ranging from 0 to 9.27 kW/m²/min. Changes to the fiber surface topochemistry were investigated by atomic force microscopy (AFM). The AFM studies were complemented by inverse gas chromatography (IGC), contact angle evaluation, poly-electrolyte titration, viscosity testing and determination of water retention value (WRV). The static coefficient of friction and zero-span tensile index of sheets were also evaluated. Low dielectric-barrier discharge treatment levels resulted in increased surface energy and roughness. Fibers treated at high applied power levels showed surface energies and roughness levels near that of reference samples as well as evidence of degradation and decreased fiber swelling.     

Application of Enzyme for Improvement of Acacia APMP Pulping and Refining of Mixed Pulp for Printing Papermaking in Vietnam

This study assesses the influence of commercial enzyme (FibreZyme? LBR) treatment applied to APMP pulp and to the mixture of 55 % Acacia CTMP75 pulp, 30 % soft-wood bleached chemical pulp (LBKP 90 from Chile) and 15 % hard-wood bleached chemical pulp (NPKP 90 from Indonesia). The treatment was conducted at different temperatures, reaction times and enzyme dosages. The APMP and mixed pulp treated with the enzyme showed a significant decrease of refining time to achieve the same refining degree (Schopper–Riegler freeness, °SR) and better mechanical–physical properties due to the development of fibrillation. The fibre morphology difference between before and after treatment was revealed by the microscopic observations performed by a scanning electron microscope (SEM). The SEM analysis showed that the surface of the enzyme-treated fibre had some swelling and fibrillar phenomenon that lead to strong paper properties such as tear index, tensile index and burst index.     

Introducing carboxyl and aldehyde groups to softwood-derived cellulosic fibers by laccase/TEMPO-catalyzed oxidation

For more cost-effective and/or value-added utilization of cellulosic fibers in pulp and paper industry, fiber engineering is an important concept. Essentially, fibers can be engineered via various mechanical, chemical, and biological processes. In the current study, the combined use of laccase and TEMPO was applied to introduce carboxyl and aldehyde groups to softwood-derived cellulosic fibers (bleached softwood kraft pulp). The process conditions in preparation of the engineered fibers were optimized. Under the conditions studied, the maximum increases in carboxyl and aldehyde contents were 360 % and 225 %, respectively. The effectiveness of the laccase/TEMPO system could be well explained by the reaction cycles in catalytic oxidation pathways. The findings of the current work may provide useful insights into the enzymatic modification of cellulosic fibers for papermaking applications.     

Determination of xylo-oligosaccharides in enzymatically hydrolysed pulp by liquid chromatography and capillary electrophoresis

Three different commercial β-1,4-endoxylanase preparations were used to hydrolyze bleached kraft pulp. Xylo-oligosaccharides in the produced filtrates were separated and quantified using both high performance liquid chromatography (HPLC) and capillary electrophoresis (CE). All the determinations were performed without sample derivatization. The analytical methods were used to highlight the differences between the enzymes behaviour in terms of hydrolysates, but also to estimate the productivity of xylo-oligosaccharides from kraft pulp when the bleached material would be used in biorefining industry. The research showed that the glycosyl hydrolase family 10 enzyme produced by Aspergillus oryzae released xylobiose and xylotriose from the pulp material. The major oligosaccharides released by the family 11 enzyme produced by Bacillus sp. were xylotriose, xylobiose and xylotetraose. On the contrary, another family 11 enzyme produced by A. oryzae produced also xylose. The HPLC results agreed well with the xylose concentrations obtained after acid hydrolysis. The CE data showed the same trend, but much lower concentrations were identified than with HPLC. At the same time the HPLC method was able to separate only small oligosaccharides, whereas CE could be used for separation of all the xylo-oligosaccharides from xylobiose to xylohexaose. The highest xylo-oligosaccharide yield was achieved with Shearzyme at pH 5 corresponding to 22 % of total xylan from bleached birch kraft pulp.     

Grafting of acrylamide onto cellulosic fibers via dielectric-barrier discharge

Fully bleached kraft pulp (BKP) and thermomechanical pulp (TMP) fibers were grafted with acrylamide via dielectric-barrier discharge treatment at various treatment dosages. The results indicate that increased dielectric-barrier discharge treatment leads to the increased polymerization and incorporation of acrylamide onto fiber surfaces. Greater incorporation of poly(acrylamide) occurs on the BKP fibers than the TMP at the same treatment conditions. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and scanning electron microscopy (SEM) indicate that dielectric-barrier discharge initiated modifications to fiber surface topo-chemistry occur across the fiber such that the sheet is randomly peppered with modified areas; however, it occurs in patches on individual fibers as opposed to occurring as an evenly distributed thin film. SEM and elemental analysis also showed that the incorporation of acrylamide onto the fiber surface increases with increased treatment dosages.