Bleached Hardwood Kraft Pulp Research Articles

Cellulose nanofibers isolated by TEMPO-oxidation and aqueous counter collision methods

In this research, cellulose nanofiber (CNF) was isolated by the combination of chemical 2,2,6,6-tetramethylpiperidine-1-oxylradical (TEMPO)-oxidation and physical aqueous counter collision (ACC) methods The combination of TEMPO-oxidation and ACC is an efficient method to isolate CNFs by reducing chemical usage in TEMPO-oxidation and saving energy in ACC along with controlling the size of CNFs. Two cellulose sources, hardwood bleached kraft pulp (HW) and softwood bleached kraft pulp (SW), were used for the CNF isolation with different TEMPO oxidation time and a defined number of ACC pass. The CNF properties were investigated and compared in term of morphology, crystallinity index, transparency and birefringence. The width of the isolated CNFs from HW is in the range of 15.1 nm–17.5 nm, and that of the SW CNFs is between 18.4 nm and 22 nm depending on the TEMPO oxidation time. This difference is due to the fact that SW is less oxidized than HW under the same chemical dosage, which results in larger width of SW-CNFs than HW-CNFs. The HW-CNF treated with TEMPO for over 2 h and isolated using ACC with 5 pass offers almost 90% transparency. Birefringence of CNFs exhibits that HW-CNFs show better birefringence phenomenon than SW-CNFs. The combination of TEMPO-oxidation and ACC methods is useful for isolating CNFs with its size control.

A xylanase-aided enzymatic pretreatment facilitates cellulose nanofibrillation

Although biological pretreatment of cellulosic fiber based on endoglucanases has shown some promise to facilitate cellulose nanofibrillation, its efficacy is still limited. In this study, a xylanase-aided endoglucanase pretreatment was assessed on the bleached hardwood and softwood Kraft pulps to facilitate the downstream cellulose nanofibrillation. Four commercial xylanase preparations were compared and the changes of major fiber physicochemical characteristics such as cellulose/hemicellulose content, gross fiber properties, fiber morphologies, cellulose accessibility/degree of polymerization (DP)/crystallinity were systematically evaluated before and after enzymatic pretreatment. It showed that the synergistic cooperation between endoglucanase and certain xylanase (Biobrite) could efficiently “open up” the hardwood Kraft pulp with limited carbohydrates degradation (<7%), which greatly facilitated the downstream cellulose nanofibrillation during mild sonication process (90Wh) with more uniform disintegrated nanofibril products (50–150nm, as assessed by scanning electron microscopy and UV–vis spectroscopy).

Effect of enzyme beating on grinding method for microfibrillated cellulose preparation as a paper strength enhancer

Hardwood bleached Kraft pulp was treated with an endoglucanase prior to Valley beating. The Valley-beaten pulp slurry was further ground with a particle grinder in order to evaluate the effect of enzyme beating on preparation of microfibrillated cellulose (MFC). The time required to make 100 mL Canadian Standard Freeness pulp slurry was greatly reduced by enzyme pre-treatment. The viscosity of the enzyme-beaten MFC slightly increased with grinder pass number; however, the rate of change in viscosity was much lower than that of non-enzyme-beaten MFC. The crystallinity of MFC decreased with grinder pass number for both cases. The drainage of the pulp slurry containing enzyme-beaten MFC was higher than that of the pulp slurry containing non-enzyme-beaten MFC. Further, the enzyme-beaten MFC subjected to the 10 passes grinding had the same tensile index as the MFC subjected to the 15 passes grinding. Thus, the mechanical energy for MFC manufacturing can be greatly reduced with enzyme beating.

Green all-cellulose nanocomposites made with cellulose nanofibers reinforced in dissolved cellulose matrix without heat treatment

Green all-cellulose nanocomposites were fabricated by adding reinforcing cellulose nanofiber (CNF) to a matrix of dissolved cellulose. CNFs were isolated from one dried native hardwood bleached Kraft pulp and office waste recycled deinked copy/printing paper (DIP) by using the TEMPO oxidation method. The cellulose was dissolved by using DIP and DMAc/LiCl solvent without heat treatment and solvent exchange to form a matrix of the all-cellulose nanocomposites. The DIP was not only selected for CNF isolation, but also for the cellulose matrix. The isolated CNFs and the all-cellulose nanocomposites were characterized by atomic force microscopy, thermogravimetry–differential thermal analysis, X-ray diffraction and mechanical tensile testing. The green all-cellulose nanocomposites made without heat treatment offered better thermal stability, crystallinity and mechanical properties than the heat treated ones. CNFs isolated from two resources show similar reinforcement capacity in all-cellulose nanocomposites. All-cellulose nanocomposite fabrication by dissolving cellulose without heat treatment and solvent exchange is a simple way that saves energy and chemicals.

Cationic cellulosic derivatives as flocculants in papermaking

Water-soluble cationic cellulose derivatives were synthesized by three different procedures, cationizing bleached hardwood kraft pulp with (3-chloro-2-hydroxypropyl) trimethylammonium chloride. The first procedure involved a previous depolymerization step with orthophosphoric acid. The second one consisted on dissolving cellulose in NaOH/urea before cationization. For the third procedure, the reaction medium was heterogeneous since it was carried out with a part of cellulose with high degree of polymerization. Oppositely to the common methods, cationization occurred under mild conditions. Differences among the three derivatives are illustrated by X-ray diffraction patterns of pretreated samples, infrared spectra, and determinations of the degree of substitution, the zeta potential, the charge density and the molecular weight. The performance of these polyelectrolytes for the flocculation of mineral fillers used in papermaking was tested by laser diffraction spectrometry. The flocculant with the highest degree of polymerization and charge originated the best results, particularly when the filler used was kaolin, proving that water-soluble cationic cellulose derivatives can aid in the flocculation of fillers used in papermaking. On the contrary, the shortest-chained derivative was not effective. The results were interpreted in terms of the characteristics of the cellulose derivatives flocculants and of the fillers, and neutralization and patching were proposed as the dominant mechanisms.

Effect of CMC Addition on Grinding Characteristics of Hardwood Bleached Kraft Pulp

Effect of CMC Addition on Grinding Characteristics of Hardwood Bleached Kraft Pulp

Multivariate Analysis of Hemicelluloses in Bleached Kraft Pulp Using Infrared Spectroscopy.

The hemicellulose composition of a pulp significantly affects its chemical and physical properties and thus represents an important process control variable. However, complicated steps of sample preparation make standard methods for the carbohydrate analysis of pulp samples, such as high performance liquid chromatography (HPLC), expensive and time-consuming. In contrast, pulp analysis by attenuated total internal reflection Fourier transform infrared spectroscopy (ATR FT-IR) requires little sample preparation. Here we show that ATR FT-IR with discrete wavelet transform (DWT) and standard normal variate (SNV) spectral preprocessing offers a convenient means for the qualitative and quantitative analysis of hemicelluloses in bleached kraft pulp and alkaline treated kraft pulp. The pulp samples investigated include bleached softwood kraft pulps, bleached hardwood kraft pulps, and their mixtures, as obtained from Canadian industry mills or blended in a lab, and bleached kraft pulp samples treated with 0-6% NaOH solutions. In the principal component analysis (PCA) of these spectra, we find the potential both to differentiate all pulps on the basis of hemicellulose compositions and to distinguish bleached hardwood pulps by species. Partial least squares (PLS) multivariate analysis gives a 0.442 wt% root mean square errors of prediction (RMSEP) for the prediction of xylan content and 0.233 wt% RMSEP for the prediction of mannan content. These data all support the idea that ATR FT-IR has a great potential to rapidly and accurately predict the content of xylan and mannan for bleached kraft pulps (softwood, hardwood, and their mixtures) in industry. However, the prediction of xylan and mannan concentrations presented a difficulty for pulp samples with modified cellulose crystalline structure.

Effects of fibrillation on the wood fibers’ enzymatic hydrolysis enhanced by mechanical refining

The hardwood bleached kraft pulp (HBKP) fibers were pretreated by PFI mill to obtain the substrates, the effects of fibrillation on HBKP fibers’ enzymatic hydrolysis was studied. The results showed that the enzymatic hydrolysis efficiency was enhanced obviously by mechanical refining. The mechanical refining alterated the fibers’ characteristics such as fibrillation degree, specific surface area, swelling ability, crystallinity, fiber length and fines content. All these factors correlating to the enzymatic hydrolysis were evaluated through mathematical analysis. Among these factors, the fibrillation degree has the profoundest impact on the enzymatic hydrolysis of wood fibers. Consequently, the mechanical refining aiming for a high fibrillation degree was feasible to enhance the enzymatic hydrolysis of lignocellulosic biomass.

Effect of mechanical treatment on properties of cellulose nanofibrils produced from bleached hardwood and softwood pulps

Bleached hardwood and softwood South African kraft pulps were passed through a commercially available micro grinder for varying number of passes and the properties of the resultant pulps were assessed periodically using microscopy, Fourier transform infrared spectroscopy (FTIR), X-ray crystallography (XRD) and Thermogravimetric analysis (TGA). The ultrastructural analysis of the pulp fibres revealed that after 120 passes both hardwood and softwood bleached fibres showed the presence of cellulose nanofibres (CNFs). The FTIR analysis showed no modification to the cellulose structure and side groups upon treatment with the supermasscolloider (SMC). Both hardwood and softwood pulp fibres showed a decline in crystallinity after SMC treatment. For the hardwood pulps there were no major differences between the untreated pulps and those passed through the SMC. In the case of the softwood pulps, the SMC treatment resulted in more thermally stable CNFs compared with the untreated bleached pulps. This was observed at several levels of treatment (40, 120 and 200 passes). After 200 passes both the hardwood and softwood kraft pulp fibres produced CNFs with an average width of 11 nm and lengths with several micrometers.

Manipulation of Surface Carboxyl Content on TEMPO-Oxidized Cellulose Fibrils

Simple methods of conductometric titration and infrared spectroscopy were used to quantify the surface carboxyl content of cellulose fibrils isolated by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation. The effects of different cellulose sources, post or assisted-sonication oxidation treatment, and the amount of sodium hypochlorite addition on the carboxyl content of cellulose were reported. This study showed that post sonication treatment had no influence on the improvement of surface carboxyl charge of cellulose macrofibrils (CMFs). However, the carboxyl content increased for the isolated cellulose nanofibrils (CNFs). Thus the carboxyl content of CNFs is different from those of their corresponding bulk oxidized cellulose and CMFs. Filter paper as a CNF source imparted a higher surface charge than did hardwood bleached kraft pulp (HWBKP) and microcrystalline cellulose (MCC). It was considered that the crystallinity and microstructure of the initial cellulose affected oxidation efficiency. In addition, the carboxyl content of cellulose was successfully controlled by applying sonication treatment during the oxidation reaction and adjusting the amount of sodium hypochlorite.

The influence of strain rate and pulp properties on the stress-strain curve and relaxation rate of wet paper

Sufficient tension of the wet web is crucial for paper machine runnability. As profitability pressures have been increasing, the potential to improve runnability is of interest. The runnability of wet paper is especially important for paper machines running at high speeds, making paper at lower grammage, and using large amounts of filler or recovered paper. The typical location of web breaks depends on the paper grade and paper machine. A break typically takes place when the paper is wet and a fast draw is applied to the web. Because information on wet paper is scarce, especially information on the effect of strain rate on the tensile properties, we investigated the effects of strain rate on the tension-strain curve and relaxation of wet paper and how they depend on pulp type, refining, solids content, and fines. Higher strain rate leads to higher tensile strength, tensile stiffness, and relaxation rate. The initial wet strength and stiffness of the studied pulps, bleached softwood kraft pulp and bleached hardwood kraft pulp, were increased by increasing the solids content, fines, wet pressing, and refining. At a constant strain rate and constant strain, the tension at a certain moment depended strongly on the initial tension and thus on the tensile stiffness.

Efficacy of carbohydrate polymers in filler preflocculation for use in papermaking

Preflocculation of inorganic fillers added to the paper could improve the inter-fiber bonding and enhance paper strength. Selection of a suitable flocculant and flocculating conditions for improved efficacy of the process is highly desired. The flocculating process conditions such as stirring speed, concentration of filler suspension and retention time were optimized through image analysis of the filler flocs when using cationic starch as flocculant. Two carbohydrate polymers, cationic and amphoteric starch, were used at 0.1%, 0.4% and 0.8% doses for the preflocculation of talc filler under optimized conditions. The colloidal charge and particle size distribution of the native and preflocculated fillers were analyzed. The native and preflocculated fillers were added to bleached mixed hardwood kraft pulp for preparing laboratory handsheets of 60g/m2 targeting varying ash levels of 15–24%. Various paper properties such as tensile, burst, tear indices, light scattering coefficient, Cobb60 and contact angle were analyzed for the native as well as preflocculated fillers. The median particle size of native filler was 6.0μm which on preflocculation using 0.8% dosage of cationic and amphoteric starch increased to 12.0μm and 14.8μm i.e. 100% and 146% increase in particle size, respectively. The preflocculated filler increased the physical and hydrophobic properties of the sheets as compared with the native filler. The increase in tensile index was about 20% when filler was preflocculated using 0.8% dose of amphoteric starch.

Effects of Kneading Concentration on Characteristics of HwBKP Fibers

In this study, effects of kneading concentration on characteristics of hardwood bleached kraft pulp (HwBKP) fibers were elucidated. A laboratory two-shaft kneader was utilized for kneading. Kneading concentration was varied in the range of 15-30% (w/w) and the number of kneading treatment was adjusted between 0 and 6 passes. It was found that kneading concentration influenced fiber characteristics. At 15% of pulp concentration, fiber length slightly increased with increasing the number of kneading passes, while other morphological properties such as fiber width and curl decreased: fiber straightening occurred. In addition, the increase in WRV and the decrease in CSF were the largest at 15% kneading concentration, meanings that fibrillation mainly occurred. In contrast, at higher kneading concentration exceeding 20%, fiber deformation like curl was mainly occurred. Also, at kneading concentration of 20% and 30%, fiber length decreased with the number of kneading passes while other morphological properties such as fiber width, and WRV increased. Severe fiber entanglement was found at 30% kneading, which shall be removed during papermaking.

Effects of Kneading Treatment on the Properties of Various Pulp Fibers

In this study, effects of kneading treatment on the properties of hardwood bleached kraft pulp (HwBKP), softwood bleached kraft pulp (SwBKP) and hardwood bleached chemi-thermo-mechanical pulp (HwBCTMP) were elucidated with a laboratory two-shaft kneader. Kneading treatment was performed at 30% (w/w) of pulp concentration and the number of passes through the kneader was adjusted from 0 to 10 passes. Then, changes in properties of pulp fibers were evaluated. It was found that fiber characteristics were influenced by kneading treatment. Fiber length was decreased with kneading while other morphological properties such as fiber width, curl and kink became increased as the number of passes through the kneader increased from 0 to 5 passes. The magnitude of changes in the morphological properties of softwood chemical pulp was the largest, followed by hardwood chemical pulp. The morphological properties of HwBCTMP were little influenced by kneading treatment. Swelling of fiber measured by WRV was increased with kneading except of HwBCTMP.

Amino-functionalized nanocrystalline cellulose as an adsorbent for anionic dyes

In this present work, amino-functionalized nanocrystalline cellulose (ANCC) was prepared by a process involving, (1) extraction of nanocrystalline cellulose (NCC) from fully bleached hardwood kraft pulp by sulfuric acid hydrolysis, (2) sodium periodate oxidation of NCC to yield the corresponding C-2/C-3 dialdehyde nanocellulose (DANC) and (3) grafting with ethylenediamine to obtain ANCC through a reductive amination treatment. Properties of DANC and ANCC were characterized by conductometric titration, Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction and atomic force microscopy. It was found that the primary amine groups of ANCC (0.77–1.28 mmol g−1) increased with the increase of ethylenediamine dosage. The successful grafting was further evidenced by Kaiser test and FT-IR analysis. Zeta potential measurements showed that ANCCs were amphoteric, and their isoelectric points were between pH of 7–8. Chemical modifications of the cellulose nanowhiskers reduced the crystallinity but the initial cellulose I polymorph was retained. The cross-sectional dimension of nanowhiskers was slightly decreased from about 5–10 to 3–8 nm after the oxidation, and a better dispersibility was observed. ANCC sample was then applied as an adsorbent to remove anionic dyes in aqueous solutions. It demonstrated the maximum removal efficiency at acidic conditions. The acid red GR adsorption on ANCC fitted well with the Langmuir model, with a maximum theoretical adsorption capacity of 555.6 mg g−1. The adsorption of congo red 4BS, acid red GR and reactive light yellow K-4G followed pseudo second order kinetics, indicating a chemisorption nature.

Modification of xylan in alkaline treated bleached hardwood kraft pulps as classified by attenuated total-internal-reflection (ATR) FTIR spectroscopy

The glucuronoxylan composition of a pulp affects the bonding between cellulosic fibres, and thus correlates with such network properties as tensile strength. Here, we demonstrate the promise of attenuated total-internal-reflection (ATR) FTIR spectroscopy as a rapid means for classifying the xylan contained in commercial bleached kraft pulps. This study draws upon samples composed of bleached eucalyptus kraft pulps and combinations of eucalyptus with other commercial bleached kraft pulps. We subject these pulp samples to systematic extraction by sodium hydroxide solutions with concentrations ranging from 0.5% to 6% to build a standard sample library with varying xylan content, quantified by acid hydrolysis, HPLC carbohydrate separation and titration. This pulp chemistry of mild alkaline extraction removes up to two-thirds of the xylan. In the NaOH concentration regime of 0.5–4%, the infrared spectral variance reflects the decrease in hemicellulose concentration as well as the cellulose crystallinity. A residual xylan component remains resistant to base solutions of higher concentrations. Principal component analysis of infrared spectra distinguishes this residual xylan as structurally variant. Both partial least squares multivariate analysis and univariate analysis confined to a feature at 964cm−1 in normalized second derivative IR spectra show a very good correlation with xylan content quantified by HPLC.

Adsorption of cationized eucalyptus heteropolysaccharides onto chemical and mechanical pulp fibers

Adsorption of native eucalyptus heteropolysaccharides onto bleached softwood and hardwood kraft pulps and bleached CTMP was explored in this work to potentially improve the mechanical properties of the final furnish. It was found that adsorption of native heteropolysaccharides onto softwood kraft pulp was slightly higher than hardwood; however, heteropolysaccharides with low arabinose content were preferentially adsorbed onto the hardwood fibers. Adsorption onto CTMP was the lowest, although the general phenomenon of native absorption was rather low under the applied conditions. A strategy to increase the absorption required cationizing the heteropolysaccharides with 2,3-epoxy propyltrimethylamonium chloride that in general significantly increased the overall phenomenon, again with the same general tendencies as observed for the native adsorption.

Cellulose nanocrystals' production in near theoretical yields by 1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO4)-mediated hydrolysis.

We report on near theoretical yield production of cellulose I nanocrystals (CNCs) using a two-step hydrolysis with the mildly acidic ionic liquid (IL) 1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO4) in aqueous solution from common cellulosic sources. Two successive Taguchi experimental plans were performed to evaluate the impact of selected reaction parameters (T, t, H2O:IL ratio) and their interactions on the CNCs' yield from bleached softwood kraft pulp (SWP), bleached hardwood kraft pulp (HWP) and microcrystalline cellulose (MCC). With these experimental plans, the molar yield for extraction of nanocrystals was optimized to near theoretical levels, reaching 57.7±3.0%, 57.0±2.0%, and 75.6±3.0%, for SWP, HWP and MCC, respectively. The reaction yields corresponded to a relative crystalline region recovery of 84.1±5.3%, 71.7±1.3%, 76.0±2.0% from SWP, HWP and MCC, respectively. The collected nanocrystals exhibited high aspect ratios (36-43), negligible sulfur content (0.02-0.21%) and high solvent dispersibility in comparison to those obtained with the traditional sulfuric acid method. Additionally these near theoretical yields were achieved for mild reaction conditions with the combined severity factor of 2 and 3 for MCC and pulp, respectively. Overall this two-stage IL-mediated preparation of nanocrystals combines the advantages of achieving high product quality, high reaction yields and mild conditions.

Manufacture of Low Density Paper by Cationic Fatty Acid Bulky Promotor Treatment (1)

ABSTRACT As a part of the study on manufacture of low density paper by organic bulky agent treatment, the effects of cationic fatty acid bulky agent on physical and optical properties of handsheets were elucidated. The research on change of physical and optical properties of paper samples according to bulky agent concen-tration, pulp type, and pulp combination werecarried out. The results demonstrated that an increase of the concentration of cationic fatty acid bulky agent was proportional to an increase of the bulky properties of paper samples while tensile strength decreased. Also, the more the treated concentration of cationic fatty acid bulky agent increased, the more the ISO brightness of paper samples decreased while the opac-ity increased. The effectiveness of bulky agent with softwood bleached kraft pulp (SwBKP) was higher than that with hardwood bleached kraft pulp (HwBKP). In addition, the effectiveness with mixed pulps was higher than that with single pulp. Keywords: Bulky agent, low density paper, cationic fatty acid amine, bulky agent concentration, pulp type

Changes in the Handsheet Properties by Low Concentration Sodium Hydroxide Swelling and Beating

ABSTRACT Effects of alkali swelling of HwBKP (hardwood bleached kraft pulp) at a low concentration below 2 per-cent (based on the oven-dried weight of pulp) on handsheet properties were investigated. Swelling treat-ment of HwBKP was performed at various low NaOH concentrations with/without beating. Then, the changes in handsheet properties were evaluated in terms of bulk, optical and strength properties. It was found that bulk was slightly increased when the alkali concentration was increased. When the pulp was only swollen without beating, paper optical and strength properties was slightly decreased or not changed with alkali concentration. When the pulp was alkali-swollen after beating, paper strength and opacity showed almost no changes while brightness was increased. When the pulp was beaten after NaOH swel-ling, alkali concentration showed almost no effect on brightness and opacity of paper. Paper strength was slightly decreased with alkali concentration, suggesting that alkali pretreatment before refining could ad-versely affect refining efficiency.