Laboratory and synchrotron validation of µ-XRF for sulfur mapping in CTMP paper samples

The insertion of oat husk lignin onto chemithermomechanical pulp (CTMP) fibers was studied to increase fiber hydrophobicity. The pretreated pulp samples were subsequently used for preparation of handsheets for characterization. Treatment of CTMP with laccase in the presence of oat husk lignin resulted in a significant increase in hydrophobicity of the handsheet surface, as indicated by dynamic contact angle analysis. Water absorption time of 8 s was obtained with initial contact angle of 118°. Although the handsheet's brightness was reduced by 33%, tensile index was only subtly decreased. Neither laccase nor oat husk lignin alone gave much improved water absorption times. Therefore, handsheets made of laccase-treated pulp with and without oat husk lignin were further examined by XPS, which suggested that both laccase and oat husk lignin were inserted onto CTMP fibers. The oat husk lignin was distributed as heterogeneous aggregates on the handsheet surface whereas laccase was uniformly distributed. Evidence was obtained that the adsorbed laccase layer formed a noncovalent base for the insertion of oat husk lignin onto fiber surfaces.

Surface properties of chemithermomechanical pulp (CTMP) fibers produced from enzymatically pretreated eucalyptus wood chips prior to refining were investigated by Field Emission Scanning Electron Microscope (FE-SEM), Transmission Electron Microscope (TEM) and X-ray Photoelectron Spectroscopy (XPS). The results showed that in a traditional CTMP refining process most fiber disruptions occur in the middle lamella (ML) leaving behind a significant amount of hydrophobic materials on the resulting fiber surface. However, in a Bio-CTMP refining process, fiber fractures preferentially take place in the primary (P) and secondary 1 (S1) layers or the S1 and secondary 2 (S2) layers, which results in more fibrillation being generated in the subsequent refining thus improving inter-fiber bonding strength and paper strength. XPS chemical composition analysis together with pulp physical strength property showed that the surfaces of Bio-CTMP fibers become enriched with a greater proportion of carbohydrates in comparison with CTMP fiber surface, which supports FE-SEM and TEM observations.

Crude ligninolytic enzyme extracts from Phanerochaete chrysosporium fungi were applied to sugarcane bagasse, prior to thermomechanical (TMP) and chemithermomechanical pulping (CTMP), and their properties were compared with the normal TMP and CTMP and also with TMP and CTMP pretreated with Ceriporiopsis subvermispora and P. chrysosporium fungi. The sugarcane bagasse was impregnated with the crude enzyme extract containing lignin peroxidase (LiP), manganese peroxidase (MnP), and laccase (Lac). The results show that pretreatment with enzyme crude extract is an advantageous way to produce TMP and CTMP from sugarcane bagasse, as compared with only fungal pretreatment. Enzymatic pretreatments need only hours to enhance pulping and paper properties, compared with the weeks necessary for fungal treatments. Higher pulp yields were obtained compared with the fungal pretreatments. Enzymatic pretreatment reduced the energy consumption in a proportion similar to that of C. subvermispora fungal pretreatment and increased the pulp tensile index compared with the normal TMP and CTMP pulps, although the tensile strength was somewhat lower than that for pulps from C. subvermispora fungal pretreatment before CTMP processing. An advantage of enzymatic pretreatment is that brightness is increased compared with normal TMP and CTMP processes, whereas fungal pretreatments reduce the brightness.

This article proposes a mechanism for a significant improvement in the mechanical performance of a simulated waste fraction, composed of an immiscible low‐density polyethylene (LDPE) and high‐impact polystyrene (HIPS) blend (70:30 proportion), when chemithermomechanical pulp (CTMP) fibers and maleic acid anhydride grafted styrene–ethylene/butylene–styrene block copolymer (MAH‐SEBS) were added. SEM micrographs of composites showed an increased contact between the continuous LDPE phase and CTMP fibers when the functionalized compatibilizer (MAH‐SEBS) was used. By employing a model study using LDPE and regenerated cellulose, we investigated the interphase properties between the plastic phase and the cellulosic component. The model study utilized ESCA, FTIR, and contact angle analysis to follow the reaction between the cellulose surface and the functionalized compatibilizer. All three methods showed that MAH‐SEBS was bonded to the surface of the cellulose. The single‐fiber fragmentation test showed that the adhesion between cellulose fibers and the plastic matrix was significantly improved for MAH‐SEBS–modified samples. The effect of enhanced adhesion on increased mechanical properties of cellulose composites is also discussed, and a prediction of composite strength given, based on interfacial adhesion promotion and fiber properties. © 1995 John Wiley & Sons, Inc.

CTMP-based cellulose fibers modified with core–shell latex for reinforcing biocomposites

Changes of anionic groups in alkaline peroxide-impregnated aspen chemithermomechanical pulp during subsequent alkaline peroxide bleaching

Wood-derived cellulosic fibers prepared in different ways were successfully employed to absorb simulated crude oil, demonstrating their possible use as absorbents in the case of oil spills. When dry fibers were used, the highest sorption capacity (six parts of oil per unit mass of fiber) was shown by bleached softwood kraft fibers, compared to hardwood bleached kraft and softwood chemithermomechanical pulp(CTMP) fibers. Increased refining of CTMP fibers decreased their oil uptake capacity. When the fibers were soaked in water before exposure to the oil, the ability of the unmodified kraft fibers to sorb oil was markedly reduced, whereas the wet CTMP fibers were generally more effective than the wet kraft fibers. Predeposition of lignin onto the surfaces of the bleached kraft fibers improved their ability to take up oil when wet. Superior ability to sorb oil in the wet state was achieved by pretreating the kraft fibers with a hydrophobic sizing agent, alkenylsuccinic anhydride (ASA). Contact angle tests on a model cellulose surface showed that some of the sorption results onto wetted fibers could be attributed to the more hydrophobic nature of the fibers after treatment with either lignin or ASA.

Utilization of rapidly growing trees, such as eucalypts, for high-yield mechanical pulps is limited by low brightness owing to high contents of alkali and neutral extractives. Wood supply problems have developed in many areas of the world and new sources of high-yield pulp are needed. Ten Eucalyptus globulus trees were selected from two plantation sites to evaluate suitability as raw material for high-quality and high-yield pulp. Chemithermomechanical pulp (CTMP) was prepared from tree chips pretreated with sodium sulfite prior to refining. Characteristics of the CTMP were correlated with chemical and physical properties of the wood. There was a linear relationship between the content of alcohol-benzene extractives in wood and CTMP brightness. Klason lignin content in wood was inversely correlated with pulp sheet density, which is an important characteristic affecting the physical properties of pulp. The content of alkali extractives were inversely correlated with pulp yields. Color reversion was tested by exposing CTMP sheets to heat and light. Heat-induced yellowing of CTMP was of a low level and satisfied requirements for printing paper. The rate of yellowing was inversely associated with extractives and can be reduced by antioxidants.

Unlike fossil-based plastics, wood-based packaging materials can be produced in an ecofriendly manner using wood chip residuals from sawmills and pulpwood. To produce high-yield pulp like chemithermomechanical pulps (CTMPs) for paperboard and liquid packaging, it is crucial to reduce the electric energy consumption during fiber separation. The ultimate objective is to revolutionize paperboard production by achieving a middle-layer CTMP process that consumes less than 200 kilowatt-hours per metric ton (kWh/t), significantly improving from the current 500•600 kWh/t energy demand. Optimizing the CTMP impregnation process of sodium sulfite (Na2SO3) in wood chips is crucial for achieving uniform softening, ideally at the fiber level. The properties of the fibers are significantly affected by the content of lignin sulfonates within the walls of the fiber and the middle lamellae. In this study, we employed in-house developed X-ray fluorescence (XRF) techniques, validated by beamline measurements, to map the distribution of sulfonated lignin within fibers. It also seemed possible to enhance the surface area of lignin-rich pulp fibers while losing minimal bulk by refining them with well-optimized low consistency (LC) refining. We aimed to achieve a highly efficient separation of coniferous wood fibers by co-optimizing the sulfonation and the temperature in the preheater and chip refiner. Additionally, we explored how lignin’s softening behavior and potential crosslinking influence subsequent unit operations, including pressing, peroxide bleaching, and drying, following the defibration process. In defibration during chip refining, the maximum softening of wood fibers is preferred to maximize fiber preservation and minimize energy consumption. However, optimizing the stiffness of finished pulp fibers is preferable to reduce bulk loss during paperboard production. It can strive to optimize processes to develop stronger, lighter, and more sustainable composite packaging materials. Reducing environmental impact and electric energy can help create a more sustainable future.

CaCO3-pulp composite was prepared via precipitation of calcium hydroxide in the presence of pulp. In order to investigate the precipitation selectivity and mechanism, the substrate pulps and the obtained composites were fractionated (R30, R100, R200, R400 and a sedimented fraction that passed the 400 mesh wire) using a Bauer-McNett unit. The main fractionation criterion was therefore fiber length. The pulp used was CTMP (chemithermomechanical pulp), yielding a precipitated calcium carbonate-chemithermomechanical pulp (PCC-CTMP) composite with a targeted PCC-to-CTMP ratio of 1:1. The PCC consisted primarily of nano-sized primary particles which formed aggregates and clusters on the fibers. When the fiber morphology, zeta potential and surface charge density of the fractions were determined, a correlation was found between the surface charge density of the CTMP and the ash content of the corresponding PCC-CTMP fractions. This supports the hypothesis that the precipitation on the CTMP fiber is driven by the charge interparticle interaction. The use of refined CTMP furnishes and fractionation of the PCC-CTMP furnishes demonstrates that PCC is preferably fixed on fines and fibrils since it appears at a higher content in the fines fractions. Fiber activation via fiber split, removal of primary wall and surface defibrillation enhanced the affinity of the PCC for the fibrils. The laboratory handsheets prepared from the material demonstrated the importance of controlling the substrate fiber properties for the mineral-fiber composite, e.g. via refining, as differences between the refining levels and fractions were found to lead to differences in both optical properties and bonding.Graphic abstract

High-yield pulps (HYPs), such as CTMP (chemi-thermo-mechanical pulp), are attractive due to their low cost and high wood utilization. However, their drawback of rapid brightness reversion (yellowing) limits wide use of the HYPs. In this study, a fungus, Fusarium concolor X4, was applied to treat poplar CTMP for exploring the effects of biotreatment on brightness and light-induced yellowing of the pulp. The results indicated that the biotreatment with Fusarium concolor X4 could improve the brightness of poplar CTMP and inhibit light-induced yellowing of the pulp. The yellowing inhibition mechanism was explored by the analysis of enzyme production regularity during biotreatment, changes in chemical components, and the UV-Vis absorption spectra and FTIR-ATR spectra of pulps before and after biotreatment.

The changes at molecular level induced by cold argon plasma treat-ments on fibers obtained from chemi-thermo-mechanical pulp (CTMP) fibers were investigated. The radicals formed on CTMP fibers after treatments were identified and quantified by Electron Paramagnetic Resonance (EPR) spectroscopy. The plasma conditions which maximize the formation of radicals on fibers were assessed: after treatment with 0.4 mbar Ar pressure and 75 W radiofrequency power, phenoxy radicals triple their concentration in only 60 s and reach a value 4 times higher than that reported for laccase-catalyzed lignin oxidation. It was found that in plasma-treated fibers, the formation of radicals competes with their coupling. This latter result leads to cross-linkages of the lignin mono-meric units and formation of new intermonomeric C-C and C-O bonds, for the first time assigned to specific molecular interactions through Heteronuclear Single Quantum Coherence (2D-HSQC) spectroscopy and Nuclear Magnetic Resonance spectroscopy of carbon (13C-NMR). These results were confirmed by Nuclear Magnetic Resonance spectros-copy of phosphorous (31P-NMR). The lack of evidences of inter-fiber bond interactions, deduced from Gel Permeation Chromatography (GPC) data, suggests the possible application of plasma treatments for the production of wood fiber-based composites.

Air drying scalable production of hydrophobic, mechanically stable, and thermally insulating lignocellulosic foam

It has been a challenge to develop rapid online characterisation techniques for nanocellulose given the fibrillar structure of the nanoparticles. The crill optical analyser uses optical response signals in the infrared (IR) and ultraviolet (UV) wavelength ranges to evaluate the particle size properties of micro/nanofibrillar cellulosic materials. In this work, the crill analyser was used to measure the projected areas of UV and IR light sources by measuring the light blocked by nanocellulosic particles. This work uses the crill methodology as a new, simplified technique to characterise the particle size distribution of nanocellulosic material based on chemi-thermomechanical pulp (CTMP), thermomechanical pulp (TMP), and sulphite pulp (SP). In the first part, hydrogen peroxide pretreatment of CTMP and TMP in a wing mill refiner followed by high-pressure homogenisation to produce microfibrillated cellulose (MFC) was evaluated using the crill method. In the second part, TEMPO oxidation of CTMP and SP combined with high-shear homogenisation to produce MFC was studied using the crill method. With 4 % hydrogen peroxide pretreatment, the crill values of the unhomogenised samples were 218 and 214 for the TMP and CTMP, respectively, improving to 234 and 229 after 18 homogenisation passes. The results of the TEMPO method indicated that, for the 5 mmol NaClO SP-MFC, the crill value was 108 units at 0 min and 355 units after 90 min of treatment, a 228 % improvement. The CTMP and TMP fibres and the MFC were freeze dried and fibrillar structure of the fibres and microfibrils was visualised using scanning electron and transmission electron microscopy.

Evaluating chemi-mechanical pulping processes of agricultural residues: High-yield pulps from wheat straw for fiber-based bioproducts