Effect of drying conditions on cellulose microfibril aggregation and “hornification”

Holzforschung, 2010

Changes in supramolecular properties of cellulose I, namely its lateral fibril aggregate dimension (LFAD), in bleached hardwood acid bisulphite pulp during drying was studied using cross-polarization/magic angle spinning carbon-13 nuclear magnetic resonance (CP/MAS 13C-NMR) in combination with spectral fitting. A significant change in aggregate dimensions was noticed when each of the pulp grades were oven dried. The effect of drying was further investigated with pulp samples subjected to different drying methods. A comparison of a harsh oven drying, mild and rapid air drying, and a very mild and slow condition drying showed that the LFAD of the material decreases in the following order: oven drying > air drying > condition drying. The correlation between the total extractable material S10 (%) and LFAD and also the LFAD increment (ΔLFAD in %) are presented and shown to be intimately related. This means that the method of drying influences the size of the fibril aggregate dimens...

Nordic Pulp and Paper Research Journal

Microfibrillated cellulose (MFC) is known to enhance strength properties of paper. Improved strength usually means increased bonding which is strongly connected to dimensional instability of paper.

Carbohydrate Polymers, 2021

Commercializing dried microfibrillated cellulose (MFC) has always been a challenge mainly due to the tendency of MFC to aggregate. In this study MFC samples were submitted to drying/redispersion cycles at different temperatures. Morphology, crystallinity and mechanical performance of films were analyzed throughout the cycles. Microscopy images, particle size and stability in water showed that aggregation happens more severely with 5 drying/redispersion cycles and at drying temperatures of 75 and 100 • C. Particles once-dried at 20 • C formed the same size and web-like structure as the MFC-control. Crystallinity and crystallite sizes increased with drying/redispersion cycles especially when dried at 75 and 100 • C, however drying/redispersion cycles also led to a reduction in mechanical performance due to aggregation. While oven-drying is not the most suitable method, milder action at room temperature once-drying led to suspension stability in water, morphology and mechanical properties close to never-dried MFC, which makes this treatment a feasible option to maintain cellulose quality.

BioResources, 2022

Environmental and economic concerns are driving tissue paper manufacturers to improve understanding of the relationships between fibres, the networks they form, the forming process, and the final tissue paper properties. This work investigated how pulp fractionation, refining, or addition of microfibrillated cellulose (MFC) affect the compromise between absorbency and strength of 33 ± 2 g/m² model papers made of bleached eucalyptus kraft pulp. The results showed that the compromise of properties was better when fibres were refined than when MFC was added. The absorbency capacity of 2%wt MFC-paper was almost 20% lower than the capacity of the refined paper at the same dry strength. The calculated additional storage capacity due to water-induced deformations of the fibre network was 40% lower in the same range of bulk. By forming a high viscosity gel at inter-fibre contacts, MFC could limit the occurrence of major fibre and network deformation mechanisms when water was imbibing the pa...

The macro-and microstructural evolution of water swollen and ethanol swollen regenerated cellulose gel beads have been determined during drying by optical microscopy combined with analytical balance measurements, small-angle X-ray scattering (SAXS), and wide-angle X-ray scattering (WAXS). Two characteristic length scales, which are related to the molecular dimension of cellulose monomer and elongated aggregates of these monomers, could be identified for both types of beads by SAXS. For ethanol swollen beads, only small changes to the structures were detected in both the SAXS and WAXS measurements during the entire drying process. However, the drying of cellulose from water follows a more complex process when compared to drying from ethanol. As water swollen beads dried, they went through a structural transition where elongated structures changed to spherical structures and their dimensions increased from 3.6 to 13.5 nm. After complete drying from water, the nanostructures were characterized as a combination of rodlike structures with an approximate size of cellulose monomers (0.5 nm), and spherical aggregates (13.5 nm) without any indication of heterogeneous meso-or microporosity. In addition, WAXS shows that cellulose II hydrate structure appears and transforms to cellulose II during water evaporation, however it is not possible to determine the degree of crystallinity of the beads from the present measurements. This work sheds lights on the structural changes that occur within regenerated cellulose materials during drying and can aid in the design and application of cellulosic materials as fibers, adhesives, and membranes.

MRS Proceedings, 1992

Recent advances in understanding the structure of cellulose are used as the basis for analyzing the structural changes that occur in pulp fibers during papermaking, particularly in the drying stage. These changes are responsible for the degradation of papermaking properties, and they must be reversed during recycling if the maximum papermaking potential of the virgin fibers is to be recovered. A number of studies have assessed the structural transformations that can occur in cellulosic fibers upon exposure to elevated temperatures. The researchers have invariably observed that the changes occur at the secondary and tertiary levels of structure, the levels that can have significant effects on the properties of fibers. In addition, some studies have focused specifically on the structural effects of recycling; clear correlations of structural change with changes in paper characteristics have been reported. The results of the various studies point to directions for further investigations into enhancing the recovery of papermaking value from recycled fibers.

Bioresources, 2023

Understanding cellulose hornification provides crucial information regarding drying of pulp, paper, and other cellulosic materials as well as recycling them. By measuring drainage, fiber width, and water retention value of hardwood and softwood pulps before and after sheet forming and after different drying procedures at different achieved levels of solids, the hornification was evaluated. The water retention value was also measured for the pulps when dried from acetone to observe what happens when hydrogen bonds are not available in the liquid phase. The drainage and fiber width decreased with increasing solids content; the fibers became increasingly stiff with increased water removal. Water retention measurements indicated that hornification is a stepwise process with large drops in fiber flexibility as soon as the fibers are being processed and later after a certain amount of water has been removed. In sum, the fibers must achieve a certain solids content to show hornification, and hydrogen bonds in water draw the cellulose surfaces together to create hornification. The mechanism of hornification is believed to be driven by hydrogen bonds and related to the distance between cellulose chains inside the fiber wall. Other types of bonds are probably also present and help with the irreversibility of hornification.

The water retention value (WRV) as a measure of the capability of cellulose fibres to retain water (swelling of fibres) was evaluated during accelerated ageing of acidic wood pulp newspaper containing 20% chemical fibres. It has been found that the WRV considerably decreases with accelerated ageing. Relations between the WRV properties and the mechanical properties of paper have also been evaluated. The characterization of samples by mercury microporosimetry has shown that the cumulative column of the pores increases with the period of ageing. On the other hand, the average radius of the pores, as well as their specific surface, decreases. This supports the process of hornification, which occurs during accelerated ageing of paper, as the small pores get smaller and the larger ones get even larger as a result of shrinkage of fibres. When considering accelerated ageing, hornification of fibres as one of the outcomes of fibre brittleness has to be taken into account.

Bioresource Technology, 2010

The interactions with water and the physical properties of microfibrillated celluloses (MFCs) and associated films generated from wood pulps of different yields (containing extractives, lignin, and hemicelluloses) have been investigated. MFCs were produced by combining mechanical refining and a high pressure treatment using a homogenizer. The produced MFCs were characterized by morphology analysis, water retention, hard-to-remove water content, and specific surface area. Regardless of chemical composition, processing to convert macrofibrils to microfibrils resulted in a decrease in water adsorption and water vapor transmission rate, both important properties for food packaging applications. After homogenization, MFCs with high lignin content had a higher water vapor transmission rate, even with a higher initial contact angle, hypothesized to be due to large hydrophobic pores in the film. A small amount of paraffin wax, less than 10%, reduced the WVTR to a similar value as low density polyethylene. Hard-to-remove water content correlated with specific surface area up to approximately 50 m 2 /g, but not with water retention value. The drying rate of the MFCs increased with the specific surface area. Hornified fibers from recycled paper also have the potential to be used as starting materials for MFC production as the physical and optical properties of the films were similar to the films from virgin fibers. In summary, the utilization of lignin containing MFCs resulted in unique properties and should reduce MFC production costs by reducing wood, chemical, and energy requirements.

Cellulose, 2021

Moisture absorption in the cell wall structure of wood is well known to induce considerable swelling of the wood exerting high expansion forces. This swelling is mainly induced by the sorptive action of the hydroxyl groups of the carbohydrate wood polymers; cellulose and hemicelluloses. On the ultrastructural level, there are, however, still questions with regard to the detailed deformations induced by this moisture absorption. Here, FTIR spectroscopy and synchrotron-radiation-based X-ray diffraction were used on paper samples to study the deformation of the cellulose crystals as a consequence of moisture absorption and desorption. Both techniques revealed that the moisture absorption resulted in a transverse contraction of the cellulose crystals accompanied by a somewhat smaller elongation in the cellulose chain direction. The deformations were found to be a direct response to the increased moisture content and were also found to be reversible during moisture desorption. It is hypo...