Capillary forces play an important role during the dewatering and drying of nanocellulosic materials. Traditional moisture removal techniques, such as heating, have been proved to be deterimental to the properties of these materials and hence, there is a need to develop novel dewatering techniques without affecting the desired properties of materials. It is, therefore, important to explore novel methods for dewatering these high-added-value materials without negatively influencing their properties. In this context, we explore the effect of electric field on the capillary forces developed by a liquid-water bridge between two cellulosic surfaces, which may be formed during the water removal process following its displacement from the interfibrillar spaces. All-atom molecular dynamics (MD) simulations have been used to study the influence of an externally applied electric field on the capillary force exerted by a water bridge. Our results suggest that the equilibrium contact angle of water and the capillary force exerted by the water bridge between two nanocellulosic surfaces depend on the magnitude and direction of the externally applied electric fields. Hence, an external electric field can be applied to manipulate the capillary forces between two particles. The close agreement between the capillary forces measured through MD simulations and those calculated through classical equations indicates that, within the range of the electric field applied in this study, Young-Laplace equations can be safely employed to predict the capillary forces between two particles. The present study provides insights into the use of electric fields for drying of nanocellulosic materials.

Hypothesis: The incorporation of carbon dioxide into a sodium hydroxide solution containing cellulose may induce the formation of a transient cellulose carbonate intermediate, which readily hydrolyzes to carbonate ion, and this process is responsible for the instantaneous formation of loose cellulose aggregates. Simulations: We employed molecular dynamics simulations to gain insight into the role of carbon dioxide and related ions in the cellulose aggregation process. By performing free energy calculations using OPLS/AA force fields between cellulose chains at different ionic environments, we were able to gain additional information regarding the behavior and thermodynamics of the involved species and propose a potential mechanism for the aggregation of cellulose in these systems. Findings: Our hypothesis of the formation of an intermediate cellulose carbonate in the solution, which strongly favors carbon dioxide absorption and carbonate ion formation, is supported by the simulation results. These results suggest that the aggregation process is driven by entropy upon the introduction of carbonate ions into the system.

Microfibrillated cellulose (MFC) is a biobased material with unique properties that can be used in a multitude of applications. Water removal from the dilute product streams is, however, challenging and hinders its commercial attractiveness. One possible method of improving dewatering is the use of electroassisted filtration, in which an electric field is applied across part of the filter chamber. In this work, a bench-scale dead-end filter press, modified to allow for electroassisted filtration, was used to dewater a suspension of MFC produced via 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-mediated oxidation. A filter cake was produced with a channeled structure related to the design of the anode mesh, indicating that the cellulose microfibrils were aligned in the direction of the electric field. This was investigated, qualitatively and quantitively, using scanning electron microscopy and wide-angle X-ray scattering, which showed a preferred orientation on a microscopic level but only a partial orientation on a molecular level (fc between 0.49 and 0.57). The influence of the density of the anode mesh, in terms of the structure/permeability of the filter cake and dewatering rate, was also evaluated using two different anode mesh densities (5 x 5 and 10 x 10 mm). It was not, however, found to have any major impact on the dewatering rate.

This study investigates the influence of the ionic strength on the dead-end filtration of microcrystalline cellulose (MCC) suspensions in the range of 0.1–1 g/L NaCl, in altering the electrostatic interactions between particles. The formation of larger agglomerates of increasing ionic concentration was observed using Focused Beam Reflectance Measurement (FBRM®). Local filtration properties were investigated as the experimental set-up allowed for measurements of local hydrostatic pressure and solidosity to be made. The results show that the addition of ions decreases both the average and local filtration resistance. The formation of a resistant skin layer was observed for the suspension without the addition of NaCl but was counteracted when ions were added. Furthermore, the ionic strength did not seem to have any notable effect on the structure of the cake in the range 0.15–1.0 g/L NaCl. However, the pressure dependency of the solidosity at lower ionic concentration was higher. The local filtration properties were fitted to semi-empirical relations, which indicated the formation of moderately to highly compressible cakes when NaCl was added.

An electroassisted filtration technique has been employed to improve dewatering of a suspension of micro-fibrillated cellulose (MFC) produced via 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-mediated oxidation. In addition, all-atom molecular dynamic (MD) simulations were performed to deepen the understanding of the complicated dewatering mechanism on a molecular level. Both the experimental and the simulation results implied that the dewatering rate was not only improved when electroassisted filtration was used but also found to be proportional to the strength of the electric field. A channeled dewatered structure was observed for these experiments and may have contributed to enhanced dewatering by providing high overall permeability. The MD simulations revealed that the electric field had a significant impact on the fibril movement, whereas the impact of pressure was limited. The simulations also suggested that the increased filtrate flow upon the application of an electric field was not only due to electroosmotic flow but also due to electrophoretic movement of the fibrils toward the anode that led to the release of water that had been trapped between the fibrils, allowing it to be pressed out together with the rest of the bulk water. This study shows that electroassisted filtration has the potential to improve the dewatering of TEMPO-MFC, and the MD simulations provide further insights into the dewatering mechanism.

Hypothesis: Interfacial tensions play an important role in dewatering of hydrophilic materials like nanofibrillated cellulose, and are affected by the molecular organization of water at the interface. Application of an electric field influences the orientation of water molecules along the field direction. Hence, it should be possible to alter the interfacial free energies to tune the wettability of cellulose sur face through application of an external electric field thus, aiding the dewatering process. Simulations: Molecular dynamics simulations of cellulose surface in contact with water under the influence of an external electric field have been conducted with GLYCAM-06 forcefield. The effect of variation in electric field intensity and directions on the spreading coefficient has been addressed via orientational preference of water molecules and interfacial free energy analyses. Findings: The application of electric field influences the interfacial free energy difference at the cellulosewater interface. The spreading coefficient increases with the electric field directed parallel to the cellulose-water interface while it decreases in the perpendicular electric field. Variation in interfacial free energies seems to explain the change in contact angle adequately in presence of an electric field. The wettability of cellulose surface can be tuned by the application of an external electric field.