Relationships between Size Distribution, Morphological Characteristics, and Viscosity of Cellulose Nanofibril Dispersions.

Rheological parameters of cellulose nanofibril dispersions (CNF) are relevant and commonly used as quality control for producing of this type of material. These parameters are affected by morphological features and size distribution of the nanofibrils. Understanding the effect of size distribution is essential for analyzing the rheological properties, viscosity control, performance of CNFs, and potential dispersion applications. This study aims at comprehending how the morphological characteristics of the CNFs and their size distribution affect the rheological behavior of dispersions. The CNF dispersions were fractionated by size, obtaining six fractions of each, which were analyzed for their morphology and rheology (viscosity, intrinsic viscosity). In the dilute region, the viscosity and intrinsic viscosity behavior of CNF dispersions are linear concerning the size distribution present in the dispersion. In the semi-dilute region, the size of the fibrils and the fiber aggregates have a relevant effect on the viscosity behavior of CNF dispersions, which are satisfactorily related (R2 = 0.997) using the rule of logarithmic additivity of the dispersion viscosities of size fractions.

The Role of Eucalyptus Species on the Structural and Thermal Performance of Cellulose Nanocrystals (CNCs) Isolated by Acid Hydrolysis.

Cellulose nanocrystals (CNCs) are attractive materials due to their renewable nature, high surface-to-volume ratio, crystallinity, biodegradability, anisotropic performance, or available hydroxyl groups. However, their source and obtaining pathway determine their subsequent performance. This work evaluates cellulose nanocrystals (CNCs) obtained from four different eucalyptus species by acid hydrolysis, i.e., E. benthamii, E. globulus, E. smithii, and the hybrid En × Eg. During preparation, CNCs incorporated sulphate groups to their structures, which highlighted dissimilar reactivities, as given by the calculated sulphate index (0.21, 0.97, 0.73 and 0.85, respectively). Although the impact of the incorporation of sulphate groups on the crystalline structure was committed, changes in the hydrophilicity and water retention ability or thermal stability were observed. These effects were also corroborated by the apparent activation energy during thermal decomposition obtained through kinetic analysis. Low-sulphated CNCs (E. benthamii) involved hints of a more crystalline structure along with less water retention ability, higher thermal stability, and greater average apparent activation energy (233 kJ·mol-1) during decomposition. Conversely, the high-sulphated species (E. globulus) involved higher reactivity during preparation that endorsed a little greater water retention ability and lower thermal stability, with subsequently less average apparent activation energy (185 kJ·mol-1). The E. smithii (212 kJ·mol-1) and En × Eg (196 kJ·mol-1) showed an intermediate behavior according to their sulphate index.

Effects on Lignin Redistribution in Eucalyptus globulus Fibres Pre-Treated by Steam Explosion: A Microscale Study to Cellulose Accessibility.

The objective of this study was to investigate structural changes and lignin redistribution in Eucalyptus globulus pre-treated by steam explosion under different degrees of severity (S0), in order to evaluate their effect on cellulose accessibility by enzymatic hydrolysis. Approximately 87.7% to 98.5% of original glucans were retained in the pre-treated material. Glucose yields after the enzymatic hydrolysis of pre-treated material improved from 19.4% to 85.1% when S0 was increased from 8.53 to 10.42. One of the main reasons for the increase in glucose yield was the redistribution of lignin as micro-particles were deposited on the surface and interior of the fibre cell wall. This information was confirmed by laser scanning confocal fluorescence and FT-IR imaging; these microscopic techniques show changes in the physical and chemical characteristics of pre-treated fibres. In addition, the results allowed the construction of an explanatory model for microscale understanding of the enzymatic accessibility mechanism in the pre-treated lignocellulose.

Chemoenzymatic lignin valorization: Production of epoxidized pre-polymers using Candida antarctica lipase B.

An innovative chemoenzymatic catalytic system for functionalizing lignin from Organosolv and Kraft pulping processes to obtain oxirane rings was investigated. Novozym435 (immobilized C. antarctica lipase B: CalB) was used to catalyze the peroxidation of caprylic acid to peroxycaprylic acid, which in turn reacted with unsaturated CC bonds to form the oxirane ring. The conversion of OH groups to oxirane rings (epoxides) reached 90% and 55% after 12 h for the two processes, respectively. The residual enzyme activity over the time course of the reactions indicated transient denaturing due to association with the lignin substrate (10-50%) as well as irreversible denaturation due to exposure to hydrogen peroxide. Functionalized lignin has potential applications in the production of epoxy adhesive resins, and chemoenzymatic synthesis represents a "greener" pathway to this synthesis.