The influence of temperature on cellulose swelling at constant water density.

We have in this paper investigated how water sorbs to cellulose. We found that both cellulose nanofibril (CNF) and cellulose nanocrystal (CNC) films swell similarly, as they are both mainly composed of cellulose. CNF/CNC films subjected to water at 0.018 kg/m3 at 25 °C and 39 °C, showed a decrease in swelling from ~ 8 to 2%. This deswelling increased the tensile index of CNF-films by ~ 13%. By molecular modeling of fibril swelling, we found that water sorbed to cellulose exhibits a decreased diffusion constant compared to bulk water. We quantified this change and showed that diffusion of sorbed water displays less dependency on swelling temperature compared to bulk water diffusion. To our knowledge, this has not previously been demonstrated by molecular modeling. The difference between bulk water diffusion (DWW) and diffusion of water sorbed to cellulose (DCC) increased from DWW - DCC ~ 3 × 10-5 cm/s2 at 25 °C to DWW - DCC ~ 8.3 × 10-5 cm/s2 at 100 °C. Moreover, water molecules spent less successive time sorbed to a fibril at higher temperatures.

Influence of Compounding Parameters on the Tensile Properties and Fibre Dispersion of Injection-Moulded Polylactic Acid and Thermomechanical Pulp Fibre Biocomposites.

Thermomechanical pulp (TMP) fibres can serve as renewable, cost-efficient and lightweight reinforcement for thermoplastic polymers such as poly(lactic acid) (PLA). The reinforcing ability of TMP fibres can be reduced due to various factors, e.g., insufficient dispersion of the fibres in the matrix material, fibre shortening under processing and poor surface interaction between fibres and matrix. A two-level factorial design was created and PLA together with TMP fibres and an industrial and recyclable side stream were processed in a twin-screw microcompounder accordingly. From the obtained biocomposites, dogbone specimens were injection-moulded. These specimens were tensile tested, and the compounding parameters statistically evaluated. Additionally, the analysis included the melt flow index (MFI), a dynamic mechanical analysis (DMA), scanning electron microscopy (SEM) and three-dimensional X-ray micro tomography (X-µCT). The assessment provided insight into the microstructure that could affect the mechanical performance of the biocomposites. The temperature turned out to be the major influence factor on tensile strength and elongation, while no significant difference was quantified for the tensile modulus. A temperature of 180 °C, screw speed of 50 rpm and compounding time of 1 min turned out to be the optimal settings.

CO2 in Lyotropic Liquid Crystals: Phase Equilibria Behavior and Rheology.

The CO2 absorption of liquid crystalline phases of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (Pluronic L92, (EO)8(PO)47(EO)8), monoethanolamine (MEA), and water, with a composition of 60% L92/10% MEA/30% water has been investigated to assess potential use in carbon capture and storage applications. Vapor⁻liquid equilibrium data of the liquid crystalline system with CO2 was recorded up to a CO2 partial pressure of 6 bar, where a loading of 38.6 g CO2/kg sample was obtained. Moreover, the phase transitions occurring during the loading process were investigated by small angle X-ray scattering (SAXS), presenting a transition from lamellar + hexagonal phase to hexagonal (at 25 °C). In addition, the rheology of samples with varying loadings was also studied, showing that the viscosity increases with increasing CO2-loading until the phase transition to hexagonal phase is completed. Finally, thermal stability experiments were performed, and revealed that L92 does not contribute to MEA degradation.

CO2 in Lyotropic Liquid Crystals: Monoethanolamine-Facilitated Uptake and Swelling.

Ternary systems consisting of amphiphilic block copolymers/water/monoethanolamine (MEA) have been studied as potential solvents for carbon capture and storage (CCS). The phase behavior of two poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) copolymers with average compositions (EO)8(PO)47(EO)8 (L92) and (EO)3(PO)50(EO)3 (L81) have been investigated by cross-polarized visual observation and small angle X-ray scattering (SAXS). The respective ternary phase diagrams have been studied for systems containing MEA and the equivalent systems containing CO2-loaded MEA. The presence of MEA loaded with CO2 hinders self-association, preventing the formation of liquid crystalline phases. One-phase liquid crystalline regions were found at low MEA concentrations (below 20 wt %) in L92. In the case of L81, only one one-phase region consisting of coexisting lamellar and disordered aggregates was found at 5 wt % MEA. The swelling of the liquid crystalline phases with MEA was investigated along designated dilution lines. The lattice parameters of L92 liquid crystals decrease upon addition of MEA, whereas L81 aggregates show the opposite behavior.