Rheological measurement of wax-oil gel breakage is highly susceptible to the phenomenon of adhesive breakage, hindering instrument-scale replication of cohesive breakage processes. Adhesive breakage measurements are notoriously irreproducible, due to strongly non-affine gel deformation. Efforts to ensure mechanical fixation give rise to spatially inhomogeneous deformation fields in the measuring geometry, particularly with respect to azimuthal and radial location. In order to elucidate the functional role of mechanically fixating geometries during gel breakage processes, 3 model solutions were prepared containing 5 wt%, 7.5 wt%, and 10 wt% macro-crystalline wax in dodecane. Rheograms were acquired in controlled deformation mode at imposed shear rates in the range of 0.1-1.0 s −1 using a vane or a cone and plate geometry. Yield stress values, nominally ascribed to primary peak height, were established based on 95% confidence intervals. Yielding trends confirm that adhesive breakage is particularly pronounced in high solid-fraction gels. A solid-fraction threshold delineates cohesive breakage in low solidfraction gels from inherent adhesive breakage in high solid-fraction gels. Mechanical fixation in a vane geometry precludes wall slippage, ensuring cohesive breakage; resultant yield stress values follow a modified power-law dependency on total wax content, characterized by a power law exponent of ∼1.25. Nonuniform deformation within the vane geometry confers a modest (artificial) reduction in apparent yield stress value as a consequence of azimuthal integration of the torque signal. Nonuniform deformation also confers a distinct (artificial) broadening of the breakage peak, and is accompanied by the appearance of a new shoulder-peak located at a deformation value of ∼5. Conversely, in the cone and plate geometry, adhesive breakage occurs inherently for high solid-fraction gels, and is manifested by a substantial reduction in measured yield stress, albeit without a concomitant peak broadening. Hence, the practical utility of the cone and plate geometry is limited to low solid-fraction gels that inherently exhibit cohesive breakage behavior. Mechanical fixation afforded by the vane geometry effectively precludes wall slippage, enhancing measurement reproducibility while simultaneously ensuring cohesive breakage of high solid-fraction wax-gels that otherwise rupture in adhesive mode.

Integrated water electrolysis is a core principle of new process configurations for decarbonized heavy industries. Water electrolysis generates H2 and O2 and involves an exchange of thermal energy. In this manuscript, we investigate specific traditional heavy industrial processes that have previously been performed in nitrogen-rich air environments. We show that the individual process streams may be holistically integrated to establish new decarbonized industrial processes. In new process configurations, CO2 capture is facilitated by avoiding inert gases in reactant streams. The primary energy required to drive electrolysis may be obtained from emerging renewable power sources (wind, solar, etc.) which have enjoyed substantial industrial development and cost reductions over the last decade. The new industrial designs uniquely harmonize the intermittency of renewable energy, allowing chemical energy storage. We show that fully integrated electrolysis promotes the viability of decarbonized industrial processes. Specifically, new process designs uniquely exploit intermittent renewable energy for CO2 conversion, enabling thermal integration, H2 and O2 utilization, and sub-process harmonization for economic feasibility. The new designs are increasingly viable for decarbonizing ferric iron reduction, municipal waste incineration, biomass gasification, fermentation, pulp production, biogas upgrading, and calcination, and are an essential step forward in reducing anthropogenic CO2 emissions.

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This review is the first part of a comprehensive review of hydrophobisation of lignocellulosic materials. The purpose of this review has been to compare physical hydrophobisation methods of lignocellulosic materials. We have compared molecular physical adsorption with plasma etching and grafting. Adsorption methods are facile and rely upon the simple mixing or coating of the substrate with the hydrophobing agent. However, none of the surfactant-based methods reviewed here reach contact angles above 90°, making them unsuitable for applications where a high degree of hydrophobisation is required. Nevertheless, surfactant based methods are well suited for compatibilising the lignocellulosic material with a hydrophobic matrix/polymer in cases where only a slight decrease in the hydrophilicity of the lignocellulosic substrate is required. On the other hand, wax- and lignin-based coatings can provide high hydrophobicity to the substrates. Plasma etching requires a more complex set-up but is relatively cheap. By physically etching the surface with or without the deposition of a hydrophobic coating, the material is rendered hydrophobic, reaching contact angles well above 120°. A major drawback of this method is the need for a plasma etching set-up, and some researchers co-deposit fluorine-based layers, which have a negative environmental impact. An alternative is plasma grafting, where single molecules are grafted on, initiated by radicals formed in the plasma. This method also requires a plasma set-up, but the vast majority of hydrophobic species can be grafted on. Examples include fatty acids, silanes and alkanes. Contact angles well above 110° are achieved by this method, and both fluorine and non-toxic species may be used for grafting. Graphical abstract

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