LAS glass–ceramic scaffolds by three-dimensional printing

Highly porous (>60% open porosity) glass–ceramic scaffolds with remarkable mechanical properties (compression strength of ～15 MPa) were produced by indirect 3D printing. Precursor glass powders were printed into 3D ordered structures and then heat treated to sinter and develop crystalline phases. The final glass–ceramic contained a β-spodumene solid solution together with a secondary phase of lithium disilicate.The precision of the printed geometry and the density of the struts in the scaffold depended on several processing parameters (e.g. powder size and flowability, layer thickness) and were improved by increasing the binder saturation and drying time. Two types of powders with different particle size distribution (PSD) and flowability were used. Powders with a larger PSD, could be processed within a wider range of printing parameters due to their good flowability; however, the printing precision and the struts density were lower compared to the scaffolds printed using the powder in a smaller average PSD.     

Rheological evaluation of the influence of polymer concentration and molar mass distribution on the formation and performance of asymmetric gas separation membranes prepared by dry phase inversion

Asymmetric gas separation membranes were prepared by the dry-casting technique from PEEKWC, a modified amorphous glassy poly(ether ether ketone). The phase inversion process and membrane performance were correlated to the properties of the polymer and the casting solution (molar mass, polymer concentration, solution rheology and thermodynamics). It was found that a broad molar mass distribution of the polymer in the casting solution is most favourable for the formation of a highly selective membrane with a dense skin and a porous sub-layer. Thus, membranes with an effective skin thickness of less than 1 μm were obtained, exhibiting a maximum O₂/N₂ selectivity of 7.2 and a CO₂/CH₄ selectivity of 39, both significantly higher than in a corresponding thick dense PEEKWC membrane and also comparable to or higher than that of the most commonly used polymers for gas separation membranes. The CO₂ and O₂ permeance were up to 9.5×10⁻³ and 1.8×10⁻³ m³/(m² h bar) (3.5 and 0.67 GPU), respectively.     

Honeycomb supports with high thermal conductivity for gas/solid chemical processes

The scope of this review article is to address the use of novel monolithic catalysts with high thermal conductivity in externally cooled tubular reactors for gas/solid exothermic chemical processes in place of conventional packed beds of catalyst pellets.

After discussing the analysis and the implications of heat conduction in honeycomb monolith structures, we review herein simulation studies and experimental investigations showing that near-isothermal reactor operation can be achieved even under very high thermal loads by adopting specific materials and designs of the honeycomb supports associated with high effective radial thermal conductivities. For such monoliths, the limiting thermal resistance is located at the interface between the monolith and the inner tube wall (“gap resistance”). Recent measurements of the “gap” heat transfer coefficient point to very large values (>400 W/(m² K)), which are controlled both by the tube–monolith clearance at the actual operating conditions and by the thermal conductivity of the process gas.     

The critical role of water in spider silk and its consequence for protein mechanics

Due to its remarkable mechanical and biological properties, there is considerable interest in understanding, and replicating, spider silk's stress-processing mechanisms and structure-function relationships. Here, we investigate the role of water in the nanoscale mechanics of the different regions in the spider silk fibre, and their relative contributions to stress processing. We propose that the inner core region, rich in spidroin II, retains water due to its inherent disorder, thereby providing a mechanism to dissipate energy as it breaks a sacrificial amide-water bond and gains order under strain, forming a stronger amide-amide bond. The spidroin I-rich outer core is more ordered under ambient conditions and is inherently stiffer and stronger, yet does not on its own provide high toughness. The markedly different interactions of the two proteins with water, and their distribution across the fibre, produce a stiffness differential and provide a balance between stiffness, strength and toughness under ambient conditions. Under wet conditions, this balance is destroyed as the stiff outer core material reverts to the behaviour of the inner core.     

Cavitand-Based Coordination Cages: Achievements and Current Challenges

The research results obtained in the self-assembly of cavitand-based coordination cages are presented. Cavitands are ideal multidentate ligands for the creation of coordination cages due to their structural rigidity, concave structure, and great versatility in terms of synthetic modularity. The introduction of the ligand moieties on the resorcinarene building block proceeds at the upper rim of the cavity, to take full advantage of the structural rigidity of the cavitand scaffold. Two different synthetic strategies are employed for the formation of multidentate cavitand ligands: (a) functionalization at the apical positions and (b) introduction of the ligands as bridging units. The key features to control the cage self-assembly process emerging from this overview are the preorganization, for the cavitands, and kinetic versus thermodynamic stability of the resulting complexes, for the connecting metal. The versatility of this class of coordination cages is demonstrated by the formation of their heterotopic and heteronuclear versions, as well as their self-assembly on gold and silicon surfaces. Desymmetrization of the cages is appealing because of the resulting differentiation of the inner cavities in terms of shape and interactivity, while surface self-assembly represents an important opportunity to expand the application range of these objects.     

Electrodeposition of porous Co layers and their conversion to electrocatalysts for methanol oxidation by spontaneous deposition of Pd

Electrocatalysts for methanol oxidation were prepared through a two stage deposition process: porous cobalt layers were deposited, by cathodic reduction of Co²⁺ ions, and then modified by spontaneous deposition of Pd. A basic sulphate solution and a mildly acid chloride solution were compared as media for the electrodeposition of Co. Deposits with the highest surface roughness were obtained in the chloride solution, at large current densities. Pd was deposited onto the Co porous layers by immersing them in acid deaerated PdCl₂ solutions, at open circuit. The Pd loading and the Pd surface area were estimated by UV–visible spectroscopy and by cyclic voltammetry, respectively. The Pd-modified Co electrodes were tested as anodes for methanol oxidation and compared to the similarly prepared Pd-modified Ni electrodes. The former exhibited better stability of performance and higher methanol oxidation peak currents per unit Pd mass, ca. 200 A g⁻¹.     

Visible spectroelectrochemical characterization of Geobacter sulfurreducens biofilms on optically transparent indium tin oxide electrode

We report visible spectroelectrochemical (SEC) characterization of cytochrome c₅₅₂ (cyt c₅₅₂) in viable Geobacter sulfurreducens biofilms on tin-doped indium oxide (ITO) electrodes poised at 0.24 V vs. SHE. G. sulfurreducens biofilms were grown in minimal medium with acetate as electron donor (turnover conditions), followed by 24 h incubation in electron donor-depleted medium (non-turnover conditions). The electronic absorption spectra of G. sulfurreducens biofilms showed the lowest energy absorption band in the reduced state at 552 nm, which indicated excess of cyt c₅₅₂ in the biofilm. The spectra under non-turnover conditions displayed gradual reduction of the cyt c₅₅₂, following the step-wise decrease of electrode potential from 0.0 V to −0.6 V vs. standard calomel electrode (SCE). The spectral changes were fully reversible in both positive and negative direction of the scan potential, with average midpoint potential value of −0.42 V vs. SCE. Confocal microscopy analysis revealed that the thickness of biofilms under turnover conditions and non-turnover conditions was approximately 35 and 3.5 μm, respectively. This is the first study to observe the reversible redox conversion of cyt c₅₅₂ in viable G. sulfurreducens biofilms.     

Application of the Shvo catalyst in homogeneous hydrogenation of bio-oil obtained from pyrolysis of white poplar: New mild upgrading conditions

Upgrading of bio-oils obtained from the fast pyrolysis of biomasses requires the development of efficient catalysts able to work under mild conditions and to cope with the complex chemical nature of the reactant. The present work focuses on the use of the ruthenium based Shvo homogeneous catalyst for the hydrogenation of model mixtures (vanillin, cinnamaldehyde, methylacetophenone, glycolaldehyde, acetol, acetic acid) and of a real bio-oil. The hydrogenation of model compounds has been investigated both in mono- and biphasic mixtures under a P(H₂) = 10 atm in the temperature range of 90-145 °C varying the substrate to catalyst molar ratio from 2000:1 to 200:1. Employing the most active reaction conditions (substrate/catalyst 200:1, T = 145 °C, P(H₂) = 10 atm) the Shvo catalyst maintains its performances under acidic “bio-oil conditions” leading to the almost quantitative conversion of the polar double bonds within 1 h. The activity of the Shvo catalyst was also investigated for the hydrogenation of a bio-oil from poplar in solvent free conditions. Hydrogenation deeply changed the chemical nature of the pyrolysis oil. Aldehydes, ketones and non-aromatic double bonds were almost totally hydrogenated. The catalytic system also promoted the hydrolysis of sugar oligomers into monomers.     

Residual Stresses in Alumina/Zirconia Composites: Effect of Cooling Rate and Grain Size

Alumina/zirconia composites with various compositions at the zirconia-rich part of the phase diagram have been prepared with various grain sizes of the starting alumina powders. After firing under identical conditions, the pellets have been cooled systematically, changing the cooling rates from 0.5 to 8000 K/min. Subsequently, the residual stresses in alumina have been determined by monitoring the frequency shifts of the R ₂ luminescence line of alumina (14 430 cm⁻¹). The data indicate that the stress in alumina is compressive in all cases, with increasing absolute values of the stress with decreasing alumina content. Within the same composition, the residual stress as a function of the cooling rate presents a minimum for values between 10 and 100 K/min, with no clear dependence on the alumina or zirconia grain size. An interpretation of the experimental data in terms of a Coble-type diffusional relaxation applies for intermediate cooling rates (from 10 to 800 K/min), but it fails to account for the large stresses at low cooling rates. The width of the stress distribution is narrow (∼150 MPa) and constant for all compositions and grain sizes at low cooling rates, but it increases for cooling rates >10 K/min, depending on the grain size but not on the composition. For fast cooling rates, a correlation is found when reporting the average width of the stress distribution as function of the average sintered grain-size distribution of alumina. Overall, zirconia grain size seems to influence the average stress, whereas alumina grain size determines the stress distribution.