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.     

Blends of polyamide 6 with bisphenol-A polycarbonate. I. Thermal properties and compatibility aspects

Blends of polyamide 6 (PA6) and polycarbonate (PC) have been investigated, over a full range of composition, to check interactions between them. SEM observations show that the mixtures are characterized by domains of clearly segregated homophases and voids between the two polymers. DSC and DMTA data indicate the presence of two T_g' s, corresponding to two separate phases, with the T_g of the PC phase decreasing on increasing the PA6 amount. Moreover, the crystallization kinetics of PA6 is slightly showed down by the PC. Chemical reactions between the two polymers are supposed to give rise to low molar mass compounds, as shown by GPC; these species plasticize the PC and partially dissolve into the molten polyamide, causing decrease of PC T_g and reduction of overall crystallization rate of PA6. Apparent influence of PC on melting temperature and enthalpy of PA6 is also discussed.     

An experimental investigation of Fischer–Tropsch synthesis over washcoated metallic structured supports

In principle, the application of monolithic catalysts to the Fischer–Tropsch synthesis can solve many of the problems related to the classical Fischer–Tropsch reactors, in particular concerning the necessity to operate with short diffusion distances and low pressure drops, preferably according to the ideal plug-flow behavior, while still maintaining a reasonable inventory of catalytic material in the reactor volume.The preparation of prototype cobalt-based catalysts, washcoated onto metallic structured supports with different geometries, is described herein, together with the evaluation of the catalytic properties of such systems in the Fischer–Tropsch synthesis at industrially relevant process conditions (220–235 °C, 20 bar, 2.1  mol_H2/mol_CO,  5000 cm³(STP)_CO+H2/h/g_cat). Comparative tests with the same catalyst in the powdered form were also carried out at the same process conditions.It was found that the structured catalysts maintained the activity and the selectivity of the original powdered catalyst, provided that the washcoat thickness is sufficiently thin.     

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.     

Crystalline Nanorods as Possible Templates for the Synthesis of Amorphous Biosilica during Spicule Formation in Demospongiae

In tandem : High‐resolution TEM shows that during the initial stages of demosponge spicule formation, a primordial crystalline structure is formed within the axial filament. The recently developed electron diffraction tomography technique (ADT) reveals that the nanorods have a layered structure that matches smectitic phyllosilicates. These intracellular nanorods have been considered as precursors of mature spicules.

     

Design of Electroceramics for Solid Oxides Fuel Cell Applications: Playing with Ceria

Nanostructured samaria- and gadolinia-doped ceria (SDC and GDC) powders were synthesized at low temperature (400°C) using diamine-assisted direct coprecipitation method. Fast-firing (f.f.) processes, where sintering temperatures are reached in a short time to promote lattice diffusion, were compared with conventional sintering, for the formation of dense microstructures from the nanostructured powders. Highly dense SDC and GDC samples (96%) with reduced grain size (150 nm) were obtained by f.f. even at 1300°–1400°C and, unexpectedly, high electrical conductivity and low blocking effect at grain boundary was obtained. Conventionally sintered samples showed that the grain boundary resistivity decreased with increasing the grain size, in agreement with the increase in geometrical bulk volume/grain boundary area ratio. Conversely, f.f. samples showed grain boundary resistivity smaller for small grain size. The above effect was observed only for high dopant (>10% molar) contents. The combined effect of powder grain size, dopant content, and sintering temperature–time profile, can be exploited to tune ceria microstructures for specific ionic device applications.     

Effect of stress state on the high temperature workability of AZ31 Mg alloy

The influence of stress state on the high temperature workability of rolled AZ31 Mg alloy was investigated on the basis of a processing map. To construct the processing map, high temperature compression tests were carried out on samples oriented parallel to the rolling direction at various temperatures (25 °C∼450 °C) and strain rates (10⁻³ s⁻¹∼5s⁻¹), and then the results were compared with those of a torsion test. The overall efficiency profiles of both the compression and torsion processing maps were similar to each other, but the index of dissipation efficiency in the torsion was somewhat lower than that in the compression. The microstructure of the compressed specimens revealed much finer grained structure than that of the torsion specimens. Such microstructural differences were attributed to the different tendencies of twin formation and texture evolution depending on the stress state.     

Cold sintering of diatomaceous earth

Diatomite, a natural silicate-based sedimentary rock, was densified by cold sintering at room temperature and 150°C under various pressures (100, 200, and 300 MPa) and using different NaOH water solutions (0–3 M). The relative density of cold sintered diatomite can be as high as 90%, a condition that can be achieved by conventional firing only at 1200–1300°C. The cold sintered materials maintain the same mineralogical composition of the starting powder (quartz, glass, and illite) and are constituted by well-deformed and flattened grains oriented orthogonally to the applied pressure. Conversely, an evident phase evolution takes place upon conventional firing with the formation of cristobalite and mullite. The bending strength of cold sintered artifacts can exceed 40 MPa and increases to ≈80 MPa after post-annealing at 800°C, such mechanical strength is much larger than that of conventionally pressed samples sintered at 800°C, which is only ≈1 MPa.     

A spectro-microscopic investigation of Fe-Co bimetallic catalysts supported on MgO for the production of thin carbon nanotubes

Fe-Co bimetallic catalysts supported on MgO were studied for the catalytic chemical vapor deposition growth of carbon nanotubes (CNTs). Different wt.% metal loadings were investigated at various deposition temperatures and times. Characterization of the products involved thermal analysis (DTA-TGA), X-ray diffraction, spectroscopy (Raman, UPS, EELS and STS) and microscopy (SEM, TEM and STM) techniques. It was found that the metal content is critical, not only to the yield and the structural quality of the synthesized carbon nanotubes, but it can be also used to tune the desired type of synthesized nanotubes. Lower (2 wt.%) loadings of Fe-Co catalysts favor the formation of single- and/or double-wall CNTs for deposition time and temperature 30 min and 800 °C, respectively. Thermal analysis and Raman measurements showed that these thin CNTs were synthesized at high amounts (CNT-per-catalyst wt.% of more than 100%), exhibiting high graphitization degree with only traces of by-products (mainly amorphous carbon) among them. Microscopy results revealed the formation of CNTs bundles, consisting of individual nanotubes with less than 2 nm outer diameter, while additional energy loss measurements pointed out that the deposited CNTs are mainly single wall. Higher (10 wt.%) Fe-Co loadings resulted to the formation of multi-wall CNTs.     

An exergetic analysis of a membrane desalination system

In this paper, the exergetic analysis of a seawater membrane-based desalination plant has been carried out. The desalination plant has been described in detail, then the exergy of the various saline water streams has been determined and a comprehensive analysis towards the exergy distribution of the major process components has been conducted. The examination of the exergy losses throughout the plant revealed that exergy destruction was mainly due to pressure drops in the membrane modules, valves and brine lines. Moreover, 12.9% of the exergy input to the system was supplied by the heater. Therefore, the most reasonable way to reduce power input to the plant, thus improving its performance and cost, has been shown (i) to be replacing the valves on the reverse osmosis brine stream by an energy recovery system, and (ii) to have thermal energy available in the plant. With the identified technical changes, energy consumption decreased from 18.3 to 2.05 kWh/m³, resulting in an annual saving of 0.17$/m³.