Decomposition of chlorofluorocarbons on TiO2ZrO2

The decomposition of chlorofluorocarbons (CFCs) in the presence of water was examined over a variety of solid acid catalysts. The TiO₂ZrO₂ catalyst was found to have the highest activity and longest life among the catalysts examined. The activity of the TiO₂ZrO₂ catalysts depended upon the content of TiO₂. At the contents of TiO₂ from 58 to 90 mole%, the TiO₂ZrO₂ catalysts exhibited high activity, and these catalysts were proven to contain TiZrO₄ crystal. From the study of the XRD peak intensity of the TiZrO₄ crystal, it was highest on the TZ-58 which contained 58 mole% of TiO₂, and decreased with increasing the content of TiO₂. Furthermore, the conversion of CFC113 measured at 673 K was highest at TZ-58, and decreased gradually with increasing TiO₂ content. Therefore, the TiZrO₄ crystal influences the activity of decomposition of CFC113. However, the TiO₂ZrO₂ catalyst was gradually deactivated during the reaction due to the elimination of titanium atoms. A good relationship was found between the activity on TiO₂ZrO₂ catalyst and bond energy of CCl in the compounds of chlorofluorocarbons and hydrochlorocarbons, suggesting that the rate controlling step was the cleavage of CCl bond.     

Consideration on the Relationship Between Dielectric Breakdown Voltage and Water Content in Fatty Acid Esters

Mineral oil is commonly used as an electrical insulating oil in transformers because of its relatively high electrical insulating ability and fluidity. Considering the depletion of resources and environmental problems, however, fatty acid esters synthesized from natural plant oils are attracting attention as an environmentally friendly insulating oil. In addition, fatty acid esters such as methyl octanoate, methyl dodecanoate, 2-ethylhexyl octanoate, and 2-ethylhexyl dodecanoate have high fluidity, and also show excellent moisture tolerance against dielectric breakdown compared to mineral oil. In the present study, to clarify the reason for the superior moisture tolerance of fatty acid esters, the status of dissolved water in esters is investigated with IR spectroscopic measurements and density functional theory (DFT) calculations. It is revealed that water molecules in fatty acid esters are trapped by the ester moiety of fatty acid esters. As a result, fatty acid esters have a higher moisture tolerance against dielectric breakdown than mineral oil.     

Graded evolution of anisotropic microstructure during sintering from crystal-oriented powder compact

Anisotropic sintering, including shrinkage and grain growth, was examined for c-axis-oriented (Sr,Ca)₂NaNb₅O₁₅ (SCNN) ceramics, which were prepared by colloidal processing under a magnetic field. In the c-axis-oriented SCNN powder compact, shrinkage and grain growth along the c-axis were higher than those along the a-axis. The anisotropic microstructural development was clearly associated with anisotropic sintering shrinkage. X-ray diffraction, scanning electron microscopy, and energy back scattering diffraction showed that the grain growth of oriented particles by including random grains contribute to the development of the oriented microstructure. Finally, the highly crystal-oriented SCNN ceramics with a densified microstructure were obtained through anisotropic sintering. These results clearly showed the potential to develop a well-defined anisotropic microstructure during sintering by designing and controlling the particle packing structure in a powder compact.     

Determination of atomistic deformation of tricalcium silicate paste with high-volume fly ash

We examined the effect of incorporating high-volume fly ash on the atomic arrangement and interatomic deformation behavior of calcium silicate hydrates in tricalcium silicate paste upon exposure to external forces. The interatomic structural changes and strains under compressive load were assessed using synchrotron in situ high-energy X-ray scattering-based atomic pair distribution function analysis. Three different types of strains, which were (a) macroscopic strains from gauges on the surfaces of specimen, (b) strains in a reciprocal space (Bragg peak shift), and (c) strains in real space (PDF peak shift), were compared to each other. All monitored and calculated strains for tricalcium silicate-fly ash (50 wt% fly ash) paste were compared with the counterparts of the pure tricalcium silicate paste. Pair distribution function analysis in the range of r < 10 Å indicated that the atomic arrangement of tricalcium silicate-fly ash was similar to that of synthetic calcium silicate hydrates followed by that of pure tricalcium silicate paste. Moreover, the pair distribution function refinement results revealed that the calcium silicate hydrate structure in tricalcium silicate-fly ash paste was similar to tobermorite 11 Å, unlike that in pure tricalcium silicate paste. The interatomic strain of tricalcium silicate-fly ash in the real space (r < 20 Å) was smaller than that of tricalcium silicate under compression, which suggested that the incompressibility of calcium silicate hydrates at atomistic scale was enhanced by the incorporation of fly ash into it. This was likely to be caused by the increased silicate polymerization of calcium silicate hydrates, which was attributed to the increase in the amount of silicate in their structure via the addition of fly ash.     

Indentation-induced ductile behavior of glass–ceramics involving layered aluminosilicates

Contact damage in materials is critical in engineering applications because it influences mechanical resistance, such as wear, erosion, and impact failure. Indentation tests were performed using a tungsten carbide ball indenter (Hertzian contact) on the surfaces of glass–ceramics containing hexagonal CaAl₂Si₂O₈ or mica crystals (fluorophlogopite), both of which have a layered structure. The stress–strain relation and the permanent deformation on the surface, as well as the observation of the microcrack zone by X-ray computed tomography using synchrotron radiation, revealed that the glass–ceramic with hexagonal CaAl₂Si₂O₈ showed ductility similar to the quasi-plastic behavior previously observed in the mica glass–ceramic. The yield stresses of the glass–ceramics were estimated from the stress deviating from the stress–strain relation assuming complete elastic response between the ball and the sample. The ratio of the yield stress to Young modulus (Y/E) of the glass–ceramic with hexagonal CaAl₂Si₂O₈ was determined to be higher than that of the mica glass–ceramic.     

Residual stress versus microstructural effects on the strength and toughness of phase-separated PbO–B2O3–Al2O3 glasses

A few authors have reasonably proposed that liquid–liquid phase-separated (LLPS) glasses could show improved fracture strength, S_f, and toughness, K_Ic, as the second phase could provide a barrier to crack propagation via deflection, bowing, trapping, or bridging. Due to the associated tensile or compressive residual stresses, the second phase could also act as a toughening or a weakening mechanism. In this work, we investigated five glasses of the PbO–B₂O₃–Al₂O₃ system spanning across the miscibility gap: Four of them undergo LLPS—three are binodal (two B₂O₃-rich and one PbO-rich) and one is spinodal—and one does not show LLPS (composition outside the miscibility gap). Their compositions were designed in such a way that the amorphous particles are under compressive residual stresses in some and under tensile residual stresses in others. The following mechanical properties were determined: the Vickers hardness, ball on three balls (B3B) strength, and toughness, K_Ic-SEVNB (single-edge V-notch beam [SEVNB]). The microstructures and compositions were analyzed using scanning electron microscopy with energy-dispersive X-ray spectrometry. The spinodal glass showed, by far, the best mechanical properties. Its K_Ic-SEVNB = 1.6 ± 0.1 MPa m^1/2, which embodies an increase of almost 50% over the B₂O₃-rich binodal composition, and 90% considering the PbO-rich binodal composition. Moreover, its fracture strength, S_f = 166 ± 7 MPa, is one of the highest ones ever reported for an LLPS glass. Fracture analyses evidenced that the spinodal composition exhibited the lowest net stress at the fracture point. Moreover, calculations indicate that the internal residual stress level is the lowest in the spinodal glass. The overall results indicate that the microstructural effect of the spinodal glass is the most significant factor for its superior mechanical properties. This work corroborates the idea that LLPS provides a feasible and stimulating solution to improve the mechanical properties of glasses.     

Electrochemical conversion of carbon dioxide to methane in aqueous NaHCO3 solution at less than 273 K

The electrochemical reduction of CO₂ on a Cu electrode was investigated in aqueous NaHCO₃ solution, at low temperature. A divided H-type cell was employed, the catholyte was 0.65 mol dm⁻³ NaHCO₃ aqueous solution and the anolyte was 1.1 mol dm⁻³ KHCO₃ aqueous solution. The temperature during the electrolysis of CO₂ was decreased stepwise to 271 K. Methane and formic acid were obtained as the main products. The maximum Faradaic efficiency of methane was 46% at −2.0 V and 271 K. The efficiency of hydrogen formation, a competing reaction of CO₂ reduction, was significantly depressed with decreasing temperature. Based on the results of this work, the proposed electrochemical method appears to be a viable means for removing CO₂ from the atmosphere and converting it into more valuable chemicals. The synthesis of methane by the electrochemical method might be of practical interest for fuel production and the storage of solar energy.     

Conversion of methane to syngas in a solid oxide fuel cell with Ni-SDC anode and LSGM electrolyte

A solid oxide fuel cell constructed from Ni-SDC anode and LSGM electrolyte was applied to the partial oxidation of methane to syngas (CO+H₂) at 700-800 °C with the merits of co-generation of electricity and controllable O₂ supply. It was found that the co-generated syngas at H₂/CO ratio of 1.4-2.0 varied with applied current densities, CH₄ flow rates and operating temperatures. The cell voltage at 100 mA cm⁻² and 800 °C was 0.90 V, i.e. about 90 mW cm⁻² power density could be obtained. The cell operating at 50 mA cm⁻² for 24 h almost showed no degradation of the cell performance. The observed carbon deposition seemed mainly taking place by CH₄ cracking reaction.     

Size dependence of crystallization within spherical microdomain structures

We have investigated the size dependence of crystallization within spherical microdomains formed in various poly(ε-caprolactone)-block-polybutadiene diblock copolymers (PCL-b-PB). The crystallinity (χ) and melting temperature (T_m) of the PCL block are considerably lower than those of PCL homopolymer, and χ decreases steadily and T_m decreases only slightly with decreasing radius of PCL spheres (R) for a series of PCL-b-PB with a same molecular weight (M_n). When PCL-b-PB is compared with the similar R but different M_n, χ is significantly different, suggesting that the sphere size is not the unique factor to control crystallization within spherical microdomains.     

Intrinsic Elastic, Dielectric, and Piezoelectric Losses in Lead Zirconate Titanate Ceramics Determined by an Immittance-Fitting Method

The material coefficients of "soft" and "hard" lead zirconate titanate (PZT) ceramics were determined as complex values by the nonlinear least-squares-fitting of immittance data measured for length-extensional bar resonators. The piezoelectric d -constant should be a complex value to obtain a best fitting between observed and calculated results. Because the elastic, dielectric, and piezoelectric losses determined in this process were not "intrinsic" losses, a calculation process to evaluate the "intrinsic" losses was proposed. It was confirmed that the intrinsic losses were smaller than the corresponding extrinsic losses. The intrinsic piezoelectric loss existed in both soft and hard PZTs; ∼50% of the loss of piezoelectric d -constant was derived from the elastic and dielectric losses. The most notable difference between the soft and hard PZTs was observed in their elastic losses.