Effect of an abrupt change in pulling rate on microstructures of directionally solidified Al2O3-Er3Al5O12 eutectic and off-eutectic composite ceramics

Directionally solidified microstructures of Al₂O₃-Er₃Al₅O₁₂ eutectic and off-eutectic in situ composite ceramics were explored under abrupt-change pulling rate conditions. Corresponding temperature distributions and interface locations were studied. In eutectic composition, fluctuation of eutectic spacing occurred when the pulling rate increased abruptly. A gradually increase or abrupt increase in eutectic spacing was observed when the pulling rate decreased abruptly. In hypoeutectic and hypereutectic compositions, formation of the primary phases were suppressed when the pulling rate increased abruptly from 10?µm/s to 100?µm/s, while primary phases precipitated when the pulling rate decreased abruptly from 100?µm/s to 10?µm/s. The interface altitude decreased after the pulling rate increased abruptly, but increased after the pulling rate decreased abruptly. The liquid composition restriction (around the eutectic composition) at the eutectic interface plays an important role in the suppression of the primary dendrite and coupled eutectic oxides can be obtained in off-eutectic compositions even under higher solidification rate conditions.     

Formation of Chlorotriophenoxy Radicals from Complete Series Reactions of Chlorotriophenols with H and OH Radicals

The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600–1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH.     

Potential for rice straw ethanol production in the Mekong Delta,Vietnam

This study is to evaluate the potential for development of a cellulosic ethanol facility in Vietnam. Rice straw is abundant in Vietnam and highly concentrated in the Mekong Delta, where about 26 Mt year⁻¹ of rice straw has been yearly produced. To minimize the overall production cost (PC) of ethanol from rice straw, it is crucial to choose the optimal facility size. The delivered cost of rice straw varied from 20.5 to 65.4 $ dry t⁻¹ depending on transportation distance. The Mekong Delta has much lower rice straw prices compared with other regions in Vietnam because of high density and quantity of rice straw supply. Thus, this region has been considered as the most suitable location for deploying ethanol production in Vietnam. The optimal plant size of ethanol production in the region was estimated up to 200 ML year⁻¹. The improvement in solid concentration of material in the hydrothermal pre-treatment step and using residues for power generation could substantially reduce the PC in Vietnam, where energy costs account for the second largest contribution to the PC, following only enzyme costs. The potential for building larger ethanol plants with low rice straw costs can reduce ethanol production costs in Vietnam. The current estimated production cost for an optimal plant size of 200 ML year⁻¹ was 1.19 $ L⁻¹. For the future scenario, considering improvements in pre-treatment, enzyme hydrolysis steps, specific enzyme activity, and applying residues for energy generation, the ethanol production cost could reduce to 0.45 $ L⁻¹ for a plant size of 200 ML year⁻¹ in Vietnam. These data indicated that the cost-competitiveness of ethanol production could be realized in Vietnam with future improvements in production technologies.     

Grain size influence on the flexibility and luminous intensity of inorganic CaTiO3:Pr3+ crystal nanofibers

Traditional inorganic materials exhibit rigidity owing to the lack of polymer chains in polymer materials or atom slipping in metals. However, nanometerization has been recently proposed for the conversion of inorganic oxide materials into flexible materials. Herein, the flexible inorganic luminescent material, CaTiO₃:0.2%Pr³⁺, was synthesized through electrospinning, and the macroscopic flexibility of pure inorganic CaTiO₃:0.2%Pr³⁺ was achieved. The flexible membrane was characterized via X-ray diffraction, thermogravimetry, scanning electron microscopy (SEM), and photoluminescence analyses. The grain size was analyzed at various calcination temperatures via SEM, and the results suggested that the increase in the calcination temperature resulted in the growth of crystal grains. Studies have reported that the growth of crystal grains is beneficial for improving the luminescence performance; however, to obtain better flexibility, smaller crystal grains are required. This study provides an important reference for the design of flexible inorganic materials.     

An approach to measure infill matric suction of irregular infilled rock joints under constant normal stiffness shearing

Rock joints infilled with sediments can strongly influence the strength of rock mass. As infilled joints often exist under unsaturated condition, this study investigated the influence of matric suction of infill on the overall joint shear strength. A novel technique that allows direct measurement of matric suction of infill using high capacity tensiometers (HCTs) during direct shear of infilled joints under constant normal stiffness (CNS) is described. The CNS apparatus was modified to accommodate the HCT and the procedure is explained in detail. Joint specimens were simulated by gypsum plaster using three-dimensional (3D) printed surface moulds, and filled with kaolin and sand mixture prepared at different water contents. Shear behaviours of both planar infilled joints and rough joints having joint roughness coefficients (JRCs) of 8–10 and 18–20 with the ratios of infill thickness to asperity height (t/a) equal to 0.5 were investigated. Matric suction shows predominantly unimodal behaviour during shearing of both planar and rough joints, which is closely associated with the variation of unloading rate and volumetric changes of the infill material. As expected, two-peak behaviour was observed for the rough joints and both peaks increased with the increase of infill matric suction. The results suggest that the contribution of matric suction of infill on the joint peak normalised shear stress is relatively independent of the joint roughness.     

Effects of SiC content on the densification,microstructure, and mechanical properties of HfB2–SiC composites

To investigate the effects of SiC on microstructure, hardness, and fracture toughness, 0, 10, 20, and 30 vol% SiC were added to HfB₂ and sintered by SPS. Upon adding SiC to 30 vol%, relative density increased about 4%; but HfB₂ grain growth had a minimum at 20 vol% SiC. This may be due to grain boundary silicate glass, responsible for surface oxide wash out, enriched in SiO₂ with higher fraction of SiC. By SiO₂ enrichment, the glass viscosity increased and higher HfO₂ remained unsolved which subsequently lead to higher grain growth. Hardness has increased from about 13 to 15 GPa by SiC introduction with no sensible variation with SiC increase. Residual stress measurements by Rietveld method indicated high levels of tensile residual stresses in the HfB₂ Matrix. Despite the peak residual stress value at 20 vol% SiC, fracture toughness of this sample was the highest (6.43 MPa m^0.5) which implied that fracture toughness is mainly a grain size function. Tracking crack trajectory showed a mainly trans-granular fracture, but grain boundaries imposed a partial deflection on the crack pathway. SiC had a higher percentage in fracture surface images than the cross-section which implied a weak crack deflection.     

Effect of in-situ formation of columnar mullite and pore structure refinement on high temperature properties of corundum casatbles

The effects of in-situ synthesis columnar mullite and pore structure on the hot modulus of rupture (HMOR), thermal shock resistance and corrosion resistance of corundum castables have been investigated in this paper. When 2% nano silica was added, the pore diameters of castables could be decreased to 15 nm (at 110 °C), 1 μm (1100 °C) and 6 μm (1500 °C), respectively. The corresponding reducing magnitude of pore size is 98.5%, 83.3% and 33.3%. The HMOR of castables fired at 1500 °C increased by 110% to 3.64 MPa. Furthermore, after three thermal shock cycles, the residual strength ratio of castables increased from 5.2% to 15.3%. A large amount of cross-distributed columnar mullite was formed between nano silica and α-Al₂O₃ by the two-dimensional nucleation mechanism, which remarkably enhanced the high temperature properties. The penetration index reduced from 30.86% to 19.88%, suggesting that smaller pore size and higher viscosity had a great influence to the penetration process.     

Tribological behaviour of a 3Y-TZP/Ta ceramic-metal biocomposite against ultrahigh molecular weight polyethylene (UHMWPE)

This study aims to evaluate the tribological behaviour of 3Y-TZP/Ta (20 vol%) ceramic-metal composites and 3Y-TZP monolithic ceramic prepared by spark plasma sintering (SPS) against ultrahigh molecular weight polyethylene (UHMWPE). According to the results of pin (UHMWPE)-on-flat wear test under dry conditions, the UHMWPE – 3Y-TZP/Ta system exhibited lower volume loss and friction coefficient than the UHMWPE – monolithic ceramic combination due to the presence of an autolubricating layer that provides sufficient lubrication for reducing the friction. Owing to the lubrication of the liquid media, under wet conditions obtained using simulated body fluid (SBF), similar behaviour is observed in both cases. Additionally, the ceramic and biocomposite materials were subjected to a low temperature degradation (LTD) process (often referred to as “ageing”) to evaluate the changes in the tribological behaviour after this treatment. In this particular case, the wear properties of the UHMWPE-biocomposite system were found to be less influenced by ageing in contrast to the case of the UHMWPE-zirconia monolithic material. In addition to their exceptional mechanical performance, 3Y-TZP/Ta composites also showed high resistance to low temperature degradation and good tribological properties, making them promising candidates for biomedical applications, especially for orthopaedic implants.     

Group sequential crossover trial designs with strong control of the familywise error rate

Crossover designs are an extremely useful tool to investigators, and group sequential methods have proven highly proficient at improving the efficiency of parallel group trials. Yet, group sequential methods and crossover designs have rarely been paired together. One possible explanation for this could be the absence of a formal proof of how to strongly control the familywise error rate in the case when multiple comparisons will be made. Here, we provide this proof, valid for any number of initial experimental treatments and any number of stages, when results are analyzed using a linear mixed model. We then establish formulae for the expected sample size and expected number of observations of such a trial, given any choice of stopping boundaries. Finally, utilizing the four-treatment, four-period TOMADO trial as an example, we demonstrate that group sequential methods in this setting could have reduced the trials expected number of observations under the global null hypothesis by over 33%.