Colored amorphous silica-based powder with TiN nanocrystals precipitated by ammonolysis of Ti–Si–O ternary glass

Coloration of amorphous silica powder containing titania was investigated by nitridation in an ammonia flow. The oxide precursors were obtained by the hydrolysis of a mixture of tetraethyl orthosilicate (TEOS) and tetrabutoxy titanium (TBT). The color changed with the amount of TBT in the mixture, the hydrolysis pH and the ammonolysis temperature. The original white color of the 8 mol% TBT powder hydrolyzed under basic pH conditions changed to pale goldenrod at 700°C, then to dark olive green at 800°C, and further darkened with increasing ammonolysis temperature. A steel-blue color appeared at 900°C for the powder obtained with 3 mol% TBT, and increased in darkness at 1000°C. A similar bluish color was observed for powders obtained by acidic hydrolysis after ammonolysis above 900°C, and this was independent of the amount of titania, although the chroma decreased with increasing firing temperature for the powder with 3 mol% TBT. The ammonolysis powder products were characterized using X-ray diffraction (XRD), electron probe micro analysis (EPMA), transmission electron microscopy-electron energy-loss spectroscopy (TEM-EELS), scanning transmission electron microscopy-high-angle annular dark-field imaging (STEM-HAADF) and Ti–K edge X-ray absorption fine structure (XAFS). The color change was related to both precipitated TiN nanocrystals and residual titanium in the amorphous silica matrix. The TiN exhibited a goldish reflection and also plasmonic absorption from light blue to gray depending on the TiN crystallite size. The plasmonic absorption and resonance of nanocrystalline TiN will be useful similarly to that of gold in nanotechnology for various kinds of energy application.     

γ-radiation effects on metal oxide particles and their wetted surfaces

ABSTRACT

Typical metal oxide corrosion products of structural materials have been irradiated with γ-rays in ultra-pure water to investigate the effect of radiation on the surface oxide and the nature of adsorbed water. Analysis techniques including thermal gravimetric analysis, differential thermal analysis, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray photoelectron spectroscopy before and after γ-irradiation were employed to investigate surface structural effects and adsorbed water behaviour. The production of H₂ in the oxide nanoparticle mixtures was investigated by gas chromatography to probe the mechanism of radiolysis in the water/oxide mixtures and the relationship with surface water. The nature of water at the surface of the oxides was affected by γ-radiation and the relationship was dependent on the particle composition. The rate of H₂ production was shown to be oxide dependent, and higher rates of H₂ formation were attributed to the decomposition of surface adsorbed water. Changes to the surface chemistry and H₂ production rates were found to be highly dependent on the surface chemistry of the metal oxide nanoparticle and no bulk structural changes were observed.     

Effect of Talc Size on Surface Roughness and Glossiness of Polypropylene Injection Molding Application to Automotive Plastics

Talc-containing polypropylene (PP) resin is extensively employed in automobiles. Herein, considering the microstructure transfer process in injection molding, the effect of the talc's dispersibility and particle size on this process and its impact on the gloss level of the product were investigated. Results show that a fine unevenness of about several micrometers was self-formed by the shrinkage of PP in nontransferred areas due to the blending of talc. Additionally, the amount of self-formed unevenness tended with an increase in the average particle size of talc. Furthermore, due to PP shrinkage and different densities of talc, it was observed that a fine tiger-stripe pattern was self-formed using special molds with modified microstructure. This self-formed fine unevenness changes the gloss level owing to the diffused light reflection effect. This study proposes controlling this change by controlling the average particle size of talc and structure of the mold. POLYM. ENG. SCI., 60:132–139, 2020. © 2019 Society of Plastics Engineers     

Effect of addition of corrosion inhibitors on corrosion behaviors of PCV material under diluted artificial seawater environment

ABSTRACT

Fukushima Daiichi nuclear power plants (1F) were damaged by unprecedented severe accident in the great east Japan earthquake, and seawater and freshwater had been injected as an emergency countermeasure for the core cooling. Although, the primary containment vessel (PCV) was not supposed to be exposed to diluted seawater, the PCV will be exposed to diluted seawater environment until fuel debris removal is completed. Therefore, it is necessary to establish a countermeasure of corrosion for the PCVs made of carbon steel. In this study, the effect of the addition of corrosion inhibitor, which is one of the corrosion countermeasures, was investigated by two types of corrosion tests. As a result of the immersion corrosion test, it was found that any of the three kinds of corrosion inhibitor could suppress corrosion of carbon steel. In addition, as a result of the inhibitor interim addition test, it was found that corrosion of carbon steel covered with corrosion products could be suppressed by optimizing the additive amount of corrosion inhibitor in the cooling water.     

Influence of design and operating conditions on the performance of tandem photoelectrochemical reactors

Solar-driven photoelectrochemical water splitting technology is a promising avenue for a sustainable hydrogen production. In this work, a comprehensive 2-dimensional model is developed and numerically simulated with hematite (α-Fe₂O₃) as the principal photoelectrode. The model evaluates light absorption, charge transport and electrochemical reactions to elucidate the effects of light transmitting materials, electrolyte height and electrolyte velocity on hydrogen and oxygen gas production. Results indicated that major losses in photocurrents are attributed to the transparent conducting oxide while losses due to the electrolyte increase with its height. Gas concentrations increase with increasing photocurrent densities and also in the direction of the flow. Gas bubbles however decrease with increasing electrolyte velocity. From these results, light reception in the reactor is uneven and poses a bigger challenge due to the bias in gas bubble distribution. Prospects of upscaling tandem schemes hence not only lie in the semiconductor material combinations but rather in the proper integration of system components and operating conditions.     

Performance enhancement of direct methanol fuel cell using multi‐zone narrow flow fields

New serpentine and spiral flow field configurations were developed to enhance the performance of direct methanol fuel cells (DMFCs). The new configurations are based on two primary concepts, namely, narrowing the flow field and partitioning the total active area of the fuel cell. Three flow channel heights of 0.8, 0.4, and 0.2 mm were investigated in serpentine and spiral flow fields. The main active area is considered a single zone and is partitioned into two‐ and four‐zone designs while maintaining the total inlet mass flow rate of the reactant and oxidant. To determine the performance parameters of the newly proposed designs, a three‐dimensional single‐phase isothermal model was developed, numerically simulated, and validated through experimental measurements. The findings of the current study indicate that a serpentine flow field configuration with a channel height of 0.2 mm and two zones attains an enhancement of the net power density of 37% compared to a conventional single‐zone design with a flow channel height of 0.8 mm. Similarly, for a spiral flow field design, the maximum net power density increased by 26% using a two‐zone configuration with a channel height of 0.2 mm, in comparison to the conventional design of a single‐zone and a flow channel height of 0.8 mm. The newly developed designs utilize the lower height of the flow fields to decrease the dimensions of the fuel cell stacks and reduce the material costs required.     

Aerobic Exercise Ameliorates Cancer Cachexia-Induced Muscle Wasting through Adiponectin Signaling

Cachexia is a multifactorial syndrome characterized by muscle loss that cannot be reversed by conventional nutritional support. To uncover the molecular basis underlying the onset of cancer cachectic muscle wasting and establish an effective intervention against muscle loss, we used a cancer cachectic mouse model and examined the effects of aerobic exercise. Aerobic exercise successfully suppressed muscle atrophy and activated adiponectin signaling. Next, a cellular model for cancer cachectic muscle atrophy using C2C12 myotubes was prepared by treating myotubes with a conditioned medium from a culture of colon-26 cancer cells. Treatment of the atrophic myotubes with recombinant adiponectin was protective against the thinning of cells through the increased production of p-mTOR and suppression of LC3-II. Altogether, these findings suggest that the activation of adiponectin signaling could be part of the molecular mechanisms by which aerobic exercise ameliorates cancer cachexia-induced muscle wasting.     

Small-angle X-ray scattering studies on melting and recrystallization behaviors of poly(oxyethylene) crystallites in poly(d,l-lactide)/poly(oxyethylene) blends

Direct determination of the discrete distribution for crystalline lamellar thickness has been performed for poly(d,l-lactic acid)/poly(oxyethylene) (PDLLA/PEG) blends by conducting small-angle X-ray scattering (SAXS) measurements using synchrotron radiation. The PDLLA used was an random (racemic) copolymer of bio-based poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) with the lactide monomer ratio of l:d = 50:50. It is known that PLA is miscible with PEG in the amorphous state. In the current paper, we report comprehensive results on structural analyses of PDLLA/PEG blends in the course of heating and cooling process using SAXS to elucidate the change in the thickness distribution of the lamellae. As a consequence, it was found that the distribution of the lamellar thickness moves toward the larger value (in other words, lamellar thickening) as temperature approaches the melting point. Typically, the thickness distribution was dispersed in the range of 10–20 nm at room temperature and it changed toward 40 nm in the vicinity of the melting temperature. To the best of our knowledge, this is the first report of direct determination of the discrete distribution for the crystalline lamellar thickness and their in-situ changes in the course of the lamellar thickening process. As a result, the lamellar thickening was found to occur at much lower temperature for the blend samples with 10% and 20% of PDLLA contents as compared to the PEG 100% sample. This phenomenon can be ascribed to the melting point depression owing to the miscibility between PEG and PDLLA. Thereby, thinner lamellae were melted and thicker ones appeared at much lower temperature for the blends than for the PEG 100% sample. As for the average repeating distance (long period) of the lamellar stacks, an abrupt increase similar to the critical divergence was observed (from 25 nm to 50 nm) in the heating process. Not only for the melting behavior but also in the course of recrystallization, change in the lamellar-thickness distribution was uncovered, which shows strong hysteresis depending on what temperature the sample was cooled down from.     

Perpendicular oriented cylinders via directional coalescence of spheres embedded in block copolymer films induced by solvent annealing

Polystyrene-b-poly(methyl acrylate) (PS-b-PMA) block copolymer with PS volume fraction of 25.2 vol% was synthesized by atom transfer radical polymerization. Non-pretreated silicon wafers were used as the substrates to prepare perpendicular oriented PS cylinders in PMA matrix via solvent annealing which could induce the transformation of spheres to vertically oriented and hexagonally packed cylinders. The spherical microdomains were formed after the evaporation of solvents from the solutions of the block copolymer in selective solvents mixed from methanol, acetone and dichloromethane. The thickness of films could be as thick as 1000 nm, which were much thicker than usual cases and the cylinders came from the directional coalescence of the spheres, thus any pre-treatments of the substrates were not required for perpendicular orientation. The structures were characterized by small angle X-ray scattering (SAXS), transmission electron microscope (TEM), atom force microscopy (AFM) and grazing incidence small angle X-ray scattering (GISAXS).     

Additive Sintering,Postannealing, and Dielectric Properties of SrTaO2N

The maintaining of the chemical composition and electrical insulativity of SrTaO₂N ceramics was investigated during sintering and annealing, using powders prepared by the nitridation of Sr₂Ta₂O₇. Due to the low thermal stability of SrTaO₂N, the partial loss of SrO and nitrogen induced the formation of a TaO_0.9 impurity after heat‐treating at above 1100°C. The sintering additive SrCO₃ and postannealing in NH₃ were employed to compensate for the loss of SrO and nitrogen to obtain ceramics with the original chemical composition. The as‐sintered SrTaO₂N ceramics with various relative density (RD) were annealed in NH₃ to observe the recovery of color and electrical insulativity. It was found that the inner part of the well‐sintered samples with RD = 95.1% could not be recovered by annealing, and continued to exhibit semiconducting behavior and a black color. On the other hand, for the as‐sintered SrTaO₂N ceramics with RD < 84%, both the nitrogen content and electrically insulating behavior were completely recovered after annealing. The postannealed SrTaO₂N ceramics (RD = 83.3%) possessed a relatively large dielectric constant of 450 with a low dielectric loss of less than 0.1 at 100 Hz, almost independent of frequency and temperature.