Charge transport in CaTiO3: I. Electrical conductivity

The present paper reports the electrical conductivity of polycrystalline undoped CaTiO₃ in the temperature range 973–1323 K under controlled oxygen partial pressure (10–10⁵ Pa). The electrical conductivity data are considered in terms of defect disorder and related semiconducting properties of CaTiO₃. The values of the p(O₂) exponent of electrical conductivity at high p(O₂), that vary between 1/4.3 and 1/6.2 at 973 and 1323 K, respectively, are considered in terms of theoretical defect disorder model of p-type CaTiO₃ and increasing effect of minority charge carriers (electrons) with temperature on p-type conduction. The activation energy of the electrical conductivity, assuming 125.3 kJ/mol at 10 Pa and 94.4 kJ/mol at 72 kPa, has been considered in terms of the formation of defect and their mobility. The band gap, determined from the minimum of electrical conductivity corresponding to the n–p transition is equal to 2.77 eV.     

Manipulation of Charge Transport by Metallic V13O16 Decorated on Bismuth Vanadate Photoelectrochemical Catalyst

Conductive metal oxides represent a new category of functional material with vital importance for many modern applications. The present work introduces a new conductive metal oxide V₁₃O₁₆, which is synthesized via a simplified photoelectrochemical procedure and decorated onto the semiconducting photocatalyst BiVO₄ in controlled mass percentages ranging from 25% to 37%. Owing to its excellent conductivity and good compatibility with oxide materials, the metallic V₁₃O₁₆‐decorated BiVO₄ hybrid catalyst shows a high photocurrent density of 2.2 ± 0.2 mA cm^?2 at 1.23 V versus reversible hydrogen electrode (RHE). Both experimental characterization and density functional theory calculations indicate that the superior photocurrent derives from enhanced charge separation and transfer, resulting from ohmic contact at the interface of mixed phases and superior electrical conductivity from V₁₃O₁₆. A Co–Pi coating on BiVO₄–V₁₃O₁₆ further increases the photocurrent to 5.0 ± 0.5 mA cm^?2 at 1.23 V versus RHE, which is among the highest reported for BiVO₄‐based photoelectrodes. Surface photovoltage and transient photocurrent measurements suggest a charge‐transfer model in which photocurrents are enhanced by improved surface passivation, although the barrier at the Co–Pi/electrolyte interface limits the charge transfer.     

Interfacial Reactions Between Anorthite (CaAl2Si2O8) and Al 7075 Alloy at 850°C and 1150°C

The present work reports an investigation of the interactions of Al 7075 alloy and anorthite at 850°C (150 h) and 1150°C (24 h). Transmission electron microscopy, electron probe microanalysis, X‐ray diffraction, and scanning electron microscopy coupled with energy‐dispersive spectroscopy were used to identify the mineralogical and microstructural changes at the metal–ceramic interface. At 850°C, the phase formation mechanisms were (a) Si⁴⁺–Al³⁺ interdiffusion between the Al alloy and anorthite to form calcium dialuminate (CA₂) and Ca²⁺–Mg²⁺ interdiffusion between the Al alloy and calcium dialuminate to form spinel. At 1150°C, spinel + Al₂O₃ and calcium hexaluminate (CA₆) + CA₂ were the major and minor phase mixtures, respectively in the corroded area. A thin layer of calcium monoaluminate (CA), gehlenite, and Si was present in the immediate vicinity of anorthite. The early stages of corrosion at 1150°C and 850°C were identical. However, due to thickening of the corroded region (viz., spinel formation) and enhanced evaporation of Mg at the higher temperature, the interdiffusion path evolves from Si⁴⁺–Al³⁺ + Ca²⁺–Mg²⁺ to Si⁴⁺–Al³⁺ + Ca²⁺–Al³⁺, thus establishing the following phase evolution path at the interface:      

General model for comparative tensile mechanical properties of composites fabricated from fly ash and virgin/recycled high‐density polyethylene

The present work on the mechanical properties of ≤10 wt% fly ash additions in 2.5 wt% increments to recycled high‐density polyethylene (RHDPE) synthesizes experimental data from three similar published reports. The present work shows, as a function of increasing fly ash addition level, maxima at the initial fly ash addition level of 2.5 wt% for the tensile elastic modulus (+25%) and tensile strength (+10%); a slight general increase in the yield stress (+6%); and significant general decreases in the yield strain (?61%), elongation at break (?92%), and Charpy impact strength (?55%). Combining these data with data for higher‐level additions of fly ash (≤40 wt%/23 vol%) and cenospheres (≤39 vol%) to HDPE or RHDPE provides the basis for design parameters and a generalized model for the interpretation of failure of composites of hard brittle spherical dispersant additions in ductile polymeric matrices. The relevant load‐extension plots are characterized by three behavioral regions: ductile deformation (dispersion strengthening and stress concentration), crazing (debonding and cavitation), and brittle failure (fibril failure). The locations of these regions and their transitions are a function of five dependent variables: dispersant volume, dispersant particle size, intrinsic flaw size (viz., dispersant size), generated flaw size (viz., void size), and interfacial bond strength and associated load transfer. POLYM. ENG. SCI., 56:1096–1108, 2016. © 2016 Society of Plastics Engineers     

Suppression of Liquid Film Migration and Improvement of Dielectric Properties in Niobium-Doped Strontium Titanate

In an attempt to improve the dielectric properties of SrTiO₃-based boundary-layer capacitors (BLCs), the effects of infiltrant composition on the liquid film migration and dielectric properties in 0.2-mol%-Nb₂O₅-doped SrTiO₃ were investigated. Powder compacts were sintered at 1480°C for 5 h in 5H₂·95N₂ and infiltrated with 80Bi₂O₃·20( x CaO–(1 – x )BaO) at 1300°C for various times in air. When the value of x was 0, 0.2, 0.7, and 1.0, liquid film migration occurred, which formed a new solid-solution layer containing solute species. On the other hand, when x = 0.5, no liquid film migration was observed. The effective dielectric constant was the highest in the sample with x = 0.5 (no liquid film migration), and it decreased as the migration distance increased. In addition, the loss tangent was the lowest, <1%, in the sample with x = 0.5. Agreement between the estimated effective dielectric constants and the measured values showed that the suppression of liquid film migration improved the dielectric constant. The agreement further indicated that the prediction of the dielectric constant in SrTiO₃-based BLCs was possible using a two-layer model with a liquid-infiltrated layer and a SrTiO₃-based oxidized layer.     

Alignment of YBa2Cu3O7-x and Ag─YBa2Cu3O7-x Composites at ∼930°C by Eutectic Formation

The present work describes a new technique to synthesize aligned YBa₂Cu₃O_{7- x} and Ag─YBa₂Cu₃O_{7- x} superconducting composites from Ba- and Cu-deficient compositions (relative to YBa₂Cu₃O_{7- x} ) plus BaCuO₂. For YBa₂Cu₃O_{7- x} , high transition temperature midpoint T_c (91 K), temperature of zero resistivity T ₀ (90 K), and critical current density J_c (>3000 A°Cm⁻² at 77 K) were achieved by using this technique. This procedure provides the potential for using a reliable and reproducible densification and alignment technique alternative to partial or full melting. The composite is highly aligned, with an average grain size of ∼1 to 2 mm and domains of width greater than 5 mm. The initial phase assemblage consists of YBa₂Cu₃O_{7- x} (123) as the major phase plus YBa₂CuO₅ (211) CuO as minor phases. The BaCuO₂ is added to the Ba- and Cu-deficient starting composition in order to assist in the formation of a CuO-rich liquid as well as to compensate for the Ba and Cu deficiences in 123. Since the liquid forms at ∼900°C and is compatible with 123, it can be used to facilitate alignment of 123 at ∼930°C. The addition of Ag to the system results in eutectic formation with the (solidified) liquid, substantial filling of the pores during sintering, and improved alignment.     

Chemical diffusion of (La,Sr)CoO3 and (La,Sr)FeO3

The present work reports equilibration kinetics for (La_0.8,Sr_0.2)CoO₃(LSC) and (La_0.72,Sr_0.18)FeO₃(LSF) in the temperature range 876–1114 K using a gravimetric method. Chemical diffusion determined in this way that depends on oxygen partial pressure, can be expressed by the following temperature dependence at low and high O₂), respectively, for LSC:

Fabrication and photocatalytic performance of Sn-doped titania hollow spheres using polystyrene as template

Sn-doped anatase hollow spheres were fabricated using a template method involving polystyrene spheres as core and anatase coating as shell. The synthesis route included the preparation of PS spheres, followed by their coating by Sn-doped TiO₂ sol-gel precursor and subsequent removal of the PS cores by pyrolysis and recrystallization at 500 °C for 2 h. The observation of minor amounts of rutile suggests that Sn promotes the anatase → rutile phase transformation. At doping levels of ≤ 1.0 mol% Sn, the unsaturated solubility and increasing defect densities enhanced nucleation. At 1.0–2.0 mol% Sn, the solubility remained unsaturated but increasing Sn incorporation reduced crystallinity owing to lattice deformation and partial amorphization. At 2.0–3.0 mol% Sn, solid solution saturation occurred, resulting in excess dopant precipitation, leading to grain boundary pinning and partial blockage of surface-active sites. Ionic radii, thermodynamic, phase equilibria, intervalence charge transfer, and defect chemistry considerations suggest that Sn⁴⁺ exhibits substitutional solid solubility in the TiO₂ lattice. The photocatalytic performance was in the order 1.0 > 1.2 > 1.5 ≈ 0.7 > 2.0 > 0.0 > 3.0 mol% Sn. This ranking is consistent with the dominant role of crystallinity such that, at ≤ 1.0 mol% Sn, the performance increased owing to enhanced nucleation from low defect density and increasing crystallinity while, at 1.0–2.0 mol% Sn, the performance decreased from increased lattice strain and effective partial amorphization, and, at 2.0–3.0 mol% Sn, it decreased from maximal lattice strain and blockage of active sites.     

Thermodynamic and microstructural analyses of photocatalytic TiO2 from the anodization of biomedical-grade Ti6Al4V in phosphoric acid or sulfuric acid

TiO₂ coatings were fabricated by anodization of Ti6Al4V in 1 M H₃PO₄ or H₂SO₄, at room temperature at 120 V for 10 min, and followed by annealing at 300° or 500 °C for 8 h. Analyses include mineralogy (GAXRD, Raman), chemistry (XPS), morphology and microstructure (FESEM, FIB, 3D confocal microscopy), thermodynamic, optical (UV–Vis), and photocatalytic performance (MB degradation). The present work highlights factors that govern the nature of the materials and their performance. The influence of the oxidation strength of the acid is pervasive in that it impacts on the crystallinity, microstructural homogeneity, coating thickness, Ti³⁺ concentration, gas generation during arcing to form pores, and resultant pore size and distribution density. A key observation is that the pores form a subsurface network of variable continuity, which has a significant impact on the surface area and associated density of photocatalytically active sites, access by liquids and gases inside the coating, penetration depth of incident radiation, gas condensation, and residual liquid trapping. These data and the related thermodynamic analyses of the acids, anodization processes, and oxidation processes facilitate the generation of schematic models for the anodization mechanisms and the resultant surface, bulk, and microstructural effects that dominate the photocatalytic performance.