Disorders and oxygen vacancies in p-type Sn2B2O7 (B = Nb,Ta): Role of the B-site element

Sn₂Nb_2−xTa_xO₇ (x = 0.0–2.0) with pyrochlore structure is a promising material for p-type oxide semiconductors. A systematic study of its Nb/Ta ratio indicated that the hole–generation efficiency of the Nb end (Sn₂Nb₂O₇) was an order of magnitude lower than that of the Ta end (Sn₂Ta₂O₇). Although this occurs due to differences in oxygen-vacancy formation, the origins of the hole–generation efficiencies remain unclear due to limited information on local and global crystal-structure disorders in pyrochlore Sn₂Nb₂O₇ and Sn₂Ta₂O₇. In this study, the crystal structures of Sn₂B₂O₇ (B = Nb, Ta), composed of BO₆ octahedra and Sn₄O tetrahedra, were investigated using X-ray absorption spectroscopy and X-ray diffraction. A detailed investigation of the local and global crystal structures indicated a larger amount of disorder in the Sn₄O tetrahedra in Sn₂Nb₂O₇ compared to Sn₂Ta₂O₇; disorder in the BO₆ octahedra occurred only in Sn₂Ta₂O₇. This study indicates that an appropriate selection of the B-site element is vital for suppressing defect and disorder formation in Sn₄O tetrahedra and subsequently improving the hole–carrier–generation efficiency.     

Synthesis and characterization of CeO2 nano-rods

We report a synthesis of two types of CeO₂ nano-rods via the facile and efficient hydrothermal process free from any surfactant and template. The synthesized nano-rods are chemically identified as CeO₂ with the standard fluorite structure but their morphologies are different. The nano-rods prepared with cerium nitrate hexahydrate and sodium phosphate are thicker and shorter with diameter of ∼30 nm and length of ∼100 nm, and those prepared with cerium acetate hydrate and dibasic sodium phosphate are thinner and longer with ∼10 nm in diameter and ∼400 nm in length. Microstructural analyses reveal that the two species of nano-rods have low-energy {111} surfaces and grow along the 〈112〉 direction. As a consequence of their morphologies, the two types of synthesized nano-rods exhibit excellent UV-absorption ability in comparison to the irregular CeO₂ nanoparticles.     

Rolling Motion of a Ball on Pressure Sensitive Adhesives

Rolling motion of a ball on pressure sensitive adhesives was carefully observed under well-controlled conditions. Rolling distance was measured as a function of time by means of stroboscopic photography, and rollout distance was measured as a function of initial height of a ball. Both rolling distances and rollout distances were analysed according to a unified theory, where rolling friction coefficient (f) of a pressure sensitive adhesive is involved. It is suggested that f depends on viscoelastic properties of the adhesives.     

Estimation of the Surface Energy of Polymer Solids

The methods to estimate the surface tension of polymer solids using contact angles have been reviewed in the first part. They are classified into the following three groups depending on the theories or the equations applied: (1) the methods using the Young's equation alone, (2) the methods using the combined equation of Young and Good-Girifalco, and (3) the methods using the equations of work of adhesion. Some notes and comments are given for each method and results are compared with each other. The two-liquids method for rather high energy surface is also introduced.

Next, some new possibilities to evaluate the surface tension of polymer solids are presented by our new contact angle theory in consideration of the friction between a liquid drop and a solid surface. The advancing and receding angles of contact (θ _a and θ _r ) are explained by the frictional tension γ_F and accordingly two kinds of the critical surface tension γ_C (γ_Ca and γ_Cr ) are given.

This work has shown that one of the recommendable ways to evaluate γ_S is either the maximum γ_LV cos θ_a or the maximum γ_C using the advancing contact angle θ_a alone, and another way is the arithmetic or the harmonic mean of the γ_Ca and γ_Cr . A depiction to determine the γ_C such as ln(1 + cos θ₀ ) vs. γ_LV with cos θ₀ = (cos θ₀ + cos θ_r )/2 has also been proposed.     

Improving the mechanical properties of isosorbide copolycarbonates by varying the ratio of comonomers

Polycarbonates were synthesized by transesterification polymerization of isosorbide, bisphenol A, and diphenyl carbonate in the presence of n‐BuSn(?O)OH as the catalyst. The polymers were prepared by varying the ratio of the two monomers. The polymers exhibited good thermal stability, rigidity, and strength. The storage moduli for the polymers were 2.6 to 3.2 GPa at 25°C and increased with increasing isosorbide content. The dynamic mechanical analysis indicated that the storage moduli (E′) of the polymers are constant to higher temperatures than that of bisphenol A polycarbonate. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

An Additional Insight into the Correlation between the Distribution Ratios and the Aqueous Acidity of the TODGA System

Abstract

Extraction of Eu(III) and Am(III) from HNO₃ into the organic solvents using N,N,N′,N′‐tetraoctyl‐diglycolamide (TODGA) was investigated in order to study the detailed extraction reaction. The chemical species: 1:2 for metal:TODGA complex is present in polar diluents. On the other hand, the metal complexes need three or more TODGA molecules to remain stable in non‐polar diluents. The HNO₃ concentration dependence on the distribution ratio suggests that HNO₃ participates in the metal extraction. Infrared spectra indicate that the carbonyl oxygen coordinates with Eu(III), and luminescence lifetimes suggest that there are no water molecules in the inner coordination sphere of the extracted Eu‐complex.     

Core-Shell Type Polymer Microspheres Prepared from Diblock Copolymer Films

In the first part of this article, the preparation method for core-shell type polymer microspheres from diblock copolymer films is reviewed. The core-shell type polymer microspheres were obtained from the crosslinking reaction in spherical microdomains formed by diblock copolymer film. In the second section, the solution and solid properties of core-shell type microspheres are reviewed. The micelle of core-shell type microsphere moved like pseudolatex. Its solubility depended strongly on that of shell segments. Finally, the miscibility behaviors of binary core-shell type microsphere blends are reported briefly.     

Heterogeneous Catalysis by Heteropoly Compounds of Molybdenum and Tungsten

Heteropolyanions are polymeric oxoanions which are formed by the condensation of more than two different oxoanions [Eq. (1)l. Polyanions consisting of one kind of oxoanion are called isopolyanions [Eq. (2)]. Acidic elements such as Mo, W, V, Nb, and Ta are present as oxoanions in aqueous solutions and polymerize to form polyanions at low pH. Free acids (or acid forms) of these species are called heteropoly and isopoly acids, respectively. Here, the term “heteropoly compounds” is used for heteropoly acids and their salts.     

Adhesion between side surface of an elastic beam and flat surface of a rigid body

A theory of adhesion between an elastic beam and a rigid body is proposed using linear beam theory. Normalized force between the elastic beam and the rigid body considering adhesion of the side surface of the elastic beam is investigated theoretically. Adhesion of an elastic beam is important to analyze gecko adhesion, and peeling mechanism of an adhered film. This adhesion is also important in design of grip-and-release devices. The force between an elastic beam and a rigid body is investigated by considering shear force and total energy, and is obtained as a function of the displacement of the elastic beam. The proposed theory is different from Kendall’s thin-film peeling theory in terms of the elastic energy. The proposed theory considers bending elastic energy, whereas Kendall’s theory considers extension elastic energy. Two different contacts, line contact and area contact, are taken into account to discuss the loading and unloading processes in terms of the relation between the force and the displacement. Non-dimensional parameter, which relates to the work of adhesion and the specifications of the elastic beam, is introduced to explain the normalized maximum tensile force.     

Burning Characteristics of Ammonium Nitrate‐Based Composite Propellants Supplemented with Fe2O3

Ammonium nitrate (AN)‐based composite propellants have attracted a considerable amount of attention because of the clean burning nature of AN as an oxidizer. However, such propellants have several disadvantages such as poor ignition and a low burning rate. In this study, the burning characteristics of AN‐based propellants supplemented with Fe₂O₃ as a burning catalyst were investigated. The addition of Fe₂O₃ is known to improve the ignitability at low pressure. Fe₂O₃ addition also increases the burning rate, while the pressure exponent generally decreases. The increasing ratio (R) of the burning rate of the AN/Fe₂O₃ propellant to that of the corresponding AN propellant vs. the amount of Fe₂O₃ added (ξ) depends on the burning pressure and AN content. R decreases at threshold value of ξ. The most effective value of ξ for increasing the burning rate was found to be 4 % for the propellant at 80 % AN, and the value generally decreased with decreasing AN content. According to thermal decomposition kinetics, Fe₂O₃ accelerates the reactions of AN and binder decomposition gases in the condensed‐ and/or gas‐phase reaction zones. The burning characteristics of the AN‐based propellant were improved by combining catalysts with differing catalytic mechanisms instead of supplementing the propellant with a single catalyst owing to the multiplicative effect of the former.