Heat of immersion of iron(III) oxides in water at 25°C

The heat of immersion in water was measured at 25°C for three iron(III) oxides using a twin-type microcalorimeter. One of the samples was commercial α-Fe₂O₃ (sample C) and the other two (samples M and F) were prepared by calcining magnetite and iron(III) hydroxide in air at various temperatures, T_p, from 300 to 700°C. The samples were evacuated at outgassing temperature, T_o, between room temperature and 500°C at a pressure of 1 × 10^?2?2.7 × 10^?2N m^?2 for 6 h. The heat of immersion, h_i(J m^?2), of samples C and M increased with an increase in T_o and showed the maximum h_i at T_o =400°C, while sample F did not show the maximum up to T_o =500°C. The systematic correlation was not observed between h_i and T_p of sample F. The heat of reproduction of the surface hydroxyl group on sample F was approximately estimated as 6.6 × 10⁴ J mole^?1 H₂O.     

DTA study of the chlorination of fly ash and bauxite in the presence of carbon

The chlorination processes of fly ash and bauxite in the presence of carbon were studied by means of a gas-flow type DTA, X-ray analysis and SEM observation, and the reactivity of Al-compounds as their constituents was compared. In the case of fly ash, the exothermic peak due to the formation of AlCl₃ (mainly) and FeCl₃ appeared at about 790–920°C. The reactivity of Al estimated from the DTA peak temperature depended on the particle size, carbon content and preparation temperature of fly ash, and was much lower than that of bauxite. Fractional conversion of Al was about 60–70%, when fly ash (?300 mesh) was heated up to 900°C in Cl₂ at 5°C min^?1 of heating rate. In the case of bauxite, two exothermic peaks due to the chlorination of Fe and Al appeared at about 270 and 490°C, respectively. The chlorination of Al was completed at 550°C under the above conditions.     

Thermoanalytical study on the chlorination of hydrated aluminas and transition aluminas

The chlorination processes of four hydrated aluminas (bayerite, gibbsite, pseudoboehmite, boehmite) and four transition aluminas (η-,γ-,δ-,θ-Al₂O₃) were studied in the presence of active carbon by means of a gas-flow DTA apparatus. In the case of hydrated alumina systems three exothermic peaks appeared at about 230, 460 and 500°C or above, which corresponded to the formation of hydrogen chloride, white needle-like crystals and the chlorination of hydrated aluminas, respectively. On the other hand, in transition alumina systems, only one exothermic peak due to the chlorination of transition alumina appeared at 580–670°C. The relationship between the chlorination behavior and structure of transition aluminas was discussed.     

Nuclear magnetic resonance of poly-β-alanine

Nuclear magnetic resonance of poly-β-alanine samples differing in solubility in water was studied over a wide temperature range as part of an investigation of their physical properties. Water-soluble poly-β-alanine has more branches and a lower degree of crystallinity than water-insoluble poly-β-alanine. NMR spectra of poly-β-alanine show one component at 77°K. which splits into two components, broad and narrow, at room temperature. Two transition regions were observed in curves for line width and second moment versus temperature. The higher transition temperature, corresponding to the glass transition of the polymer, appears to decrease with increasing water content. The second moment for the water-soluble polymer differs from that of the water-insoluble polymer at 77°K. This is interpreted in terms of the difference in the degree of crystallinity of the polymers.     

Trace inequalities on a generalized Wigner-Yanase skew information

We introduce a generalized Wigner-Yanase skew information and then derive the trace inequality related to the uncertainty relation. This inequality is a non-trivial generalization of the uncertainty relation derived by S. Luo for the quantum uncertainty quantity excluding the classical mixture. In addition, several trace inequalities on our generalized Wigner-Yanase skew information are argued.     

Kinetics of the dehydration of boehmites prepared under different hydrothermal conditions

The kinetics of the dehydration of five boehmites, which were prepared under different hydrothermal conditions (300°C, 85 atm, 20 h — 150°C, 4.5 atm, 5 h), were studied by means of isothermal TG at an air pressure of 150 mm Hg and at a constant flow rate of nitrogen (30 ml min^?1) containing water vapor of partial pressures between 10^?4 and 23.8 mm Hg. It was found that the dehydration temperature of boehmites was lowered as the preparation conditions became more mild. Moreover, the rate-controlling step of the dehydration of boehmites varied with their preparation conditions. The water vapor pressure led to decreases in the rate of dehydration.     

Thermoanalytical study of the solid-state reactions in MgO-Cr2O3 and ZnO-Cr2O3 systems

The solid-state reactions in MgO-Cr₂O₃ and ZnO-Cr₂O₃ systems under atmospheres of oxygen, air and nitrogen were investigated by means of DTA and isothermal kinetic techniques. It was shown that the application of DTA to the solid-state reactions affords useful information with respect to the initial reaction stage: oxidation of Cr₂O₃ to CrO₃ in the presence of MgO or ZnO, followed by the formation of a thin layer of spinel, which consisted of an imperfect lattice, on the surface of the MgO or ZnO grains.     

Chain contraction and nonlinear stress damping in primitive chain network simulations

Doi and Edwards (DE) proposed that the relaxation of entangled linear polymers under large deformation occurs in two steps: the fast chain contraction (via the longitudinal Rouse mode of the chain backbone) and the slow orientational relaxation (due to reptation). The DE model assumes these relaxation processes to be independent and decoupled. However, this decoupling is invalid for a generalized convective constraint release (CCR) mechanism that releases the entanglement on every occasion of the contraction of surrounding chains. Indeed, the decoupling does not occur in the sliplink models where the entanglement is represented by the binary interaction (hooking) of chains. Thus, we conducted primitive chain network simulations based on a multichain sliplink model to investigate the chain contraction under step shear. The simulation quantitatively reproduced experimental features of the nonlinear relaxation modulus G(t,γ). Namely, G(t,γ) was cast in the time-strain separable form, G(t,γ)=h(γ)G(t) with h(γ)=damping function and G(t)=linear modulus, but this rigorous separability was valid only at times t comparable to the terminal relaxation time, although a deviation from this form was rather small (within ±10%) at t>τ(R) (longest Rouse relaxation time). A molecular origin of this delicate failure of time-strain separability at t～τ(R) was examined for the chain contour length, subchain length, and subchain stretch. These quantities were found to relax in three steps, the fast, intermediate, and terminal steps, governed by the local force balance between the subchains, the longitudinal Rouse relaxation, and the reptation, respectively. The contributions of the terminal reptative mode to the chain length relaxation as well as the subchain length/stretch relaxation, not considered in the original DE model, emerged because the sliplinks (entanglement) were removed via the generalized CCR mechanism explained above and the reformation of the sliplinks was slow at around the chain center compared to the more rapidly fluctuating chain end. The number of monomers in the subchain were kept larger at the chain center than at the chain end because of the slow entanglement reformation at the center, thereby reducing the tension of the stretched subchain at the chain center compared to the DE prediction. This reduction of the tension at the chain center prevented completion of the length equilibration of subchains at t～τ(R) (which contradicts to the DE prediction), and it forces the equilibration to complete through the reptative mode at t?τ(R). The delicate failure of time-strain separability seen for G(t,γ) at t～τ(R) reflects this retarded length equilibration.     

Influence of the preparation history of α-Fe2O3 on its reactivity for hydrogen reduction

TG experiments on the hydrogen reduction of α-Fe₂O₃ were carried out to elucidate the influence of the preparation history of the oxide on its reactivity. α-Fe₂O₃ samples were prepared by the thermal decomposition of seven iron salts in a stream of oxygen, air or nitrogen at temperatures of 500–1200°C for 1 h. Thirteen metal ions such as Cu²⁺, Ni²⁺, etc. were used as doping agents. The reactivity of the oxide was indicated by the initial reduction temperature (T_i. α-Fe₂O₃ prepared at lower temperatures showed lower T_i values and the reduction proceeded stepwise (Fe₂O₃ → Fe₃O₄ → Fe). T_i values increased with the rise in the preparation temperature of the oxide. The oxides prepared at higher temperatures showed that two reduction steps (Fe₂O₃ → Fe₃O₄ → Fe) proceed simultaneously. the preparation in oxygen gave higher T_i than that in air or nitrogen. The doping by metal ions, except Ti⁴⁺, lowered the T_i of α-Fe₂O₃. The Cu²⁺ ion showed the lowest T_i, while Ti⁴⁺ showed the highest T_i and the inhibition effect.The reduction process was expressed by two equations; Avrami—Erofeev's equation for α-Fe₂O₃ → Fe₃O₄ and Mampel's equation for Fe₃O₄ → Fe.     

Development of a multi-point LDV by using semiconductor laser with FFT-based multi-channel signal processing

 An advanced multi-point LDV with FFT-based multi-channel signal processing, using a 1-bit FFT approach has been developed. A semiconductor laser light sheet, a 96-channel plastic optical fiber array, 16-Si APDs and a 16-channel capacious (1 M word) memory system with 1 bit were used in order to attain 16 individual Doppler frequencies simultaneously. Several experiments were conducted in this study to test the performance of the advanced multi-point LDV. We confirmed that the advanced multi-point LDV could be a useful, compact and inexpensive optical measuring instrument for obtaining the information of a velocity field as a function of time and position. Received: 24 October 1996/Accepted: 30 June 1997