A kinetic study of nonoxidative dissolution of galena in aqueous acid solution

This paper presents the results obtained through a kinetic study of the nonoxidative dissolution of natural galena in hydrochloric acid and perchloric acid solutions with and without the addition of sodium chloride. Under the experimental conditions employed in this study, the dissolution rates were controlled by a chemical reaction on the surface of the galena sample. The galena dissolution rate is of the first order with respect to hydrochloric ion activity in hydrochloric acid and perchloric acid solutions. The addition of sodium chloride to the acid solutions greatly enhanced the dissolution rate. The effect of sodium chloride has two possible interpretations: First, it may be the result of an increase in hydrogen ion activity. Second, the enhancement of the dissolution rate observable at high sodium chloride concentration may be due to the specific adsorption of chloride ions or the surface complexing of chloride ions on the galena surface.     

Activities of oxygen in liquid thallium and indium from electrochemical measurements

Modified coulometric titrations on the galvanic cell;O in liquid Tl or In/ZrO₂(+CaO)/Air, Pt, were performed at 973, 1073, and 1173 K to determine the oxygen activities in liquid thallium and liquid indium. The standard Gibbs energies of solution of oxygen in liquid thallium and liquid indium for l/2 O₂ →O (1 at. pct) were determined respectively to be δG‡(in Tl) = -22000 + 0.74T (±300) cal/g-atom = -92000 + 3.10T (±1300) J/g-atom, δG‡(in In) = -42450+ 3.30T (±350) cal/g-atom = -177600 + 13.8T (±1500) J/g-atom, where the reference state for dissolved oxygen was an infinitely dilute solution. It was reconfirmed that the apparent initial oxygen concentration observed in the range of very low oxygen concentration in liquid metal was attributed to the oxygen released from the solid electrolyte.     

Activities of oxygen in liquid copper and silver from electrochemical measurements

Modified coulometric titrations on the galvanic cell:O in liquid Cu or Ag / ZrO₂( + CaO) / Air, Pt, were performed to determine precisely the oxygen activities in liquid copper and silver in the range of relatively low oxygen concentration. The present experimental results were remarkably reproducible in comparison with the published data. The standard Gibbs energies of solution of oxygen in liquid copper and liquid silver for 1/2 O₂(l atm) → O(l at. pct) were determined respectively to be ΔG° (in Cu) = −18040 −0.03 T(K) (± 120) cal · g-atom−1 = −75500 −0.12 T(K)(± 500) J · g-atom−1, ΔG°(inAg)= -3860+ 1.56 T(K) (±90) cal · g-atom−1 = −16140 + 6.52 T(K)(±380) J · g-atom−1 where the reference state for dissolved oxygen was an infinitely dilute solution. The present value of the partial entropy of oxygen dissolved in liquid copper differs significantly from that suggested by many investigators. Further, the present equation for liquid copper has been found to be consistent with a correlation proposed previously by the present authors. The equation for liquid silver is in good agreement with the published ones.     

Study of the stress corrosion cracking of GFRP: effect of the toughness of the matrix resin on the fatigue damage and stress corrosion cracking of GFRP

The stress corrosion cracking of glass fibre-reinforced plastic (GFRP) accompanies a phenomenon of catastrophic failure as a result of the rapid fall in strength owing to corrosion breaking of the glass fibres. This produces a flat surface without pulling fibres out of the plane. Attack on the glass fibres can only occur by contact with an acid which must first diffuse into the matrix resin. It is confirmed, however, that no diffusion occurs or that it is too slow to be detected. The relationship between fatigue damage and stress corrosion in an acidic environment, has been investigated, focusing on the effect of matrix toughness on the resistance to stress corrosion failure of GFRP. Three types of GFRP, made from matrices with different toughness, were studied after subjecting them to fatigue damage at different levels.     

Validation of MAAP model enhancement for Fukushima Dai-ichi accident analysis with Phenomena Identification and Ranking Table (PIRT)

The Modular Accident Analysis Program (MAAP) model enhancement items to improve the simulation capability for molten corium behavior in the accidents at the Fukushima Dai-ichi nuclear power plants were validated with the Phenomena Identification and Ranking Table (PIRT). The importance ranks of the identified phenomena were evaluated for each time phase through brainstorming and discussion with the experts in the Atomic Energy Society of Japan and the members of the MAAP model enhancement project. When the current MAAP evaluation models were reviewed with the PIRT, it is found that 95 of the 386 high-ranked phenomena were not considered in MAAP 5.0.1. While 62 of these phenomena will have been addressed in the MAAP enhancement project and 25 others are not suitable to be analyzed by MAAP, 8 important phenomena should be considered in post-MAAP enhancement project with additional experiments or fundamental studies.     

Impact of Al in Cu alloy interconnects on electro and stress migration reliabilities

The reliability of Cu interconnects was successfully improved by applying a CuAl alloy seed. However, the effect of additive Al on the reliability is not fully understood. In order to reveal the reliability improvement mechanism, Cu films using CuAl alloy seed were investigated in detail. As stress induced voiding (SIV) as well as electromigration is caused by migration of vacancies and/or Cu atoms, the measured activation energy value of electromigration using CuAl indicates that the fast diffusion paths are Cu grain boundaries. The analysis using high lateral resolution scanning type secondary ion mass spectrometry (nano-SIMS) clarifies that additive Al in ECP-Cu film is mainly localized at grain boundaries. Furthermore, positron annihilation was used to probe vacancy-type defects in Cu films. The CuAl films before recrystallization contain larger and higher density vacancy-type defects. Whereas, the recrystallized CuAl films after annealing above 250 °C contain smaller and lower density defects. Furthermore, CuAl films with annealing above 350 °C contain less Al inside the grains. These results represent that Al atoms in Cu films with annealing above 350 °C are exhausted from inside grains to the grain boundaries, and the spewed Al atoms existing at Cu grain boundary effectively prevents the diffusion of Cu and/or vacancies.     

Specifying and proving properties of timed I/O automata using Tempo

Timed I/O automata (TIOA) is a mathematical framework for modeling and verification of distributed systems that involve discrete and continuous dynamics. TIOA can be used for example, to model a real-time software component controlling a physical process. The TIOA model is sufficiently general to subsume other models in use for timed systems. The Tempo Toolset, currently under development, is aimed at supporting system development based on TIOA specifications. The Tempo Toolset is an extension of the IOA toolkit, which provides a specification simulator, a code generator, and both model checking and theorem proving support for analyzing specifications. This paper focuses on the modeling of timed systems and their properties with TIOA and on the use of TAME4TIOA, the TAME (Timed Automata Modeling Environment) based theorem proving support provided in Tempo, for proving system properties, including timing properties. Several examples are provided by way of illustration.     

Enzymatic properties and transglycosylation of α-galactosidase from Penicillium oxalicum SO

Penicillium oxalicum SO α-galactosidase demonstrated weak hydrolysing activity but a high rate of transglycosylation in the reaction with melibiose, where the major product was 6-α-galactosyl melibiose. The transfer ratio was 83.6% and was maintained over a long reaction time of 80 h. The molecular weight was estimated to be 124,000 by SDS–PAGE. The optimal pH was ∼3 and a stable pH, with a range of 2.4–9.5, was found. The optimal temperature was ∼60 °C and the activity was stable below 60 °C. With respect to acceptor specificity, mono-alcohols, sugar alcohols and sugars were poor acceptors, but the di-alcohol ethylene glycol and the tri-alcohol glycerin were good acceptors. The percentage of transglycosylation to glycerin increased up to 41.7%, as that to melibiose decreased, with the initial glycerin concentration of 40%. The production of α-d-galactosylglycerol was 293 mg for each gram of melibiose used by the enzymatic reaction.