Effect of a catalyst on heterogeneous nucleation in pure and Fe-Ni alloys

In order to elucidate the nature of the heterogeneous nucleation, a differential scanning calorimetry (DSC) thermal analysis of pure Fe and Fe-Ni alloys (Ni content: 1.0 to 29.3 mass pct) containing TiN, Al₂O₃, and Ti₂O₃ was conducted. Then, special attention was paid to the difference in the phase of the primary crystal nucleated by the triggering effect of a catalyst (nucleating agent). The solidification and transformation mode appearing during cooling in these alloys is classified into three cases: F mode, FA mode, and A mode. The change of modes and the critical undercooling (ΔT) depend on the kind of catalyst used as well as the chemical composition (Ni content). In addition, in spite of the kind of primary crystal, the value of ΔT is always small in the order of TiN, Al₂O₃, and Ti₂O₃. As a matter of fact, only TiN has a practical effect as a catalyst on the triggered nucleation of the primary crystal of the δ phase. None of them has a practical effect on the nucleation of the primary crystal of the γ phase. This article is based on a presentation given in the Mills Symposium entitled “Metals, Slags, Glasses: High Temperature Properties & Phenomena,” which took place at The Institute of Materials in London, England, on August 22–23, 2002.     

Effect of superfine particles of alumina incorporated in the cavities of mordenite in enhancing selectivity

Alumina has been incorporated in the cavities of mordenite by the hydrolysis of Al³⁺ ions in the cavities with moist ammonia gas, following calcination at 450°C. The incorporation of the superfine particles of alumina into the cavities of the mordenite is assessed on the basis of the data of MAS ²⁷Al NMR measurements, X-ray powder diffraction and the amount of saturated adsorption of nitrogen for FAL/MZ. The acid properties, assessed using NH₃ TPD and FTIR studies, show the presence of Brønsted and Lewis acid sites on the catalyst, and an increase in acidic sites on incorporating alumina. The dehydrogenation selectivities of FAL/MZ, Al³⁺/MZ, H⁺/MZ, and Na⁺/MZ have been investigated. Brønsted acid sites largely enhance the ring-cleavage, whereas this incorporation of superfine particles of alumina significantly suppresses the ring-cleavage. Therefore, the incorporation of the superfine particles increases remarkably in the cyclohexene selectivity.     

Specific heat anomaly of nonstoichiometric U4O9−y

A λ-type specific heat anomaly of U₄O_9?y, which occurs slightly above room temperature, was measured for the samples with different O/U ratios. The transition temperatures obtained from the peak of λ-type specific heat anomaly are in fairly good agreement with the data by X-ray diffraction and electrical conductivity measurements. The entropy increment for the transition was obtained to be 0.46 e.u. for UO_2.250, 0.56 e.u. for UO_2.240 and 0.70 e.u. for UO_2.228, depending on O/U ratio. On the basis of the entropy change with O/U ratio, the mechanism of the phase transition is discussed. The entropy change due to the phase transition is mainly divided into two terms: one is due to the order-disorder rearrangement of U(IV) and U(V) ions,the other is associated with the displacement of oxygens ions. The former term is estimated to be rather smaller than the entropy change calculated by the Bragg-Williams approximation, and the latter is calculated using the X-ray diffraction data with the assumption of the Willis model.     

An analysis of creep crack propagation on the basis of the plastic singular stress field

In order to gain an insight into creep crack propagation problems a mechanics approach is presented in this paper on the basis of the plastic singular stress field near a crack tip under the Mode III and I steady-state creep conditions, in combination with a generalized creep damage hypothesis. Closed form equations which predict rates of creep crack propagation are obtained analytically. According to this analysis, it is found that $\text{b}{}_1\text{(n + 1)}$ is the index which characterizes the effect of damage accumulation in front of a crack, where n is the creep exponent and b₁ is the exponent involved in the creep damage hypothesis used in this analysis. The tendency of the predicted crack propagation behaviors is consistent with experimental data available in the literature.     

Phase relation and defect structures of nonstoichiometric U4O9±y and UO2+x at high temperatures

Phase relations in the composition range from $\text{UO}{}_{\mathrm{2+x}}$ to $\text{U}{}_3\text{O}{}_{\mathrm{8?z}}$ were studied by electrical-conductivity measurements and X-ray diffraction in the ranges $\text{1025°C ? T ? 1140°C}$ and . The plot of log σ versus log showed straight lines with distinct slopes, which corresponded to four regions ($\text{UO}{}_{\mathrm{2+x}}$, $\text{U}{}_4\text{O}{}_{\mathrm{9?y}}$, $\text{U}{}_4\text{O}{}_{\mathrm{9+y}}$ and $\text{U}{}_3\text{O}{}_{\mathrm{8?z}}$). The existence of the hyperstoichiometric $\text{U}{}_4\text{O}{}_{\mathrm{9+y}}$ phase was suggested in the temperature range from 1025 to 1126°C. The peritectoid temperature ($\text{U}{}_4\text{O}{}_{\mathrm{9\pm y}}\text{= UO}{}_{\mathrm{2+x}}\text{+ U}{}_3\text{O}{}_{\mathrm{8?z}}$) was estimated to be present between 1126 and 1131°C. The partial free enthalpies and entropies for the two-phase equilibrium ($\text{U}{}_4\text{O}{}_{\mathrm{9+y}}\text{+ U}{}_3\text{O}{}_{\mathrm{8?z}}$, and $\text{U}{}_4\text{O}{}_{\mathrm{9?y}}\text{+ UO}{}_{\mathrm{2+x}}$) were calculated and compared with previous results. From the dependence of the electrical conductivity on the oxygen partial pressure the nonstoichiometric defect structures of $\text{UO}{}_{\mathrm{2+x}}$ and $\text{U}{}_4\text{O}{}_{\mathrm{9\pm y}}$ were interpreted as consisting of doubly charged oxygen interstitials (O_i'') and doubly charged oxygen vacancies (V_O''). At room temperature, the homogeneity range of the U₄O₉ phase was investigated with a Debye-Scherrer camera.     

Existence of hypostoichiometric chromium sesquioxide at low oxygen partial pressures

The nonstoichiometric composition of $\text{Cr}{}_2\text{O}{}_{\mathrm{3\pm x}}$ was measured by means of thermogravimetry in the range of $\text{1173 ≦ T/K ≦ 1318}$ and . The compositional deviation from stoichiometry, $\text{x}$, in the hyperstoichiometric Cr₂O_3+x phase was observed to be smaller than 2 × 10^?4, irrespective of temperatures, provided that the hyperstoichiometric Cr₂O_3+x exists. The existence of the hypostoichiometric Cr₂O_3?x phase was first established in this study in the region of low oxygen partial pressure below 10^?5 Pa. From the oxygen partial pressure dependence of $\text{x}$ in Cr₂O_3?x, the defect structure was discussed with the neutral chromium interstitials in the composition near stoichiometry and with the triply charged ones far from stoichiometry. The partial molar enthalpy and entropy of oxygen of Cr₂O_3?x showed the complex compositional dependences, suggesting the change of the type of the predominant defect.     

Phase transitions in U3O8−z: I, heat capacity measurements

The heat capacity of U₃O_8−z with various O/U ratios was measured in the range from 250 to 750 K, and λ-type heat capacity anomalies were found in each sample. The transition temperatures were 487 and 573 K for UO_2.663, 490 and 576 K for UO_2.656 and 508, 562 and 618 K for UO_2.640. The entropy changes of the transitions were 0.44 and 0.39 J K⁻¹mol⁻¹ for UO_2.663, 0.58 and 0.47 J K⁻¹mol⁻¹ for UO_2.656 and 0.62, 0.51 and 0.25 J K⁻¹mol⁻¹ for UO_2.640, increasing as O/U decreases. The enthalpy change due to the transition varied linearly with the transition temperature except for UO_2.640, showing the presence of the same mechanism of phase transition among the samples with various O/U ratios. The mechanism of the phase transition was discussed on the assumption that the transition is originated from the order-disorder rearrangement of U⁵⁺ and U⁶⁺ with a consequent displacement of atoms, similarly to the case of U₄O_9−y.