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.     

Vaporization study on nonstoichiometric NbO2 ± x by mass-spectrometric method

The vapor pressures over nonstoichiometric NbO_{2 ± x}(s) (1.972?2.037) were measured by mass-spectrometric method in the temperature range 1958–2326 K. The congruently vaporizing composition in the NbO_{2 ± x} phase was determined to be stoichiometric NbO_2.000 from the composition dependence of the total vapor pressures. The partial pressures of oxygen were calculated as a function of temperature and O/Nb composition from the partial pressures of the gaseous species NbO₂(g) and NbO(g) over nonstoichiometric NbO_{2 ± x}, from which the partial molar enthalpies and entropies of oxygen were calculated as a function of O/Nb composition. The composition dependence of the partial molar enthalpy and entropy obtained suggested the existence of some kind of short-range ordering in the nonstoichiometric NbO_{2 ± x}(s) phase. The enthalpies of formation of nonstoichiometric NbO_{2 ± x}(s) were also determined as a function of composition by combining the partial molar enthalpies of oxygen with the enthalpy of formation of stoichiometric NbO_2.00(s). The phase diagram around NbO_{2 ± x} at high temperatures was determined from the vaporization study.     

Deposition of chlorophyll-a Langmuir-Blodgett films onto an SnO2 optically transparent electrode

The deposition of chlorophyll-a monolayers onto an SnO₂ optically transparent electrode was studied in relation to the deposition ratio. The values of the deposition ratio, which were approximately 0.95 for the upward movement and very small but non-zero for the downward movement, suggest that the multilayers prepared are Z-type films containing a small fraction of the Y-type component corresponding to the non-zero value. This is consistent with the photo- electrochemical behaviour of the pigmented electrodes which is markedly dependent on the deposition ratios, indicating structural inhomogeneity or imperfection of the multilayers.     

An electrical conductivity and X-ray study of a high-temperature transition in U4O9

The high temperature transition in U₄O₉ has been studied by electrical conductivity measurements and X-ray diffraction. From the electrical conductivity measurements, a similar variation of log σ$\text{T}$ with reciprocal temperature to that in the transition range near room temperature is observed in the temperature range from about 300 to 800°C. Like the low temperature transition, a small lattice contraction is also observed in that temperature range by means of X-ray diffractometry, and the transition temperature increases from 530 to 620°C with increasing O/U ratio. After the transition the intensity of $\text{4a}{}_0$ superlattice reflections increases, but that of $\text{8a}{}_0$ superlattice reflections disappears. The mechanism of this high temperature transition is considered to be a second-order transition of the order—disorder type based on the configurational change of U⁴⁺ and U⁵⁺ with the shift of some portions of the lattice oxygen atoms from the lattice sites to the interstitial positions. The phase diagram of U₄O₉ is presented on the basis of the electrical conductivity and X-ray data.     

Boiling two-phase flow under microgravity

To study the effects of reduced gravity on the flow regime and the heat transfer characteristics of a boiling two-phase horizontal flow, parabolic flight experiments were performed by using an aircraft. The gravity level during the parabolic flight and the duration time were about −0.01g_e +0.01g_e and 20 s, respectively. Under earth gravity, many small bubbles are detached very frequently from the heater rod surface, flowing into the upper stream due to the buoyancy and resulting in a stratified flow in the cases of lower inlet fluid velocity and higher heat flux. Under microgravity conditions, bubbles are hardly detached from the heater rod, growing and coalescing to become much larger along the heater rod, surrounding the heater rod in the downstream. This tendency was more noticeable in the cases of lower inlet fluid velocity, higher heat flux and lower inlet fluid subcooling. The local heat transfer coefficients at the bottom of the heater rod tend to decrease slightly under microgravity compared with those under earth gravity because of the reduction of the heat removal due to natural convection. On the other hand, the local heat transfer coefficients at the top of the heater rod tend to increase slightly under microgravity. However, the differences of the local heat transfer coefficients are very small in spite of large differences of the flow regimes under earth gravity and microgravity.     

Novel method for producing amorphous rice flours by milling without adding water

The present study investigated a novel milling method for producing amorphous rice starch without adding water. A new type of milling machine was developed (termed the shear and heat milling machine (SHMM)), which is capable of applying mechanical shear and heat during the milling process. The SHMM consisted of a pair of rice mortars attached to a servomotor and a ring heater. The heater was installed on the upper mortar; the temperature of the upper mortar was monitored and controlled by a thermal controller. Wide‐angle X‐ray diffraction (WAXD) analysis was used to determine the crystallinities of starch in rice flour samples produced using the SHMM at different milling temperatures. The WAXD data for milled rice flour that had been heated exhibited no diffraction peaks. This experimental result demonstrates that the developed SHMM produces amorphous rice starch easily by milling with heating without the addition of water. The milling conditions such as the shear and heat applied can be used to control the crystallinity of starch in rice.     

PVDF/PMMA composite nanofiber fabricated by electrospray deposition: Crystallization of PVDF induced by solvent extraction of PMMA component

The crystallization of poly(vinylidene fluoride) (PVDF) was observed after the poly(methyl methacrylate) (PMMA) component was extracted from the PVDF/PMMA (50/50) composite nanofiber fabricated by electrospray deposition, even though the original composite showed a completely amorphous pattern in the wide‐angle X‐ray diffraction. The content of the β‐crystal form in the crystalline region depended on the PVDF/PMMA composite ratios and the type of solvents used for the extraction of the PMMA component, e.g., chloroform and toluene. Thus, the content of the β‐crystal form can be controlled by selecting the original PVDF/PMMA composition and the solvent used to extract the PMMA component. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009