Heat capacity measurements of MnxFe3−xO4

Heat capacities of Mn_xFe_3?xO₄ with the composition x = 1.0, 1.5, and 2.0 were measured from 200 to 740 K. λ-type heat capacity anomalies due to the ferri-paramagnetic transition were observed for all the compositions. The transition temperatures were 577, 471, and 385 K for the composition x = 1.0, 1.5 and 2.0, respectively, which are in good agreement with the results of magnetic measurements. The difference in heat capacities between the different samples was small except for the temperature range of the transition. The magnetic contribution to the observed heat capacity was obtained by assuming that the heat capacity can be expressed by the sum of the lattice heat capacity C_v (l), the dilation contribution C(d), and the magnetic contribution C(m). Entropy changes due to the transition were obtained from C(m) as 55.5, 50.7 and 49.2 J K^?1 mole^?1 for the composition x = 1.0, 1.5, and 2.0, respectively. The entropy changes were also calculated by assuming the randomization of unpaired electron spins on each ion, but they were from 6 to 10 J K^?1 mole^?1 smaller than the observed ones. The difference between the experimental and the calculated values is roughly explained by taking into account the cation exchange reaction between the tetrahedral and the octahedral sites in the spinel structure.     

On the topology of compact smooth three-dimensional Levi-flat hypersurfaces

We study topological conditions that must be satisfied by a compactC ^∞ Levi-flat hypersurface in a two-dimensional complex manifold, as well as related questions about the holonomy of Levi-flat hypersurfaces. As a consequence of our work, we show that no two-dimensional complex manifold admits a subdomain Ω with compact nonemptyC ^∞ boundary such that Ω ? ?².     

Distribution and dynamics of radionuclides and stable elements in the coastal waters off Rokkasho Village, Japan, prior to the opening of a nuclear reprocessing facility

A nuclear fuel reprocessing facility is currently under construction in Rokkasho Village, Aomori, Japan. After completion and start-up, this facility will discharge radionuclides into the Pacific Ocean through an outlet pipe set on the seafloor offshore. For future assessments of the stability of these radionuclides in the environment, a sufficient understanding of the behavior of radionuclides in this ocean ecosystem before the start-up of the facility is necessary. To understand the processes by which radionuclides and various other types of elements are eliminated from seawater, we measured the sedimentation flux of suspended particles in the coastal waters off Rokkasho Village where the sea emissions pipes will be placed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Anodic behavior of nickel-based alloys in the electrolytic production of NF3

The Ni-based alloys, such as Ni-Co, Ni-Mn, Ni-Ag, Ni-Cu, Ni-Al and Ni-Si, prepared by hot isostatic pressing (HIP) at 1000 °C under 2 × 10⁸ Pa for 2 h were employed as the anodes for electrolytic production of NF₃. The current efficiencies for NF₃ formation were 42-38, 52-40, 52-47, 63-62, 50 and 41% for Ni-Co, Ni-Mn, Ni-Ag, Ni-Cu, Ni-Al and Ni-Si alloys, respectively. The current efficiencies only on Ni-Cu alloys with Cu concentrations lower than 10 mol% were almost the same as those on Ni sheet and HIPed Ni anodes, whereas those on the other alloys used in this study were smaller compared with those on both Ni anodes. On the other hand, the current losses caused by anodic dissolution of Ni-Co, Ni-Mn, Ni-Ag, Ni-Cu, Ni-Al and Ni-Si alloy electrodes were 7.95-4.42, 6.40-7.02, 5.60-6.30, 3.34-6.33, 5.10 and 0.18%, respectively. The anode consumptions of Ni-5 mol% Cu and Ni-5 mol% Si alloys were almost the same or smaller compared with those of Ni sheet and HIPed Ni electrodes, though those of other alloys used were large compared with those of both Ni anodes. Consequently, addition of Cu to the nickel matrix is available for a cheaper cost of anode with keeping a same current efficiency as that on the Ni anode and addition of Si to the nickel matrix is effective for decreasing anode consumption largely. A Ni sheet electrode containing a trace of impurities, such as Co, Mn, Ag and Al, is also favorable as the anode for electrolytic production of NF₃.     

The Effects of Sulphate and Tartrate Ions on the Molecular Organization of Water: Towards Understanding the Hofmeister Series (VI)

Using the 1-propanol (1P) probing methodology we have developed earlier, we characterized the effects of sulphate and tartrate anions on the molecular organization of H₂O. The results indicate that these two large anions belong to a new class of ??hydrophobe-like hydration center??. That is, sulphate and tartrate ions act as ??hydration centers?? with the hydration number 14±3 for both, and leave the bulk H₂O, away from hydration shells, unperturbed in the absence of the probing 1-propanol. As the mole fraction of the probe increases, however, the hydrogen bond probability of bulk H₂O away from hydration shells appears to decrease smoothly, as occurs with ??hydrophobes?? in H₂O. We plot the negative hydration number against the power to reduce the hydrogen bond probability of bulk H₂O for the two large anions. We also plotted the characteristic indices for ??hydrophiles?? and ??hydration centers?? whose characteristics we determined in the same manner earlier. H₂O defines the origin on this map. We found that a typical Hofmeister ranking for each anion matches reasonably well with that of the distance from the origin for each ion, in decreasing order starting from ions plotted in the north-west quadrant (representing the ??hydrophobe-like?? behavior) of the map and then in increasing order from the origin towards the south on the ordinate, the ??hydrophile-like?? behavior. These findings could be useful in understanding the Hofmeister series, pointing to the importance of the contribution made by the effect of each ion on H₂O, in addition to helping understand direct ion-protein interactions.     

Stereoregular Polymerization of Alkyl Propiolate Catalyzed by Rh Complex

Abstract

The polymerizations of alkyl esters of propiolic acid by Rh complex catalysts were investigated. [Rh(norbornadiene)Cl]₂, which was the most active among the catalysts examined, gave rise to poly(alkyl propiolate) in a fairly high yield (～80%) in the presence of alcohol as the polymerization solvent. The polymers formed were a pale yellow powder soluble in common organic solvents except for poly(methyl propiolate). The structures of the polymers obtained were investigated by IR, ₁₃C-NMR, CP MAS ₁₃C-NMR, and laser Raman spectroscopies, together with the x-ray diffraction method. Based on these spectroscopic data, it was concluded that this Rh complex can be called a stereoregular polymerization catalyst of alkyl propiolate because the poly(alkyl propiolate) obtained has a cis-transoidal structure.     

Distribution of aquatic plants and absorption of radionuclides by plants through the leaf surface in brackish Lake Obuchi, Japan, bordered by nuclear fuel cycle facilities

We investigated the distribution of aquatic plants and the absorption of radionuclides by them in the brackish Lake Obuchi, Japan, which is bordered by nuclear fuel cycle facilities. We studied 5 species of submerged plants: Zannichellia palustris, Ruppia maritima, Potamogeton pectinatus, Zostera japonica, and Z. marina. The plants contained many elements, including radionuclides. The concentrations of ²³⁸U, ¹³⁷Cs, and ⁹⁰Sr in Z. marina were 11.3-12.4, 0.000-0.144, and 0.151-0.202 Bq^.kg^-1 dw, respectively. Those in Z. japonica were 5.2-8.8, 0.000-0.267, and 0.081-0.175 Bq^.kg^-1 dw, respectively. The concentrations of these radionuclides in the plants tended to be higher in higher-salinity regions than in lower-salinity regions of the lake. We found a close relationship between photosynthetic activity and the absorption of stable Sr by plants in the laboratory. Salinity, illumination, and water temperature influenced the photosynthetic activity of the plants and the consequent absorption of elements.     

Temperature Characteristics of Vibrating Type Sensor Using Micromachined Optical Fiber-Tip

An optical sensor using a quartz core microcantilever was fabricated by etching clad layer from optical fiber. The temperature dependence of the resonance frequency of this sensor was measured in atmosphere and water. The temperature coefficient of the resonance frequency in water was 1.3×10⁻³/°C, which was about one order larger than that (2.3×10⁻⁴/°C) in atmosphere. This was caused by increase of additional mass due to temperature dependence of the viscosity of water, while, the increase of the resonance frequency in atmosphere was caused by temperature dependence of Young’s modulus of the quartz core. These results were evaluated theoretically using a “string-of-beads” model.     

Isotope-dependent crystalline phases at ambient temperature: Spectroscopic and calorimetric evidence for a deuteration-induced phase transition at 320 K in α-DCrO2

The heat capacities of HCrO₂ and DCrO₂ have been measured at temperatures between 5 and 360 K. A lambda anomaly occurred at 320 K for DCrO₂ but not for HCrO₂. Infrared spectra were recorded at temperatures between 5 and 405 K. The spectrum of DCrO₂ changed at 320 K with respect to the peak wave-number and splitting of some of the vibrations, while those of HCrO₂ depended smoothly on temperature. These experimental results are discussed in terms of a deuteration-induced phase transition.     

Infrared laser radar technique using heterodyne detection for range-resolved sensing of air pollutants

An infrared, pulsed heterodyne laser radar using differential absorption technique with tunable lasers is proposed as a practical means of measuring dispersed air pollutants with range resolution. A system analysis shows that this scheme offers an adequate sensitivity for ranges up to several km.