The nanosecond pulse radiolysis technique has been applied to study the rate constants for charge transfer and substitution reactions of radical ions. Electron transfer from biphenyl anion to styrene derivatives shows a correlation with the reduction potential of the acceptors expected from the Marcus theory. The positive charge transfer from biphenyl cation to the same acceptors shows a much larger rate constant, suggesting a considerable shift of the free energy relationship to the positive side of Go. The substitution reaction of fluorenone anion with organic halides shows an SN2 character, while that of diethyl fumarate shows electron transfer nature. The dimerization of radical anions has been proven for benzophenone and fluorenone, when their lifetime of the parent anions are prolonged by countercations.
We investigated the influence of ionic strength on migration behaviors of Sr and Eu in the presence of humic acid (HA). The
breakthrough curve of Sr through a quartz sand column in the presence of HA was identical to that in the absence of HA. Europium
migration in quartz sand was enhanced by the presence of HA at low ionic strength. At high ionic strength, Eu migration in
the presence of HA was hindered compared to that in the absence of HA. Adsorption of europium on quartz sand in the absence
of HA decreases with increased ionic strength.
Authors:C. Mothé, C. de Araujo, M. de Oliveira, and M. Yoshida
Polyurethane composites with bagasse of sugar cane (BSC) at different proportions: 5, 10 and 20 mass/mass% were prepared by
melt mixing method. The thermal behavior of these composites were studied by thermogravimetry (TG/DTG). The influence of fiber
concentration on the kinetic parameters of the composites was studied and a better interaction was suggested between PU/BSC
with 5mass/mass% of fiber. Scanning electron microscopy was carried out to investigate surface morphology.
Authors:M. Arisaka, T. Kimura, H. Suganuma, and Z. Yoshida
Coordination states of Eu(III) in anion exchange resin (AG 1X8) systems with LiCl-H2O/alcohol mixed media were determined from the luminescence lifetimes and the emission spectra of Eu(III). The sorption equilibrium of Eu(III) was discussed on the basis of the correlation between the distribution coefficients and the coordination states in the solution and resin phases. The sorption of Eu(III) was mainly caused by the formation of an anionic Eu(III)-chloro complex in the resin phase, which was enhanced by the decrease of 'free' water activity due to the addition of alcohol. The effect of ethanol added was larger than that of methanol.
Authors:M. Yoshida, S. Sumiya, H. Watanabe, and K. Tobita
A rapid separation method was developed for determination of low level promethium-147 and samarium-151. The rapid method, applied to environmental samples, provided speed and efficiency for the respective separation of Pm and Sm from other lanthanides with the simplified technique of high performance liquid chromatography (HPLC) system. The separation time of Pm and Sm in HPLC separation was shortened by stepwise eluent method of -hydroxyisobutyric acid as compared with a gradient eluent method of lactic acid with HPLC despite increase in sample volume for significant determination of Pm-147 and Sm-151. This method permitted the detection limit around 0.1 Bq/kg-dry-soil for Pm-147 and Sm-151 in 200 g soil sample by counting for 500 min with a liquid scintillation counter.
Authors:D. Ishii, T. Yamada, M. Nakagawa, T. Iyoda, and H. Yoshida
thermally induced structural transformation of a hydrogen-bonded crystal formed
from an amphoteric molecule of 6-[2-methoxy-4-(pyridylazo)phenoxy]hexanoic
acid MeO was studied using differential scanning calorimetry (DSC), Fourier
transform infrared spectroscopy (FTIR) and X-ray diffraction measurement (XRD).
Crystal form of the hydrogen-bonded crystal was measured by single crystal
four circle diffractometer (Mo-Kα radiation). As
a result, the crystal of MeO was stabilized by many C–H⋅⋅⋅O hydrogen
bonds, and the C–H⋅⋅⋅O hydrogen bonds were broken by thermal energy
reversibly. After transformation the supramolecular architecture was composed
of supramolecular polymer including free-rotation pentamethylene main chains.
Authors:D. Ishii, T. Yamada, M. Nakagawa, T. Iyoda, and H. Yoshida
Summary Thermally induced structural transformation of fibrous hydrogen-bonded molecular assemblage formed from an amphoteric pyridinecarboxylic acid of 6-[2-propyl- 4-(4-pyridylazo)phenoxy]hexanoic acid (C5PR) was studied using differential scanning calorimetry (DSC), differential thermal analysis (DTA), and thermogravimetry (TG). The organized fibrous morphology formed in an aqueous solution was stable at temperatures below 150°C. The ordered crystalline solid phase (K1) of the original fibrous material altered to a disordered crystalline solid phase (K2) at 150°C and subsequently to an isotropic phase (I) at 172°C. In the isotropic state, the C5PR molecule was slowly decomposed by decarboxylation. Once the molecular assemblage was subjected to the mesophase by heating, another ordered crystalline solid phase (K3) appeared reversibly at 17°C. The heat budget analyses by DSC indicated that a conformational entropy change such as the side-chain propyl group and the main-chain pentamethylene unit in the hydrogen-bonded molecular assemblage took place between the two ordered crystalline solid phases K1 and K3.
Authors:R. Ozao, H. Yoshida, Y. Ichimura, T. Inada, and M. Ochiai
The thermal change of anodic alumina (AA), particularly the exothermic peak followed by the endothermic peak at ca 950C was
studied in detail by mainly using simultaneous TG-DTA/FTIR. The gradual loss of mass up to ca 910C is attributed to dehydration.
When heated at a constant rate by using TG-DTA, an exothermic peak with subsequent endothermic peak is observed at ca 950C,
but the exothermic peak becomes less distinct with decreasing heating rate. It has been found that gaseous SO2 accompanying a small amount of CO2 is mainly discharged at this stage. The reaction in this stage can be considered roughly in two schemes. The first scheme
can be said collectively as crystallization, in which the migration of S or C trapped inside the crystal lattice of the polycrystalline
phase (γ-, δ-, and θ-Al2O3, which presumably accompanies a large amount of amorphous or disordered phase) occurs. In the second scheme, the initial
polycrystalline (+amorphous) phase crystallizes into a quasi-crystallineγ-Al2O3-like metastable phase after amorphization. Conclusively,after the distinct exo- and endothermic reactions, the amorphous
phase crystallizes intoγ-Al2O3, presumably accompanying small amount of δ-Al2O3. It is also found that, when maintained isothermally, the metastable phases undergo transformation into the stable α-Al2O3 at 912C.
Authors:R. Ozao, M. Ochiai, H. Yoshida, Y. Ichimura, and T. Inada
Gamma-alumina membrane was prepared from anodic (amorphous) alumina (AA) obtained in a sulphuric acid electrolyte. The transformation
scheme, i.e., the crystallization to form metastable alumina polymorphs and the final transition to α-Al2O3 with heating was studied by TG-DTA and X-ray diffraction (XRD) using fixed time (FT) method. When heating at a constant rate,
the crystallization occurred at 900C or higher and the final formation of α-Al2O3 occurred at 1250C or higher, which temperatures were higher than the case of using anodic (amorphous) alumina prepared from
oxalic acid electrolyte. Relative content of S of the products was obtained by transmission electron microscope (TEM)-energy
dispersive spectroscopy (EDS). The proposed thermal change of anodic alumina membrane prepared from sulphuric acid is as follows:
1. At temperatures lower than ca 910C: Formation of a quasi-crystalline phase or a polycrystalline phase (γ-, δ- and θ-Al2O3);
2. 910–960C: Progressive crystallization by the migration of S toward the surface within the amorphous or the quasi-crystalline
phase, forming S-rich region near the surface;
3. 960C: Change of membrane morphology and the quasi-crystalline phase due to the rapid discharge of gaseous SO2;
4. 960–1240C: Crystallization of γ-Al2O3 accompanying δ-Al2O3; and
5. 1240C: Transition from γ-Al2O3 (+tr. δ-Al2O3) into the stable α-Al2O3.
The amorphization which occurs by the exothermic and the subsequent endothermic reaction suggests the incorporation of SO3 groups in the quasi-crystalline structure.