The Effect of Organic Diluent on the Extraction of Eu(III) by HEH[EHP]

ABSTRACT

Because there are fewer tools available to probe the interactions therein, the effect of the fundamental chemistry of the organic diluent on solvent extraction equilibria has been under-characterized relative to the aqueous. As a result, diluents for solvent extraction are often selected for an application not for their utility as a medium for reaction, but for other (often equally) important reasons (like low flammability). To begin to improve this imbalance in the science, twenty different diluents have been used in a study of the extraction of radiotracer ^152/154Eu³⁺ from dilute nitric acid solutions using the extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]). To increase the utility of the study and to honor the memory of Professor Jan Rydberg, this investigation was conducted by a cadre of comparatively inexperienced separation scientists (who are as a result no longer inexperienced separation scientists) as a radioanalytical chemistry and solvent extraction educational exercise. Slope analysis was used to determine the apparent stoichiometry of the extracted metal complex. The results discussed in the following indicate that, while the pH dependence exhibits the expected three H⁺ exchanged per metal ion extracted, the extractant dependence suggests that the number of protonated extractant molecules in the extracted complex changes with the organic diluent. The experimentally observed “extractant dependency” ranges from 2.5 to 3.0 dimer equivalent molecules per extracted metal ion. Ironically, in the diluents exhibiting the highest apparent M:(HA)₃ stoichiometry, HEH[EHP] extracts Eu³⁺ less efficiently. Europium luminescence spectroscopy was used to probe for changes in the first coordination sphere of the complex in different diluents. A model and conceptual framework for understanding these observations is described.     

Loss of Curing Agent During Thin Film (Droplet) Curing of Thermoset Material

Recently, it has been reported by our group and others^1.2 that loss of curing agent is encountered during the curing of small droplets or thin films of amine cured epoxies. In our earlier study³ results were reported on loss of curing agent in small droplets used in conducting the rnicrobond, single fiber test for determination of interfacial shear strength (ISS). It was reported that use of a volatile curing agent (meta-phenylene diamine (m-PDA) with DGEBA resin) resulted in increasing amounts of curing agent being lost (as measured by T₈ of the cured droplets) with decreasing droplet size during the processing procedure. Droplets smaller than 150 micrometers were seen to lose up to 40% of the curing agent leading to alteration of the mechanical properties of the droplet and, therefore, causing measured values of ISS to be exceedingly low. Use of a less volatile curing agent (Jeffamine 700, a polyether diamine, Texaco Specialty Chemicals) in combination with DGEBA resin produced results which indicated that loss of curing agent was not occuring. This study was undertaken to show the relationships between film (or droplet) size and the amount of curing agent lost (during the processing) for three different aminecured epoxy systems.     

Stoichiometry of Fully Oxidized PuO2-NdO1.5 and PuO2-YO1.5 Solid Solutions

A new method has been established to calculate sensitivity coefficients of cell parameters based on generalized perturbation theory using the collision probability method. The proposed method does not require the calculation of the changes of collision probabilities due to cross section changes, so it is as powerful as the commonly used generalized perturbation theory in diffusion theory, We demonstrate the validity of the method by comparing the calculated sensitivity coefficients with those obtained from the direct cell calculations. AS an application, we calculate the sensitivity coefficients of neutronic properties in cells with different moderator to fuel volume ratios, and discuss the physical meaning of the difference between the sensitivity coefficients.     

Effect of composition of starting materials of Mo–Si on self-propagating high temperature SHS reaction

Abstract

An experimental study of the self-propagating high temperature synthesis of Mo–Si alloys was conducted from elemental powder compacts. Test specimens with seven compositions, including Mo/Si?=?1∶1·25, 1∶1·50, 1∶1·75, 1∶2·00, 1∶2·25, 1∶2·50 and 1∶2·75 respectively, were employed. Experimental evidence showed that a combustion wave featuring a spinning reaction zone can be observed. When the powder compacts are from Mo∶1·25Si to Mo∶1·75Si, the combustion temperature and the propagation velocity of combustion wave increase with increasing silicon in the sample, and the combustion products are composed of MoSi₂, Mo₅Si₃ and Mo. However, when the powder compacts are from Mo∶2·25Si to Mo∶2·75Si, the combustion temperature and the propagation velocity decrease rapidly as the silicon in the compact increases, and the combustion products are composed of MoSi₂ and Si. The sample with Mo/Si?=?1∶2·00 possesses the highest combustion temperature (1628·9 K) and propagation velocity (3·13 mm s^?1). A single-phase MoSi₂ is synthesised by the Mo/Si?=?1∶2·00 sample.     

Electrode characteristics of non-stoichiometric Ml(NiMnAlFe)_x alloys

1　ＩＮＴＲＯＤＵＣＴＩＯＮＭｉｓｃｈｍｅｔａｌｂａｓｅｄＡＢ5 ｔｙｐｅＭｍ (ＮｉＣｏＭｎＡｌ) 5ａｌｌｏｙｓａｒｅｎｏｗｗｉｄｅｌｙｕｓｅｄａｓｔｈｅｎｅｇａｔｉｖｅｅｌｅｃｔｒｏｄｅｍａｔｅｒｉａｌｓｏｆＮｉ/ＭＨｂａｔｔｅｒｉｅｓ.Ａｍｏｎｇｔｈｅｅｌｅｍｅｎｔｓｏｆｔｈｅａｌｌｏｙｓ,Ｃｏｈａｓｂｅｅｎｂｅｌｉｅｖｅｄｔｏｈａｖｅｔｈｅｅｆｆｅｃｔｏｆｌｏｗｅｒｉｎｇｔｈｅｖｏｌｕｍｅｅｘｐａｎｓｉｏｎｏｆｔｈｅｃｏｍｐｏｕｎｄｏｎｈｙｄｒｏｇｅｎａｔｉｏｎ[1 ] ａｎｄｐｒｅｖｅｎｔｉｎｇｔｈ…     

X射线三轴晶衍射法测量半绝缘GaAs单晶的化学配比

采用X射线三轴晶衍射法,根据As间隙原子对作为过量As在GaAs单晶材料中存在的主要形式的模型,可以无损、高精度测量半绝缘GaAs单晶的化学配比.并探讨了引起晶格变化的原因及其与熔体组分的关系,对于制备高质量GaAs单晶及其光电器件具有重要的意义.     

SHS of shape memory CuZnAl alloys

Aiming at preparation of shape memory alloys (SMAs), we explored the SHS of Cu_{1 − x} Zn_{1 − y} Al_{1 − z} alloys (0.29 < x < 0.30, 0.74 < y < 0.75, and 0.83 < z < 0.96). The most pronounced shape memory effect was exhibited by the alloys of the following compositions (wt %): (1) Cu(70.6)Zn(25.4)Al(4.0), (2) Cu(70.1)Zn(25.9)Al(4.0), and (3) Cu(69.9)Zn(26.1)Al(4.0). The effect of process parameters on the synthesis of CuZnAl alloys was studied by XRD, optical microscopy, and scanning electron microscopy (SEM). The grain size of CuZnAl was found to depend on the relative amount of the primary CuZn and AlZn phases. Changes in the transformation temperature and heat of transformation are discussed in terms of ignition intensity and compaction. Mechanism of the process depends on the level of the temperature attained relative to the melting point of components. At the melting point of AlZn, the process is controlled by the solid-state diffusion of AlZn into a product layer. The ignition temperature for this system depends on the temperature of the austenite-martensite transformation in CuZnAl alloys. The composition and structure of the products was found to markedly depend on process parameters. The SHS technique has been successfully used to prepare a variety of SMAs.      

电子束蒸发沉积碲锗铅薄膜的微结构和化学组分研究

为了探寻碲锗铅(Pb_(1-x)Ge_xTe)薄膜的最佳沉积方式,在硅基片上采用电子束蒸发沉积碲锗铅(Pb_(0.78)Ge_(0.22)Te)薄膜。使用X射线衍射(XRD)、电子扫描显微镜(SEM)、能量散射X射线分析(EDAX)等手段对薄膜的微结构和化学配比特性进行了分析。发现碲锗铅薄膜为多晶结构,具有明显的择优取向,晶粒多为矩形,薄膜中未出现其它相关氧化物。与热蒸发膜层相比,电子束蒸发沉积的膜层有更为完善的晶体结构。