CIAC COMPREHENSIVE INFORMATION-SYSTEM OF RARE-EARTHS

The CIAC (Changchun Institute of Applied Chemistry) Comprehensive information System of Rare Earths is composed of three subsystems, namely, extraction data, physicochemical properties, and reference data. This paper describes the databases pertaining to the extraction of rare earths and their physicochemical properties and discusses the relationships between data retrieval and optimization and between the structures of the extractants and the efficiency with which they are extracted. Expert systems for rare earth extraction and calculation of thermodynamic parameters are described, and an application of pattern recognition to the problems of classification of compounds of the rare earths and prediction of their properties is reported.

THERMODYNAMICS OF COMPLEXATION OF RARE EARTHS BY L-METHIONINE

The protonation constant of the ligand and stability constants of it complexes with rare earths have been determined by potentiometric titration at 25 degrees C and ionic strength mu=0.15 mol - L-1. The results indicate that rare earth elements can form 1:1 complexes with L methionine. There is an apparent "tetrad effect" in this system. Shift of the yttrium position to the vicinity of Gd can he explained by the different polarisation between the Ln(3+) and the ligand. The enthalpy changed (Lambda H-101) of the coordination reaction as represented by the reaction (M + L (sic) ML) here been measured by calorimetric titration, where M and L. denote are eartus and L-Mer respectively. The Lambda G(101) and Delta S-101 of these reaction have been calculated by using Gibbs' equation, Furthermore, the stability of rare earth complexes with L-Met has been compared with that of Ca3+ Zn3+, Fe2+, Fe3+ complexes with L-Met.

IR AND RAMAN-SPECTRA STUDIES OF THE RARE EARCH COMPLEXES WITH GLUTATHIONE

The complexes of rare earth ions with glutathione were prepared and charactrized by IR and Raman spectroscopy in the solid state. Based on the spectral results, the structure and coordination sites of the ligand in these complexes were determined.

A review of high magnetic moment thin films for microscale and nanotechnology applications

The creation of large magnetic fields is a necessary component in many technologies, ranging from magnetic resonance imaging, electric motors and generators, and magnetic hard disk drives in information storage. This is typically done by inserting a ferromagnetic pole piece with a large magnetisation density MS in a solenoid. In addition to large MS, it is usually required or desired that the ferromagnet is magnetically soft and has a Curie temperature well above the operating temperature of the device. A variety of ferromagnetic materials are currently in use, ranging from FeCo alloys in, for example, hard disk drives, to rare earth metals operating at cryogenic temperatures in superconducting solenoids. These latter can exceed the limit on MS for transition metal alloys given by the Slater-Pauling curve. This article reviews different materials and concepts in use or proposed for technological applications that require a large MS, with an emphasis on nanoscale material systems, such as thin and ultra-thin films. Attention is also paid to other requirements or properties, such as the Curie temperature and magnetic softness. In a final summary, we evaluate the actual applicability of the discussed materials for use as pole tips in electromagnets, in particular, in nanoscale magnetic hard disk drive read-write heads; the technological advancement of the latter has been a very strong driving force in the development of the field of nanomagnetism.

Geochemistry of Rare Erath Elements and Trace Metals along the Western Continental Shelf of India

Rare earth elements have occupied an important role in marine geochemical research, particularly as used in the format of REE abundance patterns to describe the geochemical pathways in marine sedimentation and authigenesis. This study concentrates on the distribution pattern of Rare earth elements in the sediments, behavior of Eu and Ce with respect to their occurrence in multiple oxidation states. It also concentrate the depth wise variation of sediment REEs from near shore areas (30m) to deeper depths 200m) in the Arabian Sea. It includes the downcore variation of REEs and other trace elements in the sediment cores and a comparison between the REE distributions of Arabian Sea sediment with the sediments of Andaman Sea. The study gives a general introduction regarding the importance of RRE studies, its occurrence and abundance, electronic configuration, lanthanide contraction, oxidations states and REE supply to the ocean, seawater and sediments.

Studies on grain refinement and alloying additions on the microstructure and mechanical properties of Mg-8Zn-4Al alloy

MAGNESIUM ALLOYS have strong potential for weight reduction in a wide range of technical applications because of their low density compared to other structural metallic materials. Therefore, an extensive growth of magnesium alloys usage in the automobile sector is expected in the coming years to enhance the fuel efficiency through mass reduction. The drawback associated with the use of commercially cheaper Mg-Al based alloys, such as AZ91, AM60 and AM50 are their inferior creep properties above 100ºC due to the presence of discontinuous Mg17A112 phases at the grain boundaries. Although rare earth-based magnesium alloys show better mechanical properties, it is not economically viable to use these alloys in auto industries. Recently, many new Mg-Al based alloy systems have been developed for high temperature applications, which do not contain the Mg17Al12 phase. It has been proved that the addition of a high percentage of zinc (which depends upon the percentage of Al) to binary Mg-Al alloys also ensures the complete removal of the Mg17Al12 phase and hence exhibits superior high temperature properties.ZA84 alloy is one such system, which has 8%Zn in it (Mg-8Zn-4Al-0.2Mn, all are in wt %) and shows superior creep resistance compared to AZ and AM series alloys. These alloys are mostly used in die casting industries. However, there are certain large and heavy components, made up of this alloy by sand castings that show lower mechanical properties because of their coarse microstructure. Moreover, further improvement in their high temperature behaviour through microstructural modification is also an essential task to make this alloy suitable for the replacement of high strength aluminium alloys used in automobile industry. Grain refinement is an effective way to improve the tensile behaviour of engineering alloys. In fact, grain refinement of Mg-Al based alloys is well documented in literature. However, there is no grain refiner commercially available in the market for Mg-Al alloys. It is also reported in the literature that the microstructure of AZ91 alloy is modified through the minor elemental additions such as Sb, Si, Sr, Ca, etc., which enhance its high temperature properties because of the formation of new stable intermetallics. The same strategy can be used with the ZA84 alloy system to improve its high temperature properties further without sacrificing the other properties. The primary objective of the present research work, “Studies on grain refinement and alloying additions on the microstructure and mechanical properties of Mg-8Zn-4Al alloy” is twofold: 1. To investigate the role of individual and combined additions of Sb and Ca on the microstructure and mechanical properties of ZA84 alloy. 2. To synthesis a novel Mg-1wt%Al4C3 master alloy for grain refinement of ZA84 alloy and investigate its effects on mechanical properties.

Magnetische Kopplungen in magneto-optischen Speicherschichten

Im Rahmen dieser Arbeit wurden magneto-optische Speicherschichten und ihre Kopplungen untereinander untersucht. Hierzu wurden zum Einen die für die magneto-optische Speichertechnologie "klassischen" Schichten aus RE/TM-Legierungen verwendet, zum Anderen aber auch erfolgreich Granate integriert, die bisher nicht in diesem Anwendungsgebiet verwendet wurden. Einleitend werden die magneto-optischen Verfahren, die resultierenden Anforderungen an die dünnen Schichten und die entsprechenden physikalischen Grundlagen diskutiert. Außerdem wird auf das Hochfrequenz-Sputtern von RE/TM-Legierungen eingegangen und die verwendeten magneto-optischen Messverfahren werden erläutert [Kap. 2 & 3]. Die Untersuchungen an RE/TM-Schichten bestätigen die aus der Literatur bekannten Eigenschaften. Sie lassen sich effektiv, und für magneto-optische Anwendungen geeignet, über RF-Sputtern herstellen. Die unmittelbaren Schicht-Parameter, wie Schichtdicke und Terbium-Konzentration, lassen sich über einfache Zusammenhänge einstellen. Da die Terbium-Konzentration eine Änderung der Kompensationstemperatur bewirkt, lässt sich diese mit Messungen am Kerr-Magnetometer überprüfen. Die für die Anwendung interessante senkrechte magnetische Anisotropie konnte ebenfalls mit den Herstellungsbedingungen verknüpft werden. Bei der Herstellung der Schichten auf einer glatten Glas-Oberfläche (Floatglas) zeigt die RE/TM-Schicht bereits in den ersten Lagen ein Wachstumsverhalten, das eine senkrechte Anisotropie bewirkt. Auf einer Quarzglas- oder Keramik-Oberfläche wachsen die ersten Lagen in einer durch das Substrat induzierten Struktur auf, danach ändert sich das Wachstumsverhalten stetig, bis eine senkrechte Anisotropie erreicht wird. Dieses Verhalten kann auch durch verschiedene Pufferschichten (Aluminium und Siliziumnitrid) nur unwesentlich beeinflusst werden [Kap. 5 & Kap. 6]. Bei der direkten Aufbringung von Doppelschichten, bestehend aus einer Auslese-Schicht (GdFeCo) auf einer Speicherschicht (TbFeCo), wurde die Austausch-Kopplung demonstriert. Die Ausleseschicht zeigt unterhalb der Kompensationstemperatur keine Kopplung an die Speicherschicht, während oberhalb der Kompensationstemperatur eine direkte Kopplung der Untergitter stattfindet. Daraus ergibt sich das für den MSR-Effekt erwünschte Maskierungsverhalten. Die vorher aus den Einzelschichten gewonnen Ergebnisse zu Kompensationstemperatur und Wachstumsverhalten konnten in den Doppelschichten wiedergefunden werden. Als Idealfall erweist sich hier die einfachste Struktur. Man bringt die Speicherschicht auf Floatglas auf und bedeckt diese direkt mit der Ausleseschicht [Kap. 7]. Weiterhin konnte gezeigt werden, dass es möglich ist, den Faraday-Effekt einer Granatschicht als verstärkendes Element zu nutzen. Im anwendungstauglichen, integrierten Schichtsystem konnten die kostengünstig, mit dem Sol-Gel-Verfahren produzierten, Granate die strukturellen Anforderungen nicht erfüllen, da sich während der Herstellung Risse und Löcher gebildet haben. Bei der experimentellen Realisierung mit einer einkristallinen Granatschicht und einer RE/TM-Schicht konnte die prinzipielle Eignung des Schichtsystems demonstriert werden [Kap. 8].

Optical and electrical characterization of samaria-doped ceria

Ce(0.8)SM(0.2)O(1.9) and CeO(2) nanomaterials were prepared by a solution technique to produce an ultrafine particulate material with high sinterability. In this work, the structural characteristics, the photoluminescent behavior and the ionic conductivity of the synthesized materials are focused. The thermally decomposed material consists of less than 10 nm in diameter nanoparticles. The Raman spectrum of pure CeO(2) consists of a single triple degenerate F(2g) model characteristic of the fluorite-like structure. The full width at half maximum of this band decreases linearly with increasing calcination temperature. The photoluminescence spectra show a broadened emission band assigned to the ligand-to-metal charge-transfer states O -> Ce(4+). The emission spectra of the Ce(0.8)Sm(0.2)O(1.9) specimens present narrow bands arising from the 4G(5/2) -> (6)H(J) transitions (J = 5/2, 7/2, 9/2 and 11/2) of Sm(3+) ion due to the efficient energy transfer from the O -> Ce(4+) transitions to the emitter 4G(5/2) level. The ionic conductivity of sintered specimens shows a significant dependence on density. (C) 2009 Elsevier B.V. All rights reserved.

Potentiostatic control of ionic liquid surface film formation on ZE41 magnesium alloy

The generation of potentially corrosion-resistant films on light metal alloys of magnesium have been investigated. Magnesium alloy, ZE41 [Mg−Zn−Rare Earth (RE)-Zr, nominal composition 4 wt % Zn, 1.7 wt % RE (Ce), 0.6 wt % Zr, remaining balance, Mg], was exposed under potentiostatic control to the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate, denoted [P_6,6,6,14][DPP]. During exposure to this IL, a bias potential, shifted from open circuit, was applied to the ZE41 surface. Electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA) were used to monitor the evolution of film formation on the metal surface during exposure. The EIS data indicate that, of the four bias potentials examined, applying a potential of −200 mV versus OCP during the exposure period resulted in surface films of greatest resistance. Both EIS measurements and scanning electron microscopy (SEM) imaging indicate that these surfaces are substantially different to those formed without potential bias. Time of flight-secondary ion mass spectrometry (ToF-SIMS) elemental mapping of the films was utilized to ascertain the distribution of the ionic liquid cationic and anionic species relative to the microstructural surface features of ZE41 and indicated a more uniform distribution compared with the surface following exposure in the absence of a bias potential. Immersion of the treated ZE41 specimens in a chloride contaminated salt solution clearly indicated that the ionic liquid generated surface films offered significant protection against pitting corrosion, although the intermetallics were still insufficiently protected by the IL and hence favored intergranular corrosion processes.

An electrochemical impedance study of ionic liquid film formation and aqueous corrosion of magnesium alloy ZE41

Ionic liquid surface treatments are proposed as a method of controlling corrosion processes on magnesium alloys. An important magnesium alloy, ZE41 (nominally 4% Zn and 1% rare earth), was treated with the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate (P₆₆₆₁₄DPP). Impedance spectra were acquired at intervals during the treatment, indicating the development of a film and allowing a measure of the film formation process to be obtained over time. Mechanically polished and electro-polished surfaces were prepared; these surfaces, treated and untreated, were subsequently exposed to 0.1 M NaCl aqueous solutions. The corrosion behavior of the prepared surfaces were assessed using impedance spectroscopy and optical microscopy. The results indicated a significant role for the method of surface preparation used and, in both cases, the ionic liquid treatment produced a more corrosion-resistant surface.

Solute segregation and texture modification in an extruded magnesium alloy containing gadolinium

The alloy Mg-1.5Gd has been extruded at different temperatures to produce two significantly different textures. At lower extrusion temperatures there was significant solute clustering in the matrix, coupled with segregation of solute to the grain boundaries. At higher temperatures these two phenomena were both less pronounced. It is suggested here that segregation of solute to the grain boundaries plays a significant role in the texture modification effect that rare earth elements have in magnesium alloys.

The corrosion inhibition of aluminium alloy 7075-T651 with cerium and Mischmetal di phenyl phosphate

Previous studies have shown that cerium diphenyl phosphate (Cedpp) 3 is a very effective inhibitor of corrosion of aluminium alloys in chloride solutions. This paper describes the results of further studies using electrochemical and constant immersion corrosion tests to compare the effectiveness of Ce(dpp) 3 and Mischmetal diphenyl phosphate Mm(dpp) 3 as inhibitors of corrosion pitting on AA7075-T651 aluminium alloy. The results shows that both Ce(dpp) 3 and Mm(dpp) 3 are excellent inhibitors of pitting corrosion of this alloy in very aggressive environments of continuously aerated 0.1M and 1.0M sodium chloride (NaCl) solutions. Polarisation tests indicate that these compounds act as a cathodic inhibitors by reducing the rate of the oxygen reduction reaction, which results in a decreased corrosion current density and a separation of the corrosion potential from the pitting potential. This inhibition is thought to be due to the formation of a surface film consisting of rare earth metal oxide, aluminium oxide and a cerium-aluminium organo-phosphate complex. Surface analysis data from scanning electron microscopy and X-ray Energy Dispersive Spectroscopy show the complex nature of this protective film. This work further develops our understanding about the mechanisms through which these complex films form, and how inhibition occurs in the presence of these compounds.

Nanostructured hybrid films containing nanophosphor: Fabrication and electronic spectral properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nanosized lead lanthanum titanate (PLT) ceramic powders synthesized by the oxidant peroxo method

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Yttrium oxysulfide nanosized spherical particles doped with Yb and Er or Yb and Tm: efficient materials for up-converting phosphor technology field

This work reports on the preparation, structural and luminescent studies of nanosized up-converter phosphors Y2O2S:Yb(4%), Er(0.1%) and Y2O2S:Yb(4%), Tm(0.1%),both from polymeric and basic carbonate precursors. The precursors were submitted to a sulphuration process that was previously developed for oxysulfide preparation from basic carbonate. From XRD data, all phosphors presented the oxysulfide phase and the mean crystallite size estimated from the Scherrer formula in the range of 15-20 nm. Polymeric precursor leads to the smallest crystallite size independent on the doping ion. SEM and TEM results confirmed that basic carbonate leads to spherical particles with narrow size distribution and mean diameter of 150 nm, and polymeric precursor smaller spherical particles with diameter between 20 and 40 nm. Up-conversion studies under 980 nm laser excitation showed that Er-doped phosphors present strong green emission related to H-2(11/2), S-4(3/2) --> I-4(15/2) Er transitions as well as the red ones, F-4(9/2) --> I-4(15/2). Tm-doped samples show strong blue emission assigned to (1)G(4) --> H-3(6) and also the red ones, related to (1)G(4) --> F-3(4). Therefore, the sulphuration method was successfully applied to prepare nanosized and nanostructured blue and green up-converter oxysulfide phosphors starting from basic carbonate and polymeric precursors. (C) 2003 Elsevier B.V. All rights reserved.