THE ROLE OF RARE EARTH CHLORIDES IN THE PACK-TiC COATING AGENT

If 1% rare earth chloride is added to the coating agent containing 5% AlCl_3,the coating efficiency of TiC will be increased greatly.A protective crust consisting of Al_2(SiO_3)_3 and SiO_2 will form on top of the coating agent in the temperature range of 850～1000℃ when SiO_2 powder of a thickness of 5～10 mm is spread on top of it.The protective crust can offer a good air-proof property and increase the denseness of the coating structure.

ELECTRONIC STRUCTURE AND BOND CHARACTER OF COMPLEXES OF RARE EARTH CHLORIDES WITH CROWN ETHERS

A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemical calculation.The calculated results are in good agreement with that obtained in the experiments.Three Cl atoms are on the same side of Ln in LnCl_3·15-C-5 and the crown ring on the other side.forming a complex molecule with coordination number 8.LnCl_3·15-C-5 is easily hygroscopic in air because of its unsaturated coordination,which differs sharply from the stable Ln(NO_3)_3·15-C-5 com- plex of coordination number 11.The HOMO and neighboring occupied MOs are composed of Cl 3p and O2p, and the LUMO and neighboring unoccupied MOs are composed of Ln orbitals.The level structure easily pro- duces Ln3d satellite in XPS caused by L→Ln charge transfer transition.Due to the coordination,the absolute values of the charge are decreased at Ln and O atoms,but increased at Cl atoms,which is in agreement with XPS results.

Calculation of RECl_3-CaCl_2-LiCl Phase Diagrams(RE=La, Ce, Pr, Nd)

Based on the assessment and optimization of nine experimental sub-binary phase diagramsand thermodynamic data (RECl3-LiCl, RECl3-CaCl2 and CaCl2-LiCl), four phase diagrams of theRECl3-CaCl2-LiCl systems are calculated and brieflly discussed.

Process optimization of rare earth and aluminum leaching from weathered crust elution-deposited rare earth ore with compound ammonium salts

In order to intensify the leaching process of rare earth（RE） and reduce the impurities in the leachate, ammonium chloride（NH4Cl） and ammonium nitrate（NH4NO3） were mixed as a compound leaching agent to treat the weathered crust elution-deposited RE ore. Effects of molar ratio of NH~＋_4Cl and NH_4NO_3, ammonium（NH_4） concentration, leaching agent pH and flow rate on the leaching process of RE were studied and evaluated by the chromatographic plate theory. Leaching process of the main impurity aluminium（Al） was also discussed in detail. Results showed that a higher initial ammonium concentration in a certain range could enhance the mass transfer process of RE and Al by providing a driving force to overcome the resistance of diffusion. pH almost had no effects on the mass transfer efficiency of RE and Al in the range of 4 to 8. The relationship between the flow rate and height equivalent to a theoretical plate（HETP） could fit well with the Van Deemter equation, and the flow rate at the lowest HETP was determined. The optimum conditions of column leaching for RE and Al were 1：1（molar ratio） of NH_4Cl and NH_4NO_3, 0.2 mol/L of ammonium concentration, pH 4–8 of leaching agent and 0.5 mL /min of flow rate. Under this condition, the mass transfer efficiency of RE was improved, but no change was observed for Al compared with the most widely used ammonium sulfate. Moreover, the significant difference value（around 20 mL） of retention volume at the peak concentration between RE and Al provided a possibility for their separation. It suggested the potential application of the novel compound leaching agent（NH_4Cl/NH_4NO_3）. It was found that the relative concentration of RE in the leachate could be easily obtained by monitoring the pH of leachate.

Ce_(1–x)La_xO_y solid solution prepared from mixed rare earth chloride for soot oxidation

Ce_（1–x）La_xO_y solid solution was simply prepared using mixed rare earth chloride（RECl_3·x H_2O, RE=Ce, La99%, containing unseparated Ce and La from rare earth metallurgical industry） as precursor by ultrasonic-assisted co-precipitation method with different ultrasonic frequencies（CLf, f=200, 400, 600, 800, 1000 Hz）. A compared Ce_（1–x）La_xO_y solid solution（CL＊） was also prepared by the same mothod with 10% less precipitant. X-ray diffraction results confirmed the formation of Ce1–xLaxOy solid solution, and the crystal structures of these catalysts were not very sensitive to ultrasonic frequency and precipitant amount. However, both of the factors had obvious effect on morphology and surface area of CL, and precipitant amount seem to play a more crucial role than ultrasonic frequency for Ce_（1–x）La_xO_y solid solution preparation. When soot and catalyst were tight contacted, the peak temperature（Tpeak） of soot oxidation and oxygen reducing temperature for CLf catalysts decreased linearly with increasing surface area. Under loose contact condition, the Tpeak had obvious negative correlation with H_2 consumption. It was inferred that good reducibility of the Ce_（1–x）La_xO_y solid solution favored the soot oxidation reaction. The Ce_（1–x）La_xO_y solid solution prepared from unseparated rare earth chloride showed a good soot oxidaiton activity. Controlling the preparation conditions to prepare a CL catalyst would high surface area will enhance its reducibility and activity.

Electrochemical behavior of praseodymium and Pr-Al intermetallics in LiCl-KCl-AlCl_3-PrCl_3 melts

The electrochemical behavior of Pr（Ⅲ） and formation process of Pr-Al intermetallics were investigated by different electrochemical methods. The reduction of Pr（Ⅲ） ion to metallic Pr is an one-step three-electrons reaction. The reversibility of Pr（Ⅲ）/Pr（0） system was evaluated by cyclic voltammograms with different scan rates. The co-reduction of Pr（Ⅲ） and Al（Ⅲ） ions formed three different Pr-Al intermetallics at electrode potentials around-1.40,-1.80,and-1.95V vs.Ag/AgCl at 723 K,respectively.Open-circuit chronopotentiometry and electromotive force（emf） measurements were carried out to estimate the relative molar Gibbs energies of Pr for the formation of different Pr-Al intermetallics in the temperature range of 723–843K.The activities of Pr in the Pr-Al intermetallic compounds were calculated.