The study of the crystalline phosphates of kosnarite type structure containing different alkali metals

The incorporation possibilities of different alkali elements into crystalline phosphates A_1−xA′_xHf₂(PO₄)₃ (A=Li, Na, K, Rb, Cs) were studied, the formation regions of kosnarite solid solutions were determined. Na_0.5K_0.5Hf₂(PO₄)₃ crystal structure was studied by powder X-ray diffraction, and the distribution of alkali metals in kosnarite structure was found out. The phosphate crystallizes in the space group R3?c, with a=8.7295(1) Å, c=23.2023(4) Å, V=1531.24(4) Å³, Z=6; R_wp=6.15, R_p=4.43. The concentration region knowledge of the kosnarite phase existence and peculiarities of their phase formation in the A_1−xA′_xM₂(PO₄)₃ (M=Ti, Zr, Hf) systems allow us to choose phosphate matrice compositions suitable for solidification of reprocessing wastes of spent U-Pu nuclear fuels.     

ACE applied to the quantitative characterization of benzo‐18‐crown‐6‐ether binding with alkali metal ions in a methanol–water solvent system

ACE was applied to the quantitative evaluation of noncovalent binding interactions between benzo‐18‐crown‐6‐ether (B18C6) and several alkali metal ions, Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺, in a mixed binary solvent system, methanol–water (50/50 v/v). The apparent binding (stability) constants (K_b) of B18C6–alkali metal ion complexes in the hydro‐organic medium above were determined from the dependence of the effective electrophoretic mobility of B18C6 on the concentration of alkali metal ions in the BGE using a nonlinear regression analysis. Before regression analysis, the mobilities measured by ACE at ambient temperature and variable ionic strength of the BGE were corrected by a new procedure to the reference temperature, 25°C, and the constant ionic strength, 10 mM . In the 50% v/v methanol–water solvent system, like in pure methanol, B18C6 formed the strongest complex with potassium ion (log K_b=2.89±0.17), the weakest complex with cesium ion (log K_b=2.04±0.20), and no complexation was observed between B18C6 and the lithium ion. In the mixed methanol–water solvent system, the binding constants of the complexes above were found to be about two orders lower than in methanol and about one order higher than in water.     

ICP-AES测定口香糖中的7种元素

对比了碱熔法和湿法消解两种不同的方法处理样品,用电感耦合等离子体-原子发射光谱法（ICP-AES）测定口香糖中的Ti、Mn、Al、Ca、As、Pb、Cd元素。并对结果比较好的湿法消解方法进行了加标回收实验,平均回收率在97.5%—102.5%之间。     

Processes of the excitation energy migration and transfer in Ce-doped alkali gadolinium phosphates studied with time-resolved photoluminescence spectroscopy technique

Spectral-kinetic characteristics of Gd³⁺ and Ce³⁺ luminescence from a series of Ce³⁺-doped alkali gadolinium phosphates of MGdP₄O₁₂ type (M=Li, Na, Cs) have been studied within 4.2-300 K temperature range using time-resolved luminescence spectroscopy techniques. The processes of energy migration along the Gd³⁺ sub-lattice and energy transfer between the Gd³⁺ and Ce³⁺ ions have been investigated. Peculiarities of these processes have been compared for MGdP₄O₁₂ phosphate hosts with different alkali metal ions. A contribution of different levels from the ⁶P_j multiplet of the lowest Gd³⁺ excited state into the energy migration and transfer processes has been clarified. The phonon-assisted occupation of high-energy ⁶P_{5/2, 3/2} levels by Gd³⁺ in the excited ⁶P_j state has been revealed as a shift of Gd³⁺⁶P_j→⁸S_7/2 emission into the short-wavelength spectral range upon the temperature increase. The relaxation of excited Gd³⁺ via phonon-assisted population of Gd³⁺⁶P_5/2 level (next higher one to the lowest excited ⁶P_7/2) is supposed to be responsible for the rise in probability of energy migration within the Gd³⁺ sub-lattice initiating the Gd³⁺→Ce³⁺ energy transfer at T<150 K, whereas further intensification of Gd³⁺→Ce³⁺ energy transfer at T>150 K is explained by the increase in probability of Gd³⁺ relaxation into the highest ⁶P_3/2 level of the ⁶P_j multiplet. An efficient reversed Ce³⁺→Gd³⁺ energy transfer has been revealed for the studied phosphates at 4.2 K.     

Synthesis and characterization of doped apatite-type lanthanum silicates for SOFC applications

A series of iron- and/or aluminium-doped apatite-type lanthanum silicates (ATLS) La_9.83Si_{6 ‐ x ‐ y}Al_xFe_yO_26 ± δ (x = 0, 0.25, 0.75, and 1.5, y = 0, 0.25, 0.75, and 1.5) were synthesized using the mechanochemical activation (MA), solid state reaction (SSR), Pechini (Pe) and sol-gel (SG) methods. The total conductivity of the prepared materials was measured under air in the temperature range 600-850 °C using 4-probe AC impedance spectroscopy. Its dependence on composition, synthesis method, sintering conditions and powder particle size was investigated. It was found that for electrolytes of the same composition, those prepared via mechanochemical activation exhibited the highest total specific conductivity, which was improved with increasing Al- and decreasing Fe-content. The highest conductivity value at 700 °C, equal to 2.04 × 10^− 2 S cm^− 1, was observed for the La_9.83Si₅Al_0.75Fe_0.25O_26 ± δ electrolyte. La_9.83Si_4.5Fe_1.5O_26 ± δ electrolyte samples synthesized using the Pechini method exhibited higher conductivity when sintered conventionally than when spark-plasma sintering (SPS) was used.     

All solid state ion-conducting cesium source for atomic clocks

Cesium containing glass with solid metal electrodes was used as a Cs atom source in a high vacuum system. A silver anode provides an injection source of highly mobile ions which sweep Cs to the cathode surface, from which they evaporate into the vacuum. Cathode metallization with finger patterns was used leaving bare glass for Cs evaporation. Laser absorption measurements show Cs vapor generation synchronous with an applied DC voltage.     

SPECTROPHOTOMETRIC STUDY OF COMPLEX FORMATION BETWEEN SOME ALKALI AND ALKALINE EARTH CATIONS AND SEVERAL CONVENTIONAL (N,N), (N,O) AND (O,O) LIGANDS IN 95% ETHANOL

Abstract

The complexation of Li⁺, Na⁺, Mg²⁺ and Ca²⁺ with 1,10-phenanthroline, 2,2′-bipyridine, 1,2-phenylenediamine, 2-aminopyridine, 8-hydroxyquinoline, catechol and ethylene glycol was studied in 95% ethanol by means of a competitive spectrophotometric method using murexide as indicator. Formation constants of 1:1 conplexes were determined. In the case of all ligands used, the stability of the complexes was found to vary in the order Mg²⁺ > Ca²⁺ > Li⁺ > Na⁺. It was found that the structure influences the formation and stability of resulting complexes. Effects of various parameters on complexation are discussed.