新铌酸盐Ba_3Ni_(0.33)Nb_(4.67)O_(15)的合成与X射线衍射分析

在BaO -Ni2O3 -Nb2O5 三元系统中 ,用固相反应法合成了新铌酸盐Ba3Ni0.33Nb4.67O15。以BaCl2 和B2O3为主要助熔剂制备了Ba3Ni0.33Nb4.67O15 的单晶体。利用四圆单晶衍射仪测定晶胞参数 ,然后采用X射线粉晶衍射法进行了物相分析,对该化合物的粉晶衍射数据进行了指标化 ,并报道了其X射线衍射数据。分析结果表明 ,该化合物属于填满型四方钨青铜结构 ,空间群P4bm(100),晶胞参数为 :a=1.26092(5)nm ,c=0.40096(4)nm ,α=β=γ=90°,Z=2。     

铌酸盐Ba6FeNb9O30的XRD研究

在BaO -Fe2O3-Nb2O5 三元系统中 ,新发现存在铌酸盐Ba6FeNb9O30,利用四圆单晶衍射仪进行了晶胞参数测定 ,然后采用X射线粉晶衍射法获得该化合物的粉晶衍射数据 ,并进行了指标化 ,F30 =32(0.016,58)。XRD分析结果表明 ,该化合物属于填满型四方钨青铜结构 ,晶胞参数为 :a=1.25812(4)nm ,c=0.3992(4)nm ,α=β=γ=90°。     

铌酸盐 Ba5YTi3 Nb7 O30的结构与介电性能

在BaO-TiO2-Mb2O5体系中通过掺Y3－合成了铌酸盐Ba5YTi3Nb7O30 ,采用粉晶X射线衍射（XRD）对其结构进行了分析,并测试了其烧结体的介电特性,结果表明,在室温下Ba4YT3 Nb7O30属于填满型四方钨青铜结构,晶胞参数,a=1.24332(2)nm,c=0.39453(1)nm,α=β=γ＝90度,Ba5TYi3Nb7O30在100度从铁电相转变为顺电相。     

新钽酸盐Ba2LnTi2Ta3O15(Ln=Y、La)的结构与介电性能

通过固相反应法合成了四方钨青铜结构新钽酸盐Ba2LaTi2Ta3O15与Ba2YTi2Ta3O15,分别进行了X射线衍射分析与介电性能测试.结果表明, Ba2LaTi2Ta3O15室温时晶胞参数为a=1.242 64(5) nm, c=0.391 57(2) nm,为四方钨青铜结构顺电相；Ba2YTi2Ta3O15室温时晶胞参数为a=1.236 46(4) nm, c=0.388 60(2) nm,为四方钨青铜结构铁电相,铁电相与顺电相转变温度为180 ℃.频率为1 MHz时, Ba2LaTi2Ta3O15陶瓷的室温相对介电常数为194,介电损耗也降低至8×10－4. Ba2YTi2Ta3O15陶瓷的室温相对介电常数为107.     

钽酸盐Ba5YTi3Ta7O30的X射线衍射分析及其介电特性

在BaO -TiO2-Ta2O5 体系中通过掺Y3 +合成了钽酸盐Ba5YTi3Ta7O30,采用粉晶X射线衍射 (XRD)对其结构进行了分析 ,并测试了其陶瓷体的介电特性;结果表明 ,Ba5YTi3Ta7O30 在室温下属于填满型四方钨青铜结构顺电相,晶胞参数为a=1.24387(2)nm,c=0.39178(1)nm ,α= β=γ=90° ;频率为1MHz时Ba5YTi3Ta7O30 陶瓷的室温相对介电常数为155 ;而且介电损耗低至0.0009。     

吡啶-2-甲酸镍的合成及其晶体结构

以吡啶 2 甲酸和Ni(ClO4)2·6H2O为原料反应制得配合物[Ni(C5H4NCOO)2(H2O)2]2H2O,并通过X 射线衍射法测定其晶体结构.该化合物属于单斜晶系,空间群P21/n,晶胞参数:a=0.97351(15)nm,b=0.52254(8)nm,c=1.4483(2)nm,β=90.119(3)°,V=0.7367(2)nm3,Z=2,Dc=1.690g/cm3,μ=1.362mm 1,F(000)=388,结构偏离因子R1=0.0316,wR2=0.0902,共收集到4771个强度数据,其中1700个独立衍射点,1489个(I>2σ(I))可观测点.X 射线分析表明晶体是由分子间氢键和π π弱相互作用堆积而成的二维层状结构.     

新钽酸盐Ba3TiTa4O15的结构与介电性能

在BaO Ta2O5系统通过掺Ti4＋合成了新钽酸盐Ba3TiTa4O15,用粉晶XRD对其结构进行了分析,并测试了其烧结体的介电特性.结果表明:Ba3TiTa4O15在室温下属于填满型四方钨青铜结构,晶胞参数a=1.256 27(6)nm, c=0.395 86(4)nm; Ba3TiTa4O15在－35 ℃从铁电相转变为顺电相.     

钙钛矿型层状化合物K2Sm2Ti3O10的合成及XRD表征

在K2CO3-镧系元素氧化物(Sm2O3)-TiO2三元体系中,用固相反应法合成了K2Sm2Ti3O10,利用X射线粉晶衍射仪对K2Sm2Ti3O10进行扫描测定,获得X射线衍射数据,并进行指标化.XRD分析结果表明,K2Sm2Ti3O10为四方晶系,空间群(S.G.)I4/mmm,晶胞参数:a=0.384 28 nm;c=2.971 8 nm;V=0.438 85 nm3;D0=5.165 6 g·mL-1;晶胞分子数Z=2.     

新钽酸盐K_6FeTa_(15)O_(42)的合成与表征

在K2O -Fe2O3-Ta2O5 三元系统中 ,新发现存在钽酸盐K6FeTa15O42,使用X射线衍射(XRD)、电子探针微区分析(EPMA)、扫描电镜(SEM)、差热分析(DTA)等方法对该化合物的晶体结构、成分、形态、光学性质、溶解性、熔点及密度进行了研究。新化合物K6FeTa15O42 晶体属于六方晶系,空间群P63/mcm,晶胞参数a=0.91221(1)nm,c=1.21084(4)nm,Z=1,V=0.87258nm3。     

新铌酸盐Ba5LnZnNb9O30(Ln=Y,La)的合成、结构与介电性能

在BaO-Ln2O3-ZnO-Nb2O5(Ln=Y,La)体系中通过固相反应法合成了填满型钨青铜结构的新铌酸盐Ba5YZnNb9O30与Ba5LaZnNb9O30.采用X射线衍射分析和扫描电镜进行了结构分析,并进行了介电性能测试.结果表明,Ba5YZnNb9O30为弛豫性铁电体,10kHz时的居里温度为25℃;室温时为四方钨青铜结构铁电相,晶胞参数a=1.25255(4)nm,c=0.39530(2)nm;1MHz时陶瓷体的室温相对介电常数为456.Ba5YZnNb9O30在室温下为四方钨青铜结构顺电相,晶胞参数a=1.25731(3)nm,c=0.39812(2)nm;频率为1MHz时,其陶瓷的室温相对介电常数为316.     

KCl-KBO2-K2CO3, K2MoO4-KBO2-K2CO3, and K2WO4-KBO2-K2CO3 ternary systems

phase diagrams of KCl-KBO₂-K₂CO₃, K₂MoO₄-KBO₂-K₂CO₃, and K₂WO₄-KBO₂-K₂CO₃ ternary systems were studied by a calculation-experimental method and differential thermal analysis (DTA). The coordinates of ternary eutectics were determined to be E ₁: 622°C, 8.5 mol % KBO₂, 56.5 mol % KCl, and 35 mol % K₂CO₃; E ₂: 710°C, 23 mol % KBO₂, 43 mol % K₂CO₃, and 34 mol % K₂MoO₄; E ₃: 710°C, 23 mol % KBO₂, 43 mol % K₂CO₃, and 34 mol % K₂WO₄. The specific heats of melting of the eutectics were determined.     

Phase relations in the K2W2O7-K2WO4-KPO3-Bi2O3 system and structure of K6.5Bi2.5W4P6O34

The phase relations in the cross-section of the K₂W₂O₇-K₂WO₄-KPO₃ containing 15 mol% Bi₂O₃ were undertaken using flux method. Crystallization fields of K_6.5Bi_2.5W₄P₆O₃₄, K₂Bi(PO₄)(WO₄), Bi₂WO₆, KBi(WO₄)₂ and their cocrystallization areas were identified. Novel phase K_6.5Bi_2.5W₄P₆O₃₄ was characterized by single-crystal X-ray diffraction: sp. gr. P−1, a=9.4170(5), b=9.7166(4), c=17.6050(7) Å, α=90.052(5)°, β=103.880(5)° and γ=90.125(5)°. It has a layered structure, which contains {K₇Bi₅W₈P₁₂O₆₈}_∞ layers stacked parallel to ab plane and sheets composed by potassium atoms separating these layers. Sandwich-like {K₇Bi₅W₈P₁₂O₆₈}_∞ layers are assembled from [W₂P₂O₁₃]_∞ and [BiPO₄]_∞ building units, and are penetrated by tunnels with K/Bi atoms inside. FTIR-spectra of K₂Bi(PO₄)(WO₄) and K_6.5Bi_2.5W₄P₆O₃₄ were discussed on the basis of factor group theory.     

Sol-gel synthesis of K3InF6 and structural characterization of K2InC10O10H6F9, K3InC12O14H4F18 and K3InC12O12F18

K₃InF₆ is synthesized by a sol-gel route starting from indium and potassium acetates dissolved in isopropanol in the stoichiometry 1:3, with trifluoroacetic acid as fluorinating agent. The crystal structures of the organic precursors were solved by X-ray diffraction methods on single crystals. Three organic compounds were isolated and identified: K₂InC₁₀O₁₀H₆F₉, K₃InC₁₂O₁₄H₄F₁₈ and K₃InC₁₂O₁₂F₁₈. The first one, deficient in potassium in comparison with the initial stoichiometry, is unstable. In its crystal structure, acetate as well as trifluoroacetate anions are coordinated to the indium atom. The two other precursors are obtained, respectively, by quick and slow evaporation of the solution. They correspond to the final organic compounds, which give K₃InF₆ by decomposition at high temperature. The crystal structure of K₃InC₁₂O₁₄H₄F₁₈ is characterized by complex anions [In(CF₃COO)₄(OH_x)₂]^(5−2x)− and isolated [CF₃COOH_2−x]^(x−1)− molecules with x=2 or 1, surrounded by K⁺ cations. The crystal structure of K₃InC₁₂O₁₂F₁₈ is only constituted by complex anions [In(CF₃COO)₆]³⁻ and K⁺ cations. For all these compounds, potassium cations ensure only the electroneutrality of the structure. IR spectra of K₂InC₁₀O₁₀H₆F₉ and K₃InC₁₂O₁₂F₁₈ were also performed at room temperature on pulverized crystals.     

Solubility in the Na2Cr2O7-(NH4)2Cr2O7-K2Cr2O7-H2O system

Solubility in the Na₂Cr₂O₇-(NH₄)₂Cr₂O₇-K₂Cr₂O₇-H₂O four-component water-salt system at 25, 50, and 75°C was studied for the first time. Phase field boundaries for individual salts and potassium and ammonium dichromate solid solutions, monovariant lines, and invariant points were determined. Experimental data were used to optimize the looped isohydric process of potassium dichromate preparation involving additional salts.     

NaBO2-NaCl-Na2CO3, NaBO2- Na2CO3-NaMoO4, NaBO2- Na2CO3-NaWO4, and NaBO2-NaCl-Na2WO4 ternary systems

The phase diagrams of the NaBO₂-NaCl-Na₂CO₃, NaBO₂-Na₂CO₃-Na₂MoO₄, NaBO₂- Na₂CO₃-Na₂WO₄, and NaBO₂-NaCl-Na₂WO₄ ternary systems were studied by a calculation-experimental method and differential thermal analysis. The coordinates of ternary eutectics were determined: E ₁: 612°C, 16 mol % NaBO₂, 42 mol % NaCl, and 42 mol % Na₂CO₃; E ₂: 568°C, 12 mol % NaBO₂, 28 mol % Na₂CO₃, and 60 mol % Na₂MoO₄; E ₃: 575°C, 12 mol % NaBO₂, 32 mol % Na₂CO₃, and 56 mol % Na₂WO₄; E ₄: 628°C, 8 mol % NaBO₂, 20 mol % NaCl, and 72 mol % Na₂WO₄; and E ₅: 655°C, 9 mol % NaBO₂, 53 mol % NaCl, and 38 mol % Na₂WO₄.     

Li2SO4-Na2SO4-H2O和Li2SO4- K2SO4-H2O溶液的体积性质

本文用高精度数字式振荡管密度计测定了288K至318K温度范围内Li₂SO₄ + Na₂SO₄ + H₂O和 Li₂SO₄ + K₂SO₄ + H₂O三元体系的密度。混合溶液的离子强度范围从0.1到4.5 mol.kg_–1,混合溶液中Na₂SO₄和K₂SO₄的离子强度分数为0.2,0.4,0.6和0.8。用密度实验值拟合得到了不同温度下Pitzer离子相互作用模型混合参数θ_V和 ψ_V,模型的计算值与实验值的偏差在±0.002 g.cm_–3以内。用Pitzer模型计算了不同离子强度下三元体系的混合体积。     

Extension of the La7Mo7O30 structural type with La7Nb3W4O30 and La7Ta3W4O30 compounds

Two compounds of formula La₇A₃W₄O₃₀ (with A=Nb and Ta) were prepared by solid-state reaction at 1450 and 1490 °C. They crystallize in the rhombohedric space group R-3 (No. 148), with the hexagonal parameters: , and , . The structure of the materials was analyzed from X-ray, neutron and electronic diffraction. These oxides are isostructural of the reduced molybdenum compound La₇Mo₇O₃₀, which are formed of perovskite rod along [111]. An order between (Nb, Ta) and W is observed.     

SnSbBiS4-SnS and SnSbBiS4-Sn2Sb6S11 sections of the SnS-Sb2S3-Bi2S3 ternary system

SnSbBiS₄-SnS and SnSbBiS₄-Sn₂Sb₆S₁₁ sections were studied by physicochemical methods (DTA, X-ray powder diffraction, microstructure observation, and microhardness measurements). These sections were found to be eutectic quasi-binary sections of the SnS-Sb₂S₃-Bi₂S₃ ternary system. Solid solution regions based on the initial components were found on either side of the sections. Alloys in the solid solution region are p-type semiconductors.     

Theoretical study of polyoxide clusters B20O30, Al20O30, V20O50, Si20O30H20, and Si20O30F20

The structural, electronic, and vibrational characteristics and energies of the isolated polyoxide clusters B₂₀O₃₀, Al₂₀O₃₀, V₂₀O₅₀, Si₂₀O₃₀H₂₀, and Si₂₀O₃₀F₂₀ and their complexes with the H⁻ ion and ammonia complexes Al₂₀O₃₀ · nNH₃ have been calculated by the density functional theory B3LYP method with different basis sets. The computation results show that the symmetric closo structure I _h with oxygen bridges located above the centers of the faces of an empty [M₂₀] dodecahedron is more favorable for V₂₀O₅₀, Si₂₀O₃₀H₂₀, and Si₂₀O₃₀F₂₀. For B₂₀O₃₀, the cage closo isomer is also more favorable than the other isomers, but its structure is severely distorted as compared to a dodecahedron and has a symmetry close to C ₃ . For Al₂₀O₃₀, the I _h structure corresponds to a high-lying local minimum of the potential energy surface. For Al₂₀O₃₀, a set of unusual puckshaped isomers of symmetry C _i , with different numbers of four-coordinate atoms ^IVAl and three-coordinate atoms ^IIIO, was localized; these structures are more than 90 kcal/mol more favorable than the dodecahedron I _h . The most favorable isomer of Al₂₀O₃₀ contains twelve four-coordinate atoms ^IVAl and four five-coordinate atoms ^VAl. The energies of dissociation of the most favorable M₂₀O₃₀ clusters into the M₂O₃ (C _2v ) and M₄O₆ (T _d ) fragments and, in the case of Al₂₀O₃₀, also into the Al₈O₁₂ (O _h ) and Al₁₂O₁₈ (D _3d ) fragments, have been estimated. The conclusion has been drawn that these clusters can, in principle, exist and can be experimentally detected in the isolated state. Analogous calculations have been performed for ammonia complexes Al₂₀O₃₀ · nNH₃ with n varying from 1 to 20. The effect of solvation on the relative stability of the dodecahedral and puckshaped isomers of the Al₂₀O₃₀ cluster is observed. The isomers with ammonia molecules in their first coordination sphere become much closer to one another on the energy scale; however, the dodecahedron remains a considerably less favorable intermediate. Original Russian Text ? O.P. Charkin, N.M. Klimenko, D.O. Charkin, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 4, pp. 624–635.     

Structural chemistry of Sr3Cr2WO9, Ca3Cr2WO9, and Ba3Cr2WO9

We have studied the preparation and crystallographic structure of three perovskite-type compounds: Sr₃Cr₂WO₉, cubic, the lattice parameter of which is a = 7.812Å; Ca₃Cr₂WO₉, tetragonal, the lattice parameters of which are a = 5.408 Å and c = 7.635Å; and Ba₃Cr₂WO₉, hexagonal, the lattice parameters of which are a = 5.691 Å and c = 13.957Å. We have compared these three structures and shown the relationship between the dimensions of the alkaline-earth metal and the existence of the different structures.