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1.
The phase relations in the cross-section of the K2W2O7-K2WO4-KPO3 containing 15 mol% Bi2O3 were undertaken using flux method. Crystallization fields of K6.5Bi2.5W4P6O34, K2Bi(PO4)(WO4), Bi2WO6, KBi(WO4)2 and their cocrystallization areas were identified. Novel phase K6.5Bi2.5W4P6O34 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 K6.5Bi2.5W4P6O34 were discussed on the basis of factor group theory.  相似文献   

2.
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(OHx)2](5−2x)− and isolated [CF3COOH2−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.  相似文献   

3.
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.  相似文献   

4.
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.  相似文献   

5.
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.  相似文献   

6.
The Pb5Sb4S11-Pb2SnSb2S6 system was studied by a number of physicochemical methods, and its phase diagram was constructed. It was found that the system under investigation is a quasi-binary eutectic type section of the SnS-PbS-Sb2S3 ternary system. The coordinates of the eutectic are found to be 33 mol % Pb5Sb4S11 and 750 K. Regions of solid solutions based on Pb5Sb4S11 (6 mol % Pb2SnSb2S6) and Pb2SnSb2S6 (4 mol % Pb5Sb4S11) were determined.  相似文献   

7.
Alloys in the As2S3-TlAs2S2Se2 section of the As2S3-As2Se3-TlS ternary system were studied and a phase diagram was constructed using physicochemical methods (differential thermal analysis, microstructural analysis, X-ray powder diffraction, also microhardness and density measurements). The diagram in the As2S3-TlAs2S2Se2 section is a non-quasi-binary diagonal section of the As2S3-As2Se3-TlSe quasi-ternary system. It was found that all the alloys in the section under ordinary conditions are obtained in the vitreous state. At low As2S3 concentrations in the section, solid solutions form up to 2.5 mol %, and at low TlAs2S2Se2 concentrations, their extent is 3 mol %.  相似文献   

8.
The In3As2Se6-In3As2S3Se3 system has been investigated by methods of physicochemical analysis (DTA, X-ray powder diffraction, MSA) and by microhardness and density measurements. The phase diagram of the system, which is the quasi-binary section of the As-In-S-Se quaternary system, has been constructed. The region of the In3As2Se6-based solid solutions is extended to 7 mol %, and the In 3As2S3Se3-based region to 15 mol %. A new quaternary compound In6As4S3Se9 is found in the system. Original Russian Text ? I.I. Aliev, R.S. Magammedragimova, A.A. Farzaliev, Dzh. Veliev, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 4, pp. 691–694.  相似文献   

9.
一些具有NASICON型网格结构的固体电解质具有高的电导率和好的稳定性,NASICON的意思是Na Super Ionic Conductor[1]。当NaZr2(PO4)3中P5 被Si4 部分取代时便可以得到具有NASICON结构的Na1 xZr2SixP3-xO12体系,其具有高的钠离子电导率。然而有相同结构的Li1 xZr2SixP3-xO12体系的离子电导率却很低,这是因为Li 半径太小,而NASICON三维网格结构的离子通道太大,两者不匹配而使电导率下降[2]。但当LiZr2(PO4)3中Zr4 被离子半径小些的Ti4 取代,所得LiTi2(PO4)3的通道就与Li 半径相匹配,适合于锂离子的迁移,从而使其电导率…  相似文献   

10.
The magnetic ordering of the Fe2P-type Tb6FeTe2, Tb6CoTe2 Tb6NiTe2 and Er6FeTe2 phases (space group P6¯2m) has been investigated through magnetization measurement and neutron powder diffraction. Tb6FeTe2, Tb6CoTe2 and Tb6NiTe2 demonstrate high-temperature ferromagnetic and low-temperature spin reorientation transitions, whereas Er6FeTe2 shows antiferromagnetic transition, only.The Tb6FeTe2 and Tb6NiTe2 phases show same high-temperature collinear ferromagnetic structure, whereas Tb6FeTe2 is the commensurate non-collinear ferromagnet and Tb6NiTe2 is the canted ferromagnetic cone with K1=[0, 0, ±3/10] and K2=[±2/9, ±2/9, 0] wave vectors at 2 K. The magnetic structure of Er6FeTe2 is a flat spiral with K1=[0, 0, ±1/10] at 2 K. The magnetic entropy change for Tb6NiTe2 is ΔSm=−4.86 J/kg K at 229 K for the field change Δμ0H=0-5 T.In addition, novel Fe2P-type Gd6FeTe2, Zr6FeTe2, Hf6FeTe2, Dy6NiTe2, Zr6NiTe2 and Hf6NiTe2 phases have been obtained.  相似文献   

11.
The luminescence properties of Cs3Bi2Cl9, α-Cs3Sb2Cl9, and β-Cs3Sb2Cl9 are reported and compared with those of Cs3Bi2Br9. The first two compounds have comparable luminescence properties which can be described in terms of a band model. Deep center emission is observed for both compounds, whereas edge emission is observed only for Cs3Bi2Cl9. The optical transitions of β-Cs3Sb2Cl9 are localized on the Sb3+ ion. The orientation of the lone-pair orbitals of the ns2 ions seems to play an important role in the formation of the cationic valence band. The α-β transformation must therefore have a considerable influence on the spectral properties of Cs3Sb2Cl9.  相似文献   

12.
Magnetic diphase nanostructures of ZnFe2O4/γ-Fe2O3 were synthesized by a solvothermal method. The formation reactions were optimized by tuning the initial molar ratios of Fe/Zn. All samples were characterized by X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, and Raman spectra. It is found that when the initial molar ratio of Fe/Zn is larger than 2, a diphase magnetic nanostructure of ZnFe2O4/γ-Fe2O3 was formed, in which the presence of ZnFe2O4 enhanced the thermal stability of γ-Fe2O3. Further increasing the initial molar ratio of Fe/Zn larger than 6 destabilized the diphase nanostructure and yielded traces of secondary phase α-Fe2O3. The grain surfaces of diphase nanostructure exhibited a spin-glass-like structure. At room temperature, all diphase nanostructures are superparamagnetic with saturation magnetization being increased with γ-Fe2O3 content.  相似文献   

13.
Four definite compounds exist in the Sm2O3Ga2O3 binary phase diagram, namely: Sm3GaO6, Sm4Ga2O9, SmGaO3, and Sm3Ga5O12. The 31 compound is orthorhombic (space group Pnna - Z.4) with the cell parameters: a = 11.400Å, b = 5.515Å, c = 9.07Å and belongs to the oxysel family. Sm3GaO6 and SmGaO3 melt incongruently at 1715 and 1565°C; Sm4Ga2O9 and Sm3Ga5O12 have a congruent melting point at 1710 and 1655°C. With regard to the Gd2O3Ga2O3 system three definite compounds have been identified: Gd3GaO6, Gd4Ga2O9, and Gd3Ga5O12. Only the garnet melts congruently at 1740°C with the following composition: Gd3.12Ga4.88O12. Gd3GaO6, and Gd4Ga2O9 melt incongruently at 1760 and 1700°C. GdGaO3 is only obtained by melt overheating which may yield an equilibrium or a metastable phase diagram.  相似文献   

14.
The following complex oxynitride perovskites have been prepared: LaMg1/3Ta2/3O2N, LaMg1/2Ta1/2O5/2N1/2, and BaSc0.05Ta0.95O2.1N0.9. Synchrotron X-ray powder diffraction analyses show that LaMg1/3Ta2/3O2N and LaMg1/2Ta1/2O5/2N1/2 are isostructural to the oxide La2Mg(Mg1/3Ta2/3)O6 (space group P21/n), whereas BaSc0.05Ta0.95O2.1N0.9 has a simple cubic symmetry similarly to BaTaO2N. The orderings of octahedral cations are markedly diminished in the above oxynitrides, as compared with the related oxides such as La2Mg(Mg1/3Ta2/3)O6 and Ba2ScTaO6. The optical band gaps are similar for the homologous compositions, LaMg1/3Ta2/3O2N, LaMg1/2Ta1/2O5/2N1/2 and LaTaON2 (1.9 eV), and BaSc0.05Ta0.95O2.1N0.9 and BaTaO2N (1.8 eV), while the absorption edges become broader for the complex derivatives. As revealed from the impedance spectroscopic analysis, the oxynitrides have clearly different dielectric components from those of comparable oxides containing Ta5+. Impedance spectroscopy reveals interesting capacitor geometry in BaSc0.05Ta0.95O2.1N0.9 in which the semiconducting oxynitride grains are separated by insulating secondary phases. Most notably BaSc0.05Ta0.95O2.1N0.9 has a bulk component with a high relative permittivity (κ=7300) and the grain boundary component with an even higher κ.  相似文献   

15.
Single crystals of Zr3Al3C5—a carbide previously reported with the formula ZrAlC2−x—were isolated from a sample prepared by reaction of ZrC with an excess of aluminum. The carbides ScAl3C3and UAl3C3were synthesized from the elemental components by arc-melting. The crystal structures of these three compounds were redetermined from four-circle X-ray diffractomter data. In the original structure determination of ZrAlC2−x, the metal positions were found to form close-packed layers in the space groupP63/mmc, while the carbon atoms were assumed to occupy 5/6 of the octahedral voids at random. The present structure determination in the space groupP63/mc(R=0.024 for 519 structure factors and 23 variable parameters) shows that all carbon positions are fully occupied and one has a trigonal bipyramidal aluminum coordination. The structures of ScAl3C3and UAl3C3also have originally been determined in the space groupP63/mmc. The present structure refinements in the space groupP63mc(ScAl3C3:R=0.031 for 282Fvalues and 16 variables; UAl3C3:R=0.029 for 217Fvalues and 16 variables) essentially confirms the structures with the exception of one aluminum site. In all of these structures the metal atoms are arranged in close-packed layers and together with the previously reported structure of U2Al3C4they form a homologous series with the general formulaT1+nAl3C3+n, wheren=0, 1, 2 for ScAl3C3, U2Al3C4, and Zr3Al3C5, respectively. The packing of the metal atoms is represented by the Zhdanov symbols (4)2, (5)2, and (6)2. The arrangement of the aluminum atoms is very similar to that of the binary carbide Al4C3, while the other metal atoms form a cubic stacking sequence, as it is found in the binary carbidesTC with NaCl type structure.  相似文献   

16.
The NaCdVO4-Cd3V2O8 and CdO-V2O5 sections of the ternary system Na2O-CdO-V2O5 have been studied and the crystal structures of Cd3V2O8 and Cd18V8O38 compounds were determined from single-crystal X-ray diffraction data. Cd3V2O8 crystallizes with the maricite-type structure in space group Pnma, a=9.8133(10) Å, b=6.9882(10) Å, c=5.3251(10) Å and Z=4, whereas Cd18V8O38 crystallizes in space group P1 with a new-type structure, a=8.5761(14), b=8.607(3), c=12.896(2) Å, α=95.64(1), β=102.45(1), γ=108.42(1)° and Z=1. The Cd3V2O8 structure is made up of Cd1O4 infinite chains of edge-sharing Cd1O6 octahedra which are parallel to the b direction. The Cd1O4 chains are linked together by VO4 tetrahedra and strongly distorted Cd2O4 tetrahedra. The structure of Cd18V8O38 is based on an ordered three-dimensional framework of cadmium and vanadium polyhedra that share corners. The distorted CdO6 octahedra, CdO5 trigonal bipyramids and CdO5 square pyramids share corners, edges or faces.  相似文献   

17.
New compounds CaY2Ge3O10 and CaY2Ge4O12 were prepared by heating mixtures of CaCO3, Y2O3 and GeO2 at 1200 °C. CaY2Ge3O10 is stable at 1300 °C, while CaY2Ge4O12 decomposes into a melt and CaY2Ge3O10 at approximately 1250 °C. We obtained single crystals of CaY2Ge3O10 by cooling a sample with an initial composition of Ca:Y:Ge=1:2:8 from 1300 °C with a rate of −6 °C/h. The crystal structure of CaY2Ge3O10 was determined by single crystal X-ray diffraction. CaY2Ge3O10 crystallizes in the monoclinic space group P21/c with a=6.0906(8), b=6.8329(8), and β=109.140(3)°, Z=4, and R1=0.029 for I>2σ(I). In the structure of CaY2Ge3O10, Ca and Y atoms are situated disorderly in three 7-fold coordination sites between isolated germanate groups of triple GeO4 tetrahedra, Ge3O10. The structural formula of CaY2Ge3O10 is expressed as (Ca0.45Y0.55)(Ca0.46Y0.54)(Ca0.09Y0.91)Ge3O10. The crystal structure of CaY2Ge4O12 was analyzed by the Rietveld method for the X-ray powder diffraction pattern. CaY2Ge4O12 is isotypic with SrNa2P4O12, crystallizing in the orthorhombic space group P4/nbm, a=9.99282(6), , Z=2, Rwp=0.092, Rp=0.067. CaY2Ge4O12 contains four-membered GeO4-tetrahedra rings, Ge4O12. Eight-fold coordinated square-anitiprism sites and 6-fold octahedral sites between the layers of the Ge4O12 rings are occupied by Y atom and Ca/Y atoms, respectively The structural formula is Y(Ca0.5Y0.5)2Ge4O12.  相似文献   

18.
A serial of samples in Y2O3-Ga2O3-Tm2O3 pseudo-ternary system are prepared by solid-state chemical reaction method. The range of solid solution in (Y1−xTmx)3GaO6 is 0<x<0.384. Powder X-ray diffraction shows that the compounds crystallize in Gd3GaO6 (Cmc21)-type structure. The solid solubilities of Y3+xGa5−xO12 (x=0-0.77) and Tm3+xGa5−xO12 (x=0-0.62) are 37.5-47.11 at% Y2O3, and 37.5-45.26 at% Tm2O3, respectively. PL spectra of Tm-doped Y3GaO6 show that there is a sharp blue emission at ∼456 nm from the 1D23F4 transition at room temperatures with two lifetimes (∼5 and ∼15 μs) and a narrow saturation range of PL intensity for the Tm3+ content from x=0.005 to 0.03. The sharp emission and long lifetime of (Y1−xTmx)3GaO6 indicate that Y3GaO6 is a potential phosphor and laser crystal host material.  相似文献   

19.
The Tl2S-Sb2S3-Bi2S3 quasi-ternary system (system A) was studied using DTA, X- ray powder diffraction, microstructure examination, and microhardness measurements. TlSbS2-Tl4Bi2S5(TlBiS2, Bi2S3), Sb2S3-TlBiS2, Tl3SbS3-TlBiS2(Bi2S3), and [TlSb0.5Bi0.5S2]-Tl2S isopleths; isothermal sections at 500 K; and liquidus surface projection of system A were constructed. Characteristic features of the title system are extensive fields of solid solutions extended along the TlSbS2-TlBiS2 quasi-binary section and a continuous solubility belt 1–2 mol % wide extended along the Sb2S3-Bi2S3 binary subsystem. Primary separation fields of phases and the types and coordinates of invariant and monovariant equilibria in system A were determined.  相似文献   

20.
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.  相似文献   

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