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1.
Zr1−xLnxW2O8−x/2 solid solutions (Ln=Eu, Er, Yb) of different substitution fractions x have been synthesized. Their X-ray diffraction (XRD) patterns have been indexed and lattice parameters calculated based on the α-ZrW2O8 structure. The coefficients of thermal expansion (CTEs) of these solid solutions were estimated to be −10.3×10−6 K−1 in temperature range of 30-100 °C. The solubility of lanthanide ions in these solid solutions decreases linearly with the increase in the radius of substituted lanthanide ions. Based on the concentration dependence of phase transition temperatures, a novel method for determination of solubility of the lanthanide ions in Zr1−xLnxW2O8−x/2 solid solutions has been developed. This method seems to be more sensitive as compared with that based on XRD technique. 相似文献
2.
Yongfang Shi Xi Chen Jingsa Han Hui Ma Xiaoxia Li Xiaojing Yang Xinhua Zhao 《Journal of solid state chemistry》2009,182(8):2030-2035
A systematical study on cubic ZrW2−xMoxO8 (x=0.73, 0.53, 0.33, 0.11) solid solutions reveals that their temperature-dependent phase transition behaviors are related to the Mo fraction x. A phase diagram of cubic ZrW2−xMoxO8 solid solutions has been drawn over a wide temperature range (298–1473 K) on the basis of the temperature-dependent phase transition behaviors observed. 相似文献
3.
F. Goubin P. Deniard M.-H. Whangbo S. Jobic 《Journal of solid state chemistry》2004,177(12):4528-4534
Various compositions of solid solutions K3P(Mo1−xWx)12O40 (0?x?1) were prepared using two solid state synthetic routes. The crystallite size was determined by linewidth refinements of X-ray diffraction patterns using the Warren-Averbach method, and the grain size distribution by laser scattering experiments. Optical properties were determined by diffuse reflectance measurements in the UV-visible range. The optical gap Eg was found to increase exponentially from ∼2.5 to ∼3.30 eV with increasing x, and is systematically shifted to a higher energy when the grain size decreases. The relation between Eg and x was analyzed by calculating the HOMO-LUMO gaps of the [P(Mo1−xWx)12O40]3− anions on the basis of tight-binding electronic structure calculations. 相似文献
4.
Virginia Lea Miller Wei-li Lee Nai-Phuan Ong 《Journal of solid state chemistry》2005,178(5):1508-1512
We report the synthesis and elementary properties of the Co7Se8−xSx (x=0-8) and Ni7Se8−xSx (x=0-7) solid solutions. Both systems form a NiAs-type structure with metal vacancies. In general, the lattice parameters decrease with increasing x, but in the Ni7Se8−xSx system c increases on going from x=5 to 7. Magnetic susceptibility measurements show that all samples exhibit temperature-independent paramagnetism from 25-250 K. Samples within the Co7Se8−xSx system, as well as Ni7Se8 and Ni7SeS7, were found to be poor metals with resistivities of ∼0.20 and ∼0.06 mΩ cm at 300 K, respectively. The Sommerfeld constant (γ) was determined from specific heat measurements to be ∼13 mJ/molCoK2 and ∼7 mJ/molNiK2 for Co7Se8−xSx and Ni7Se8−xSx, respectively. 相似文献
5.
Oxides in the system PrCo1−xMgxO3 (x=0.0, 0.05, 0.10, 0.15, 0.20, 0.25) were synthesized by citrate technique and characterized by powder X-ray diffraction and scanning electron microscope. All compounds have a cubic perovskite structure (space group ). The maximum ratio of doped Mg in the system PrCo1−xMgxO3 is x=0.2. Further doping leads to the segregation of Pr6O11 in PrCo1−xMgxO3. The substitution of Mg for Co improves the performance of PrCoO3 as compared to the electrical conductivity measured by a four-probe electrical conductivity analyzer in the temperature range from 298 to 1073 K. The substitution of Mg for Co on the B site may be compensated by the formations of Co4+ and oxygen vacancies. The electrical conductivity of PrCo1−xMgxO3 oxides increases with increasing x in the range of 0.0-0.2. The increase in conductivity becomes considerable at the temperatures ?673 K especially for x?0.1; it reaches a maximum at x=0.2 and 1073 K. From x>0.2 the conductivity of PrCo1−xMgxO3 starts getting lower. This is probably a result of the segregation of Pr6O11 in PrCo1−xMgxO3 , which blocks oxygen transport, and association of oxygen vacancies. A change in activation energy for all PrCo1−xMgxO3 compounds (x=0-0.25) was observed, with a higher activation energy above 573 K and a lower activation energy below 573 K. The reasons for such a change are probably due to the change of dominant charge carriers from Co4+ to Vö in PrCo1−xMgxO3 oxides and a phase transition mainly starting at 573 K. 相似文献
6.
Cathode materials Li[CoxMn1−x]O2 for lithium secondary batteries have been prepared by a new route—precursor method of layered double hydroxides (LDHs). In situ high-temperature X-ray diffraction (HT-XRD) and thermogravimetric analysis coupled with mass spectrometry (TG-MS) were used to monitor the structural transformation during the reaction of CoMn LDHs and LiOH·H2O: firstly the layered structure of LDHs transformed to an intermediate phase with spinel structure; then the distortion of the structure occurred with the intercalation of Li+ into the lattice, resulting in the formation of layered Li[CoxMn1−x]O2 with α-NaFeO2 structure. Extended X-ray absorption fine structure (EXAFS) data showed that the Co-O bonding length and the coordination number of Co were close to those of Mn in Li[CoxMn1−x]O2, which indicates that the local environments of the transitional metals are rather similar. X-ray photoelectron spectroscopy (XPS) was used to measure the oxidation state of Co and Mn. The influences of Co/Mn ratio on both the structure and electrochemical property of Li[CoxMn1−x]O2 have been investigated by XRD and electrochemical tests. It has been found that the products synthesized by the precursor method demonstrated a rather stable cycling behavior, with a reversible capacity of 122.5 mAh g−1 for the layered material Li[Co0.80Mn0.20]O2. 相似文献
7.
Miaojun Wang 《Journal of solid state chemistry》2005,178(4):1182-1189
Lithium substituted Li1+xMn2−xO4 spinel samples in the entire solid solution range (0?x?1/3) were synthesized by solid-state reaction. The samples with x<0.25 are stoichiometric and those with x?0.25 are oxygen deficient. High-temperature oxide melt solution calorimetry in molten 3Na2O·4MoO3 at 974 K was performed to determine their enthalpies of formation from constituent binary oxides at 298 K. The cubic lattice parameter was determined from least-squares fitting of powder XRD data. The variations of the enthalpy of formation from oxides and the lattice parameter with x follow similar trends. The enthalpy of formation from oxides becomes more exothermic with x for stoichiometric compounds (x<0.25) and deviates endothermically from this trend for oxygen-deficient samples (x?0.25). This energetic trend is related to two competing substitution mechanisms of lithium for manganese (oxidation of Mn3+ to Mn4+ versus formation of oxygen vacancies). For stoichiometric spinels, the oxidation of Mn3+ to Mn4+ is dominant, whereas for oxygen-deficient compounds both mechanisms are operative. The endothermic deviation is ascribed to the large endothermic enthalpy of reduction. 相似文献
8.
C. Tenailleau A. Pring Y. Liu S. Tarantino M.A. Carpenter 《Journal of solid state chemistry》2005,178(3):882-891
Composition-induced structural phase changes across the high temperature, fast oxide ion conducting (Ba1−xLax)2In2O5+x, 0?x?0.6, system have been carefully analysed using hard mode infrared (IR) powder absorption spectroscopy, X-ray powder diffraction and electron diffraction. An orthorhombic brownmillerite to three-dimensionally disordered cubic perovskite phase transition in this system is signalled by a drastic change in slope of both wavenumber and average line widths of IR spectra as a function of composition. Some evidence is found for the existence of an intermediate tetragonal phase (previously reported to exist from electron diffraction data) around x∼0.2. The new spectroscopic data have been used to compare microscopic and macroscopic strain parameters arising from variation in composition. The strain and spectroscopic data are consistent with first-order character for the tetragonal→orthorhombic transition, while the cubic→tetragonal transition could be continuous. Differences between the variation with composition of spectral parameters and of macroscopic strain parameters are consistent with a substantial order/disorder component for the transitions. There is also evidence for precursor effects within the cubic structure before symmetry is broken. 相似文献
9.
Sylvie Daviero-Minaud Chanapa Kongmark Rose-Noëlle Vannier 《Journal of solid state chemistry》2009,182(2):289-294
The actual oxygen environment of the tungsten dopant in the Ba2In2−xWxO5+3x/2 solid solution was revealed by combining X-ray absorption spectroscopy at the tungsten LI and LIII edges and at the indium LI edge. Whatever the substitution ratio, the tungsten atoms exhibit a regular octahedral environment. When the substitution ratio increases, the oxygen vacancies are progressively filled until their total occupancy for x=2/3. For x?0.3, the perovskite structure is stabilised; the tungsten atoms are randomly distributed in the structure. Although X-ray diffraction revealed a cubic symmetry for these compositions, a local distortion of the indium environment is observed when a tungsten atom is in its surrounding. 相似文献
10.
Christophe T.G. Petit 《Journal of solid state chemistry》2010,183(6):1231-6194
A-site substituted cerium orthovanadates, Ce1−xSrxVO4, were synthesised by solid-state reactions. It was found that the solid solution limit in Ce1−xSrxVO4 is at x=0.175. The crystal structure was analysed by X-ray diffraction and it exhibits a tetragonal zircon structure of space group I41/amd (1 4 1) with a=7.3670 (3) and c=6.4894 (1) Å for Ce0.825Sr0.175VO4. The UV-vis absorption spectra indicated that the compounds have band gaps at room temperature in the range 4.5-4.6 eV. Conductivity measurements were performed for the first time up to the strontium solid solution limit in air and in dry 5% H2/Ar with conductivity values at 600 °C ranging from 0.3 to 30 mS cm−1 in air to 30-45 mS cm−1 in reduced atmosphere. Sample Ce0.825Sr0.175VO4 is redox stable at a temperature below 600 °C although the conductivity is not high enough to be used as an electrode for solid oxide fuel cells. 相似文献
11.
Ba(R,R′)2CuO5 (R,R′=lanthanides and Y) plays an important role as a flux-pinning agent in enhancing the superconducting properties of the Ba2(R,R′)Cu3O6+x (R,R′=lanthanides and Y) coated conductors. Using X-ray diffraction and neutron diffraction, we found that the Ba(NdxY2−x)CuO5 solid solution adopts two structure types. In the Nd-rich region (1.8?x?2.0), the materials are of brown color (commonly referred to as the ‘brown phase’), and the structure is tetragonal with space group I4/mbm (no. 127). In the Y-rich region (0.0?x?1.4), the materials are green (commonly referred to as the ‘green phase’) and the structure is orthorhombic with space group Pnma (no. 62). A two-phase region (1.4<x<1.8) exists between the orthorhombic and tetragonal phases. The crystal chemistry and crystallography of the orthorhombic ‘green phase’ series, Ba(NdxY2−x)CuO5 (isostructural to BaY2CuO5), are discussed in this paper. 相似文献
12.
Richard Harrington Gabrielle C. Miles Anthony R. West 《Journal of solid state chemistry》2008,181(2):334-339
Zn7Sb2O12 forms a full range of Co-containing α solid solutions, Zn7−xCoxSb2O12, with an inverse-spinel structure at high temperature. At low temperatures for x<2, the solid solutions transform into the low temperature β-polymorph. For x=0, the β→α transition occurs at 1225±25 °C; the transition temperature decreases with increasing x. At high x and low temperatures, α solid solutions are formed but are non-stoichiometric; the (Zn+Co):Sb ratio is >7:2 and the compensation for the deficiency in Sb is attributed to the partial oxidation of Co2+ to Co3+. From Rietveld refinements using ND data, Co occupies both octahedral and tetrahedral sites at intermediate values of x, but an octahedral preference attributed to crystal field stabilisation, causes the lattice parameter plot to deviate negatively from the Vegard's law. Sub-solidus compatibility relations in the ternary system ZnO-Sb2O5-CoO have been determined at 1100 °C for the compositions containing ?50% Sb2O5. 相似文献
13.
A series of lithium europium double tungsto-molybdate phosphors LiEu(WO4)2−x(MoO4)x (x=0, 0.4, 0.8, 1.2, 1.6, 2.0) have been synthesized by solid-state reactions and their crystal structure, optical and luminescent properties were studied. As the molybdate content increases, the intensity of the 5D0→7F2 emission of Eu3+ activated at wavelength of 396 nm was found to increase and reach a maximum when the relative ratio of Mo/W is 2:0. These changes were found to be accompanied with the changes in the spectral feature, which can be attributed to the crystal field splitting of the 5D0→7F2 transition. As the molybdate content increases the emission intensity of the 615 nm peak also increases. The intense red-emission of the tungstomolybdate phosphors under near-UV excitation suggests them to be potential candidate for white light generation by using near-UV LEDs. In this study the effect of chemical compositions and crystal structure on the photoluminescent properties of LiEu(WO4)2−x(MoO4)x is investigated and discussed. 相似文献
14.
Danzhen Li 《Journal of solid state chemistry》2007,180(9):2630-2634
An excellent visible-light-responsive (from 400 to 550 nm) TiO2−xNx photocatalyst was prepared by a simple wet method. Hydrazine was used as a new nitrogen resource in this paper. Self-made amorphous titanium dioxide precursor powders were dipped into hydrazine hydrate, and calcined at low temperature (110 °C) in the air. The TiO2−xNx was successfully synthesized, following by spontaneous combustion. The photocatalyst was characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), transmission electron microscope (TEM), UV-Vis diffuse reflectance spectrometer (DRS), and X-ray photoelectron spectroscopy (XPS). Analysis of XPS indicated that N atoms were incorporated into the lattice of the titania crystal during the combustion of hydrazine on the surface of TiO2. Ethylene was selected as a target pollutant under visible-light excitation to evaluate the activity of this photocatalyst. The newly prepared TiO2−xNx photocatalyst with strong photocatalytic activity and high photochemical stability under visible-light irradiation was firstly demonstrated in the experiment. 相似文献
15.
Fride Vullum 《Journal of solid state chemistry》2008,181(10):2580-2585
The solid solubility between LaNbO4 and LaTaO4 was investigated by X-ray diffraction, and a two-phase region was observed in the composition region LaNb1−xTaxO4 where 0.4?x?0.8. Single-phase LaNb1−xTaxO4 (0?x?0.4) with the monoclinic Fergusonite structure at ambient temperature, was observed to transform to a tetragonal Scheelite structure by in-situ high-temperature X-ray diffraction, and the phase transition temperature was shown to increase with increasing Ta-content. This ferroelastic to paraelastic second-order phase transition was described by Landau theory using spontaneous strain as an order parameter. The thermal expansion of LaNb1−xTaxO4 (0?x0.4) was shown to be significantly higher below the phase transition than above. Single-phase LaNb1−xTaxO4 (0.8?x?1) with another monoclinic crystal structure at ambient temperature was shown to transform to an orthorhombic crystal structure by X-ray diffraction and differential scanning calorimetry. The phase transition temperature was observed to decrease with decreasing Ta-content. Finally, orthorhombic LaTaO4 could also be transformed to monoclinic LaTaO4 at ambient temperature by applying a uniaxial pressure of 150-170 MPa, reflecting the lower molar volume of monoclinic LaTaO4. 相似文献
16.
A new complete solid solution of NASICON-type compounds between LiZr2(PO4)3 and La1/3Zr2(PO4)3 was evidenced with the general formula Li1−xLax/3Zr2(PO4)3 (0?x?1). These phases were synthesized by a complex polymerizable method and structurally characterized from Rietveld treatment of their X-ray and neutron powder diffraction data. This solid solution results from the substitution mechanism Li+→1/3La3++2/3□ leading to an increase of the vacancies number correlated to an increase of the La content. According to this substitution mechanism, the general formula can then be written Li1−xLax/3□2x/3Zr2(PO4)3 (0?x?1) in order to underline the correlation between the La content and the vacancies rate. For all the compounds, the structure is clearly related to that of the NASICON family with three crystallographic domains evidenced. For 0?x?0.5, all the members adopt at high temperature the typical NASICON-type structure (s.g. R3¯c), while at lower temperature, their structure distorts to a triclinic form (s.g. C 1¯), as observed for LiZr2(PO4)3 prepared above 1100 °C. Moreover, in this domain, the reversible transition is clearly soft and the transition temperature strongly depends of the x value. For 0.6?x?0.9, the compounds crystallize in a rhombohedral cell (s.g. R3¯), while for x=1, the phase La1/3Zr2(PO4)3 is obtained (s.g. P3¯, Z=6, a=8.7378(2) Å, c=23.2156(7) Å).This paper is devoted to the structure analysis of the series Li1−xLax/3Zr2(PO4)3 (0?x?1), from X-ray and neutron powder thermo diffraction and transmission electron microscopy (TEM) studies. 相似文献
17.
A systematic study of the chemical interaction of Ba2YCu3O6+y and Gd3NbO7 was conducted under two processing conditions: purified air (21% po2), and 100 Pa po2 (0.1% po2). Phases present along the pseudo-binary join Ba2YCu3O6z and Gd3NbO7 were found to be in two five-phase volumes within the system. Three common phases that are present in all samples are (Y,Gd)2Cu2O5, Ba(Y,Gd)2CuO5 and Cu2O or CuO (depending on the processing conditions). The assemblies of phases can be categorized in three regions, with Ba2YCu3O6+y: Gd3NbO7 ratios of (I)<5.5:4.5; (II)=5.5:4.5; and (III)>5.5:4.5. The lowest melting temperature of the system was determined to be ≈938 °C in air, and 850 °C at 100 Pa po2. Structure determinations of two selected phases, Ba2(GdxY1−x)NbO6 (Fm3¯m, No. 225), and (GdxY3−x)NbO7 (C2221, No. 20 and Ccmm, No. 63), were completed using the X-ray Rietveld refinement technique. Reference X-ray powder diffraction patterns for selected phases of Ba2(GdxY1−x)NbO6 (x=0.2, 0.4, 0.6, and 0.8) and (GdxY3−x)NbO7 (x=0.6, 1.2, 1.8, 2.4 and 3) have been prepared for inclusion in the Powder Diffraction File (PDF). 相似文献
18.
The microstructure and phase stability of nanocrystalline mixed oxide LuxCe1−xO2−y (x=0-1) are described. Nano-sized (3-4 nm) oxide particles were prepared by the reverse microemulsion method. Morphological and structural changes upon heat treatment in an oxidizing atmosphere were studied by transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman and Yb3+ emission spectroscopy, the latter ion being present as an impurity in the Lu2O3 starting material. Up to 950 °C, the samples were single phase, with structure changing smoothly with Lu content from fluorite type (F) to bixbyite type (C). For the samples heated at 1100 °C phase separation into coexisting F- and C-type structures was observed for 0.35<x<0.7. It was also found that addition of Lu strongly hinders the crystallite growth of ceria during heat treatment at 800 and 950 °C. 相似文献
19.
J.L. Cui W.J. Xiu L.D. Mao P.Z. Ying X. Qian 《Journal of solid state chemistry》2007,180(3):1158-1162
Ag-doped n-type (Bi2Te3)0.9-(Bi2−xAgxSe3)0.1 (x=0-0.4) alloys were prepared by spark plasma sintering and their physical properties evaluated. When at low Ag content (x=0.05), the temperature dependence of the lattice thermal conductivity follows the trend of (Bi2Te3)0.9-(Bi2Se3)0.1; while at higher Ag content, a relatively rapid reduction above 400 K can be observed due possibly to the enhancement of scattering of phonons by the increased defects. The Seebeck coefficient increases with Ag content, with some loss of electrical conductivity, but the maximum dimensionless figure of merit ZT can be obtained to be 0.86 for the alloy with x=0.4 at 505 K, about 0.2 higher than that of the alloy (Bi2Te3)0.9-(Bi2Se3)0.1 without Ag-doping. 相似文献
20.
采用水热法,在较低温度下合成了系列Bi2Mo1-xWxO6固溶体。结果表明,W的替代抑制了固溶体的晶粒生长,导致了较小的晶粒尺寸。随着x的增加,红外光谱中840cm-1处M-O键的振动频率νM-O有规律地向低频率方向移动,表明Mo6+离子逐步被W6+替代,生成了无限互溶的固溶体。光吸收性能研究表明,随着W6+逐步替代Mo6+,带隙出现了先降后升的趋势,x=0.4时带隙最小。而固溶体的光催化性能随着x的增加,出现了先增后减的趋势,x=0.4时光催化活性最高。此外,含W样品的光催化活性高于Bi2MoO6。这与固溶体的带隙、带结构和晶粒尺寸变化有关。 相似文献