Synthesis, structure, negative thermal expansion, and photocatalytic property of Mo doped ZrV2O7

A new series of compounds identified in the phase diagram of ZrO(2)-V(2)O(5)-MoO(3) have been synthesized via the solution combustion method. Single crystals of one of the compounds in the series, ZrV(1.50)Mo(0.50)O(7.25), were grown by the melt-cool technique from the starting materials with double the MoO(3) quantity. The room temperature average crystal structure of the grown crystals was solved using the single crystal X-ray diffraction technique. The crystals belong to the cubic crystal system, space group Pa3 (No. 205) with a = 8.8969 (4) ?, V = 704.24 (6) ?(3), and Z = 4. The final R(1) value of 0.0213 was achieved for 288 independent reflections during the structure refinement. The Zr(4+) occupies the special position (4a) whereas V(5+) and Mo(6+) occupy two unique (8c) Wyckoff positions. Two fully occupied O atoms, (24d) and (4b), one partially occupied O atom (8c) have been identified for this molybdovanadate, which is a unique feature for these crystals. The structure is related to both ZrV(2)O(7) and cubic ZrMo(2)O(8). The temperature dependent single crystal studies show negative thermal expansion above 370 K. The compounds have been characterized by powder X-ray diffraction, solid-state UV-vis diffuse reflectance spectra, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The photocatalytic activity of these compounds has been investigated for the degradation of various dyes, and these compounds show specificity toward the degradation of non-azoic dyes.     

Charge-transfer phase transition and zero thermal expansion in caesium manganese hexacyanoferrates

A series of caesium manganese hexacyanoferrates is prepared; Cs(I)(1.78)Mn(II)[Fe(II)(CN)6]0.78[Fe(III)(CN)6](0.22) (1), Cs(I)(1.57)Mn(II)[Fe(II)(CN)6]0.57[Fe(III)(CN)6](0.43) (2), Cs(I)(1.51)Mn(II)[Fe(II)(CN)6]0.51[Fe(III)(CN)6](0.49) (3), and Cs(I)(0.94)Mn(II)[Fe(II)(CN)6]0.21[Fe(III)(CN)6](0.70).0.8H2O (4). 1-3 show charge-transfer phase transitions between the high-temperature (HT) and low-temperature (LT) phases with transition temperatures (T(1/2 downward arrow), T(1/2 upward arrow)) of (207 K, 225 K) (1), (190 K, 231 K) (2), and (175 K, 233 K) (3) at a cooling and warming rates of 0.5 K min(-1). Variable temperature IR spectra indicate that the valence states of the LT phases of 1-3 are Cs(I)(1.78)Mn(II)(0.78)Mn(III)(0.22)[Fe(II)(CN)6], Cs(I)(1.57)Mn(II)(0.57)Mn(III)(0.43)[Fe(II)(CN)6], and Cs(I)(1.51)Mn(II)(0.51)Mn(III)(0.49) [Fe(II)(CN)6], respectively. The XRD measurements for 1-3 show that crystal structures of the HT and LT phases are cubic structures (Fm3[combining macron]m), but the lattice constants decrease from the HT phase to the LT phase; a = 10.5446(17) --> 10.4280(7) A (1), 10.5589(17) --> 10.3421(24) A (2), and 10.5627(11) --> 10.3268(23) A (3). The magnetization vs. temperature curves and the magnetization vs. external magnetic field curves show that the LT phases are ferromagnetic with Curie temperatures of 4.3 (1), 5.0 (2), and 5.6 K (3). At a cooling rate of -0.5 K min(-1), 4 does not show the charge-transfer phase transition, but does show a behavior of zero thermal expansion with a thermal expansivity of +0.2 x 10(-6) K(-1) throughout the temperature range 300 and 20 K.     

Transport properties of ZrV2O7-V2O5 composites with liquid-channel grain boundary structure

Transport properties (conductivity, transport numbers of oxygen ions, oxygen permeability) are studied for new composites of ZrV₂O₇-25, 30, 35, 40 mol % of V₂O₅ with a liquid-channel grain boundary structure (LGBS) at 680–740°C. It is shown that the composite of ZrV₂O₇-40 mol % of V₂O₅ with LGBS has high selective oxygen permeability of 1.1 × 10^?8 mol cm^?2 s^?1 (T = 740°C, $P'_{O_2 } $ = 0.21 atm, $P''_{O_2 } $ = 0.003 atm, L = 2 mm) and can be used as an ion-transport membrane for separation of oxygen from air.     

The structural phase transition in SrV6O11

Single‐crystal X‐ray diffraction and specific heat studies establish that strontium hexavanadium undecaoxide, SrV₆O₁₁, undergoes a P6₃/mmc to inversion twinned P6₃mc structural transition as the temperature is lowered through 322 K. The P6₃/mmc and P6₃mc structures have been determined at 353 K and at room temperature, respectively. For the room‐temperature structure, seven of the ten unique atoms lie on special positions, and for the 353 K structure all of the seven unique atoms sit on special positions. The P6₃/mmc to P6₃mc structural phase transition, accompanied by a magnetic transition, is a common characteristic of AV₆O₁₁ compounds, independent of the identity of the A cations.     

Low temperature structural phase transition of Ba3NaIr2O9

Single crystal X-ray and synchrotron X-ray powder diffraction have been used to probe the structure of Ba₃NaIr₂O₉ from 300 K down to 20 K. Ba₃NaIr₂O₉ is found to undergo a structural transition from hexagonal symmetry, P6₃/mmc, at ambient temperature to monoclinic symmetry, C2/c, at low temperature. The evolution of the unit cell volume upon cooling is indicative of a higher order structural transition, and the symmetry breaking becomes apparent as the temperature is decreased. The low temperature monoclinic structure of Ba₃NaIr₂O₉ contains strongly distorted [NaO₆] and [IrO₆] octahedra in comparison to the room temperature hexagonal structure.     

Phase transition of negative thermal expansion Zr1-xHfxW2O8 solid solutions

A powder X-ray diffraction experiment was performed on cubic Zr_1-xHf_xW₂O₈ (x=0.25, 0.50 and 0.75) solid solutions from 90 to 560 K. The lattice parameters of Zr_1-xHf_xW₂O₈ at 121 K decreased linearly with increasing Hf contents, due to smaller ionic radius of hafnium than that of zirconium. Transition temperatures due to α-β structural phase transition increased with increasing Hf contents, reflecting the decrease of lattice free volume related to the orientation of unshared vertex of WO₄. Anomaly in the heat capacity of Zr_0.5Hf_0.5W₂O₈ was observed around 450 K which was 9 K lower than that by X-ray diffraction method. Transition entropy of Zr_0.5Hf_0.5W₂O₈ was 2.1 J mol^-1 K^-1, consistent with those of ZrW₂O₈ and HfW₂O₈. This consistent entropy supports that Zr_1-xHf_xW₂O₈ (x=0-1.0) has the same order-disorder phase transition mechanism. This revised version was published online in August 2006 with corrections to the Cover Date.     

Negative thermal expansion in rare earth molybdates

Negative thermal expansion in rare earth molybdates of A₂Mo₃O₁₂ family (A=Y, Er, Yb and Lu) is measured by high temperature X-ray diffraction and dilatometry. Rare earth molybdates which are isostructural with the corresponding rare earth tungstates, also exhibit this phenomena attributed to transverse acoustic vibrations. The rare earth molybdates of A₂M₃O₁₂ family with an orthorhombic structure (A=Y, Er, Yb and Lu) are highly hygroscopic and exhibit negative thermal expansion after the complete removal of water molecules. Axial thermal expansion co-efficient calculated from high temperature X-ray diffraction (RT-1073K) shows rare earth size effect. As the ‘A’ cation decreases in size, the thermal expansion co-efficient along ‘b’ axis and the linear thermal expansion co-efficient become less negative. The thermal expansion behaviour of the tetragonal La₂Mo₃O₁₂ is also reported to demonstrate the effect of crystal structure.     

Negative thermal expansion in oriented crystalline polymers

Measurements on the thermal expansivity α_∥ and α_? (along and normal to the draw direction, respectively) have been carried out for a series of oriented polymers with widely different crystallinities (0.36–0.81) and draw ratios (1–20) and over large temperature ranges covering the major amorphous transitions in each case. While α_? increases with temperature, α_∥ tends to decrease sharply above the transition temperature. For highly crystalline polymers, α_∥ decreases to values typical of polymer crystals (?1 × 10^?5 K^?1) and this can be attributed to the constraining effect of the crystalline bridges connecting the crystalline blocks. However, for polymers of lower crystallinity, α_∥ may become an order of magnitude more negative and this remarkable phenomenon is attributed to the rubber–elastic contraction of taut tie-moleucles. Since taut tie-molecules and bridges have drastically different effects on α_∥ at high temperatures, this allows a rough determination of their relative fractions.     

Study of negative thermal expansion and shift in phase transition temperature in Ti4+- and Sn4+-substituted ZrW2O8 materials

The negative-thermal-expansion material ZrW(2)O(8) is known to undergo an order-disorder phase transition which affects its expansion behavior. In this study, Ti(4+) and Sn(4+) are examined as possible substituting ions for the Zr(4+) position in ZrW(2)O(8). This substitution leads to a decrease in cell parameters, as the ionic radii of the substituents are smaller than the Zr(4+) ionic radius. A remarkable decrease in transition temperature is noticed. DSC is used to quantify the enthalpy and entropy changes during the phase transition in order to reveal the mechanisms behind this decrease. It is shown that the strength of the M-O bond plays an important role, as it is a partner in the rigid unit mode motion and the order-disorder transition mechanism.     

Negative thermal expansion of water in hydrophobic nanospaces

The density and intermolecular structure of water in carbon micropores (w = 1.36 nm) are investigated by small-angle X-ray scattering (SAXS) and X-ray diffraction (XRD) measurements between 20 K and 298 K. The SAXS results suggest that the density of the water in the micropores increased with increasing temperature over a wide temperature range (20-277 K). The density changed by 10%, which is comparable to the density change of 7% between bulk ice (I(c)) at 20 K and water at 277 K. The results of XRD at low temperatures (less than 200 K) show that the water forms the cubic ice (I(c)) structure, although its peak shape and radial distribution functions changed continuously to those of a liquid-like structure with increasing temperature. The SAXS and XRD results both showed that the water in the hydrophobic nanospaces had no phase transition point. The continuous structural change from ice I(c) to liquid with increasing temperature suggests that water shows negative thermal expansion over a wide temperature range in hydrophobic nanospaces. The combination of XRD and SAXS measurements makes it possible to describe confined systems in nanospaces with intermolecular structure and density of adsorbed molecular assemblies.     

Anomalous structural phase transition properties in ReSe2 and Au-doped ReSe2

The high pressure induced phase transition in rhenium diselenides (ReSe(2)) and gold-doped rhenium diselenides (Au-ReSe(2)) at ambient temperature have been investigated using angular-dispersive x-ray diffraction (ADXRD) under high pressure up to around 10.50 and 9.98 GPa, respectively. In situ ADXRD measurements found that the phase transition pressures of ReSe(2) and Au-ReSe(2) began at 9.98 and 8.52 GPa, respectively. Compressibilities analysis shows the relationship of along c-axis > along a-axis > along b-axis. The linear compressibility of the pressure dependence of α, β, and γ of ReSe(2) shows that a phase transition can be related to a counterclockwise rotational trend of the selenium atoms around the chain of Re(4) atoms during the decrease of the c-axis distance by a combination of stresses due to the bending effect of α and stretching effect of β. The cause of the reduction of the phase transition pressure of Au-ReSe(2) is attributed mainly to a structural distortion as evidenced by the observation of a weak clockwise rotational trend of Se atoms around the chain of Re(4) atoms in the pressure range 3.99-4.99 GPa which subsequently reversed to counterclockwise rotation under higher pressure.     

Synthesis, structural, electrical and thermal properties of Ti-doped Bi2Sn2O7 pyrochlore

Polycrystalline ceramic samples of Bi₂Sn_2?xTi_xO₇ (x?=?0.0, 0.2, 0.4, 0.6, 0.8) have been synthesized by conventional solid-state reaction method. The effect of homovalent cation (titanium) substitution on the Sn-site on the structural, morphological, electrical and thermal properties of the pure Bi₂Sn₂O₇ ceramics have been studied by X-ray diffraction (XRD) followed by scanning electron microscopic techniques, dc conductivity and modulated differential scanning calorimetry. The XRD analysis carried out by performing the Rietveld refinement using the space group Fd3m indicates that the increase of titanium contents do not lead to any secondary phase. The grain size distributions of all the samples were investigated by SEM. It was found that the grain sizes are strongly influenced by the addition of titanium to the system. The frequency and temperature dependent dielectric studies have been carried out. The dc conductivity measurement was carried out for all the compounds and the activation energies were calculated using the relation ???=???0 exp(?E _a/kT). The modulated differential scanning calorimetry has been used to investigate the effect of substitution on the specific heat, heat flow and other thermal parameters of the compounds. The results are discussed in detail.     

Thermoluminescence and linear thermal expansion of MgAl2O4

The co-efficient of linear thermal expansion (α _av) and dose dependence of thermoluminescence (TL) in MgAl₂O₄(s) were measured. The change in length per unit length was recorded as a function of temperature between room temperature to 1,273 K at a heating rate of 8 K min^?1, in flowing argon atmosphere. The average of three measurements was quoted as the α _av for MgAl₂O₄(s). The linear thermal expansion was measured to an accuracy of ±3 %. The dose dependence of the TL was found to be super linear in the dose range of 0–10 kGy with a k value of 0.503 indicating that the MgAl₂O₄(s) ceramic is ideally suited for the dose estimation of self-irradiated inert matrix fuel in a once through fuel cycle for actinide burning.     

Negative thermal expansion in single-component systems with isotropic interactions

We have devised an isotropic interaction potential that gives rise to negative thermal expansion (NTE) behavior in equilibrium many-particle systems in both two and three dimensions over a wide temperature and pressure range (including zero pressure). An optimization procedure is used in order to find a potential that yields a strong NTE effect. A key feature of the potential that gives rise to this behavior is the softened interior of its basin of attraction. Although such anomalous behavior is well-known in material systems with directional interactions (e.g., zirconium tungstate), to our knowledge, this is the first time that NTE behavior has been established to occur in single-component many-particle systems for isotropic interactions. Using constant-pressure Monte Carlo simulations, we show that as the temperature is increased, the system exhibits negative, zero, and then positive thermal expansion before melting (for both two- and three-dimensional systems). The behavior is explicitly compared to that of a Lennard-Jones system, which exhibits typical expansion upon heating for all temperatures and pressures.     

Characterization of phase transition of Ba2-xSrxIn2O5 by thermal analysis and high temperature X-ray diffraction

The phase transitions of Ba_2-xSr_xIn₂O₅ were investigated with various thermal analyses and high-temperature X-ray diffraction. It was clarified that crystal structure of Ba_2-xSr_xIn₂O₅ with x=0.0~0.4 varies from brownmillerite through distorted perovskite to another distorted perovskite with increase of temperature. The phase transition from brownmillerite to distorted perovskite was revealed to be first order, whereas transition from distorted perovskite to another one was second order. The specimen with x≥0.5 showed only one first order phase transition from brownmillerite to distorted perovskite. The phase diagram of Ba_2-xSr_xIn₂O₅ was established and existence of tricritical point at ~1100°C with x=0.4~0.5 was suggested. This revised version was published online in August 2006 with corrections to the Cover Date.     

Engineering of highly conductive and mesoporous ZrV2O7: a cathode material for lithium secondary batteries

Journal of Solid State Electrochemistry - The performance of the cathode materials can be enhanced significantly by manipulating the surface properties through a nano-structuring. Porous ZrV2O7 is...     

Temperature evolution of structural and magnetic properties of stoichiometric LiCu2O2: Correlation of thermal expansion coefficient and magnetic order

Temperature-dependent crystallographic and magnetic studies on stoichiometric single crystals of LiCu₂O₂ are reported. The temperature dependence of the lattice parameters was extracted from X-ray powder diffractograms collected on crushed single crystals, from 12 K to 295 K. The magnetic properties are similar to earlier findings demonstrating antiferromagnetic ordering below 25 K. Evidence of magnetoelastic coupling is observed in the thermal expansion along the c-direction; not only at the low temperature antiferromagnetic transitions, but an anomalous behavior of the thermal expansion indicate magnetoelastic coupling also to the magnetic ordering related to a weak spontaneous magnetic moment appearing at 150 K. Ac-susceptibility measurements at different frequencies and superposed dc-fields are employed to further characterize this magnetic anomaly.     

Viscosity and thermal expansion of soda-lime-silica glass doped with Gd2O3 and Y2O3

In order to reveal the effects of rare earth elements on the rheological behavior of silicate melt, the properties of viscosity and thermal expansion of soda-lime-silica glass doped with Gd₂O₃ and Y₂O₃ were investigated by the rotating crucible viscometer and dilatometry. The results show that, introduction of Gd₂O₃ and Y₂O₃ increases the coefficient of thermal expansion and decreases viscosity of soda-lime-silica glass. When the amount of Gd₂O₃ and Y₂O₃ increases from 0 to 1.00 mol%, the coefficient of thermal expansion of soda-lime-silica glass increases firstly from 7.67 to 7.79 and 8.05, and then decreases to 7.78 and 7.66 ( × 10⁻⁶ °C⁻¹) respectively. In the case of melting temperature, its value decreases from 1830K to 1714 K, and then elevates to 1727 K as the content of Gd₂O₃ up to 1.00 mol%, however, as Y₂O₃ content increases from 0 to 1.00 mol% the melting temperature decreases monotonously from 1830K to 1737 K. The viscosity, melting temperature and coefficient of thermal expansion of soda-lime-silica glasses co-doped with Gd₂O₃ and Y₂O₃ are larger, comparing with glasses doped solely with Gd₂O₃ or Y₂O₃. The effect of co-doping with Gd₂O₃ and Y₂O₃ on thermal expansion and viscosity properties of soda-lime-silica glass, which is similar with the mixed-alkali effect in silicate glasses, is also observed.