Negative thermal expansion in silicalite-1 and zirconium silicalite-1 having MFI structure

In situ high temperature X-ray diffraction (HTXRD) studies on monoclinic silicalite-1 (S-1, silica polymorph of ZSM-5) and an orthorhombic metallosilicate molecular sieve, zirconium silicalite-1 (ZrS-1) with MFI structure (Si/Zr = 50) have been carried out using a laboratory X-ray diffractometer with an Anton Parr HTK 1600 attachment. While the structure of the S-1 collapsed at 1123 K forming α-cristobalite. S-1 and ZrS-1 showed a complex thermal expansion behavior in the temperature range 298–1023 K, ZrS-1 was stable. Powder X-ray diffraction (PXRD) data taken in this region have shown strong negative lattice thermal expansion coefficient, α_V = −6.75 × 10⁻⁶ and −17.92 × 10⁻⁶ K⁻¹ in the temperature range 298–1023 K⁻¹ for S-1 and ZrS-1 samples, respectively. The thermal expansion behavior of S-1 and ZrS-1 is anisotropic, with the relative strength of contraction along a axis is more than that along b and c axes. Three different thermal expansion regions could be identified in the overall temperature range (298–1023 K) studied, corroborating with the three steps of weight loss in the TG curve of ZrS-1 sample. While the region between 298 and 423 K, displays positive thermal expansion coefficient with α_V = 2.647 × 10⁻⁶ and 4.24 × 10⁻⁶ K⁻¹, the second region between 423 and 873 K shows strong negative thermal expansion (NTE) coefficient α_V = −7.602 × 10⁻⁶ and −15.04 × 10⁻⁶ K⁻¹, respectively, for S-1 and ZrS-1 samples. The region between 873 and 1023 K, shows a very strong NTE coefficient with α_V = −12.08 × 10⁻⁶ and −45.622 × 10⁻⁶ K⁻¹ for S-1 and ZrS-1, respectively, which is the highest in the whole temperature range studied. NTE seen over a temperature range 298–1023 K could be associated with transverse vibrations of bridging oxygen atoms in the structure which results in an apparent shortening of the Si–O distances.     

Synthesis of nanocrystalline zirconia by amorphous citrate route: structural and thermal (HTXRD) studies

Nanocrystalline zirconia powder with a fairly narrow particle size distribution has been synthesized by the amorphous citrate route. The sample obtained has a high BET surface area of 89 m² g⁻¹. Rietveld refinement of the powder X-ray diffraction (XRD) profile of the zirconia sample confirms stabilization of zirconia in the tetragonal phase with around 8% monoclinic impurity. The data show the presence of both anionic as well as cationic vacancies in the lattice. Crystallite size determined from XRD is 8 nm and is in close agreement with the particle size determined by TEM. The in situ high temperature-X-ray diffraction (HTXRD) study revealed high thermal stability of the mixture till around 1023 K after which the transformation of tetragonal phase into the monoclinic phase has been seen as a function of temperature till 1473 K. This transformation is accompanied by an increase in the crystallite size of the sample from 8 to 55 nm. The thermal expansion coefficients are 9.14 × 10⁻⁶ K⁻¹ along ‘a’- and 15.8 × 10⁻⁶ K⁻¹ along ‘c’-axis. The lattice thermal expansion coefficient in the temperature range 298-1623 K is 34.6 × 10⁻⁶ K⁻¹.     

Lattice thermal expansion studies of V2GeO4F2: A topaz type oxide-fluoride

A new compound V₂GeO₄F₂ was earlier found to exist in the V₂O₃-VF₃-GeO₂ system and the structure elucidation revealed it to be iso-structural to the mineral topaz. Herein, we report the lattice thermal expansion data of this compound. The lattice thermal expansion of V₂GeO₄F₂ was studied in the temperature range of 298-873 K under a flowing helium atmosphere by the high temperature XRD (HTXRD). The coefficients of axial thermal expansions of V₂GeO₄F₂ were found to be as: α_a = 3.5 × 10⁻⁶, α_b = 6.1 × 10⁻⁶ and α_c = 7.6 × 10⁻⁶ K⁻¹. The coefficient of volume (α_V) thermal expansion was 17.3 × 10⁻⁶ K⁻¹, which is relatively low compared to many analogues silicates.     

Heat capacity and thermal expansion of samarium titanate

Samarium titanate (Sm₂TiO₅) was prepared by solid-state synthesis and characterized by X-ray diffraction (XRD). Heat capacity measurements were carried out by differential scanning calorimeter (DSC) in the temperature range 298-800 K. Thermal expansion characteristics have been studied by high temperature X-ray diffraction technique (HTXRD) in the temperature range 298-1573 K. The heat capacity value at 298 K is 170 J K^− 1 mol^− 1. The percentage linear thermal expansion in the temperature range 298-1573 K along a, b and c axes are 0.96, 0.89 and 1.07 respectively. The average coefficient of thermal expansion value obtained in the present study for samarium titanate up to 1573 K is 10.8 × 10^− 6 K^− 1.     

Structure and properties of ternary manganese nitride Mn3CuNy thin films fabricated by facing target magnetron sputtering

Deposition of Mn₃CuN_y thin films on single crystal Si (1 0 0) at various substrate temperatures (T_sub) by facing target magnetron sputtering is reported. The crystal structure and composition were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results confirmed that the crystalline antiperovskite Mn₃CuN_y thin film with (2 0 0) highly preferred texture had been obtained at T_sub = 180 °C. Furthermore, for the resulting Mn₃CuN_y thin film, it showed different properties compared with the bulk counterpart. There was a paramagnetic to ferrimagnetic transition at 225 K with decreasing temperature. The change of the lattice constant with temperature presented positive thermal expansion behavior and no structural transition was observed. The average linear thermal expansion coefficient (α) is 2.49 × 10⁻⁵ K⁻¹ from 123 K to 298 K. More interestingly, the temperature dependence of resistivity displayed a semiconductor-like behavior, i.e. an obvious monotonous decrease of resistivity with increasing temperature.     

Oxygen ionic conduction in brownmillerite CaAl0.5Fe0.5O2.5+δ

The oxygen permeability of CaAl_0.5Fe_0.5O_2.5+δ brownmillerite membranes at 1123-1273 K was found to be limited by the bulk ionic conduction, with an activation energy of 170 kJ/mol. The ion transference numbers in air are in the range 2×10⁻³ to 5×10⁻³. The analysis of structural parameters showed that the ionic transport in the CaAl_0.5Fe_0.5O_2.5+δ lattice is essentially along the c axis. The largest ion-migration channels are found in the perovskite-type layers formed by iron-oxygen octahedra, though diffusion in tetrahedral layers of the brownmillerite structure is also possible. Heating up to 700-800 K in air leads to losses of hyperstoichiometric oxygen, accompanied with a drastic expansion and, probably, partial disordering of the CaAl_0.5Fe_0.5O_2.5+δ lattice. The average thermal expansion coefficients of CaAl_0.5Fe_0.5O_2.5+δ ceramics in air are 16.7×10⁻⁶ and 12.6×10⁻⁶ K⁻¹ at 370-850 and 930-1300 K, respectively.     

Crystal structure, thermal expansion and electrical properties of a new compound Al0.33DyGe2

A new ternary compound Al_0.33DyGe₂ has been synthesized and studied from 298 K to773 K by means of X-ray powder diffraction technique. The crystal structural refinement of Al_0.33DyGe₂ has been performed by using the Rietveld method. The ternary compound Al_0.33DyGe₂ crystallizes in the orthorhombic of the defect CeNiSi₂-type structure (space group Cmcm, a = 0.41018(2)nm, b = 1.62323(6)nm, c = 0.39463(1)nm, Z = 4 and D_calc = 8.004 g/cm³). The average thermal expansion coefficients α_a, α_b and α_c of Al_0.33DyGe₂ are 1.96 × 10^− 5 K^− 1, 0.93 × 10^− 5 K^− 1 and 1.42 × 10^− 5 K^− 1, respectively. The bulk thermal expansion coefficient α_V is 4.31 × 10^− 5 K^− 1. The resistivity is observed to fall from 387 to 308 µΩ cm between room temperature and 25 K.     

Thermal expansion studies of Gd2Mo3O12 and Gd2W3O12

Simultaneous thermogravimetric/differential thermal analysis of Gd₂Mo₃O₁₂ showed an irreversible phase transition at 1178 K where as Gd₂W₃O₁₂ showed reversible phase transition at 1433 K, which were confirmed by powder X-ray diffraction. The thermal expansion behavior of α-Gd₂Mo₃O₁₂ (room temperature phase), β-Gd₂Mo₃O₁₂ (phase obtained by heating Gd₂Mo₃O₁₂ at 1223 K) and Gd₂W₃O₁₂ have been investigated using high temperature X-ray diffractometer. The cell volume of α-Gd₂Mo₃O₁₂, β-Gd₂Mo₃O₁₂ and Gd₂W₃O₁₂, fit into polynomial expression with respect to temperature, showed positive thermal expansion up to 1073, 1173 and 1173 K, respectively. The average volume expansion coefficients for α-Gd₂Mo₃O₁₂, β-Gd₂Mo₃O₁₂ and Gd₂W₃O₁₂ are 39.52 × 10⁻⁶, 21.23 × 10⁻⁶ and 37.96 × 10⁻⁶ K⁻¹, respectively.     

Structural and electrical properties of La2−xBaxMo2O9−x/2 (x = 0-0.18)

La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) have been prepared by solid state reaction method. The lattice parameter of La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) determined by XRD data refinement shows a linear dependence on the dopant Ba content x. For the specimen with a La/Ba molar ratio of 0.18-0.2, additional reflection of secondary phase exists in the XRD pattern, so the value of solubility limit for Ba in La₂Mo₂O₉ is defined in range of 0.18 < x < 0.2. As the replacement degree of La³⁺ by Ba²⁺ increases, the bulk conductivity of La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) decreases initially and then increases, a minimum value at La_1.9Ba_0.1Mo₂O_8.95 exists. Hebb-Wagner studies in argon atmosphere, which use an oxide-ion blocking electrode, show that La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) are predominantly oxide-ion conducting in the temperature ranging from 773 to 1173 K. The average thermal expansion coefficient of La_1.84Ba_0.16Mo₂O_8.92 determined by high-temperature XRD was deduced as great as 17.5 × 10⁻⁶ K⁻¹ between 298 and 1173 K.     

The first bulk synthesis of ReO3-type tungsten trioxide, WO3, from nanometric precursors

A perovskite form of WO₃ has been synthesized in bulk for the first time at 0.66 GPa and 973 K with a=3.7823(4) Å [a₀=3.7719(4) Å, at ambient conditions] from nanometric powder of WO₃ with an average crystallite size of 35 nm. Data collected during tests to determine both the likelihood of retaining the structure at room temperature and the effect of high pressure on distortion have afforded analysis of thermal expansivity and compressibility of this phase. These result in V_T=53.407(5)exp(−3.9(12)×10⁻⁶(T−298)+1.91(9)×10⁻⁸(T²−298²)) Å³ and equation of state parameters of V₀=53.67(4) Å³, K₀=41.8(19) GPa with ∂K/∂P=K′=5.6(12).     

Transport properties and thermal expansion of La2Mo2O9-based solid electrolytes

The oxygen ion transference numbers of La_1.7Bi_0.3Mo₂O₉, La₂Mo_1.7W_0.3O₉ and La₂Mo_1.95V_0.05O₉ ceramics, determined by modified faradaic efficiency and e.m.f. methods at 973-1173 K, vary in the range 0.995-0.977 in air, decreasing when temperature increases. The activation energies for the ionic and electronic transport are 61-71 kJ/mol and 123-141 kJ/mol, respectively. Reducing oxygen chemical potential leads to increasing n-type electronic contribution to the total conductivity, which remains, however, essentially p(O₂)-independent down to oxygen pressures of 10⁻⁴-10⁻³ atm and exhibits reversible drop on further reduction, probably due to phase decomposition. Doping La₂Mo₂O₉ with calcium results in segregation of a CaMoO₄-based phase, accompanied with increasing electronic transport. The average thermal expansion coefficients of La₂Mo₂O₉-based materials, calculated from dilatometric data in air, are (14.4-14.8) × 10⁻⁶ K⁻¹ at 300-700 K and (16.4-22.5) × 10⁻⁶ K⁻¹ at 700-1070 K.     

Synthesis and structural characterization of Tm:Lu2O3 nanocrystals. An approach towards new laser ceramics

Nanocrystals of Tm³⁺ Thulium doped cubic sesquioxides, Tm:Lu₂O₃, with a maximum size around 30 nm have been synthesized by a modified Pechini sol-gel method. The calcination temperature for the synthesis is 1073 K. Electron microscopy was used to analyze the presence of aggregates, and the type of boundary between the nanocrystals. The linear coefficient of thermal expansion for these nanocrystals has been determined to be around 7.5 × 10⁻⁶ K⁻¹. The growth of the nanocrystals has been studied in terms of temperature and time. Nanocrystals start to grow at temperatures around 1267 K. Finally, the grain growth activation energy of this material has been evaluated to be 76 kJ/mol, indicating a diffusion growth mechanism. Linear thermal expansion of prepared nanocrystals is ≈7.5 × 10⁻⁶ K⁻¹.     

Hygroscopicity and bulk thermal expansion in Y2W3O12

Negative thermal expansion material, Y₂W₃O₁₂ has been synthesized by the solid-state method and bulk thermal expansion of the material has been investigated from 300 to 1100 K. The material reversibly forms a trihydrate composition whose X-ray diffraction pattern can be indexed to an orthorhombic unit cell with a = 10.098(1) Å, b = 13.315(3) Å, c = 9.691(4) Å. The cell volume of the hydrated pattern is 7% smaller than the unhydrated cell volume. According to the dilatometric studies, the material shows a 3-6% increase in the linear strain at about 400 K, which can be attributed to the removal of water. Sintering the material at 1473 K leads to large grain size of >100 μm, which results in a large hysteresis in the bulk thermal expansion behavior. Hot pressing at 1273 K under a uniaxial pressure of 25 MPa results in a fine-grained (2-5 μm) ceramic. Glazing the ceramic prevents moisture pick up and a linear thermal expansion over the entire temperature range 1100-300 K and an average linear thermal expansion co-efficient of −9.65 × 10⁻⁶/K is observed. The effect of water on the thermal expansion behavior of this system is discussed.     

Oxygen nonstoichiometry, thermal expansion and high-temperature electrical properties of layered NdBaCo2O5+δ and SmBaCo2O5+δ

Layered LnBaCo₂O_5+δ (Ln = Nd, Sm) with the cation-ordered double perovskite structure were synthesized by the solid-state reaction route and characterized by X-ray diffraction, thermogravimetric analysis and dilatometry. For NdBaCo₂O_5.73 and SmBaCo₂O_5.61 equilibrated with atmospheric oxygen at low temperatures, tetragonal and orthorhombic polymorphs were found to form, respectively. The oxygen content at 300-1300 K decreases with decreasing rare-earth cation size, whilst δ variations and chemical contribution to the apparent thermal expansion in air are substantially lower compared to the disordered (Ln, A)CoO_3−δ (A = Ca, Sr) analogues. The average thermal expansion coefficients are 23.1 × 10⁻⁶ K⁻¹ for NdBaCo₂O_5+δ and 20.8 × 10⁻⁶ K⁻¹ for SmBaCo₂O_5+δ at 300-1370 K and atmospheric oxygen pressure. These values are comparable to those of Bi₂O₃-based ionic conductors, but are incompatible with common electrolytes such as stabilized zirconia or doped ceria. The oxygen partial pressure dependencies of the total conductivity and Seebeck coefficient, studied in the P(O₂) range from 10⁻¹⁰ to 1 atm, confirm predominant p-type electronic conductivity.     

High temperature thermoelectric properties of (Ca, Ce)4Mn3O10

Thermoelectric (TE) properties such as resistivity (ρ), Seebeck coefficient (S), and thermal conductivity (κ) of Ca_4−3xCe_3xMn₃O₁₀ (0<x≤0.03) polycrystalline samples were measured from room temperature to 1000 K. ρ shows an obvious decrease with the increment of Ce content. The hopping conduction mechanism is used to explain the conduction behavior of these samples. The negative S values indicate that these materials are n-type. The sample of x=0.03 has the largest power factor, 0.52×10⁻⁴ Wm⁻¹ K⁻² at 1000 K. The value of κ and the dimensionless figure of merit of this sample is 1.51 Wm⁻¹ K⁻¹ and 0.034 at 1000 K, respectively.     

Thermal expansion coefficient of ZnSe crystal between 17 and 1080 °C by interferometry

The thermal expansion of ZnSe was measured by Fabry-Perot interferometry from 17 to 1080 °C during the heat-up of a seeded crystal growth experiment of ZnSe. The measured thermal expansion follows the two-step heating schedule very well. A single linear interpolation between the measured thermal expansion at 17 and 1080 °C gives a value for the thermal expansion coefficient, a as 4.95 × 10^− 6 °C^− 1. The estimated errors associated with a give its range of 4.60 to 4.99 × 10^− 6 °C^− 1.     

Hydro and thermal stability of die drawn wood polymer composites in comparison to solid wood

Both isotropic and oriented wood polymer composites (WPC) based on 40% w/w of a softwood powder/hardwood powder and polypropylene (PP), together with solid pieces of wood, were subjected to water immersion and thermal expansion tests. Although generally die drawing increased the amount of water absorbed by the WPC by about 2-fold when compare to isotropic WPC, the oriented WPC exhibited extremely high hydro-dimensional stability. The values of the longitudinal and transverse swelling/shrinkage of the WPC oscillated only between 0 and −2.3% compared to values of between 4 and 14% for the solid woods. Incorporation of soft/hard wood powders into PP also substantially decreased its thermal expansion coefficient α in both the isotropic and the oriented states. This extremely positive effect was enhanced by increasing the draw ratio. In the longitudinal direction, α decreased from about 80 × 10⁻⁶ °C⁻¹ (for the isotropic PP) to 5 × 10⁻⁶ °C⁻¹ for the highly drawn PP filled with softwood.     

Growth and properties of Ca0.28Ba0.72Nb2O6 single crystals

Calcium barium niobate Ca_0.28Ba_0.72Nb₂O₆ (CBN-28) crystals were successfully grown by the Czochralski method. X-ray powder diffraction experiments indicated that CBN single crystals are tetragonal with a = 12.432(±0.002) Å and c = 3.957(±0.001) Å, which have almost the same structure as the Sr_0.50Ba_0.50Nb₂O₆ (SBN-50) crystal. The thermal expansion coefficient perpendicular to Z-direction had been measured to be 1.25 × 10⁻⁵ K⁻¹ between 293.15 and 572.15 K, and along Z-axis was negative between 298.15 and 543.15 K. The specific heat of the crystal had been measured by the differential scanning calorimetric experiments. The transmittance spectra from 200 to 3200 nm were also measured. The measured temperature dependence of dielectric constants showed that the Curie temperature of the CBN-28 crystals is 260 °C, which is about 200 °C higher than that of the (SBN) crystal.     

Characterization and electrochemical performance of (Ba0.6Sr0.4)1−xLaxCo0.6Fe0.4O3−δ (x = 0, 0.1) cathode for intermediate temperature solid oxide fuel cells

La-doped Ba_0.6Sr_0.4Co_0.6Fe_0.4O_3−δ perovskites were synthesized and investigated as new cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs). The structural characteristics, thermal expansion coefficient (TEC), electrical conductivity and electrochemical properties were characterized by X-ray diffraction (XRD), dilatometry, DC four-terminal method, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques. The TEC of (Ba_0.6Sr_0.4)_0.9La_0.1Co_0.4Fe_0.6O_3−δ (BSLCF) was 14.9 × 10⁻⁶ K⁻¹ at 30-800 °C, lower than Ba_0.6Sr_0.4Co_0.4Fe_0.6O_3−δ (BSCF) of 15.6 × 10⁻⁶ K⁻¹. The electrical conductivity of BSCF was improved by La-doping, e.g. a value of 122 S cm⁻¹ for BSLCF vs. 52 S cm⁻¹ for BSCF at 500°C, respectively. In addition, La-doping enhanced the electrochemical activity for oxygen reduction reaction. The polarization resistance of BSLCF was 0.18 Ω cm² at 700 °C, about a quarter lower than that of BSCF. The improved electrochemical performance of BSLCF should be ascribed to the higher conductivity as well as the improved oxygen adsorption/desorption and oxygen ions diffusion processes.