Ba2La2TiNb2O12: A new microwave dielectric of A4B3O12-type cation-deficient perovskites

A new A₄B₃O₁₂-type cation-deficient perovskite Ba₂La₂TiNb₂O₁₂ was prepared by the conventional solid-state reaction route. The phase and structure of the ceramics were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM). The compound crystallizes in the trigonal system with unit cell parameter a = 5.6726(3) Å, c = 27.740(2) Å, V = 773.04(9) ų and Z = 3. The microwave dielectric properties of the ceramic were studied using a network analyzer, and it shows a high dielectric constant of 42.70, a high quality factor with Q × f of 31,130 GHz, and a small negative τ_f of − 4.2 ppm °C^− 1.     

Preparation,characterization and dielectric properties of Ba5LnZnTa9O30 (Ln=La,Sm) ceramics

Ba₅LnZnTa₉O₃₀ (Ln=La, Sm) ceramics were prepared by high temperature solid-state reaction route. The samples were characterized by X-ray diffraction, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC) methods. They belong to paraelectric phase of filled tetragonal TB structure at room temperature with unit cell a=12.5909(4) Å, c=3.9622(2) Å for Ba₅LaZnTa₉O₃₀; and a=12.5777(4) Å, c=3.9544(2) Å for Ba₅SmZnTa₉O₃₀. At 1 MHz, Ba₅LaZnTa₉O₃₀ has high dielectric constants of 89 with low dielectric loss 0.0067, and temperature coefficients of the dielectric constant (τ_ε) −811 ppm °C⁻¹; Ba₅LaZnTa₉O₃₀ has dielectric constants of 74 with low dielectric loss 0.0035, and τ_ε −474 ppm °C⁻¹.     

Neutron flux measurements with a Li2B4O7 crystal

The effect of neutron irradiation on a lithium tetraborate (Li₂B₄O₇, LBO) single crystal has been investigated. The crystals of high optical quality are found to be quite stable under high neutron fluence. This study shows that LBO crystals can be used as a proportional counter for neutron fluxes of the order 10⁹ cm⁻² s⁻¹ and higher. The detectors fabricated were found to have a sensitivity of ∼3×10⁻¹⁸ A (nv)⁻¹.     

Optical and thermal properties of crystalline Tb: KLu(WO4)2

A single crystal of Tb: KLu(WO₄)₂ with dimensions of 40 mm × 40 mm × 18 mm has been grown by the top-seeded solution growth (TSSG) method. The color of the crystal is brown. Absorption and fluorescence spectra were measured at room temperature. The measured specific heat is a little lower than that of Yb: KLW (0.365 J/g K) at 90 °C. The measured mean linear coefficients of thermal expansion are α_a = 17.1643 × 10^− 6 K^− 1_, α_a^⁎ = 14.0896 × 10^− 6 K^− 1, α_b = 8.7938 × 10^− 6 K^− 1, α_c = 23.1745 × 10^− 6 K^− 1, α_c^⁎ = 20.2866 × 10^− 6 K^− 1. The results indicate that the crystal has a large anisotropy. The refractive index was measured.     

Preparation,phase structure and microwave dielectric properties of CoLi2/3Ti4/3O4 ceramic

A new low loss microwave dielectric ceramic with composition of CoLi_2/3Ti_4/3O₄ was prepared by a conventional solid-state reaction method. The compound has a cubic spinel structure [Fd-3m (227)] similar to MgFe₂O₄ with lattice parameters of a = 8.3939 Å, V = 591.42 Å³, Z = 8 and ρ = 4.30 g/cm³. This ceramic has a low sintering temperature (～1050 °C) and good microwave dielectric properties with relative permittivity of 21.4, Q × f value of 35,000 GHz and τ_f value of ?22 ppm/°C. Furthermore, the addition of BaCu(B₂O₅) (BCB) can effectively lower the sintering temperature from 1050 °C to 900 °C and does not induce much degradation of the microwave dielectric properties. Compatibility with Ag electrode indicates that the BCB added CoLi_2/3Ti_4/3O₄ ceramics are good candidates for LTCC applications.     

Oxygen partial pressure dependence of the structural properties of CdO thin films deposited by a modified reactive vacuum evaporation process

Thin films of cadmium oxide were thermally deposited on glass substrates at partial pressures of oxygen, pO₂ in the range 1.33×10⁻² to 0.133 Pa at a substrate temperature of 160 °C. Energy dispersive analysis of X-ray fluorescence (EDAX) revealed that the CdO films deposited at pO₂ value of 4.00×10⁻² Pa were nearly stoichiometric. X-ray diffractometry (XRD) confirmed the polycrystalline nature of the film structure. All the films showed an fcc structure of the NaCl-type, as the dominant phase. The films exhibited preferred orientation along the (1 1 1) diffraction plane. The texture coefficients calculated for the various planes at different oxygen partial pressures (pO₂) indicated that the maximum preferred orientation of the films occurred along the (1 1 1) plane at an oxygen partial pressure of 4.00×10⁻² Pa. This was interpreted in terms of oxygen chemisorption and desorption processes. The lattice parameters determined from the diffraction peaks were in the range 4.655–4.686 Å. The average lattice parameter a₀ found by extrapolation using the Nelson–Riley function was 4.696 Å. Both the lattice parameter and the crystallite size were found to increase with increased partial pressure of oxygen. On the other hand, the strain and dislocation density were found to decrease as the partial pressure of oxygen was raised. A maximum (80%) in the optical transmittance at λ=600 nm and minimum in the electrical resistivity (9.1×10⁻⁴ Ω cm) of the films occurred at an optimum partial pressure of oxygen of 4.00×10⁻² Pa. The results are discussed.     

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.     

Low-temperature superplasticity of Al2O3(p)/Ni–Co nanocomposites

Nanocomposites of Al₂O₃/Ni–Co prepared using Al₂O₃ of various particle sizes were fabricated by pulse current electrodeposition. Their superplastic tensile deformation was investigated at strain rates of 8.33 × 10⁻⁴ s⁻¹ and 1.67 × 10⁻³ s⁻¹ and temperatures of 723–823 K. The Al₂O₃ particle sizes and the deformation temperature had significant influence on the elongation of the deposited materials. The optimal superplastic condition and the maximum elongation were determined. A low temperature superplasticity with elongation of 632% was achieved at a strain rate of 1.67 × 10⁻³ s⁻¹ and 823 K. Scanning electron microscopy and transmission electron microscopy were used to examine the microstructures of the deposited and deformed samples. The grains grew to a micrometer dimensions and were elongated along the tensile direction after superplastic deformation. Superplasticity in electrodeposited nanocomposites is related to the presence of S at grain boundaries and to deformation twinning.     

Preparation,crystal structure and characterization of α-NaSbP2S6 and β-NaSbP2S6 phases

The new phases α-NaSbP₂S₆ and β-NaSbP₂S₆ were synthesized by ceramic and reactive flux methods at 773 K. The structures of α-NaSbP₂S₆ and β-NaSbP₂S₆ were determined by the single-crystal X-ray diffraction technique. α-NaSbP₂S₆ crystallizes in the monoclinic space group P2₁/c with a = 11.231(2) Å, b = 7.2807(15) Å, c = 11.640(2) Å, β = 108.99(3)°, V = 900.0(3) Å³ and z = 4. β-NaSbP₂S₆ crystallizes in the monoclinic space group P2₁ with a = 6.6167(13) Å, b = 7.3993(15) Å, c = 9.895(2) Å, β = 92.12(3) °, V = 484.10(17) Å³ and z = 2.The α- and β-phases of NaSbP₂S₆ are closely related, the main difference lies in the stacking of the [Sb[P₂S₆]]_nⁿ⁻ layers. The structure of α-NaSbP₂S₆ consists of two condensed layers (MPS₃ type) to give an ABAB… sequence with Na⁺ cations located in the interlayer space. The packing of β-NaSbP₂S₆ is formed by monolayers of [Sb[P₂S₆]]_nⁿ⁻ stacked in an AA… fashion separated by a layer of Na⁺ cations. Both phases are derivates of the M¹⁺M³⁺P₂Q₆ family.The optical band gaps of α-NaSbP₂S₆ and β-NaSbP₂S₆ were determined by UV–vis diffuse reflectance measurements to be 2.17 and 2.25 eV, respectively.     

High-temperature electrical resistivity and heat capacity studies on nano-crystalline geikielite

We report here for the first time the temperature dependence of the electrical resistivity and heat capacity of nano-crystalline MgTiO₃ geikielite of up to 1000 K. The temperature dependence of heat capacity of nano-crystalline geikielite expressed as C_p = 46.44(5) + 0.0502(2)T − 4.56 × 10⁶T² + 1.423 × 10³T^− 0.5 − 8.672 × 10^− 6T^− 2, where C_p = is specific heat expressed in J/mol. K and T is the temperature in K. Both the electrical resistivity and heat capacity behaviour show that the geikielite (both the natural and synthetic nano-crystalline samples) are stable and remains electrically insulating up to 1000 K.     

Synthesis and crystal structure of tetramethylammonium fluoride octadecasil

Octadecasil, a clathrate-type inclusion compound, has been synthesized hydrothermally at 453 K with a gel having the composition 1.0SiO₂:0.53tetramethylammonium (TMA⁺):0.54fluoride:86H₂O. The crystal structure has been determined based on powder X-ray diffraction data taken at 298 K, and has been refined using Rietveld method. The result confirms the AST-type, all-silica framework model developed by Caullet et al. [P. Caullet, J.L. Guth, J. Hazm, J.M. Lamblin, H. Gies, Eur. J. Solid State Inorg. Chem. 28 (1991) 345]. Furthermore, by using a rigid body model the position and orientation of the occluded TMA⁺ cation in the rhombododecahedral [4⁶6¹²] cage can be determined; F⁻ anion has been located in the hexahedral [4⁶] cage. The unit cell parameters, in the tetragonal space group I4/m, have been refined as: a = b = 9.07 Å, c = 13.44 Å, cell volume = 1104.97 Å³. The refined unit cell composition is |[N(CH₃)₄⁺]_2.0F⁻_1.9|[Si₂₀O₄₀], i.e., both TMA⁺ and F⁻ ions possess near full occupancies, and compensate each other's electronic charges. The crystallization of the AST framework structure is the result of a cooperative structure-directing effect of both ions.     

High-pressure synthesis and magnetic properties of complex oxide Y2Cd2/3Re4/3O7

A new complex oxide Y₂Cd_2/3Re_4/3O₇ with hexagonal cell parameters a = 7.3564(2) Å, c = 17.7092(5) Å (space group P3₁21, z = 6, zirkelite structure type) was synthesized from Y₃ReO₈, ReO₂, metallic Re and CdO under pressure 6 GPa and temperature 1500 °C. Magnetic susceptibility measured in the temperature range from 2 to 300 K depends little on temperature above ∼50 K and is indicative of a delocalized or intermediate character of d electrons of Re⁵⁺ cations.     

Hydrothermal synthesis,crystal structure and characterization of LiCoP5O14·H2O: A new condensed layered penta phosphate crystals

A new family of condensed hydrated lithium cobalt penta phosphate (LiCoP₅O₁₄·H₂O) crystals were synthesized by hydrothermal technique and characterized by X-ray diffraction method. The compound crystallizes in monoclinic system with space group P21/c and cell parameters a = 10.788(4) Å, b = 9.761(3) Å, c = 9.788(5) Å, β = 101.249(1) Å, Z = 4, exhibiting layer type polymeric structure. DTA study indicates that this compound has low thermal stability and magnetically frequency dependent paramagnetic behaviour.     

Structural and optical studies on dc reactive magnetron sputtered Cu2O films

Cuprous oxide (Cu₂O) thin films were deposited by dc reactive magnetron sputtering technique onto glass substrates by sputtering of pure copper target in a mixture of argon and oxygen gases under various oxygen partial pressures in the range 8 × 10^− 3–1 × 10^− 1 Pa at a constant substrate temperature of 473 K and a sputtering pressure of 4 Pa. The dependence of cathode potential on the oxygen partial pressure was explained in terms of cathode poisoning effect. The influence of oxygen partial pressure on the structural and optical properties of Cu₂O films was systematically studied. Single phase films of Cu₂O were obtained at an oxygen partial pressure of 2 × 10^− 2 Pa. The films formed at an oxygen partial pressure of 2 × 10^− 2 Pa were polycrystalline with cubic structure and exhibited an optical band gap of 2.04 eV.     

Synthesis of RuSr2GdCu2O8 − δ superconductors by the sol–gel route

The RuSr₂GdCu₂O_8 − δ (Ru-1212) superconductors have been prepared through the sol–gel route. We found that 1030 °C is the optimum annealing temperature for the formation of the Ru-1212 superconductors synthesized by the sol–gel route. X-ray powder diffraction analysis indicates that nearly all the peaks from the samples can be indexed to a single phase of Ru-1212, tetragonal symmetry with lattice parameters a = b = 3.382 Å, c = 11.478 Å and space group I4/mmm. The RuSr₂GdCu₂O_8 − δ superconductors prepared by the sol–gel method exhibit onset transition temperature T_c-onset near 55 K and zero resistance temperature T_c-zero at 45 K.     

Third-order nonlinear optical properties of bis(tetrabutylammonium)bis(4,5-dithiolato-1,3-dithiole-2-thione)copper

Bis(tetrabutylammonium)bis(4,5-dithiolato-1,3-dithiole-2-thione)copper (BCDT) was synthesized and its third-order optical nonlinearity was characterized using picosecond Z-scan at 1064 nm. The Z-scan spectra reveal a large negative nonlinear refraction coefficient n₂ as high as 4.0 × 10⁻¹⁸ m²/W and a slight two-photon absorption β, which is determined to be 3.4 × 10⁻¹² m/W. The molecular second-order hyperpolarizability γ was calculated to be 6.5 × 10⁻³² esu. All these results suggest that this material has potential for the application of all-optical switching.     

Effects of interstitial Li+ ions on the properties of novel Li4.08Zn0.04Si0.96O4 ceramic electrolyte

The aim of this work was to investigate the effects of interstitial ions in the novel Li_4 + 2xZn_xSi_1 − xO₄ (x = 0.04) compound prepared via sol gel method. The compound was indexed to the monoclinic unit cell in the space group P2_1/m and the chemical composition of the compound was very close to the designed composition. The introduction of two interstitial Li⁺ ions increased charge carrier concentration in the doped system resulting in an enhancement of conductivity by an order of magnitude as compared to that of the parent compound, Li₄SiO₄. The compound of Li_4.08Zn_0.04Si_0.96O₄ exhibited total conductivity values of 2.51 × 10^− 5 S cm^− 1 at ambient temperature and 3.01 × 10^− 3 S cm^− 1 at 500 °C. Ionic transference number corresponding to Li⁺ ion transport was also found to be higher than the value obtained for the parent compound. This proved that interstitial Li⁺ ions contributed to the total conductivity in the sample. Linear sweep voltammetry result showed that the Li_4.08Zn_0.04Si_0.96O₄ ceramic electrolyte was electrochemically stable up to 5.80 V versus a Li/Li⁺ reference electrode.     

Structure and magnetism in Pr3RuO7

The crystal structure of the ordered fluorite, Pr₃RuO₇, was refined from powder neutron diffraction data in Cmcm. An interesting structural feature is the presence of relatively well separated zig-zag chains of corner sharing RuO₆ octahedra, Ru–Ru interchain distance 6.61 Å vs. Ru–Ru intrachain distance of 3.76 Å. Magnetic susceptibility data show a Curie–Weiss behavior for T>225 K with C=5.96(4) emu K mol⁻¹ and θ_c=+11(2) K. In an attempt to separate the contributions of Pr(3+) and Ru(5+), the properties of isostructural Pr₃TaO₇ were also measured, yielding C=4.63(3) emu K mol⁻¹. Thus, the contribution of Ru(5+), 4d³, S=3/2, to the measured Curie constant is estimated to be 1.33 emu K mol⁻¹, not far from the spin-only value of 1.87 emu K mol⁻¹. This supports the view that the Ru 4d electrons are localized and magnetic, not itinerant. A susceptibility maximum at about 50 K is attributed to long-range magnetic order and this is substantiated by neutron diffraction data. There is little evidence for one-dimensional antiferromagnetic correlations in this material but behavior characteristic of short-range ferromagnetic correlations attributed to Pr–Ru exchange interactions are found in the temperature range 50–200 K, consistent with the positive θ_c.     

Spatial anisotropy of photoelastic and acoustooptic properties in β-BaB2O4 crystals

The paper deals with the spatial anisotropy of photoelastic and acoustooptical properties in β-BaB₂O₄ (BBO) crystals. Our method is based on the construction and analysis of the indicative surfaces describing the spatial anisotropy of the longitudinal and transverse photoelastic effects. By means of the stereographic projections we have determined the maximum values of photoelastic interaction and the anisotropy power. Having the complete photoelastic tensor we calculated the effective photoelastic constant p_ef and the efficiency of isotropic and anisotropic acoustooptical diffractions (the figure of merit M) for different geometries of acoustooptical interactions. The most optimal sample geometries suitable for acoustooptical applications were determined within the computer simulations based on the optimization procedure, namely we have found the sample geometries characterizing by the maximal efficiency for the isotropic (M = 6.3 × 10⁻¹⁵ s³/kg) and anisotropic (M = 40 × 10⁻¹⁵ s³/kg) diffractions. Taking into account that BBO is known as a rather strong radiation-steady crystal it may be considered as new efficient acoustooptical material for applications in optical systems with superpower laser irradiation.     

Crystal structure of a new organic dihydrogenomonophosphate (C6H8N3O)2(H2PO4)2

Chemical preparation, X-ray single-crystal, thermal behavior, and IR spectroscopy investigations are given for a new organic cation dihydrogenomonophosphate (C₆H₈N₃O)₂(H₂PO₄)₂ (denoted IAHP) in the solid state. This compound crystallizes in the orthorhombic space group P2₁2₁2₁. The unit cell dimensions are: a = 7.422(3) Å, b = 12.568(5) Å, c = 20.059(8) Å with V = 1871.1(13) Å³ and Z = 4. The structure has been solved using direct method and refined to a reliability R factor of 0.029. The atomic arrangement can be described as inorganic layers of H₂PO₄⁻ anions between which are located the organic groups (C₆H₈N₃O)⁺ through multiple hydrogen bonds.