Polymorphism of the Ag8S4O4 and Ag6S3O4 compounds

Experimental results of the reaction occurring between aqueous solutions of AgNO₃ and Na₂S₂O₃ were presented in this work. It has been demonstrated that these reagents form two phases to which the summary formulas: -Ag₈S₄O₄ and -Ag₆S₃O₄ were ascribed. The -Ag₈S₄O₄ phase crystallizes in a tetragonal system and has the following parameters of the unit cell: a = b = 0.72052 nm, c = 0.51140 nm, V = 0.26550 nm³, Z = 1, d_x = 6.60 g/cm³. At 223°C -Ag₈S₄O₄ undergoes an irreversible, endothermic polymorphic transition. The heat of this transition amounts 8.03 × 10^–3 J/mol. A high-temperature polymorphic form -Ag₈S₄O₄ melts at 400°C. The -Ag₆S₃O₄ phase crystallizes in a monoclinic system and has the following parameters of the unit cell:a = 2.09616 nm, b = 0.53118 nm, c = 1.49885 nm, = 102.78°, V = 1.62753 nm³, Z = 8, d_x = 6.59 g/cm³. -Ag₆S₃O₄ also undergoes an irreversible, endothermic polymorphic transition at 221°C. The heat of this transition amounts 7.65 × 10^–3 J/mol. A high-temperature form, -Ag₆S₃O₄, melts at 390°C.     

Electronic and two-magnon light scattering in oxide superconducting crystals

From investigations of two-magnon Raman scattering (RS) under high pressures up to 430 kbar in Eu₂CuO₄ and YBa₂Cu₃O_6.2 crystals, it was shown that the dependence of the superexchange integralJ on the distance between Cu and O atoms in CuO₂ planesa is anomalously weak (Ja^–n, n=3±0.5). The large value ofJ indicates strong initial overlapping of Cu and O wave functions in high-T _c , materials. It was found that an increase in free carrier concentration results in a rapid increase of magnon damping and the disappearance of the two-magnon peak from RS spectra. A detailed study of electron Raman scattering has been carried out in superconducting and insulating YBa₂Cu₃O_6–x , single crystals. The spectral redistribution at frequencies<600 cm^–1 in different polarizations indicate that the superconducting gap is strongly anisotropic. In the normal (metallic) phase the behavior of the imaginary part of the response functionR() in the polarization (xx) corresponds to the model of a marginal Fermi liquid, and in the polarization (xx), this behavior is independent of the temperature. In insulating crystals,R() is independent of temperature toT200 K in both polarizations.     

EPR and magnetic susceptibility studies of xCr2O3-(1-x) 3B2O3-PbO glasses

By using X-ray diffraction analysis, EPR and magnetic measurements, the chromium-ion distribution in xCr₂O₃-(1–x) [3B₂O₃-PbO] glasses with 0x35 mol% Cr₂O₃ was studied. EPR investigation evidenced the presence of both Cr³⁺ and Cr⁵⁺ ions, the latter being in small proportion, in agreement with the atomic magnetic moment values. For concentrations x20 mol% Cr₂O₃ the isolated Cr³⁺ ions coexist with those coupled by super-exchange magnetic interactions, the isolated ones prevailing only for x<3 mol% Cr₂O₃. For x>20 mol % Cr₂O₃ microcrystalline precipitates were detected, giving rise to an antiferromagnetic transition with Néel temperature, N _N310 K and paramagnetic Curie temperature, _p=–480 K.     

Thermal Conductivity of the Four-Leg Spin-Ladder System La2Cu2O5 Single Crystal

We have investigated the magnetic susceptibility, , and the thermal conductivity, , in magnetic fields for the four-leg spin-ladder system La₂Cu₂O₅ single crystal. The in a magnetic field parallel to the ladder exhibits a kink at 130 K in correspondence to the magnetic ordering. The along the ladder exhibits a peak at 25 K and a shoulder at 14 K, which are probably related to the thermal conductivity due to magnons, _magnon, and that due to phonons, _phonon, respectively. The perpendicular to the ladder, on the other hand, exhibits only one broad peak related to _phonon. The observed large anisotropy of has been explained based upon the anisotropy of _magnon.     

Surface nucleation and cellular growth kinetics of cordierite glass ceramics containing 3 mol % Y2O3-ZrO2

Cordierite-based glass ceramics of the 2MgO2Al₂O₃5SiO₂ composition with t-ZrO₂ (3 mol% Y₂O₃-ZrO₂) and P₂O₅ addition, was heat-treated isothermally and isochronically for crystallization studies. Major crystalline phases incurred by the heat treatment were t-ZrO₂ and -cordierite. Surface nucleation predominated when edge and corner nucleation in these samples were suppressed regardless of their radii of curvature. Crystallization began with the formation of -quartz S.S. and its transformation to -cordierite was followed by prolonged heating. Cellular growth of -cordierite on the surface of the quenched glass plates, gave a linear kinetics. The activation energy for cellular growth was 410 kJ mol^–1.     

Some electrical characteristics of lithium and yttrium sialons

Some electrical properties of hot-pressed lithium sialons, Li _x/8Si_6–3x/4Al_5x/8O _x N_8–x havingx<5 and an yttrium sialon were measured between 291 and 775 K; the former consisted essentially of a single crystalline phase whereas the latter contained 98% glassy phase. For lithium sialons, the charging and discharging current followed al(t) t ^–nlaw withn=0.8 at room temperature. The d.c. conductivities were about 10^–13 ohm^–1 cm^–1 at 291 K and rose to 5×10^–7 ohm^–1 cm^–1 at 775 K. At high temperatures electrode polarization effects were observed in d.c. measurements. The variation of the conductivity over the frequency range 200 Hz to 9.3 GHz followed the () ⁿ law. The data also fitted the Universal dielectric law,() ^n–1 well, and approximately fitted the Kramers-Kronig relation()/()– =cot (n/2) withn decreasing from 0.95 at 291 K to 0.4 at 775 K. The temperature variations of conductivities did not fit linearly in Arrhenius plots. Very similar behaviour was observed for yttrium sialon except that no electrode polarization was observed. The results have been compared with those obtained previously for pure sialon; the most striking feature revealed being that _d.c. for lithium sialon can be at least 10³ times higher than that of pure sialon. Interpretation of the data in terms of hopping conduction suggests that very similar processes are involved in all three classes of sialon.     

Specific heat measurements of intercalation compounds M x TiS2 (M=3d transition metals) using ac calorimetry technique

Specific heats of 3d transition metal intercalates of 1T-CdI₂-type TiS₂, M _x TiS₂ (M=V, Cr, Mn, Fe, Co, and Ni; 0x1), have been measured in the temperature range 1.6–300 K using an ac calorimetry technique. The electronic specific heat coefficient (2–100 mJ/mole K²) and the Debye temperature _D (240–430 K) are found to depend on the guest 3d metals and their concentrations. All the intercalates show anomalous specific heat at low temperatures following an – lnT dependence ( and are constants), as found in dilute alloys.     

Charged defects-controlled conductivity in Ge-ln-Se glasses

The variation of the d.c. electrical conductivity, , with composition and temperature was investigated for glasses of the Ge-In-Se system. The results indicate a decrease in the activation energy for electrical conductivity, E, and an increase in on introduction of indium into Ge-Se glasses. The changes in E and with composition (selenium content in the glasses) are identical for the Ge_x In₅ Se_95–x and Ge_x In₈Se_92–x families. The results have been traced to the conduction controlled by charged defects in these chalcogenide glasses. The changes in E and have been explained by a shift in the Fermi level, being brought by the introduction of indium.     

Incommensurate Dynamical Properties of Optimally Doped YBa2Cu3O6.9

The resonance and incommensurate peaks in optimally doped high-T _c superconductor YBa₂Cu₃O_6.9 are observed by means of TOF neutron scattering technique. Obtained overall dynamical properties in a wide Q-E space show distinct incommensurate structure around antiferromagnetic (AF) zone center (, ). The incommensurability of =0.1 at 36 meV corresponds to the previous triple-axis neutron measurement. Variation of temperature dependence suggests the spectral weight of antiferromagnetic fluctuation observed around 25 meV at (, ) shifts to resonance peak position below T _c. Moreover obtained results with E _i=80 meV neutron energy indicate new feature of dynamical incommensurate structure at higher frequency region up to 53 meV.     

Cu2+ ions in sodium fluoride-sodium borate glasses studied by EPR and optical absorption techniques

Electron paramagnetic resonance (EPR) and optical absorption spectra of Cu²⁺ ions in 80Na₂B₄O₇-(20 – x)NaF – xCuO (NFNB) glass system with 0 x 6 mol% have been studied. EPR spectra of all the glass samples exhibit resonance signals characteristic of Cu²⁺ ions. The values of spin-Hamiltonian parameters indicate that the Cu²⁺ ions in sodium fluoride-sodium borate (NFNB) glasses were present in octahedral sites with tetragonal distortion. The number of spins (N) participating in resonance was calculated as a function of temperature for NFNB glass sample containing 1 mol% of Cu²⁺ ions and the activation energy was calculated. From the EPR data, the paramagnetic susceptibility () was calculated at various temperatures and the Curie constant was calculated from the 1/ – T graph. The optical absorption spectra of these samples show a broad absorption band centered at 13280 cm^–1 which is assigned to the ² B _1g ² B _2g transition of Cu²⁺ ions in distorted octahedral sites. The optical band gap energy (E _opt) and Urbach energy (E) are calculated from their ultraviolet edges. It is observed that as the copper ion concentration increases, E _opt decreases while E increases. This has been explained as due to the creation of additional localized states by CuO, which overlap and extend in the mobility gap of the matrix. By correlating the EPR and optical data, the molecular orbital coefficients have been evaluated.     

AC electrical conductivity of electron beam evaporated Cu-GeO2 thin cermet films

AC electrical properties of 410 nm think 30 at.wt% Cu-70 at.wt% GeO₂ thin films are reported for the frequency range 10⁴ to 10⁶ Hz and temperature range 150 to 425 K. The loss tangent (tan ) and the dielectric loss (/₀) are found to show striking minima around a cut-off frequency 10⁵ Hz. In the lower frequency range (10⁵ Hz), ₁() ^s T ⁿ is obeyed with s (0 to 0.51) increasing as a function of temperature and n (0.10 to 0.14) showing a very weak temperature dependence. In the higher frequency region (10⁵ Hz), ₁() and /₀ increase sharply leading to the quadratic behavior of ₁() with s equal to 2. These processes are discussed by analyzing an equivalent circuit which shows that at lower frequencies, the effects of series resistance in leads and contacts can be neglected, while at higher frequencies such effect give rise to spurious ² dependance for the conductance. A weakly activated AC conductivity and a frequency exponent s that increases with increasing temperature suggest that the low frequency behavior originates from carrier migration by tunneling process.     

Microstructural development and mechanical properties of pressureless-sintered SiC with plate-like grains using Al2O3-Y2O3 additives

Dense SiC ceramics with plate-like grains were obtained by pressureless sintering using -SiC powder with the addition of 6 wt% Al₂O₃ and 4 wt% Y₂O₃. The relationships between sintering conditions, microstructural development, and mechanical properties for the obtained ceramics were established. During sintering of the -SiC powder compact the equiaxed grain structure gradually changed into the plate-like grain structure that is closely entangled and linked together through the grain growth associated with the phase transformation. With increasing holding time, the fraction of phase transformation, the grain size, and the aspect ratio of grains, increased. Fracture toughness increased from 4.5 MPa m^1/2 to 8.3 MPa m^1/2 with increasing size and aspect ratio of the grains. Crack deflection and crack bridging were considered to be the main operative mechanisms that led to improved fracture toughness.     

Polymorphism in Sr3Fe2O7−x

The compound Sr₃Fe₂O_7–x , with variable iron valence, was investigated by X-ray powder techniques, both at room and at high temperatures. If the material is examined in massive form, a single phase called -Sr₃Fe₂O_7–x appears as previously reported in the literature. This -phase is tetragonal and exhibits the lattice parameters: a=3.874 and c=40.314 Å. Two other phases, called and -Sr₃Fe₂O_7–x , respectively, can be obtained on heating the finely powdered material when laid on a flat platinum support. The form is stable up to 1275° C, while the form is revealed only above 1275° C and changes always into -Sr₃Fe₂O_7–x when quenched. Both and phases are tetragonal, with a=4.001 and c= 58.251 for the form and a=4.013, c=57.092 Å for the form. The transition involves a true phase equilibrium, while the transformation is possible only by means of a suitable mechanical treatment of the material.     

Interaction between a dislocation and an impurity in KCl: Mg2+ single crystals

The interaction between a dislocation and the impurity in KCl: Mg²⁺ (0.035 mol% in the melt) was investigated at 77–178 K with respect to the two models: one is the Fleischer's model and the other the Fleischer's model taking account of the Friedel relation. The latter is termed the F-F. The dependence of strain-rate sensitivity due to the impurities on temperature for the specimen was appropriate to the Fleischer's model than the F-F. Furthermore, the activation enthalpy, H, for the Fleischer's model appeared to be nearly proportional to the temperature in comparison with the F-F. The Friedel relation between effective stress and average length of the dislocation segments is exact for most weak obstacles to dislocation motion. However, above-mentioned results mean that the Friedel relation is not suitable for the interaction between a dislocation and the impurity in the specimen. Then, the value of H(T _c) at the Fleischer's model was found to be 0.61 eV. H(T _c) corresponds to the activation enthalpy for overcoming of the strain field around the impurity by a dislocation at 0 K. In addition, the Gibbs free energy, G ₀, concerning the dislocation motion was determined to be between 0.42 and 0.48 eV on the basis of the following equation ln / = G ₀/(kT_p0)1 – (T/T _c)^{1/2 –1}(T/T _c)^1/2 + ln ₀/where k is the Boltzmann's constant, T the temperature, T _c the critical temperature at which the effective stress due to the impurities is zero, _p0 the effective shear stress without thermal activation, and ₀ the frequency factor.     

Dielectric dispersion in ZnF2-Bi2O3-TeO2 glass system

Dielectric constant , loss tan and ac conductivity of ZnF₂-Bi₂O₃-TeO₂ glasses with varying concentrations of Bi₂O₃ (from 5 to 20%) are studied as a function of frequency and temperature over moderately wide ranges. The dielectric breakdown strength for these glasses is also determined in air medium. From the analysis of these studies along with the IR spectra & DTA recordings of these glasses, the structural changes in ZnF₂-Bi₂O₃-TeO₂ glass system with change in the concentration of Bi₂O₃, are discussed.     

The effect of MgAl2O4 on the formation kinetics of Al2TiO5 from Al2O3 and TiO2 fine powders

The formation of Al_2(1–x)Mg _x Ti_(1+x)O₅ solid solutions from Al₂O₃-TiO₂-MgAl₂O₄ powder mixtures of 1 m particle size and moderate purity has been studied at 1300°C for different final composition values: x=0 (pure Al₂TiO₅), 10^–3, 10^–2 and 10^–1. Analysis of the kinetic data and microstructural observation indicates that MgAl₂O₄ affects the mechanism of Al₂TiO₅ formation by providing active nuclei for the growth of the new phase. These nuclei are probably constituted by Mg_0.5AlTi_1.5O₅, i.e. the equimolar Al₂TiO₅-MgTi₂O₅ solid solution, and are formed by reaction between MgAl₂O₄ and TiO₂ at temperatures above 1150 °C. As the value of x increases, the number of titanate particles per unit volume accordingly increases and the conversion of the original oxides is faster. At values of x10^–2, the prevailing mechanism is the nucleation and growth of Al₂TiO₅ nodules for fractional conversion up to 0.8. Further conversion of the residual Al₂O₃ and TiO₂ particles dispersed into the titanate nodules is slower and controlled by solid-state diffusion through Al₂TiO₅. At x=0.1, a large number of nucleation sites is present, and solid-state diffusion through Al₂TiO₅ becomes important even in the initial stage of reaction, as the diffusion distances are strongly reduced. The study of Al₂TiO₅ formation under non-isothermal conditions in the temperature range 1250–1550°C shows that reaction proceeds between 1300 and 1350 °C for x=0.01 and between 1250 and 1300 °C for x=0.1. Densification of the titanate becomes important at temperatures above 1300°C for x=0.1, but only above 1450 °C for x=0.01.     

Subsolidus phase relations in the ZnS-In2S3 system: 600 to 1080° C

Eleven ternary compounds were synthesised, of which nine are new. The seven most ZnS-rich compounds form a series. Each has a primitive hexagonal lattice witha=3.85±0.01 Å. Thec-dimension varies from 37.47 Å (39 ZnS8 In₂S₃) to 18.63 Å (18 ZnS8 In₂S₃) with a periodicity of 3.14 Å which can be related to a decrease in the ZnS content. One of the four remaining compounds (12 ZnS8 In₂S₃) is triclinic, but at least two polytypes are present. The more common variety has the parameters:a=3.86 Å,b=15.48 Å,c=3.54 Å,=90° 16,=120° 02 and=89° 47. The structure of the other polytype and of compounds 17 ZnS:8 In₂S₃ and 10 ZnS8 In₂S₃ have not been determined. Stoichiometric ZnIn₂S₄ has a rhombic hexagonal lattice (a=3.86 Å,c=36.95 Å). This ternary compound which has been synthesised previously is the only one to show appreciable solid solution. Approximately 2 mole % ZnS is soluble in ZnIn₂S₄ at 600° C; this increases to 8 mole % at 1080° C.     

Comparative study of solubilities of hydrogen,nitrogen and carbon in α-iron

Solubility data of hydrogen, nitrogen and carbon in -iron are analysed on the basis of statistical thermodynamics. Present analysis appears to yield realistic values for the enthalpy term of the solutions of these interstitial elements into -Fe, while the entropy terms remain ambiguous. During the course of this analysis a parameter _x, which refers to the solubility limit of the specific interstitial element X (X=hydrogen, nitrogen or carbon), is also estimated; _H< _N< _C. This order of _X values appears to be in accord with the observation that, under normal conditions, the solubility of carbon is the highest and that of hydrogen the lowest in -Fe, while the atomic size increases with the order hydrogen相似文献   

Coupling of order parameter collective modes to spin density in3He-B

We derive a general expression for the dynamic spin susceptibility of³He-B which is valid for all magnetic fields. The coupling of real and imaginary modes by particle-hole asymmetry is taken into account. Then we calculate the contribution of the mode at frequency =2 – 1/4 ( is the effective Larmor frequency) to the transverse susceptibility. The spectral weight of this mode in magnetic resonance absorption is proportional to (/)^1/2 (–)², where and are particle-hole asymmetry parameters. From the experimental coupling strength of the real squashing mode to sound we estimate (–)²10^–4. The dynamic susceptibility satisfies the sum rules of Leggett. Finally we point out the difficulties in calculating the transverse NMR frequency of³He-B. These difficulties arise from theS _z =0 Cooper pairs and from the coupling ofJ _z =±1 modes forJ=1 andJ=2.