Isotope Studies of the CMR Compounds La1?xCaxMnO3+δ

Oxygen isotope effect studies of the ferromagnetic Curie temperature T _c of La_1–x Ca _x MnO₃ are presented. The isotope exponent ₀=–lnT _c/lnm ₀ changes from 0.4 to 0.14 in the range 0.2<x<0.43. The isotope exponent decreases strongly with increasing tolerance factor, or decreasing lattice distortion. Above Tc the conductivity is characteristic of small polarons. Raman scattering shows a prominent peak at 230 cm–1. The peak width could be related to site-dependent Jahn–Teller distortions above T _c, becoming significantly smaller at and below T _c. IR reflectivity data show a much larger zero frequency IR conductivity than dc conductivity. The IR peaks are independent of temperature between 150 and 295 K.     

The influence of composition on the formation and stability of Ni-Si-B metallic glasses

The influence of composition on the formation and stability of Ni-based glassy alloys containing Si and B has been investigated systematically. Depending on the SiB ratio certain compositions, with total metalloid contents in the range 17 to 49 at% (a wider range than has hitherto been reported for metal-metalloid glasses), have been vitrified by melt-spinning to an average thickness of 17 m. For metalloid concentrations greater than 36 to 40 at% the amorphous phase is brittle in the as-quenched state. The highest crystallization temperatures, T _x, occur at 32 to 38 at% metalloid, the actual value of T _x again depending on the SiB ratio. It is shown that, over a wide composition range, the glass-forming boundary corresponds closely with a value for the reduced crystallization temperature isometric of 0.52. This value corresponds to a critical cooling rate for glass formation of about 10⁶ K sec^–1, predicted from kinetic theories and assuming that T _x is a good estimate of the glass transition temperature, T _g. This agrees quite closely with the cooling rate for approximately 17 m thick tape predicted from thermal studies of the melt-spinning process. Hence, T _x/T _liq usefully describes the glass-forming ability (GFA) for much of the composition range studied, although preliminary results suggest that near the centre of the glass-forming range the GFA may be over-estimated. Substitution of Si by other metalloid elements from Groups IIIb–Vb in Ni₇₈Si₁₀B₁₂ glassy alloy generally decreases the thermal-stability.     

Viscous flow behaviour of NixZr100−x metallic glasses from Ni30Zr70 to Ni64Zr36

The compositional dependence of viscous flow in the Ni _x Zr_100–x amorphous system was investigated under non-isothermal conditions at a heating rate of 10 K min^–1in the compositional range fromx=30 tox=64 at % with the aid of a Hereaus TMA 500 dilatometer. The crystallization behaviour of the same glassy alloys under the same non-isothermal conditions was studied with a Perkin-Elmer DSC 7 differential scanning calorimeter. The characteristic crystallization and viscous flow parameters (the onset temperature,T _x, of crystallization; the temperature,T _m, of maximum heat evolution of the first crystallization step; the enthalpy, H _x, of crystallization; the activation energy,Q _x, of crystallization; the glass transition temperature,T _g; the viscosity values (T _g) and _min; and the activation energy for viscous flowQ (T>T _g), were shown to be dependent on composition. This dependence was examined on the basis of the equilibrium phase diagram of the Ni-Zr-system, and it is shown that glassy alloys possessing eutectic compositions manifest the greatest thermal stability because of the long-range atomic diffusion needed for crystallization to occur. Glassy alloys with nearly peritectoid compositions show low thermal stability, as no long-range diffusion is needed for the formation of the stable crystallization end-products NiZr₂ and NiZr. In all cases, the crystallization process is governed by viscosity flow of these glassy alloys.     

Preparation and study of Ca1 − xMgx(PO3)2 glassy and crystalline phases

The structure of Ca_{1 – x} Mg _x (PO₃)₂ crystalline and glassy samples was investigated in the whole concentration region of x = 0–1.0. From X-ray diffraction data it was found that, in the crystalline samples, solid solutions are formed for x < 0.3 on the calcium-side of the system, with the structure of -Ca(PO₃)₂, and for x > 0.6 on its magnesium-side, with the structure of Mg₂P₄O₁₂. Similar results were obtained from the study of their infrared and Raman spectra. In the glassy state, homogeneous glasses were formed within the whole concentration region. The values of their transformation temperatures, T _g, and crystallization temperature, T _c, change slightly with the composition and lie within the region of T _g = 529–544 °C and T _c = 631–677 °C.     

Optical properties of CH3NH3PbX3 (X = halogen) and their mixed-halide crystals

Thin films of microcrystalline CH₃NH₃PbX₃ (X = halogen) as well as their mixed-halide crystals were fabricated by the spin-coating technique, and their optical properties were investigated. X-ray diffraction investigation revealed that CH₃NH₃PbBr_{3 – x} Cl _x (x = 0–3) were successfully formed on glass substrate self-assembly and oriented with the a-axis. Owing to due to their large exciton binding energy, these materials showed clear exciton absorption and free-exciton emission in the visible region at room temperature. Replacing Br with CI made it possible to control the band structure of these materials. As a result, the peak position of the exciton band shifted continuously towards blue region with increasing the CI content in the films.     

Devitrification and vitrification of tellurite glasses

The crystallization of pure tellurite glass during various heating rates was studied. The activation energy for crystallization was 115 × 10²² eV mol^–1. The glass transformation, T _g, starting crystallization, T _x, crystallization, T _c and melting temperatures, T _m, have been reported for binary tellurite glasses of the form (1 – x) TeO₂–xA_nO_m [A_nO_m = MnO₂, Co₃O₄ and MoO₃]. Among many different parameters of the glass forming potential the two-thirds rule, T _g/T _m, the glass stabilization range, T= T _x – T _g, and the glass forming tendency, K _g= (T _c– T _g)/(T _m – T _c), are reported for the first time for tellurite glasses.     

Spin glass behaviour in the Co2−xZnxTiO4 compound

A.c. susceptibility measurements were carried out on the disordered spinel system Co_2–x Zn _x TiO₄ (0<x<1) between 10 and 80 K. Our measurements show three peaks in the versus T curve for Co₂TiO₄ and CoZnTiO₄ compounds. In both compounds two peaks are very close to each other, indicating that the Néel and semi-spin glass temperatures are very close. A third peak indicates the presence of the semi-spin glass to spin glass transition. In Co_1.5Zn_0.5TiO₄ only one peak is observed which indicates spin glass ordering at 26 K. Furthermore, the A-site canting present in Co₂TiO₄ and CoZnTiO₄ has a collinear and magnetic structure, indicating strong A-B coupling. X-ray analysis indicated that compounds of the system Co₂Zn_xTiO₄ synthesized with cubic symmetry. From transport properties it was found that the activation energy and thermoelectric coefficient decrease with increasing concentration of Zn in the system. The mobility of the system calculated from infrared measurements is typically of the order of 10^–9cm²V^–1s^–1.     

Kinetic studies of the glass transition in (Se65Te35)100−x Sb x by differential scanning calorimetry

Calorimetric studies of chalcogenide glasses, (Se₆₅T₃₅)_100–x Sb _x , obtained by ice-water quenching, were performed by a non-isothermal method. An X-ray diffraction study, as a function of temperature, was carried out, with samples of different compositions. The activation energy for relaxation time, was determined from the heating-rate dependence of values of the glass transition temperature, as a function of x. A maximum in E _t versus antimony concentration occurs at 1–2 at%. ¹²¹Sb Mössbauer results confirm the formation of Sb₂Se₃, by crystallization.     

Crystallization kinetics of bulk amorphous Se80−xSbxTe20

Crystallization kinetics of the Se_80–x Sb _x Te₂₀ (0x9) alloys have been studied using differential scanning calorimetry. The activation energies for the glass transition and that for crystallization have been determined from the heating rate dependence of the glass transition temperature and the peak crystallization temperature. The results have been analysed using the modified Kissinger's and Matusita's equations for the non-isothermal crystallization of materials. The variation of glass transition temperature with composition suggests that a small amount of Sb ( 4 at %) leads to an increase in the chain length of Se-Te, whereas further increase in Sb atomic per cent increases the number of Se-Te chains in the alloys.     

Correlation between thermal diffusivity and activation energy of ordering of lead free solder alloys Sn65?xAg25Sb10Cux rapidly solidified from molten state

Internal friction Q^–1, thermal diffusivity D_th, and thermal properties of the melts of Sn_65–xAg₂₅Sb₁₀ Cu_x (0–2.5 wt.%) solder alloys are investigated and studied by means of vibration resonance technique and calibrated differential thermal analysis respectively. The thermal analysis technique is used to measure the temperature dependence of the specific heat, C_p, the solidus temperature, T_s, the liquidus temperature T₁, and the activation energy of ordering U. It is found that T_s and T₁ show strong dependence on copper content. The activation energy of ordering U show critical dependence on the amount of the copper added. A typical dependence of D_th and U for all studied alloys is obtained. The formation of intermetallic compound of AgSb and Sb phases in the range of composition investigated causes a pronounced increase in the electrical resistivity.     

Density,differential thermal analysis and direct-current conductivity of Sb10S90 −x Ge x chalcogenide glasses

The glass-transition temperature,T _g, and the crystallization temperature,T _c for glassy Sb₁₀S_{90 –x} Ge _x samples were increased by increasing the Ge content. This was attributed to the closeness of the network by bridging Sb and/or S atoms with additional Ge atoms to form harder Ge&#x2013;Sb and/or Ge&#x2013;S bonds. The direct current (d.c.) electrical conductivity for the system Sb₁₀S_{90 –x} Ge _x shows semiconducting behaviour with increasing temperature. At low temperatures, the conductivity was attributed to a hopping conduction mechanism, while at high temperatures it was due to regular band-type conduction. The activation energy, E and the conductivity, ₀ were increased at low Ge contents. This may be related to the entrance of Ge atoms into the S&#x2013;S chains. On the other hand, the increase of the Ge content above 20 at % lead to a conversion of the behaviour of the E and ₀ from the insulating character of S to the semiconducting character of Ge.     

Anelastic relaxation associated with the motion of domain walls in barium titanate ceramics

The mechanical loss (Q ^–1) and shear modulus (G) were measured as a function of temperature in the range 130 K < T < 430 K for BaTiO₃ ceramics by an inverted pendulum at low frequencies ranging between 1-0.01 Hz. The Q ^–1 (T) and G(T) curves exhibit the three phase transitions observed in BaTiO₃. Each phase transition induces a loss peak and an anomaly in the elastic modulus. Moreover, three other loss peaks (R) are located below the phase transition temperature. These peaks can be described by an Arrhenius relationship, and the activation energies are determined as 0.92, 0.68, and 0.45 eV for the peak located in the tetragonal-, orthorhombic-, and rhombohedral-phase, respectively. These peaks are due to the interaction between the domain walls and the diffusion of oxygen vacancies in the domains.     

Glass transition temperature-structural studies of tungstate tellurite glasses

Raman, IR and DSC studies have been carried on the (100 − x)TeO₂–xWO₃ (TW) glasses with 10 ≤ x ≤ 40 mol%. The Raman, IR spectra of these samples show that glass network consists of [TeO₃]/[TeO₃₊₁], [TeO₄], [WO₄] and [WO₆] groups as basic structural units. The W ion coordination state changes from 4 to 6 when WO₃ concentration increases beyond 30 mol%. Addition of WO₃ oxide to the TW glasses increases the amount of lower coordination of [TeO₃]/[TeO₃₊₁] units and decreases the higher coordination [TeO₄] units, Te–O–Te chains. From DSC thermogram, thermal properties such as the glass transition temperature (T_g), onset crystallization (T_o) of the glass systems were calculated. The compositional variation of glass transition temperature (T_g) is found to linear with an increase in WO₃ content.     

Structural transformation-induced magnetic ordering in degenerate magnetic semiconductors

Electrical properties and molar specific heats have been measured in the temperature range 2–300 K of Bridgman-grown Sn_1–x Cr _x Te crystals. In addition to the paramagnetic-to-ferro or ferrimagnetic transition temperatureT _c (= 150–300 K), in this magnetic system there is another characteristic temperatureT _AHE (= 4–5 K), above which the anomalous Hall effects vanish and around which the specific heats show a small peak, indicating an extra magnetic transition. The low-temperature transition is considered as induced by a cubic-to-rhombohedral structural phase transition of the host SnTe crystal occurring at a critical temperature ofT _s (= 80–100 K). Data on the isothermal annealing of these crystals are also presented.     

Deposition rates of titanium nitride plates prepared by chemical vapour deposition of TiCl4+NH3 system

Titanium nitride plates (TiN_x,x = 0.74–1.0, about 2 mm thick maximum) were prepared by chemical vapour deposition (CVD) using TiCI₄, NH₃ and H₂ as source gases. The effects of CVD conditions, i.e. gas molar ratio (m _N/Ti = NH₃/TiCI₄) and deposition temperature (T_dep), on deposition rates and surface morphology were examined, and the deposition mechanism of the CVD-TiN_x plates was discussed. The relationship between m_N/Ti and deposition rates showed a maximum peak at certainm _N/Ti, and this maximum peak shifted to lowerm _N/Ti with increasing_{T dep}. The activation energy for the formation of CVD-TiN_x plates was about 80 kJ mol^–1 in the lower temperature range. The decomposition reaction of NH₃ gas could be associated with the rate-controlling step. At higher temperatures, the diffusion process may be the rate-controlling step, and a large amount of powder (mainly NH₄Cl) was formed in the gas phase. The highest deposition rate obtained in the present work was 1.06×10^–7 ms^–1 (0.38 mmh^–1) atT _dep = 1773 K andm _N/Ti = 0.87.     

Electrical properties of ZnSe-CdS alloy films

Thin films of ZnSe _x CdS_1–x (t 0.6 m) over the entire range of x, were deposited on glass substrates at two temperatures, T _s (350 and 470 K) by vacuum evaporation. X-ray diffraction studies showed that all the films were polycrystalline in nature. Films prepared at 470 K were nearly stoichiometric. Grain size increased with substrate temperature, T _s. The electrical conductivity and Hall measurements were carried out by d.c. van der Pauw technique. Hall effect studies/hot probe test showed that all the films were of n-type conductivity. Hall mobility increased with T _s. In addition, mobilities increased with temperature in films of all compositions, indicating the dominance of grain-boundary scattering. Grain-boundary potentials were in range 0.03–0.06 eV.     

The effect of nitrogen on viscosity of La-Si-Mg-O-N glasses by compressive creep and dilatometry

Viscosity as a function of temperature and nitrogen content and the glass transition temperature (T_g) were investigated in 20La-60Si-20Mg-O-N glasses with nitrogen contents varying from 0 to 28 eq.% (e/o) using compressive creep and dilatometric experiments. Although T_g obtained from dilatometry were 6–12°C lower than the lower limit of the transition temperature range from creep, both methods revealed identical and linear dependencies of T_g on N content. The average activation energy was 1184 ± 36 kJ/mol and viscous flow remains the deformation mechanism in all glasses regardless of nitrogen content. Addition of 28 e/o N in oxide glass resulted in an increase of T_g by 94–105°C and an increase in viscosity of around 5 orders of magnitude. These changes are greater than those reported in similar Al-containing glasses. Linear increase of T_g and compactness of the glass with nitrogen content result from enhanced cross-linking of the glass network.     

High-T c superconducting Bi(Al)-Ca-Sr-Cu-O glass-ceramic fibres drawn from glass preforms

Bi(Al)-Ca-Sr Cu-O glass-ceramic fibres over 100 cm in length were successfully drawn from a glass preform above the crystallization temperature,T _x. The diameters of the uniformly drawn fibres with circular cross-section could be controlled in the range from 25–200 m and the drawing speed was as high as 200 cm min^–1. In this work Al₂O₃ was used to modify the properties of the glass. It increased the glass transition and crystallization temperatures but did not significantly increase the glass working range. Shrinkage and increase of density during heat treatment of the glass fibres were observed. The annealed (825°C/12 h in air) Bi₄Al_0.1Ca₃Sr₃Cu₄O_y glass-ceramic fibre showed aT _c(onset) of 82 K and aT _c(zero) of 71 K.     

Pseudoelastic behavior in Y1−xPrxBa2Cu3Oy compounds

Tensile tests show that ferroelastic loops always occur at 100–150 K, 200–250 K and room temperature in the Y_1–xPr_xBa₂Cu₃O_y samples withx=0 and 0.1 for whichT _c is 92 K and 82.5 K respectively, and the shape memory effect is always observed in the compact sample near 130 K, just similar to that of thermal elastic martensitic alloys. The loss fraction (W/W) which is proportional to the area of ferroelastic loop as a function of temperature shows that there always exist static hysteresis (W/W) peaks at 130 K and 110 K which are attributed to the phaselike transition (PLT) characterized by the jump of lattice parameters. No ferroelastic loops and shape memory effect are observed in the range of 100 K to 150 K for the lowerT _c samples withx=0.3, 0.4 and 0.6.     

Dielectric properties and polarizability of molybdenum tellurite glasses

The dielectric behaviour of the [TeO₂]_1–x [MoO₃] _x , x=0.2, 0.3 and 0.45 mol%, glassy system is reported for the temperature range 300–573 K and the frequency range of 0.1–10 kHz. Both the static and high frequency dielectric constants for these binary tellurite glasses decrease with increasing MoO₃ content. The temperature dependence of the dielectric constants of these glasses are positive. The frequency dependence of the dielectric constant identifies a frequency dependence which does not show a flattening at low frequency. The room temperature static dielectric polarizability is discussed in terms of the MoO₃ concentration. The temperature dependence of the dielectric constant has been analysed in terms of the temperature changes of both volume and polarizability and also a volume change of the polarizability.