Crystallization kinetics of Zr-rich FexZr0−x0−x0−x(20 ⩽ x ⩽ 40) metallic glasses

The crystallization kinetics of the melt-spun Fe-Zr metallic glasses in the iron-rich region has been investigated by means of DSC and X-ray diffraction. The crystallization mode changes with iron concentration. In the lower iron region, 20 x 25, the Fe _x Zr100–x glasses crystallize into -Zr and Ti₂Ni-type FeZr₂ with an accompanying sharp and large exotherm at the first crystallization step and immediately after this step, they transform into orthorhombic FeZr₃. On the other hand, the alloys with 35 x 40 exhibit a gradual exotherm which initiates from a temperature far below the definite crystallization temperature (T _x). The Fe-Zr metallic glasses in this concentration region crystallize polymorphously into the oxygenstabilized Ti₂Ni-type FeZr₂ with accompanying relatively small and composite exotherms. The annealing at a temperature where the gradual exotherm occurs for the alloys with 30 x 40 does not cause any changes of X-ray halo pattern but results in the reduction of the heat of exotherm due to the crystallization.     

Conduction in nanostructured La1?x Sr x FeO3 (0 ≤ x ≤ 1)

We investigated electrical properties of nanostructured La_1?x Sr _x FeO₃ (0 ?? x ?? 1) from 300 K?C400 K. The nanostructured La_1?x Sr _x FeO₃ (0 ?? x ?? 1) was synthesized by citrate gel method requiring no pH control. X-ray diffraction pattern showed that single phase LaFeO₃ with an orthorhombic structure was formed. The structure changed into rhombohedral for x = 0.5 and it became cubic for x = 1.0. For x ?? 0.5, our material showed non-linear current-voltage characteristics and for x > 0.5 it showed linear current-voltage characteristics. Poole Frenkel type conduction mechanism was found to be operative in LaFeO₃ from 300 K?C400 K. The experimental values of field-lowering coefficient were by 2.56?C6.41 times higher than the predicted value and were attributed to the presence of localized fields. The increase in conductance with Sr content was due to formation of Fe⁴⁺ ions in addition to Fe³⁺ with the increase in Sr content. Impedance spectroscopy and ac conductivity analysis of La_1?x Sr _x FeO₃ (0 ?? x ?? 1) was also carried out in the temperature range from 300 K?C400 K and frequency was varied from 20 Hz - 2 MHz. The ac conduction followed the correlated barrier hopping model in La_0.9Sr_0.1FeO₃.     

Plastic behaviour of Cd x Hg1−x Te (0⩽ x⩽1) crystals

Cd _x Hg_1–x Te (0x1) single crystals were strained by microhardness and by constant strain rate uniaxial compression tests, in the temperature range 300 to 600 K. Hardness curves as function of temperature can be described by empirical relations. Stress-strain curves, relaxation tests and dislocation observations using transmission electron microscopy show that the deformation is controlled by a thermally activated Peierls mechanism. Moreover, dislocations are dissociated with a stacking fault energy which does not depend on thex composition.     

Spin canting phenomenon in cadmium doped cobalt ferrites, CoCd x Fe2−x O 4 ( x = 0·0, 0·2, 0·4, 0·6, 0·8 and 1·0), synthesized using sol–gel auto combustion method

Synthesis of non-collinear (spin canted) ferrites having the formula, CoCd _x Fe_2???x O ₄ (x?= 0·0, 0·2, 0·4, 0·6, 0·8 and 1·0), has been carried out using the sol–gel auto combustion method. The ferrite samples show an interesting magnetic transition from Neel to Yafet–Kittel configuration, as the Cd^2?+? concentration is increased beyond x?= 0·4. The FT–IR spectra confirm the formation of the metal oxide bond as they exhibit two frequency bands in the range of ~595 cm^???1 and ~450 cm^???1, corresponding to the tetrahedral and the octahedral stretching vibrations of the metal oxide, respectively. The structural evolutions of the nanophase investigated using powder X-ray diffraction (XRD) technique show that the average crystallite size is ~ 35 nm. The magnetic studies reveal that the saturation magnetization, M _s , increases up to x?= 0·4 and decreases when the value of x is >0·4. It is proposed that the incorporation of Cd^2?+? ion takes place into the tetrahedral sites and up to x?= 0·4, Neel’s model is followed. But for x?> 0·4, canting of spins occurs, as explained by Yafet–Kittel (Y–K) model. The d.c. resistivity decreases as a function of temperature, indicating semiconducting nature of the ferrites and the positive value of Seebeck coefficient establishes p-type conduction behaviour for all the ferrite samples.     

Electrical conductivity and chemical stability of BaCe0·8 − x A x Gd0·2O3 − δ (A = In, Zr, Ta; x = 0, 0·1) ceramics

BaCe_0·8???x A _x Gd_0·2O_3???δ (A = In, Zr, Ta; x?=?0, 0·1) ceramics were synthesized by solid-state reaction method. Microstructure and electrical properties of BaCe_0·8???x A _x Gd_0·2O_3???δ ceramics were investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and complex impedance analysis at intermediate temperatures of 573–1073 K in different atmospheres. BaCe_0·8Gd_0·2O_3???δ , BaCe_0·7In_0·1Gd_0·2O_3???δ and BaCe_0·7Zr_0·1Gd_0·2O_3???δ ceramics exhibit a single cubic perovskite structure. BaCe_0·7In_0·1Gd_0·2O_3???δ ceramic has the highest conductivity of 4·6 × 10^???2 S·cm^???1 in air at 1073 K. BaCe_0·7In_0·1Gd_0·2O_3???δ and BaCe_0·7Zr_0·1Gd_0·2O_3???δ ceramics exhibit an excellent chemical stability against boiling water. Indium is a suitable doping element to promote the sintering densification and to enhance both electrical conductivity and chemical stability of Gd-doped BaCeO₃ at operating temperatures.     

Magnetic Properties and Metamagnetic Transition in SmCo1−x Fe x AsO (0≤x≤0.2)

Polycrystalline SmCo_1?x Fe _x AsO (x=0, 0.05, 0.1, 0.2) materials with single phase have been synthesized by solid-state reaction. According to the X-ray diffraction patterns, the a-lattice parameter shrinks, but the c-lattice parameter expends with the increased amount of Fe doping. Complicated magnetisms consist of antiferromagnetic, ferromagnetic, and paramagnetic have been observed between 5 K and 300 K in the present system. Magnetic measurement shows that with increasing Fe content, antiferromagnetic order of SmCoAsO is suppressed and ferromagnetic order is enhanced. Below their antiferromagnetic transition temperature, metamagnetic transition can be detected in samples with x<0.2, and the transition field decreases with increasing Fe content. When Fe content reaches 0.2, no metamagnetic transition is observed down to 5 K. A canting of the spins plays a crucial role in metamagnetic behavior of the present system.     

Structural and Magnetic Studies of Ca2?x Sm x MnO Compounds (x=0–0.4)

The Ca_2?x Sm _x MnO₄ (x=0?C0.4) compounds were synthesized by a solid?Csolid method and characterized by XRD at room temperature. The XRD profiles were indexed with a tetragonal structure (I/4mmm space group) for x??0.3 and orthorhombic one (Pnma space group) for x=0.4. The magnetic measurements were studied as a function of temperature (T=2?C300?K) and applied field (?? ₀ H=0?C10?T). When the temperature decreases, each compound has shown first a ferromagnetic?Cparamagnetic (FM?CPM) transition and then an antiferromagnetic?Cferromagnetic (AFM?CFM) one. The transition temperatures are found to be Sm-doping dependent. For all compounds, a spin-glass phenomenon is evidenced by FC/ZFC magnetization curves.     

Electrical properties of Sr x Ba1 − x Fe 0·6 Sn 0·4 O3 − ε NTC thermistors

Polycrystalline thermistor ceramics with the stoichiometric formula, Sr _x Ba_1???x Fe_0·6Sn_0·4O_3???ε (0·2 ≤ x ≤ 0·8), had been prepared by a standard solid state reaction route. X-ray diffraction analysis indicates that the ceramic system remains cubic perovskite structure with a very small lattice change. The electrical properties of Sr _x Ba_1???x Fe_0·6Sn_0·4O_3???ε thermistors were studied using a digital thermometer over a wide range of 298–400 K. The thermistors showed an excellent negative temperature coefficient (NTC) thermistor behaviour. The values of resistivity at 298 K (ρ ₂₉₈), thermistor constant (B _298/358) and activation energy (E _a) of the Sr _x Ba_1???x Fe_0·6Sn_0·4O_3???ε thermistors, decreasing with the increase of Sr content, were in the range of 0·37–11·0 kΩ ·cm, 2466–3703 K and 0·212–0·319 eV, respectively. For the thermistors with the compositions x?= 0·2 and 0·4, the fitting equivalent circuit was composed of three RCPE elements corresponding to grain, grain boundary and ceramic–electrode interface, respectively. From the impedance plots, it was found that the fitting data showed good agreement with the experimental data. The extracted grain boundary resistance exhibited a NTC thermistor behaviour.     

Cu-NQR Study on Single Crystals Sr14−x Ca x Cu24O41 with x = 0–11.5

Cu-nuclear quadrupole resonance (NQR) measurements have been performed on single crystals Sr_14–x Ca _x Cu₂₄O₄₁ (Ca _x ) with x = 0–11.5, in order to clarify the relation between the magnetic order around x = 11.5 and local environments at the Cu sites upon x. Cu-NQR frequency _Q for the ladders at 4.2 K increases linearly with increasing x, whereas _Q for the nonmagnetic Zhang–Rice (ZR) sites in the chains does not. Detailed site assignment of the spectra, which are different from those in the previous paper, is presented.     

Carbon monoxide oxidation on (Mg6−x Al x )MnO8 (0⩽x⩽0.6)

Murdochite-type (Mg_6–x Al _x )MnO_m8 (0x0.6) was synthesized at low temperature (700 °C) with the sol-gel process. The specific surface area, crystallite size, catalytic activity for the CO oxidation, and adsorption isotherms of oxygen on (Mg_6–x Al _x )MnO₈ were measured. The increase of the specific surface area with increasing Al³⁺ ion content was explained by the decrease of the particle size. The catalytic activity increased with increasing Al³⁺ ion content, and this increase was caused by the valence deviation from the Mn⁴⁺ ion to the Mn^3.5+ ion.     

Mn valence state and electrode performance of perovskite-type cathode La0·8Sr0·2Mn1 − x Cu x O3 − δ (x = 0, 0·2) for intermediate-temperature solid oxide fuel cells

Cu-free and Cu-doped LSM system, La_0·8Sr_0·2Mn_1???x Cu _x O_3???δ (x?=?0, 0·2), with perovskite structure were prepared using an EDTA combined citrate process and the effects of Cu ion at B-site were investigated. Electrical conductivity and polarization resistance of the Cu-doped LSM were 210 S·cm^???1 at 750 °C, and 2·54 Ω · cm² at 800 °C, respectively which were better than those of the Cu-free LSM. This indicated that the electrode performance of LSM was improved by the addition of Cu. The oxidation state of Mn ions increased with addition of Cu. The increase in the oxidation state of Mn ions was due to the formation of Mn^4?+? ions and oxygen vacancies. The addition of Cu ions to LSM systems could lead to enhanced electrode performance for oxygen reduction reactions originating from the change in valence of Mn ions.     

Magnetocaloric study of monovalent-doped manganites Pr0.6Sr0.4−x Na x MnO3 (x = 0–0.2)

A systematic investigation of structural, magnetic, and magnetocaloric properties is reported for a series of monovalent sodium-doped manganites Pr_0.6Sr_0.4?x Na _x MnO₃ (x = 0, 0.05, 0.1, 0.15, and 0.2). Rietveld refinements of the X-ray diffraction patterns show that all powder samples are single-phased and crystallized in the orthorhombic structure with Pnma space group. Magnetic characterization and Arrott plot confirm the second-order phase transition at Curie temperature T _C decreasing from 310 K for x = 0 down to 272 K for x = 0.2. Magnetic entropy change is largest for x = 0 reaching 1.95 J kg^?1 K^?1 at 2 T field. This corresponds to a large relative cooling power of 102 J kg^?1 . Magnetic field sensitivity of magnetic entropy change and relative cooling power are analyzed and discussed.     

Electrical transport properties of Nd0.67−x Eu x Sr0.33MnO3 (0 ≤ x ≤ 0.67) manganites

A systematic investigation of electrical transport properties viz., electrical conductivity and thermopower of Eu-doped Neodymium-based colossal magnetoresistive manganites with compositional formula, Nd_0.67−x Eu _x Sr_0.33MnO₃ (x = 0–0.67) has been undertaken. These materials were prepared by citrate gel route and characterized by X-ray diffraction, scanning electron microscopy, AC susceptibility, and electrical resistivity measurements. With a view to understand the complex conduction mechanism of these materials, electrical resistivity and thermoelectric power (TEP) data have been analyzed using various theoretical models. It has been concluded that the ferromagnetic metallic part of the conduction mechanism is explained by grain/domain boundary, electron–electron, and magnon scattering mechanisms, while that of high temperature paramagnetic insulating region might be due to small polaron hopping mechanism. The sign change of charge carriers observed in TEP measurements is attributed to the oxygen deficiency of the samples.     

Appearance of Griffiths Phase in La0.7−x Pr x Ba0.3MnO3 (0 ≤x≤ 0.2)

Polycrystalline La_0.7?x Pr _x Ba_0.3MnO₃ (0 ≤x≤ 0.2) samples were prepared using solid-state reaction and checked by X-ray diffraction. Magnetization measurements versus temperature and applied magnetic field were used to investigate their magnetic properties. For samples with x= 0.2, the Griffiths phase is observed when the inverse of susceptibility (1/ χ vs. T) is analyzed.     

Diffusion of mercury into for HgxCd(1−x)Te 0≤x≤0.03

Experiments carried out to fabricate Hg_xCd_(1-x)Te by diffusing mercury into CdTe slices from the vapour, resulted in obtaining slices with a maximum value of x=0.004. Measurements on the diffusion of mercury into such slices, where 0≤x≤0.03, under saturated vapour pressure conditions, resulted in two component profiles, each profile giving two values of D. These results were similar to ones obtained earlier, indicating that the diffusion was rate-limiting. In addition, the diffusivities were found to be independent of x. This revised version was published online in July 2006 with corrections to the Cover Date.     

High-temperature thermoelectric properties of Ca0.9Y0.1Mn1−x Fe x O3 (0 ≤ x ≤ 0.25)

Polycrystalline compounds of Ca_0.9Y_0.1Mn_{1? x} Fe _x O₃ for 0 ≤ x ≤ 0.25 were prepared by solid-state reaction, followed by spark plasma sintering process, and their thermoelectric properties from 300 to 1200 K were systematically investigated in terms of Y and Fe co-doping at the Ca- and Mn-sites, respectively. Crystal structure refinement revealed that all the investigated samples have the O′-type orthorhombic structure, and the lattice parameters slightly increased with increasing Fe concentration, causing a crystal distortion. It was found that with increasing the content of Fe doping, the Seebeck coefficient of Ca_0.9Y_0.1Mn_{1? x} Fe _x O₃ tended to increase, while the tendency toward the electrical conductivity was more complicated. The highest power factor was found to be 2.1 × 10^?4 W/mK² at 1150 K for the sample with x = 0.05 after annealing at 1523 K for 24 h in air. Thermal conductivity of the Fe-doped samples showed a lower value than that of the x = 0 sample, and the highest dimensionless figure of merit, ZT was found to be improved about 20 % for the sample with x = 0.05 as compared to that of the x = 0 sample at 1150 K.     

Ni1−x Pt x (x=0–0.08) films as the photocathode of dye-sensitized solar cells with high efficiency

Films of Ni_1−x Pt _x (x=0, 0.02, 0.04, 0.06, and 0.08) have been prepared on fluorine-doped tin oxide-coated (FTO) glass substrates by a chemical plating method and used as the photocathode for dye-sensitized solar cells (DSCs). The Ni_0.94Pt_0.06 film consisted of nanoparticles with a size of 4–6 nm and a Pt loading of 5.13 μg/cm². The Ni_0.94Pt_0.06 photocathode exhibited high catalytic performance toward triiodide reduction, high light reflectance, and low charge-transfer resistance. The DSC assembled with the Ni_0.94Pt_0.06 photocathode gave a short-circuit photocurrent density (J _sc) of 16.79 mA/cm², an open-circuit photovoltage (V _oc) of 736 mV, and a fill factor (FF) of 66.4%, corresponding to an overall conversion efficiency of 8.21% under standard AM 1.5 irradiation (100 mW/cm²), which is higher than that for the DSC with a pure Pt photocathode obtained by conventional thermal decomposition. Furthermore, the DSC based on the Ni_0.94Pt_0.06 photocathode showed good stability. The results indicate that Ni_0.94Pt_0.06 films are promising lowcost and high-performance photocathodes for use in DSCs. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users.     

Synthesis, microstructure and thermal expansion studies on Ca0·5+x/2Sr0·5+x/2Zr4P6−2x Si2x O24 system prepared by co-precipitation method

We report on the synthesis, microstructure and thermal expansion studies on Ca_0·5?+?x/2Sr_0·5?+?x/2Zr₄P_6???2x Si_2x O₂₄ (x = 0·00 to 1·00) system which belongs to NZP family of low thermal expansion ceramics. The ceramics synthesized by co-precipitation method at lower calcination and the sintering temperatures were in pure NZP phase up to x = 0·37. For x ≥ 0·5, in addition to NZP phase, ZrSiO₄ and Ca₂P₂O₇ form as secondary phases after sintering. The bulk thermal expansion behaviour of the members of this system was studied from 30 to 850 °C. The thermal expansion coefficient increases from a negative value to a positive value with the silicon substitution in place of phosphorous and a near zero thermal expansion was observed at x = 0·75. The amount of hysteresis between heating and cooling curves increases progressively from x = 0·00 to 0·37 and then decreases for x > 0·37. The results were analysed on the basis of formation of the silicon based glassy phase and increase in thermal expansion anisotropy with silicon substitution.     

Crystal Structures and Magnetic Properties of the Co2Mn1−x V x Sb (0 ≤ x ≤ 1) Heusler Compounds

Crystal structure and magnetic properties of the Co₂Mn_1?x V _x Sb (0 ≤ x ≤ 1) Heusler compounds have been studied by X-ray powder diffraction (XRD), magnetometric measurements, and full-potential linearized augmented plane wave (FP–LAPW) method. All compounds crystallize in a cubic Cu₂MnAl-type crystal structure with the space group Fm–3m. The samples for x<0.8 have the Curie temperatures above room temperature, while the Curie temperature is observed at 68 K for the sample with x = 0.8. The saturation magnetization at 5 K decreases linearly with increasing vanadium concentration x. The values of the saturation magnetization obtained by FP–LAPW–local density approximation (LDA) calculations are in better agreement with the experimental results compared with the results obtained by FP–LAPW–generalized gradient approximation (GGA) calculations.