Calorimetric study and Kissinger analysis of melt-spun DyMn6−xGe6−xFexAlx (1 ⩽ x ⩽ 2.5) alloys

Thermal properties of rapidly quenched alloys from the DyMn_6?xGe_6?xFe_xAl_x (1 ? x ? 2.5) series produced by melt-spinning have been investigated by differential scanning calorimetry (DSC). The DSC curves show two exothermic effects connected with crystallization processes. Crystallization temperatures and enthalpies ΔH have been estimated. The systematic changes in these parameters allow concluding that the crystallization exothermic events are independent. Effective activation energies E have been determined using the Kissinger analysis and relatively high values up to 480 ± 20 kJ/mol for DyMn₄Ge₄Fe₂Al₂ have been found indicating high thermal stability of the amorphous state in this alloy series.     

Formation and mechanical behavior of (Fe0.5Ni0.5)80−xMoxB20 (x = 0–8) amorphous alloys

Glass forming ability, thermal stability and mechanical behavior of (Fe_0.5Ni_0.5)_80?xMo_xB₂₀ (x = 0, 2, 4, 6, 8) amorphous alloys were studied by XRD, TEM, SEM, DSC, tensile test, microhardness test and tearing test. The effects of Mo addition on glass formation, strength and ductility of (Fe_0.5Ni_0.5)_80?xMo_xB₂₀ amorphous alloys were discussed. The substitution of Mo for Fe and Ni simultaneously causes improvement in glass forming ability and thermal stability, and changes the crystallization process. The tensile fracture strength of amorphous alloy depends on both hardness and ductility; the alloy with high hardness and good ductility simultaneously also has a high tensile fracture strength. The (Fe_0.5Ni_0.5)₇₈Mo₂B₂₀ amorphous alloy exhibits good glass forming ability and the highest tensile fracture strength among (Fe_0.5Ni_0.5)_80?xMo_xB₂₀ alloys. Micro-plastic deformation occurred in ductile and brittle amorphous alloys that both show viscous flow characteristics. The mechanical behavior of (Fe_0.5Ni_0.5)_80?xMo_xB₂₀ amorphous alloys is related to the average outer shell electron concentration of metal atoms.     

Nano-heterogeneous structure of (1-x)KNbO3–xSiO2 glasses in the low glass-forming oxide content range 0.05 ≤ x ≤ 0.3

Glasses with a high content of niobium oxide are of significant interest for electro-optics and nonlinear optics. In the present paper we report the results of the investigation of the submicroscopic structure and nonlinear optical properties of (1-x)KNbO₃–xSiO₂ (KNS) glasses (x = 0.05–0.30) by XRD, SANS, electron microscopy and second harmonic generation (SHG) technique. Vitreous samples were fabricated by rapid melt cooling, via pressing the melt by steel plates, quenching between rotating metal rolls or splat cooling in air or nitrogen flow. Glasses with x < 0.15 are shown to possess a micro-inhomogeneous structure with regions enriched by SiO₂. On the contrary, as-quenched glasses with x > 0.15 are found by SANS to be homogeneous, but form nanostructures enriched by SiO₂ after heat-treatment. At temperatures below ~(T_g + 50 °C), SiO₂-enriched regions grow slightly, whereas their chemical composition shifts considerably closer to SiO₂. The data on the nano-inhomogeneous structure enables clarifying the complicated T_g(x) dependence of KNS glasses. SHG-active KNbO₃ phase precipitates at later stages of crystallization when the glass starts to lose its transparency, and crystallization of perovskite-like KNbO₃ is accompanied by the enhancement of SHG efficiency by several orders of magnitude.     

Epitaxial lateral overgrowth of non-polar GaN(1 1̄ 0 0) on Si(1 1 2) patterned substrates by MOCVD

m-Plane GaN was grown selectively by metal–organic chemical vapor deposition (MOCVD) on patterned Si(1 1 2) substrates, where grooves aligned parallel to the Si〈1 1 0〉 direction were formed by anisotropic wet etching to expose the vertical Si{1 1 1} facets for growth initiation. The effect of growth conditions (substrate temperature, chamber pressure, and ammonia and trimethylgallium flow rates) on the growth habits of GaN was studied with the aim of achieving coalesced m-plane GaN films. The epitaxial relationship was found to be GaN(1 1? 0 0) || Si(1 1 2), GaN[0 0 0 1] || Si[1 1 –1], GaN[1? 1? 2 0] || Si[1 1? 0]. Among all growth parameters, the ammonia flow rate was revealed to be the critical factor determining the growth habits of GaN. The distribution of extended defects, such as stacking faults and dislocations, in the selectively grown GaN were studied by transmission electron microscopy in combination with spatially resolved cathodoluminescence and scanning electron microscopy. Basal-plane stacking faults were found in the nitrogen-wing regions of the laterally overgrown GaN, while gallium-wings were almost free of extended defects, except for the regions near the GaN/Si{1 1 1} vertical sidewall interface, where high dislocation density was observed.     

Electronic properties calculation of Ge1 − x − ySixSny ternary alloy and nanostructure

The band structure of Ge_{1 ? x ? y}Si_xSn_y ternary alloys, which are easier to grow than binary Ge_1-xSn_x alloys, and clearly offer a wider tunability of their direct band-gap and other properties, was calculated and investigated by using the empirical pseudo-potential plane wave method with modified Falicov pseudo-potential formfunction. The virtual crystal approximation (VCA) and 2 × 2 × 2 super-cell (mixed atoms) method were adopted to model the alloy. In order to calculate all of these properties, the empirical pseudo-potential code was developed. The lattice constant of the alloy varies between 0.543 to 0.649 nm. The regions in the parameter space that corresponds to a direct or indirect band gap semiconductor are identified. The Ge_{1 ? x ? y}Si_xSn_y ternary alloy shows the direct band gap for appropriate composition of Si, Ge and Sn. The direct energy gap is in the range 0–1.4 eV (from the VCA calculation), and 0–0.8 eV (from the super-cell calculation), depending on the alloy composition. Therefore, this alloy is a promising material for optoelectronic applications in both visible and infrared range, such as interband lasers or, solar cells. Furthermore, strain-free heterostructures based on such alloys are designed and, using the effective-mass Hamiltonian model, the electronic structure of GeSiSn quantum wells with arbitrary composition is investigated, in order to understand their properties and the potential of their use in devices.     

Optical and electrical properties of as-prepared and annealed (Se80Te20)100 − xAgx (0 ≤ x ≤ 4) ultra-thin films

Optical and electrical properties of the (Se₈₀Te₂₀)_100 ? xAg_x (0 ≤ x ≤ 4) ultra-thin films have been studied. The ultra-thin films were prepared by thermal evaporation of the bulk samples. Thin films were annealed below glass transition temperature (328 K) and in between glass transition temperature and crystallization temperature (343 K). Thin films annealed at 343 K showed crystallization peaks for Se–Te–Ag phases in the XRD spectra. The transmission and reflection of as-prepared and annealed ultra-thin films were obtained in the 300–1100 nm spectral region. The optical band gap has been calculated from the transmission and reflection data. The refractive index has been calculated by the measured reflection data. It has been found that the optical band gap increases, but the refractive index, extinction coefficient, real and imaginary dielectric constant decrease with increase in Ag content. The optical band gap and refractive index show the variation in their values with increase in the annealing temperature. The extinction coefficient increases with increasing annealing temperature. The surface morphology of ultra-thin films has been determined using a scanning electron microscope (SEM). The measured dc conductivity, under a vacuum of 10^? 5 mbar, showed thermally activated conduction with single activation energy in the measured temperature range (288–358 K) and it followed Meyer–Neldel rule. The dc activation energy decreases with increase in Ag content in pristine and annealed films. The results have been analyzed on the bases of thermal annealing effects in the chalcogenide thin films.     

Magnetic behavior,transport properties and nanocrystallization of melt-spun YxCe50 − xCu42Al8 (0 ≤ x ≤ 50) amorphous system

Amorphous Y_xCe_50 ? xCu₄₂Al₈ (0 ≤ x ≤ 50) ribbons prepared by melt-spinning on the Cu wheel were subjected to X-ray diffractometry (XRD), differential scanning calorimetry (DSC) and to the measurements of magnetization and resistivity in the temperature range from 1.7 to 300 K. Effective activation energies, characteristic crystallization temperatures and enthalpies of as-quenched alloys have been determined. Two stages of crystallization have been observed in most samples (except shallow effects in Ce₅₀Cu₄₂Al₈). The activation energies have been calculated from the Kissinger relation to be 247 ± 18 and 570 ± 56 kJ/mol for Y₂₅Ce₂₅Cu₄₂Al₈ and Y₅₀Cu₄₂Al₈, respectively. The absence of the endothermic effect for x = 50, usually associated with a glass transition, below the primary crystallization event, indicates the presence of dispersed polyamorphous packing with a wide range of local glass transitions. The magnetization versus temperature plot for Y₂₅Ce₂₅Cu₄₂Al₈ points to a magnetic ordering at temperatures considerably below 50 K. This observation has been confirmed by the temperature dependence of resistivity, which exhibits a singularity at the same temperature. Moreover, a negative temperature coefficient of resistivity, characteristic of disordered systems, was observed. The electrical resistivity in the Y₂₅Ce₂₅Cu₄₂Al₈ amorphous alloy is governed by the weak localization of electrons.     

Crystallization kinetics of a-Se75Te25 − xGax (x = 0, 5, 10 and 15 at wt %) glassy system

Bulk glasses of a-Se₇₅Te_25 ? xGa_x (x = 0, 5, 10 and 15 at wt %) have been prepared by melt quenching technique. These samples were structurally characterized by using X-ray diffraction. Kinetic of crystallization in these glasses was studied under non-isothermal conditions using differential thermal analysis (DTA). DTA is performed at different heating rates of 5, 10, 15, 20 and 30 °C/min. The values of glass transition (T_g) and crystallization peak temperature (T_p) are found to be composition and heating-rate dependent. The obtained results have been analyzed in terms of activation energy of glass transition (E_g) using Kissinger's and Mahadevan et al. relations. Values of E_g obtained by the two relations are in agreement with each other. The results indicate that the crystallization process is a three-dimensional growth.     

Square-wave voltammetry and impedance spectroscopy in tin doped melts with the compositions xNa2O · 15Al2O3 · (85 − x)SiO2 (x = 8.5, 11 and 16)

Glasses with the base compositions xNa₂O · 15Al₂O₃ · (85 ? x)SiO₂ (x = 8.5, 11 and 16) doped with 0.5 mol% SnO₂ were investigated by both square-wave voltammetry and impedance spectroscopy in the temperature range from 1300 to 1600 °C. Each recorded square-wave voltammogram exhibits a well pronounced peak attributed to the Sn²⁺/Sn⁴⁺-redox pair. Impedance spectra were measured in a frequency range from 0.1 to 10⁵ s^?1 as a function of the superimposed dc-potential and were simulated using an equivalent circuit taking into account the resistivity of the melt, the electrochemical double layer, a resistor attributed to a kinetically hindered electron transfer and a Warburg parameter which accounts for the diffusion process of Sn⁴⁺ and Sn²⁺ to and from the electrode. Additionally, two impedance elements, a resistor and a capacitance both attributed to adsorption processes were necessary to fit the impedance spectra.     

Phase transformations in the La1−xNdxNi3.5Al1.5–H2 (x = 0.1 and 0.2) system

Interactions in the La_1?xNd_xNi_3.5Al_1.5-Н₂ (x = 0.1 and 0.2) system was studied from room temperature up to 950 °C at the initial hydrogen pressure of 5 MPa through differential thermal (DTA) and X-ray phase analyses. Heating two-phase alloys (x = 0.1 and 0.2) in hydrogen results in their disproportionation (at 530 and 560 °С, respectively) and the formation of NiAl and unidentified amorphous products. The single-phase La_0.9Nd_0.1Ni_3.5Al_1.5 alloy decomposes in hydrogen at 900 °С into a hydride of rare-earth metals and an Ni₃Al intermetallic; traces of NiAl and hydride of a phase of the CaCu₅-type structure have also been observed. Heating the disproportionated samples in vacuum to 520–550 °С leads to their recombination into a homogenized phase with a CaCu₅-type structure. In other words, the increase of neodymium content shifts the reaction equilibrium of La_1?xNd_xNi_3.5Al_1.5 alloys with hydrogen towards recombination.     

Microstructural analysis of Ga2S3–2MCl (M = K, Rb, Cs) glasses using Raman scattering

Raman scattering spectra of Ga₂S₃–2MCl (M = K, Rb, Cs) glasses have been conducted at room temperature. Based on the analysis of the local co-ordination surroundings of Cs⁺ ions, the similarities and differences of Raman spectra for the glass Ga₂S₃–2CsCl and the bridged molecular GaCl₃ were explained successfully. Through considering the effect of M⁺ ions on mixed anion units [GaS_4?xCl_x] and bridged units [Ga₂S_6?xCl_x] and the corresponding microstructural model, the Raman spectral evolution of the Ga₂S₃–2MCl (M = K, Rb, Cs) glasses was reasonably elucidated.     

Growth of Pb on Si(3 3 5)–Au surface

The growth, crystallographic structure and electronic properties of ultrathin Pb films grown on a vicinal silicon surface are investigated with reflection high energy electron diffraction (RHEED) and specific resistivity measurement techniques. A Si(3 3 5) surface with a perfect distribution of monoatomic steps separated with (1 1 1) terraces induced by a submonolayer amount of Au is used as a substrate. In the early stage, Pb growth is anisotropic. Apparently, the presence of steps forces the growth of short crystalline Pb chains along the steps. The layer is amorphous in the perpendicular direction. With the increasing thickness, a phase transition takes place between 3 and 4 monolayers (ML) that makes crystalline order also across the terraces. A further increase in thickness causes the layer surface to repeat the substrate morphology. It consists of regularly distributed monoatomic steps and narrow (1 1 1) terraces.     

Structural behavior of CuxZr100−x metallic glass (x = 35−70)

The structural behavior of rapidly quenched amorphous Cu_xZr_100?x alloys was investigated in a wide composition range between 35 and 70 at.% Cu content. High-energy X-ray diffraction patterns, atomic pair correlation functions, mass density and the thermal stability behavior of the alloys all exhibit monotonic changes with composition. Partial pair correlation functions were determined assuming that they remain unchanged in the different amorphous Cu_xZr_100?x alloys and only the weight fractions become altered with changes in composition. The experimental results can be well described by a solid solution-like replacement of Cu and Zr atoms in the whole composition range. No indications are observed neither for the existence of a special atomic arrangement at a particular chemical composition nor for the presence of phase separation in the glassy state of the binary Cu–Zr system.     

Crystallization behavior of Ce70−xAl10Cu20Cox (x = 0, 1, 3, 5 at.%) amorphous alloys

The effect of Co addition (substituting for Ce) on crystallization behavior of Ce₇₀Al₁₀Cu₂₀ amorphous alloys has been investigated using X-ray diffraction (XRD), differential thermal analysis (DTA) and transmission electron microscopy (TEM). The Co addition has an obvious effect on topological short-range ordering of Ce–Al–Cu–(Co) amorphous alloys. Moreover, the Co addition can slightly improve the thermal stability of Ce–Al–Cu based amorphous alloys. The 1 and 3 at.% Co additions do not obviously change the crystallization behavior of the Ce–Al–Cu–(Co) amorphous alloys, and the final crystallization products are FCC–CeAlCu(Co)O. However, the 5 at.% Co addition can alter the crystallization behavior of the Ce₇₀Al₁₀Cu₂₀ amorphous alloys. Proper content of Co can effectively suppress the formation of oxide phases during annealing of the Ce–Al–Cu–(Co) amorphous alloys.     

Optical properties of amorphous (As0.33S0.67)100−xTex (x = 0, 1, 5 and 10) chalcogenide thin films,photodoped step-by-step with silver

We have analysed in detail the effect of silver-content on the optical properties of Ag-photodoped amorphous (As_0.33S_0.67)_100?xTe_x (with x = 0, 1, 5 and 10 at.%) chalcogenide thin films; the chalcogenide host layers were prepared by vacuum thermal evaporation. Films of composition Ag_y[(As_0.33S_0.67)_100?xTe_x]_100?y, with y ? 18 at.%, were successfully obtained by successively photodissolving about 20- or 40-nm-thick layers of silver. The optical constants (n, k) have been accurately determined by an improved envelope method [J.M. González-Leal, R. Prieto-Alcón, J.A. Angel, D.A. Minkov, E. Márquez, Appl. Opt. 41 (2002) 7300], based on the two envelope curves of the optical-transmission spectrum, obtained at normal incidence. The dispersion of the refractive index of the Ag-photodoped chalcogenide films is analysed in terms of the Wemple–DiDomenico single-effective-oscillator model: $n^2(?\omega )=1-E_{\text{o}}{E}_{\text{d}}/(E_{\text{o}}^2-(?\omega {)}^2)$, where E_o is the single-oscillator energy, and E_d the dispersion energy. We found that the refractive index of the Ag-doped samples strongly increases with the Ag-content, whereas the optical band gap, $E_{\text{g}}^{\text{opt}}$, decreases also notably. For instance, in the particular case of x = 10 at.%, the largest Te-content, $E_{\text{g}}^{\text{opt}}$ decreases from 2.17 down to 1.67 eV. It should also be mentioned that, in the case of the undoped samples, when the Te-concentration increases from zero up to 10 at.%, the value of $E_{\text{g}}^{\text{opt}}$ decreases from 2.49 down to 2.17 eV.     

Specific effects of nanometer scale size on magnetic ordering in La1−xCaxMnO3 (x = 0.1, 0.3 and 0.6) manganites

To check the impact of nano-size originated effects on the magnetic ordering in doped manganites, X-band electron magnetic resonance measurements were performed on nanometer sized and bulk samples of La_1?xCa_xMnO₃ (x = 0.1, 0.3 and 0.6). The model fittings of EPR signal parameters and complementary magnetic measurements indicate that bulk La_0.9Ca_0.1MnO₃ shows inhomogeneous confinement of charge carriers, leading to its mixed magnetic ordering. The carriers mobility within impurity-like band and ferromagnetic (FM)-like ground state are observed on nanocrystals of the same composition. The bulk La_0.7Ca_0.3MnO₃ demonstrates homogeneous FM order and band-like carrier mobility. The surface magnetic disorder in its nano-counterpart leads to appearance of two magnetic phases – a core phase (bulk-like in properties) and a surface phase with notably reduced temperature of magnetic ordering; neither double-exchange interaction nor carriers mobility exist between these phases. The size reduction induced effects in La_0.4Ca_0.6MnO₃ are: an increase of surface FM-like component and a decrease of the charge-ordering temperature. These findings allow us to conclude that the nano-scale effect on magnetic ordering in La_1?xCa_xMnO₃ system weakens progressively upon stabilization of the low temperature magnetic ground state with Ca-doping.     

Structural characterization and phase transformation kinetics of Se58Ge42−xPbx (x = 9, 12) chalcogenide glasses

The glass transition behavior and crystallization kinetics of Se₅₈Ge_42?xPb_x (x = 9, 12) have been investigated using Differential Scanning Calorimetry (DSC) at five different heating rates under non-isothermal conditions. It has been observed that these glassy systems exhibit single glass transition and double crystallization on heating. The XRD pattern revealed that the considered glasses get crystallized into GeSe₂ and PbSe/Se phases after annealing at 633–643 K for 2 h. The GeSe₂ and Se phases were found to crystallize in monoclinic structure while, PbSe phase crystallizes in cubic structure. Besides this, a mixed phase was also observed in DSC thermograms after annealing. The kinetic studies include determination of various parameters such as Avrami exponent (n), frequency factor (K_o), dimensionality of growth (m), the activation energy for glass transition (E_t) and for crystallization (E_c). The values of E_t increases while that of E_c decreases after annealing. Also, dimensionality of growth decreases to one dimension from two and three dimensions after annealing.     

Structural analysis of xCsCl(1 − x)Ga2S3 glasses

Sulphide glasses doped with rare-earth ions have been demonstrated to be suitable for photonic applications such as optical amplifiers, up-converters and fiber lasers. The substitution of metal halides into the glass network has been shown to result glasses with desirable properties in terms of quantum efficiency and fiber manufacture [J.R. Hector, J. Wang, D. Brady, M. Kluth, D.W. Hewak, W.S. Brocklesby, D.N. Payne, Journal of Non-Crystalline Solids 239 (1998) 176]. To assist in the understanding of this improvement a structural analysis of glasses with a composition xCsCl(1 ? x)Ga₂S₃ has been undertaken in order to examine the nature of the gallium environment. Information collected by high energy X-ray diffraction and neutron diffraction have been analyzed to permit the identification of the structural units as Ga centered tetrahedra. The interconnection between the tetrahedra was found to be predominantly corner sharing.     

Amorphous Ni59Nb40PtxM1−x (M = Ru, Sn) electrocatalysts for oxygen reduction reaction

The oxygen reduction reaction, ORR, on amorphous Ni₅₉Nb₄₀Pt₁, Ni₅₉Nb₄₀Pt_0.6Ru_0.4 and Ni₅₉Nb₄₀Pt_0.6Sn_0.4 electrocatalysts was analyzed by electrochemical techniques such as cyclic voltammetry, CV; rotating disk, RDE, and ring-disk electrodes, RRDE, in a 0.5 M H₂SO₄ solution. The reduced amount of platinum and the incorporation of transition metals in the amorphous catalysts were found to have significant effect on the kinetic parameters of the cathodic reaction. The kinetics study (RRDE) performed on the amorphous catalysts showed a high activity towards the ORR, preferentially proceeding via multi-electron (4e^?) charge transfer pathway toward water formation, with less than 2.8% H₂O₂ in the region of PEMFC applications. The performance on Ni₅₉Nb₄₀Pt₁ was different, which may be related to changes in the electrode surface enrichment of one or two of the amorphous alloy constituents. The performance towards the cathodic reaction allows to envisage that incorporation of small amounts of Pt in the catalyst, may lead to the fabrication of good amorphous electrocatalytic materials with possible applications as cathode electrodes in polymer electrolyte fuel cells.