Study of non-isothermal kinetics, electrical and optical properties of (GaSeTe) films

Ternary Ga_xSe_86−xTe₁₄ amorphous films (x=15 and 36) were prepared by thermal evaporation. The results of differential scanning calorimetry (DSC) at different heating rates are reported and discussed. The glass transition activation energy, E_t, and the crystallization activation energy, E_c, were evaluated by measuring the heating rate dependence of the glass transition, crystallization onset and peak crystallization temperatures. The average calculated values of E_t and E_c are 140.29 and 97.89 kJ/mol, respectively. The electrical conductivity of amorphous Ga_xSe_86−xTe₁₄ thin films with different thickness has been measured in the temperature range (263.2-333.3 K) and this allows the effect of introducing a metallic impurity to be observed. It was observed that conductivity increases with increasing activation energy and with a lowering of the pre-exponential factor, which suggests the results can be explained in terms of hopping conduction. The optical constants of these films were determined by transmission and reflection measurements at normal incidence in the spectral range of 500-800 nm. The refractive index has anomalous behavior in the spectral range 400-500 nm. The refractive index dispersion can be fitted to a single oscillator model.     

Crystallization kinetics in as-synthesis high yield of a-Se100−xTex nanorods

The paper reports the synthesis of high yield of a-Se_100−xTe_x (x = 3, 6, 9 and 12) nanorods using one of the simplest approaches i.e. melt quenching technique. The morphology and microstructure of as-prepared alloys is studied using scanning Electron Microscopy (SEM) and transmission electron microscopy (TEM). From SEM investigation, it is observed that these powder samples of a-Se_xTe_100−x contain high yield of nanorods and their diameter is of the order of several hundred nanometers. The XRD patterns of these samples suggest that these nanorods are amorphous in nature. Crystallization kinetics in these nanorods of amorphous Se_xTe_100−x glasses are studied at different heating rates (5, 10, 15 and 20 K min⁻¹) under non-isothermal condition using differential scanning calorimetry. It is observed that the value of glass transition temperature and crystallization temperature varies with the composition and heating rate. From the heating rate dependence of glass transition temperature and crystallization temperature, the activation energy for structural relaxation (ΔE_t), the activation energy of crystallization (ΔE_c) and the order parameter (n) have been calculated. The composition dependence of the activation energy for thermal relaxation and activation energy for crystallization is discussed in terms of the structure of Se–Te glassy system.     

Crystallization kinetics of magnetron-sputtered amorphous CoNbZr thin films

For non-isothermal and isothermal annealing, the crystallization kinetics of magnetron sputtered Co_85.5Nb_8.9Zr_5.6 amorphous alloy thin films have been investigated by differential scanning calorimetry measurements. As a result, in the case of non-isothermal crystallization, one distinct exothermic peak is observed at 470 °C, which is due to the crystallization of hcp α-Co. With the Kissinger method, the apparent activation energy was obtained to be 99.82 kJ/mol. By using the Deloy-Ozawa method, the local activation energy of non-isothermal crystallization was calculated. For isothermal crystallization, the Avrami exponents were determined by means of the Johson-Mehl-Avrami equation, which is in the range of 1.19-1.37. Based on an Arrhenius relationship, the local activation energy was analyzed, which yields an average value E_c=88.51 kJ/mol. Finally, the local Avrami exponent was used for discussing the details of the nucleation and growth behaviour during the isothermal crystallization.     

The effect of Fe on the crystallization behavior of Al–Mm–Ni–Fe amorphous alloys

The crystallization behavior and thermal stability of Al₈₆Mm₄Ni_10–x Fe _x alloys were investigated as a function of Fe content. Alloys, produced by a single roll melt-spinner at a circumferential speed of 52 m/s, revealed fully amorphous structures. The thermal stability of the present amorphous alloys increased with the increase of Fe content. The activation energy for crystallization of -Al increased as the Fe content increased. This increase of activation energy resulted in the simultaneous precipitation of -Al and intermetallic phase observed especially in Al₈₆Mm₄Ni₅Fe₅ and Al₈₆Mm₄Ni₂Fe₈ alloys. The glass transition was observed in DSC thermogram only after proper annealing treatment. The effect of alloy composition on the thermal stability could be explained in terms of the atomic structure of the amorphous alloy.     

Synthesis and thermal properties of polystyrene-graft-PEG copolymers as new kinds of solid–solid phase change materials for thermal energy storage

A series of polystyrene-graft-PEG₆₀₀₀ copolymers were synthesized as new kinds of polymeric solid–solid phase change materials (SSPCMs). The synthesized SSPCMs storage latent heat as the soft segments PEG₆₀₀₀ of the copolymers transform from crystalline phase to amorphous phase and therefore they can keep its solid state during the phase transition processing. The graft copolymerization reaction between polystyrene and PEG was verified by Fourier transform infrared (FT-IR) and ¹H NMR spectroscopy techniques. The morphology of the synthesized SSPCMs was characterized by polarization optical microscopy (POM). Thermal energy storage properties, thermal reliability and thermal stability of the synthesized SSPCMs were investigated by differential scanning calorimetry (DSC) and thermogravimetric (TG) analysis methods. The DSC results showed that the synthesized SSPCMs had typical solid–solid phase transition temperatures in the range of 55–58 °C and high latent heat enthalpy in the range of 116–174 J g⁻¹. The TG analysis findings showed that the synthesized SSPCMs had high thermal durability above their working temperatures. Also, thermal conductivity measurements indicated that the synthesized PCMs had higher thermal conductivity compared to that of polystyrene. The synthesized polystyrene-graft-PEG₆₀₀₀ copolymers as new kinds of SSPCMs could be used for thermal energy storage.     

Crystallization kinetics of V2AlC

X-ray amorphous V₂AlC and hexagonal (V,Al)₂C_x thin films were synthesized by magnetron sputtering from a compound target with the composition of V₂AlC. The crystallization kinetics was investigated by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). During continuous heating up to 1200 °C, one exothermal peak is observed between 565 and 675 °C. XRD data suggest that the DSC peak is associated with the formation of V₂AlC. The activation energy of crystallization of V₂AlC is ~ 308 kJ/mol based on the Kissinger approach. This value is close to the 287 kJ/mol activation energy obtained here for the transformation of magnetron sputtered (V,Al)₂C_x thin films to V₂AlC. The here reported phase formation temperature of V₂AlC is about 800 °C lower than during hot pressing of elemental powders.     

Fast amorphization and crystallization in Al-Fe binary system by high-energy ball milling

Large amount of amorphous phase of Al-Fe binary system was obtained by MA of elemental powders using a high-energy ball mill at milling intensity of 150G (G is the gravitational acceleration). XRD, HRTEM and DSC were used to analyze the process of amorphization and crystallization. The time required achieving almost complete amorphous state is only 4.2 ks for Al-25 at.%Fe system and 3 ks for Al-30 at.%Fe system, respectively. The time of amorphous formation is very shorter than that of previous reports on Al-Fe binary system. Further milling causes rapid crystallization of the amorphous phase. By analysis of S(Q), the presence of a strong Al-Fe chemical short-range order in the amorphous matrix is suggested. Moreover, the superstructure of these Al-Fe clusters in the amorphous matrix is similar to the solid structure of Al₅Fe₂, and the clusters transform into the nucleus of Al₅Fe₂ intermetallic compound under the action of milling energy.     

Development of nanocrystals in an amorphous alloy Zr47Ni30Ti23

Development of nanocrystals during crystallization of an amorphous alloy Zr₄₇Ni₃₀Ti₂₃ is studied using differential scanning calorimetry (DSC), X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). Up on heating the amorphous ribbon in DSC, three exothermic peaks including a broad peak are observed. Stable nanocrystals embedded in the amorphous matrix form through primary crystallization. The nanocrystals have uniform sizes after prolonged annealing at 400°C for 180 minutes. Ni plays an important role for the stability of the nanocrystals. Due to the Ni partitioning between the nanocrystals and the residual matrix, the crystallization temperature (T _xI) of the residual amorphous matrix increases as crystallization proceeds. The formation of nanocrystal-amorphous composites that have high microstructural stability is possible through the controlled crystallization of the amorphous alloy Zr₄₇Ni₃₀Ti₂₃.     

The adsorption properties of PdZnx alloy on Pd(1 0 0): Preparation and characterization

The formation of PdZn_x alloy on Pd(1 0 0) and its characteristics were investigated by various methods, such as photoelectron, auger-electron, electron energy loss, thermal desorption spectroscopic methods and work-function measurement. The alloy was produced by the decomposition of diethyl zinc on Pd(1 0 0). The alloy surface reacts with O₂ and ZnO_x is formed. The reactivity of alloy to hydrogen is similar to that of K/Pd. The stability of adsorbed CO is lower than on clean Pd(1 0 0).     

Fabrication of tungsten-based metallic glasses by low purity industrial raw materials

Quaternary W₃₀Fe₃₈B_32−xC_x (x = 5, 7, 10, 13, 15 at.%) alloys have been investigated by melt-spinning method to produce metallic glasses using low purity industrial raw materials. The phase structure of these ribbons is investigated by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). The thermal stabilities of W₃₀Fe₃₈B_32−xC_x (x = 5, 7, 10, 13, 15 at.%) alloys are analyzed by differential scanning calorimeter (DSC). It is found that W₃₀Fe₃₈B₂₂C₁₀ metallic glass with 45 μm in thickness and 2 mm width can be successfully fabricated. And other alloys with the same thickness and width as W₃₀Fe₃₈B₂₂C₁₀ alloy are observed with some crystalline peaks on the halo patterns. The DSC measurements show that each alloy undergoes a two-step crystallization with the onset temperature of the first crystallization being as high as 984-1067 K. Vickers hardness and density values of W₃₀Fe₃₈B_32−xC_x (x = 7, 10, 13, 15 at.%) alloys at room temperature are 11.9-12.8 GPa and 14.5 g/cm³ at least, respectively. The effect of C addition on GFA in the W-Fe-B alloy system is discussed.     

Giant electrical conductivity enhancement in BaO–V2O5–Bi2O3 glass by nanocrystallization

The effects of the annealing of 20BaO–30V₂O₅–50Bi₂O₃ glass on the structural and electrical properties were studied by scanning electron micrographs (SEM), X-ray diffraction (XRD), differential scanning calorimeter (DSC) density (d) and dc conductivity (σ). The XRD and SEM observations have shown that the sample under study undergoes structural changes: from amorphous at the beginning, to partly crystalline after nanocrystallization at crystallization temperature (T_c) for 1 h and to colossal crystallization after the annealing at the same temperature for 24 h. The average size of these grains after nanocrystallization at T_c for 1 h was estimated to be about 25–35 nm. However, the glass heat treated at T_c = 580 °C for 24 h the microstructure changes considerably. The nanomaterials obtained by nanocrystallization at T_c for 1 h exhibit giant improvement of electrical conductivity up to four order of magnitude and better thermal stability than the as-received glass. The major role in the conductivity enhancement of this nanomaterial is played by the developed interfacial regions “conduction tissue” between crystalline and amorphous phases, in which the concentration of V⁴⁺–V⁵⁺ pairs responsible for electron hopping is higher than inside the glassy matrix. The annealing at T_c for 24 h leads to decrease of the electronic conductivity. This phenomena lead to disappearance of the abovementioned “conduction tissue” for electrons and substantial reduction of electronic conductivity. The high temperature (above θ/2) dependence of conductivity could be qualitatively explained by the small polaron hopping (SPH) model. The physical parameters obtained from the best fits of this model are found reasonable and consistent with the glass compositions.     

Crystallization kinetics of an amorphous Al<Subscript>75</Subscript>Ni<Subscript>10</Subscript>Ti<Subscript>10</Subscript>Zr<Subscript>5</Subscript> alloy

The formation and crystallization behaviors of a mechanically alloyed Al₇₅Ni₁₀Ti₁₀Zr₅ amorphous alloy were studied by X-ray diffraction, transmission electron microscopy, and differential scanning calorimetry in the present study. The effective activation energy of the crystallization was determined by the Kissinger and Ozawa equations, respectively. The two equations yield close results and the average activation energy is 252 ± 13 kJ/mol. The resultant crystalline products were Al and Al₃Ni, and the crystallization mechanism is two- or three-dimensional nucleation and growth controlled by the diffusion of atoms. The thermal stability of the alloy was evaluated by a continuous transformation diagram obtained by the extended Kissinger equation.     

Thermal crystallization kinetics and crystallite size distribution of amorphous ITO film deposited in the presence or absence of water vapor

The isothermal crystallization process of amorphous indium tin oxide films was investigated by examining the peak intensity, obtained through high-temperature X-ray diffraction analysis. The introduction of water vapor (5 × 10^− 5 Torr) during sputtering-deposition significantly reduced the rate of crystallization. This can be attributed to the presence of chemically bonded hydrogen. Classical kinetic analysis based on the Kolmogorov-Johnson-Mehl-Avrami equation indicated three distinct changes caused by the introduction of water vapor: it reduced the kinetic exponent (n) from approximately 5/2 (2.59 ± 0.12) to 3/2 (1.53 ± 0.10), increased the activation energy (E_a) from 79.9 to 116 kJ/mol, and increased the average crystallite size from 54 to 93 nm. Site-saturated and continuous nucleation models are tentatively proposed, to account for the crystallization of amorphous ITO films deposited in the presence and absence of water vapor, respectively.     

Nanocrystalline Hf and Ta containing FeCo based alloys for high frequency applications

FeCo based nanocrystalline materials have excellent soft magnetic properties even at high temperature, but are limited to low frequency applications due to their relatively low electrical resistivities, ρ_e, resulting in high eddy current losses. Amorphous alloys of (Fe₈₁Co₁₉)₈₄M₉B₇ where M = (Hf, HfTa, Ta) were prepared by meltspinning and annealed for increasing times at their respective crystallization temperatures. The nanocrystalline alloys had coercivities less than 0.4 Oe and saturation inductions greater than 1 T. The electrical resistivities of the amorphous ribbons were all similar with values of ρ_e ? 180 μΩ cm. After annealing at the crystallization temperature, the M = Ta alloy had the largest ρ_e of 140 ± 3 μΩ cm. The Ta alloy also had the best high frequency properties, with an initial permeability of 822 at 1 MHz.     

Assessment of glass-forming ability and the effect of La2O3 on crystallization mechanism of barium-lead-zinc phosphate glasses

Differential scanning calorimetry (DSC) was used in this work to study the effect of La₂O₃ addition on crystallization mechanism of barium-lead-zinc phosphate glasses. Bulk glasses from two different routes (using P₂O₅ and H₃PO₄ as starting materials) presented only one crystallization peak. An assessment of glass-forming ability (GFA) was performed from recent theory that is connected to glass stability (GS), and is also correlated to critical cooling rate, q_cr. Systems with high La₂O₃ content presented some of the highest GS values and estimated critical cooling rates (q_cr) lower than 0.079 K/s. For both routes were determined the activation enthalpies for crystallization, that were 126 ± 12 kJ/mol (for P₂O₅) and 110 ± 32 kJ/mol (for H₃PO₄). The calculated Avrami n parameters, based on exothermic crystallization peaks, were 3.50 ± 0.33 (for P₂O₅) and 3.09 ± 0.91 (for H₃PO₄), considering data from the lowest heating rate (5 K/min). These values suggest that the DSC peaks should be associated to volume crystallization, due to La₂O₃ influence, and crystallization did not change significantly using different routes.     

A study of thermal stability in electrodeposited nanocrystalline Fe-Ni invar alloy

The grain growth of an electrodeposited nanocrystalline Fe-Ni invar alloy was studied with differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The results showed very limited grain growth below the temperature of 0.36T_m, and the activation energy was 40 ± 3 kJ/mol in the low temperature range, which implied the possible mechanism of grain growth as re-ordering of grain boundaries; an abrupt grain growth happened above 0.36T_m with a DSC exothermic peak detected, of which the heat release was about 14 ± 2 J/g; at temperatures above 0.36T_m, the grain growth activation energy was obtained through Kissinger analysis and isothermal kinetics analysis, both of the results suggested the grain growth mechanism as grain boundary diffusion.     

Crystallization mechanisms of (In15Sb85)100−xBix phase change recording thin film

The (In₁₅Sb₈₅)_100−xBi_x films (x = 0–18.3) were deposited on nature oxidized Si wafer and glass substrate at room temperature by magnetron co-sputtering of Sb target and InBi composite target. The optical and thermal properties of the films were examined by reflectivity thermal analyzer. Microstructures of the films were analyzed by X-ray diffraction and transmission electron microscope. The crystallization activation energy of the (In₁₅Sb₈₅)_100−xBi_x film (x = 0–18.3) was decreased with increasing Bi content, this indicated that the crystallization speed was improved by doping Bi. The structure of as-deposited (In₁₅Sb₈₅)_100−xBi_x films was amorphous and it would transform to Sb, InSb, Bi, and BiIn₂ coexisting phases after annealing at 250 °C for 30 min.     

Hump peak formation and the crystallization in amorphous Al87Co10Ce3 alloy

A distinct hump peak was observed at the scattering angle 2θ ≈ 44° in the X-ray diffraction (XRD) pattern of rapidly quenched amorphous Al₈₇Co₁₀Ce₃ alloy. From the XRD patterns of amorphous Al-Co-Ce alloys with different compositions, it is found that the intensity of the hump peak increases as the Co/Ce atomic ratio increases, while the prepeak which characterizes the medium-range order (MRO) becomes weak. The hump peak has a close relationship with the glass forming ability in the Al-Co-Ce system. Furthermore, the crystallization behavior of Al₈₇Co₁₀Ce₃ alloy was investigated by the DSC and XRD methods. Compared with Al₈₇Ni₁₀Ce₃ alloy, Al₈₇Co₁₀Ce₃ alloy did not show a single process of grain growth for fcc-Al particle. The formation of a hump peak is presumed to be associated with the presence of pre-existing nuclei of fcc-Al and Co₂Al₉ in as-quenched amorphous Al₈₇Co₁₀Ce₃ alloy.     

The phase transformation and crystallization kinetics of (1 − x)Li2O–xNa2O–Al2O3–4SiO2 glasses

The phase transformation and crystallization kinetics of (1 − x)Li₂O–xNa₂O–Al₂O₃–4SiO₂ glasses have been studied by using differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron diffraction (ED) analysis. The crystallization temperature at the exothermic peak increases from 1171 to 1212 K when the Na₂O content increases from 0 to 0.6 mol. The crystalline phase is composed of spodumene crystallization when the Na₂O content increases from 0 to 0.6 mol. The activation energy of spodumene crystallization decreases from 444.0 ± 22.2 to 284.0 ± 10.8 kJ mol⁻¹ when the Na₂O content increases from 0 to 0.4 mol. Moreover, the activation energy increases from 284.0 ± 10.8 to 446.0 ± 23.2 kJ mol⁻¹ when the Na₂O content increases from 0.4 to 0.6 mol. The crystallization parameters m and n approach 2, indicating that the surface nucleation and two-dimensional growth are dominant in (1 − x)Li₂O–xNa₂O–Al₂O₃–4SiO₂ glasses.     

Calorimetric studies of non-isothermal crystallization in amorphous Cu x Ti100−x alloys

The present paper reports the composition dependence of pre-exponential factor and activation energy of non-isothermal crystallization in amorphous alloys of Cu _x Ti_100?x system using differential scanning calorimeter (DSC) technique. The applicability of Meyer-Neldel relation between the pre-exponential factor and activation energy of non-isothermal crystallization for amorphous alloys of Cu-Ti system was verified.