Calorimetric studies of Se80−xTe20Bix bulk samples

The crystallization kinetics of the bulk Se_80−xTe₂₀Bi_x chalcogenide glasses were studied by using differential scanning calorimetry with different heating rates (5,10,15 and 20 K/min) under non-isothermal conditions. The values of glass transition temperature, peak crystallization temperature and melting temperature are found to increase with increase in heating rate as well as with bismuth content. The activation energy for glass transition and that for crystallization have been determined using the Kissinger equation and Matusita equation. The thermal stability and glass-forming tendency have also been studied.     

Kinetics of non-isothermal crystallization and glass transition phenomena in Ga10Se87Pb3 and Ga10Se84Pb6 chalcogenide glasses by DSC

The crystallization process affects solid properties through the crystal structure and morphology established during the transition process. An important aspect of the crystallization process is its kinetics, both from the fundamental point of view of amorphous material as well as the modeling and phase transition. In the present research work, non-isothermal crystallization data in the form of heat flow vs. temperature curves has been studied by using some well known models for amorphous Ga₁₀Se₈₇Pb₃ and Ga₁₀Se₈₄Pb₆ chalcogenide glasses, prepared by the melt quenching technique. The glass transition phenomena and crystallization of these glasses have been studied by using non-isothermal differential scanning calorimetery (DSC) measurements at constant heating rates of 5, 10, 15, 20, 25 and 30 K/min. The glass transition temperature (T_g), crystallization temperature (T_c), and melting temperature (T_m) were determined from DSC thermograms. The dependence of T_g and T_c on the heating rate was used to determine different crystallization parameters such as the order parameter (n), the glass transition energy (ΔE_g) and the crystallization activation energy (ΔE_c). The results of crystallization were discussed on the basis of different models such as Kissinger's approach and the modification for non-isothermal crystallization in addition to Johnson, Mehl, Ozawa and Avrami.     

Crystallisation kinetics,glass forming ability and thermal stability in glassy Se100 − xInx chalcogenide alloys

Differential scanning calorimetry (DSC) studies have been done under non-isothermal conditions at different heating rates for glassy Se_100 ? xIn_x (5 ≤ x ≤ 20) alloys. DSC traces with well-defined endothermic and exothermic troughs and peaks at glass transition (T_g), crystallisation (T_c) and melting (T_m) temperatures were observed. The crystallisation kinetics parameters, Avrami index (n), activation energy for crystallisation (E_c) and frequency factor (K_o), have been calculated on the basis of the classical Johnson–Mehl–Avrami (JMA) model and related methods derived by Kissinger, Augis–Bennett and Mahedevan. Activation energy for glass transformation (E_t) has been evaluated on the usual two different non-isothermal methods developed by Moynihan and Kissinger. An extension of the Augis–Bennett method well known for evaluating E_c to calculate E_t has been explored with satisfactory results. Results obtained from these methods are in close agreement with each other. Close correlation between E_t, E_c and heating rate (β) was observed. The glass forming ability (GFA) and thermal stability parameters have been calculated for each glass system. It was found that the proportion of indium additive changed significantly the values of glass/crystal transformation, GFA and thermal stability of the studied system.     

Critical analysis of endo-thermal effect in the glass transition process in chalcogenide glasses

Free volume model is widely used as a tool for understanding the nature of glass transition phenomenon and the related consequences. Recently, an analytical derivation of Kissinger's equation has been proposed in literature using free volume model. In this derivation, the glass transition activation energy has been assumed constant throughout the whole glass transition temperature range. The present paper investigates the applicability of free volume model for derivation of Kissinger's relation by checking the constancy of the glass transition activation energy (E_g) throughout the glass transition temperature range. Performing series of experiments, we have legalized the possibility for usage of the Kissinger relation for determination of the glass transition activation energy if the peak value of the endo-thermal effect is taken as temperature of glass transition.     

Crystallization kinetics and optical band gap studies of Se96In4 glass before and after slow neutron irradiation

Results of differential scanning calorimetry (DSC) under non-isothermal condition on Se₉₆In₄ semiconducting chalcogenide glass before and after slow neutron irradiation, for different exposure times, have been reported and discussed. Some of Sn atoms have been injected into the glass by nuclear transmutation processes and the binary glass is converted into a ternary. This is accompanied by an increase in the activation energy of crystallization, E_c, and in the glass transition temperature, T_g and a decrease in the glass transition activation energy, E_t, in the onset crystallization temperature, T_c and in the peak temperature of crystallization T_p. Optical band gap measurements have also been carried out, before and after irradiation, on identical thin pellets of Se₉₆In₄ glass. The energy band gap, E_g, is found to decrease upon irradiation. These effects have been attributed to a structural change upon doping and to irradiation induced defects.     

Thermal,phase transition and spectral studies in erythromycin pseudopolymorphs: dihydrate and acetone solvate

The thermal, phase transition and spectral studies of erythromycin A dihydrate and acetone solvate were performed by Differential Scanning calorimetry (DSC), Thermo Gravimetry (TG‐DTA), X‐Ray Powder Diffraction (XRPD) and Fourier Transform Infra‐Red (FTIR) spectrum. The non‐thermal kinetic analysis of erythromycin A dihydrate was carried out by DSC at different heating rates in dynamic nitrogen atmosphere. The result showed that heating rate has substantial influence on the thermal behavior of erythromycin dihydrate. The Arrhenius parameters were estimated according to the Kissinger method. Corresponding to dehydration of dihydrate, melting of dehydrated dihydrate, phase transition from dehydrated dihydrate to anhydrate, and melting of anhydrate, the calculated activation energy were 39.60, 269.85, 261.23, and 582.16 kJmol^–1, the pre‐exponential factors were 3.46 × 10³, 8.06 × 10³², 9.23 × 10³⁰, and 7.29 × 10⁶³ s^–1, respectively. Ozawa method was used to compare activation energy values calculated by Kissinger method. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystallization behavior of rare-earth doped fluorochlorozirconate glasses

A series of fluorochlorozirconate (FCZ) glasses, each doped with a different rare-earth, was prepared and examined to determine thermal stability and activation energy, E_a, of the dopant dependent BaCl₂ crystallization. Non-isothermal differential scanning calorimetry (DSC) measurements were done to investigate the endothermic and exothermic reactions upon heat treatment of the glass samples. In comparison to the rare-earth free FCZ glass, significant changes in the Hruby constant, H_r, and E_a were found due to the addition of a rare-earth and also between the individual dopants.     

Structural transformation on Se0.8Te0.2 chalcogenide glass

Using X-ray diffraction and differential scanning calorimetry (DSC), the structure and the crystallization mechanism of Se_0.8Te_0.2 chalcogenide glass has been studied. The structure of the crystalline phase has been refined using the Rietveld technique. The crystal structure is hexagonal with lattice parameter a = 0.443 nm and c = 0.511 nm. The average crystallite size obtained using Scherrer equation is equal 16.2 nm, so it lies in the nano-range. From the radial distribution function, the short range order (SRO) of the amorphous phase has been discussed. The structure unit of the SRO is regular tetrahedron with (r₂/r₁) = 1.61. The Se_0.8Te_0.2 glassy sample obeys the chemical order network model, CONM. Some amorphous structural parameters have been deduced. The crystallization mechanism of the amorphous phase is one-dimensional growth. The calculated value of the glass transition activation energy (E_g) and the crystallization activation energy (E_c) are 159.8 ± 0.3 and 104.3 ± 0.51 kJ/mol, respectively.     

Structural characterization of light-induced crystal growth in Se98Sb2 chalcogenide glass

The present paper reports the detailed study of crystallization morphology of light-induced crystal growth in Se₉₈Sb₂ chalcogenide glass using DSC, XRD and SEM techniques. Thermally-activated crystallization of the samples in powder form is analyzed by Differential Scanning Calorimetry (DSC) at different heating rates under non-isothermal conditions. The activation energy of crystallization has been calculated by analyzing the data using the classical Johnson–Mehl–Avrami (JMA) model.Amorphous thin films of Se₉₈Sb₂ are used for light-induced crystal growth. The d.c. conductivity of the films is taken as a characteristic quantity to measure the extent of light-induced crystal growth. X-ray diffraction (XRD) analysis has been carried out on Se₉₈Sb₂ samples for different illumination time and their diffractograms are analyzed to obtain information about various crystallographic aspects. Scanning electron microscopy has been used to confirm light-induced crystal growth.     

Phase transformation and crystallization kinetics of melt-spun Ni60Nb20Zr20 amorphous alloy

The glass transition and crystallization kinetics of melt-spun Ni₆₀Nb₂₀Zr₂₀ amorphous alloy ribbons have been studied under non-isothermal and isothermal conditions using differential scanning calorimetry (DSC). The dependence of glass transition and crystallization temperatures on heating rates was analyzed by Lasocka's relationship. The activation energies of crystallization, E_x, were determined to be 499.5 kJ/mol and 488.6 kJ/mol using the Kissinger and Ozawa equations, respectively. The Johnson–Mehl–Avrami equation has also been applied to the isothermal kinetics and the Avrami exponents are in the range of 1.92–2.47 indicating a diffusion-controlled three-dimensional growth mechanism. The activation energy obtained from the Arrhenius equation in the isothermal process was calculated to be E_x = 419.5 kJ/mol. The corresponding three dimensional (3D) time–temperature–transformation (TTT) diagram of crystallization for the alloy has been drawn which provides the information about transformation at a particular temperature. In addition, the intermetallic phases and morphology after thermal treatment have been identified by X-ray diffraction (XRD) and scanning electron microscope (SEM).     

Optical Properties of Bi2Se3‐xAsx Single Crystals

Bi₂Se_3‐xAs_x single crystals with the As content of c_As = 0 to 2.0x10¹⁹ atoms/cm³ prepared from the elements of 5N purity by means of a modified Bridgman method were characterized by measurements of infrared reflectance and transmittance. Values of the plasma resonance frequency omega_p, optical relaxation time tau, and high‐frequency permittivity were determined by fitting the Drude‐Zener formulas to the reflectance spectra. It was found that the substitution of As atoms for Se atoms in the Bi₂Se₃ crystal lattice leads to a decrease in the omega_p values. This effect is accounted for by a model of point defects in the crystal lattice of Bi₂Se_3‐xAs_x. The dependences of the absorption coefficient K on the energy of incident photons were determined from the transmittance spectra. The optical width of the energy gap is found to decrease with increasing As content. The values of the exponent b from the relation of K ∼ lamda^b for the long‐wavelength absorption edge range within the interval 2.0 to 2.3, i.e. the dominant scattering mechanism of free current carriers in Bi₂Se_3‐xAs_x crystals is the scattering by acoustic phonons.     

Crystallization kinetics in Cu46Zr45Al7Y2 bulk metallic glass by differential scanning calorimetry (DSC)

Crystallization transformation kinetics in isothermal and non-isothermal (continuous heating) modes were investigated in Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass by differential scanning calorimetry (DSC). In isochronal heating process, activation energy for crystallization at different crystallized volume fraction is analyzed by Kissinger method. Average value for crystallization in Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass is 361 kJ/mol in isochronal process. Isothermal transformation kinetics was described by the Johnson-Mehl-Avrami (JMA) model. Avrami exponent n ranges from 2.4 to 2.8. The average value, around 2.5, indicates that crystallization mechanism is mainly three-dimensional diffusion-controlled. Activation energy is 484 kJ/mol in isothermal transformation for Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass. These different results were discussed using kinetic models. In addition, average activation energy of Cu₄₆Zr₄₅Al₇Y₂ bulk metallic glass calculated using Arrhenius equation is larger than the value calculated by the Kissinger method in non-isothermal conditions. The reason lies in the nucleation determinant in the non-isothermal mode, since crystallization begins at low temperature. Moreover, both nucleation and growth are involved with the same significance during isothermal crystallization. Therefore, the energy barrier in isothermal annealing mode is higher than that of isochronal conditions.     

Indium phosphide nanofibers prepared by electrospinning method: Synthesis and characterization

Nine sets of (3 × 3) InP nanofiber samples have been successfully prepared at three different voltages (20, 25, 30 kV) and at three separate heights (5, 7, 10 cm) by electrospinning with a constant precursor flow rate of 0.3 mLh⁻¹. The crystalline structure, thermal, morphologies and nanostructure, electrical, and optical properties of the samples are characterized by X‐ray powder diffractometer (XRD) and thermal gravity‐differential scanning calorimeter (TG‐DSC), scanning electron microscopy (SEM), by Four‐Point Probe Technique (FPPT,) and ultraviolet/visible spectrometry (UV/VIS), respectively. From these measurements, we have found the formation of stoichiometric nanostructured InP with zinc‐blende structure and having lattice parameter of a = 5.874 Å, weight loss of 64.59% and crystallization temperature of 500°C, average fiber diameter of 65.82 nm, the activation energies, E_a, of the samples, and band gap energy, E_g, of the nanofibers developed at constant applied voltage 30 kV. The band gap energies determined at different distances 5, 7, and 10 cm are found to be as 1.29, 1.37, and 1.30 eV, respectively.     

Crystallization of some semiconducting chalcogenide glasses in the AsSeBi system

Isothermal crystallization in vacuum and in air was studied in glassy As Se_1.5Bi_0.05 at 240 and 260°C. Electrical properties, density, and microhardness were measured. X-ray diffraction of the annealed samples was also examined.Unlike As Se_1.5, As Se_1.5Bi_0.05 easily crystallizes. The first process of devitrification has an induction period (characteristic parameters suffer little changes). As crystallization increases, the density of the alloys also increases and the microhardness decreases. The electrical conductivity increases at 20°C by 6–7 orders of magnitude and the activation energy of electrical conductivity decreases by about 1.7 eV.     

Refractive index dispersion of spinel Zn2TiO4 single crystal

The transmittance and absorption spectra of a high‐quality Zn₂TiO₄ single crystal have been measured along the a‐axes at room‐temperature in the range of 200‐1000 nm. The wavelength dependent refractive index, extinction coefficient, real and imaginary parts of the complex dielectric constant of the Zn₂TiO₄ crystal have been derived from the measured T and α spectra. By fitting the refractive index spectrum, the Sellmeier dispersion equation of the Zn₂TiO₄ crystal has been obtained. The validity of Cauchy‐Sellmeier equation has been evaluated in the energy range of 2.90–3.20 eV representing the Urbach tail. Applying the single‐effective oscillator model, the dispersion energy E_d and the oscillator energy E₀ have been determined as 18.76 and 5.05 eV, respectively. The obtained dispersion energy E_d takes on ionic crystal value. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermal properties of chalcogenide glasses in the GeSe2–As2Se3–CdSe system

In the present work, thermal properties of GeSe₂–As₂Se₃–CdSe glasses were investigated via DSC measurements. The dependences of glass transition temperature and thermal stability on glass composition were discussed. XRD measurement was also performed to validate the effect of cadmium on the thermal properties of glasses. The calculated Avrami exponent was used to demonstrate the three-dimensional growth of crystals in the glass matrices. The crystallization kinetics for the glasses was studied by using the modified Kissinger and Ozawa equations.     

Crystallization behaviour of an amorphous Ti50Be40Zr10 alloy

The crystallization behaviour of an amorphous Ti₅₀Be₄₀Zr₁₀ alloy during a continuous heating mode from room temperature to 973 K and isothermal annealing at temperatures above the glass transition temperature is examined by differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS) measurement and large-angle X-ray diffractometry (LAXD). DSC indicated two well-defined exothermic peaks, a slight shoulder at the higher temperature side of the second peak and a small heat evolution at higher temperature. The Kissinger plot for the first and the second peak gives a straight line, from which the apparent activation energy is estimated to be 269 and 413 kJ/mol respectively; the enthalpies for the first and second crystallization process are 1.04 kJ/mol and 4.39 kJ/mol for a heating rate of 20 K/min. The SAXS intensities increase sharply after annealing at about 673 K (corresponding to the first peak in the DSC curves); the scattering is due to the formation of fine-scale crystalline Ti particles by the LAXD. The size of the particles does not change significantly while the number of scattering particles increases, indicating that the reaction is almost nucleation controlled and the growth is very limited. Another crystalline phase would appear in addition to the Ti particles on annealing at temperatures above about 753 K (corresponding to the second peak in the DSC curves), where the SAXS intensities decrease compared with those for only the first-stage of crystallization. The crystalline phase might be a metastable cubic phase with the lattice parameter a₀?0.2994 nm.The sequence in the crystallization of the initial non-crystalline material is amorphous → microcrystalline (MS I) → crystalline (MS II; S III), although the structure of crystalline phase in the final stage (S III) was not identified. It is also likely that cold-rolling does not have a perceptible effect on the crystallization behaviour of the present amorphous alloy.     

Kinetic theory of crystallization of amorphous materials

Careful analysis of the Avrami equation [x = 1 ?exp(?Atⁿ)] shows that an activation energy for crystallization (E_c) for amorphous materials can be defined over a selected range of temperatures. This activation energy can be determined experimentally using non-isothermal differential scanning calorimetry (DSC) by determining the crystallization temperature (T_c) as a function of heating rate (φ). A plot of (ln(φ/T_c) has a slope equal to E_c/n. The activation energy for the crystallization of amorphous arsenic obtained by this non-isothermal method is found to be in fair agreement with that obtained from an isothermal DSC experiment.     

NMR and infrared study of cation motion in vitreous and polycrystalline TlPO3

The activation energy for Tl⁺ conduction in TlPO₃ glass is obtained from analysis of temperature-dependent motional narrowing for Tl²⁰⁵ NMR spectra and determinations of the localized far infrared (FIR) vibrational frequency for Tl⁺. Use is made of the phenomenological equation of Hendrickson and Bray to analyze the NMR data, yielding E_a = 1.19 eV; the measured FIR Tl⁺ vibrational frequency of 80 cm^?1 yields E_a = 1.09 eV. No significant ionic conduction is observed in polycrystalline TlPO₃. Differential scanning calorimeter measurements yield a glass transition temperature T_g of 96°C and the onset of crystallization temperature of 132°C. Measurements of the Tl²⁰⁵ chemical shift interaction as a function of frequency indicate that (1) the Tl⁺ sites in both polycrystalline and glassy TlPO₃ are ionic, the sites in the polycrystal being slightly more ionic than in the glass; (2) the chemical shift interaction is anisotropic in the glass and isotropic in the polycrystal; and (3) distributions in the values of the principal components of the chemical shift tensor exist in the glass, corresponding to a variety of TlO bond lengths and bond strengths.     

Comments on “Kinetics of non-isothermal crystallization and glass transition phenomena in Ga10Se87Pb3 and Ga10Se84Pb6 chalcogenide glasses by DSC” by Al-Agel et al.

A critical review of a recent paper by Al-Agel et al. (J. Non Cryst. Solids, 358 (2012) 564) on kinetics of non-isothermal crystallization and glass transition phenomena in Ga₁₀Se₈₇Pb₃ and Ga₁₀Se₈₄Pb₆ chalcogenide glasses is presented. A number of possible errors in procedures have been noticed. In particular, X-ray diffraction, Differential Scanning Calorimetry and Field Emission Scanning Electron Microscopy data may have been misinterpreted. Kinetic parameters deduced from data derived from the DSC results and using approaches developed by Kissinger, Ozawa and Matusita and others are discussed. Activation energies and Avrami exponents have been re-calculated from the experimental data presented by Al-Agel et al.