Model fitted and model free approaches for crystallization kinetics in Se85Te15-xBix glasses

In this research work, we have described the model-fitted and model free approaches for the study of crystallization kinetics in Se₈₅Te_15-xBi_x chalcogenide glasses. Se₈₅Te_15-xBi_x bulk alloys were synthesized by melt quenching technique. High Resolution X- Ray diffraction (HRXRD) was used to confirm the amorphous nature of prepared alloys. Non-isothermal Differential Scanning Calorimetry (DSC) measurements were done at heating rates of 5, 10, 15, 20 and 25 K/min for crystallization kinetics studies in Se₈₅Te_15-xBi_x glasses. The various characteristic temperatures, such as glass transition (T_g), on-set crystallization (T_c) temperature, peak crystallization temperature (T_p) and melting temperatures (T_m) have been obtained from various DSC thermograms. The activation energies of glass transition (ΔE_t) were calculated by using Kissinger and Moynihan approaches and found to be minimum for Se₈₅Te₁₂Bi₃ chalcogenide glass which indicates that this alloy has maximum probability to jump into a less configurational energy state and has larger stability. The model-free approaches; Kissinger–Akahira–Sunose (KAS), Flynn-Wall-Ozawa (FWO), Tang and Straink (TS) reveal that the activation energy of crystallization varies with crystallization degree and temperature both. This variation shows that amorphous to crystalline phase transformation in Se₈₅Te_15-xBi_x chalcogenide glasses is a complex process with various nucleation and growth mechanisms.     

Glass transition,thermal stability and glass-forming ability of Se90In10− x Sb x (x = 0, 2, 4, 6, 8, 10) chalcogenide glasses

Differential scanning calorimetry (DSC) has been employed to investigate the glass transition activation energy E _g, thermal stability and glass-forming ability (GFA) of Se₉₀In_{10? x} Sb _x (x = 0, 2, 4, 6, 8, 10) chalcogenide glasses. DSC runs were performed at six different heating rates. Well-defined endothermic and exothermic peaks were obtained at glass transition and crystallization temperature. The dependence of glass transition temperature T _g on heating rate (α), as well as composition of Sb, has been studied. From the dependence of glass transition temperature on heating rate, the E _g has been calculated on the basis of the Kissinger [Anal. Chem. 29 (1957) p.1702] and Moynihan [J. Phys. Chem. 78 (1974) p.267] models. Thermal stability has been monitored through the calculation of temperature differences T _c–T _g, the stability parameter S, and the enthalpy released during crystallization H _c. The GFA has been investigated on the basis of the Hruby parameter H _r, which is strong indicator of GFA. Results for GFA are in good agreement with fragility index F _i calculations, indicating that Se₉₀In₆Sb₄ is an excellent glass-former.     

Thermal stability and crystallization kinetics of Ge–Se–Cd glasses

The effect is reported of varying cadmium concentration on the glass transition, thermal stability and crystallization kinetics of Ge₂₀Se_{80? x} Cd _x (x = 2.5, 5, 7.5 and 10 at. %) glasses. Differential scanning calorimetry results under non-isothermal conditions for the studied glasses are reported and discussed. The values of the glass transition temperature (T_g ) and the peak temperature of crystallization (T_p ) were found to be dependent on heating rate and Cd content. From the heating rate dependence of T_g and T_p , the values of the activation energy for glass transition (E_g ) and the activation energy for crystallization (E_c ) were evaluated and their composition dependence discussed. The thermal stability of the glasses was evaluated using various thermal stability criteria such as ΔT, H_g and S. The stability calculations emphasize that the thermal stability decreases with increasing Cd content.     

Observation of phase separation in some Se-Te-Sn chalcogenide glasses

Differential scanning calorimeter (DSC) and X-ray diffraction (XRD) techniques were employed here to investigate the glass transition behavior and crystallization kinetics of Se_80−x Te₂₀Sn_x (x=0.0, 2.5 and 5) alloys, which were prepared by the conventional melt quenching method. Two exothermic peaks have been observed in the DSC scans for the samples that contain Sn. Three crystalline phases (Se_7.68Te_0.32, SnSe and SnTe) were classified after heat treating the Se_77.5 Te₂₀Sn_2.5 glass at temperature corresponding to the second crystallization peaks for 3 h. All the characteristic temperatures such as glass transition temperature (T_g), crystallization temperature (T_c) and crystallization peak temperatures (T_p) were found to depend on both the heating rate and the composition. This dependence has been used to deduce the activation energy of the glass transition (E_g), the activation energy of crystallization (E_c), the Avrami exponent (n), thermal stability and the fragility index (F_i).     

Calorimetric study of Te15(Se100− x Bi x )85 glassy alloys using differential thermal analysis

A calorimetric study of Te₁₅(Se_{100? x} Bi _x )₈₅ glassy alloys (x = 0, 1, 2, 3 and 4 at. %) is reported. Differential thermal analysis (DTA) was performed at heating rates of 10, 15, 20 and 25 K/min. The spectra were used to determine the glass transition temperature, T_g , the crystallisation temperature, T_c and the melting temperature, T_m . All these parameters shift to higher values with increasing heating rate, β. The glass transition temperature and the melting temperature increase, and the crystallisation temperature decreases, with increase in the Bi content, x. The activation energy of the glass transition, E_g , was evaluated using the Moynihan and Kissinger methods. The activation energy of crystallisation, E_c , was calculated using modified Kissinger and Matusita approaches. The thermal stability of these glasses has been studied and found to decrease with increase in Bi content. The results obtained are explained on the basis of a chemically ordered network model and an average coordination number.     

Kinetic study of non-isothermal crystallization of BixSe100−x chalcogenide glasses

Results of differential thermal analysis (DTA) under non-isothermal conditions on four glasses of Bi_xSe_100−x (x=5, 10, 15 and 25 at%) are reported and discussed. The glass transition temperatures (T_g), the onset crystallization temperatures (T_c) and the peak temperatures of crystallization (T_p) were found to be dependent on the compositions and the heating rates. From the dependence on the heating rates of (T_g) and (T_p), the activation energy for glass transition, E_g, and the activation energy for crystallization, E_c, are calculated and their composition dependence is discussed. The crystalline phases resulting from DTA and scanning electron microscopy (SEM) have been identified using X-ray diffraction. According to the Avrami exponent (n), the results show a one-dimensional growth for the composition Bi₅Se₉₅ and two-dimensional growth for the compositions Bi₁₀Se₉₀, Bi₁₅Se₈₅ and Bi₂₅Se₇₅. The kinetic parameters determined have made it possible to discuss the glass-forming ability.     

Calorimetric study of characteristic temperatures and crystallization behavior in Ge-As-Se-Te glass system

Results of differential scanning calorimetry of high purity Ge_xAs_40−xSe₄₀Te₂₀ (x=0-40) chalcogenide glasses are reported. The glass transition temperatures and crystallization behavior were studied under non-isothermal conditions at different heating rates (2.5-35 K/min). The glass transition temperature changes from 140 °C up to 320 °C with increasing the Ge content in Ge_xAs_40−xSe₄₀Te₂₀ glass. The studied glasses with x≤35 have no exothermal peaks of crystallization, indicating their high glass-forming ability. The glass of Ge₄₀Se₄₀Te₂₀ composition has one-stage glass transition and double-stage crystallization process during phase change. The activation energy of the glass transition (E_g), the activation energy of crystallization (E_c), the Avrami exponent (n), the frequency factor (K₀) and the crystallization criteria of Ge₄₀Se₄₀Te₂₀ glass were determined.     

Crystallization kinetics, glass transition kinetics, and thermal stability of Se70−xGa30Inx (x=5, 10, 15, and 20) semiconducting glasses

Crystallization and glass transition kinetics of Se_70−xGa₃₀In_x (x=5, 10, 15, and 20) semiconducting chalcogenide glasses were studied under non-isothermal condition using a Differential Scanning Calorimeter (DSC). DSC thermograms of the samples were recorded at four different heating rates 5, 10, 15, and 20 K/min. The variation of the glass transition temperature (T_g) with the heating rate (β) was used to calculate the glass transition activation energy (E_t) using two different models. Meanwhile, the variation of the peak temperature of crystallization (T_p) with β was utilized to deduce the crystallization activation energy (E_c) using Kissinger, Augis-Bennet, and Takhor models. Results reveal that E_t decreases with increasing In content, while both T_g and E_c exhibit the opposite behavior, and the crystal growth occurs in one dimension. The variation of these thermal parameters with the average coordination number <Z> was also discussed, and the results were interpreted in terms of the type of bonding that In makes with Se. Assessment of thermal stability and glass forming ability (GFA) was carried out on the basis of some quantitative criteria and the results indicate that thermal stability is enhanced while the crystallization rate is reduced with the addition of In to Se-Ga glass.     

Kinetics of glass transition and thermal stability of?Se58Ge42?xPbx?(9≤x≤20) glasses

Se₅₈Ge_42−x Pb _x (9≤x≤20) glasses have been prepared using conventional melt quenching technique. Differential Scanning Calorimetric (DSC) measurements show single glass transition and double crystallization, which indicate the occurrence of phase separation in the samples. The phases present in the samples were identified using XRD. The kinetics of the glass transition has been studied in terms of the variation of glass transition temperature with composition and heating rate. In addition to this, activation energy of the glass transition (E _t ) has also been evaluated and its composition dependence is also investigated. The thermal stability of these glasses has been investigated using various stability criteria: Deiztal first glass criterion, ΔT, Saad and Poulain weighted thermal stability, H′ and the S-parameter. The values of these parameters were obtained using various characteristic temperatures such as the glass transition temperature, T _g , the onset temperature of crystallization, T _c , and the peak crystallization temperature, T _p . The values of stability parameters show that the phase corresponding to second crystallization is more stable than the phase corresponding to first one. The stability in terms of the lead (Pb) content has been determined considering the values of stability parameters of the phase corresponding to second peak. It was found that the stability increases with the lead content.     

Pre-exponential factor for non-isothermal crystallization of glassy Se85− x Te15Sb x (0 ≤ x ≤ 10) alloys

We report observations of the Meyer–Neldel rule for the non-isothermal crystallization of glassy Se_{85? x} Te₁₅Sb _x (x =?0, 2, 4, 6, 8, 10) alloys. We found a strong co-relation between the pre-exponential factor K ₀ of the rate constant K(T) for crystallization and the activation energy of crystallization E _c. This indicates the presence of a compensation effect for the non-isothermal crystallization process in this glassy system. The composition dependence of the crystallization temperature T _c and the activation energy for crystallization E _c is discussed.     

Effect of Pb additive on crystallization kinetics of Se80In20 glassy matrix

The crystallization kinetics of bulk Se₈₀In_20−xPb_x (x=0, 5, 10 and 15) chalcogenide glasses have been studied using a differential scanning calorimeter (DSC) with different heating rates (5, 10, 15 and 20 K/min) under non-isothermal conditions. Various kinetic parameters of crystallization, such as crystallization temperature T_c, peak crystallization temperature T_p, activation energy for crystallization E_c and order parameters n, m have been determined to study nucleation and growth during crystallization. The reaction rate constant K and pre-exponential factor K₀ also have been determined. The composition dependence of these parameters may be explained on the basis of modification of chemical bonds present in the Se–In system due to addition of Pb content.     

Effect of topological thresholds on thermal behaviour of germanium telluride glasses containing metallic additive

Differential Scanning Calorimetric (DSC) studies on Ag_xGe₁₅Te_85-x glasses have been undertaken over a wide range of compositions, to understand the effect of topological thresholds on thermal properties. It is found that the compositional dependence of glass transition temperature (T _g ), crystallization temperature (T _c ), activation energy for crystallization and thermal stability show anomalies at the rigidity percolation threshold. Unusual variations also observed in different thermal properties at the composition x = 20, clearly establishes the occurrence of chemical threshold in these glasses. Received: 27 January 1998 / Revised: 12 June 1998 / Accepted: 3 July 1998     

Crystallization kinetics and Avrami index of Sb-doped Se–Te–Sn chalcogenide glasses

Bulk amorphous samples of Sb-substituted Se_78?xTe₂₀Sn₂Sb_x (0 < x < 6) have been prepared using melt quench technique. The structure of Se_78?xTe₂₀Sn₂Sb_x (x = 0, 2, 4, 6) glassy alloys has been investigated using X-ray diffraction technique. Calorimetric studies of the prepared samples have been performed under non-isothermal conditions using differential scanning calorimetry (DSC) and glass transition temperature as well as crystallization temperature has been evaluated using DSC scans. The activation energy of crystallization kinetics (E_c) has been determined using model-free approaches such as Kissinger, Ozawa, Tang and Starink methods. The Avrami index (n) and frequency factor (K_o) have been calculated by Matusita and Augis–Benett method.     

Metal-induced effects on the glass transition kinetics of glassy Se70Te30 alloy

The calorimetric measurements have been made in glassy Se₇₀Te₃₀ and Se₇₀Te₂₈M₂ (M?=?Ag, Cd, and Zn) alloys using non-isothermal differential scanning calorimetry technique to see the effects of Ag, Cd, and Zn additives on the glass transition kinetics of binary Se₇₀Te₃₀. From the heating rate dependence of glass transition temperature, T _g, different kinetic parameters of glass transition have been evaluated. The composition dependence of glass transition temperature T _g and the related activation energy (E_t ) is also discussed.     

The effect of indium additive on crystallization kinetics and thermal stability of Se-Te-Sn chalcogenide glasses

The crystallization kinetics of bulk Se_90−xTe₅Sn₅In_x (x=0, 3, 6 and 9) multi-component chalcogenide glasses have been studied using differential scanning calorimetry (DSC) with heating rates 5, 10, 15 and 20 K/min under non-isothermal conditions. Values of various kinetic parameters of crystallization, such as onset crystallization temperature (T_c), peak crystallization temperature (T_p), activation energy of crystallization (E_c), rate constant (K_p), Hruby number (K_gl) and the order parameter (n) have been determined. It was found that activation energy of crystallization and rate constant (K_p) are minimum at 9 at% In. On the basis of the obtained experimental data the temperature difference (T_c−T_g) and K_gl increase with In concentration, which further indicates that 9 at% In glass is most thermally stable in the entire composition range of investigation.     

Role of Bi incorporation on glass transition kinetics in glassy Se78Te20Sn2 alloy

In this communication, we report the results of calorimetric measurements on the samples of recently synthesized multi-component glassy alloys of Se_78?xTe₂₀Sn₂Bi_x (0 ≤ x ≤ 6) system. For calorimetric study of glass transition kinetics, differential scanning calorimetry (DSC) technique has been used in non-isothermal mode. Peak glass transition temperature (T_g) is determined using the DSC scans. Kinetic parameters A and B of glass transition are determined using heating rate dependence of T_g. Activation energy of glass transition (E_g) has been calculated using Moynihan and Kissinger methods. Glass-forming ability and thermal stability are also determined using Hurby and Saad–Poulin relations, respectively.     

Amorphous to crystalline phase transition in glassy Se65Te20Ag15 alloy

In the present work, the amorphous to crystalline phase transition of chalcogenide glass Se₆₅Te₂₀Ag₁₅ has been studied using differential scanning calorimetric (DSC) measurements. The heating rate dependence of crystallization peaks has been used for the determination of activation energies of glass transition (E _g) and crystallization (E _c). Different non-isothermal methods have been used for this purpose. Other useful kinetic parameters such as the order parameter (n), the numerical factor of crystallization mechanism (m) and the frequency factor (K _o) of the rate constant (K) have been also determined.     

A comparative study on the glass-forming ability of some alloys in the Sb-As-Se system by differential scanning calorimetry

The glass-forming ability and devitrification of alloys in the Sb-As-Se system have been studied by differential scanning calorimetry (DSC). A comparison of various simple quantitative methods to assess the level of stability of glassy materials in the above-mentioned system is presented. All these methods are based on the characteristic temperatures, obtained by heating of the samples in non-isothermal regime, such as the glass transition temperature, T_g, the temperature at which crystallization begins, T_in, the temperature corresponding to the maximum crystallization rate, T_p, or the melting temperature, T_m. In this work, a kinetic parameter K_r(T) is added to the stability criteria. The thermal stability of some ternary compounds of Sb_xAs_{0.60−(2x+y)}Se_0.40+x+y-type has been evaluated experimentally and correlated with the activation energies of crystallization by this kinetic criterion and compared with those evaluated by other criteria.     

Thermal kinetics and short range order parameters of Se80X20 (X = Te,Sb) binary glasses

Bulk Se₈₀Te₂₀ and Se₈₀Sb₂₀ glasses were prepared using the melt–quench technique. Differential scanning calorimetry (DSC) curves measured at different heating rates (5 K/min≤α≤50 K/min) and X-ray diffraction (XRD) are used to characterize the as-quenched specimens. Based on the obtained results, the activation energy of glass transition and the activation energy of crystallization (E _g, E _c) of the Se₈₀Te₂₀ glass are (137.5, 105.1 kJ/mol) higher than the corresponding values of the Se₈₀Sb₂₀ glass (106.8, 71.2 kJ/mol). An integer n value (n=2) of the Se₈₀Te₂₀ glass indicates that only one crystallization mechanism is occurring while a non-integer exponent (n=1.79) in the Se₈₀Sb₂₀ glass means that two mechanisms are working simultaneously during the amorphous–crystalline transformations. The total structure factor, S(K), indicates the presence of the short-range order (SRO) and the absence of the medium-range order (MRO) inside the as-quenched alloys. In an opposite way to the activation energies, the values of the first peak position and the total coordination number (r ₁, η ₁), obtained from a Gaussian fit of the radial distribution function, of the Se₈₀Te₂₀ glass are (2.42 nm, 1.99 atom) lower than the corresponding values (2.55 nm, 2.36 atom) of the Se₈₀Sb₂₀ specimens.     

Crystallization kinetics in new Sb14As29Se52Te5 amorphous glass

Differential scanning calorimetry (DSC) under non-isothermal conditions is used to study the crystallization kinetics of Sb₁₄As₂₉Se₅₂Te₅ chalcogenide glass. In addition, two approaches are used to analyze the dependence of glass transition temperature (T_g) on the heating rate (α). One is empirical linear relationship between (T_g) and ln(α). The second approach is the use of straight line vs. 1/T_g for the evaluation of the activation energy for glass transition. The phases at which the alloy crystallizes after the thermal treatment have been identified by using X-ray diffraction. The diffractogram of the transformed material shows the presence of some crystallites of As, Te, AsSb, As₂Se₃, Sb₂Se₃ and AsSe_.5Te_.5 in the residual amorphous matrix.