Determination of kinetics parameters of glass transition in glassy Se and glassy Se98M2 alloys using DSC technique

Glassy Se and Se₉₈M₂ (M = Ag, Cd, Zn) alloys are obtained by the melt quenching technique. Differential Scanning Calorimetry (DSC) technique (under non-isothermal conditions) has been applied to see the effects of Ag, Cd, and Zn additives on the glass transition kinetics of Se-rich glassy alloys at different heating rates. The variation of glass transition temperature, T _g with the heating rate, β has been used to investigate the glass transition kinetics. The values of various kinetic parameters such as glass transition temperature, activation energy of glass transition, overall mean bond energy 〈E〉, heat of atomization H _S , bond strength (Se–M) have also been calculated.     

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.     

Crystallization kinetics and thermal stability in Se85-xTe15Sbx chalcogenide glasses

Crystallization process of Se_85-xTe₁₅Sb_x (x = 2.7, 7.5, 10 and 15 at %) chalcogenide glasses has been studied by using differential scanning calorimetry (DSC) with different heating rates. These glasses are found to have a double glasses transition and overlapped crystalline phases for Se₇₀Te₁₅Sb₁₅ glass while single glasses transition and single crystallization stage for other glasses. Glass transition temperature, T_g, onset crystallization temperature, T_c, and peak crystallization temperature, T_p, are found to be dependent on composition and heating rates. Values of various kinetic parameters such as activation energy of glass transition, E_g, activation energy of crystallization, E_c, Hurby number, H_r, thermal stability, S_p, rate constant, K_p, and Avrami exponent, n, are determined for the present systems. Results indicate that rate of crystallization is dependent on thermal stability and glass-forming ability. Crystallization mechanism occurs in two dimensions for studied compositions. Crystalline phases resulting from DSC and scanning electron microscopy have been identified by using X-ray diffraction.     

Thermal characterization of Se78Ge22 and Se68Ge22M10 (M=Cd,In, Pb) chalcogenide glasses

The paper reports studies on the glass transition kinetics of Se₇₈Ge₂₂ and Se₆₈Ge₂₂M₁₀ (M?=?Cd, In, Pb) chalcogenide glasses. Differential scanning calorimetry (DSC) was performed at different heating rates under non-isothermal conditions. Different kinetic parameters, such as glass transition temperature (T _g) and the activation energy of the glass transition (E _t) have been calculated to investigate the effects of Cd, In and Pb additives on the glass transition kinetics of glassy Se₇₈Ge₂₂ alloy.     

Thermal and optical analysis of Te-substituted Sn–Sb–Se chalcogenide semiconductors

Bulk amorphous samples of Te-substituted Sn₁₀Sb₂₀Se_70−X Te _X (0≤X≤12) were prepared using a melt quenching technique. Calorimetric studies of the samples were performed using differential scanning calorimetry (DSC) and the glass transition temperature and crystallization temperature were evaluated from DSC scans. The glass transition temperature T _g exhibits a sharp decrease for small Te substitution of X=2, thereafter increases with increase in Te content up to X=10, and then decreases for further Te substitution. The apparent activation energy for glass transition and the activation energy for crystallization were calculated using Kissinger, modified Kissinger, and Matusita equations. The change in glass transition temperature T _g has been explained based on the bond formation energy of different heteropolar bonds. The optical band gap of thermally evaporated thin films of Sn₁₀Sb₂₀Se_70−X Te _X (0≤X≤12) was calculated from reflectance and transmittance data. The optical band gap variation with tellurium content exhibits a sharp decrease for an initial tellurium substitution of X=2 similar to that of the glass transition temperature and thereafter a peak is observed in optical band gap around X=4 composition.     

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.     

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.     

Thermal diffusion near glass transition in Ge-Se glasses measured by photoacoustics

The glass transition in Ge _x Se_1−x ) (0·1 ⩽x ⩽ 0·25) glasses has been investigated using the photoacoustic (PA) technique. It is found that the PA amplitude and phase undergo anomalous changes at the glass transition temperatureT _g. The amplitude has critical minimum and phase has maximum values atT _g. The variation of the thermal diffusivity, determined by measuring the frequency dependence of the PA amplitude and phase, with temperature shows sharp decrease near the glass transition temperature. The temperature dependence of the optical energy gap also has been measured and it shows a decrease with temperature for all compositions, the rate of decrease being higher for temperatures greater thanT _g.     

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).     

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.     

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.     

Calorimetric study of specific heat in glassy Se–Te–Sn–Bi system using MDSC technique: effect of Bi incorporation

Bismuth has historical significance as a modifier in chalcogenide glasses due to the p- to n-type transition at a particular composition of definite glassy systems after its incorporation. We have synthesized some new quaternary glasses using Bi as a modifier in ternary Se₇₈Te₂₀Sn₂ alloy as parent glass in light of this information. Modulated differential scanning calorimetry measurements have been made on glassy Se_{78? x} Te₂₀Sn₂Bi _x (0?≤?x?≤?6) alloys for specific heat studies. We have observed an expected enormously large increase in the specific heat values in the glass transition region. The composition dependence of specific heat values above the glass transition temperature (C_pe ) and below the glass transition (C_pg ) is also discussed in this article.     

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.     

Electrical transport and crystallization studies of glassy semiconducting Si20Te80 alloy at high pressure

The effect of pressure on the electrical resistivity of bulk Si₂₀Te₈₀ glass is reported. Results of calorimetric, X-ray and transmission electron microscopy investigations at different stages of crystallization of bulk Si₂₀Te₈₀ glass are also presented. A pressure induced glass-to-crystal transition occurs at a pressure of 7 GPa. Pressure and temperature dependence of the electrical resistivity of Si₂₀Te₈₀ glass show the observed transition is a pressure induced glassy semiconductor to crystalline metal transition. The glass also exhibits a double T_g effect and double stage crystallization, under heating. The differences between the temperature induced crystallization (primary crystallization) and pressure induced congruent crystallization are discussed.     

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     

Dielectric parameters in Se70Te30 and Se70Te28Zn2 chalcogenide glasses

Temperature and frequency dependence of dielectric constant (ε′) and dielectric loss (ε″) are studied in glassy Se₇₀Te₃₀ and Se₇₀Te₂₈Zn₂. The measurements have been made in the frequency range (8-500 kHz) and in the temperature range 300 to 350 K. An analysis of the dielectric loss data shows that the Guintini's theory of dielectric dispersion based on two-electron hopping over a potential barrier is applicable in the present case.No dielectric loss peak is observed in glassy Se₇₀Te₃₀. However, such loss peaks exist in the glassy Se₇₀Te₂₈Zn₂ in the above frequency and temperature range. The Cole-Cole diagrams have been used to determine some parameters such as the distribution parameter (α), the macroscopic relaxation time (τ₀), the molecular relaxation time (τ) and the Gibb's free energy for relaxation (ΔF).     

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.     

The sound velocity of liquid TeSe mixtures

We have measured the sound velocity of liquid Te₇₀Se₃₀, Te₅₀Se₅₀ and Te₃₀Se₇₀ mixtures and obtained their adiabatic compressibility β_s. There appear prominent maxima in the temperature variations of β_S. It is concluded that the pressure-induced semiconductor-to-metal transition previously observed for liquid Te-Se mixtures is associated with the structural change from Se-like loosely packed to Te-like densely packed structure.     

Confinement and processing effects on glass transition temperature and physical aging in ultrathin polymer films: Novel fluorescence measurements

Fluorescence intensity measurements of chromophore-doped or -labeled polymers have been used for the first time to determine the effects of decreasing film thickness on glass transition temperature, T _g, the relative strength of the glass transition, and the relative rate of physical aging below T _g in supported, ultrathin polymer films. The temperature dependence of fluorescence intensity measured in the glassy state of thin and ultrathin films of pyrene-doped polystyrene (PS), poly(isobutyl methacrylate) (PiBMA), and poly(2-vinylpyridine) (P2VP) differs from that in the rubbery state with a transition at T _g. Positive deviations from bulk T _g are observed in ultrathin PiBMA and P2VP films on silica substrates while substantial negative deviations from bulk T _g are observed in ultrathin PS films on silica substrates. The relative difference in the temperature dependences of fluorescence intensity in the rubbery and glassy states is usually reduced with decreasing film thickness, indicating that the strength of the glass transition is reduced in thinner films. The temperature dependence of fluorescence intensity also provides useful information on effects of processing history as well as on the degree of polymer-substrate interaction. In addition, when used as a polymer label, a mobility-sensitive rotor chromophore is demonstrated to be useful in measuring relative rates of physical aging in films as thin as 10 nm. Received 21 August 2001