Kinetic consideration for the incubation of the phase transformation and its application to the crystallization of amorphous alloy

Though much progress has been made on the phase transformation kinetics model, little attention has been paid to the incubation reaction before the transformation initiates. In this study, the kinetics characteristics of the incubation time during isothermal reaction and the onset temperature during isochronal one are indicated. A model is established with the consideration of the incubation time corresponding to its annealing temperature during the isothermal case and the onset temperature corresponding to its heating rate during the isochronal case, from which a correlation between the incubation time and the onset temperature can be drawn. Finally, the proposed model has been applied well to the crystallization of Mg₆₅Cu₂₅Y₁₀ amorphous alloy.     

Effects of nickel on the crystallization of Zr70Cu20Ni10 amorphous alloy

Differential scanning calorimetry (DSC) and x-ray diffraction (XRD) are employed to investigate the effects of nickel on the crystallization of the amorphous Zr₇₀Cu₂₀Ni₁₀ alloy. We have found that the crystallization process of the amorphous Zr₇₀Cu₂₀Ni₁₀ alloy is strongly influenced by the addition of nickel. Addition of 10 at% Ni to the Zr₇₀Cu₃₀ amorphous alloy makes the crystallization process proceed from a single-stage mode to a double-stage mode. The activation energy for crystallization of the amorphous Zr₇₀Cu₂₀Ni₁₀ alloy is calculated to be about 388kJ·mol^-1 on the basis of the Kissinger equation. The effects of nickel on the crystallization of the amorphous Zr₇₀Cu₂₀Ni₁₀ alloy are discussed in terms of the genetics of metals.     

Calorimetric studies of the crystallization process in a-Se75S25−xAgx chalcogenide glasses

Calorimetric studies of amorphous Se₇₅S_25−xAg_x (x = 2, 4, 6 and 8) chalcogenide glasses are made at different heating rates (5, 10, 15 and 20 K/min) under non-isothermal condition using Differential scanning calorimetry. The values of glass transition temperature and crystallization temperature are observed to be composition and heating rate dependence. 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. It is observed that Se₇₅S₁₉Ag₆ has a minimum value of activation energy for structural relaxation (ΔE_t), which indicates that this particular glass has a larger probability to jump to a state of lower configurational energy and higher stability in the glassy region. On the basis of the obtained experimental data the temperature difference (T_c − T_g) is found to be maximum for Se₇₅S₁₉Ag₆, which further indicate that this glass is the thermally most stable in the entire composition range of investigation.     

Investigation on the undercooling and crystallization of Ni–Fe alloy coating melt by DSC

The undercooling of Ni–Fe alloy coating melt was in situ investigated by differential scanning calorimeter with flux processing technique. The highest undercooling of Ni–Fe alloy with 426 K was obtained as the thermal treatment temperature of the melt being 1904 K and the cooling rate being 50 K min^?1. When cooling rate is fixed, the undercooling depends on the melt processing temperature, and increases rapidly at the first stage. The effects of thermal treatment temperature and cooling rates on the undercooling were discussed.     

Cosmic rays and variations of the concentration of active nuclei of condensation and crystallization in the Earth’s atmosphere

A possible mechanism of the influence of cosmic rays on the concentration of neutral active nuclei of condensation and crystallization in the Earth’s atmosphere is considered. The mechanism is based on the variation in the transparency of the atmosphere under cosmic rays. It is shown that the concentration of active nuclei of condensation increase at low and middle altitudes, while the concentration of stable ice nuclei decreases. This effect and the change in the growth rate of drops can lead to correlation between the galactic cosmic rays and cloud cover anomalies at low altitudes and to the absence of correlation at middle altitudes. It is shown that the correlation between galactic cosmic rays and cloud cover anomalies can be absent at high altitudes.     

The effect of Bi content on the thermal stability and crystallization of Se–Te chalcogenide glass

Glass formation and devitrification of intermediate alloys in the Se–Te–Bi system were studied by differential scanning calorimetry. A comparison of various simple quantitative methods to assess the level of stability of the glassy materials in the above-mentioned system is presented. All of these methods are based on characteristic temperatures, such as the glass transition temperature, T _g, the onset temperature of crystallization, 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 several compositions of Se–Te–Bi was evaluated experimentally and correlated with the activation energies of crystallization by this kinetic criterion and compared with those evaluated by other criteria. All the results confirm that the thermal stability decreases with increasing Bi content in this glassy system. The crystallization results are analysed and the activation energy and mechanism of crystallization characterized.     

In situ transmission electron microscopy observations of?the?crystallization of?amorphous?Ge?films

The crystallization of amorphous Ge films has been studied as a function of annealing temperature between 400 and 700°C by in situ transmission electron microscopy (TEM). It is found that crystallization does not occur until the annealing temperature reaches 650°C, which is nearly 250°C higher than the crystallization temperature in previous reports. The high crystallization temperature and average crystal size obtained by in situ TEM are in agreement with those from Raman spectroscopy and X-ray diffraction measurement. The kinetics analysis indicates that homogeneous nucleation is the dominant crystallization mode and the activation energy is up to about 3.1 eV.     

Possibilities for achieving steady-state growth conditions during oriented crystallization of gallium antimonide by the vertical Bridgman method using the “Polizon” setup

The possibility of controlling the heat-and-mass transfer processes to achieve steady-state conditions of gallium antimonide crystallization by the vertical Bridgman method with a upper heat supply was studied using the “Polizon” setup. Steady-state conditions near the crystallization front are achieved due to elimination of the Marangoni convection, growth axis orientation along the gravity vector, minimization and optimization of the radial and axial temperature gradients, respectively, and crystallization during steady motion of the temperature field along a cell with a sample without its mechanical motion with respect to heaters. The experimental results were compared with numerical calculations of the heat-and-mass transfer processes and crystallization parameters, including those for microgravity conditions.     

Microstructural studies and analysis of residual stresses in Co–TiC composites obtained by the spontaneous crystallization method

Microstructural studies and analysis of internal stresses in Co–TiC composites prepared by the spontaneous crystallization method (high-temperature solution technique) have been performed. Metallographic observations and X-ray phase analysis of the obtained Co–TiC composite ingots were carried out. The microstructure of the Co–TiC interface was studied using transmission electron microscopy and high-resolution transmission electron microscopy. The Co–TiC composites were also subjected to numerical analysis by the finite-element method. The presented results of calculations include the analysis of the state of internal stresses generated in the composite during its cooling from the crystallization temperature to room temperature. On the basis of these results the internal stress distribution and its level were determined for the obtained Co–TiC composites.     

Nanocrystalline silicon films prepared by laser—induced crystallization

The excimer laser-induced crystallization technique has been used to investigate the preparation of nanocrystalline silicon (nc-Si) from amorphous silicon ($\al$-Si) thin films on silicon or glass substrates. The $\al$-Si films without hydrogen grown by pulsed-laser deposition are chosen as precursor to avoid the problem of hydrogen effluence during annealing. Analyses have been performed by scanning electron microscopy, atomic force microscopy, Raman scattering spectroscopy and high-resolution transmission--electron microscopy. Experimental results show that silicon nanocrystals can be formed through laser annealing. The growth characters of nc-Si are strongly dependent on the laser energy density. It is shown that the volume of the molten silicon predominates essentially the grain size of nc-Si, and the surface tension of the crystallized silicon is responsible for the mechanism of nc-Si growth.     

Effect of TiO2 addition on the crystallization of quenched glasses in the SiO2–Al2O3–ZrO2 system

The glass formation in the SiO₂-rich region of the ternary oxide system Al₂O₃–ZrO₂–SiO₂ with MgO, CaO, and TiO₂ as melting aids was analyzed. The crystallization of glasses with different content of TiO₂ and phase evolution with the temperature was studied by X-ray diffraction, infrared, laser Raman spectroscopy and transmission electron microscopy. The use of TiO₂ favored formation and crystallization of the glasses due to the decrease of the viscosity of melts and acting as a nucleating agent. The crystalline phase of t-ZrO₂ was developed at temperatures as low as 880°C whereas in as prepared specimens without TiO₂ its presence was not detected. For the specimens with TiO₂, t-ZrO₂ and mullite were the principal phases at 1000°C. TiO₂ addition did not change the crystallization sequence but decreased the formation temperature of the crystalline phases. Most of Ti⁴⁺ ions entered into t-ZrO₂ and only a small portion in mullite, but the surplus was detected in ZrTiO₄.     

From the melt via mesomorphic and granular crystalline layers to lamellar crystallites: A major route followed in polymer crystallization?

Based on broad and detailed evidence from a large variety of experiments on several polymer systems carried out by other authors and ourselves, a novel concept for understanding the crystallization of polymers from the melt is developed. The experiments generally indicate that the formation and growth of the lamellar crystallites is a multi-step process passing over intermediate states. We suggest a specific route which is compatible with the observations. It is proposed that the initial step is always the creation of a mesomorphic layer which spontaneously thickens, up to a critical value, where it solidifies through a cooperative structural transition. The transition produces a granular crystalline layer, which transforms in the last step into homogeneous lamellar crystallites. The model leads to predictions about the temperature dependencies of the crystal thickness and the growth rate which are at variance with conventional views but in agreement with findings in recent experiments. Received 17 February 2000 and Received in final form 30 March 2000     

Reaction-diffusion-induced explosive crystallization in a metal–selenium nanometer film structure

Experimental data for reaction-diffusion-induced explosive crystallization in a nanodimensional metal (Cu, Ag)/selenium structure are presented. It is found that after the metal layer has completely diffused into the amorphous Se film, the electrical potential rises from 0.14 to 1.21 V in the Cu(30 nm)/Se(140 nm) heterolayer and from 0.01 to 1.17 V in the Ag(30 nm)/Se(140 nm) heterolayer. The metals diffusing into the amorphous Se layer interact with Se, forming nuclei of a new phase (CuSe or Ag₂Se). The intense growth of the CuSe and Ag₂Se crystallization centers results in a considerable liberation of latent energy in the form of phase transformation heat and in explosive growth of CuSe and Ag₂Se nanocrystalline particles. The mean size of CuSe and Ag₂Se crystallites equals 25 and 50 nm, respectively.     

Theoretical analysis of nanosecond crystallization kinetics of phase-change optical recording films

A theoretical investigation of nanosecond crystallization kinetics of the phase-change optical recording films is presented. An extended Kissinger equation for the square-root heating is derived, which properly describes the temperature evolution of the films by nanosecond laser heating. The extended Kissinger equation was used to explain our previous experimental results.     

Thermal phase change and activation energy of crystallization of Ge-Sb-Te-Sn thin films

To improve the optical storage performance, Sn was doped into Ge2Sb2Te5 phase change thin films. The optical and thermal properties of Sn-doped Ge2Sb2Te5 film were investigated. The crystal structures of the as-sputtered and the annealed films were identified by the X-ray diffraction (XRD) method. The differential scanning calorimeter (DSC) method is used to get the crystallization temperature and crystallization energy (Ea). It was found that proper Sn-doping could highly improve storage performance of the Ge2Sb2Te5 media.     

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.     

Induced crystallization and the physical properties of PbO–Sb2O3–As2O3: MoO3 glass system

PbO–Sb₂O₃–As₂O₃ glasses mixed with different concentrations of MoO₃ (ranging from 0 to 1.0 mol%) were crystallized. The samples were characterized by X-ray diffraction, scanning electron microscopy and differential thermal analysis techniques. The X-ray diffraction and the scanning electron microscopic studies have revealed the presence of Pb₅Sb₂O₈, PbSb₂O₆, SbAsO₄, Sb₂MoO₆, Sb₄Mo₁₀O₃₁, As₄Mo₃O₁₅, Pb₅Sb₄O₁₁ crystalline phases in these samples. The differential thermal analysis indicated that the surface crystallization prevails over the bulk crystallization as the concentration of the crystallizing agent is increased. The infrared (IR) spectral studies exhibit bands due to MoO₄ structural units in addition to the conventional bands due to various antimonate and arsenate structural groups. The studies on PbO–Sb₂O₃–As₂O₃: MoO₃ glass-ceramics with respect to various physical properties viz., dielectric properties over a range of frequency and temperature, optical absorption, electron spin resonance (ESR) and magnetic susceptibility at room temperature have also been reported. The optical absorption, ESR and magnetic susceptibility studies indicated that the molybdenum ions exist in Mo⁵⁺ state in addition to Mo⁶⁺ state in these samples. The redox ratio found to increase as the concentration of the MoO₃ is increased. The variations observed in all these properties with the concentration of the crystallizing agent have been analyzed in the light of different oxidation states and environment of molybdenum ions in the glass ceramic network.     

Kinetics of the apparent isothermal and non-isothermal crystallization of the α-Fe phase within the amorphous Fe81B13Si4C2 alloy

Kinetics of the apparent isothermal and the non-isothermal crystallization of α-Fe phase within the amorphous Fe₈₁B₁₃Si₄C₂ alloy were investigated by an X-ray diffraction (XRD) and by a differential scanning calorimetry (DSC). It was established that the apparent isothermal crystallization of α-Fe phase within amorphous Fe₈₁B₁₃Si₄C₂ alloy could be described by the Johnson-Mehl-Avrami (JMA) kinetic model (with parameter n_iso=4.0). The apparent isothermal crystallization process includes a constant rate of nucleation and three-dimensional growth of nuclei. The results of X-ray diffraction (XRD) data of the isothermally crystallized samples confirmed the above established kinetic model. From the kinetic analysis of the non-isothermal crystallization of the α-Fe phase within this amorphous alloy, it was concluded that the autocatalytic two-parameter Šesták-Berggren (SB) reaction model (with kinetic exponents M=0.72 and N=1.02) describes well the studied process under the given conditions. The non-isothermal crystallization process involves the constant nucleation rate of stable nuclei with additional secondary two-dimensional (surface) nucleation and overlapping of the growing nuclei on account of the non-isothermal activation.