Non-isothermal crystallization kinetics of Ti<Subscript>20</Subscript>Zr<Subscript>20</Subscript>Hf<Subscript>20</Subscript>Be<Subscript>20</Subscript>(Cu<Subscript>50</Subscript>Ni<Subscript>50</Subscript>)<Subscript>20</Subscript> high-entropy bulk metallic glass

The crystallization transformation kinetics of Ti₂₀Zr₂₀Hf₂₀Be₂₀(Cu₅₀Ni₅₀)₂₀ high-entropy bulk metallic glass under non-isothermal conditions are investigated using differential scanning calorimetry. The alloy shows two distinct crystallization events. The activation energies of the crystallization events are determined using Kissinger, Ozawa and Augis–Bennett methodologies. Further, we observe that similar values are obtained using the three equations. The activation energy of the initial crystallization event is observed to be slightly small as compared to that of the second event. This implies that the initial crystallization event may have been easier to be occurred. The local activation energy (E(x)) maximizes in the initial stage of crystallization and keeps dropping in subsequent crystallization process. The non-isothermal crystallization kinetics are further analyzed using the modified Johnson–Mehl–Avrami (JMA) equation. Further, the Avrami exponent values are observed to be 1.5 < n(x) < 2.5 for approximately the entire period of the initial crystallization event and for most instances (0.1 < x < 0.6) of the second crystallization event, which implies that the mechanism of crystallization is significantly controlled by diffusion-controlled two- and three-dimensional growth along with a decreasing nucleation rate.     

Kinetics analysis of the isothermal crystallization of Cu55Zr45 metallic glass by differential scanning calorimetry

The crystallization kinetics of Cu₅₅Zr₄₅ (at%) glassy alloy is studied under isothermal condition using differential scanning calorimetry (DSC). The plot of correlation between the crystallized volume fraction α and annealing time t shows a sigmoid-type curve, which is steeper with higher annealing temperature. Furthermore, in isothermal crystallization condition, local activation energy E_α values, determined using the Arrhenius equation, range from 181.1 to 187.8 kJ/mol, which is nearly a constant. The local Avrami exponent n(α) values, obtained by the Johnson-Mehl-Avrami equation, which range from 2.2 to 4.0 at different annealing temeperatures, which indicates that the crystallization mechanism is diffusion-controlled transformation. Moreover, n(α) becomes greater with increasing annealing temperature, which indicates that annealing temperature can affect nucleation rate and growth type.     

Crystallization kinetics and thermal stability of an amorphous Fe<Subscript>77</Subscript>C<Subscript>5</Subscript>B<Subscript>4</Subscript>Al<Subscript>2</Subscript>GaP<Subscript>9</Subscript>Si<Subscript>2</Subscript> bulk metallic glass

The thermal stability, kinetics and glass forming ability of an Fe₇₇C₅B₄Al₂GaP₉Si₂ bulk amorphous alloy have been studied by differential scanning calorimetry. The activation energy, frequency factor and rate constant corresponding to the multiple crystallization steps were determined by the Kissinger method. X-ray diffraction and transmission electron microscopy studies revealed that the crystallization starts with the primary precipitation of α-Fe from the amorphous matrix. The kinetics of nucleation of the α-Fe nanoparticles was investigated by two different methods, i.e. isothermal annealing and continuous heating after partial annealing.     

Thermal analysis study of Bi<Subscript>2</Subscript>Sr<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3-x</Subscript>Er<Subscript>x</Subscript>O<Subscript>10+δ</Subscript> glass-ceramic system

Summary We have fabricated glasses in the Bi-2223 HT_c superconductor system with Bi₂Sr₂Ca₂Cu_3-xEr_xO_{10+ δ} nominal composition, where x=0.5 and 1.0, by the glass-ceramic technique. Using an analysis developed for non-isothermal crystallization studies, information on some aspects of crystallization temperature and thermal properties has been obtained. The crystallization studies were made using DTA with several uniform rates. The calculations of crystallization activation energies, E_a, and the Avrami parameters, n, were made based on the non-isothermal kinetic theory of Kissinger and the Ozawa’s equations. The DTA data of the samples showed that the first crystallization temperature, T_x1, increases and the second crystallization temperature, T_x2, decreases by increasing the Er concentration. This suggests that the Er substitution had significant effect on the glassification of the BSCCO material due to change on the surface nucleation and increased ionic activities at high temperature region. The activation energy for crystallization, E_a, of the samples was also showed an increase at high Er concentration case. However, the Avrami parameter, n, decreased from 2.5 to 1.7 for x=0.5 and 1.0 samples, respectively. This suggests that the growth mechanism is diffusion-controlled and three-dimensional parabolic growth takes place near the first crystallization temperature. The oxidization rates and the activation barrier for oxygen out-diffusion process, E, was calculated using the TG data. It was found that the total mass gain in the x=0.5 sample is comparably smaller than that of the x=1.0 sample. This shows that the oxygen absorption of the x=1.0 sample is faster than the x=0.5 sample, leading to increase in the oxidization rate in the x=1.0 material.     

Study of the crystallization kinetics in amorphous Fe83P17 alloy

The crystallization kinetics of Fe₈₃P₁₇ amorphous alloy has been studied by Mössbauer spectroscopy and X-ray diffractometry. The samples were annealed isothermally at two different temperatures (315 °C and 325 °C). During isothermal annealing of the samples three phases were observed: crystalline Fe₃P phase, crystalline -Fe phase and the amorphous phase. The value of the Avrami exponent was found to be about 2.0 at each annealing temperature. This suggests that the growth rate of the crystals is controlled by volume diffusion and the nucleation rate decreases during crystallization. The activation energy obtained for the overall crystallization process was 193±43 kJ mol^–1.     

Study of non-isothermal crystallization of amorphous Cu<Subscript>50</Subscript>Ti<Subscript>50</Subscript> alloy

The crystallization kinetics of amorphous Cu₅₀Ti₅₀ has been studied using differential scanning calorimetry (DSC) under non-isothermal conditions. The curves at different linear heating rates (2, 4, 8 and 16 K min^–1) show sharp crystallization peaks. The crystallization peak shifts to higher temperatures with increasing heating rate. The Kissingers method of analysis of the shift in the transformation peak is applied to evaluate the activation energy (E _c). The KJMA formalism, which is basically developed for isothermal experiments, is also used to obtain E _c and the Avrami parameter (n).The DSC data have been analysed in terms of kinetic parameters, viz. activation energy (E _c), Avrami exponent (n) and frequency factor K ₀ using three different theoretical models. It is observed that the activation energy values derived from KJMA approach and modified Kissinger equation agree fairly well with each other. The activation energy values obtained from normal Kissinger method, and Gao and Wang expression underestimate the activation energy.The financial support provided by All India Council for Technical Education (AICTE), New Delhi (Govt. of India) is gratefully acknowledged.     

Nanocrystallization of hydrogen-charged Mg<Subscript>76</Subscript>Ni<Subscript>19</Subscript>Y<Subscript>5</Subscript> amorphous alloy

The crystallization of a hydrogen-charged melt-spun Mg₇₆Ni₁₉Y₅ amorphous alloy was studied in order to understand the influence of hydrogen absorbed on the crystallization kinetics and mechanism. Hydrogenation does not affect the thermal stability, but decreases significantly the enthalpy of crystallization. The glass transition, which is well manifested in the hydrogen-free alloy, is not observed after hydrogen charging. The main crystalline phases in the H-free and H-charged alloys are the same after complete transformation, but with finer microstructure for the hydrogenated samples.Analysis of the crystallization kinetics reveals that during annealing of hydrogen charged Mg₇₆Ni₁₉Y₅ growth of nanocrystals surrounded by amorphous phase takes place just in the beginning of the transformation, followed by grain growth in fully crystallized material, which is the main process.This revised version was published online in November 2005 with corrections to the Cover Date.     

Crystallization kinetics study of melt-spun Zr66.7Ni33.3 amorphous alloy by electrical resistivity measurements

In this paper, the electronic transport properties of as-spun Zr_66.7Ni_33.3 alloys were studied in detail by a combination of electrical resistivity and absolute thermoelectric power measurements over a temperature range from 25 up to 400 °C. Moreover, the isochronal and isothermal crystallization kinetics of Zr_66.7Ni_33.3 glassy alloy has been investigated based on the electrical resistivity measurements. The comparative study of the crystallization kinetics of these binary amorphous alloys was carried out, for the first time to our knowledge, using an accurate method for electrical resistivity measurements. In the isochronal heating process, the apparent activation energy for crystallization was determined to be, respectively, 371.4 kJ mol⁻¹ and 382.2 kJ mol⁻¹, by means of Kissinger and Ozawa methods. The Johnson–Mehl–Avrami model was used to describe the isothermal transformation kinetics, and the local Avrami exponent has been determined in the range from 2.97 to 3.23 with an average value of 3.1, implying a mainly diffusion-controlled three-dimensional growth with an increasing nucleation rate. Based on an Arrhenius relationship, the local activation energy was analyzed, which yields an average value E_x = 376.2 kJ mol⁻¹.

     

Crystallization kinetics of poly(vinylidene fluoride)/MMT,SiO<Subscript>2</Subscript>, CaCO<Subscript>3</Subscript>, or PTFE nanocomposite by differential scanning calorimeter

The nonisothermal crystallization kinetics of poly(vinylidene fluoride) (PVDF) in PVDF/MMT, SiO₂, CaCO₃, or PTFE composites was investigated through differential scanning calorimetry measurements. The enhanced nucleation of PVDF in its nanocomposites with four types of nanoparticle, and their impact on the crystallization kinetics and melting behaviors were discussed. The modified Avrami method and combined Ozawa–Avrami approaches successfully described the primary crystallization of PVDF in nanocomposite samples under the nonisothermal crystallization process. The activation energy was determined according to the Friedman method and it was quite fit with the results of the analysis according to the modified Avrami model and a combined Ozawa–Avrami model.     

Glass transition and crystallization study of chalcogenide Se<Subscript>70</Subscript>Te<Subscript>15</Subscript>In<Subscript>15</Subscript> glass

Differential scanning calorimetry data at different heating rates (5, 10, 15 and 20 °C min⁻¹) of Se₇₀Te₁₅In₁₅ chalcogenide glass is reported and discussed. The crystallization mechanism is explained in terms of recent analyses developed for use under non-isothermal conditions. The value of Avrami exponent (n) indicates that the glassy Se₇₀Te₁₅In₁₅ alloy has three-dimensional growth. The average values of the activation energy for glass transition, E _g, and crystallization process, E _c, are (154.16 ± 4.1) kJ mol⁻¹ and (98.81 ± 18.1) kJ mol⁻¹, respectively. The ease of glass formation has also been studied. The reduced glass transition temperature (T _rg), Hruby’ parameter (K _gl) and fragility index (F _i) indicate that the prepared glass is obtained from a strong glass forming liquid.     

Effects of gaseous hydrogenation on crystallization behavior of melt-spun Mg<Subscript>63</Subscript>Pr<Subscript>15</Subscript>Ni<Subscript>22</Subscript> amorphous ribbons

Effects of gaseous hydrogenation on crystallization behavior of melt-spun Mg₆₃Pr₁₅Ni₂₂ amorphous ribbons have been investigated. The crystallization peak temperature T _p1 shifted to higher temperature with increasing heating rate for the un-hydrogenated Mg₆₃Ni₂₂Pr₁₅ metallic glass, however, it is nearly unchanged for the hydrogenated sample. The present work indicates that the crystallization is a nucleation-and-growth process for the un-hydrogenated Mg₆₃Ni₂₂Pr₁₅ metallic glass. However, the crystallization of hydrogenated sample begins with nucleation and then diffusion-controlled growth takes place.     

Shear influence on the phase behavior of systems containing a homopolymer A and a block copolymer AB

Cloud point temperatures (T_cp) and crystallization temperatures (T_l/s) of the ternary system tetrahydronaphthalene/poly(ethylene oxide)/poly(dimethyl siloxane-b-ethylene oxide) have been measured at different constant shear rates using a rheo-optical device and an advanced rheometer. The cloud points temperatures (UCST-type phase diagram) are reduced by several degrees as the system flows; i.e. the shear can suppress the phase separation and enlarge the homogenous region. The crystallization kinetics of PEO in the ternary mixtures has been investigated isothermally and non-isothermally at quiescent state and under shear. The shear could strongly enhance the crystallization i.e. the (T_l/s) shifts to higher temperatures and the induction time, t₀ (the time needs for the onset of crystallization) substantially decreases with increasing shear rate during the non-isothermal and isothermal crystallization processes, respectively. The isothermal crystallization kinetics at quiescent state and at different shear rates was analyzed on the bases of Avrami approach. The Avrami exponent which provides qualitative information about the nature of the nucleation and growth process, was found to be shear rate and temperature dependent. The Avrami exponent increased from ∼3 at the quiescent state to as large as 9 at &&ggr;dot; = 100 s⁻¹.     

Effect of Re addition on the crystallization,heat treatment and structure of the Cu–Ni–Si-Cr alloy

Differential scanning calorimetry (DSC) was used to investigate the thermal behavior and non-isothermal crystallization kinetics of the Fe₆₇Nb₅B₂₈ metallic glasses prepared by melt-spinning method. DSC traces exhibit that the crystallization takes place through a single exothermic reaction, and it processes a good thermal stability in thermodynamics. The activation energies for nucleation and grain growth processes were calculated to be 536 ± 22 and 559 ± 20 kJ mol^?1 by Kissinger equation, respectively, and 551 ± 24 and 574 ± 20 kJ mol^?1 by Ozawa equation, respectively. It means that the grain growth process is more difficult than the nucleation process. The variation of local Avrami exponent n(x) with crystallized fraction x demonstrates that the crystallization mechanism varies at different stages. The n(x) is larger than 2.5 at the initial stage of 0 < x < 0.3, implying a mechanism of diffusion-controlled three-dimensional growth with increasing nucleation rate. The n(x) decreases from 2.5 to 1.5 in the range of 0.3 < x < 0.65, suggesting that the crystallization belongs to three-dimensional nucleation and grain growth with decreasing nucleation rate. And n(x) lies between 1.0 and 1.5 in the range of 0.65 < x < 0.95, indicating that the crystallization corresponds to the growth of particles with an appreciable initial volume. Low-temperature annealing corresponds to the precipitation of α-Fe, Fe₂B, and Fe₂₃B₆ phases, and further annealing leads to the formation of α-Fe, Fe₂B, and FeNbB phases. The magnetic properties in relation to microstructure change of the Fe₆₇Nb₅B₂₈ metallic glasses are discussed.     

Non-isothermal studies on crystallization kinetics of tellurite 20Li<Subscript>2</Subscript>O-80TeO<Subscript>2</Subscript> glass

Structural and thermal properties of the 20Li₂O-80TeO₂ glass were studied using X-ray diffraction analysis and differential scanning calorimetry techniques to understand and control the crystallization process on this glass. The γ-TeO₂, α-TeO₂ and α-Li₂Te₂O₅ phases were identified during the crystallization in this glass. Activation energies and Avrami exponent n were calculated from non-isothermal measurements for glasses with different particle size. The mean values of Avrami exponent were obtained for glasses with 63–75 and 45–63 μm particle sizes such as , but glasses with particle size 38–45 μm and smaller than 38 g,m presented .     

Effect of nucleating agents on the crystallization of Li<Subscript>2</Subscript>O-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system glass

The processes of nucleation of Li₂O-Al₂O₃-SiO₂ glasses with TiO₂ and TiO₂+ZrO₂ as nucleating agents were discussed. The DTA peak temperature and DTA peak height shown a strong dependence on the nucleation temperature in the glass with TiO₂, while in the glass with TiO₂+ZrO₂ this tendency was small. The optimum nucleation temperatures were 745 and 760°C for two glasses. It suggested that with TiO₂+ZrO₂ as nucleating agents, the crystallization had lower sensitivity for nucleation temperature, and the glass had higher nucleation efficiency than with TiO₂.     

SAXS/WAXS/DSC studies on crystallization of a polystyrene-b-poly(ethylene oxide)-b-polystyrene triblock copolymer with lamellar morphology and low glass transition temperature

Crystallization of a polystyrene-b-poly(ethylene oxide)-b-polystyrene (S-EO-S) triblock copolymer, S₄₀EO₁₃₆S₄₀, with lamellar morphology in the melt and low glass transition temperature (T_g=47 °C) of the S block was studied. The triblock copolymer was cooled from ordered melt and isothermal crystallization was conducted at crystallization temperatures (T_c) near the T_g of the S block. It is found that crystallization behavior of S₄₀EO₁₃₆S₄₀ strongly depends on T_c. When T_c is far below T_g, an Avrami exponent n=0.5 is observed, which is attributed to diffusion-controlled confined crystallization. As T_c slightly increases, the Avrami exponent is 1.0, indicating that crystallization is confined and crystallization rate is determined by the rate of homogeneous nucleation. When T_c is just below the T_g of the S block, crystallization tends to become breakout and accordingly Avrami exponent changes from 1.0 to 3.2. Crystallinity and melting temperature of the EO block in breakout crystallization are slightly higher than those in confined crystallization. Time-resolved small and wide angle X-ray scattering (SAXS/WAXS) were used to monitor isothermal crystallization of S₄₀EO₁₃₆S₄₀. It shows that the long period is constant in confined crystallization, but it gradually increases during breakout crystallization. WAXS result reveals that confined or breakout crystallization has no effect on the crystal structure of the EO block.     

Influence of graphene nanosheets on stereocomplex crystallization behaviors of star‐shaped poly (D(L)‐lactide) stereoblock copolymer

The nanocompsites of star‐shaped poly(D‐lactide)‐co‐poly(L‐lactide) stereoblock copolymers (s‐PDLA‐PLLA) with two‐dimensional graphene nanosheets (GNSs) were prepared by solution mixing method. Crystallization behaviors were investigated using differential scanning calorimetry, polarized optical microscopy, and wide angle X‐ray diffraction. The results of isothermal crystallization behaviors of the nanocompsites clearly indicated that the GNS could remarkably accelerate the overall crystallization rate of s‐PDLA‐PLLA copolymer. Unique stereocomplex crystallites with melting temperature about 207.0°C formed in isothermal crystallization for all samples. The crystallization temperatures of s‐PDLA‐PLLAs shifted to higher temperatures, and the crystallization peak shapes became sharper with increasing GNS contents. The maximum crystallization temperature of the sample with 3 wt% GNS was about 128.2°C, ie, 15°C higher than pure s‐PDLA‐PLLA. At isothermal crystallization processes, the halftime of crystallization (t_0.5) of the sample with 3 wt% GNS decreased to 6.4 minutes from 12.9 minutes of pure s‐PDLA‐PLLA at 160°C.The Avrami exponent n values for the nanocomposites samples were 2.6 to 3.0 indicating the crystallization mechanism with three‐dimensional heterogeneous nucleation and spherulites growth. The morphology and average diameter of spherulites of s‐PDLA‐PLLA with various GNS contents were observed in isothermal crystallization processes by polarized optical microscopy. Spherulite growth rates of samples were evaluated by using combined isothermal and nonisothermal procedures and analyzed by the secondary nucleation theory. The results evidenced that the GNS has acceleration effects on the crystallization of s‐PDLA‐PLLA with good nucleation ability in the s‐PDLA‐PLLA material.     

Isothermal crystallization kinetics of poly(trimethylene terephthalate) under the influence of self-seeding nucleation

The effect of self-seeding nucleation on the crystallization behavior of poly(trimethylene terephthalate) (PTT) was studied. Differential scanning calorimetry (DSC) indicated that the crystallization temperature of PTT notably increased after self-seeding nucleation. Avrami equation was applied in the analysis of the isothermal crystallization process of PTT. The resulting average value of the Avrami exponent at n = 3.34 suggests that primary crystallization may correspond to a three-dimensional spherulitic growth. Self-seeding nucleation, leading to a decrease in active energy for crystallization and chain folding work, promotes the overall crystallization process of PTT. Translated from Acta Polymerica Sinica, 2006, (3): 414–417 (in Chinese)     

Solubility isotherm for the Na<Subscript>2</Subscript>MoO<Subscript>4</Subscript>-Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>-H<Subscript>2</Subscript>O system

Solubility in the Na₂MoO₄-Na₂SO₄-H₂O system was studied using isothermal saturation at 5–100°C. The boundaries of crystallization fields were determined for sodium sulfate and sodium molybdate. Solid solutions were not observed within the range of the temperatures studied. The density, refractive index, and dynamic viscosity of the saturated solutions of the system were determined, and these data were used to calculate the molar volume, kinematic viscosity, and apparent molar volume of the sum of salts in these solutions. All property isotherms of solutions are in a strict correlation with the solubility in the system; this correlation is represented as an isobaric-isothermal diagram.     

Crystallization Behaviors and Regime Kinetics Analysis of Poly(<Emphasis Type="Italic">L</Emphasis>-lactide)-poly(butylene adipate)-poly(<Emphasis Type="Italic">L</Emphasis>-lactide) Based Multiblock Thermoplastic Polyurethanes

Poly(L-lactide)-based (PLLA) poly(ester-urethane)s are particularly relevant and gain significant attention due to their environment-friendly degradability and elastomeric shape memory capability. The tensile properties, resilience and degradation are strongly affected by their crystallization. This work was to investigate crystallization behaviors of the poly(L-lactide)-poly(butylene adipate)-poly(L-lactide) (PLLA-PBAPLLA) based thermoplastic polyurethane elastomers (PLAEUs) we synthesized previously. Dynamic scanning calorimetry (DSC) and polarized optical microscopy (POM) in combination with Avrami, Jezioney and Hoffman-Weeks models were used to analyze the impact of the PLLA block length on the crystallization temperature T_c, degree of crystallinity X_c, nucleation and spherulite growth mode and crystallization regime kinetics of the PLAEUs. The results indicate the low melting point poly(butylene adipate) (PBA) block resides in the amorphous domains while the PLLA block resides in both crystalline and amorphous phases. The X_c of the PLAEUs increase with the increased length of the PLLA block (i.e. higher content of PLLA block). The analyses with Avrami and Jezioney models show the PLAEU copolymers follow a disc-like spherulite growth. The covalently bonded PBA block decreases both nucleation velocity and spherulite growth rate in the isothermal crystallization. Such an impact is lessened as PLLA block length increases. The PLLA homopolymers demonstrate crystallization regime transition from II to III at a certain T_c of isothermal crystallization, while the crystallization regime kinetics of PLLA block in the PLAEUs are explained by a single regime III at low molecular weights of PLLA and the transition is restored as the PLLA block length increases (i.e. regime II to III).