Non-isothermal crystallization kinetic studies on MgO–Al2O3–SiO2–TiO2 glass

Thermal stability and crystallization kinetics of the glass 21% MgO, 21.36% Al₂O₃, 53.32% SiO₂ and 4.11% TiO₂ (mol%) has been studied using differential thermal analysis (DTA), dilatometry and X-ray diffraction (XRD). Glass in both bulk and frit forms were produced by melting in platinum crucible at 1600 °C for 1–2 h. From variation of DTA peak maximum temperature with heating rate, the activation energies of crystallization were calculated to be 340 kJ mol⁻¹ and 498 kJ mol⁻¹ for first and second crystallization exotherms, respectively. Crystallization of bulk glass was carried out at various temperatures and for different time durations in the range of 850–1000 °C. The influence of the addition of TiO₂ on the crystallization sequence of the glass was experimentally determined and discussed.     

Effects of microalloying with 3d transition metals on glass formation in AlYFe alloys

The effects of microalloying on glass formation and stability were systematically investigated by substituting 0.5 at.% of all 3d transition metals for Al in Al₈₈Y₇Fe₅ alloys. X-ray diffraction and isothermal differential scanning calorimetry studies indicate that samples containing microadditions of Ti, V, Cr, Mn, Fe and Co were amorphous, while those alloyed with Ni and Cu were not. The onset temperatures for crystallization (devitrification) of the amorphous alloys were increased with microalloying and some showed a supercooled liquid region (ΔT_x = T_x − T_g) of up to 40 °C. In addition, microalloying changes the glass structure and the devitrification sequence, as determined by differential scanning calorimetry (DSC), X-ray diffraction (XRD), transmission electron microscopy (TEM), differential thermal analysis (DTA) and high energy X-ray diffraction. The results presented here suggest that the order induced in the alloy by the transition metal microaddition decreases the atomic mobility in the glass and raises the barrier for the nucleation of α-Al, the primary devitrifying phase in most cases. New intermetallic phases also appear with microalloying and vary for different transition metal additions.     

Amorphization and crystallization processes of the ball-milled Al–Y–Fe–TM alloys (TM = Ni,Co, Cu,and Fe)

High-energy ball milling was used to synthesize aluminum-based alloys containing amorphous and nanocrystalline phases to investigate the compositional effects of transition metals (TM) on the amorphization and crystallization processes of the ball-milled Al₈₅Y₇Fe₅TM₃ alloys (TM = Ni, Co, Cu, and Fe) were investigated. The crystallization kinetics of the ball-milled Al–Y–Fe–TM nanocomposite powders were studied using differential scanning calorimetry (DSC). The DSC results of Al₈₃Y₇Fe₅Ni₅ show that the crystallization temperature and the activation energy of crystallization are 668 K and 310 kJ/mol, respectively. In-situ high-temperature X-ray diffraction showed that the crystallization was a complex process involving growth of the nanocrystalline phase along with crystallization of the amorphous matrix phase.     

Plastic deformation behavior of amorphous Fe78Si9B13 alloy at elevated temperature

The plastic deformation behavior of amorphous Fe₇₈Si₉B₁₃ alloy was investigated under uniaxial tension and gas pressure bulging. The deformed specimens were studied by means of XRD and SEM. It is shown that amorphous Fe₇₈Si₉B₁₃ ribbon has good deformation ability in the temperature range from 450 °C to 500 °C. The elongation of 36.3% and the relative bulging height (RBH) of 0.45 were obtained at 500 °C. In the uniaxial tension test, the amount of the crystalline α-Fe phase increases with deformation temperature below the crystallization temperature, which also suggests that the tensile stress promotes the crystallization of amorphous Fe₇₈Si₉B₁₃ ribbon. The suitable gas pressure bulging conditions for the specimens are 500 °C, 3.4 MPa and 30 min.     

Calorimetric study and Kissinger analysis of melt-spun DyMn6−xGe6−xFexAlx (1 ⩽ x ⩽ 2.5) alloys

Thermal properties of rapidly quenched alloys from the DyMn_6?xGe_6?xFe_xAl_x (1 ? x ? 2.5) series produced by melt-spinning have been investigated by differential scanning calorimetry (DSC). The DSC curves show two exothermic effects connected with crystallization processes. Crystallization temperatures and enthalpies ΔH have been estimated. The systematic changes in these parameters allow concluding that the crystallization exothermic events are independent. Effective activation energies E have been determined using the Kissinger analysis and relatively high values up to 480 ± 20 kJ/mol for DyMn₄Ge₄Fe₂Al₂ have been found indicating high thermal stability of the amorphous state in this alloy series.     

In-situ crystallization of amorphous Fe73−xNbxAl4Si3B20 alloys through synchrotron radiation

In the present work Fe_73−xNb_xAl₄Si₃B₂₀ (x = 5, 10) alloys have been processed by melt-spinning with the aim of studying the crystallization sequence through annealing in suitable temperatures. Melt-spun ribbons were characterized by differential scanning calorimetry (DSC), X-ray diffractometry (XRD) through Cu-Kα (λ = 1.54 Å) and synchrotron radiation (λ = 1.77 Å) and transmission electron microscopy (TEM). Soft magnetic properties were measured through the hysteresis loop tracer. In-situ XRD through synchrotron radiation was very accurate in phase identification. Fe_73−xNb_xAl₄Si₃B₂₀ (x = 5, 10) alloys showed the possibility of forming ferromagnetic amorphous alloys composed of commercial Fe-based master alloys with fine nanocrystalline structure and good soft magnetic properties.     

Magnetic behavior,transport properties and nanocrystallization of melt-spun YxCe50 − xCu42Al8 (0 ≤ x ≤ 50) amorphous system

Amorphous Y_xCe_50 ? xCu₄₂Al₈ (0 ≤ x ≤ 50) ribbons prepared by melt-spinning on the Cu wheel were subjected to X-ray diffractometry (XRD), differential scanning calorimetry (DSC) and to the measurements of magnetization and resistivity in the temperature range from 1.7 to 300 K. Effective activation energies, characteristic crystallization temperatures and enthalpies of as-quenched alloys have been determined. Two stages of crystallization have been observed in most samples (except shallow effects in Ce₅₀Cu₄₂Al₈). The activation energies have been calculated from the Kissinger relation to be 247 ± 18 and 570 ± 56 kJ/mol for Y₂₅Ce₂₅Cu₄₂Al₈ and Y₅₀Cu₄₂Al₈, respectively. The absence of the endothermic effect for x = 50, usually associated with a glass transition, below the primary crystallization event, indicates the presence of dispersed polyamorphous packing with a wide range of local glass transitions. The magnetization versus temperature plot for Y₂₅Ce₂₅Cu₄₂Al₈ points to a magnetic ordering at temperatures considerably below 50 K. This observation has been confirmed by the temperature dependence of resistivity, which exhibits a singularity at the same temperature. Moreover, a negative temperature coefficient of resistivity, characteristic of disordered systems, was observed. The electrical resistivity in the Y₂₅Ce₂₅Cu₄₂Al₈ amorphous alloy is governed by the weak localization of electrons.     

Kinetic analysis of Al3Ti intermetallic powder after mechanical treatment in hydrogen

We present results of mechanochemical processing experiments performed on intermetallic powder, Al₃Ti milled under hydrogen and helium atmospheres using a magnetically controlled Uniball device. Milling products were investigated by X-ray diffractometry (XRD), transmission electron microscopy (TEM) and advanced differential thermal analysis (DTA and DSC). Milling in both H₂ and in He resulted in breakdown of the intermetallic structure and, after extended milling, formation of nanostructural products comprising, predominately, a solid solution of Ti in fcc Al, with some possible additional Al_1+xTi_1−x (x = 0.3) phase. Detailed kinetic analysis was preformed on the Al₃Ti sample milled for 6 days in hydrogen. Under isothermal annealing, the crystallization of the Al₅Ti₂ was found to follow the JMA kinetics, with constant activation energy E¹ and Avrami exponent n decreasing from 2.5 to 1.5.     

Nanocrystallization and structure of Fe78.5Ni1.0Mo0.5Si6.0B14.0 amorphous alloy

The effect of Ni and Mo alloying additions on crystallization of an Fe–Si–B based amorphous alloy was studied by applying various experimental techniques – DSC, XRD and TEM. It was shown that both alloying additions Ni and Mo change the crystallization temperature as well as the activation energy of primary crystallization. The phases formed during primary crystallization for the Fe₈₀Si₆B₁₄ and Fe_78.5Ni₁Mo_0.5Si₆B₁₄ alloys were the same, however the morphologies were significantly different. The addition of 1.0 at.% of Ni and 0.5 at.% Mo changed the crystallization mechanism and the type of formed phases. Such additions also resulted in formation of nanocrystals. The kinetic and thermodynamic characteristics of annealed specimens of amorphous metallic Fe₈₀Si₆B₁₄ and Fe_78.5Ni₁Mo_0.5Si₆B₁₄ alloys were established. These characteristics were determined based on measurements of instantaneous changes of electrical strength. It was shown that the method of electromotive force measurements was more sensitive to structural changes and the phase composition of amorphous metallic electrodes in comparison with the X-ray method.     

Microstructure evolution and grain size distribution in nanocrystalline FeNbBCu from synchrotron XRD and TEM analysis

The microstructure evolution during nanocrystallization of an Fe₇₇Nb₇B₁₅Cu₁ amorphous alloy is investigated using in situ synchrotron X-ray diffraction (XRD) and transmission electron microscopy (TEM). The microstructure of the nanocrystallized alloy consists in dispersion of bcc-Fe nanocrystals of 4–6 nm of diameter embedded in a stabilized amorphous remaining matrix. The grain size distribution of the nanocrystalline Fe₇₇Nb₇B₁₅Cu₁ alloy was obtained using three different methodologies: statistical analysis of TEM images, the Warren–Averbach and Langford methods to analyse the XRD patterns and modelling of the diffraction pattern from the Debye equation. A lognormal distribution function has been assumed in all three methods in order to obtain comparable results. A good agreement is found in the calculated average radius and dispersion although some deviations are found with the Langford approach. The microstructure evolution during crystallization was obtained from the XRD patterns during heating (5.0 · 10^?3 K s^?1) at temperatures between 700 and 900 K. A decrease and prompt saturation of the growth rate is obtained, indicative of the diffusion barrier caused to the overlap between the concentration gradients at the interface of growing grains (soft impingement). A simple model assuming nucleation and initial fast growth of the crystalline grains followed by reduced growth capable of predicting microstructural evolution is presented. The modelling results agree with the experimental observations.     

Synthesis and characterization of a multicomponent Fe-based bulk amorphous alloy

A new bulk metallic glass (BMG) Fe₆₀B₁₅Zr₁₀Co₇Mo_5.5Y₂Si_0.5 was synthesized by Cu mold casting. The alloy was characterized by X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS) techniques. The thermal stability and glass-forming ability (GFA) of the alloy have been discussed by evaluating a number of thermal parameters. The maximum values of the key thermal parameters like T_rg (T_g/T_m, T_g/T_l), γ, δ and β parameters were found to be ～(0.66, 0.64), 0.407, 1.84 and 3.83, respectively. The alloy showed double stage crystallization process. The activation energies for crystallization were found to be 606.6 and 623.1 kJ/mol by Kissinger and Ozawa equations, which indicate the high thermal stability. Crystallization behavior of the alloy was explored by XRD. Mechanical properties like Vicker’s hardness, nanohardness and elastic modulus are found to be very promising.     

Investigations of the non-isothermal crystallization of Bi4Ge3O12 (2:3) glasses

Amorphous Bi₄Ge₃O₁₂ glass samples were produced by melt quenching procedure stating with Bi₄Ge₃O₁₂ (BGO) powder, obtained by solid state reaction between oxides. The kinetics of non-isothermal crystallization of BGO nano-crystals has been investigated. Differential Thermal Analysis (DTA) can give the main parameters of crystallization with an exothermic peak from 813 K to 851 K depending on the heating rate, which was assigned to the crystallization of cubic BGO in the amorphous matrix and compared with the X-Ray Diffraction (XRD) patterns. The nano-crystal dimensions were calculated from the XRD patterns by using the Debye–Scherrer method and were compared with Transmission Electron Microscopy (TEM) images. It was shown that the Ozawa model is most suitable for describing the behavior of non-isothermal crystallization of BGO nano-crystals within the glass matrix. Experimental results suggest a disk-shape type growth mechanism for the Bi₄Ge₃O₁₂ nano-crystallites. The Flynn–Wall–Ozawa method has shown that the average activated energy value is 385 ± 14 kJ/mol which was computed within the same model and agrees very well with the activation energy of the crystallization.     

Preparation of thin ribbon and bulk glassy alloys in CoFeBSiNb(Ga) using planar flow casting and suction casting methods

Co-based ferromagnetic bulk glassy alloy (BGA) system is promising for future applications as new structural and functional materials. In the present paper as-cast Co₄₇Fe_20.9B_21.2Si_4.6Nb_6.3 bilayer, ribbon, rods with diameter up to 5 mm and [Co₄₇Fe_20.9B_21.2Si_4.6Nb_6.3]₉₈Ga₂ as-cast ribbon as well as rod with 4 mm diameter were investigated. Co based master ingots with the composition Co₄₇Fe_20.9B_21.2Si_4.6Nb_6.3 have been prepared in a vacuum furnace. The as-prepared master ingots were then purified by fluxing. Small amount of gallium (2 at.%) was added into one part of the purified master alloy. Ribbons, bilayer and bulk samples in form of rods were prepared by subsequent planar flow casting and suction casting method, respectively. Glassy structure of as-cast samples was examined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Thermal stability associated with glass transition temperature (T_g), crystallization temperature (T_x) and supercooled liquid region (?T_x = T_x – T_g) were examined by differential scanning calorimetry (DSC). The Curie temperature of the investigated ribbons and rods was determined by magnetic thermogravimetry analysis (TGA). Using special disc-shaped samples field dependencies of magnetostriction in parallel and perpendicular directions of the applied magnetic field were obtained by direct measurement.     

Microstructure evolution and thermal properties in FeMoPCB alloy during mechanical alloying

Fe_79.3Mo_4.5P_8.1C_6.75B_1.35 amorphous alloy composite powder from respective element powders of Fe, Mo, C, B, and Fe–P intermediate compound, was synthesized by mechanical alloying. Microstructure evolution analysis indicates that the synthesized amorphous alloy composite powder after a milling time of 70 h encompasses predominately amorphous matrix embedded by nanocrystalline α-Fe with a grain size of about 5.5 nm. However, unlike other Fe-based amorphous alloys, the synthesized amorphous alloy composite powder exhibits no obvious supercooled liquid region with only crystallization temperature. The corresponding crystallization onset temperature and exothermic enthalpy measured from DSC curves are about 762 K and 15.86 J/g, respectively. The results obtained provide good candidate materials for fabricating bulk metallic glass composites and related bulk nanocrystalline materials.     

Crystallization of amorphous Al2O3–SiO2 precursors doped with nickel

The crystallization of amorphous diphasic Al₂O₃–SiO₂ precursors doped with nickel has been studied by differential scanning calorimetry (DSC), XRD diffraction (XRD) and scanning and transmission electron microscopy (SEM, TEM) equipped with energy dispersive X-ray spectroscopy (EDS). Diphasic gels with constant atomic ratio (Al + Ni)/Si = 3:1, where 0, 1, 2 and 3 at.% of aluminum were replaced by nickel, have been prepared by hydrolyzing of TEOS in aqueous solution of aluminum nitrate. Crystallization of Ni-containing γ-Al₂O₃ preceded the crystallization of Al–Si spinel. Activation energy of 603 ± 16 kJ mol⁻¹ for crystallization of Ni-containing γ-Al₂O₃ was obtained in non-isothermal conditions. Ni-incorporated γ-Al₂O₃ transforms gradually with the temperature increase into Ni aluminate spinel, while Al–Si spinel reacts with amorphous silica forming mullite at about 1200 °C. Rietveld structure refinement of phases present in the samples annealed at 1600 °C and SEM-EDS and TEM-EDS analyses of related phases have shown that nickel predominantly crystallizes as NiAl₂O₄, but small amount of nickel is incorporated in mullite structure, as well as, dissolved in the glassy phase of the system.     

The thermal behavior of 8 mol% yttria-stabilized zirconia nanocrystallites prepared by a sol–gel process

Eight mole percent yttria-stabilized zirconia (8YSZ) nanocrystallites were synthesized at a relatively low temperature using ZrOCl₂ · 8H₂O and Y(NO₃)₃ · 6H₂O as starting materials in an ethanol–water solution by a sol–gel process. The thermal behavior of the 8YSZ nanoparticles was investigated by differential thermal analysis, Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy and electron diffraction. The crystallization temperature of the 8YSZ gel powders was estimated to be about 729 K by DTA analysis. When calcined from 773 to 1273 K, the crystallization of the cubic phase was observed by XRD. The crystallite size of the 8YSZ increased from 7.14 to 20.10 nm with calcining temperature increasing from 773 to 1273 K. The activation energy for growth of 8YSZ nanoparticles was found to be 7.26 kJ/mol.     

Nano-crystallization behavior of Zr–Cu–Al bulk glass-forming alloy

The glass-forming ability and devitrification behavior of a Zr₅₅Cu₃₅Al₁₀ bulk glass-forming alloy were examined to elucidate the very high nanocrystallization product density (> 10²³ m^?3). The crystallization kinetics and structural changes in the glassy alloy were studied using X-ray diffraction, transmission electron microscopy, differential scanning and isothermal calorimetry methods. The observed sequential phase formation during isothermal reaction and the high nanocrystal density are consistent with the influence of residual oxygen even at low levels (< 500 ppm) to promote nucleation.     

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).     

Kinetics of crystallization process of Mg–Cu–Gd based bulk metallic glasses

The crystallization behavior of Mg₆₁Cu₂₈Gd₁₁ and (Mg₆₁Cu₂₈Gd₁₁)₉₈Cd₂ bulk metallic glasses was studied using DSC in the mode of continuous and isothermal heating, and its crystallization process and microstructure were confirmed by XRD and TEM. In continuous heating, the activation energies of glass transition, onset and peak crystallization were determined by the Kissinger method, which yields 110 ± 12, 77 ± 9 and 79 ± 10 kJ/mol, respectively, for Mg₆₁Cu₂₈Gd₁₁ glassy alloy, and 144 ± 10, 126 ± 6 and 131 ± 5 kJ/mol, respectively, for (Mg₆₁Cu₂₈Gd₁₁)₉₈Cd₂ glassy alloy. The isothermal kinetics was modeled by the Johnson-Mehl-Avrami equation. The Avrami exponent of the base alloy was in the range from 1.98 to 2.56 (± 0.01), which indicated a decreasing nucleation rate and a diffusion-controlled growth. For Cd-added glassy alloy, the Avrami exponent was in the range from 3.26 to 4.08, which indicated an increasing nucleation rate. The activation energies in isothermal process were calculated to be 88 ± 2 and 132 ± 2 kJ/mol, respectively, for the base and Cd-added glassy alloys. It was found that Mg₂Cu phase was the primary phase in the initial crystallization and the strong affinity between Cd and Mg/Gd tended to impose resistance to the formation of Mg₂Cu phase and thus improves the thermal stability.     

Structural evolution of Fe33Zr67 and Fe90Zr10 metallic glasses

We report on the structural evolution of melt-spun Fe₃₃Zr₆₇ and Fe₉₀Zr₁₀ glasses. These glasses are subjected to isothermal annealing over a wide temperature range, varying from the onset of crystallization up to near the melting point, for 20–300 min. Over 733–1223 K, the phase evolution sequence of the Fe₃₃Zr₆₇ glass follows: fcc FeZr₂ → fcc FeZr₂ + bct FeZr₂ → bct FeZr₂. In contrast, annealing of the Fe₉₀Zr₁₀ glass over 903–1173 K leads to a mixture of α-Fe, Fe₃Zr and Fe₂Zr phases. Some Fe₂Zr crystals are not developed perfectly, showing a special twin lamellar structure. The annealing temperature and alloy composition dependence of grain size in the present Fe–Zr system is discussed.