New structural features of non-crystalline tetrahedrally bonded networks: A modeling approach

A large model of amorphous silicon (2052 atoms) with 0.5% dangling bonds has been built and investigated. The refinement of the coordinates evidenced the presence of small domains with advanced ordering. These domains preclude the formation of crystallization nuclei and play an essential role in the redistribution of the defects in the material with homogenization of the free energy and stabilization against aging. An effect of amorphization of the ordered nuclei due to free energy redistribution is assessed. The glass relaxation of a-Si (a-Ge) occurring during heating below T_g receives a natural explanation as a structural change from local quasi-ordering to homogeneous disordering.     

Two-order-parameter model of the liquid–glass transition. I. Relation between glass transition and crystallization

Recently we proposed a two-order-parameter model of liquid to understand the liquid–glass transition, liquid–liquid transition, and anomalies of water-type liquids in a unified manner. Here we discuss the relation between our model and previous models of the liquid–glass transition, focusing on the difference in the basic standpoint among the models. We argue that (i) actual liquids universally have a tendency of spontaneous formation of locally favored structures and (ii) liquid–glass transition is controlled by the competition between long-range density ordering toward crystallization and short-range bond ordering toward the formation of locally favored structures due to the incompatibility in their symmetry. Thus, we regard vitrification as phenomena that are intrinsically related to crystallization. Previous models, on the other hand, regard vitrification as a result of (a) an homogeneous increase in the density and the resulting cooperativity in molecular motion or (b) the frustration intrinsic to a liquid state itself. Accordingly, they presuppose the kinetic avoidance of crystallization and thus do not put focus on ‘crystallization’. This leads to the essential difference in the physical picture between our model and previous models. By comparing models, we aim at gaining further insight into what is the physical origin of the liquid–glass transition and its possible connection with crystallization.     

On the anomalies in density,Young's modulus and glass temperature of PdSi glasses

The densities, Young's moduli and glass transition temperatures have been measured for binary PdSi glassy alloys. These glassy alloys exhibit a negative deviation from Vegard's law an enhancement in Young's modulus and a tendency to lower the glass transition temperature in the region of the eutectic composition. The observed nonlinearity in these physical properties is shown to be better agreement with an alloy mixing effect rather than the structural ordering model.     

The thermal study of oxyfluoride glass with strontium fluoride

A thulium (Tm 3+) doped oxyfluoride glass ceramic containing SrF2 nanocrystals has been presented. Transparent glass ceramic was obtained by heat treating the glass from the SiO2-Al2O3-ZnO-SrF2 system at the first crystallization temperature. Cerammization of glass was studied by DTA/DSC, XRD and SEM methods. It has been found that nanocrystallization of SrF2 strongly depends on the ratio between the components and amount of SrF2. Moreover the rare earth dopant Tm3+ influenced on the thermal properties of glass. The formation of SrF2 nanocrystals in glass ceramic was confirmed by X-ray diffraction. X-ray diffraction analysis of the transparent glass ceramic revealed that the SrF2 nanocrystals are precipitated in the glass matrix. Analysis of the local atomic interactions in the structure of oxyfluoride glass has been used to explain the course of the crystallization.     

Ordering and magnetostriction in Fe alloy single crystals

Short-range and long-range ordering in α-Fe terminal solid solution phase (A2 phase with bcc structure) influences its physical, mechanical, magnetic and magnetostrictive behavior. Single crystal sample forms are ideal for examining order in these alloys using X-ray and neutron scattering techniques. Limited structural information available suggests that the lattice of A2 phase at room temperature contains a mixture of regions with local atomic environments similar to those expected in the long-range ordered structures in stable/metastable equilibrium with the A2 phase. The nature and extent of these regions are sensitive to alloy composition and the thermal history. The lattice strain modulations result from the nature of solute atom distribution (short-range ordering) in each region and impact the physical, mechanical, corrosion and magnetic behaviors. A need for a fundamental understanding of ordering in Fe and other alloys through structural evaluations of local atomic environments in alloy single crystals is suggested in this review.     

A study of the crystallization of two non-crystalline CuZr alloys

Two CuZr alloys, Cu-50 at% Zr and Cu-54 at% Zr, were splat quenched to the non-crystalline state using a piston and anvil device. The glass transition and crystallization temperatures, as well as the enthalpy releases observed during crystallization were measured using differential scanning calorimetry of as-splat specimens and specimens aged below T_g. Transmission electron microscopy and X-ray diffraction experiments were utilized to monitor phase and structural changes in the alloys as they were transformed to the crystalline state.The results of the investigation indicated that the non-crystalline to crystalline transformation of these two alloys in constant heating rate experiments above T_g was a two-step process. The initial step, which is associated with a large exothermic reaction, results in the appearance of crystallites in a matrix of non-crystalline material. The final step, associated with a smaller exothermic reaction, results in the total transformation of glass to the crystalline state and the formation of the equilibium crystalline phases.The effect of aging these splat-quenched non-crystalline alloys at temperatures below T_g was also investigated. It was determined from these experiments that crystallization does occur when the non-crystalline alloys are aged ～ 15°C below T_g. However, the incubation time for crystalline nucleus formation was found to be substantially greater for the Cu₅₀Zr₅₀ glass. Finally, it was determined that the thermal stability of the aged glass relative to the spontaneous crystallization observed during the constant heating rate experiments above T_g decreases as a function of aging time.     

Local order and nanostructure induced by microalloying in Al-Y-Fe amorphous alloys

Extended X-ray absorption fine structure (EXAFS) measurements show that the dramatic improvement in glass formation in Al-Y-Fe alloys made with a small additions of Ti and V has a structural origin. The EXAFS spectra show that a well-defined Al atomic structure exists around the V and Ti atoms that is different from that around the major constituent Al, Y and Fe atoms, even at the lowest concentrations. The local Ti- and V-Al clusters have a size of about 1 nm. Around the V atoms, the local order can be described by a small face centered cubic cluster. Around the Ti atoms, the local structure seems to evolve from a face centered cubic nano-cluster towards a body centered cubic one when the concentration increases from 0.5% to 2%. These measurements demonstrate that Ti and V form strong interactions with Al, with a significant shortening of the bond length. This should raise the barrier for nucleation of α-Al, explaining the greater stability of the glasses containing Ti or V.     

Glass formation and crystallization in highly undercooled Te-Cu alloys

The large undercoolings required for glass formation have been achieved by the slow cooling (10-20°C/min) of liquid Te-Cu alloys in the form of a fine droplet emulsion. Within the region of glass formation, between 19 and 39 at.% Cu, DTA measurements indicate that the glass (T_g) and crystallization (T_c) temperatures during heating exhibit a broad maximum at the eutectic. During slow cooling of Te-rich alloy droplets, the maximum undercooling for nucleation increases from 213°C for pure Te to 264°C for Te-12.5 at.% Cu. An enhanced depression of the nucleation (T_n) temperature compared with the change of the liquidus develops in Te-rich alloys upon approaching the glass forming composition range and can be a useful feature in assessing the glass forming tendency. Thermal cycling experiments indicate that even at an undercooling of 181°C crystallization in an eutectic Te-29 at.% Cu alloy is limited by an inadequate nucleation rate in clean droplet samples. For a eutectic alloy, at undercoolings in excess of 200°C crystal nucleation does develop in the droplet samples, but complete crystallization is hindered by a rapidly rising liquid viscosity with increased undercooling.     

Chemical aspects of glass formation in telluride systems

The compositional dependence of the electrical activation energy, the optical absorption and the glass transition temperature in typical binary, pseudo-binary and ternary glass forming telluride systems has been measured in an effort to correlate chemical binding with physical properties. A modification of the valency satisfaction model to include chemical ordering effects is required to account for the property singularities observed in the GeTe system at the composition GeTe₂. The ordering effects in Te-based alloys containing Ge are further verified by an endothermic disordering reaction in these liquids peaking between 400–475°C depending on composition.     

Crystallization behavior of Ce70−xAl10Cu20Cox (x = 0, 1, 3, 5 at.%) amorphous alloys

The effect of Co addition (substituting for Ce) on crystallization behavior of Ce₇₀Al₁₀Cu₂₀ amorphous alloys has been investigated using X-ray diffraction (XRD), differential thermal analysis (DTA) and transmission electron microscopy (TEM). The Co addition has an obvious effect on topological short-range ordering of Ce–Al–Cu–(Co) amorphous alloys. Moreover, the Co addition can slightly improve the thermal stability of Ce–Al–Cu based amorphous alloys. The 1 and 3 at.% Co additions do not obviously change the crystallization behavior of the Ce–Al–Cu–(Co) amorphous alloys, and the final crystallization products are FCC–CeAlCu(Co)O. However, the 5 at.% Co addition can alter the crystallization behavior of the Ce₇₀Al₁₀Cu₂₀ amorphous alloys. Proper content of Co can effectively suppress the formation of oxide phases during annealing of the Ce–Al–Cu–(Co) amorphous alloys.     

A comparison of the crystallization behavior of liquid-quenched and vapor-quenched amorphous Cu60Ti40

The crystallization behavior of two Cu₆₀Ti₄₀ amorphous alloys, one prepared by a vapor-quench (VQ) process and one by a liquid-quench (LQ) process, has been studied using differential scanning calorimetry, X-ray diffraction, and transmission electron microscopy. Microstructural studies show that the two alloys have the same transformation sequence under similar annealing conditions. However DSC measurements of the crystallization temperature during isochronal annealing and of the incubation time for crystallization during isothermal annealing show that the LQ alloy is more thermally stable and therefore more structurally relaxed. TEM analysis of the partially annealed microstructures gives some insight into the mode of crystal nucleation and growth as a function of temperature. During isothermal annealing significant differences are observed for the two alloys in the shape and orientation of the crystals and in the crystal structure formed. Whereas the VQ alloy transforms polymorphicaly into the intermetallic Cu₃Ti₂, the LQ alloy forms the Ti-rich phase, Cu₄Ti₃. The two phases are closely related in structure and composition. The differences observed for the two alloys are discussed in terms of greater structural relaxation and short range order in the LQ alloy resulting from the mode of synthesis.     

An anomalous X-ray structural study of an amorphous La55Al25Ni20 alloy with a wide supercooled liquid region

The atomic structures of amorphous La₅₅Al₂₅Ni₂₀ alloys which have a wide supercooled liquid region and a high reduced glass transition temperature have been studied using anomalous X-ray scattering (AXS) at the Ni K-absorption edge as well as the ordinary X-ray diffraction with Mo K radiation. The interference functions and the radial distribution functions were determined for the amorphous alloys as-quenched and after annealing at various temperatures and also for a fully crystallized sample. These systematic structural studies revealed a drastic change in Ni environment upon crystallization. The need for such atomic rearrangements around the Ni atoms during crystallization may be the reason why the amorphous phase is thermally stable.     

Reduced glass transition temperature and glass forming ability of bulk glass forming alloys

Onset temperature (solidus) T_m and offset temperature (liquidus) T_l of melting of a series of bulk glass forming alloys based on Zr, La, Mg, Pd and rare-earth elements have been measured by studying systematically the melting behaviour of these alloys using DTA or DSC. Bulk metallic glass formation has been found to be most effective at or near their eutectic points and less effective for off-eutectic alloys. Reduced glass transition temperature T_rg given by T_g/T_l is found to show a stronger correlation with critical cooling rate or critical section thickness for glass formation than T_rg given by T_g/T_m.     

The structural relaxation and glass transition of La---Al---Ni and Zr---Al---Cu amorphous alloys with a significant supercooled liquid region

An amorphous phase with a wide supercooled liquid region, > 50 K, was found to form over wide composition ranges in the La---Al---Ni and Zr---Al---Cu systems. The largest values for the temperature span between the crystallization temperature, T_x, and the glass transition temperature, T_g, ΔT_x(-T_x−T_g), are 69 K for La₅₅ Al₂₅Ni₂₀ and 88 K for Zr₆₅Al_7.5Cu_27.5. The structural relaxation behavior on annealing was examined for the two amorphous alloys with the largest ΔT_x values. The magnitude of the structural relaxation increases gradually with increasing annealing temperature, T_a, and then rapidly in the T_a range slightly below T_g and decreases significantly on annealing T_g. The rapid increase in the magnitude of the structural relaxation on annealing near T_g is due to the glass transition. The single-stage structural relaxation indicates that there is no distinct difference in relaxation times (atomic bonding forces) between the constituent atoms in the two metal-metal-type amorphous alloys. The existence of an optimum bonding state is thought to cause the wide supercooled liquid region for the two amorphous alloys.     

Crystallization processes of Ag–Ge–Se superionic glasses

The interest in superionic systems has increased in recent years because of the potential application of these materials as solid electrolytes. In this field, amorphous materials present important advantages when compared to the crystalline solids: larger conductivity, isotropy and absence of grain boundaries. In this work, amorphous alloys of compositions (Ge₂₅Se₇₅)_100−yAg_y with y=10, 15, 20 and 25 at.% have been studied. Amorphous samples in bulk were obtained from the liquid by water quenching (melt-quenching technique). The crystallization kinetics of the amorphous alloys have been studied under continuous heating and isothermal conditions by means of differential scanning calorimetry. A glass transition and two exothermic transformations were observed in all the samples. The quenched samples and the crystallization products have been characterized by X-ray diffraction. The primary crystallization of the ternary phase Ag₈GeSe₆ and the secondary phase GeSe₂ was observed. The glass and crystallization temperatures, the activation energy and the crystallization enthalpy are reported. The first step of the crystallization of the Ag₈GeSe₆ phase in all the (Ge₂₅Se₇₅)_100−yAg_y samples is modelled taking into account the Johnson–Mehl–Avrami–Kolmogorov theory and considering that the changes in the composition only modify the viscosity of the undercooled liquid. The transformation diagrams (TTT and THRT) are calculated and the glass forming ability is analyzed. The experimental results are discussed and correlated with the structures proposed for the glass. The present results and conclusions are also compared with those reported by other authors.     

Electrical and magnetic properties of rare-earth — Gold glasses

We present magnetic and electrical properties of amorphous rare-earth alloys of composition (R₇₅Au₂₅)_100−xB_x (R = Pr, Gd, Tb, Er and X = 0, 10). Low-field susceptibility, electrical resistivity and high-field magnetization measurements were made between 1.6 and 300 K. Resistivity measurements show both positive and negative temperature coefficients and in some cases maxima and minima that are associated with magnetic ordering and Kondo-like scattering respectively. For all the samples except those containing Gd, the local random anisotropy produces asperomagnetic ordering and high coercive fields. Large magnetic after-effects have been observed down to liquid helium temperatures particularly for the Tb glass. Metamagnetic effects have been found in (Er₇₅Au₂₅)_90B10.     

Evaluation of glass-forming ability criterion from phase-transformation kinetics

Applying kinetic analysis upon crystallization of metallic glass, a quantitative relation between the critical cooling rate and the onset temperature of crystallization was obtained for glass-forming alloys. Effects of the onset temperature of crystallization, the liquidus temperature and the glass transition temperature on the critical cooling rate were analytically described. Three rules guiding the development of more reliable glass-forming ability criteria are suggested.     

Phase separation and crystallization in amorphous Pd-Si-Sb

It is found that replacing some of the Si in a Pd-Si-Sb glass with Sb can make it more resistant to crystallization than the pure binary material. This is shown by the calorimetric results, in which the crystallization temperature increases and the glass temperature decreases with increasing Sb substitution, and also by the finding that certain alloys, such as Pd_80.5 Si_16.5Sb₃ may be quenched into amorphous rods (by the gradient-quench method) up to 0.5 mm thick.

Calorimetry and small-angle X-ray scattering data show that certain alloys in this system phase separate in the amorphous state. The two phases thus produced independently crystallize. Isothermal measurements indicate that the rate of crystallization of one of the phases is interface-limited, with most nuclei initially present. The other crystallization process does not fit an Avrami law, possibly due to a transformation of the crystalline phase.

A method called “gradient-quenching” (GQ) was used to prepare samples from the melt in such a way that the quench-rate was non-uniform, so all stages of crystallization in slowly-quenched alloys are displayed. Nucleation was frequently found to take place on voids and inclusions.

The use of the calorimetric and GQ methods in conjunction to gather information about crystallization processes in metallic glasses is discussed.     

Effect of substitution of rare earth by mischmetal on the devitrification process of Al-X-Ni-Co (X = Y, Ce, Mm) alloys

The effect of substitution of Ce or Y by mischmetal (Mm) on the glass transition and the kinetics of crystallization of quaternary Al-Ni-Co-(Ce, Y, Mm) alloys was studied using isothermal and non-isothermal calorimetry and X-ray experiments. The alloy containing Mm shows more similarity to Ce containing alloy in all the studied properties than to Y containing alloy. The glass transition is less evident for Ce and Mm containing alloys than for the alloy containing Y. For the two former alloys, the first and the second crystallization stages are strongly overlapped and yield a fully crystallized alloy. Whereas for Y alloy, the first and the second stages are well resolved and the primary crystallization yields nanosized α-Al particles embedded in a residual amorphous matrix.     

Structural analysis of some sodium and alumina rich high-level nuclear waste glasses

Sodium- and aluminum-rich high-level nuclear waste glasses are prone to nepheline (NaAlSiO₄) crystallization. Since nepheline removes three moles of glass-forming oxides (Al₂O₃ and SiO₂) per mole of Na₂O, the formation of this phase can result in severe deterioration of the chemical durability in a given glass. The present study aims to investigate the relationships between the molecular-level structure and the crystallization behavior of sodium alumino-borosilicate-based simulated high-level nuclear waste glasses with infrared spectroscopy (FTIR) and X-ray diffraction, respectively. The molecular structure of most of the investigated glasses comprise a mixture of Q² and Q³ (Si) units while aluminum and boron are predominantly present in tetrahedral and trigonal coordination, respectively. The increasing boron content has been shown to suppress the nepheline formation in the glasses. The structural influence of various glass components on nepheline crystallization is discussed.