Time and amplitude dependences of the damping decrement and shear modulus upon irreversible structural relaxation in a Zr-Cu-Ni-Al-Ti bulk metallic glass

The time dependences of the irreversible relaxation of the damping decrement and the shear modulus of a Zr_52.5Ti₅Cu_17.9Ni_14.6Al₁₀ bulk metallic glass are investigated using an inverse torsion pendulum in the range from room temperature to ～650 K. The spectrum of activation energies of irreversible structural relaxation is evaluated from the results obtained. Analysis of the amplitude dependences of the damping decrement and the shear modulus allows the conclusion that the relaxation centers responsible for the amplitude dependence differ from those associated with the irreversible structural relaxation at temperatures below and in the vicinity of the glass transition point.     

Shear viscosity of the Pd<Subscript>40</Subscript>Cu<Subscript>40</Subscript>P<Subscript>20</Subscript> metallic glass under conditions of isochronous heating below the glass transition temperature

The shear viscosity is measured under conditions of isochronous (linear) heating below the glass transition temperature of the Pd₄₀Cu₄₀P₂₀ metallic glass, which is characterized by the polymorphic crystallization into the Pd₂Cu₂P tetragonal phase with a lower density than the initial glass. It is shown that the rate dependence of the shear viscosity can be interpreted as a result of the irreversible structural relaxation by analogy with the case of the previously studied metallic glasses despite the unusual ratio of the densities of the material in noncrystalline and crystalline states.     

Structural relaxation and viscous flow in amorphous ZrAlCu

The ternary metallic glass Zr₆₅Al_7.5Cu_27.5 offers a wide temperature range between glass transition temperature and crystallization temperature and is therefore well suited for investigation of the glass transition and the state of the super cooled liquid. The non-linear viscosity change caused by structural relaxation has been measured caused by structural relaxation has been measured using tensile creep experiments on as quenched samples. The increase of viscosity can be described by bimolecular annihilation kinetics of flow defects. The Arrhenius plot of equilibrium viscosity shows a kink at a temperature which seems to be the glass transition temperature. The activation energies of viscous flow below and above that glass transition temperature differ by nearly a factor two. Different microscopic processes responsible for viscous flow in the two regimes of temperature are therefore conceivable. This view is also encouraged by Dynamic-Mechanical-Analysis on relaxed samples, a method to examine the viscoelastic behaviour of glassy materials on different time scales and by recent diffusion measurements on a different system.     

Structural relaxation of metallic glasses studied by Mössbauer spectroscopy

We present microscopic evidence of structural relaxation in the purely metallic glass Zr₆₇Ni₁₀Cu₂₃ doped with 0.5 at.% of⁵⁷Fe. The Mössbauer spectra under different heat treatments were analyzed by a six-parameter model. Two regimes of structural relaxation, irreversible and reversible relaxation, are clearly distinguished and the latter involves different atomic processes over different temperature regions.     

Structural relaxation and viscous flow in amorphous ZrAlCu

The ternary metallic glass Zr₆₅Al_7.5Cu_27.5 offers a wide temperature range between glass transition temperature and crystallization temperature and is therefore well suited for investigation of the glass transition and the state of the super cooled liquid. The non-linear viscosity change caused by structural relaxation has been measured caused by structural relaxation has been measured using tensile creep experiments on as quenched samples. The increase of viscosity can be described by bimolecular annihilation kinetics of flow defects. The Arrhenius plot of equilibrium viscosity shows a kink at a temperature which seems to be the glass transition temperature. The activation energies of viscous flow below and above that glass transition temperature differ by nearly a factor two. Different microscopic processes responsible for viscous flow in the two regimes of temperature are therefore conceivable. This view is also encouraged by Dynamic-Mechanical-Analysis on relaxed samples, a method to examine the viscoelastic behaviour of glassy materials on different time scales and by recent diffusion measurements on a different system.     

Stress relaxation and viscosity of a bulk Pd<Subscript>40</Subscript>Cu<Subscript>30</Subscript>Ni<Subscript>10</Subscript>P<Subscript>20</Subscript> metallic glass under isochronous heating conditions

Isochronous relaxation of tensile stresses is measured in a bulk Pd₄₀Cu₃₀Ni₁₀P₂₀ metallic glass in the initial state and after certain thermal treatments. The results of measurements are used to find the energy spectrum of irreversible structural relaxation, from which the temperature dependence of shear viscosity is then calculated. This dependence is also found independently from measurements of creep in the same glass. The calculated viscosity is shown to agree well with the experimental data.     

Isothermal creep of bulk glassy Zr52.5Ti5Cu17.9Ni14.6Al10 below T g

The results of an isothermal creep investigation of Zr_52.5Ti₅Cu_17.9Ni_14.6Al₁₀ bulk metallic glass at temperatures below the glass transition temperature are presented. The long-time (t > (2–4) × 10³?s) creep regularities were found to be the same as those known for ribbon metallic glasses, in spite of the pronounced difference in the production quenching rates. It is argued that creep behaviour of bulk metallic glass is determined by the rate of irreversible structural relaxation. The apparent activation energy spectrum reconstructed from isothermal creep measurements agrees well with that determined from linear heating creep data.     

Creep strain recovery of Fe-Ni-B amorphous metallic ribbon

Creep strain recovery and structural relaxation of the amorphous metallic glass Fe₄₀Ni₄₁B₁₉ after longtime loading at different annealing temperatures below the glass transition temperature have been studied using anisothermal differential scanning calorimetry (DSC) and dilatometry (TMA). It has been demonstrated that structural relaxation effects depend on the stress-annealing temperature of the amorphous ribbon. The structural relaxation states of the amorphous ribbon annealed at different temperatures under and without applied stress have been compared. The activation energy spectra were calculated from the anisothermal dilatometric measurements using the modern method based on the Fourier transformation technique. The influence of the annealing temperature on the shape of creep strain recovery spectra has been analyzed.      

Initial stage of physical ageing in network glasses

An atomistic view on Johari–Goldstein secondary β-relaxation processes responsible for structural relaxation far below the glass transition temperature (T_g ) in network glasses is developed for the archetypal chalcogenide glass, As₂₀Se₈₀, using positron annihilation lifetime, differential scanning calorimetry, Raman scattering and nuclear magnetic resonance techniques. Increased density fluctuations are shown to be responsible for the initial stage of physical ageing in these materials at the temperatures below T_g . They are correlated with changes in thermodynamic parameters of structural relaxation through the glass-to-supercooled liquid transition interval. General shrinkage, occurred during the next stage of physical ageing, is shown to be determined by the ability of system to release these redundant open volumes from the glass bulk through the densification process of glass network.     

Stress relaxation in an Zr<Subscript>52.5</Subscript>Ti<Subscript>5</Subscript>Cu<Subscript>17.9</Subscript>Ni<Subscript>14.6</Subscript>Al<Subscript>10</Subscript> bulk metallic glass

The isothermal relaxation of stresses in a bulk metallic glass is measured at temperatures below the glass transition point. The kinetic law of relaxation is determined. It is argued that the stress relaxation in the temperature range covered is due to the irreversible structural relaxation oriented by an external stress and characterized by a distribution of activation energies.     

The kinetics of the structural relaxation process in PHEMA-silica nanocomposites based on an equation for the configurational entropy

The enthalpy relaxation of polymer-silica nanocomposites prepared by simultaneous polymerization of poly(2-hydroxyethyl methacrylate) (PHEMA) and tetraethyloxysilane, TEOS, a silica precursor, is investigated. Both the glass transition temperature, T_g, and the temperature interval of the glass transition, ΔT _g , increase as the silica content in the sample does. Structural relaxation experiments show that the temperature interval in which conformational motions take place broadens as the silica content in the hybrid increases. A phenomenological model based on the evolution of the configurational entropy during the structural relaxation process, the SC model, has been used for determining the temperature dependence of the relaxation times during the process. The results show an increase of the fragility of the polymer as the silica content increases, a feature that can be related to the broadening of the distribution of relaxation times characterized by the β parameter of the stretched exponential distribution. On another hand the silica content increase produces a significant change of the relaxation times in the glassy state.     

Isothermal kinetics and relaxation recovery of high-frequency shear modulus in the course of structural relaxation of Pd<Subscript>40</Subscript>Cu<Subscript>30</Subscript>Ni<Subscript>10</Subscript>P<Subscript>20</Subscript> bulk glass

Isothermal kinetics of relaxation of the high-frequency (1.4 MHz) shear modulus during structural relaxation of Pd₄₀Cu₃₀Ni₁₀P₂₀ bulk metallic glass below the glass transition temperature is studied by an in situ method of contactless electromagnetic acoustic transformation. The kinetic law of relaxation is established. It is shown that quenching of aged samples from the supercooled liquid state leads to a decrease in the absolute value of shear modulus to below the initial value; the degree of subsequent isothermal relaxation of the modulus may be several times higher than the initial value. Possible reasons for relaxation and recovery of the shear modulus are considered.     

Temperature Dependence of Structural Relaxation in Glass-Forming Liquids and Polymers

Understanding the microscopic mechanism of the transition of glass remains one of the most challenging topics in Condensed Matter Physics. What controls the sharp slowing down of molecular motion upon approaching the glass transition temperature T_g, whether there is an underlying thermodynamic transition at some finite temperature below T_g, what the role of cooperativity and heterogeneity are, and many other questions continue to be topics of active discussions. This review focuses on the mechanisms that control the steepness of the temperature dependence of structural relaxation (fragility) in glass-forming liquids. We present a brief overview of the basic theoretical models and their experimental tests, analyzing their predictions for fragility and emphasizing the successes and failures of the models. Special attention is focused on the connection of fast dynamics on picosecond time scales to the behavior of structural relaxation on much longer time scales. A separate section discusses the specific case of polymeric glass-forming liquids, which usually have extremely high fragility. We emphasize the apparent difference between the glass transitions in polymers and small molecules. We also discuss the possible role of quantum effects in the glass transition of light molecules and highlight the recent discovery of the unusually low fragility of water. At the end, we formulate the major challenges and questions remaining in this field.     

Ca70Mg30金属玻璃形成过程热力学、 动力学和结构特性转变机理的模拟研究

采用分子动力学方法对Ca₇₀Mg₃₀合金快速凝固玻璃形成过程进行了计算机模拟, 深入分析了液-固玻璃转变过程热力学、 动力学和结构特性的转变机理, 对不同方法所确立的玻璃转变温度之间的关系进行了探讨. 结果表明: 本模拟计算所获得的Ca₇₀Mg₃₀金属玻璃的结构因子和玻璃转变温度均与实验结果符合, 而且二十面体局域结构对Ca₇₀Mg₃₀金属玻璃的形成起决定性作用. 由于周围原子形成的瞬时"笼子效应", 过冷液体动力学特性逐渐偏离Arrhenius规律而满足模态耦合理论的幂指数规律. 动力学玻璃转变温度接近于微观结构玻璃转变温度, 但高于热力学玻璃转变温度; 而且它们与理想动力学玻璃转变温度之间满足Odagaki关系.     

Cu60Zr30Ti10非晶合金弛豫和晶化过程的小角X射线散射研究

应用小角X射线散射技术研究了Cu₆₀Zr₃₀Ti₁₀非晶合金从300到813 K之间微结构的演化情况.发现在淬火状态下Cu₆₀Zr₃₀Ti₁₀非晶合金中存在直径30 nm左右的富Cu区.非晶的结构弛豫包括573 K之前的低温结构弛豫和573 K到玻璃转变温度的高温结构弛豫，弛豫的结果是产生含有有序原子团簇的富Cu区，这些有序原子团簇的富Cu区是随后晶化过程中晶核产生的基础.Porod曲线分析表明，晶化生成的纳米体心立方CuZr相和基体之间有明锐的界面. 关键词： 小角X射线散射 非晶合金 结构弛豫 晶化     

Microscopic origin of reversible relaxation in metallic glasses

Mössbauer spectroscopy has been used to measure changes associated with structural relaxation in the glass Pd₄₀Ni₄₀P₂₀. When taken with data from X-ray diffraction, the results characterize the differences between irreversible and reversible relaxation, and show that the latter involves at least two distinct processes.     

Dynamic light scattering in solid polymers

The viscosity of an amorphous polymeric solid above its glass transition [T _g (T,P)] increases as the temperature of the solid is decreased or the pressure is increased. Under changes in temperature or pressure, molecular subunits in the polymeric solid undergo configurational changes. Such changes or relaxations have a distribution of relaxation strengths and times. As the solid is cooled or as the hydrostatic pressure on the solid is increased, the relaxation strengths increase and the relaxation times increase. These changes in relaxation or dynamic properties are very dramatic as the empirical T _g is approached. Near T _g the polymeric solid is no longer in volume equilibrium; continued cooling or pressuring at a time rate faster than the average relaxation time will produce a polymeric glass. This glass is a nonequilibrium, amorphous solid. If the glass is held at a fixed temperature and pressure very close to, but below, T _g , the volume of the glass will be observed to relax to its equilibrium value. For temperatures and pressures well below T _g , equilibrium is a much more conjectural concept since the relaxation times become extremely long. It has been proposed^1,2 that there is a characteristic temperature T _g at which an amorphous polymer undergoes a second-order transition to an equilibrium glass with zero configurational entropy (i.e., a noncrystallizable solid).     

Configurational Entropy Relaxation of Silica Glass—Molecular Dynamics Simulations

Vitreous silica was modelled using molecular dynamics (MD). The glass structure was transferred into an undirected graph and decomposed into disjoint structural units that were ideally mixed to calculate the configurational entropy. The Debye relaxation model was suggested to simulate the evolution of entropy during the cooling of the system. It was found that the relaxation of the configurational entropy of MD corresponds to the effective cooling rate of 6.3 × 10⁶ Ks⁻¹ and its extrapolation to 0.33 Ks⁻¹ mimics the glass transition with T_g; close to the experimental value. Debye relaxation correctly describes the observed MD evolution of configurational entropy and explains the existence of freezing-in temperature and the shape of the curve in the transition region.     

Structural relaxation of Zr60Al15Ni25 amorphous ribbon: experimental evidence of the electrical resistivity

In order to study the structural relaxation of the Zr₆₀Al₁₅Ni₂₅ amorphous ribbon, the electrical resistivity was experimentally investigated. The changes in the resistivity before glass transition temperature were observed. Two temperature points (423?K and 573?K) were chosen for cyclic heating experiments. The results showed that both irreversibility and reversibility of structural changes existed in amorphous alloys, which were related to the selected temperature and cycle times. Based on the scattering mechanism of electron conduction in metal, the structural defects model was used to explain the changes of electrical resistivity. The sample was in a highly disorder state after experienced thermal cycling of high temperature (573?K). The number and kind of atoms may be changed to increase the crystallisation range.