非晶合金中的流变单元

非晶合金是一类具有诸多优异性能的先进金属材料,同时也是研究非晶态物质的模型体系.最近,大量的实验和模拟证据显示,在非晶合金中可能存在类似晶体中缺陷的"流变单元",这些动力学单元和非晶合金的的流变、物理、力学性能密切关联.本文主要综述了流变单元提出的背景、实验证据、流变单元的特征、激活与演化过程、相互作用以及相关的理论.文中提供了大量实验证据证明流变单元模型不仅可以帮助理解非晶态物质中如形变、玻璃转变、弛豫动力学以及非晶结构和性能的关系等重要的基本物理问题,而且可以指导非晶合金性能的调控和设计,获得性能优异的非晶合金材料.     

Evidence of distributed interstitialcy-like relaxation of the shear modulus due to structural relaxation of metallic glasses

The interstitialcy theory is used to calculate the kinetics of shear modulus relaxation induced by structural relaxation of metallic glasses. A continuous distribution of activation energies is shown to be a salient feature of the relaxation. High precision in situ contactless electromagnetic acoustic-transformation shear modulus (600- kHz) measurements performed on a Zr-based bulk metallic glass are found to strongly support the approach under consideration. It is revealed that the activation energy spectra derived from isothermal and isochronal shear modulus measurements are in good agreement with each other. It is concluded that the increase of the shear modulus during structural relaxation can be understood as a decrease of the concentration of structural defects similar to dumbbell interstitials in simple crystalline metals.     

Investigation of the creep and glass transition of elastomers by the microindentation method: Epoxy resin and related nanocomposites

The experimental procedure and theoretical grounds of the applicability of the microindentation method as one of the effective techniques of relaxation spectrometry of solid-state polymers have been developed. It has been shown that the glass transition temperature and rheological parameters of the material (unrelaxed and relaxed elastic moduli, strain viscosity coefficients) can be determined from measurements of the temperature dependence of the microhardness of polymers in a high-elasticity state and in the glass transition region with the recording of the long-term creep under the indenter. These measurements provide sufficient information for the formulation of a rheological model of the material under investigation. The results of these measurements are supplemented by the concepts of thermally activated motion of molecular segments as the microscopic mechanism of structural relaxation in polymers, which makes it possible to obtain empirical estimates for the activation energies and vibrational frequencies of the molecular segments. The method is implemented in experiments on the microindentation of the epoxy resin and its composites with the addition of carbon nanotubes in the temperature range 230–300 K. The glass transition of these polymers has been observed at temperatures near 260 K, the unrelaxed and relaxed Young’s moduli have been measured, and two thermally activated relaxation processes determining the glass transition, as well as the shortterm and long-term creeps of these materials (α- and α′-processes), have been revealed.     

Atomic structure and strength of inorganic glasses

The role of the atomic structure in the fracture processes is considered using borate, silicate, and phosphate glasses as an example. Primary attention is focused on the degree of connectivity of the atomic structure. It is shown that the degree of connectivity is a major factor responsible for the structural strength of glasses under conditions excluding the influence of both accidental surface defects and the environment. The change in the Young’s modulus as a measure of elastic deformation and the change in the hardness as a characteristic of irreversible deformation are analyzed. The ultimate elastic strain experienced by a glass at the instant of fracture is examined. It is found that the ultimate elastic strain is approximately equal to 10% for glasses with a three-dimensional atomic structure and 5% for glasses with a two-dimensional (layered) or chain structure. It is assumed that this behavior of the strength as a function of the degree of connectivity of the atomic structure is associated with the degree of uniformity of the external load distribution over atomic bonds.     

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.      

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.     

Beta relaxation versus high frequency wing in the dielectric spectra of a binary molecular glass former

The binary molecular glass former 2-picoline in tri-styrene is investigated by means of broadband dielectric spectroscopy with the aim of understanding the role of secondary relaxation processes that emerge during the glass transition. It is shown that the "high frequency wing," which is seen in neat picoline, becomes a separate process in the mixture and exhibits all the features of a Johari-Goldstein relaxation. In particular, the previously found relation between activation energy and Tg is recovered. In addition, below Tg the width parameter of this secondary relaxation is shown to be governed by a common temperature dependence, and the time scale is characterized by an isokinetic point. Above Tg pronounced deviations from an Arrhenius behavior are observed.     

Kinetics of isothermal creep in metallic glasses including the statistical distribution of activation parameters

A generalized theoretical model is proposed for the structural relaxation of metallic glasses under load. Structural relaxation is treated as a set of irreversible, uncorrelated, two-stage atomic displacements in some regions of the structure, the “relaxation centers.” In loaded samples structural relaxation acquires a directional character, leading to the buildup of plastic deformation in accordance with the magnitude and orientation of the applied mechanical stress. General equations are obtained for creep kinetics including a continuous statistical distribution of the principal activation parameters. These equations are compared with the results of a special experiment. The model is found to provide an adequate interpretation of the observed creep kinetics, except for the first 10¹–10² seconds after loading. It is argued that the initial stage of creep is determined by reversible atomic realignments in relaxation centers having symmetric two-well potential. Fiz. Tverd. Tela (St. Petersburg) 39, 2008–2015 (November 1997)     

Microstructure of fragile metallic glasses inferred from ultrasound-accelerated crystallization in Pd-based metallic glasses

By utilizing ultrasonic annealing at a temperature below (or near) the glass transition temperature Tg, we revealed a microstructural pattern of a partially crystallized Pd-based metallic glass with a high-resolution electron microscopy. On the basis of the observed microstructure, we inferred a plausible microstructural model of fragile metallic glasses composed of strongly bonded regions surrounded by weakly bonded regions (WBRs). The crystallization in WBRs at such a low temperature under the ultrasonic vibrations is caused by accumulation of atomic jumps associated with the beta relaxation being resonant with the ultrasonic strains. This microstructural model successfully illustrates a marked increase of elasticity after crystallization with a small density change and a correlation between the fragility of the liquid and the Poisson ratio of the solid.     

大块金属玻璃Zr41Ti14Cu12.5Ni10Be22.5的流变行为研究

采用静态拉伸方法在连续升温条件下动态地测量了大块金属玻璃Zr41Ti14Cu12.5Ni10Be22.5（Vit1）的黏度随温度的变化关系.在应变速率与温度的关系曲线中，观测到了与玻璃转变和晶化过程相联系的多个应变速率峰.在玻璃转变温度Tg以上，大块金属玻璃Zr41Ti14Cu12.5Ni10Be22.5的过冷液体呈现Newton流体特征，其黏度与温度的关系符合Vogel Fulcher-Tammann (VFT)关系式，拟合得到脆度D*＝36，VFT温度T0＝319K，脆度参数m＝30，这说明Zr41T 关键词： 大块金属玻璃 应变速率 剪切黏度 自由体积     

Irreversible structural relaxation in a bulk Pd-Cu-Ni-P metallic glass

The evolution of the shear modulus and the damping decrement during irreversible structural relaxation in a bulk Pd₄₀Cu₃₀Ni₁₀P₂₀ metallic glass in a temperature range below the glass transition temperature has been studied with an inverse torsion pendulum at a frequency of ～25 Hz. It is shown that the irreversible relaxation can be recovered via quenching from temperatures above the glass transition temperature. The spectrum shape, the characteristic activation energies, and the attempt frequencies of the irreversible structural relaxation are estimated.     

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.     

Defect-related relaxation processes in irradiated rare gas solids

Electronic and atomic relaxation processes in preirradiated solid Ar doped with N 2 were studied with a focus on the role of radiative electronic transitions in relaxation cascades. Combining methods of activation spectroscopy - thermally stimulated and photon-stimulated exoelectron emission, a new channel of relaxation induced by photon emission from metastable N atoms was detected. It was shown that in insulating materials with a wide conduction band photons of visible range can release electrons from both kinds of traps - shallow (lattice defects) and deep thermally disconnected ones. Correlation in the charge recombination reaction yield and the yield of low temperature desorption - important relaxation channel in a preirradiated solid - clearly demonstrates interconnection between atomic and electronic processes of relaxation.     

Semiclassical approach to resonance-optics polarization effects in coherent and squeezed fields

Equations are derived for the atomic density matrix and relaxation operator for a broadband squeezed field in an arbitrary polarization state and resonance atomic energy levels with an arbitrary degree of degeneracy. It is shown that suppression of the relaxation of the quadrature component of the atomic polarization depends strongly on the type of resonance transition and the polarization state of the squeezed and coherent perturbing fields. When the resonance levels are strongly degenerate, the relaxation of the quadrature component of the atomic polarization under conditions of maximum suppression is nonexponential in character. The mathematical apparatus developed here makes it possible to calculate polarization-related aspects of the multifrequency optical behavior of atomic and molecular systems resonantly excited both by coherent light and by broadband squeezed fields. Zh. éksp. Teor. Fiz. 111, 25–43 (January 1997)     

金属玻璃Tg附近内耗理论分析

本文根据自由体积模型和固体材料的力学理论分析并讨论了金属玻璃在玻璃转变温度T_g附近的内耗行为。当考虑到体系中固状区和液状区的比例之后,得出了应力与应变之间的关系式。理论上把内耗和模量变化与玻璃转变过程有机地结合起来。证明了在T_g附近可以出现具有弛豫型特征的内耗降,并在玻璃转变过程中模量明显下降。理论与实验结果基本相符。 关键词：     

非晶材料玻璃转变过程中记忆效应的热力学

低温下处于非平衡态的非晶材料升温到玻璃转变以上,要先后发生弛豫和回复最终达到平衡过冷液态,其中弛豫过程中释放的能量在回复过程中以等量的方式获取,表现出明显记忆行为.本文基于氧化物、金属与小分子等多种非晶形成体系,全面探讨了在围绕玻璃转变的一个冷却加热循环过程中的焓弛豫特征,建立了弛豫谱,发现弛豫焓在数值上与熔化焓密切相关.基于弛豫焓与非晶材料动力学Fragility之间的关联,展示了非晶体系在动力学极限(m=175)条件下的玻璃转变热力学基本特征,与热力学二级相变进行了对比.研究深化了对非晶弛豫与玻璃转变热力学的理解.     

A mechanism for spontaneous relaxation of glass at room temperature

Silicate glasses kept at ambient temperature densify spontaneously, and their properties change with time. This is known as ageing of a glass. The spontaneous change occurs according to first-order rate kinetics, with a characteristic (relaxation) time much shorter than that of the α-relaxation process. According to the mechanism proposed here, there are local regions in the network structure of a silicate glass which collapse spontaneously with time by simultaneous motions of atoms seen as β or the Johari-Goldstein relaxation. The collapse causes the Si-O-Si bond angles in the immediate surroundings to change, and these angles become elastically strained. This strain biases the potential energy in a two-site model for oxygen-atom displacement, which occurs at a faster rate and rapidly dissipates the strain. Thus the glass densifies homogeneously on ageing, by two processes: process I, spontaneous collapse of local regions; process II, subsequent dissipation of strain energy resulting from the collapse. The first process, which is much slower, determines the kinetics of ageing. A fictive temperature T_f,β corresponding to the freezing out of the localized motions of the Johari-Goldstein relaxation process is proposed. For silicate glasses, T_f,β is 40-45% of the usual fictive temperature for the α-relaxation process. The volume lost during ageing may be recovered on heating the aged glass to a temperature far below T _g in a time- and temperature-dependent manner, as has already been found from zero-point measurements of a glass thermometer.     

The relaxation-element method in models of the plastic strain of structurally inhomogeneous materials

It is shown that it is possible to represent a continuous field of plastic strain with high gradients in local regions of a material by methods of the continual theory of defects. A practical method of constructing highly inhomogeneous fields of plastic strain in local regions of a solid under load is proposed, and the stress fields connected with them are determined. The method is used to propose a principle of a unique connection between the process of inelastic deformation and stress relaxation in local volumes of the material. This enables one to simulate the inhomogeneous fields of plastic strain and stresses connected with the external stress without discontinuities and singularities at the interfaces between the phases and crystallites.Institute of Physics of the Strength and Study of Materials, Siberian Branch, Russian Academy of Sciences. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 16–22, February, 1994.     

The synergetic theory of the glass transition in liquids

The glass transition is treated as a spontaneous emergence of the shear components of strain and stress elastic fields upon cooling a liquid at a rate exceeding the critical value. The stationary elastic strains and stresses and the effective relaxation time are determined within the adiabatic approximation. It is shown that the glass transition process occurs through the mechanism of a first-order kinetic transition with allowance made for the strain dependence of the shear modulus. The critical cooling rate turns out to be proportional to the thermal diffusivity and unrelaxed shear modulus and inversely proportional to the temperature derivative of the relaxed shear modulus and the square of the heat conductivity length of the sample.