Residual stress engineering is very widely used in the design of new advanced lightweight materials. For metallic glasses the attention has been on structural changes and rejuvenation processes. High energy scanning X-ray diffraction strain mapping reveals large elastic fluctuations in metallic glasses after deformation under triaxial compression. Microindentation hardness mapping hints to a competing hardening-softening mechanism after compression and further reveals the complementary effects of stress and structure modulation. Transmission electron microscopy proves that structure modulation under room temperature deformation relates to the shear band formation that closely correlates to the distribution of elastic heterogeneities. Molecular dynamics simulations provide an atomistic understanding of the complex shear band activity in notched metallic glasses and the related fluctuations in the strain/stress heterogeneity. Thus, future focus should be given to stress engineering and elastic heterogeneity that together with structure modulation may allow to design metallic glasses with enhanced ductility and strain hardening ability.
Modulating energy states of metallic glasses (MGs) is significant in understanding the nature of glasses and control their properties. In this study, we show that rejuvenation in enthalpy can be achieved and preserved in bulk MGs by using high pressure (HP) annealing, which is a controllable method to continuously alter the energy states of MGs. Contrary to the decrease in enthalpy by conventional annealing at ambient pressure, such rejuvenation can occur and be enhanced by increasing both of annealing temperature and pressure. By using double aberration corrected scanning transmission electro…
Cycling of a metallic glass between ambient and cryogenic temperatures can induce higher-energy states characteristic of glass formation on faster cooling. This rejuvenation, unexpected because it occurs at small macroscopic strains and well below the temperatures of thermally induced structural change, is important, for example, in improving plasticity. Molecular-dynamics simulations elucidate the mechanisms by which thermal cycling can induce relaxation (reaching lower energy) as well as rejuvenation. Thermal cycling, over tens of cycles, drives local atomic rearrangements progressively eras…
The glassy paramagnetic Meissner phase of a Bi$_2$Sr$_2$CaCu$_2$O$_x$ superconductor ($x$ = 8.18) is investigated by squid magnetometry, using ``dc-memory'' experiments employed earlier to study spin glasses. The temperature dependence of the zero-field-cooled and thermo-remanent magnetization is recorded on re-heating after specific cooling protocols, in which single or multiple halts are performed at constant temperatures. The 'spin' states equilibrated during the halts are retrieved on re-heating. The observed memory and rejuvenation effects are similar to those observed in Heisenberg-like …
Cryogenic rejuvenation in metallic glasses reported in Ketov et al 's experiment (Nature(2015)524,200) has attracted much attention, both in experiments and numerical studies. The atomic mechanism of rejuvenation has been conjectured to be related to the heterogeneity of the glassy state, but the quantitative evidence is still elusive. Here we use molecular dynamics simulations of a model metallic glass to investigate the heterogeneity in the local thermal expansion. We then combine the resulting spatial distribution of thermal expansion with a continuum mechanics calculation to infer the inte…
We theoretically investigate high-pressure effects on the atomic dynamics of metallic glasses. The theory predicts compression-induced rejuvenation and the resulting strain hardening that have been recently observed in metallic glasses. Structural relaxation under pressure is mainly governed by local cage dynamics. The external pressure restricts the dynamical constraints and slows down the atomic mobility. In addition, the compression induces a rejuvenated metastable state (local minimum) at a higher energy in the free energy landscape. Thus, compressed metallic glasses can rejuvenate and the…
Negative Strain-Rate Sensitivity in Metallic Glasses Driven by Rejuvenation-Relaxation Competition: Kinetic Monte Carlo Simulations and a Minimal Effective Model
Faculty of Mechanical Engineering, Kanazawa University（金泽大学机械工程学院）；Department of Mechanical Science and Bioengineering, The University of Osaka（大阪大学机械科学生物工程系）；Department of Earth and Space Science, The University of Osaka（大阪大学地球空间科学系）
We rejuvenate well-aged quasi-2D binary colloidal glasses by thermal cycling, and systematically measure both the statistical responses and particle-level structural evolutions during rejuvenation. While the moduli and boson peak are continuously rejuvenated with increasing number of cycles, the mean square displacement (MSD) fluctuates significantly between different groups of thermal cycles. The decoupling between the thermodynamical and dynamical evolutions suggests different microscopic origins for different bulk properties of glasses. We find that a small fraction of structural rearrangem…
The influence of static stress and alternating loading direction on the potential energy and mechanical properties of amorphous alloys is investigated using molecular dynamics simulations. The model glass is represented via a binary mixture which is first slowly annealed well below the glass transition temperature and then subjected to elastostatic loading either along a single direction or along two and three alternating directions. We find that at sufficiently large values of the static stress, the binary glass becomes rejuvenated via collective, irreversible rearrangements of atoms. Upon in…
The structural relaxation, potential energy states, and mechanical properties of a model glass subjected to thermal cycling are investigated using molecular dynamics simulations. We study a non-additive binary mixture which is annealed with different cooling rates from the liquid phase to a low temperature well below the glass transition. The thermal treatment is applied by repeatedly heating and cooling the system at constant pressure, thus temporarily inducing internal stresses upon thermal expansion. We find that poorly annealed glasses are relocated to progressively lower levels of potenti…
Using molecular dynamics simulations, we investigate the effect of uniaxial elastostatic compression on the potential energy, structural relaxation, and mechanical properties of binary glasses. We consider the three-dimensional Kob-Andersen binary mixture, which was initially cooled from the liquid state to the glass phase with a slow rate at zero pressure. The glass was then loaded with a static stress at the annealing temperature during extended time intervals. It is found that the static stress below the yielding point induces large-scale plastic deformation and significant rejuvenation whe…
Motivated by results of the topological theory of glasses accounting for geometric frustration, we develop the simplest possible continuum mechanical model of defect dynamics in metallic glasses that accounts for topological, energetic, and kinetic ideas. The model is aimed towards the development of a microscopic understanding of the plasticity of such materials. We discuss the expected predictive capabilities of the model vis-a-vis some observed physical behaviors of metallic glasses.
We report that both shear and bulk moduli, not only shear modulus, are critical parameters involved in both homogeneous and inhomogeneous flows in metallic glass. The flow activation energy (ΔF) of various glasses when scaled with average molar volume Vm, which is defined as flow activation energy density ρ_E =ΔF/Vm, can be expressed as: D=(10G+K)/11 . The extended elastic model is suggestive for understanding the glass transition and deformation in metallic glasses.
Studying the primary α- and secondary β-relaxation process has contributed significantly to the understanding of the structure and rheology of metallic glasses. In this letter, we report on a third relaxation mechanism indicated by a maximum in the loss modulus at low temperatures, which we term γ-relaxation. Contrary to the α- and β-relaxation mechanisms, this irreversible, low energy excitation causes a macroscopic rejuvenation, which we assign to non-affine atomic rearrangements in the matrix that are driven by thermal stresses during cooling. Observed in three different glassy alloys, the …
Plastic deformation of metallic glasses performed well below the glass transition temperature leads to the formation of shear bands as a result of shear localization. It is believed that shear banding originates from individual stress concentrators having quadrupolar symmetry. To elucidate the underlying mechanisms of shear band formation, microstructural investigations were carried out on sheared zones using transmission electron microscopy. Here we show evidence of a characteristic signature present in shear bands manifested in the form of sinusoidal density variations. We present an analyti…
A recent paper by Juntao Huo et al [Chin. Phys. Lett. 39 (2022) 0464011] reported a correlation between the entropy of mixing (and the corresponding energy state) and the thermal stability and mechanical parameters, for three Zr-Ti-Cu-Ni-Be metallic glasses (MG) including a high-entropy one (HEMG). The authors dismissed a possible compositional contribution to the variations of the thermal stability and mechanical parameters studied.
Boson peak and beta-relaxation are two intrinsic and markedly different dynamic modes of glasses, and their structural origins are long-standing issues. Through tuning atomic packing of a model metallic glass with microalloying of different types of elements, we find that low-temperature boson heat capacity peak evolves hand in hand with high-temperature beta-relaxation. A linear correlation between the boson peak temperature and the activation energy of beta-relaxation is disclosed. The coupling of the boson peak and the beta-relaxation indicates their common structural origin of the loosely …
Tuning anisotropy in bulk metallic glasses, ideally isotropic, is of practical interest in optimizing properties and of fundamental interest in understanding the amorphous structure and its instability. By employing the quasi-elastic asymmetric mechanical cycling method, we effectively induce the mechanical polarity of a model bulk metallic glass, without damaging the sample or introducing significant annealing or rejuvenation effects. Moreover, the polarized anelastic limit can be well controlled by regulating the amplitude of mechanical cycling. Through the atomic-level analysis of nonaffine…
Mechanical behaviors of bulk metallic glasses (BMGs) including heterogeneous and homogeneous deformation are interpreted by phenomenological shear transformation zones (STZs) model. Currently, information about STZs, i.e. size and density, is only extracted by fitting model equation to the data obtained from macroscopic mechanical tests. This is inadequate since structural features of STZs theory cannot be assessed. Here, we develop anisotropic pair distribution function (PDF) method for directly characterizing mechanical response of deformation defects. Our results reveal the physical picture…
Universal Dynamic Scaling for Sub-Yield Aging and Over-Yield Rejuvenation in A Cyclically Driven Metallic Glass
School of Materials Science and Engineering, Anhui University of Technology（安徽工业大学材料科学与工程学院）；Advanced Interdisciplinary Science Research Center (AiRCenter), Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences（中国科学院宁波材料技术与工程研究所先进交叉科学研究院）；State Key Laboratory of High Performance Roll Materials and Composite Forming, School of Material Science and Engineering, Hebei University of Technology（河北工业大学材料科学与工程学院高性能轧辊材料及复合成形省部共建国家重点实验室培育基地）
Planar flow casting (PFC) is a method that can be used to make thin, long, and wide metallic alloy foils by extruding molten liquid through a thin and wide nozzle and immediately quenching on a moving roller. The quenching rates are high enough that amorphous metallic glasses may be formed which have many desirable properties for a wide variety of applications. This paper reviews how PFC processes were developed, examines the typical operability range of PFC, and reviews the defects that commonly form. The geometrical similarities between PFC and slot coating process are apparent, and this pap…
Micro-alloying was performed using additions of Co and Fe to monolithic Pd40Ni40P20 bulk metallic glass to study selectively the influence on the plastic behavior in uniaxial compression and three-point bending tests. The corresponding Poisson's ratios were determined by ultrasonic measurements. The microstructure of the individual bulk metallic glasses was characterized by electron microscopy, X-ray diffraction and calorimetry. A plastic strain of 13% was found for the Co addition (1 at.%), whereas the Fe addition (0.6 at.%) led to immediate failure after reaching the elastic limit. Surprisin…
Metallic glasses are known to have a remarkably robust yield strength, admitting Weibull moduli as high as for crystalline engineering alloys. However, their post-yielding behavior is strongly varying, with large scatter in both flow stress levels and strains at failure. Using x-ray tomography we reveal for the first time how a strain-dependent internal evolution of shear-band cavities underlies this unpredictable post yielding response. We demonstrate how macroscopic strain-softening coincides with the first detection of internal shear-band cavitation. Cavity growth during plastic flow is fou…
The interaction of shear bands with crystalline nanoprecipitates in Cu-Zr-based metallic glasses is investigated by a combination of high-resolution TEM imaging and molecular-dynamics computer simulations. Our results reveal different interaction mechanisms: Shear bands can dissolve precipitates, can wrap around crystalline obstacles, or can be blocked depending on size and density of the precipitates. If the crystalline phase has a low yield strength, we also observe slip transfer through the precipitate. Based on the computational results and experimental findings, a qualitative mechanism ma…
Metallic glasses are excellent candidates for biomedical implant applications due to their inherent strength and corrosion resistance. Use of metallic glasses in structural applications is limited, however, because bulk dimensions are challenging to achieve. Glass-forming ability (GFA) varies strongly with alloy composition and becomes more difficult to predict as the number of chemical species in a system increases. Here we present a theoretical model - implemented in the AFLOW framework - for predicting GFA based on the competition between crystalline phases, and apply it to biologically rel…
Though extensively studied, hardness, defined as the resistance of a material to deformation, still remains a challenging issue for a formal theoretical description due to its inherent mechanical complexity. The widely applied Teter's empirical correlation between hardness and shear modulus has been considered to be not always valid for a large variety of materials. Here, inspired by the classical work on Pugh's modulus ratio, we develop a theoretical model which establishes a robust correlation between hardness and elasticity for a wide class of materials, including bulk metallic glasses, wit…
The icosahedral-like polyhedral fraction (ICO-like fraction) has been studied as a criterion for predicting the glass-forming ability of bulk ternary metallic glasses, Al90Sm8X2 (X = Al (binary), Cu, Ag, Au), using ab initio molecular dynamics (AIMD) simulations. We found that the ICO-like fraction can be determined with adequate precision to explore correlations with AIMD simulations. We then demonstrated that ICO-like fraction correlates with the critical cooling rate, which is a widely used intrinsic measure of glass forming ability. These results suggest that the ICO-like fraction from AIM…
By microalloying of Gd atoms with 4f electrons into CuZrAl or MgCuY glassy alloys, they display a variety of puzzling behaviors such as the characteristic of Kondo effect. The ground states of the Gd-alloyed systems are determined to have non-Fermi-liquid characteristics which derive from the strong structural disorder. The Kondo effect in these glassy alloys is attributed to the strong structural disorder. The coexistence of the Kondo effect and strong structural disorder has implications for the understanding the origin of the puzzling non-Fermi-liquid behavior.
A quinary (La0.5Ce0.5)65Al10(Co0.6Cu0.4)25 alloy with superior glass-forming ability (GFA), identified by the formation of fully glassy rod of 32 mm in diameter by tilt-pour casting, was reported. By comparing with the GFA of quarternary (La0.5Ce0.5)65Al10TM25 and ternary Ln65Al10TM25 alloys (Ln = La or Ce; TM = Co or Cu), we suggest that the strong frustration of crystallization by utilizing the coexistence of La-Ce and Co-Cu to complicate competing crystalline phases is helpful to construct BMG component with superior GFA.
Crystallization from an amorphous atomic structure is usually seen as a spontaneous process in pursuit of a lower energy state, but for alloy systems it is often hard to elucidate because of the intrinsic structural and compositional complexity. Here, by means of electron beam irradiation, we found surface-limited, and thus size-dependent crystallization in a system of monoatomic Pd metallic glass, which is ascribed to the structural differences between the surface and the interior. The equilibrium thickness of the surface crystallization is controllable, presenting a promising approach to fab…
Experimentally resolving atomic-scale structural changes of a deformed glass remains challenging owing to the disordered nature of glass structure. Here, we show that the structural anisotropy emerges as a general hallmark for different types of glasses (metallic glasses, oxide glass, amorphous selenium, and polymer glass) after thermo-mechanical deformation, and it is highly correlates with local nonaffine atomic displacements detected by the high-energy X-ray diffraction technique. By analyzing the anisotropic pair density function, we unveil the atomic-level mechanism responsible for the pl…
The process of crystal nucleation can be accelerated or retarded by ultrasonic vibration, which is particularly attractive for the addictive manufacture and thermoplastic forming of metallic glasses, however, the effect and mechanism of oscillatory loading on the nucleation process are still elusive. By using molecular dynamics simulation, the changes in the time-temperature-transformation (TTT) curve under oscillatory external loading are systematically investigated in two typical binary alloys. A glass forming ability dependent response to the external loading is found, and the shortest incu…
Investment in brighter sources and larger detectors has resulted in an explosive rise in the data collected at synchrotron facilities. Currently, human experts extract scientific information from these data, but they cannot keep pace with the rate of data collection. Here, we present three on-the-fly approaches - attribute extraction, nearest-neighbor distance, and cluster analysis - to quickly segment x-ray diffraction (XRD) data into groups with similar XRD profiles. An expert can then analyze representative spectra from each group in detail with much reduced time, but without loss of scient…
An empirical potential that has been widely used to perform molecular dynamics studies on the fracture behavior of FeP metallic glasses is shown to exhibit spinodal decomposition in the composition range commonly studied. The phosphorous segregation induces a transition from ductility to brittleness. During brittle fracture the atomically sharp crack tip propagates along a percolating path with higher P concentration. This embrittlement is observed to occur over a wide range of chemical compositions, and toughness decreases linearly with the degree of compositional segregation over the entire …
The atomistic mechanisms occurring during the processes of aging and rejuvenation in glassy materials involve very small structural rearrangements that are extremely difficult to capture experimentally. Here we use in-situ X-ray diffraction to investigate the structural rearrangements during annealing from 77 K up to the crystallization temperature in Cu44Zr44Al8Hf2Co2 bulk metallic glass rejuvenated by high pressure torsion performed at cryogenic temperatures and at room temperature. Using a measure of the configurational entropy calculated from the X-ray pair correlation function, the struct…
Primary crystallization in high Al-content metallic glasses is driven by nanometer-diameter regions with internal structure similar to fcc Al. Comparison of fluctuation electron microscopy (FEM) data to FEM simulations of fcc Al clusters dispersed in a dense-random packed matrix is used to extract the diameter and volume fraction of the ordered regions in a Al88Y7Fe5 base glass and in glasses with 1 at.% Cu substituted for Y or Al. The size and density of nanocrystals were measured as a function of isothermal annealing time for the same alloys. The volume fraction of crystalline material grows…
Using molecular dynamics simulations, we have studied the atomic correlations characterizing the second peak in the radial distribution function (RDF) of metallic glasses and liquids. The analysis was conducted from the perspective of different connection schemes of atomic packing motifs, based on the number of shared atoms between two linked coordination polyhedra. The results demonstrate that the cluster connections by face-sharing, specifically with three common atoms, are most favored when transitioning from the liquid to glassy state, and exhibit the stiffest elastic response during shear…
Nanocrystalline metals contain a large fraction of high-energy grain boundaries, which may be considered as glassy phases. Consequently, with decreasing grain size, a crossover in the deformation behaviour of nanocrystals to that of metallic glasses has been proposed. Here, we study this crossover using molecular dynamics simulations on bulk glasses, glass-crystal nanocomposites, and nanocrystals of Cu64Zr36 with varying crystalline volume fractions induced by long-time thermal annealing. We find that the grain boundary phase behaves like a metallic glass under constraint from the abutting cry…
The glass-formation range of bulk metallic glasses (BMGs) based on lanthanum and cerium was pinpointed in La-Al-Co, Ce-Al-Co and pseudo-ternary (La-Ce)-Al-Co system respectively by copper mold casting. Through the stepwise substitution of La for solvent Ce in (LaxCe1-x)65Al10Co25 alloys (0<x<1), the fully glassy rods of the (La0.7Ce0.3)65Al10Co25 alloy can be successfully produced up to 25 mm in diameter by tilt-pour casting. Comparing with the glass-forming ability (GFA) of single-lanthanide based alloys, La65Al10Co25 and Ce65Al10Co25, the coexistence of La and Ce with similar atomic size and…
A new amorphous alloy system $(TiZrNbCu)_{1-x}Co_x$ covering a broad composition range from the high-entropy (HEA) to Co rich alloys (x$\leqslant$ 0.43) has been fabricated, characterized and investigated. A comprehensive study of the chemical compositions, homogeneity, thermal stability, electronic structure and magnetic and mechanical properties has been performed. All properties change their variations with x within the HEA range. In particular, the average atomic volume deviates from the Vegard's law for x$\ge 0.2$, where also the average atomic packing fraction suddenly changes. The valen…
We study nonequilibrium roughening during compressive plastic flow of initially flat Cu$_{50}$Zr$_{50}$ metallic glass using large-scale molecular dynamics simulations. Roughness emerges at atomically flat interfaces beyond the yield point of the glass. A self-affine rough topography is imprinted at yield and is reinforced during subsequent deformation. The imprinted topographies have Hurst exponents that decrease with increasing strain-rate and temperature. After yield, the root-mean-square roughness amplitude grows as the square-root of the applied strain with a prefactor that also drops wit…
Recent studies (J. Alloys Compd. 695 (2017) 2661) of the electronic structure and properties of $(TiZrNbCu)_{1-x}$$Ni_{x}$ (x$\leq$0.25) amorphous high entropy alloys (a-HEA) have been extended to x=0.5 in order to compare behaviours of a-HEA and conventional Ni-base metallic glasses (MG). The amorphous state of all samples was verified by thermal analysis and X-ray diffraction (XRD). XRD indicated a probable change in local atomic arrangements, i.e. short-range-order (SRO) for x$\geq$0.35. Simultaneously, thermal parameters, such as the first crystallization temperature $T_{x}$ and the liquid…
Break-down of the relationship between α-relaxation and equilibration in hydrostatically compressed metallic glasses
Institut Néel, Université Grenoble Alpes and Centre National de la Recherche Scientifique（格勒诺布尔阿尔卑斯大学内尔研究所与法国国家科学研究中心）；Institut Lumière Matière UMR CNRS 5306, Université Claude Bernard Lyon 1, CNRS（里昂第一大学克劳德·贝尔纳物质光研究所（CNRS联合研究单位5306））；European Synchrotron Radiation Facility（欧洲同步辐射装置）；Chair of Metallic Materials, Saarland University（萨尔兰大学金属材料系）；Department of physics, Institute of Energy Technologies, Universitat Politècnica de Catalunya- BarcelonaTech（加泰罗尼亚理工大学能源技术学院物理系）；Donostia International Physics Center（圣塞巴斯蒂安国际物理中心）；Centro de Física de Materiales (CSIC–UPV/EHU)（材料物理中心（西班牙高等科研理事会-巴斯克国立大学））；Chair of Metallic Materials, Berlin Institute of Technology (TU-Berlin)（柏林工业大学金属材料系）；Laboratoire Magmas et Volcans CNRS, IRD, OPGC, Université Clermont Auvergne（克莱蒙奥弗涅大学火山与岩浆实验室（CNRS、IRD、OPGC联合实验室））
We studied solid solution effects on the mechanical properties of nanocrystalline (NC) $\mathrm{Pd}_{\mathrm{100-x}} \mathrm{Au}_{\mathrm{x}}$ alloys ($0 \leq \mathrm{x} < 50 \mathrm{at.\%}$) at the low end of the nanoscale. Concentration has been used as control parameter to tune material properties (elastic moduli, Burgers vector, stacking fault energies) at basically unaltered microstructure (grain size $D\approx 10\mathrm{ nm}$). In stark contrast to coarse grained fcc alloys, we observe solid solution softening for increasing Au-content. The available predictions from models and theories …
Thin-film based phase plates are meanwhile a widespread tool to enhance the contrast of weak-phase objects in transmission electron microscopy (TEM). The thin film usually consists of amorphous carbon, which suffers from quick degeneration under the intense electron-beam illumination. Recent investigations have focused on the search for alternative materials with an improved material stability. This work presents thin-film based phase plates fabricated from metallic glass alloys, which are characterized by a high electrical conductivity and an amorphous structure. Thin films of the zirconium-b…
Plastic flow in amorphous solids is known to be carried by localized shear transformations (STs) which have been proposed to preferentially initiate from some defect units in the structure, akin to dislocations and point defects in crystalline solids. Despite the central role of STs in the mechanical deformation of metallic glasses (MGs), our knowledge of their characteristics has so far been limited to hypothetical models, based on computer simulations using unreleastically high cooling rates. Using combined molecular dynamics (MD) and Monte Carlo (MC) simulations, here we have succeeded in s…
The origin of anomalous Hall effect (AHE) in ferromagnetic metallic glasses (MGs) is not yet understood completely. Here, the AHE is explored in Fe78Si9B13 MGs. We find the behavior of resistivity at low temperature seems to be more likely due to structure effect rather than Kondo-type effect. More importantly, we firstly find the primitive experiment anomalous Hall conductivity (σAH) without separation of extrinsic contribution has a linear magnetization (Mz) dependence when temperature is changing, which is another feature of intrinsic mechanism and indicates intrinsic contribution is domina…
