The interplay between the structural relaxation and the rheological response of a binary LJ glass former is studied via MD simulations. In the quiescent state, the model is well known for its sluggish dynamics and a two step relaxation of correlation functions at low temperatures. An ideal glass transition temperature of $T_c = 0.435$ has been identified in the previous studies via the analysis of the system's dynamics in the frame work of the mode coupling theory of the glass transition [W. Kob and H.C. Andersen, PRE 51, 4626 (1995)]. Here, we test wether a signature of this ideal glass transition can also be found under shear. Indeed, the following distinction in the structural relaxation is found: In the supercooled state, the structural relaxation is dominated by the shear at relatively high shear rates, $\dotγ$, whereas at sufficiently low $\dotγ$ the (shear-independent) equilibrium relaxation is recovered. In contrast to this, the structural relaxation of a \emph{glass} is always driven by shear. This distinct behavior of the correlation functions is also reflected in the rheological response. In the supercooled state, the shear viscosity, $η$, decreases with increasing shear rate (shear thinning) at high shear rates, but then converges toward a constant as the $\dotγ$ is decreased below a (temperature-dependent) threshold value. Below $T_c$, on the other hand, the shear viscosity grows as $η\propto 1/\dotγ$ suggesting a divergence at $\dotγ =0$. Thus, within the accessible observation time window, a transition toward a non-ergodic state seems to occur in the driven glass as the driving force approaches zero.
We describe a numerical model to predict the rheology of two-dimensional dry foams. The model accurately describes soap film curvature, viscous friction with the walls, and includes the transport of surfactant within the films and across the vertices where films meet. It accommodates the changes in foam topology that occur when a foam flows and, in particular, accurately represents the relaxation of the foam following a topological change. The model is validated against experimental data, allowing the prediction of elastic and viscous parameters associated with different surfactant solutions.
Dynamic shear-modulus data are presented for the two silicone oils DC704 and DC705 for frequencies between 1 mHz and 10 kHz at temperatures covering more than five decades of relaxation-time variation. The data are fitted to the alpha part of a phenomenological model previously shown to describe well the dynamic shear modulus of squalane, which has a large beta process [Hecksher \textit{et al.}, J. Chem. Phys. \textbf{146}, 154504 (2017)]; that model is characterized by additivity of the alpha and beta shear compliance and by a high-frequency decay of the alpha process in proportion to $ω^{-1/…
The nature of yield in amorphous materials under stress has yet to be fully elucidated. In particular, understanding how microscopic rearrangement gives rise to macroscopic structural and rheological signatures in disordered systems is vital for the prediction and characterization of yield and for the study of how memory is stored in disordered materials. Here, we investigate the evolution of local structural homogeneity on an individual particle level in amorphous jammed two-dimensional systems under oscillatory shear, and relate this evolution to rearrangement, memory, and macroscale rheolog…
Using extensive numerical simulations, we investigate the flow behaviour of a model glass-forming binary mixture whose constituent particles have a large size ratio. The rheological response to applied shear is studied in the regime where the larger species are spatially predominant. We demonstrate that the macroscopic rigidity that emerges with increasing density occurs in the regime where the larger species undergo a glass transition while the smaller species continue to be highly diffusive. We analyse the interplay between the timescale imposed by the shear and the quiescent relaxation dyna…
We study the shear induced fluidization of amorphous solids subjected to external loading by investigating the relaxation dynamics of the deformed states using computer simulation. A simple shear deformation is employed at constant rate to the thermal glassy materials. The shear localization and the plastic deformation heterogeneity with strain is investigated in terms of the non-affine displacement field. The mean square displacement shows an enhanced mobility of the particles with strain, indicating the fluidization of the material. Using the time correlation function we estimate the relaxat…
Modeling the Dielectric Relaxation in Semicrystalline Polymers -- Understanding the Role of the Interphase between the Amorphous and Crystalline Domains
When stressed sufficiently, solid materials yield and deform plastically via reorganization of microscopic constituents. Indeed, it is possible to alter the micro-structure of materials by judicious application of stress, an empirical pro- cess utilized in practice to enhance the mechanical properties of metals. Un- derstanding the interdependence of plastic flow and microscopic structure in these non-equilibrium states, however, remains a major challenge. Here, we ex- perimentally investigate this relationship, between the relaxation dynamics and microscopic structure of disordered colloidal …
The molecular mobility of glass and supercooled liquid states of nilutamide has been studied with broadband dielectric spectroscopy for a wide range of temperature and frequency. Besides primary $α$-relaxation an excess wing like secondary relaxation is observed. The temperature dependence of structural $α$-relaxation show non-Arrhenius behaviour, and follows Vogel-Fulcher-Tammann (VFT) empirical formula. The glass transition temperature, T$_{g}$=302K and fragility index, m=76 are obtained from the VFT parameters. The structural $α$-relaxation process is non-Debye with Kohlraush-Williams-Watts…
We analyse the aging dynamics of the Hébraud-Lequeux model, a self-consistent stochastic model for the evolution of local stress in an amorphous material. We show that the model exhibits initial-condition dependent freezing: the stress diffusion constant decays with time as $D\sim 1/t^2$ during aging so that the cumulative amount of memory that can be erased, which is given by the time integral of $D(t)$, is finite. Accordingly the shear stress relaxation function, which we determine in the long-time regime, only decays to a plateau and becomes progressively elastic as the system ages. The fre…
In this work we discuss possible physical origins for non-trivial exponents in the athermal rheology of soft materials at low but finite driving rates. A key ingredient in our scenario is the presence of a self-consistent mechanical noise that stems from the spatial superposition of long-range elastic responses to localized plastically deforming regions. We study analytically a mean-field model, in which this mechanical noise is accounted for by a stress diffusion term coupled to the plastic activity. Within this description we show how a dependence of the shear modulus and/or the local relaxa…
We show that non-entangled polymers display an elastic-like behaviour at a macroscopic scale (probed at some 0.100 mm thickness) up to at least hundred degrees above the glass transition temperature. This observation, found under non-slippage conditions, both for side-chain liquid crystalline polymers and ordinary polymers, is in contradiction with the typically found flow behaviour of polymer melt. Our measurements were carried out with a conventional rheometer at thicknesses of several tenths millimetres. Thus, we were probing bulk properties. The observed elasticity supposedly implies that …
We propose a simple approach to investigate the structural relaxation time and glass transition of amorphous drugs. Amorphous materials are modeled as a set of equal sized hard spheres. The structural relaxation time over many decades in hard sphere fluids is theoretically calculated using the Elastically Collective Nonlinear Langevin Equation theory associated with Kramer's theory. Then, a new thermal mapping from a real material to an effective hard sphere fluid provides temperature-dependent relaxation time, which can compare to experiments. Numerical results quantitatively agree with previ…
Fractional calculus has been proved to be very effective in representing the visco-elastic relaxation response of materials with memory such as polymers. Moreover, in modelling the temperature dependency of the material functions in thermo-visco-elasticity, the standard time-temperature superposition principle is known to be ineffective in most of the cases (thermo-rehological complexity). In this work, a novel finite element formulation and numerical implementation is proposed for the simulation of transient thermal analysis in thermo-rehologically complex materials. The parameters of the vis…
The kinetics of dissolution of an amorphous solid is studied using a simple model of a glass that captures with reasonable accuracy the dynamic heterogeneities associated with the relaxation of an amorphous material at low temperatures. The intrinsic dissolution rate is shown to be proportional to the concentration of surface particles kinetically able to exchange with the solvent, independent of temperature or the thermal history of the glass. The morphology of the dissolving surface is described and the possibility of using surface etching to image dynamic heterogeneities is explored.
We employ an atomic-scale theory within the framework of nonaffine lattice dynamics to uncover the origin of the Johari-Goldstein (JG) $β$-relaxation in metallic glasses (MGs). Combining simulation and experimental data with our theoretical approach, we reveal that the large mass asymmetry between the elements in a La$_{60}$Ni$_{15}$Al$_{25}$ MG leads to a clear separation in the respective relaxation time scales, giving strong evidence that JG relaxation is controlled by the lightest atomic species present. Moreover, we show that only qualitative features of the vibrational density of states …
Stress Relaxation Driven by Elementary Plastic Events in Non-Ageing Liquid Foams
Lund University（隆德大学）；Université Grenoble Alpes（格勒诺布尔阿尔卑斯大学）；Paul Scherrer Institut（保罗谢尔研究所）；Université Côte d’Azur（蔚蓝海岸大学）；Technical University of Denmark（丹麦技术大学）；ENS de Lyon（里昂高等师范学校）；Institut Universitaire de France (IUF)（法国高等研究院）
The process of structural relaxation in disordered solids subjected to repeated tension-compression loading is studied using molecular dynamics simulations. The binary glass is prepared by rapid cooling well below the glass transition temperature and then periodically strained at constant volume. We find that the amorphous system is relocated to progressively lower potential energy states during hundreds of cycles, and the energy levels become deeper upon approaching critical strain amplitude from below. The decrease in potential energy is associated with collective nonaffine rearrangements of…
We combine an analytically solvable mean-field elasto-plastic model with molecular dynamics simulations of a generic glass-former to demonstrate that, depending on their preparation protocol, amorphous materials can yield in two qualitatively distinct ways. We show that well-annealed systems yield in a discontinuous brittle way, as metallic and molecular glasses do. Yielding corresponds in this case to a first-order nonequilibrium phase transition. As the degree of annealing decreases, the first-order character becomes weaker and the transition terminates in a second-order critical point in th…
Theoretical approaches are formulated to investigate the molecular mobility under various cooling rates of amorphous drugs. We describe the structural relaxation of a tagged molecule as a coupled process of cage-scale dynamics and collective molecular rearrangement beyond the first coordination shell. The coupling between local and non-local dynamics behaves distinctly in different substances. Theoretical calculations for the structural relaxation time, glass transition temperature, and dynamic fragility are carried out over twenty-two amorphous drugs and polymers. Numerical results have a qua…
The influence of cyclic loading and glass stability on structural relaxation and yielding transition in amorphous alloys was investigated using molecular dynamics simulations. We considered a binary mixture cooled deep into the glass phase and subjected to cyclic shear deformation where strain varies periodically but remains positive. We found that rapidly cooled glasses under asymmetric cyclic shear gradually evolve towards states with lower potential energy and finite stress at zero strain. At the strain amplitude just below a critical value, the rescaled distributions of nonaffine displacem…
Mixtures of polymers of varying topologies and stiffnesses display complex emergent rheological properties that often cannot be predicted from their single-component counterparts. For example, entangled blends of ring and linear polymers have been shown to exhibit enhanced shear thinning and viscosity, as well as prolonged relaxation timescales, compared to pure solutions of rings or linear chains. These emergent properties arise in part from the synergistic threading of rings by linear polymers. Topology has also been shown to play an important role in composites of flexible (e.g., DNA) and s…
The relaxation dynamics and thermodynamic properties of supercooled and glassy gambogic acid are investigated using both theory and experiment. We measure the temperature dependence of the relaxation times in three polymorphs (alpha-, beta-, and gamma-form). To gain insight into the relaxation processes, we propose a theoretical approach to quantitatively understand nature of these three relaxations. The alpha-relaxation captures cooperative motions of molecules while the beta-process is mainly governed by local dynamics of a single molecule within the cage formed by its nearest neighbors. Bas…
Elucidating the nature of the glass transition has been the holy grail of condensed matter physics and statistical mechanics for several decades. A phenomenological aspect that makes glass formation a conceptually formidable problem is that structural and dynamic correlations in glass-forming liquids are too subtle to be captured at the level of conventional two-point functions. As a consequence, a host of theoretical techniques, such as quenched amorphous configurations of particles, have been devised and employed in simulations and colloid experiments to gain insights into the mechanisms res…
Yield stress fluids display a rich rheological phenomenology. Beyond the defining existence of a yield stress in the steady state flow curve, this includes in many materials rather flat viscoelastic spectra over many decades of frequency in small amplitude oscillatory shear; slow stress relaxation following the sudden imposition of a small shear strain; stress overshoot in shear startup; logarithmic or sublinear power law creep following the imposition of a shear stress below the yield stress; creep followed by yielding after the imposition of a shear stress above the yield stress; richly feat…
We present results on a meso-scale model for amorphous matter in athermal, quasi-static (a-AQS), steady state shear flow. In particular, we perform a careful analysis of the scaling with the lateral system size, $L$, of: i) statistics of individual relaxation events in terms of stress relaxation, $S$, and individual event mean-squared displacement, $M$, and the subsequent load increments, $Δγ$, required to initiate the next event; ii) static properties of the system encoded by $x=σ_y-σ$, the distance of local stress values from threshold; and iii) long-time correlations and the emergence of di…
Recent theories predict that when a supercooled liquid approaches the glass transition, particle clusters with a special "amorphous order" nucleate within the liquid, which lead to static correlations dictating the dramatic slowdown of liquid relaxation. The prediction, however, has yet to be verified in 3D experiments. Here, we design a colloidal system, where particles are confined inside spherical cavities with an amorphous layer of particles pinned at the boundary. Using this novel system, we capture the amorphous-order particle clusters and demonstrate the development of a static correlat…
We study the linear response to strain in a mean field elastoplastic model for athermal amorphous solids, incorporating the power-law mechanical noise spectrum arising from plastic events. In the "jammed" regime of the model, where the plastic activity exhibits a non-trivial slow relaxation referred to as aging, we find that the stress relaxes incompletely to an age-dependent plateau, on a timescale which grows with material age. We determine the scaling behaviour of this aging linear response analytically, finding that key scaling exponents are universal and independent of the noise exponent …
For amorphous solids, it has been intensely debated whether the traditional view on solids, in terms of the ground state and harmonic low energy excitations on top of it, such as phonons, is still valid. Recent theoretical developments of amorphous solids revealed the possibility of unexpectedly complex free energy landscapes where the simple harmonic picture breaks down. Here we demonstrate that standard rheological techniques can be used as powerful tools to examine non-trivial consequences of such complex free energy landscapes. By extensive numerical simulations on a hard sphere glass unde…
We compute the rheological properties of inelastic hard spheres in steady shear flow for general shear rates and densities. Starting from the microscopic dynamics we generalise the Integration Through Transients (\textsc{itt}) formalism to a fluid of dissipative, randomly driven granular particles. The stress relaxation function is computed approximately within a mode-coupling theory---based on the physical picture, that relaxation of shear is dominated by slow structural relaxation, as the glass transition is approached. The transient build-up of stress in steady shear is thus traced back to …
We analyse the time dependent non-linear rheology of a dilute bacterial suspension (e.g. E. coli) for a pair of impulsively started linear flows - simple shear and uniaxial extension. The rheology is governed by the bacterium orientation distribution which satisfies a kinetic equation that includes rotation by the imposed flow, and relaxation to isotropy via rotary diffusion and tumbling. The relevant dimensionless parameters are the Peclet number $Pe\equiv \dotγτ$, which dictates the importance of flow-induced orientation anisotropy, and $τD_r$, which quantifies the relative importance of the…
