No Arabic abstract
Aging amorphous polymeric materials undergo free volume relaxation, which causes slowing down of the relaxation dynamics as a function of time. The resulting time dependency poses difficulties in predicting their long time physical behavior. In this work, we apply effective time domain approach to the experimental data on aging amorphous polymers and demonstrate that it enables prediction of long time behavior over the extraordinary time scales. We demonstrate that, unlike the conventional methods, the proposed effective time domain approach can account for physical aging that occurs over the duration of the experiments. Furthermore, this procedure successfully describes time temperature superposition and time stress superposition. It can also allow incorporation of varying dependences of relaxation time on aging time as well as complicated but known deformation history in the same experiments. This work strongly suggests that the effective time domain approach can act as an important tool to analyze the long time physical behavior of aging amorphous polymeric materials. Aging amorphous polymeric materials undergo free volume relaxation, which causes slowing down of the relaxation dynamics as a function of time. The resulting time dependency poses difficulties in predicting their long time physical behavior. In this work, we apply effective time domain approach to the experimental data on aging amorphous polymers and demonstrate that it enables prediction of long time behavior over the extraordinary time scales. We demonstrate that, unlike the conventional methods, the proposed effective time domain approach can account for physical aging that occurs over the duration of the experiments. Furthermore, this procedure successfully describes time temperature superposition and time stress superposition.
Both structural glasses and disordered crystals are known to exhibit anomalous thermal, vibrational, and acoustic properties at low temperatures or low energies, what is still a matter of lively debate. To shed light on this issue, we studied the halomethane family C-Br_n-Cl_4-n (n = 0,1,2) at low temperature where, despite being perfectly translationally ordered stable monoclinic crystals, glassy dynamical features had been reported from experiments and molecular dynamics simulations. For n = 1,2 dynamic disorder originates by the random occupancy of the same lattice sites by either Cl or Br atoms, but not for the ideal reference case of CCl4. Measurements of the low-temperature specific heat (Cp) for all these materials are here reported, which provide evidence of the presence of a broad peak in Debye-reduced Cp/T^3 and in the reduced density of states g(w)/w^2 determined by means of neutron spectroscopy, as well as a linear term in Cp usually ascribed in glasses to two-level systems in addition to the cubic term expected for a fully ordered crystal. Being CCl4 a fully ordered crystal, we also performed density functional theory (DFT) calculations, which provide unprecedented detailed information about the microscopic nature of vibrations responsible for that broad peak, much alike the boson peak of glasses, finding it to essentially arise from a piling up (at around 3 - 4 meV) of low-energy optical modes together with acoustic modes near the Brillouin-zone limits.
Soft glassy materials are out of thermodynamic equilibrium and show time dependent slowing down of the relaxation dynamics. Under such situation these materials follow Boltzmann superposition principle only in the effective time domain, wherein time dependent relaxation processes are scaled by a constant relaxation time. In this work we extend effective time framework to successfully demonstrate time - temperature superposition of creep and stress relaxation data of a model soft glassy system comprised of clay suspension. Such superposition is possible when average relaxation time of the material changes with time and temperature without affecting shape of the spectrum. We show that variation in relaxation time as a function of temperature facilitates prediction of long and short time rheological behavior through time - temperature superposition from the experiments carried out over experimentally accessible timescales.
For a general class of conducting polymers with arbitrary large unit cell and different on-site Coulomb repulsion values on different type of sites, I demonstrate in exact terms the emergence possibility of an upper, interaction created effective flat band. This last appears as a consequence of a kinetic energy quench accompanied by a strong interaction energy decrease, and leads to a non-saturated ferromagnetic state. This ordered state clearly differs from the known flat-band ferromagnetism. This is because it emerges in a system without bare flat bands, requires inhomogeneous on-site Coulomb repulsions values, and possesses non-zero lower interaction limits at the emergence of the ordered phase.
A model is proposed that considers aging and rejuvenation in a soft glassy material as respectively a decrease and an increase in free energy. The aging term is weighted by inverse of characteristic relaxation time suggesting greater mobility of the constituents induce faster aging in a material. A dependence of relaxation time on free energy is proposed, which under quiescent conditions, leads to power law dependence of relaxation time on waiting time as observed experimentally. The model considers two cases namely, a constant modulus when aging is entropy controlled and a time dependent modulus. In the former and the latter cases the model has respectively two and three experimentally measurable parameters that are physically meaningful. Overall the model predicts how material undergoes aging and approaches rejuvenated state under application of deformation field. Particularly model proposes distinction between various kinds of rheological effects for different combinations of parameters. Interestingly, when relaxation time evolves stronger than linear, the model predicts various features observed in soft glassy materials such as thixotropic and constant yield stress, thixotropic shear banding, and presence of residual stress and strain.
Physical properties of out of equilibrium soft materials depend on time as well as deformation history. In this work we propose to transform this major shortcoming into gain by applying controlled deformation field to tailor the rheological properties. We take advantage of the fact that deformation field of a certain magnitude can prevent particles in an aging soft glassy material from occupying energy wells up to a certain depth, thereby populating only the deeper wells. We employ two soft glassy materials with dissimilar microstructures and demonstrate that increase in strength of deformation field while aging leads to narrowing of spectrum of relaxation times. We believe that, in principle, this philosophy can be universally applied to different kinds of glassy materials by changing nature and strength of impetus.