Comment on "Pressure dependence of fragile-to-strong transition and a possible second critical point in supercooled confined water".
Explore the source record for details and available documents.
Comment↗
Biomedical subjects
Juan Colmenero
Publications and source records attributed to Juan Colmenero.
Relaxation scenarios in a mixture of large and small spheres: dependence on the size disparity.
We present a computational investigation on the slow dynamics of a mixture of large and small soft spheres. By varying the size disparity at a moderate fixed composition different relaxation scenarios are observed for the small particles. For small disparity density-density correlators exhibit moderate stretching. Only small quantitative differences are observed between dynamic features for large and small particles. On the contrary, large disparity induces a clear time scale separation between the large and small particles. Density-density correlators for the small particles become extremely stretched and display logarithmic relaxation by properly tuning the temperature or the wave vector. Self-correlators decay much faster than density-density correlators. For very large size disparity, a complete separation between self- and collective dynamics is observed for the small particles. Self-correlators decay to zero at temperatures where density-density correlations are frozen. The dynamic picture obtained by varying the size disparity resembles features associated with mode coupling transition lines of the types B and A at, respectively, small and very large size disparities. Both lines might merge, at some intermediate disparity, at a higher-order point, to which logarithmic relaxation would be associated. This picture resembles predictions of a recent mode coupling theory for fluids confined in matrices with interconnected voids [V. Krakoviack, Phys. Rev. Lett. 94, 065703 (2005)].
Journal Article↗
Plasticizer effect on the dynamics of polyvinylchloride studied by dielectric spectroscopy and quasielastic neutron scattering.
We have studied the influence of plasticization on the microscopic dynamics of a glass-forming polymer. For this purpose we studied polyvinylchloride (PVC) with and without the commercially used plasticizer dioctylphthalate (DOP). We used dielectric spectroscopy and inelastic neutron scattering employing the neutron spin echo (NSE) technique. For both kinds of spectra the alpha relaxation could be consistently described by a model involving a distribution of individual relaxations of the Kohlrausch type. In contrast to earlier studies it turned out that an asymmetric distribution is necessary to fit the data at the lower temperatures investigated here. The shape parameters of the distribution (width, skewness) for PVC and PVC/DOP turned out to coincide when the characteristic relaxation times were the same. This means that the plasticizer only induces a remapping of the temperature dependence of the alpha relaxation. Comparison of NSE spectra S(Q,t)S(Q) at different scattering vectors Q gave the result that the slowing down at the structure factor peak Q(max) is surprisingly small for PVC while it is in the normal range for PVC/DOP.
Journal Article↗
Anomalous dynamic arrest in a mixture of large and small particles.
We present molecular dynamics simulations of the slow dynamics of a mixture of large and small soft spheres with a large size disparity. The dynamics are investigated in a broad range of temperature and mixture composition. As a consequence of the large size disparity, large and small particles exhibit very different relaxation times. As previously reported for simple models of short-ranged attractive colloids and polymer blends, several anomalous dynamic features are observed: (i) sublinear behavior for mean-squared displacements, (ii) concave-to-convex crossover for density-density correlators, by varying the temperature or wave vector, and (iii) logarithmic decay for specific wave vectors of density-density correlators. These anomalous features are observed over time intervals extending up to four decades and strongly resemble predictions of the mode coupling theory (MCT) for state points close to higher-order MCT transitions, which originate from the competition between different mechanisms for dynamic arrest. For the large particles we suggest competition between soft-sphere repulsion and depletion effects induced by neighboring small particles. For the small particles we suggest competition between bulklike dynamics and confinement, respectively induced by neighboring small particles and by the slow matrix of large particles.
Journal Article↗
Logarithmic relaxation in a kinetically constrained model.
We present Monte Carlo simulations on a coarse-grained model for relaxation in binary mixtures. The liquid structure is substituted by a three-dimensional array of cells. A spin variable is assigned to each cell, with values 0 or 1 denoting, respectively, unexcited and excited local states in a mobility field. Change in local mobility (spin flip) is permitted according to kinetic constraints determined by the mobilities of neighboring cells. We introduce two types of cells ("fast" and "slow") with very different rates for spin flip. Fast cells display anomalous relaxation, characterized by a concave-to-convex crossover in dynamic correlators by changing temperature or composition. At intermediate state points logarithmic relaxation is observed over three time decades. These results display striking analogies with dynamic correlators reported in recent simulations on polymer blends.
Journal Article↗
Is there a higher-order mode coupling transition in polymer blends?
We present simulations on a binary blend of bead-spring polymer chains. The introduction of monomer size disparity yields very different relaxation times for each component of the blend. Competition between two different arrest mechanisms, namely, bulklike dynamics and confinement, leads to an anomalous relaxation scenario for the fast component, characterized by sublinear time dependence for mean squared displacements, or logarithmic decay and convex-to-concave crossover for density-density correlators. These anomalous dynamic features, which are observed over time intervals extending up to 4 decades, strongly resemble predictions of mode coupling theory for nearby higher-order transitions. Chain connectivity extends anomalous relaxation over a wide range of blend compositions.
Journal Article↗
Describing the component dynamics in miscible polymer blends: towards a fully predictive model.
We have recently proposed [D. Cangialosi et al., J. Chem. Phys. 123, 144908 (2005)] an extension of the Adam-Gibbs [J. Chem. Phys. 43, 139 (1965)] theory, combined with the concept of self-concentration, to describe the temperature dependence of the relaxation time for the component segmental dynamics in miscible polymer blends. Thus, we were able to obtain the dynamics of each component in the blend starting from the knowledge of the dynamic and thermodynamic data of the pure polymers, with a single fitting parameter (alpha) which had to be obtained from the fitting of the experimental data. In the present work we demonstrate that this model is also suitable to describe the polymer segmental dynamics in concentrated polymer solutions. From this result we have developed a new route for determining the value of the alpha parameter associated with any given polymer. Once this value is known for the two components of a possible polymer blend, our model for polymer blends dynamics becomes fully predictive.
Journal Article↗
Heterogeneous dynamics of poly(vinyl acetate) far above Tg: a combined study by dielectric spectroscopy and quasielastic neutron scattering.
We have investigated the dynamics of poly(vinly acetate) using broadband dielectric spectroscopy (DS) covering over 14 decades in frequency up to 20 GHz and high-resolution quasielastic neutron-scattering (QENS) technique. The dielectric results have been interpreted in terms of the phenomenological Kohlrausch-Williams-Watts [G. Williams and D. C. Watts, Trans. Faraday Soc. 66, 80 (1970); F. Alvarez, A. Alegria, and J. Colmenero, Phys. Rev. B 47, 125 (1993)] description. Because of the wide frequency range covered by DS, it provides a precise determination of dynamics over a wide temperature range and it revealed a crossover in polymer dynamics at 387 K through different dielectric parameters, viz., characteristic times, asymmetric shape parameter, and dielectric strength. Moreover, shape parameter is found to be higher in comparison to other typical polymeric systems. The characteristic relaxation times observed by QENS displayed an anomalous dependence of momentum transfer, indicating the possible existence of heterogeneities in the system even at the high temperatures. In addition, spin-lattice relaxation times, T(1), were found to be decoupled from dielectric characteristic times. Based on these results, a model was proposed to account for heterogeneities where we consider coexistence of different regions with standard polymeric behavior but with different characteristic times, leading to a distribution of relaxation times. The model is found to account for the anomalous behavior and an inherent shape parameter is found to account for the shape of alpha relaxation. This model is also found to predict the T variation of T(1) characteristic time scales at all temperatures. The origin of the heterogeneous domains is believed to lie in the microstructure of polymer chains.
Journal Article↗
Out of equilibrium dynamics of poly(vinyl methyl ether) segments in miscible poly(styrene)-poly(vinyl methyl ether) blends.
The local dynamics of the low-T(g) component in a polymer blend, dynamically asymmetric poly(styrene)-poly(vinyl methyl ether) (PS-PVME), is studied below the glass transition, via dielectric relaxation spectroscopy. A particular attention has been paid to blends with a high PS content (PS weight fraction higher than 50%). A relaxation process, slower than the localized motions inducing the PVME secondary relaxations, is detected. Even though these blends fall out of equilibrium in this temperature regime, the structural recovery process is not efficient on the time scale of this PVME motional process. This relaxation is attributed to rather localized, weakly cooperative PVME motions resulting from the topological constraints imposed by the frozen PS chains.
Journal Article↗