Temperature dependence of spatial nanoheterogeneities of shear modulus in supercooled glycerol.

The boson peak in the terahertz vibrational spectrum carries information about nano-heterogeneities in the shear modulus in glass formers. Its evolution upon heating or cooling in a supercooled liquid state may shed light on the temperature dependence of heterogeneities. For this purpose, an analysis of the light scattering spectra of supercooled glycerol in the spectral range of the boson peak and fast relaxation was carried out and the parameters of the boson peak in the temperature range 180-330 K were determined. The temperature dependent frequency of the boson peak was then expressed in terms of the mean-square amplitude of the shear modulus fluctuations. This was done using the heterogeneous elasticity theory in combination with the perturbation theory on small fluctuations and Ioffe-Regel criterion for transverse vibrations in glass formers. The contribution of structural relaxation effects to phonon damping becomes significant with increasing temperature. It is shown here that structural relaxation largely determines the temperature dependence of the mean-square fluctuations of the shear modulus at high temperatures. By solving the inverse problem, the temperature dependence of shear modulus fluctuations was obtained. It shows a rapid decrease above ∼250 K with a linear extrapolation going to zero at the so-called Arrhenius temperature TA = 350 K. Comparison with literature data on the Landau-Placzek ratio shows that they have a similar temperature dependence at T < TA, which is explained by the appearance of nanometer scale spatial heterogeneities below TA. This is confirmed by the temperature dependence of the amplitude of the boson peak.

Quantum effects in dynamics of water and other liquids of light molecules.

Nuclear quantum effects in atomic motions are well known at low temperatures [Formula: see text] K, but analyses of structural relaxation in liquids and description of the glass transition traditionally neglect quantum effects at higher temperatures, [Formula: see text] K. Recent studies, however, suggested that nuclear quantum effects in systems of light molecules (e.g., water) might play an important role in structural dynamics and provide non-negligible contributions at such temperatures, and even up to ambient temperature. In this article, we discuss experimental evidences of the quantum effects in glass transition in liquids of light molecules and possible theoretical descriptions of these effects. We show that quantum effects may qualitatively change the temperature behavior of the structural relaxation time in supercooled liquids leading to deviations of some well-established properties of the glass transition when it happens at low temperatures. We also demonstrate that unusual behavior of water dynamics at low temperatures, including apparent fragile-to-strong crossover, can be ascribed to nuclear quantum effects.

Role of quantum fluctuations in structural dynamics of liquids of light molecules.

A possible role of quantum effects, such as tunneling and zero-point energy, in the structural dynamics of supercooled liquids is studied by dielectric spectroscopy. The presented results demonstrate that the liquids, bulk 3-methyl pentane and confined normal and deuterated water, have low glass transition temperature and unusually low for their class of materials steepness of the temperature dependence of structural relaxation (fragility). Although we do not find any signs of tunneling in the structural relaxation of these liquids, their unusually low fragility can be well described by the influence of the quantum fluctuations. Confined water presents an especially interesting case in comparison to the earlier data on bulk low-density amorphous and vapor deposited water. Confined water exhibits a much weaker isotope effect than bulk water, although the effect is still significant. We show that it can be ascribed to the change of the energy barrier for relaxation due to a decrease in the zero-point energy upon D/H substitution. The observed difference in the behavior of confined and bulk water demonstrates high sensitivity of quantum effects to the barrier heights and structure of water. Moreover, these results demonstrate that extrapolation of confined water properties to the bulk water behavior is questionable.

Why many polymers are so fragile: A new perspective.

Many polymers exhibit much steeper temperature dependence of their structural relaxation time (higher fragility) than liquids of small molecules, and the mechanism of this unusually high fragility in polymers remains a puzzle. To reveal additional hints for understanding the underlying mechanism, we analyzed correlation of many properties of polymers to their fragility on example of model polymer polystyrene with various molecular weights (MWs). We demonstrate that these correlations work for short chains (oligomers), but fail progressively with increase in MW. Our surprising discovery is that the steepness of the temperature dependence (fragility) of the viscosity that is determined by chain relaxation follows the correlations at all molecular weights. These results suggest that the molecular level relaxation still follows the behavior usual for small molecules even in polymers, and its fragility (chain fragility) falls in the range usual for molecular liquids. It is the segmental relaxation that has this unusually high fragility. We speculate that many polymers cannot reach an ergodic state on the time scale of segmental dynamics due to chain connectivity and rigidity. This leads to sharper decrease in accessible configurational entropy upon cooling and results in steeper temperature dependence of segmental relaxation. The proposed scenario provides a new important insight into the specifics of polymer dynamics: the role of ergodicity time and length scale. At the end, we suggest that a similar scenario can be applicable also to other molecular systems with slow intra-molecular degrees of freedom and to chemically complex systems where the time scale of chemical fluctuations can be longer than the time scale of structural relaxation.

[Stenting of the oesophagus and oesophageal anastomoses in the case of neoplastic stenosis].

The authors aimed to optimize the strategy and technology of regeneration of oesophagus patency and oesophageal anastomosis in a case of tumor stenosis. Results of endoscopic correction of neoplastic stenosis of the oesophagus were studied in 244 patients, the cases of oesophagocolic anastomosis--in 12 patients and outcomes of oesophagogastric--in 8, respectively. A protection of self-expandable stents is an effective method of regeneration of enteral feeding in patients with manifested dysphagia, which is specified by the growth of malignant tumor of the oesophagus or oesophageal anastomosis. A possibility of formation of broncho-esophageal communications limits the usage of silicone tubular and steel self-expandable stents with partial coating of a funnel by special indications: a disposition of proximal border of tumor stenosis less than 3 cm from esophageal--pharyngeal passage--for the first; a necessity of fast recovery of oesophagus patency in rigid stenosis and an impossible single-stage dilatation of constriction zone--for the second. An optimal device for oesophagus and anastomosis protection is a fiber-nitinol self-expandable stent with coating. The stents with antireflux valve should be used in the case of oesophagogastric passage lesions.

Role of quantum effects in the glass transition.

It is shown that quantum effects lead to a significant decrease of the glass transition temperature T(g) with respect to the melting temperature T(m), so that the ratio T(g)/T(m) can be much smaller than the typical value of 2/3 in materials where T(g) is near or below ~60 K. Furthermore, it is demonstrated that the viscosity or structural relaxation time in such low temperature glass formers should exhibit highly unusual temperature dependence, namely a decrease of the apparent activation energy upon approaching T(g) (instead of traditional increase).

Coherent neutron scattering and collective dynamics on mesoscale.

By combining, and modestly extending, a variety of theoretical concepts for the dynamics of liquids in the supercooled regime, we formulate a simple analytic model for the temperature and wavevector dependent collective density fluctuation relaxation time that is measurable using coherent dynamic neutron scattering. Comparison with experiments on the ionic glass-forming liquid Ca-K-NO3 in the lightly supercooled regime suggests the model captures the key physics in both the local cage and mesoscopic regimes, including the unusual wavevector dependence of the collective structural relaxation time. The model is consistent with the idea that the decoupling between diffusion and viscosity is reflected in a different temperature dependence of the collective relaxation time at intermediate wavevectors and near the main (cage) peak of the static structure factor. More generally, our analysis provides support for the ideas that decoupling information and growing dynamic length scales can be at least qualitatively deduced by analyzing the collective relaxation time as a function of temperature and wavevector, and that there is a strong link between dynamic heterogeneity phenomena at the single and many particle level. Though very simple, the model can be applied to other systems, such as molecular liquids.

Upper bound of fragility from spatial fluctuations of shear modulus and boson peak in glasses.

It is shown that the normalized rms fluctuation of the shear modulus on the medium-range order scale in glasses correlates with fragility: the higher fragility, the smaller the fluctuation amplitude. The latter is calculated within the heterogeneous elasticity theory using the data on the boson peak in glasses. On a smaller scale corresponding to cooperative structural relaxation, the normalized rms fluctuation of the infinite-frequency shear modulus was estimated using the data on the decoupling of viscosity and diffusion in supercooled liquids. These fluctuations are much smaller in amplitude, and, in contrast, they increase with increasing fragility. Extrapolation predicts intersection of both rms fluctuations and disappearing of the boson peak at the upper limit to fragility ≈180.

Poisson's ratio and the fragility of glass-forming liquids.

The nature of the transformation by which a supercooled liquid 'freezes' to a glass--the glass transition--is a central issue in condensed matter physics but also affects many other fields, including biology. Substantial progress has been made in understanding this phenomenon over the past two decades, yet many key questions remain. In particular, the factors that control the temperature-dependent relaxation and viscous properties of the liquid phase as the glass transition is approached (that is, whether the glass-forming liquid is 'fragile' or 'strong') remain unclear. Here we show that the fragility of a glass-forming liquid is intimately linked to a very basic property of the corresponding glass phase: the relative strength of shear and bulk moduli, or Poisson's ratio.

Second-order-derivative analysis of structural relaxation time in the elastic model of glass-forming liquids.

Recently it was shown [V. N. Novikov and A. P. Sokolov, Phys. Rev. E 92, 062304 (2015)10.1103/PhysRevE.92.062304] that the second derivative with respect to inverse temperature of the structural relaxation time in some supercooled molecular liquids has a sharp maximum. It marks the point at which the apparent activation energy begins to saturate with decreasing temperature. The elastic model of glass-forming liquids expresses the temperature dependence of the structural relaxation time through that of the shear modulus. In this paper, we test whether this model is able to predict the maximum of the second derivative. We confirm its presence in the elastic model by analyzing the temperature dependence of the Brillouin light scattering in salol. This is a very subtle feature of the temperature dependence, which is greatly enhanced when taking derivatives. Its presence in the Brillouin data provides strong support to the elastic model of glass-forming liquids.

Molecular cooperativity in the dynamics of glass-forming systems: a new insight.

The mechanism behind the steep slowing down of molecular motions upon approaching the glass transition remains a great puzzle. Most of the theories relate this mechanism to the cooperativity in molecular motion. In this work, we estimate the length scale of molecular cooperativity xi for many glass-forming systems from the collective vibrations (the so-called boson peak). The obtained values agree well with the dynamic heterogeneity length scale estimated using four-dimensional NMR. We demonstrate that xi directly correlates to the dependence of the structural relaxation on volume. This dependence presents only one part of the mechanism of slowing down the structural relaxation. Our analysis reveals that another part, the purely thermal variation in the structural relaxation (at constant volume), does not have a direct correlation with molecular cooperativity. These results call for a conceptually new approach to the analysis of the mechanism of the glass transition and to the role of molecular cooperativity.

Influence of pressure on the boson peak: stronger than elastic medium transformation.

We study the changes in the low-frequency vibrational dynamics of poly(isobutylene) under pressure up to 1.4 GPa, corresponding to a density change of 20%. Combining inelastic neutron, x-ray, and Brillouin light scattering, we analyze the variations in the boson peak, transverse and longitudinal sound velocities, and the Debye level under pressure. We find that the boson peak variation under pressure cannot be explained by the elastic continuum transformation only. Surprisingly, the shape of the boson peak remains unchanged even at such high compression.

Influence of Chain Rigidity and Dielectric Constant on the Glass Transition Temperature in Polymerized Ionic Liquids.

Polymerized ionic liquids (PolyILs) are promising candidates for a wide range of technological applications due to their single ion conductivity and good mechanical properties. Tuning the glass transition temperature (Tg) in these materials constitutes a major strategy to improve room temperature conductivity while controlling their mechanical properties. In this work, we show experimental and simulation results demonstrating that in these materials Tg does not follow a universal scaling behavior with the volume of the structural units Vm (including monomer and counterion). Instead, Tg is significantly influenced by the chain flexibility and polymer dielectric constant. We propose a simplified empirical model that includes the electrostatic interactions and chain flexibility to describe Tg in PolyILs. Our model enables design of new functional PolyILs with the desired Tg.

Correlation between temperature variations of static and dynamic properties in glass-forming liquids.

Detailed analysis of the static structure factor S(Q) in several glass-forming liquids reveals that the temperature variations of the width of the main diffraction peak ΔQ(T) correlate with the fragility of these liquids. This observation suggests a direct connection between rather subtle structural changes and sharp slowing down of structural relaxation in glass-forming liquids. We show that this observation can be rationalized using the Adam-Gibbs approach, through a connection between temperature variations of structural correlation length, l_{c}∼2π/ΔQ, and the size of cooperatively rearranging regions.

Correlation of fragility of supercooled liquids with elastic properties of glasses.

We present a detailed analysis of correlations between fragility and other parameters of glass-forming systems. The analysis shows the importance of the ratio between the instantaneous bulk and shear modulus of glass-forming systems, or their Poisson ratio, for structural alpha relaxation and fast dynamics. In particular, for simple glass formers, the bulk to shear modulus ratio in the glassy state correlates with fragility in the liquid state and is inversely proportional to the intensity of the boson peak. A simple relationship between the temperature dependence of the viscosity of liquids at high temperatures and near the glass transition is used to rationalize these correlations. We argue that the ratio of the moduli controls the high-temperature activation energy of the structural relaxation and in this way affects the fragility. The ratio also defines the amplitude of the structural relaxation (i.e., the nonergodicity parameter) and the latter influences the strength of the boson peak. These observations might explain the puzzling correlation observed between the fragility and fast dynamics in glass-forming systems.

Qualitative change in structural dynamics of some glass-forming systems.

Analysis of the temperature dependence of the structural relaxation time τ(α)(T) in supercooled liquids revealed a qualitatively distinct feature-a sharp, cusplike maximum in the second derivative of logτ(α)(T)at some T(max). It suggests that the super-Arrhenius temperature dependence of τ(α)(T) in glass-forming liquids eventually crosses over to an Arrhenius behavior at T

Quantum effects in the dynamics of deeply supercooled water.

Despite its simple chemical structure, water remains one of the most puzzling liquids with many anomalies at low temperatures. Combining neutron scattering and dielectric relaxation spectroscopy, we show that quantum fluctuations are not negligible in deeply supercooled water. Our dielectric measurements reveal the anomalously weak temperature dependence of structural relaxation in vapor-deposited water close to the glass transition temperature T(g)∼136K. We demonstrate that this anomalous behavior can be explained well by quantum effects. These results have significant implications for our understanding of water dynamics.

Universality of the dynamic crossover in glass-forming liquids: a "magic" relaxation time.

Analysis of experimental data on the structural relaxation time tau(alpha) in various glass formers revealed its universality at the critical temperature T(c) of the mode-coupling theory. In most glass formers studied ln tau(alpha)(T(c))=-(6.5-7.5). Possible reasons for such a universality are discussed.

Growing correlation length on cooling below the onset of caging in a simulated glass-forming liquid.

We present a calculation of a fourth-order, time-dependent density correlation function that measures higher-order spatiotemporal correlations of the density of a liquid. From molecular dynamics simulations of a glass-forming Lennard-Jones liquid, we find that the characteristic length scale of this function has a maximum as a function of time which increases steadily beyond the characteristic length of the static pair correlation function g(r) in the temperature range approaching the mode coupling temperature from above. This length scale provides a measure of the spatially heterogeneous nature of the dynamics of the liquid in the alpha-relaxation regime.