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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 â¼250 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.
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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.
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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.
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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.
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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.
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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.
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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.
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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}â¼2π/ΔQ, and the size of cooperatively rearranging regions.
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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)â¼136K. We demonstrate that this anomalous behavior can be explained well by quantum effects. These results have significant implications for our understanding of water dynamics.
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Temperatura Baixa , Hidrodinâmica , Água/química , Espectroscopia Dielétrica , Glicerol/química , Difração de Nêutrons , Temperatura de TransiçãoRESUMO
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
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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.
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Anastomose Cirúrgica , Neoplasias Esofágicas/complicações , Estenose Esofágica , Esofagoscopia , Stents , Adulto , Idoso , Idoso de 80 Anos ou mais , Anastomose Cirúrgica/efeitos adversos , Anastomose Cirúrgica/instrumentação , Anastomose Cirúrgica/métodos , Pesquisa Comparativa da Efetividade , Transtornos de Deglutição/etiologia , Transtornos de Deglutição/cirurgia , Estenose Esofágica/etiologia , Estenose Esofágica/fisiopatologia , Estenose Esofágica/cirurgia , Esofagoscopia/efeitos adversos , Esofagoscopia/instrumentação , Esofagoscopia/métodos , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Cuidados Paliativos/métodos , Índice de Gravidade de Doença , Resultado do TratamentoRESUMO
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.
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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).
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There are various arguments and models connecting the characteristic length associated with the boson peak vibrations ξ to the length scale of dynamical heterogeneity L(het). ξ is usually defined as the ratio of the transverse sound velocity to the boson peak frequency. Here we present pressure, temperature, and molecular weight dependencies of ξ, estimated using light scattering, in a few molecular and polymeric glass formers. These dependencies are compared with respective dependencies of the activation volume ΔV(#) in the same materials. Good agreement is found for the pressure and molecular weight dependencies of ξ and ΔV(#) measured at the glass transition temperature T(g). These results provide more evidence for a possible relationship between the sensitivity of structural relaxation to density (activation volume) and the heterogeneity volume. However, contrary to the expectations for L(het), ξ does not decrease with temperature above T(g) in most of the studied materials. The temperature dependence of ξ is compared to that of L(het) in glycerol and orthoterphenyl (OTP) estimated from literature data. The analysis shows a clear difference in the behavior of ξ(T) and ΔV(#)(T) at temperatures above T(g), although ΔV(#)(T)(1/3) and L(het)(T) have similar temperature dependence. Possible reasons for the observed difference are discussed.
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Vidro/química , Transição de Fase , Ligação de Hidrogênio , Peso Molecular , Polímeros/química , Pressão , Propilenoglicóis/química , TemperaturaRESUMO
We introduce a three-parameter step-response function which is based on a generalization of the Cole-Davidson (CD) and Kohlrausch (K) functions, and which provides a highly flexible susceptibility description for viscous liquids. A second parameter α characterizing the overall width, in addition to a parameter ß determining the high-frequency behavior of the susceptibility, allows for a continuous change of the spectral shape from the CD-type to the K-type. We prove that the function fulfills mathematical conditions required for a step-response function. When applying the function to interpolate dielectric spectra of neat (pure) glass formers, it is possible to keep the high-frequency parameter ß temperature-independent while varying the parameter α to account for the change of the overall width. This analysis might suggest that the failure of frequency-temperature superposition in glass formers is reflected by a broadening in the low-frequency region instead of in the high-frequency one.
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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.
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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.
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We utilize NMR field cycling relaxometry to study the crossover from glassy dynamics (t approximately > tau alpha) through Rouse to reptation behavior in a series of monodisperse polybutadienes with molecular weights M=355 to 817,000 g/mol. We separate characteristic polymer dynamics from the total spectrum dominated by glassy dynamics. The polymer dynamics show typical Rouse relaxation features that grow with M and saturate at high M. Comparing to Rouse theory, we determine the Rouse unit size MR approximately = 500 and entanglement weight Me approximately = 2000; the Rouse spectrum saturates at Mmax approximately = 4000. The local order parameter S approximately 0.11 is relatively large, indicating noticeable local packing already in the Rouse regime. The M dependence of the glass transition temperature Tg, obtained from dielectric relaxation spectra, shows distinctive kinks at MR and Me.
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Quasielastic neutron and light-scattering techniques along with molecular dynamics simulations were employed to study the influence of hydration on the internal dynamics of lysozyme. We identified three major relaxation processes that contribute to the observed dynamics in the picosecond to nanosecond time range: 1), fluctuations of methyl groups; 2), fast picosecond relaxation; and 3), a slow relaxation process. A low-temperature onset of anharmonicity at T approximately 100 K is ascribed to methyl-group dynamics that is not sensitive to hydration level. The increase of hydration level seems to first increase the fast relaxation process and then activate the slow relaxation process at h approximately 0.2. The quasielastic scattering intensity associated with the slow process increases sharply with an increase of hydration to above h approximately 0.2. Activation of the slow process is responsible for the dynamical transition at T approximately 200 K. The dependence of the slow process on hydration correlates with the hydration dependence of the enzymatic activity of lysozyme, whereas the dependence of the fast process seems to correlate with the hydration dependence of hydrogen exchange of lysozyme.