arXiv subjects

R. Casalini

Publications and source records attributed to R. Casalini.

At least 19 recordsLinked to original sources

arXiv2019

Comment on "Experimental Evidence for a State-Point-Dependent Density-Scaling Exponent of Liquid Dynamics"

Recently Sanz et al. [A. Sanz, T. Hecksher, H.W. Hansen, J.C. Dyre, K. Niss, and U.R. Pedersen, Phys. Rev. Lett. 122, 055501 (2019).] reported that the scaling exponent gamma for tetramethyl-tetraphenyl-trisiloxane (DC704) varied with temperature; i.e., was not a material constant. Such a finding is at odds with previously published results on this compound and on more than 100 other liquids and polymers. The result of Sanz et al. comes from their measurement of a pressure dependence of the relaxation time at low temperature that becomes weaker with increasing pressure. Such a result is unphysical and contrary to the behavior of all known liquids. We re-measured this pressure dependence for DC704 and find it to be linear over the studied range. Thus, the conclusion of Sans et al. is incorrect; gamma for DC704 is state-point independent, in accord with other simple liquids and polymers.

cond-mat.soft↗

arXiv2017

Pressure densification of a simple liquid

The magnitude of the high frequency, static dielectric permittivity is used to determine the density of tetramethyl tetraphenyl trisiloxane, a non-associated glass-forming liquid, as a function of temperature and pressure. We demonstrate that the properties in the glassy state are affected by the pressure applied to the liquid during vitrification. This behavior is normal for hydrogen-bonded liquids and polymers, but unanticipated by models of simple liquids.

cond-mat.soft↗

arXiv2017

Effect of density on the physical aging of pressure-densified polymethylmethacrylate

The rate of physical aging of glassy polymethylmethacrylate (PMMA), followed from the change in the secondary relaxation with aging, is found to be independent of the density, the latter controlled by the pressure during glass formation. Thus, the aging behavior of the secondary relaxation is the same whether the glass is more compacted or less dense than the corresponding equilibrium liquid. This equivalence in aging of glasses formed under different pressures indicates that local packing is the dominant variable governing the glassy dynamics. One consequence is that pressure densification yields a reduction in the glass transition temperature. The fact that pressure densification yields different glass structures is at odds with a model for non-associated materials having dynamic properties exhibited by PMMA, such as density scaling of the relaxation time and isochronal superposition of the relaxation dispersion.

cond-mat.soft↗

arXiv2017

Short Time and Structural Dynamics in Polypropylene Glycol Nanocomposite

The dynamics of polypropylene glycol, both neat and attached to silica nanoparticles, were investigated using elastic neutron backscattering and dielectric spectroscopy. The mean square displacement measured by the former is suppressed by the particles at temperatures corresponding to a dielectric secondary relaxation (that involves only a portion of the repeat unit) and the segmental relaxation (glass transition). Despite the suppression of the displacements, the motions are faster in the nanocomposite, primarily due to poorer packing (lower density) at the particle interface. At very low temperatures we discovered a new dynamic process in the polymer. Reflecting its very local nature, this process is unaffected by attachment of the chains to the silica.

cond-mat.soft↗

arXiv2016

Density Scaling and Decoupling in o-Terphenyl, Salol, and Dibutyphthalate

We present new viscosity and equation of state (EoS) results extending to high pressures for o-terphenyl, salol, and dibutylphthalate. Using these and data from the literature, we show that the three liquids all conform to density scaling; that is, their reduce viscosities and reorientational relaxation times are a function of the ratio of temperature and density with the latter raised to a constant. Moreover, the functional form of the dependence on this ratio is independent of the experimental probe of the dynamics. This means that there is no decoupling of the viscosities and relaxation times over the measured range of conditions. Previous literature at odds with these results were based on erroneous extrapolations of the EoS or problematic diamond anvil viscosity data. Thus, there are no exceptions to the experimental fact that every non-associated liquid complies with density scaling with an invariant scaling exponent.

cond-mat.soft↗

arXiv2016

Local and global dynamics in polypropylene glycol / silica composites

The local segmental and global dynamics of a series of polypropylene glycol / silica nanocomposites were studied using rheometry and mechanical and dielectric spectroscopies. The particles cause substantial changes in the rheology, including higher viscosities that become non-Newtonian and the appearance of stress overshoots in the transient shear viscosity. However, no change was observed in the mean relaxation times for either the segmental or normal mode dynamics measured dielectrically. This absence of an effect of the particles is due to masking of the interfacial response by polymer chains remote from the particles. When the unattached polymer was extracted to isolate the interfacial material, very large reductions in the relaxation times were measured. This speeding up of the dynamics is due in part to the reduced density at the interface, presumably a consequence of poorer packing of tethered chains. In addition, binding of the ether oxygens of the polypropylene glycol chains truncates the normal mode, which shifts the corresponding relaxation peak to higher frequencies.

cond-mat.soft↗

arXiv2014

Dynamic Correlation Length Scales under Isochronal Conditions

The origin of the dramatic changes in the behavior of liquids as they approach their vitreous state - increases of many orders of magnitude in transport properties and dynamic time scales - is a major unsolved problem in condensed matter. These changes are accompanied by greater dynamic heterogeneity, which refers to both spatial variation and spatial correlation of molecular mobilities. The question is whether the changing dynamics is coupled to this heterogeneity; that is, does the latter cause the former? To address this we carried out the first nonlinear dielectric experiments at elevated hydrostatic pressures on two liquids, to measure the third-order harmonic component of their susceptibilities. We extract from this the number of dynamically correlated molecules for various state points, and find that the dynamic correlation volume for non-associated liquids depends primarily on the relaxation time, sensibly independent of temperature and pressure. We support this result by molecular dynamic simulations showing that the maximum in the four-point dynamic susceptibility of density fluctuations varies less than 10% for molecules that do not form hydrogen bonds. Our findings are consistent with dynamic heterogeneity serving as the principal control parameter for the slowing down of molecular motions in supercooled materials.

cond-mat.soft↗

arXiv2014

Determination of the Thermodynamic Scaling Exponent from Static, Ambient-Pressure Quantities

An equation is derived that expresses the thermodynamic scaling exponent, g, which superposes relaxation times and other measures of molecular mobility determined over a range of temperatures and densities, in terms of static, physical quantities. The latter are available in the literature or can be measured at ambient pressure. We show for 13 materials, both molecular liquids and polymers, that the calculated g are equivalent to the scaling exponents obtained directly by superpositioning. The assumptions of the analysis are that the glass transition is isochronal and that the first Ehrenfest relation is valid; the first assumption is true by definition, while the second has been corroborated for many glass-forming materials at ambient pressure. However, we find that the Ehrenfest relation breaks down at elevated pressure, although this limitation is of no consequence herein, since the appeal of the new equation is its applicability to ambient pressure data.

cond-mat.soft↗

arXiv2011

Comparing dynamic correlation lengths from an approximation to the four-point dynamic susceptibility and from the picosecond vibrational dynamics

Recently a new approach to the determination of dynamic correlation lengths, ξ, for supercooled liquids, based on the properties of the slow (picosecond) vibrational dynamics, was carried out [L. Hong, V.N. Novikov, and A.P. Sokolov, Phys. Rev. E 83, 061508 (2011)]. Although these vibrational measurements are typically conducted well below the glass transition temperature, Tg, the assumption is that the structure of the liquid is frozen at Tg, so that the ξ characterize dynamic heterogeneity in the supercooled liquid state. We compare ξ from this method to values calculated using an approximation to the four-point dynamic susceptibility. For 26 different materials we find good correlation between the two measures; moreover, the pressure dependences are consistent within the large experimental error. However, ξ from Boson peak measurements above Tg have a different, and unrealistic, temperature dependence.

cond-mat.soft↗

arXiv2009

Density Scaling and Dynamic Correlations in Viscous Liquids

We use a recently proposed method [Berthier L.; Biroli G.; Bouchaud J.P.; Cipelletti L.; El Masri D.; L'Hote D.; Ladieu F.; Pierno M. Science 2005, 310, 1797.] to obtain an approximation to the 4-point dynamic correlation function from derivatives of the linear dielectric response function. For four liquids over a range of pressures, we find that the number of dynamically correlated molecules, Nc, depends only on the magnitude of the relaxation time, independently of temperature and pressure. This result is consistent with the invariance of the shape of the relaxation dispersion at constant relaxation time and the density scaling property of the relaxation times, and implies that Nc also conforms to the same scaling behavior. For propylene carbonate and salol Nc becomes constant with approach to the Arrhenius regime, consistent with the value of unity expected for intermolecularly non-cooperative relaxation.

cond-mat.soft↗

arXiv2008

Anomalous properties of the local dynamics in polymer glasses

The emergence of nanoscience has increased the importance of experiments able to probe the very local structure of materials, especially for disordered and heterogeneous systems. This is technologically important; for example, the nanoscale structure of glassy polymers has a direct correlation with their macroscopic physical properties. We have discovered how a local, high frequency dynamic process can be used to monitor and even predict macroscopic behavior in glassy polymers. Polyvinylethylenes vitrified by different chemical and thermodynamic pathways exhibit different densities in the glassy state. We find that the rate and amplitude of a high frequency relaxation mode (the Johari-Goldstein process involving local motion of segments of the chain backbone) can either correlate or anti-correlate with the density. This implies that neither the unoccupied (free) volume nor the configurational entropy governs the local dynamics in any general sense. Rather it is the magnitude of the fluctuations in local density that underlie these nm-scale motions. We show how properties of the dynamics and the density fluctuations can both be interpreted in terms of an asymmetric double well potential. Finally, since fluctuations underlie the macroscopic properties, we argue that information about the latter should be obtainable from characterization of the local dynamics.

cond-mat.soft↗

arXiv2007

Relationship between non-exponentiality of relaxation and relaxation time at the glass transition

By analyzing the experimental data for various glass-forming liquids and polymers, we find that non-exponentiality $β$ and the relaxation time $τ$ are uniquely related: $\log(τ)$ is an approximately linear function of $1/β$, followed by a crossover to a higher linear slope. We rationalize the observed relationship using a recently developed approach, in which the problem of the glass transition is discussed as the elasticity problem.

cond-mat.dis-nn↗

arXiv2007

An equation for the description of volume and temperature dependences of the dynamics of supercooled liquids and polymer melts

A recently proposed expression to describe the temperature and volume dependences of the structural (or alpha) relaxation time is discussed. This equation satisfies the scaling law for the relaxation times, tau = f(TV^g), where T is temperature, V the specific volume, and g a material-dependent constant. The expression for the function f is shown to accurately fit experimental data for several glass-forming liquids and polymers over an extended range encompassing the dynamic crossover, providing a description of the dynamics with a minimal number of parameters. The results herein can be reconciled with previously found correlations of the isochoric fragility with both the isobaric fragility at atmospheric pressure and the scaling exponent g.

cond-mat.soft↗

arXiv2007

Effect of entropy on the dynamics of supercooled liquids: New results from high pressure data

We show that for arbitrary thermodynamic conditions, master curves of the entropy are obtained by expressing S(T,V) as a function of TV^g_G, where T is temperature, V specific volume, and g_G the thermodynamic Gruneisen parameter. A similar scaling is known for structural relaxation times,tau = f(TV^g); however, we find g_G < g. We show herein that this inequality reflects contributions to S(T,V) from processes, such as vibrations and secondary relaxations, that do not directly influence the supercooled dynamics. An approximate method is proposed to remove these contributions, S_0, yielding the relationship tau = f(S-S_0).

cond-mat.soft↗

arXiv2006

Thermodynamic interpretation of the scaling of the dynamics of supercooled liquids

The recently discovered scaling law for the relaxation times, tau=f(T,V^g), where T is temperature and V the specific volume, is derived by a revision of the entropy model of the glass transition dynamics originally proposed by Avramov [I. Avramov, J. Non-Cryst. Solids 262, 258 (2000).]. In this modification the entropy is calculated by an alternative route, while retaining the approximation that the heat capacity is constant with T and P. The resulting expression for the variation of the relaxation time with T and V is shown to accurately fit experimental data for several glass-forming liquids and polymers over an extended range encompassing the dynamic crossover. From this analysis, which is valid for any model in which the relaxation time is a function of the entropy. we find that the scaling exponent g can be identified with the Gruneisen constant.

cond-mat.soft↗

arXiv2006

Scaling of the Local Dynamics and the Intermolecular Potential

The experimental fact that relaxation times, tau, of supercooled liquids and polymers are uniquely defined by the quantity TV^g, where T is temperature, V specific volume, and g a material constant, leads to a number of interpretations and predictions concerning the dynamics of vitrification. Herein we examine means to determine the scaling exponent g apart from the usual superpositioning of relaxation data. If the intermolecular potential can be approximated by an inverse power law, as implied by the TV^g scaling, various equations are derived relating g to the Gruneisen parameter and to a common expression for the pressure derivative of the glass temperature. In addition, without assumptions, g can be obtained directly from pressure-volume-temperature data. These methods for determining g from molecular or thermodynamic properties are useful because they enable the P- and V-dependences of tau to be obtained, and thereby various analyses of the dynamics to be explored, without the need to carry out relaxation measurements beyond ambient pressure.

cond-mat.soft↗

arXiv2006

What can we learn by squeezing a liquid

Relaxation times for different temperatures, T, and specific volumes, V, collapse to a master curve versus TV^g, with g a material constant. The isochoric fragility, m_V, is also a material constant, inversely correlated with g. From these we obtain a 3-parameter function, which fits accurately relaxation times of several glass-formers over the supercooled regime, without any divergence below Tg. Although the 3 parameters depend on the material, only g significant varies; thus, by normalizing material-specific quantities related to g, a universal power law for the dynamics is obtained.

cond-mat.soft↗

arXiv2006

Volume Effects on the Glass Transition Dynamics

The role of jamming (steric constraints) and its relationship to the available volume is addressed by examining the effect that certain modifications of a glass-former have on the ratio of its isochoric and isobaric activation enthalpies. This ratio reflects the relative contribution of volume (density) and temperature (thermal energy) to the temperature-dependence of the relaxation times of liquids and polymers. We find that an increase in the available volume confers a stronger volume-dependence to the relaxation dynamics, a result at odds with free volume interpretations of the glass transition.

cond-mat.soft↗