Predicting the Density-Scaling Exponent of a Glass-Forming Liquid from Prigogine-Defay Ratio Measurements

Gundermann, Ditte; Pedersen, Ulf R.; Hecksher, Tina; Bailey, Nicholas P.; Jakobsen, Bo; Christensen, Tage Emil; Olsen, Niels Boye; Schrøder, Thomas B.; Fragiadakis, D.; Casalini, R.

doi:10.21236/ada549977

Cited by 31 publications

(50 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The characteristic features of vitrification and structural recovery obtained under different conditions, particularly upon temperature or pressure perturbations, have been reproduced. The possibility to calculate jumps in C p , α p , or κ T at T g or p g following different simulated experimental protocols have practical applications and allows one to define and compute classical Prigogine-Defay ratio as well as linear PrigogineDefay ratio 44 or non-equilibrium Prigogine-Defay ratio. 15 While the model is able to reveal most of the principal characteristics of the glass transition, it describes also qualitatively some experimental behavior.…”

Section: Discussionmentioning

confidence: 99%

Affinity and its derivatives in the glass transition process

Garden

Guillou

Richard

et al. 2012

The Journal of Chemical Physics

View full text Add to dashboard Cite

The thermodynamic treatment of the glass transition remains an issue of intense debate. When associated with the formalism of non-equilibrium thermodynamics, the lattice-hole theory of liquids can provide new insight in this direction, as has been shown by Schmelzer and Gutzow [J. Chem. Phys. 125, 184511 (2006) (2011)]. Here, we employ a similar approach. We include pressure as an additional variable, in order to account for the freezing-in of structural degrees of freedom upon pressure increase. Second, we demonstrate that important terms concerning first order derivatives of the affinity-driving-force with respect to temperature and pressure have been previously neglected. We show that these are of crucial importance in the approach. Macroscopic non-equilibrium thermodynamics is used to enlighten these contributions in the derivation of C p ,κ T , and α p . The coefficients are calculated as a function of pressure and temperature following different theoretical protocols, revealing classical aspects of vitrification and structural recovery processes. Finally, we demonstrate that a simple minimalist model such as the lattice-hole theory of liquids, when being associated with rigorous use of macroscopic non-equilibrium thermodynamics, is able to account for the primary features of the glass transition phenomenology. Notwithstanding its simplicity and its limits, this approach can be used as a very pedagogical tool to provide a physical understanding on the underlying thermodynamics which governs the glass transition process.

show abstract

Section: Discussionmentioning

confidence: 99%

Affinity and its derivatives in the glass transition process

Garden

Guillou

Richard

et al. 2012

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…As stated, the designation "simple" refers to liquids exhibiting certain dynamic properties. DC704 is the only material for which this panoply of properties defining simple liquids has been demonstrated experimentally [33,41,42]. Theoretical models [35,36] and molecular dynamics simulations [37] both indicate materials that have these properties cannot be pressure densified.…”

mentioning

confidence: 99%

Pressure densification of a simple liquid

Casalini

Roland

2017

Journal of Non-Crystalline Solids

View full text Add to dashboard Cite

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.KEYWORDS: pressure densification, physical aging, glass formation, simple liquids _____________________________________________________ One of the curiosities regarding studies of the glass transition is the overriding focus on the properties of the liquid, rather than those of the glass. The main reasons for this are the equilibrium nature of the liquid state and the experimental inaccessibility of structural relaxation times, τ, below the glass transition temperature, Tg. These are, of course, the properties that define the glass transition -the material falls out of equilibrium as τα becomes very large. In response to this nonequilibrium structure, glass slowly reorganizes, a process known as physical aging [1,2,3,4,5,6]. Aging is an important technical aspect of glasses, affecting their stability and thus utility for many applications. A factor controlling the non-equilibrium structure is the condition of the liquid upon vitrification. For example, variation of the rate of cooling through Tg can be used to produce glasses with varying departures from equilibrium, and thus varying stability [7,8,9,10]. Another method, employed herein, is the application of pressure to the supercooled liquid. The glass transition is pressure-dependent, so that pressure affords a means to control the properties of the glass, including its physical aging behavior. Besides the material engineering value, understanding how the glass structure depends on the pressure during its formation is also important in discerning the principal control parameters and ultimately solving the "glass transition problem" [11,12,13,14,15,16,17].

show abstract

“…Strong correlation has also been experimentally verified for several van der Waals liquids [54][55][56] . RS liquids are characterized by having isomorphs in the phase diagram 35,38 .…”

Section: Roskilde-simple Liquidsmentioning

confidence: 73%

Effect of Energy Polydispersity on the Nature of Lennard-Jones Liquids

Ingebrigtsen

Tanaka

2016

J. Phys. Chem. B

View full text Add to dashboard Cite

In the companion paper [T. S. Ingebrigtsen and H. Tanaka, J. Phys. Chem. B 119, 11052 (2015)] the effect of size polydispersity on the nature of Lennard-Jones (LJ) liquids, which represent most molecular liquids without hydrogen bonds, was studied. More specifically, it was shown that even highly size polydisperse LJ liquids are Roskilde-simple (RS) liquids. RS liquids are liquids with strong correlation between constant volume equilibrium fluctuations of virial and potential energy and are simpler than other types of liquids. Moreover, it was shown that size polydisperse LJ liquids have isomorphs to a good approximation. Isomorphs are curves in the phase diagram of RS liquids along which structure, dynamics, and some thermodynamic quantities are invariant in dimensionless (reduced) units. In this paper, we study the effect of energy polydispersity on the nature of LJ liquids. We show that energy polydisperse LJ liquids are RS liquids. However, a tendency of particle segregation which increases with the degree of polydispersity leads to a loss of strong virial-potential energy correlation, but is mitigated with increasing temperature and/or density. Isomorphs are a good approximation also for energy polydisperse LJ liquids, although particle-resolved quantities display a somewhat poorer scaling compared to the mean quantities along the isomorph.

show abstract

Predicting the Density-Scaling Exponent of a Glass-Forming Liquid from Prigogine-Defay Ratio Measurements

Cited by 31 publications

References 41 publications

Affinity and its derivatives in the glass transition process

Affinity and its derivatives in the glass transition process

Pressure densification of a simple liquid

Effect of Energy Polydispersity on the Nature of Lennard-Jones Liquids

Contact Info

Product

Resources

About