Pressure-volume-temperature relations of liquid, crystal, and glass of o-terphenyl: excess amorphous entropies, and factors determining molecular mobility

Naoki, Motosuke; Koeda, Susumu

doi:10.1021/j100339a078

Cited by 107 publications

(82 citation statements)

References 2 publications

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“…The glass transition temperature is around T g = 245 K close to the value reported in Ref. 30 for the same cooling protocol. The ratio of the glass transition temperature and the melting temperature is θ = T g /T m = 0.74 is slightly higher than the value of 2/3 of the Kauzmann-Beaman rule.…”

Section: Temperature Dependence Of ξsupporting

confidence: 87%

“…As an exemplary model system, we choose o-terphenyl for which p, V, T measurements, and melting data at different pressures, are available. 30 A relaxation time constant τ (p, T) depending on temperature as well as pressure, is also available from experimental data. 31 The characteristics of the melting process are recalled in the Table I.…”

Section: Extraction Of E 0 and Vmentioning

confidence: 99%

“…The various (T m , p m , ξ eq ) are known from experimental works 30 and from the basic equation of state (Eq. (4)).…”

Section: Extraction Of E 0 and Vmentioning

confidence: 99%

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Affinity and its derivatives in the glass transition process

Garden

Guillou

Richard

et al. 2012

The Journal of Chemical Physics

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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.

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Section: Temperature Dependence Of ξsupporting

confidence: 87%

Section: Extraction Of E 0 and Vmentioning

confidence: 99%

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Affinity and its derivatives in the glass transition process

Garden

Guillou

Richard

et al. 2012

The Journal of Chemical Physics

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“…[24]. Yet, these discrepancies occur in the pressure range where a polynomial approximation of the equation of state [27] (Figure 1d). We conclude that a scaling obtained from low temperature in van der Waals glassforming liquids can be extrapolated to higher temperature, and that light-scattering, dielectric, and viscosity data yield the same scaling, provided that a reliable equation of state is available.…”

Section: I-introductionmentioning

confidence: 96%

Scaling the $\alpha $ -relaxation time of supercooled fragile organic liquids

et al. 2004

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:It was shown recently [1] that the structural α-relaxation time τ of supercooled o-terphenyl depends on a single control parameter Γ, which is the product of a function of density E(ρ), by the inverse temperature T -1 . We extend this finding to other fragile glassforming liquids using light-scattering data. Available experimental results do not allow to discriminate between several analytical forms of the function E(ρ), the scaling arising from the separation of density and temperature in Γ. We also propose a simple form for τ(Γ), which depends only on three material-dependent parameters, reproducing relaxation times over 12 orders of magnitude. I-IntroductionThe steady increase over more than 12 orders of magnitude of the shear viscosity η, or of the structural α-relaxation time τ measured by dielectric or light-scattering spectroscopic methods, is among the spectacular features that accompany the liquid-glass transition [2]. The latter can take place in a large variety of liquids ranging from mineral oxides, salts, organic polymers, metallic alloys, to simple molecular liquids. Under cooling, these liquids avoid crystallisation at the melting temperature T m and become a glass at a lower temperature T g .For low molecular weight glassforming materials, a glass is usually defined as a liquid whose relaxation times τ are larger than 10 2 seconds, a phenomenon that takes place at some temperature T g . In spite of its frequent occurrence and of continuous theoretical and experimental efforts over the last fifty years, this transition remains one of the least understood phenomena in condensed matter physics. In particular, one still does not fully grasp how and on which parameters, usually called control parameters, these relaxation times τ depend [3,4]. Obviously, in simple glassforming colloids the only control parameter is the density. Conversely, would the structural relaxation of a liquid at equilibrium be only due to jumps over energy barriers that are independent from temperature and density, τ might have a simple Arrhenius behaviour and the only control parameter would be temperature. The Angell plot [2], which represents the logarithm of relaxation times τ (or viscosity η) as a function of orders of magnitude, they showed that the data can be scaled using control parameters of the same form as in OTP, n becoming material dependent. Previously, a scaling was shown to hold in glycerol by . Also ref. [24] showed that the domain of density explored in the experiments was too small to ascertain the analytical form of E(ρ Table 1. At each pressure and temperature, the corresponding density can be obtained from the Tait interpolation formula, whose form and parameters are also collected in Table 1. Table 2 as well as that obtained from unpublished PCS data on BMPC (1,1-bis(p-methoxyphenyl)cyclohexane ) [25]. We add also the n value obtained by the scaling of the dielectric α-relaxation time in KDE (cresolphtaleine-dimethyl ether) [26].The values of n vary from 3.8 to 7.5.We note that similar result...

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“…Using the earlier reported dielectric and PVT data for commonly known glass formers such as ortho-terphenyl (OTP) [37,38], phenylphthalein-dimethylether (PDE) [39,40], 1,1'-bis (pmethoxyphenyl) cyclohexane (BMPC) [10,41], propylene carbonate (PC) [42,43], salol [12,44], and glycerol [43,45], we compare the values of dT g /dp established from the dielectric data at ambient pressure to those determined from the Eq. (9) with the scaling exponent γ also found from dielectric data.…”

Section: The Pressur Coefficient -Its Formulation Experimental Tmentioning

confidence: 99%

Pressure coefficient of the glass transition temperature in the thermodynamic scaling regime

et al. 2012

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We report that the pressure coefficient of the glass transition temperature, dT g /dp, which is commonly used to determine the pressure sensitivity of the glass transition temperature, T g , can be predicted in the thermodynamic scaling regime. We show that the equation derived from the isochronal condition combined with the well-known scaling, TV γ =const, predicts successfully values of dT g /dp for variety of glass-forming systems, including van der Waals liquids, polymers, and ionic liquids.

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Pressure-volume-temperature relations of liquid, crystal, and glass of o-terphenyl: excess amorphous entropies, and factors determining molecular mobility

Cited by 107 publications

References 2 publications

Affinity and its derivatives in the glass transition process

Affinity and its derivatives in the glass transition process

Scaling the $\alpha $ -relaxation time of supercooled fragile organic liquids

Pressure coefficient of the glass transition temperature in the thermodynamic scaling regime

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