Ultrastable glasses portray similar behaviour to ordinary glasses at high pressure.

Pressure experiments provide a unique opportunity to unravel new insights into glass-forming liquids by exploring its effect on the dynamics of viscous liquids and on the evolution of the glass transition temperature. Here we compare the pressure dependence of the onset of devitrification, Ton, between two molecular glasses prepared from the same material but with extremely different ambient-pressure kinetic and thermodynamic stabilities. Our data clearly reveal that, while both glasses exhibit different dTon/dP values at low pressures, they evolve towards closer calorimetric devitrification temperature and pressure dependence as pressure increases. We tentatively interpret these results from the different densities of the starting materials at room temperature and pressure. Our data shows that at the probed pressures, the relaxation time of the glass into the supercooled liquid is determined by temperature and pressure similarly to the behaviour of liquids, but using stability-dependent parameters.

Dielectric Investigation of Parylene D Thin Films: Relaxation and Conduction Mechanisms.

Parylene is a generic name indicating a family of polymers with the basic chemical structure of poly-p-xylylene. Parylene N and Parylene C are the most popular for applications. Curiously, Parylene D (poly( dichloro-p-xylylene), (C8H6Cl2)) was forgotten for applications. This report is the consequence of a later availability of a commercial dimer of Parylene D and also to the recent advent of fluorinated Parylenes allowing extending applications at higher temperatures. In our work, from a dielectric analysis, we present the potentialities of Parylene D for applications particularly interesting for integration in organic field-effect transistors. Dielectric and electrical properties, macromolecular structures, and dynamics interaction with electric field as a function of frequency and temperature are studied in 5.8 µm thick Parylene D grown by chemical vapor deposition. More exactly, the dielectric permittivity, the dissipation factor, the electrical conductivity, and the electric modulus of Parylene D were investigated in a wide temperature and frequency ranges from -140 to +350 °C and from 0.1 Hz to 1 MHz, respectively. According to the temperature dependence of the dielectric permittivity, Parylene D has two different dielectric responses. It is retained as a nonpolar material at very low temperature (like Parylene N) and as a polar material at high temperature (like parylene C). The dissipation factor shows the manifestation of two relaxations mechanisms: γ and ß at very low and high temperatures, respectively. The γ relaxation is assigned to the local motions of the C-H end of the chains when the cryogenic temperature range is approached. A broad peak in tan δ is assigned to the ß relaxation. It corresponds to rotational motion of some polar C-Cl groups. For temperature above 260 °C a mechanism of Maxwell-Wagner-Sillars polarization at the amorphous/crystalline interfaces was identified with two activation energies of Ea1 = 2.12 eV and Ea2 = 3.8 eV. Moreover, the conductivity and the dielectric permittivity relaxation processes have been discussed in terms of nearly constant loss (NCL) and universal dynamic regime (UDR). Finally, ionic conduction and electrode polarization effects are identified at very high temperatures and their physical origins are discussed.

Affinity and its derivatives in the glass transition process.

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)], by Möller et al. [J. Chem. Phys. 125, 094505 (2006)], and more recently by Tropin et al. [J. Non-Cryst. Solids 357, 1291 (2011); ibid. 357, 1303 (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.

Highly sensitive parylene membrane-based ac-calorimeter for small mass magnetic samples.

We report the microfabrication and operation of a highly sensitive ac-calorimeter designed to characterize small mass magnetic systems operating at very low frequencies (from 0.1 to 5 Hz) in a temperature range from 20 to 300 K. The calorimetric cell is built in the center of a 500 nm thick polymeric membrane of parylene C held up by a Cu frame. On both sides of the membrane defining a three layer structure, electrical leads, heater, and thermometer are deposited as thin film layers of NbN(x), with different nitrogen contents, taking benefit of the poor thermal conductance of niobium nitride to thermally isolate the system. This suspended structure ensures very low heat capacity addenda with values in the microJ/K over the 1 mm(2) area of the measurement cell. The structuring of the membrane along with suspending of the sensing part only by the parylene bridges leads to a highly reduced thermal link. The calorimeter has been characterized as a function of frequency, temperature, and magnetic field. The thermal link measured is really small reaching values well below 10(-8) W/K at 50 K. With these characteristics the frequency of adiabaticity is typically around few hertz and energy exchanges as small as 1 pJ can be detected. Measurements have been performed on Co/Au thin films and on the GdAl(2) microcrystal where the ferromagnetic phase transition is clearly evidenced.

Temperature of systems out of thermodynamic equilibrium.

Two phenomenological approaches are currently used in the study of the vitreous state. One is based on the concept of fictive temperature introduced by Tool [J. Res. Natl. Bur. Stand. 34, 199 (1945)] and recently revisited by Nieuwenhuizen [Phys. Rev. Lett. 80, 5580 (1998)]. The other is based on the thermodynamics of irreversible processes initiated by De Donder at the beginning of the last century [L'Affinite (Gauthier-Villars, Paris, 1927)] and recently used by Moller et al. for a thorough study of the glass transition [J. Chem. Phys. 125, 094505 (2006)]. This latter approach leads to the possibility of describing the glass transition by means of the freezing-in of one or more order parameters connected to the internal structural degrees of freedom involved in the vitrification process. In this paper, the equivalence of the two preceding approaches is demonstrated, not only for glasses but in a very general way for any system undergoing an irreversible transformation. This equivalence allows the definition of an effective temperature for all systems departed from equilibrium generating a positive amount of entropy. In fact, the initial fictive temperature concept of Tool leads to the generalization of the notion of temperature for systems out of thermodynamic equilibrium, for which glasses are just particular cases.