Unusual Transformation of Mixed Isomer Decahydroisoquinoline Stable Glasses.

Dielectric relaxation was used to characterize the ability of vapor-deposited mixtures of cis- and trans-decahydroisoquinoline (DHIQ) to form glasses with a high kinetic stability. Vapor-deposited mixtures are technologically relevant, and the effect of mixing on glass stability is a relatively unexplored area. Mixed isomers and pure trans-DHIQ form highly stable glasses that isothermally transform in approximately 104 τα (where τα is the structural relaxation time of the supercooled liquid). Isomeric composition of the glasses does not play a significant role in the maximum kinetic stability of the resulting films. Secondary relaxations in DHIQ are associated with an intramolecular conformational change and are suppressed to a significant extent in highly stable glasses. During isothermal annealing experiments, stable glasses were found to transform initially via a growth front mechanism that transitions to a homogeneous bulk mechanism. Surprisingly, the time dependence of the bulk transformation is different from that reported for other stable glasses and cannot be interpreted in terms of a simple nucleation and growth model.

Physical vapor deposition of a polyamorphic system: Triphenyl phosphite.

In situ AC nanocalorimetry and dielectric spectroscopy were used to analyze films of vapor-deposited triphenyl phosphite. The goal of this work was to investigate the properties of vapor-deposited glasses of this known polyamorphic system and to determine which liquid is formed when the glass is heated. We find that triphenyl phosphite forms a kinetically stable glass when prepared at substrate temperatures of 0.75-0.95Tg, where Tg is the glass transition temperature. Regardless of the substrate temperature utilized during deposition of triphenyl phosphite, heating a vapor-deposited glass always forms the ordinary supercooled liquid (liquid 1). The identity of liquid 1 was confirmed by both the calorimetric signal and the shape and position of the dielectric spectra. For the purposes of comparison, the glacial phase of triphenyl phosphite (liquid 2) was prepared by the conventional method of annealing liquid 1. We speculate that these new results and previous work on vapor deposition of other polyamorphic systems can be explained by the free surface structure being similar to one polyamorph even in a temperature regime where the other polyamorph is more thermodynamically stable in the bulk.

Relationship between aged and vapor-deposited organic glasses: Secondary relaxations in methyl-m-toluate.

In situ interdigitated electrode broadband dielectric spectroscopy was used to characterize the excess wing relaxations in vapor-deposited and aged glasses of methyl-m-toluate (MMT, Tg = 170 K). MMT displays typical excess wing relaxations in dielectric spectra of its supercooled liquid and glasses. Physical vapor deposition produced glasses with degrees of suppression of the excess wing relaxation that varied systematically with deposition conditions, up to a maximum suppression of more than a factor of 3. The glass deposited at a relatively high temperature, 0.96 Tg (163 K), showed the same amount of suppression as that of a liquid-cooled glass aged to equilibrium at this temperature. The suppression of the excess wing relaxation was strongly correlated with the kinetic stability of the vapor-deposited glasses. Comparisons with aged MMT glasses allowed an estimate of the structural relaxation time of the vapor-deposited glasses. The dependence of the estimated structural relaxation times upon the substrate temperature was found to be stronger than Arrhenius but weaker than Vogel-Fulcher-Tammann dependence predicted from extrapolation of relaxation times in the supercooled liquid. Additionally, this work provides the first example of the separation of primary and secondary relaxations using physical vapor deposition.

Vapor-Deposited Ethylbenzene Glasses Approach "Ideal Glass" Density.

Spectroscopic ellipsometry was used to characterize vapor-deposited glasses of ethylbenzene (Tg = 115.7 K). For this system, previous calorimetric experiments have established that a transition to the ideal glass state is expected to occur near 101 K (the Kauzmann temperature, TK) if the low-temperature supercooled liquid has the properties expected based upon extrapolation from above Tg. Ethylbenzene glasses were vapor-deposited at substrate temperatures between 100 (∼0.86 Tg) and 116 K (∼Tg), using deposition rates of 0.02-2.1 nm/s. Down to 103 K, glasses prepared in the limit of low deposition rate have densities consistent with the extrapolated supercooled liquid. The highest density glass is within 0.15% of the density expected for the ideal glass. These results support the hypothesis that the extrapolated properties of supercooled ethylbenzene are correct to within just a few Kelvin of TK, consistent with the existence of a phase transition to an ideal glass state at TK.