Molecular view of the isothermal transformation of a stable glass to a liquid

We have used neutron reflectivity to measure translational motion on the nanometer length scale in exceptionally stable glasses of tris(naphthylbenzene). These glasses are prepared by vapor deposition onto a substrate held somewhat below the glass transition temperature (T(g) = 342 K). When the most stable samples are annealed at 345 K, no translational motion is observed on the 12 nm length scale for over 10,000 s and full mixing requires more than 60,000 s. For comparison, the equilibrium supercooled liquid mixes in 1000 s at this temperature and on this length scale. These measurements provide insight into the mechanism by which a stable glass transforms into a liquid. "Melting" of the stable glass appears to occur by the growth of liquid regions into the surrounding glassy matrix, perhaps by a surface-initiated growth process. At 345 K, translational motion in the stable glass is at least 100 times slower than motion in the supercooled liquid.     

Isothermal desorption measurements of self-diffusion in supercooled o-terphenyl

Isothermal desorption of o-terphenyl thin-film bilayers was used to measure self-diffusion coefficients of supercooled o-terphenyl near the glass transition temperature (Tg=243 K). Diffusion coefficients from 10(-15.5) to 10(-12) cm2 s(-1) were obtained between 246 and 265 K. Protio and deuterio o-terphenyl were sequentially vapor deposited, then annealed to simultaneously diffuse and desorb the sample in a vacuum chamber. During the desorption of the bilayer, the concentration of each isotope was detected by a mass spectrometer, which revealed the extent of interfacial broadening. In these experiments, isotopic interdiffusion is indistinguishable from self-diffusion and the measured interfacial broadening is consistent with Fickian diffusion. The samples prepared under several different deposition conditions yielded the same self-diffusion coefficients, indicating that the experiments were conducted in the equilibrium supercooled liquid state.     

Neutron reflectivity measurements of the translational motion of tris(naphthylbenzene) at the glass transition temperature

The translational dynamics of the low molecular weight glass-former tris(naphthylbenzene) have been studied on the length scale of a few nanometers at the glass transition temperature Tg. Neutron reflectivity was used to measure isotopic interdiffusion of multilayer samples created by physical vapor deposition. Deposition with the substrate held at Tg-6 K allows observation of dynamics characterizing the equilibrium supercooled liquid. The diffusion coefficient measured at q = 0.03 A(-1) was determined to be 1x10(-17) cm2/s at 342 K (Tg). The self-part of the intermediate scattering function I(s)(q,t) decays exponentially. Samples deposited well below Tg show a substantial thermal history effect during subsequent translational motion at Tg.     

Self-diffusion of supercooled o-terphenyl near the glass transition temperature

Self-diffusion coefficients for the low molecular weight glass former o-terphenyl have been measured near Tg by isothermally desorbing thin film bilayers of deuterio and protio o-terphenyl in a vacuum chamber. We observe translational diffusion that is about 100 times faster at Tg + 3 K than the Stokes-Einstein prediction. Predictions from random first order transition theory and a dynamic facilitation approach are in reasonable agreement with our results; in these approaches, enhanced translational diffusion is associated with spatially heterogeneous dynamics. Self-diffusion controls crystallization in o-terphenyl for most of the supercooled liquid regime, but at temperatures below Tg + 10 K, the reported crystallization rate increases suddenly while the self-diffusion coefficient does not. This work and previous work on trisnaphthylbenzene both find a self-diffusion-controlled crystal growth regime and an enhancement in self-diffusion near Tg, suggesting that these phenomena are general characteristics of fragile low molecular weight glass formers. We discuss the width of the relaxation time distributions of o-terphenyl and trisnaphthylbenzene as they relate to the observation of enhanced translational diffusion.     

Temperature-ramping measurement of dye reorientation to probe molecular motion in polymer glasses

A temperature-ramping anisotropy measurement is introduced as an efficient way to study molecular motion in polymer glasses. For these experiments, fluorescent molecules were dispersed in the polymer glass and the reorientation of these dyes was used as a probe of segmental dynamics. For thick samples of polystyrene, poly (4-tert-butyl styrene), and poly(2-vinyl pyridine), temperature-ramping anisotropy measurements have a shape similar to differential scanning calorimetry measurements and nearly the same transition temperature. We present results using different fluorescent molecules and different temperature-ramping rates; such experiments show potential for accessing slow molecular motions considerably below T(g). Temperature-ramping anisotropy measurements were performed on freestanding poly (4-tert-butyl styrene) films of varying thicknesses. The anisotropy decay of a 22 nm film was shifted about 12 K lower in temperature as compared to a bulk sample.     

Hiking down the energy landscape: progress toward the Kauzmann temperature via vapor deposition

Physical vapor deposition was employed to prepare amorphous samples of indomethacin and 1,3,5-(tris)naphthylbenzene. By depositing onto substrates held somewhat below the glass transition temperature and varying the deposition rate from 15 to 0.2 nm/s, glasses with low enthalpies and exceptional kinetic stability were prepared. Glasses with fictive temperatures that are as much as 40 K lower than those prepared by cooling the liquid can be made by vapor deposition. As compared to an ordinary glass, the most stable vapor-deposited samples moved about 40% toward the bottom of the potential energy landscape for amorphous materials. These results support the hypothesis that enhanced surface mobility allows stable glass formation by vapor deposition. A comparison of the enthalpy content of vapor-deposited glasses with aged glasses was used to evaluate the difference between bulk and surface dynamics for indomethacin; the dynamics in the top few nanometers of the glass are about 7 orders of magnitude faster than those in the bulk at Tg - 20 K.     

Non-minimal and non-universal supersymmetry

I motivate and discuss non-minimal and non-universal models of supersymmetry and supergravity consistent with string unification at 10¹⁰ GeV.     

Direct measurement of molecular motion in freestanding polystyrene thin films

An optical photobleaching technique has been used to measure the reorientation of dilute probes in freestanding polystyrene films as thin as 14 nm. Temperature-ramping and isothermal anisotropy measurements reveal the existence of two subsets of probe molecules with different dynamics. While the slow subset shows bulk-like dynamics, the more mobile subset reorients within a few hundred seconds even at T(g,DSC) - 25 K (T(g,DSC) is the glass transition temperature of bulk polystyrene). At T(g,DSC) - 5 K, the mobility of these two subsets differs by 4 orders of magnitude. These data are interpreted as indicating the presence of a high-mobility layer at the film surface whose thickness is independent of polymer molecular weight and total film thickness. The thickness of the mobile surface layer increases with temperature and equals 7 nm at T(g,DSC).     

Self-diffusion of tris-naphthylbenzene near the glass transition temperature

We present a direct measurement of self-diffusion of a single-component glass-forming liquid at the glass transition temperature. Forward recoil spectrometry is used to measure the concentration profiles of deuterio and protio 1,3-bis-(1-naphthyl)-5-(2-naphthyl)benzene (TNB) following annealing-induced diffusion in a vapor-deposited bilayer. These experiments extend the range of measured diffusion coefficients in TNB by 6 orders of magnitude. The results indicate a decoupling of translational diffusion coefficients from viscosity or rotation. At T(g), D(T) is 400 times larger than expected from the Stokes-Einstein equation.     

Influence of substrate temperature on the stability of glasses prepared by vapor deposition

Physical vapor deposition of indomethacin (IMC) was used to prepare glasses with unusual thermodynamic and kinetic stability. By varying the substrate temperature during the deposition from 190 K to the glass transition temperature (Tg=315 K), it was determined that depositions near 0.85Tg (265 K) resulted in the most stable IMC glasses regardless of substrate. Differential scanning calorimetry of samples deposited at 265 K indicated that the enthalpy was 8 J/g less than the ordinary glass prepared by cooling the liquid, corresponding to a 20 K reduction in the fictive temperature. Deposition at 265 K also resulted in the greatest kinetic stability, as indicated by the highest onset temperature. The most stable vapor-deposited IMC glasses had thermodynamic stabilities equivalent to ordinary glasses aged at 295 K for 7 months. We attribute the creation of stable IMC glasses via vapor deposition to enhanced surface mobility. At substrate temperatures near 0.6Tg, this mobility is diminished or absent, resulting in low stability, vapor-deposited glasses.