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.     

Molecular packing in highly stable glasses of vapor-deposited tris-naphthylbenzene isomers

Physical vapor deposition of organic molecules can produce glasses with high kinetic stability and low enthalpy. Previous experiments utilizing wide-angle x-ray scattering (WAXS) have shown that, relative to the ordinary glasses prepared by cooling the supercooled liquid, such glasses exhibit excess scattering characteristic of anisotropic packing. We have used vapor deposition to prepare glasses of four isomers of tris-naphthylbenzene (TNB), and measured both the WAXS patterns and the kinetic stability. While vapor-deposited glasses of all four TNB isomers exhibit high and nearly uniform kinetic stability, the level of excess scattering varies significantly. In addition, for α,α,β-TNB, glasses of essentially identical kinetic stability can have excess scattering levels that vary by a factor of two. These results indicate that anisotropic packing is not the source of kinetic stability in vapor-deposited glasses but rather a secondary feature that depends upon the chemical structure of the glass-forming molecules. We also show that the time required for these stable vapor-deposited glasses to transform into the supercooled liquid greatly exceeds the structural relaxation time τ(α) of the liquid and scales approximately as τ(α) (0.6). The kinetic stability of the vapor-deposited TNB glasses matches that expected for ordinary glasses that have been aged for 10(2) to 10(7) years.     

A molecular view of vapor deposited glasses

Recently, novel organic glassy materials that exhibit remarkable stability have been prepared by vapor deposition. The thermophysical properties of these new "stable" glasses are equivalent to those that common glasses would exhibit after aging over periods lasting thousands of years. The origin of such enhanced stability has been elusive; in the absence of detailed models, past studies have discussed the formation of new polyamorphs or that of nanocrystals to explain the observed behavior. In this work, an atomistic molecular model of trehalose, a disaccharide of glucose, is used to examine the properties of vapor-deposited stable glasses. Consistent with experiment, the model predicts the formation of stable glasses having a higher density, a lower enthalpy, and higher onset temperatures than those of the corresponding "ordinary" glass formed by quenching the bulk liquid. Simulations reveal that newly formed layers of the growing vapor-deposited film exhibit greater mobility than the remainder of the material, thereby enabling a reorganization of the film as it is grown. They also reveal that "stable" glasses exhibit a distinct layered structure in the direction normal to the substrate that is responsible for their unusual properties.     

Density and birefringence of a highly stable α,α,β-trisnaphthylbenzene glass

Spectroscopic ellipsometry has been used to understand the properties of α,α,β-trisnaphthylbenzene (ααβ-TNB) glasses vapor-deposited at a substrate temperature of 295 K (0.85 T(g)). In a single temperature ramping experiment, a range of properties of the as-deposited glass can be measured, including density, fictive temperature, onset temperature, thermal expansion coefficient, and birefringence. The vapor-deposited ααβ-TNB glass is 1.3% more dense than the ordinary glass prepared by cooling at 1 K/min, is found to be birefringent, has a fictive temperature 35 K below that of the ordinary glass, and an onset temperature 20 K above that of the ordinary glass. The thermal expansion coefficient of the vapor-deposited ααβ-TNB glass is 14% lower than that of the ordinary glass, indicating that lower portions of the potential energy landscape have more harmonic potential minima than the parts accessible to the ordinary glass.     

Origin of enhanced crystal growth kinetics near Tg probed with indomethacin polymorphs

Using three crystal polymorphs of indomethacin (IMC), we tested two interpretations of the enhanced crystal growth kinetics near the glass transition temperature Tg. This enhancement refers to the stronger temperature dependence of liquid viscosity eta than crystal growth rate (corrected for thermodynamic driving force). This enhancement is attributed in the first interpretation to an increase of the number of preferred interfacial growth sites with decreasing temperature and, in the second interpretation, to the breakdown of the Stokes-Einstein relation in deeply supercooled liquids. We measured the growth rates of the IMC polymorphs (alpha, gamma, and delta) from Tg + 9 K (Tg = 314 K) to near the respective melting points. From Tg + 19 K to Tg + 69 K, the growth rates of the polymorphs changed by 10(4) fold but displayed the same temperature dependence (eta-0.78) after corrections for thermodynamic driving forces. These results argue for a liquid-state origin of the enhanced growth kinetics. Below ca. Tg + 19 K, delta IMC continued to grow in the same spherulite morphology but alpha and gamma IMC grew in different, fiberlike morphologies and, if measured consistently, at faster rates. We conclude that the liquid dynamics of IMC controls its crystal growth kinetics over a wide range of temperatures but changes of growth morphologies near Tg also lead to apparent acceleration of growth of certain polymorphs. This work also extended a previous study of D-sorbitol to lower temperatures to enable a broader analysis of crystal growth kinetics of organic molecules near Tg.     

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.     

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.     

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.     

Stability of thin film glasses of toluene and ethylbenzene formed by vapor deposition: an in situ nanocalorimetric study

Vapor deposited thin films (~100 nm thickness) of toluene and ethylbenzene grown by physical vapor deposition show enhanced stability with respect to samples slowly cooled from the liquid at a rate of 5 K min(-1). The heat capacity is measured in situ immediately after growth from the vapor or after re-freezing from the supercooled liquid at various heating rates using quasi-adiabatic nanocalorimetry. Glasses obtained from the vapor have low enthalpies and large heat capacity overshoots that are shifted to high temperatures. The stability is maximized at growth temperatures in the vicinity of 0.8 T(g) for both molecules, although glasses of ethylbenzene show superior stabilization. Our data is consistent with previous results of larger organic molecules suggesting a generalized behavior on the stability of organic glasses grown from the vapor. In addition, we find that for the small molecules analyzed here, slowing the growth rate below 0.1 nm s(-1) does not result in increased thermodynamic stability.     

Structural instability of metallic glasses under radio-frequency-ultrasonic perturbation and its correlation with glass-to-crystal transition of less-stable metallic glasses

It has been reported that the structural stability is significantly deteriorated under radio-frequency-ultrasonic perturbation at relatively low temperatures, e.g., near/below the glass transition temperature T(g), even for thermally stable metallic glasses. Here, we consider an underlying mechanism of the ultrasound-induced instability, i.e., crystallization, of a glass structure to grasp the nature of the glass-to-liquid transition of metallic glasses. Mechanical spectroscopy analysis indicates that the instability is caused by atomic motions resonant with the dynamic ultrasonic-strain field, i.e., atomic jumps associated with the beta relaxation that is usually observed for low frequencies of the order of 1 Hz at temperatures far below T(g). Such atomic motions at temperatures lower than the so-called kinetic freezing temperature T(g) originate from relatively weakly bonded (and/or low-density) regions in a nanoscale inhomogeneous microstructure of glass, which can be straightforwardly inferred from a partially crystallized microstructure obtained by annealing of a Pd-based metallic glass just below T(g) under ultrasonic perturbation. According to this nanoscale inhomogeneity concept, we can reasonably understand an intriguing characteristic feature of less-stable metallic glasses (fabricated only by rapid melt quenching) that the crystallization precedes the glass transition upon standard heating but the glass transition is observable at extremely high rates. Namely, in such less-stable metallic glasses, atomic motions are considerably active at some local regions even below the kinetic freezing temperature. Thus, the glass-to-crystal transition of less-stable metallic glasses is, in part, explained with the present nanoscale inhomogeneity concept.     

Effect of physical aging on the Johari-Goldstein and alpha relaxations of D-sorbitol: a study by thermally stimulated depolarization currents

The relaxations in amorphous D-sorbitol have been studied by thermally stimulated depolarization currents during annealing at 255 K, which is 17 K below its calorimetric glass transition temperature Tg=272 K. As the glass structurally relaxes on aging, the features of the alpha relaxation and of the Johari-Goldstein (JG) relaxation change with time. For the alpha relaxation (i) the dielectric strength decreases; (ii) the activation energy decreases; and (iii) the relaxation time increases. For the JG relaxation the dielectric strength also decreases but with a different time dependence, and there is no evidence for any modification of the kinetic features of the mobility. The amplitude of response to aging is higher for the higher temperature motional components of the Johari-Goldstein relaxation compared with the lower temperature ones.     

Fragility and thermodynamics in nonpolymeric glass-forming liquids

For nonpolymeric supercooled liquids, the empirical correlation m = 56Tg DeltaCp(Tg)/DeltaHm provides a reliable means of correlating dynamic and thermodynamic variables. The dynamics are characterized by the fragility or steepness index m and the glass transition temperature Tg, while thermodynamics enter in terms of the heat capacity step DeltaCp at Tg and the melting enthalpy DeltaHm. The combination of the above correlation with the 23 rule for the Tg/Tm ratio yields an expression, m = 40DeltaCp(Tg)/DeltaSm, which was rationalized as the correlation of the thermodynamic and kinetic fragilities. Defining a thermodynamic fragility via DeltaCp(Tg)/DeltaSm also reveals that the slopes in Kauzmann's original DeltaS(T)/DeltaSm versus T/Tm plot reflect the fragility concept [Chem. Rev. 43, 219 (1948)], so long as Tm/Tg = 1.5. For the many liquids whose excess heat capacity is a hyperbolic function of temperature, we deduce that the fragility cannot exceed m = 170, unless the Tg/Tm = 2/3 rule breaks down.     

Dynamics of glass-forming liquids. XV. Dynamical features of molecular liquids that form ultra-stable glasses by vapor deposition

The dielectric relaxation behavior of ethylbenzene (EBZ) in its viscous regime is measured, and the glass transition temperature (T(g) = 116 K) as well as fragility (m = 98) are determined. While the T(g) of EBZ from this work is consistent with earlier results, the fragility is found much higher than what has been assumed previously. Literature data is supplemented by the present results on EBZ to compile the dynamic behavior of those glass formers that are known to form ultra-stable glasses by vapor deposition. These dynamics are contrasted with those of ethylcyclohexane, a glass former for which a comparable vapor deposition failed to produce an equally stable glassy state. In a graph that linearizes Vogel-Fulcher-Tammann behavior, i.e., the derivative of -logτ with respect to T/T(g) raised to the power of -1/2 versus T/T(g), all ultra-stable glass formers fall onto one master curve in a wide temperature range, while ethylcyclohexane deviates for T ? T(g). This result suggests that ultra-stable glass formers share common behavior regarding the dynamics of their supercooled liquid state if scaled to their respective T(g) values, and that fragility and related features are linked to the ability to form ultra-stable materials.     

Interfacial oxidation of ultrathin nickel and chromium films on yttria-stabilized zirconia

The substrate-induced oxidation upon prolonged annealing in UHV of ultrathin films of Ni and Cr vapor deposited on yttria-stabilized zirconia YSZ(100) was studied by X-ray photoelectron spectroscopy (XPS) to obtain information about the oxidation mechanism, determine the available quantity of reactive oxygen in YSZ, and investigate the thermal stability of the thin oxide films. Up to about 0.8 ML of Ni deposited at room temperature was oxidized to NiO at a constant rate at 650 K via the substrate, whereas at slightly higher coverage, the oxidation rate under identical conditions was drastically reduced. In contrast to Ni, up to 4.8 ML of Cr deposited at 275 K could be oxidized via the substrate to Cr2O3 upon extensive UHV annealing at increasing temperature up to 820 K, indicating a reactive oxygen content of at least 4 x 10(-6) with respect to the lattice oxygen in the YSZ specimen. The Cr2O3 decomposed to metallic Cr above about 800 K, whereas NiO was stable up to the maximum temperature of 875 K. These results indicate that the oxidation via the substrate is kinetically analogous to the gas-phase oxidation of bulk Ni and Cr. The reactive oxygen content of the single-crystal YSZ is larger than expected, and part of it is accommodated at the surface of the substrate. The thermal stability of the thin oxide films is determined by the oxygen exchange with YSZ and not by the respective bulk oxide thermodynamic decomposition temperature.     

Orientational and translational dynamics in room temperature ionic liquids

The authors investigate the dynamics of a series of room temperature ionic liquids, based on the same 1-butyl-3-methylimidazolium cation with different anions, by means of broadband (10(-6)-10(9) Hz) dielectric spectroscopy and depolarized light scattering in the temperature range from 400 K down to 35 K. Typical ionic conductivity is observed above the glass transition temperature Tg. Below Tg the authors detect relaxation processes that exhibit characteristics of secondary relaxations, as typically observed in molecular glasses. At high temperatures, the characteristic times of cation reorientation, deduced from the light scattering data, are approximately equal to the electric modulus relaxation times related to ionic conductivity. In the supercooled regime and close to Tg, the authors observe decoupling of conductivity from structural relaxation. Overall, room temperature ionic liquids exhibit typical glass transition dynamics, apparently unaltered by Coulomb interactions.     

Freezing-in and production of entropy in vitrification

Following the classical concepts developed by Simon [Z. Anorg. Allg. Chem. 203, 219 (1931)], vitrification in the cooling of glass-forming melts is commonly interpreted as the transformation of a thermodynamically (meta)stable equilibrium system into a frozen-in, thermodynamically nonequilibrium system, the glass. Hereby it is assumed that the transformation takes place at some well-defined sharp temperature, the glass transition temperature Tg. However, a more detailed experimental and theoretical analysis shows that the transition to a glass proceeds in a broader temperature range, where the characteristic times of change of temperature, tauT=-(TT), and relaxation times, tau, of the system to the respective equilibrium states are of similar order of magnitude. In this transition interval, the interplay of relaxation and change of external control parameters determines the value of the structural order parameters. In addition, irreversible processes take place in the transition interval, resulting both in an entropy freezing-in as well as in an irreversible increase of entropy and, as a result, in significant changes of all other thermodynamic parameters of the vitrifying systems. The effect of entropy production on glass transition and on the properties of glasses is analyzed here for the first time. In this analysis, the structural order-parameter concept as developed by de Donder and van Rysselberghe [Thermodynamic Theory of Affinity (Stanford University Press, Stanford, 1936)] and Prigogine and Defay [Chemical Thermodynamics (Longmans, London, 1954)] is employed. In the framework of this approach we obtain general expressions for the thermodynamic properties of vitrifying systems such as heat capacity, enthalpy, entropy, and Gibbs' free energy, and for the entropy production. As one of the general conclusions we show that entropy production has a single maximum upon cooling and two maxima upon heating in the glass transition interval. The theoretical concepts developed allow us to explain in addition to the thermodynamic parameters also specific features of the kinetic parameters of glass-forming melts such as the viscosity. Experimental results are presented which confirm the theoretical conclusions. Further experiments are suggested, allowing one to test several additional predictions of the theory.     

Thermodynamics,viscous flow and relaxation dynamics of bulk glass-forming Pd alloys

Experimental results concerning the thermodynamic excess properties and the equilibrium shear viscosity of the undercooled liquid state are presented, which were consistently obtained on Pd-rich bulk metallic glasses of different stability by applying the concept of the limiting fictive temperature. These results are evaluated with respect to the stability criteria that are controlling vitrification. In addition, modulated-temperature calorimetry has been performed to obtain the average relaxation time of the cooperative liquid modes near the glass transition directly in dependence of temperature. The results are compared to data obtained from static non-equilibrium measurements and discussed with respect to the relation between fragility and thermal stability of Pd-rich bulk glass-forming alloys.     

Formation and spectra of clathrate hydrates of methanol and methanol-ether mixtures

Infrared spectra of mixed clathrate hydrates, with either ethylene oxide (EO) or tetrahydrofuran (THF) and methanol molecules as the guest species, have been obtained from thin films prepared by vapor deposition of D₂O mixtures in the 115–130 K range. Although methanol acts as a suppressant to the direct vapor deposition of a type I clathrate with EO, nearly complete conversion of 115 K amorphous codeposits, to the crystalline mixed clathrate, occurs upon warming near 150 K. By contrast, the type II clathrate of THF shows an increased crystalline quality when methanol is included in the vapor deposits of the mixed clathrate hydrate at 130 K. The observation of the O---D stretch-mode band of weakly bonded CD₃OD near 2575 cm⁻¹ is part of the evidence that the methanol molecules are encaged. However, as shown theoretically by Tanaka, the clathrate hydrates of methanol, even when mixed with an ether help gas, are not stable structures but form at low temperatures because of kinetic factors, only to decompose in the 140–160 K range. Attempts to prepare a simple type I or type II clathrate hydrate of methanol have produced mixed results. Limited amounts of clathrate hydrate form during deposition but annealing does not result in complete conversion to crystalline clathrates, particularly for host : guest ratios of 17 : 1.     

基底界面效应对聚苯乙烯薄膜分子运动行为的影响

本文研究了Si／Si02、Si／Si—H基底与聚苯乙烯（Ps）之间的界面相互作用对Ps薄膜的玻璃化转变及相关力学性能的影响．结果显示,无论何种基底,Ps薄膜的玻璃化转变温度（L）都随其厚度降低而降低．但相同厚度（〈110nm）下,以Si／Si-H为基底时Ps薄膜的瓦比以Si／Si02为基底的PS薄膜高．Si／Si02表面Ps薄膜疋开始下降的临界厚度为110nm,远高于以Si／Si—H为基底时的40nm．对Ps薄膜的膨胀系数和弹性模量进行研究,也得到相似的临界厚度．另外,与Si／Si02基底相比,在Si／Si-H上的Ps薄膜具有更低的膨胀系数以及较高弹性模量．可能原因是Si／Si-H与Ps具有较强的相互作用,限制了该界面分子的运动能力,导致基底／PS界面效应对薄膜分子运动的影响力增强,造成该薄膜瓦的厚度依赖性下降,并呈现出相对较硬的力学特征．     

Effect of Substrate Temperature on the Epitaxial Growth of Oriented n-Alkane Thin Films on Graphite

A complex orientational morphology is observed when n-alkane thin films are vapor deposited on highly oriented pyrolytic graphite surfaces. Substrate temperature can be used to tune the orientation and morphology of n-alkane thin films. The molecular orientation changes from lateral to normal to the surface when the substrate temperature is raised sufficiently. Under specific substrate temperature conditions, the n-alkane molecules are aligned in the plane of the sample surface, in directions reflecting the 6-fold symmetry of the graphite substrate. A series of different morphologies, from uniform thin films to oriented bars, are observed as a function of chain length and substrate temperature. The systematic evolution of these oriented morphologies is mapped as a function of deposition conditions, and the kinetic and thermodynamic factors that govern the formation of different in-plane and normal domains are considered.