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  • 1
    Publication Date: 2016-06-29
    Description: Physical vapor deposition (PVD) has been used to prepare organic glasses with very high kinetic stability and it has been suggested that molecular anisotropy is a prerequisite for stable glass formation. Here we use PVD to prepare glasses of tetrachloromethane, a simple organic molecule with a nearly isotropic molecular structure. In situ AC nanocalorimetry was used to characterize the vapor-deposited glasses. Glasses of high kinetic stability were produced by deposition near 0.8 T g . The isothermal transformation of the vapor-deposited glasses into the supercooled liquid state gave further evidence that tetrachloromethane forms glasses with high kinetic stability, with the transformation time exceeding the structural relaxation time of the supercooled liquid by a factor of 10 3 . The glass transition temperature of liquid-cooled tetrachloromethane is determined as T g ≈ 78 K, which is different from previously reported values. The frequency dependence of the glass transition was also determined and the fragility was estimated as m ≈ 118. The successful formation of PVD glasses of tetrachloromethane which have high kinetic stability argues that molecular asymmetry is not a prerequisite for stable glass formation.
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 2
    Publication Date: 2015-02-05
    Description: Glasses of ethylcyclohexane produced by physical vapor deposition have been characterized by in situ alternating current chip nanocalorimetry. Consistent with previous work on other organic molecules, we observe that glasses of high kinetic stability are formed at substrate temperatures around 0.85 T g , where T g is the conventional glass transition temperature. Ethylcyclohexane is the least fragile organic glass-former for which stable glass formation has been established. The isothermal transformation of the vapor-deposited glasses into the supercooled liquid state was also measured. At seven substrate temperatures, the transformation time was measured for glasses prepared with deposition rates across a range of four orders of magnitude. At low substrate temperatures, the transformation time is strongly dependent upon deposition rate, while the dependence weakens as T g is approached from below. These data provide an estimate for the surface equilibration time required to maximize kinetic stability at each substrate temperature. This surface equilibration time is much smaller than the bulk α -relaxation time and within two orders of magnitude of the β -relaxation time of the ordinary glass. Kinetically stable glasses are formed even for substrate temperatures below the Vogel and the Kauzmann temperatures. Surprisingly, glasses formed in the limit of slow deposition at the lowest substrate temperatures are not as kinetically stable as those formed near 0.85 T g .
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 3
    Publication Date: 2015-10-06
    Description: We examine the behavior of lamellar phases of charged/neutral diblock copolymer thin films containing mobile ions in the presence of an external electric field. We employ self-consistent field theory and focus on the aligning effect of the electric field on the lamellae. Of particular interest are the effects of the mobile ions on the critical field, the value required to reorient the lamellae from the parallel configuration favored by the surface interaction to the perpendicular orientation favored by the field. We find that the critical field depends strongly on whether the neutral or charged species is favored by the substrates. In the case in which the neutral species is favored, the addition of charges decreases the critical electric field significantly. The effect is greater when the mobile ions are confined to the charged lamellae. In contrast, when the charged species is favored by the substrate, the addition of mobile ions stabilizes the parallel configuration and thus results in an increase in the critical electric field. The presence of ions in the system introduces a new mixed phase in addition to those reported previously.
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 4
    Publication Date: 2016-12-06
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 5
    Publication Date: 2015-09-01
    Description: The reversing heat capacity of vapor-deposited o -terphenyl glasses was determined by in situ alternating current nanocalorimetry. Glasses were deposited at substrate temperatures ranging from 0.39 T g to T g , where T g is the glass transition temperature. Glasses deposited near 0.85 T g exhibited very high kinetic stability; a 460 nm film required ∼10 4.8 times the structural relaxation time of the equilibrium supercooled liquid to transform into the liquid state. For the most stable o -terphenyl glasses, the heat capacity was lower than that of the ordinary liquid-cooled glass by (1 ± 0.4)%; this decrease represents half of the difference in heat capacity between the ordinary glass and crystal. Vapor-deposited o -terphenyl glasses exhibit greater kinetic stability than vapor-deposited glasses of indomethacin, in qualitative agreement with recent surface diffusion measurements indicating faster surface diffusion on o -terphenyl glasses. The stable glass to supercooled liquid transformation was thickness-dependent, consistent with transformation via a propagating front initiated at the free surface.
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    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 6
    Publication Date: 2015-12-31
    Description: AC chip nanocalorimetry is used to characterize vapor-deposited glasses of methyl- m -toluate (MMT). Physical vapor deposition can prepare MMT glasses that have lower heat capacity and significantly higher kinetic stability compared to liquid-cooled glasses. When heated, highly stable MMT glasses transform into the supercooled liquid via propagating fronts. We present the first quantitative analysis of the temporal and spatial uniformities of these transformation fronts. The front velocity varies by less than 4% over the duration of the transformation. For films 280 nm thick, the transformation rates at different spatial positions in the film differ by about 25%; this quantity may be related to spatially heterogeneous dynamics in the stable glass. Our characterization of the kinetic stability of MMT stable glasses extends previous dielectric experiments and is in excellent agreement with these results.
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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