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.
Kearns
Kenneth L
KL
Department of Chemistry, University of Wisconsin--Madison, Madison, Wisconsin, 53706, USA.
Swallen
Stephen F
SF
Ediger
M D
MD
Wu
Tian
T
Sun
Ye
Y
Yu
Lian
L
D007700:Kinetics; D015394:Molecular Structure; D013696:Temperature; D013816:Thermodynamics; D014835:Volatilization; D014867:Water / Q000737:chemistry
D014867:Water