Although it has long been recognized that dynamics in supercooled liquids might be spatially heterogeneous, only in the past few years has clear evidence emerged to support this view. As a liquid is cooled far below its melting point, dynamics in some regions of the sample can be orders of magnitude faster than dynamics in other regions only a few nanometers away. In this review, the experimental work that characterizes this heterogeneity is described. In particular, the following questions are addressed: How large are the heterogeneities? How long do they last? How much do dynamics vary between the fastest and slowest regions? Why do these heterogeneities arise? The answers to these questions influence practical applications of glass-forming materials, including polymers, metallic glasses, and pharmaceuticals.
Selected aspects of recent progress in the study of
supercooled liquids and glasses are presented in this
review.
As an introduction for nonspecialists, several basic features of
the dynamics and thermodynamics of supercooled
liquids and glasses are described. Among these are nonexponential
relaxation functions, non-Arrhenius
temperature dependences, and the Kauzmann temperature. Various
theoretical models which attempt to explain
these basic features are presented next. These models are
conveniently categorized according to the temperature
regimes deemed important by their authors. The major portion of
this review is given to a summary of
current experimental and computational research. The utility of
mode coupling theory is addressed. Evidence
is discussed for new relaxation mechanisms and new time and length
scales in supercooled liquids. Relaxations
in the glassy state and significance of the “boson peak” are also
addressed.
Vapor deposition has been used to create glassy materials with extraordinary thermodynamic and kinetic stability and high density. For glasses prepared from indomethacin or 1,3-bis-(1-naphthyl)-5-(2-naphthyl)benzene, stability is optimized when deposition occurs on substrates at a temperature of 50 K below the conventional glass transition temperature. We attribute the substantial improvement in thermodynamic and kinetic properties to enhanced mobility within a few nanometers of the glass surface during deposition. This technique provides an efficient means of producing glassy materials that are low on the energy landscape and could affect technologies such as amorphous pharmaceuticals.
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