Are metastable, precrystallisation, density-fluctuations a universal phenomena?
In-situ observations of crystallisation in minerals and organic polymers have been made by simultaneous, time-resolved small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS) techniques. In isotactic polypropylene slow quiescent crystallisation shows the onset of large scale ordering prior to crystal growth. Rapid crystallisations studied by melt extrusion indicate the development of well resolved oriented SAXS patterns associated with long range order before the development of crystalline peaks in the WAXS region. Block copolymers self-assemble into mesophases in polymer melts above a critical chain length (or above a critical temperature) and this self-assembly process is shown to be susceptible to an incipient crystallisation. Mesophase formation is observed at anomalously high temperatures in ethylene-oxide containing block copolymers below the normal melting point of the polyoxy ethylene chains. Formation of calcium carbonate from aqueous solutions of sodium carbonate and calcium nitrate is observed to be a two-stage process and precipitation proceeds by the production of an amorphous metastable phase. This phase grows until it is volume filling and leads to the formation of the two polymorphs Calcite and Vaterite. These three sets of results suggest pre-nucleation density fluctuations, leading to a metastable phase, play an integral role in all three classes of crystallisation. In due course, this phase undergoes transformation to "normal" crystals.
Heeley
Ellen L
EL
Department of Chemistry, University of Sheffield, Sheffield, UK S3 7HF.
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