The formation of crystals is paramount to the production of an
enormous variety of products we use every day. From things as simple as sugar
or salt to revolutionary technology involving crystalline metals and silicon,
the understanding of the processes of crystal growth has been a staple of
scientific progress. However, recent research indicates that nucleation – the process
initiating the growth of a crystal – may be much more complex than previously
imagined.
The classical model of crystal growth breaks the process
down into two major steps. First, ions or molecules come together into a tiny
crystalline seed, on whose structure the properties of the emerging crystal will
depend. From that point, other solvated ions fall into place, thereby expanding
the lattice and growing the crystal. As the crystal grows, the bulk free energy
of the mass decreases; yet at the same time, the solid-liquid interface
expands, increasing free energy. Nucleation is officially defined as the point
at which the crystal reaches the critical size threshold beyond which the
energy benefit of growth exceeds the cost.
However, this model is proving to be inadequate in the face
of mounting evidence. There seem to be a variety of different mechanisms from which
a crystal structure can emerge. For instance, research done in 2002 at MIT
involved inducing crystallization in glycine using laser pulses. By altering
the polarization of the incident laser, the group produced a variety of
different crystal polymorphs.
According to MIT Chemical Engineering professor Allan
S. Myerson, such a phenomenon indicated that the laser must have been acting on
some pre-existing structure that was somewhere in between an ordered crystal
and completely solvated molecules.
A more recent study in 2014 visually examined the
microscopic behavior of calcium carbonate as it formed crystals. Calcium
carbonate represented an interesting substance for such a study due to its
tendency to form a wide variety of crystal polymorphs, including calcite,
aragonite, and vaterite. While material often appeared to nucleate into any of
the three directly, sometimes the molecules would aggregate into unstructured
blobs which then transformed into aragonite or vaterite.
This sort of behavior
may be important beyond the formation of the initial crystal ‘seedling’, as it
is possible for actual crystal growth to depend on the formation of such
viscous blobs. Perhaps individual ions or molecules are incapable of adding to
the growing crystal in isolation, and need to first form groups to proceed.
The behavior of real systems appears to be extremely
diverse. In the words of James J. De Yoreo, who lead the calcium carbonate
study, “Think up any mechanism or pathway you want, and there will probably be
some system that behaves that way.”
Written by: Aisling M Williams
Sources
Kemsley, Jyllian. "Illuminating Crystal Nucleation." Chemical & Engineering News93.2 (2015): 28-29. CEN RSS. Chemical & Engineering News, 12 Jan. 2015. Web. 13 Jan. 2015.
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