Past exam of the materials science course of the University of Cambridge / 2017 / Paper 1 / 4

The close-packed planes of a cubic close-packed structure are $\{111\}$, with $ABCABC\dots$ stacking. Each layer is a triangular array; the third layer occupies the remaining set of hollows rather than returning above the first.

The basal close-packed planes of a hexagonal close-packed structure are $\{0001\}$ in four-index Miller-Bravais index, or $\{001\}$ with three hexagonal indices. Their stacking is $ABAB\dots$: alternate layers return above the same lateral positions.

At fixed transformed volume, an equilibrium solid-state precipitate seeks a low total free energy, including the orientation-dependent interfacial energy and elastic strain energy associated with misfit and applied stress. Low-energy interface orientations occupy large faces. The Wulff construction captures surface-energy anisotropy when strain and other contributions can be neglected; a solid-state precipitate generally also pays coherency strain energy, and its optimum shape can change with size.

During formation, growth kinetics and diffusion may prevent the equilibrium shape being reached. Coherent, semicoherent and incoherent interfaces have different bonding and defect structures, so their energies and attachment rates differ. The disc shape is consistent with much cheaper broad faces than edges, but morphology alone does not uniquely measure the energies or prove equilibrium.

Choose the orientation relation $(0001{)}_{\mathrm{hcp}}\parallel (111{)}_{\mathrm{ccp}}$ with aligned close-packed rows, for example $[11\bar{2}0{]}_{\mathrm{hcp}}\parallel [1\bar{1}0{]}_{\mathrm{ccp}}$. The two phases then share matching triangular layers at the broad faces. The stacking changes from $ABCABC\dots$ to $ABAB\dots$ across the phase region, so broad coherent crystal interfaces can be made by a local change of stacking, with small mismatch if the in-plane atomic spacings are similar.

At the cylindrical edge, different layer sequences terminate against one another. Registry cannot generally be maintained everywhere, so ledges, stacking defects and possibly misfit dislocations are needed; this interface is less coherent and often more costly. Thus a low-energy basal/$(111)$ face and a higher-energy edge favour a thin plate. An ideal same-element stacking change need not imply zero edge energy or exactly zero face energy.

The disc volume is $\pi d^{2}h/4$, the combined area of its two flat faces is $\pi d^2/2$, and its cylindrical edge area is $\pi dh$. With the signed bulk driving term $\Delta G$ per volume,For favourable transformation $\Delta G$ is negative and the interfacial terms are positive. This classical nucleation theory expression neglects a separate elastic term; if coherency strain is important, its appropriate energy must be added or included explicitly in the effective volume term. $W_n$ has energy units, whereas $\Delta G$ here has energy-per-volume units.

Along the stipulated fixed-aspect-ratio pathway, substitute $h=d/k$ before differentiating:The nonzero stationary diameter isComparison with the stated diameter gives $k{\gamma }_f+2{\gamma }_e=6{\gamma }_f+2{\gamma }_e$, hence $k=d/h=6$, provided ${\gamma }_f$ is nonzero. This is a plate-like shape, qualitatively consistent with the cheaper broad coherent faces. For negative $\Delta G$, substitution shows the stationary point is a maximum along this size pathway, as required for a nucleation barrier.

A useful distinction is that this calculation holds shape fixed. Minimizing the interface energy at fixed volume separately gives $d/h={\gamma }_e/{\gamma }_f$ for the cylindrical model; if the selected aspect ratio is also an equilibrium shape, it would require ${\gamma }_e=6{\gamma }_f$. The given critical-diameter relation alone does not otherwise determine that energy ratio. In the degenerate zero-face-energy limit the coefficient comparison cannot determine $k$.