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Wulff construction

The Wulff construction is a method for determining the equilibrium shape of a droplet
or Crystal of fixed volume inside a separate phase (usually its saturated solution or
vapor.) Energy minimization arguments are used to show that certain crystal planes are
preferred over others, giving the crystal its shape.

In 1878 Josiah Willard Gibbs proposed[1] that a droplet or crystal will arrange itself such
that its Gibbs free energy is minimized by assuming a configuration of low Surface
energy. He defined the quantity

ΔGi = ∑ γjOj
j

where γj represents the surface energy per unit area of the jth crystal face, and Oj is the
area of said face. ΔGi represents the difference in energy between a real crystal composed
of i molecules with a surface, and a similar configuration of i molecules located inside an
infinitely large crystal. This quantity is therefore the energy associated with the surface.
The equilibrium shape of the crystal will then be that which minimizes the value of ΔGi

In 1901, Georg Wulff stated[2] -without proving- that the length of a vector drawn normal
to a crystal face hj will be proportional to its surface energy γj: hj = λγj. This is known as
the Gibbs-Wulff theorem.

In 1953 Conyers Herring gave a proof of the theorem and a method for determining the
equilibrium shape of a crystal, which consists of two main exercises. To begin, a polar
plot of surface energy as a function of orientation is made. This is known as the gamma
plot and is usually denoted as where denotes the surface normal, e.g. a particular
crystal face. The second part is the Wulff construction itself in which the gamma plot is
used to determine graphically which crystal faces will be present. It can be determined
graphically by drawing lines from the origin to every point on the gamma plot. A plane
perpendicular to the normal is drawn at each point where it intersects the gamma plot.
The inner envelope of these planes forms the equilibrium shape of the crystal.

Various proof of the theorem have been giving by Hilton, Liebman, von Laue[3],
Herring[4] and a rather extensive treatment by Cerf[5]. The following is after the method of
R. F. Strickland-Constable[6]. We begin with the surface energy for a crystal

which is the product of the surface energy per unit area times the area of each face,
summed over all faces, which is minimized for a given volume when
We then consider a small change in shape for a constant volume

which can be written as

the second term of which must be zero, as it represents the change in volume, and we
wish only to find the lowest surface energy at a constant volume (i.e. without adding or
removing material.) We are then given from above

and

which can be combined by a constant of proportionality as

The change in shape (δOj) must be allowed to be arbitrary, which then requires that hj =
λγj which then proves Gibbs-Wulff Theorem.