# Anisotropic Coarsening: Grain Shapes and Nonuniversal Persistence

## Abstract

We solve a coarsening system with small but arbitrary anisotropic surface tension and interface mobility. The resulting size-dependent growth shapes are significantly different from equilibrium microcrystallites, and have a distribution of grain sizes different from isotropic theories. As an application of our results, we show that the persistence decay exponent depends on anisotropy and hence is nonuniversal.

The geometrical Wulff construction  gives an explicit relation between the anisotropic surface tension and the resulting equilibrium crystal shape. This marks an early and dramatic success in quantitatively connecting morphology to the interfacial properties of a material. However, distinct Wulff microcrystallites must be in ‘splendid isolation’ — with negligible exchange between them in comparison to the internal dynamics required to equilibrate . In contrast, dilute phase separating alloys and coarsening polycrystallites exhibit growing microcrystalline droplets or grains with non-negligible interactions. While it has been shown for these and other coarsening systems that anisotropy influences the morphology , such effects have not been quantitatively understood for even the simplest models of curvature-driven growth.

The understanding of interacting isotropic phases (see, e.g., ) was significantly advanced by the models of Lifshitz and Slyozov  and Wagner  for diffusive and curvature-driven coarsening, respectively. These mean-field theories correctly capture a remarkable amount of coarsening phenomenology, and are exact in the dilute limit. With this inspiration, we generalize Wagner’s model — an interacting ensemble of coarsening droplets, evolving to continually lower their surface energy without changing their total volume — to include arbitrary anisotropy in the surface tension and the interface mobility. We solve the model perturbatively in anisotropy strength, and relate the interfacial properties to the resulting non-trivial grain shapes. These “growth shapes” are contrasted with those of equilibrium (Wulff-constructed) grains to highlight the connection between dynamics and microcrystallite morphology. We then compare our results on the ensemble of grains to Wagner’s isotropic solution to demonstrate anisotropy effects on coarsening correlations, including the effect on persistence exponents.

Our model is applicable to single-phase polycrystallite coarsening, where distinct grains are distinguished only by their crystallographic orientation (see ). Most theoretical studies of polycrystallites focus on their cellular structure, specifically on the static and dynamical description of the vertices where three or more grain boundaries meet. However, vertex-based models have significant shortcomings when anisotropy is included, since it modifies both the distribution of the number of vertices per grain  and the otherwise fixed angles formed where three grains adjoin . Furthermore, von Neumann’s law, a direct relationship in two dimensions (2D) between the number of vertices per grain and its area growth rate , no longer applies. With anisotropy, the evolution of a grain’s area requires the complete specification of grain shape — including the orientations and, in general, the non-uniform curvatures of the interfaces.

We present a complementary vertex-free approach to examine grain shape via an anisotropic dynamical mean-field theory. The neighboring grains outside the grain of interest are treated as providing an isotropic mean-field. We retain the crystallinity of the grain through an anisotropic surface tension and interface mobility, which results in the anisotropic Wagner theory. (A similar connection can be made between isotropic Wagner theory and soap froths .) Ultimately, a synthesis of the present work with vertex-based models is desirable .

We find a dynamical scaling solution typical of coarsening systems , including clean polycrystallites. The characteristic length scale grows as a power law, $`Lt^{1/2}`$, as expected for curvature driven growth . In the scaling regime the initial conditions are “forgotten,” and the morphology, when scaled by the growing length, $`L(t)`$, is invariant. Grain shapes of particular scaled size are also time-independent. These growth shapes are generally quite different from equilibrium Wulff shapes — even when the mobility is isotropic! The isotropic grain size distribution is also modified by anisotropy, as discussed later.

With our results, we can answer the question of universality in persistence decay exponents. The persistence is the fraction of the system that has not been crossed by a domain wall up to time $`t`$ . The decay of persistence to zero, $`Pt^\theta `$, even from a starting time deep within the scaling regime, implies that every point in the system will eventually “realize” that equilibrium has not yet been reached. Persistence decay is a local signature of the non-equilibrium dynamics of the system. The degree of universality of this dynamical exponent has remained an open issue since no precise results have been obtained for models with non-trivial temperature dependence . (Simulations have not yet found any temperature dependence within their accuracy .) Since anisotropy varies with temperature, our model provides such a non-trivial temperature dependence in a coarsening system that we can then analytically relate to the resulting structure and to the persistence exponent, $`\theta `$ . We find that $`\theta `$ depends on both the anisotropies of the surface tension and of the interface mobility, so the persistence exponent is nonuniversal in anisotropic systems .

We restrict ourselves to 2D, where the surface tension $`\sigma (\psi )`$ and the interface mobility $`M(\psi )`$ may be defined in terms of the angle $`\psi `$ between the interface normal and an arbitrary crystallographic axis. The anisotropic Allen-Cahn equation  is then derived from the linear response of the interface to the local drive given by the Gibbs-Thompson condition, $`[\sigma (\psi )+\sigma ^{\prime \prime }(\psi )]\kappa `$, were $`\sigma `$ is the surface tension, and $`\kappa `$ the local interface curvature. The stiffness, $`\sigma +\sigma ^{\prime \prime }`$, reflects the local change of extent and orientation of the interface due to a deformation. By allowing the interface mobility to depend on orientation , and by including an applied field $`\lambda `$ coupled to one of the phases, we obtain the normal interface velocity

$$v_n=M(\psi )\left[\{\sigma (\psi )+\sigma ^{\prime \prime }(\psi )\}\kappa \lambda \right].$$
(1)   
We now consider an ensemble of polycrystallite grains. Our mean-field approximation entails keeping only the crystalline anisotropy of each grain (ignoring its neighbors), neglecting vertices, and determining a self-consistent mean-field $`\lambda `$ to represent the effects of neighboring grains that may be growing or shrinking. The conservation of the total area of all of the grains uniquely determines $`\lambda (t)`$, resulting in precisely the anisotropic Wagner theory.

To proceed, we Fourier expand the anisotropic surface tension and mobility,

$`\sigma (\psi )`$ $`=`$ $`\sigma _0\left[1+\delta {\displaystyle \underset{k=1}{\overset{\mathrm{}}{}}}\{\sigma _k\mathrm{cos}(k\psi )+\stackrel{~}{\sigma }_k\mathrm{sin}(k\psi )\}\right],`$ (2)   
$`M(\psi )`$ $`=`$ $`M_0\left[1+\delta {\displaystyle \underset{k=1}{\overset{\mathrm{}}{}}}\{m_k\mathrm{cos}(k\psi )+\stackrel{~}{m}_k\mathrm{sin}(k\psi )\}\right],`$ (3)   
where $`\delta `$ is introduced to organize a perturbative calculation. We parameterize each grain by a polar radius $`R(\varphi )`$, as depicted in Fig. 1, from which the interface orientation follows: $`\psi (\varphi )=\varphi \mathrm{arctan}(R^{}/R)`$ where $`R^{}dR/d\varphi `$. Considering only smooth grain profiles, we relate normal and radial growth velocities, $`v_r(\varphi )=v_n\sqrt{1+(R^{}/R)^2}`$, and calculate the curvature $`\kappa (\varphi )=[R^2+2R^2RR^{\prime \prime }]/(R^2+R^2)^{3/2}`$. We then expand $`R`$,

$$R(\varphi )=R_0\left[1+\underset{k=0}{\overset{\mathrm{}}{}}\{\rho _k\mathrm{cos}(k\varphi )+\stackrel{~}{\rho }_k\mathrm{sin}(k\varphi )\}\right],$$
(4)   
with coefficients

$$\rho _k(x)=a_k(x)\delta +b_k(x)\delta ^2+\mathrm{}$$
(5)   
and similarly for $`\stackrel{~}{\rho }_k`$ . Grain sizes are labeled with a reduced length $`xR_0/L`$, where $`L(M_0\sigma _0t/2)^{1/2}`$. For $`\delta =0`$ we recover Wagner’s isotropic theory, with the familiar distribution of grain sizes (see ):

$$f(x)=ϵF_2x\mathrm{exp}[4/(2x)]/(2x)^4.$$
(6)   
(The $`ϵ`$ prefactor is the area fraction of a randomly selected subset of grains — used later to calculate persistence.) For convenience, we define $`R_0`$ by the requirement that $`x`$ maintains this isotropic grain-size distribution up to an anisotropy-dependent normalization, $`F_2=F_2^{(0)}+\delta ^2F_2^{(2)}+\mathrm{}`$. This requirement leads to non-zero $`\rho _0`$ terms in the expansion (4) but preserves the range of scaled sizes, $`x[0,2]`$. (Note that $`\stackrel{~}{\rho }_0=0`$.) Physical length scales, such as the grain perimeter, can be consistently derived from our results, as discussed below.

The resulting interface equations for the ensemble of grains may be solved order by order in $`\delta `$ . The zeroth order results reproduce the isotropic theory; the first order equations are new, and serve to determine a size-dependent grain shape through $`a_k(x)`$:

$`x(2x)^2a_k^{}(x)4(k^2+x2)a_k=`$ (7)   
$`4(1k^2)\sigma _k+4(1x)m_k,`$ (8)   
for $`k>1`$, with an identical equation for $`\stackrel{~}{a}_k`$ in terms of $`\stackrel{~}{\sigma }_k`$ and $`\stackrel{~}{m}_k`$. For $`k>1`$ the solution is

$$a_k(x)=m_k+(\sigma _km_k)(11/k^2)[1+\mathrm{\Omega }(k,v)]$$
(9)   
where $`\mathrm{\Omega }(k,v)2\mathrm{\Gamma }(2k^2,v)v^{k^22}e^v`$, and $`vk^2x/(2x)`$. We also have $`a_0(x)=a_1(x)=0`$, the latter by our choice of coordinate origin . Clearly the grain shapes depend on grain size, through $`\mathrm{\Omega }`$. Even when the surface tension is isotropic ($`\sigma _k=0`$ for all $`k>0`$), we can obtain anisotropic grain shapes through the interface mobility. This is illustrated in Fig. 2 for a particular choice of $`M(\psi )`$.

At all orders of $`\delta `$ the equations for the grain shape are similar to (7), although the right-hand side will include products of lower-order solutions. While these equations are progressively more difficult to solve, we can iteratively demonstrate that the solutions are finite at every order of $`\delta `$ .

In the special case where $`m_k=\sigma _k`$ for all $`k`$ grains of all sizes have the equilibrium Wulff shape. This result holds to all orders in $`\delta `$, and is due to a remarkable symmetry held by the interface equation (1). The equilibrium grain shape is given by

$$R_{\mathrm{eq}}(\varphi )=\frac{R_0}{\sigma _0}\underset{\varphi ^{}}{\mathrm{min}}\left|\frac{\sigma (\varphi ^{})}{\mathrm{cos}(\varphi ^{}\varphi )}\right|.$$
(10)   
For this Wulff shape, a variational calculation shows that $`[\sigma (\psi )+\sigma ^{\prime \prime }(\psi )]\kappa `$ is independent of angle , from which we obtain $`v_rM(\psi )\sqrt{1+(R^{}/R)^2}`$ for all angles. If and only if the dynamical mobility anisotropy equals that of the static surface tension — that is, $`M(\psi )\sigma (\psi )`$ — then we recover $`v_rR_{\mathrm{eq}}(\varphi )`$, the condition for Wulff grains to keep their shape while evolving. This symmetry, evident in (9), leads to size-independent drop shapes and also shows up in the drop size distribution and persistence results, as discussed below.

However, the dynamic mobility and the static surface tension will not be proportional except by special construction. Regardless, in physical systems $`M`$ and $`\sigma `$ have different temperature dependences so that equality could not be maintained as temperature varies. In the general case, we will have size-dependent drop shapes given, to first order, by (9). In comparison, the Wulff construction gives $`a_k^{\mathrm{eq}}=\sigma _k`$ as the leading contribution to the equilibrium grain shape. Even with an isotropic mobility, $`m_k=0`$, growth shapes differ from equilibrium and depend on grain size.

The isotropic grain size distribution (6) applies only to our index $`R_0`$ . Physically relevant lengths, such as extracted from the grain perimeter or the area, will generally have different distributions. For example, the area $`A=\frac{1}{2}_0^{2\pi }𝑑\varphi R(\varphi )^2`$ can be used to define $`R_A=\sqrt{A/\pi }`$ where

$$R_A=R_0\left[1+\delta ^2\left(b_0+\frac{1}{4}\underset{k}{}\{a_k^2+\stackrel{~}{a}_k^2\}\right)+O(\delta ^3)\right].$$
(11)   
A scaled size $`z=R_A/L`$ may then be introduced, which will be related to $`x`$ by $`z=x+\delta ^2h(x)+O(\delta ^3)`$. The “area radius” distribution $`g(z)`$ is then determined by $`g(z)dz=f(x)dx`$ so that

$$g(z)=f(z)\delta ^2[f(z)h^{}(z)+f^{}(z)h(z)]+O(\delta ^3)$$
(12)   
where $`f(x)`$ is the isotropic distribution . The grain perimeter distribution follows similarly, though with a different function $`h(x)`$. \[In the special symmetric case, where $`m_k=\sigma _k`$ for all $`k1`$, all physical lengths have the same distribution. Since the grain shapes are size independent, $`h(x)=h_0`$, and $`g(z)`$ and $`f(x)`$ differ only by an overall normalization.\]

We may also calculate the slow decay of persistence due to the evolution of a small area fraction $`ϵ`$ of randomly chosen grains, following . The persistence $`P_>`$ of the region outside the chosen grains decays due to growing grains via $`_tP_>=v_>P_>`$. The rate of encroachment of growing grains, $`v_>`$, can be calculated from the grain shapes and (1). The power-law decay of persistence follows directly from the result $`v_>1/t`$, with persistence exponent $`\theta =tv_>`$. Anisotropy appears at $`O(\delta ^2)`$. The calculation is lengthy and details are reported elsewhere ; however, the result simplifies to

$$\theta =\theta _0+\delta ^2\underset{k=1}{\overset{\mathrm{}}{}}\theta _k^{(2)}[(m_k\sigma _k)^2+(\stackrel{~}{m}_k\stackrel{~}{\sigma }_k)^2]+O(\delta ^3),$$
(13)   
where $`\theta _00.48797ϵ`$ is the 2D persistence exponent for the isotropic case . We find that $`\theta `$ equals the isotropic value $`\theta _0`$ only when $`M(\psi )\sigma (\psi )`$ (this holds to all orders due the symmetry mentioned earlier) and differs from $`\theta _0`$ for any other anisotropic conditions. The order $`ϵ`$ coefficients $`\theta _k^{(2)}`$ may be determined by numerical integration, and are well approximated by a large $`k`$ expansion . The persistence exponent depends continuously on both the mobility and surface tension, and consequently on the temperature. The 2D Ising model provides an explicit example: the anisotropic surface tension is known analytically for $`0TT_c`$  and the anisotropic mobility is known close to $`T=0`$ for Glauber dynamics . At $`T=0`$, and using only the leading contribution (13), we find $`\theta 1.0344\theta _0`$. The effect on the exponent is small but non-zero, and may be detectable numerically with more accurate studies.

In conclusion, we have constructed a mean-field model for 2D polycrystallite coarsening with anisotropic surface tension and mobility. We find an exact scaling solution with size-dependent grain shapes that are generally unrelated to the equilibrium Wulff shape. We use our solution to calculate the exponent describing persistence decay, and find that it is continuously dependent on anisotropy and hence nonuniversal with respect to temperature . We expect similar results to hold in three-dimensional systems.

We hope that this study stimulates further research of the connections between nonequilibrium structure and anisotropic mobility and surface tension. Our next step will be to develop the anisotropic generalization of Lifshitz-Slyozov diffusive coarsening in bulk systems . We also feel the influence of anisotropy on nonequilibrium exponents needs further study. For example, we suspect that persistence exponents and their various generalizations (see, e.g., ) will prove to be nonuniversal whenever correlation functions are anisotropy dependent. Finally, we stress that persistence decay still provides an important description of nonequilibrium dynamics, and remains universal in intrinsically isotropic systems such as binary fluids, polymer blends, and soap froths. Persistence is particularly useful in discriminating between different dynamical models and in probing the dynamics of soap froths .

We would like to acknowledge stimulating discussions with S. N. Majumdar, B. Meerson, C. Carter and J. Warren. A. D. R. thanks the NSERC, and le Fonds pour la Formation de Chercheurs et l’Aide à la Recherche du Québec for financial support; B. P. V.-L. was supported by an NRC Research Associateship for part of this work.