# Filler-Induced Composition Waves in Phase-Separating Polymer Blends

## I Introduction

The bulk properties of miscible fluid mixtures are characteristically insensitive to their microscopic fluid structure near the critical point for phase separation, where the properties are governed by large scale fluctuations in the local fluid composition. Composition fluctuations occur similarly for most near-critical fluid mixtures, so that the properties of these fluids are subject to a “universal” description. This accounts for the success of simple mathematical models of critical phenomena (e.g., Ising model, $`\varphi ^4`$-field theory) that contain the minimal physics of these fluctuation processes. Although mixtures near their critical point are susceptible to external perturbations, the influence of microscopic heterogeneities tend to become “washed out” in the large scale fluid properties, apart from changes in critical parameters describing the average properties of the fluid (e.g., critical temperature and composition, apparent critical exponents, etc.). This situation changes, however, when the fluid mixture enters the two-phase region. The fluid is then far from equilibrium and perturbations can grow to have a large-scale influence on the phase separation morphology. Perturbations in these unstable fluids can be amplified rather than washed out at larger length scales. Inevitably, the theoretical description of this kind of self-organization process is complicated by various non-universal phenomena associated with the details of the particular model or experiment under investigation . The beneficial aspect of this sensitivity of phase separation and other pattern formation processes to perturbations is that it offers substantial opportunities to control the morphology of the evolving patterns and leads to a great multiplicity of microstructures.

Many previous studies have considered the application of external influences (flow  and gravitational  fields, concentration  and temperature  gradients, chemical reactions , crosslinking , etc.) to perturb fluid phase separation, but the investigation of geometrical perturbations is more recent. There have been numerous studies on the perturbation of phase separation arising from the presence of a plane wall, which is one of the simplest examples of a geometrical perturbation of phase separation . Measurements and simulations both show the development of “surface-directed” composition waves away from plane boundaries under the condition where one component has an affinity for the surface. The scale of these coarsening surface waves grows much like those of bulk phase separation patterns . Recent simulations  and experiments  have shown that variation of the polymer-surface interaction within the plane of the film allows for the control of the local polymer composition in blends phase separating on these patterned substrates (“pattern-directed phase separation” ). Measurements have also indicated that the polymer-air boundary of phase-separating blend films on patterned substrates can be strongly perturbed by phase separation within the film  and thermal fluctuations of the polymer-air boundary can also strongly influence the structure of thin polymer films .

In the present paper we focus on the consequences of having geometrical heterogeneities of finite extent in a phase separating blend. The Cahn-Hilliard-Cook (CHC) theory  for phase separation is adapted to describe phase separation of a blend with spherical, cylindrical (fiber), and plate-like shaped filler particles. The extended dimensions of the fiber and platelet filler particles are taken to be much larger than the scale of the phase separation process. A variable polymer-surface interaction is incorporated into the filler model in a fashion similar to previous treatments of plane surfaces .

The paper is organized as follows. In section II we briefly summarize the CHC model to introduce notation, to define the relation between model parameters and those of polymer blends theory, and to explain modifications required for incorporating immobile filler particles into the CHC simulations of phase separation. Section III summarizes the results of simulations for representative situations. Key phenomena are identified: 1) Target composition patterns form in near critical composition blends. 2) Target patterns are a transient phenomenon. 3) The scale of the target patterns depends on quench depth and molecular weight. 4) Qualitative changes in the filler-induced composition patterns occur when the surface interaction is neutral and when the blend composition is off-critical. 5) Multiple filler particles induce composition waves exhibiting complex interference patterns. Section IV provides a simple analytic estimate of the scale of the target pattern based on the linearized CHC theory, and these results are tested against simulations for circular filler particles. In section V simulation results are compared to experiments on ultrathin polymer films having silica bead filler particles immobilized by the solid substrate on which the films were cast. Atomic force microscopy measurements on the filled blend films are compared to the analytical predictions. Simulations of phase separation in off-critical blend films are briefly compared to analogous experiments. Measurements on crosslinked blend films are also considered. The final section (VI) discusses generalizations of the present study to manipulate the structure of phase-separating blends.

## II The Model

### A CHC Equation

We present a brief discussion of the CHC model  to introduce notation and to explain the modifications required for incorporating filler particles. The modeling of the phase separation dynamics is based on gradient flow of a conserved order parameter $`\varphi (𝐫,t)`$,

$$\frac{}{t}\varphi (𝐫,𝐭)=M^2\frac{\delta F[\varphi ]}{\delta \varphi (𝐫)}+\zeta (𝐫,t),$$
(1)   
with $`\varphi (𝐫,t)`$ equal to the local volume fraction of one of the blend components. Incompressibility of the mixture is assumed so that the local volume fraction of the second component is $`1\varphi `$. The mobility $`M`$ is assumed to be spatially uniform and independent of concentration and the free energy functional $`F[\varphi ]`$ has the general form

$$F[\varphi (𝐫)]=\frac{d𝐫}{v}\left[\frac{1}{2}k_BT\kappa (\varphi )(\varphi )^2+f(\varphi )\mu _{eq}\varphi \right],$$
(2)   
where $`f(\varphi )`$ is the bulk Helmholtz free energy per lattice site, $`v`$ is the volume per lattice site, $`k_B`$ is Boltzmann’s constant, $`T`$ is temperature, and $`\kappa (\varphi )`$ is a measure of the energy required to create a gradient in concentration. Higher order gradient terms are neglected. The chemical potential is given by $`\mu _{eq}=f/\varphi |_{\varphi _{eq}}`$, which ensures that $`\varphi (𝐫)=\varphi _{eq}`$ is the solution of $`\delta F[\varphi ]/\delta \varphi (𝐫)=0`$. Finally, thermal fluctuations necessary to ensure a Boltzmann distribution of $`\varphi (𝐫)`$ in equilibrium are included via the Gaussian random variable $`\zeta `$. The average of $`\zeta `$ vanishes, and $`\zeta `$ obeys the relation

$$\zeta (𝐫,t)\zeta (𝐫^{},t^{})=2Mk_BT^2\delta (𝐫𝐫^{})\delta (tt^{}).$$
(3)   
For temperatures near the critical temperature $`T_c`$ the free energy can be expanded in powers of the composition fluctuation $`\psi (𝐫)=\varphi (𝐫)\varphi _c`$, giving the Ginzburg-Landau (GL) functional

$$F[\psi (𝐫)]=k_BT\frac{d𝐫}{v}[\frac{1}{2}\kappa _c(\psi )^2+\frac{1}{2}c\psi ^2+\frac{1}{4}u\psi ^4+\mathrm{}]$$
(4)   
where $`\kappa _c\kappa (\varphi _c)`$. Neglected terms are either higher order in $`\psi `$ or in $`\sqrt{c}\sqrt{TT_c}`$, which is small near the critical point. Eq. (1), in combination with (4), defines the well-known Model B ,

$$\frac{}{t}\psi (𝐫,t)=M\left(\frac{k_BT}{v}\right)^2(\kappa _c^2\psi c\psi u\psi ^3)+\zeta (𝐫,t),$$
(5)   
Eq. (5) is used to study the dynamics following a quench to the two-phase region $`T<T_c`$, where $`c<0`$. In that case, the CHC equation may be rescaled into the dimensionless form 

$$\frac{}{t}\psi (𝐫,t)=^2(^2\psi +\psi \psi ^3)+ϵ^{1/2}\eta (𝐫,t)$$
(6)   
by making the substitutions

$`𝐫`$ $``$ $`(|c|/\kappa _c)^{1/2}𝐫`$ (7)   
$`t`$ $``$ $`(Mk_BTc^2/v\kappa _c)t`$ (8)   
$`\psi `$ $``$ $`(u/|c|)^{1/2}\psi `$ (9)   
Note that this amounts to rescaling space by $`\sqrt{2}\xi _{}`$, where $`\xi _{}`$ is the thermal correlation length in the two-phase region, and time by $`\tau =D_{coll}/(2\xi _{}^2)`$, with $`D_{coll}`$ the collective diffusion coefficient. Here the noise term $`\eta (𝐫,t)`$ satisfies $`\eta (𝐫,t)=0`$ and

$$\eta (𝐫,t)\eta (𝐫^{},t^{})=^2\delta (𝐫𝐫^{})\delta (tt^{}).$$
(10)   
The only parameters left to specify the dynamics are the (conserved) average concentration $`\psi _0\varphi \varphi _c`$ and the dimensionless noise strength parameter $`ϵ`$,

$$ϵ=2u/(\kappa _c^{d/2}|c|^{(4d)/2}).$$
(11)   
Roughly speaking, the reciprocal of $`ϵ`$ is a measure of quench depth. The parameter $`ϵ`$ also arises in discussions of the width of the critical region, and the connection between thermal noise strength and the Ginzburg criterion was first noted by Binder .

### B Polymer Blends

For polymer blends we take the Flory-Huggins (FH) form of the Helmholtz free energy per lattice site,

$$\frac{f^{FH}(\varphi )}{k_BT}=\frac{\varphi }{N_A}\mathrm{ln}\left(\frac{\varphi }{N_A}\right)+\frac{1\varphi }{N_B}\mathrm{ln}\left(\frac{1\varphi }{N_B}\right)+\chi \varphi (1\varphi ).$$
(12)   
Here $`\chi `$ represents the monomer-monomer interaction energy, $`N_i`$ is the polymerization index of component $`i`$, and $`\varphi `$ is the volume fraction of component A. For the coefficient of the gradient term we use de Gennes’ random-phase approximation (RPA) result (neglecting the enthalpic contribution ),

$$\kappa (\varphi )=\frac{1}{18}\left[\frac{\sigma _A^2}{\varphi }+\frac{\sigma _B^2}{1\varphi }\right],$$
(13)   
where $`\sigma _A`$ and $`\sigma _B`$ are monomer sizes of the $`A`$ and $`B`$ blend components, given in terms of the radius of gyration of the $`i`$th component $`R_{g,i}`$ by $`\sigma _i^2=R_{g,i}^2/N_i`$.

FH theory exhibits a critical point at

$`\varphi _c`$ $`=`$ $`N_B^{1/2}/(N_A^{1/2}+N_B^{1/2})`$ (14)   
$`\chi _c`$ $``$ $`\chi (\varphi _c,T_c)=\left[N_A^{1/2}+N_B^{1/2}\right]^2/(2N_AN_B).`$ (15)   
Consequently, the coefficients of the GL functional are defined as 

$`c`$ $`=`$ $`2\chi _c(1\chi /\chi _c)`$ (16)   
$`u`$ $`=`$ $`{\displaystyle \frac{4}{3}}\chi _c^2\sqrt{N_AN_B}`$ (17)   
$`\kappa _c`$ $`=`$ $`{\displaystyle \frac{1}{18}}\left[\sigma _A^2\left(1+\sqrt{N_A/N_B}\right)+\sigma _B^2\left(1+\sqrt{N_B/N_A}\right)\right].`$ (18)   
The phase separation dynamics of polymer blends can then be described by the dimensionless CHC equation with $`ϵ`$ determined by molecular parameters,

$$ϵ=\frac{36\sqrt{2}f(x)}{\gamma ^3(\chi /\chi _c1)^{1/2}N^{1/2}},$$
(19)   
where $`N_A=N`$ and $`x=N_B/N`$, $`f(x)=(1+\sqrt{x})^3/8x`$, and $`\gamma `$ is the ratio of monomer size to lattice size,

$$\gamma =\frac{\left[\sigma _A^2(1+1/\sqrt{x})+\sigma _B^2(1+\sqrt{x})\right]^{1/2}}{2v^{1/3}}.$$
(20)   
$`\gamma `$ simplifies to $`\gamma =\sigma _{A,B}/v^{1/3}`$ for symmetric blends. Thus we see that deep quenches ($`\chi \chi _c`$) and high molecular weight polymers effectively reduce the thermal fluctuations in the rescaled dynamical equations.

### C Surface Energetics

In the presence of a surface we add a local surface interaction energy to be integrated over the boundary,

$$F_s[\psi ]=_Sd^{d1}x[h\psi +\frac{1}{2}g\psi ^2+\mathrm{}].$$
(21)   
The coupling constant $`h`$ in the leading term plays the role of a surface field which breaks the symmetry between the two phases, i.e., attracts one of the components to the filler surface. The coupling constant $`g`$ in the second term is neutral regarding the phases, and results from the modification of the interaction energy due to the missing neighbors near the surface  and chain connectivity . For studies of surface critical phenomena  and surface dynamics  one typically keeps only these terms as a minimal model of phase separation with boundaries.

There has been considerable attention given to the subject of the appropriate dynamical equations for the surface boundary conditions . We follow most authors and impose zero flux at the boundary, $`\widehat{n}𝐣_\psi =0`$, which gives

$$\widehat{n}(^2\psi +\psi \psi ^3)=0.$$
(22)   
For the second condition we impose that of local equilibrium at the surface, namely,

$$\widehat{n}\psi =h+g\psi .$$
(23)   
While more sophisticated treatments are available , they lead to dynamics which rapidly relax to equilibrium and satisfy the above condition. The details of how we implement (22) and (23) in simulations with a curved interface are presented in Appendix A.

### D Simulation Details

The equation of motion is solved using a standard central finite difference scheme for the spatial derivatives, and a first-order Euler integration of the time step . In all the simulations, the lattice spacing is taken between $`0.7`$ and $`1.0`$ in dimensionless units (sufficiently smaller than any relevant physical length scales) and the time step is taken sufficiently small to avoid numerical instability. In the present paper, all simulations are performed in $`d=2`$ on lattices up to size 128<sup>2</sup>, depending on the choice of mesh size. We note that the CHC equation is known to exhibit quantitatively similar pattern formation and coarsening kinetics in two and three dimensions. Further technical details about this type of simulation can be found in Ref. .

## III Illustrative Simulations

In Fig. 1 we show the influence of an isolated circular filler particle on the development of the phase separation pattern of a blend film having a critical composition. The thermal noise is small in these two-dimensional simulations ($`ϵ=10^5`$), corresponding to high molecular weight and/or a deep quench (low and high temperatures relative to the critical temperature for upper and lower critical solution type phase diagrams, respectively). At an early stage of the phase separation process the filler particle creates a spherical composition wave disturbance that propagates a few “rings” into the phase separating medium in which the filler particle is embedded. The target rings initially have the size of the maximally unstable “spinodal wavelength” $`\lambda _0`$ obtained from the linearized theory . As the characteristic scale of the bulk phase separation pattern coarsens to the size of the filler particle, the outer rings of the “target” pattern become disconnected and increasingly become absorbed into the background spinodal pattern. The perturbing influence of the particle becomes weak at a late stage of the phase separation where the scale of the background phase separation pattern exceeds the filler particle size. The finite extent of the filler thus limits the development of the composition waves to a transient regime.

The formation of target patterns can be described as composition waves propagating into the bulk, unstable region until they are overwhelmed by the developing background spinodal decomposition pattern. The rate of onset of spinodal decomposition is controlled by the strength of thermal fluctuations, hence the noise parameter $`ϵ`$ plays a crucial role in determining the radial extent of the composition waves. Fig. 2 shows two systems with equal surface interaction, but with varying noise strengths: (a) $`ϵ=10^3`$ and (b) $`ϵ=10^5`$. We see that the spatial extent of the target pattern is larger for smaller $`ϵ`$. Consequently, we expect deeply quenched and/or high molecular weight polymer blends to be favorable systems for observing filler induced composition waves because of the relatively low thermal noise level typical of these systems, and the relatively high viscosity of these fluids which slows the dynamics and makes measurements of intermediate stage patterns possible (e.g. via atomic force microscopy as discussed in section V). In section IV, we use the linearized CHC equation to estimate the extent of the composition wave.

We observe that the composition waves disappear when the particle radius $`R`$ becomes vanishingly small, and the persistent waves developing from planar surfaces are recovered for very large spherical particles. We then examine particles of sizes intermediate between these extreme limits and during the intermediate phase separation period in which the target patterns are well developed. Fig. 3 shows the angular-averaged composition profile $`\psi (z)`$, with $`zrR`$ the radial distance from the surface of the filler particle. We observe that the amplitude of the local composition fluctuations become more developed and more sharply defined with increasing filler size, $`R`$. In comparison to the planar surface ($`R\mathrm{}`$), the composition wave profile for $`R=10`$ is only slightly reduced in amplitude, whereas for $`R=3`$ the amplitude is reduced to half that of the wall case. We also remark that the radial extent of the target pattern is similar for all particle sizes.

We next examine the influence of the surface interaction on the formation of filler-induced target patterns. The impact of the symmetry breaking perturbation of the filler particle on the phase separation may be tuned through the surface interaction parameters $`g`$ and $`h`$. We focus our attention on $`h`$ since it has a predominant effect on the resulting pattern formation.

Fig. 4 shows CHC simulations of blend phase separation for the case where one component strongly prefers the filler, weakly prefers the filler, and has no preference for the filler ($`h=0`$). The quench depth parameter and computation times are identical in these images. We see that the target patterns do not form in the case of filler particles with a (“neutral”) non-selective interaction, but rather there is a tendency for the patterns to align perpendicularly to the interface. This type of compositional alignment, which we find is even more pronounced in the case of a planar surface, also occurs in block copolymer fluids . The perturbing influence of the boundary interaction saturates with an increase of $`h`$, as can be seen by comparison of the $`h=2.0`$ and $`h=0.1`$ cases. Below we demonstrate that the extent of the target pattern depends logarithmically on $`h`$.

Target waves are a variety of spinodal pattern with a symmetry set by the shape of the filler particle boundary. The introduction of surface patterns on a solid substrate can similarly break the symmetry of the phase separation process and can be used to impart a particular “shape” to the spinodal pattern . A previous CHC simulation by us considered this “patterned-directed” phase separation in near critical composition blend films .

The blend composition also can have a large influence on the character of the filler-induced phase separation structures in blends, particularly when sufficiently far off critical to suppress the spinodal instability. In this case we find a layer of composition enrichment (“encapsulation layer”) forms about the filler particle, but there are no target patterns . This encapsulation layer grows in time, but appears to grow slower than $`t^{1/3}`$. A non-selective interaction ($`h=0`$) leads to the absence of encapsulation by the minority phase, and minority phase nucleation occurs largely unaffected by the presence of the filler. We thus find that the development of target patterns requires the conditions of ordinary spinodal pattern formation (i.e., “near” critical composition) and the existence of a heterogeneity to initiate the wave disturbance.

A representative example of the interference between filler-induced rings at a non-vanishing filler concentration is shown in Fig. 5. Filler particles can each have an affinity for the different blend components so that the enriching phase (“charge”) can vary near the surface of the filler particle at the core of the target waves. (Sackmann has noted that composition enrichment patterns occur about membrane proteins in lipid mixtures comprising living cell membranes, and these patterns mediate protein interactions, leading to attractive or repulsive interactions depending on the “charge”.) In the low noise limit it should be possible to obtain novel wave patterns like those found in reaction diffusion models with regularly spaced sources for wave propagation , but we do not pursue this here. We do mention that the use of filler particles responsive to external fields could allow the manipulation of the large scale phase separation pattern if the external fields are used to align the filler particles.

## IV Estimation of the Spatial Extent of the Target Patterns

In this section we derive an approximate analytical expression for the spatial extent of the composition wave pattern. Our method is based on the observation above that the composition wave propagates until it is overwhelmed by the growth of the bulk spinodal decomposition background pattern. In the context of surface-directed spinodal decomposition, a qualitative explanation of this type of phenomena was proposed by Ball and Essery , who argued that the early time dynamics can be adequately described by the linearized CHC equation, in which the composition wave and the bulk spinodal decomposition add linearly. Both processes continue independently until a local non-linear threshold value of $`|\psi |\psi _t`$ is reached, which then relaxes toward the equilibrium value $`\psi =\pm 1`$.

We test this conjecture numerically in the case of the filler inclusions. First, we simulate the CHC equation in bulk, with no filler particle, and determine the time $`t_0`$ at which the root-mean-square concentration $`\psi ^2(t)^{1/2}`$ reaches the threshold value $`\psi _t=0.15`$ (our reason for this choice is given below). Next, we simulate the filled blend in the absence of noise solving for the pattern at time $`t_0`$, and then estimate the radius $`r_0`$ at which the composition wave (envelope) exceeds $`\psi _t`$. Finally, we perform the simulation with both the filler particle and the thermal noise, and find the pattern to be well-characterized by the size $`r_0`$ for a range of noise and surface interaction parameters.

Based on these ideas, we next develop an analytic estimate of the spatial extent of the pattern using the linearized CHC theory . At early times the order parameter does not deviate significantly from zero, and one linearizes (6) to obtain

$$_t\psi =^2(k_0^2+^2)\psi +ϵ^{1/2}\eta $$
(24)   
where $`k_0^2=13\psi _0^2`$. We apply this equation first to the determination of the root-mean-square order parameter $`\psi _{\mathrm{rms}}(t)\psi (t)^2^{1/2}`$, which characterizes the rate of growth of the concentration fluctuations at very early times following a quench to the two-phase region. Fourier transformation gives

$$_t\stackrel{~}{\psi }(𝐤,t)=k^2(k_0^2k^2)\stackrel{~}{\psi }+ϵ^{1/2}\stackrel{~}{\eta }(𝐤,t).$$
(25)   
The structure factor $`S(𝐤,t)=\stackrel{~}{\psi }(𝐤,t)\stackrel{~}{\psi }(𝐤,t)`$ is then,

$$S(𝐤,t)=\frac{ϵ(e^{2k^2(k_0^2k^2)t}1)}{2(k_0^2k^2)}.$$
(26)   
$`\psi _{\mathrm{rms}}`$ is found by integrating $`S(𝐤,t)`$ with respect to $`k`$,

$$\psi ^2(t)=\frac{d^dk}{(2\pi )^d}S(𝐤,t).$$
(27)   
Following , we observe that the integrand is sharply peaked about $`k=k_0/\sqrt{2}`$ and we approximate it by a Gaussian. The integral is then readily evaluated to find (to leading order in $`1/t`$)

$$\psi ^2(t)=ϵe^{\frac{1}{2}k_0^4t}\left(\frac{\pi }{2t}\right)^{1/2}\frac{d}{k_0^{4d}\mathrm{\Gamma }(1+d/2)(8\pi )^{d/2}}.$$
(28)   
This result, when tested against simulations of the fully nonlinear CHC, agrees well up to $`\psi ^2(t)^{1/2}(0.15)`$, thus motivating our choice for $`\psi _t`$ indicated above.

Finally, we equate $`\psi ^2(t_0)`$ to $`\psi _t^2`$ to determine the time $`t_0`$ at which the bulk phase separation process has reached the nonlinear threshold. The resulting transcendental equation for $`t_0`$ can be approximately solved by observing that $`\psi _t^2/ϵ1`$ in low noise conditions, and that this ratio must be compensated primarily by the $`e^{k_0^4t_0/2}`$ factor. Equating these two and then iteratively improving the estimate of $`t_0`$ yields

$$t_0\frac{2}{k_0^4}\mathrm{ln}\left(\frac{\psi _t^2}{ϵ}\right)+\mathrm{ln}\left(\frac{2\mathrm{\Gamma }(1+d/2)(8\pi )^{d/2}\sqrt{\mathrm{ln}(\psi _t^2/ϵ)}}{k_0^{d2}d}\right).$$
(29)   
Next we consider the linearized theory for the filled blend. We solve (24) for the exterior of the filler particle or fiber, and in the absence of thermal noise (the noise can simply be averaged out of the composition wave within the linearized theory). We consider idealized filler particles that are symmetric and finite in some of their coordinates and infinite (i.e., very large on the phase separation pattern scale) in the remaining coordinates defining the particle dimensions. With such symmetry, the composition wave depends only on the coordinate perpendicular to the interface, which is a radial coordinate in $`d_{}`$ dimensions. For example, a spherical particle in $`d=3`$ corresponds to $`d_{}=3`$, a cylindrical fiber is prescribed by $`d_{}=2`$, and a platelet filler reduces to the planar surface with $`d_{}=1`$. We can treat the general $`d_{}`$ case through the $`d_{}`$-dimensional Laplacian,

$$^2\psi (r)=\frac{^2\psi }{r^2}+\frac{(d_{}1)}{2}\frac{\psi }{r},$$
(30)   
yielding a fourth order partial differential equation for (24). The “source” for the composition wave comes from the boundary conditions obtained by linearization of (22) and (23), namely

$$\widehat{r}(k_0^2+^2)\psi (R)=0$$
(31)   
for conservation at the boundary, and

$$\widehat{r}\psi (R)=h+g\psi (R).$$
(32)   
This provides a pseudo one-dimensional system which can be readily integrated numerically.

The solutions for $`d_{}=1,2,3`$ presented in Fig. 6 illustrate the influence of $`d_{}`$ on the composition wave pattern. Increasing $`d_{}`$ reduces the amplitude of the composition wave. This feature can be understood to arise from the increasing volume occupied by the outer rings. The opposite situation should hold for exterior boundaries having these symmetries, so that more coherent ring structures might be anticipated in phase separation confined to these geometries, especially for spherical cavities. It may prove interesting to examine phase separation in the presence of fractal filler particles (like fumed silica) to determine whether geometry stabilizes or destabilizes the phase separation pattern and how the evolving phase separation pattern accommodates the fractal boundary structure.

Returning to the analytical estimation of the target pattern size, we expand $`\psi (r)`$ in a basis which diagonalizes the Laplacian. This amounts to performing a cosine transform for $`d_{}=1`$, a ($`J_0`$) Hankel transform in $`d=2`$, and a half-integer Hankel tranform in $`d=3`$. The last can be re-expressed as a Fourier cosine transform of $`r\psi (r)`$ rather than $`\psi `$. Here we study the extremal cases of $`d_{}=1`$ and $`3`$, and show that $`d_{}`$ has only a minor effect on the pattern size.

First, we revisit the $`d_{}=1`$ case already addressed by Ball and Essery . One can solve (24) with boundary conditions via Fourier cosine transformation with respect to $`r`$ and Laplace transform with respect to $`t`$, with the result,

$$\stackrel{~}{\psi }(k,s)=\frac{hk^2}{s[sk^2(k_0^2k^2)]}$$
(33)   
for the case $`g=0`$ (to which we restrict our attention). Inverting the Laplace transform and using a Gaussian approximation again to invert the Fourier cosine transform gives the solution

$$\psi _{d_{}=1}(z,t)\psi (0,t)e^{(z/4\lambda _0)^2}\mathrm{cos}(z/\lambda _0),$$
(34)   
where $`\psi (0,t)\frac{h}{k_0^3}\sqrt{\frac{8}{\pi t}}\mathrm{exp}\left(\frac{k_0^4t}{4}\right)`$, $`\lambda _0^1=k_0/\sqrt{2}`$, and where subdominant terms in $`1/t`$ have been neglected. A non-zero value of $`g`$, while complicating (33), would appear in this approximate solution only via the substitution $`hh+g\psi _0`$. In this $`d_{}=1`$ example, the $`R`$ dependence drops out of the linearized equation, and $`z=r`$ measures the distance from the wall.

For a given noise strength $`ϵ`$ we have a time $`t_0`$ at which the local composition of one phase reaches $`\psi _t`$. For surface interaction $`h`$ we solve for the distance $`z_0`$ out to which the envelope of $`\psi (r,t_0)`$ exceeds $`\psi _t`$. This gives the approximation,

$$z_02k_0^3t_0\left[1\frac{1}{k_0^4t_0}\mathrm{ln}\left(\frac{k_0^3\psi _t}{h}\sqrt{\frac{\pi t_0}{8}}\right)\right].$$
(35)   
Thus, the propagation front grows with a velocity $`2k_0^3`$ at long times , and the terms in square brackets are the leading correction to this long time asymptotic behavior.

The $`d_{}=3`$ composition profile may be obtained by observing that (24) and (30) yield the same equation for $`r\psi _{d_{}=3}(z,t)`$ as for the composition profile $`\psi _{d_{}=1}(z,t)`$. Thus, we impose the boundary conditions (to leading order in $`R/r`$) and follow the above derivation with the result

$$\psi _{d_{}=3}(z,t)\frac{R}{R+z}\psi _{d_{}=1}(z,t).$$
(36)   
Solving for the value $`z_0`$ at which the composition wave envelope equals $`\psi _t`$ leads to nearly the same expression as the $`d_{}=1`$ case (35), with an additional $`\mathrm{ln}(1+z_0/R)/k_0^4t_0`$ term in the square brackets. Typically $`z_010R`$, $`k_0`$ is of order unity, and $`t_0`$ ranges from 10 to 30, making this term roughly a 10% correction.

To compare with our simulations, we consider $`d_{}=d=2`$. For $`z_0`$ we simply take the arithmetic mean of the values obtained for $`d_{}=1`$ and $`d_{}=3`$ (motivated by numerical solutions). Equation (29) for $`t_0`$ is substituted into (35) to obtain a prediction for $`z_0`$ in terms of $`h`$, $`ϵ`$, and $`\psi _0`$. Here we consider critical quenches with $`\psi _0=0`$, or $`k_0=1`$. Finally, we approximate $`\mathrm{ln}t_0`$ and $`\mathrm{ln}z_0`$ with typical values, which introduces less than 10% error with the range of parameters considered here, and thus obtain

$$z_02.58.5\mathrm{log}_{10}ϵ+4.6\mathrm{log}_{10}h.$$
(37)   
A similar expression results for $`d=d_{}=3`$, with the primary difference being a change of the $`\mathrm{log}_{10}ϵ`$ coefficient to $`7.9`$.

Fig. 7 shows a comparison of this estimate with the simulations. We see that the analytic approximation provides a good rough estimate of the spatial extent of the phase separation pattern, although it predicts a size typically one oscillation larger than the outermost unbroken target.

We point out that the spherical composition waves are apparent in the average composition profiles even in the rather noisy looking ring patterns found in the late stage of target pattern formation. In Fig. 8 we show a target pattern at intermediate values of noise, as well as the radial average of the composition profile about the center of the target. Comparison shows that the ring composition pattern persists in the radial average even after the target pattern appears visually to have broken up. This provides a possible explanation of the apparent overestimate of the target size in Fig. 7.

## V Comparison with Experimental Results

While scattering measurements of the growth of composition waves are readily performed for a single plane boundary , these measurements become more difficult in filled blends where the filler particles are randomly distributed within the blend. This situation is unfortunate, given the predicted transient nature of the composition wave patterns when the particles are small. However, real space studies of blend phase separation are possible in films sufficiently thin to suppress the formation of surface-directed waves normal to the solid substrate . Under the favorable circumstances that one of the polymer components segregates to both the solid substrate and the polymer-air boundary of these nearly two-dimensional (“ultrathin”) blend films, phase separation is observed within the plane of the film . The variation of the surface tension in the film accompanying phase separation gives rise to film boundary undulations that can be measured by atomic force microscopy (AFM) and optical microscopy (OM) . The thickness of ultrathin blend films is typically restricted to small values ($`L200`$ nm) and the height contrast of the surface patterns tends to become larger in still thinner films . A film thickness in the range of 20 – 50 nm is often suited for observing well resolved phase separation surface patterns similar to those found in simulations of bulk blends. In the following we compare our results with those of a model blend utilized in ultrathin phase separation studies reported elsewhere with silica beads added as the model filler .

The spun-cast films are composed of a near-critical composition blend of polystyrene and poly(vinyl methyl) ether (PVME). The filler particles are silica beads having an average size of about 100 nm, as measured by direct imaging of the particles. This particular filler was chosen because of its tendency to be enriched by polystyrene, rather than PVME, which enriches both the solid and air surfaces. In this way, the filler particles are not competing with the solid or air surfaces for the enriching polymer. Phase separation was achieved by annealing the film approximately 15 within the two-phase region, corresponding to a fairly shallow quench. Film topography (height) was measure by AFM. Further details of the experiment are provided in Ref. .

Fig. 9(top) shows the topography of the blend film at an intermediate stage of phase separation where we expect circular filler-induced composition waves to be evident. The pattern resembles the simulated patterns under similar quench conditions. The symmetry of the film phase separation pattern is locally broken by the presence of the filler particles, leading to the formation of ring-like concentration wave patterns. Note that when observed on a larger scale \[Fig. 9(bottom)\], the phase separation pattern far from any filler particles resembles the typical spinodal decomposition pattern observed in control measurements on the same blends without filler.

It is apparent that the patterns in Fig. 9 are in a relatively late stage of phase separation, where the rings are beginning to break up along with the “background” phase separation pattern. The simulations above indicate that the target patterns are more persistently expressed in the radially averaged patterns and in Fig. 10 we show the radial average of the AFM height data centered about a representative filler particle. The target pattern in the radially averaged data extends far beyond the ring feature apparent in the image in Fig. 9. The data in Fig. 10 correspond to a shallow quench, and are comparable to the intermediate stage, shallow quench simulation data in Fig. 3.

Next we directly compare the prediction of the linearized theory to the AFM data. An exact solution of $`\psi _{d_{}=2}(z,t)`$ is difficult, but we can obtain a reasonable approximation to $`\psi _{d_{}=2}(z,t)`$ by generalizing the method described above for $`\psi _{d_{}=1}(z,t)`$. We estimate $`\psi _{d_{}=2}(z,t)`$ as a Gaussian decay function multiplied by the eigenfunction of the Laplacian in $`d=2`$ \[rather than in $`d=1`$ as in the case of (34)\]. In this approximation, $`\psi _{d_{}=2}(z,t)`$ becomes a product of a Gaussian as in Eq. (34) and a Bessel function $`J_0(2\pi z/\lambda _0)`$, and we show a fit of this function to the AFM data in Fig. 10. The fitted value of the particle radius $`R`$ is $`82`$ nm, which is comparable to the average particle radius obtained by optical microscopy ($`R100`$ nm). The scale parameters of the Gaussian and Bessel functions have been adjusted along with the prefactor which is set by the value of $`\psi _{d_{}=2}(z,t)`$ as $`z`$ tends to zero. It is clear that the oscillatory pattern scale is on the order of the background phase separation pattern, and that the linearized expression for $`\psi _{d_{}=2}(z,t)`$ has the qualitative shape of the measured profile. Such qualitative agreement is the best that can be expected from the linearized theory, which strictly speaking should hold only at very early times.

At still longer times, the phase separation pattern eventually breaks up into droplets and little difference is observed between the films with and without filler. Thus, the target patterns induced by the filler particles are transient, as observed in the simulations. Of course, the version of the CHC model used here cannot reliably describe quantitative features of these late stage processes without the incorporation of hydrodynamic interactions.

Under far off-critical conditions and a selective interaction between the filler particles and one of the polymers ($`h>0`$) the filler particles are “encapsulated” by a layer of the favored polymer so that concentration waves do not develop. The formation of droplets by nucleation or far off-critical spinodal decomposition can also have the effect of breaking the symmetry of the phase separation process, but the pattern formation is not generally the same as for critical composition mixtures. Recent measurements have reported the occurrence of filler encapsulation in a blend of polypropylene and polyamine-6 with glass bead filler particles . Encapsulation occurs when the polypropylene-rich phase having the selective interaction for the filler is the minority phase, but no encapsulation occurs when polypropylene is the majority phase. This finding compares well with the simulation results discussed in section IV.

Radiation crosslinking provides another source of heterogeneity that can be introduced readily in phase separating films. Measurements of irradiated photoreactive blends of PVME and PS with a crosslinkable side group styrene-chloromethyl styrene random copolymer (PSCMS) show the formation of striking ring composition patterns  and we reproduce one of these patterns in Fig. 11 (compare with Fig. 5). Furukawa  has interpreted these observations in terms of a model by which irradiation first brings the blend into the nucleation regime where droplets phase separate, followed by the entrance into the spinodal regime where the droplets act like the filler particles discussed in the present paper. This is a plausible interpretation of the qualitative origin of these patterns, but it is difficult to interpret these measurements directly from CHC simulations since crosslinking imparts a non-trivial viscoelasticity to the polymer blend . The crosslinking, which also increases the molecular weight of PSCMS, and the increased elasticity, both lead us to expect a decrease in the thermal noise and thus an increased tendency to form target patterns. It also seems plausible that the crosslinks themselves provide the source of heterogeneity, inducing the development of composition waves.

## VI Discussion

The presence of filler particles in a phase separating fluid mixture is found to give rise to transient composition wave patterns in simulations based on the Cahn-Hilliard-Cook model and in measurements  on ultrathin polystyrene/poly(vinylmethyl) ether blend films with silica filler particles. In both the simulation and the experiment, the composition wave patterns were found to be transient and the filler is found to have a diminishing effect as the scale of the phase separation pattern becomes larger than the filler particles. The propagation of composition waves is enhanced at lower thermal noise level so that the effect propagates to larger distances for deeper quenches and higher molecular weight blends. The finite size and the dimensionality of the filler particles are found in our simulations to have a similar effect in determining the stability of the composition wave pattern at intermediate times. The composition waves become more stable for particles large in comparison to the spinodal wavelength and the concentration waves exhibited by these larger particles are similar to planar interfaces. The composition waves about the filler particles are more stable for particles extended at great distance along more directions; i.e., surfaces are more stable than long cylinders, which are more stable than spherical filler particles. Our results compare favorably with experiments on phase-separating filled blend films which are nearly two-dimensional.

Filler particles are an example of a perturbation of phase separation by boundaries interior to the fluid. It would be interesting to investigate the influence of exterior boundaries of finite extent on phase separation. It seems likely that composition waves within confined geometries should be more stable because of the decreasing surface area of the rings farther from the surface. This should lead to well developed and more long lasting perturbations of the phase separation process. The relation between boundary shape and phase separation morphology should be very interesting for this class of measurements. Phase separation within arrays of filler particles where the distinction between interior and exterior boundaries becomes blurred and where larger perturbations of the phase separation process may be anticipated, should also prove interesting. The distinction between large and small and fixed and mobile filler particles should lead to a range of new phase separation morphologies since the development of composition waves should lead to changes in the filler-filler interaction that can influence the subsequent development of the film structure. The utilization of geometrically and chemically patterned surfaces and additives offer many opportunities for the control of the phase separation morphology and resulting properties of blend films, and the study of these surface-induced phase separation processes raise many interesting problems of fundamental and practical interest.

###### Acknowledgements.

The present work has benefitted greatly from close collaboration with experimentalists in the Polymer Blends Group at NIST. The simulations and experimental work were conducted simultaneously, and we thank Alamgir Karim and Eric Amis for many suggestions which influenced the design and interpretation of our simulations. We thank Giovanni Nisato for many useful conversations and providing the correlation function data for the filled films. We have also benefitted from conversations with Qui Tran-Cong regarding the relation of his measurements to our simulations and for contributing Fig. 11. B.P. Lee acknowledges the support of the National Research Council/NIST postdoctoral research program.    

## A Boundary Conditions on a Curved Surface

Curved boundaries complicate the implementation of boundary conditions in a spatially discretized simulation. In the present work, we use a square lattice and simulate filler particles with circular, cylindrical, and spherical symmetry. This requires a method of incorporating the boundary conditions that minimizes the effects of errors caused by approximating curved boundaries by lattices. In this appendix we present our approach to this problem.

Generally, (22) and (23) are imposed by inclusion of $`\psi `$ and $`\mu =^2\psi \psi +\psi ^3`$ values at the lattice sites on the immediate interior of the boundary (within the wall or filler), which are determined from the boundary conditions before each time step. We superimpose the circular boundary over the square lattice so that no lattice vertices lie along the boundary. Consequently, every interior point corresponds to one of two possibilities, shown as the lower left corners of Fig. 12 (a) and (b). The boundary condition at the point $`(x_0,y_0)`$ (shown as a black dot) is not set at the interior lattice site but rather at the intersection of the boundary and the radius passing through the interior lattice site.

In both cases of Fig. 12 we use the three vertices shown as open circles for the discretized representation of $`\psi (x_0,y_0)`$ and its normal derivative $`\widehat{r}\psi (x_0,y_0)`$. To highest order these representations are unique \[to $`O(\mathrm{\Delta }x^2)`$ for $`\psi `$ and $`O(\mathrm{\Delta }x)`$ for the derivative, with $`\mathrm{\Delta }x`$ the lattice spacing\]. Hence, (23) may be used to determine $`\psi _{i,j}`$, the field at the interior site, from the appropriate exterior points. We find for case (a) the relation

$$\psi _{i,j}=\frac{(1g\mathrm{})\left[(\mathrm{sin}\theta \mathrm{cos}\theta )\psi _{i,j+1}+\mathrm{cos}\theta \psi _{i+1,j+1}\right]h\mathrm{\Delta }x}{(1g\mathrm{})\mathrm{sin}\theta +g\mathrm{\Delta }x},$$
(A1)   
where $`\mathrm{}`$ is the distance from the interior lattice site to $`(x_0,y_0)`$ while $`\theta `$ is the angle between the radius and the horizontal axis. For case (b) the analogous expression is

$$\psi _{i,j}=\frac{(1g\mathrm{})\left[\mathrm{cos}\theta \psi _{i+1,j}+\mathrm{sin}\theta \psi _{i,j+1}\right]h\mathrm{\Delta }x}{(1g\mathrm{})(\mathrm{cos}\theta +\mathrm{sin}\theta )+g\mathrm{\Delta }x}.$$
(A2)   
The chemical potential $`\mu _{i,j}`$ may also be assigned at the interior point, in practice by assigning a value to $`(^2\psi )_{i,j}`$ to supplement the Laplacian derived from $`\psi `$ outside the boundary. In this way we can impose the conservation requirement (22) for case (a) via

$$\mu _{i,j}=(1\mathrm{cot}\theta )\mu _{i,j+1}+\mathrm{cot}\theta \mu _{i+1,j+1},$$
(A3)   
while for case (b),

$$\mu _{i,j}=\frac{\mathrm{cos}\theta }{\mathrm{cos}\theta +\mathrm{sin}\theta }\mu _{i+1,j}+\frac{\mathrm{sin}\theta }{\mathrm{cos}\theta +\mathrm{sin}\theta }\mu _{i,j+1}.$$
(A4)   
In simulations with thermal noise we assume a separation of time scales between thermal fluctuations and order parameter variations (as described in ), and simply supplement the above conditions with the conservation law for fluctuations at the boundary: $`\widehat{r}\nu =0`$, where $`\nu `$ is the noise current derived from $`\eta =\nu `$.