# Effect of Ordering on Spinodal Decomposition of Liquid-Crystal/Polymer Mixtures

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## Abstract

Partially phase-separated liquid-crystal/polymer dispersions display highly fibrillar domain morphologies that are dramatically different from the typical structures found in isotropic mixtures. To explain this, we numerically explore the coupling between phase ordering and phase separation kinetics in model two-dimensional fluid mixtures phase separating into a nematic phase, rich in liquid crystal, coexisting with an isotropic phase, rich in polymer. We find that phase ordering can lead to fibrillar networks of the minority polymer-rich phase.

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Mixtures of liquid crystals with a small amount of polymer (polymer-stabilized liquid crystals, or PSLC’s) show promise for electro-optic devices such as light shutters and displays , because the polymer tends to form a network that aligns the liquid crystal. Since polymers and liquid crystals tend to be immiscible, the dispersions are prepared by mixing a small amount of miscible monomer with the liquid crystal and photopolymerizing. As the polymers grow, the system phase separates into an ordered phase rich in liquid crystal and an isotropic phase rich in polymer. Long before the system reaches equilibrium, however, the polymerization “freezes” the mixture into a crosslinked network of polymer-rich domains. Thus, the fabrication of PSLC’s involves interplay among three kinetic processes: polymerization, phase separation, and phase ordering. Depending on the time scales that control these processes, a rich variety of morphologies have been observed. Because of the number of nonequilibrium processes involved, however, there is little theoretical understanding of the factors that control the domain morphology. In this Letter, we focus on the interplay between phase separation (PS) and phase ordering (PO) kinetics in mixtures of short, rigid polymers (rods) and long, flexible polymers (coils), as a first step towards rational design and control of the network morphology.

It is well known that thermodynamic factors such as the anisotropy of the isotropic/nematic interfacial tension can influence domain morphology, leading to anisotropic domain shapes. However, there are also kinetic factors that control domain morphology, such as the anisotropic diffusion coefficient of a rod. To capture these thermodynamic and kinetic effects, we use a Cahn-Hilliard framework that allows composition and orientational density to evolve in a coupled fashion as functions of position and time following a temperature quench. In contrast to earlier studies that treat orientational density as a scalar order parameter, this framework includes the orientational density’s second-order tensorial nature. Although it is instructive to study the case of two coupled scalar order parameters (Model C), a scalar cannot capture the direction of nematic order. Because a vector does not have head/tail symmetry, it is crucial to retain the tensor order parameter to obtain domain anisotropy.

To assess the effects of phase ordering, we study two systems. The first (denoted RC) is a mixture of rods and coils. The second (denoted CC) is a polymer blend, identical to RC except that the rods are replaced by flexible chains of the same length that do not align. In both cases, we solve the linearized coupled partial differential equations of motion analytically, and the nonlinear equations numerically into the late-time regime, after quenching the isotropic, homogeneous mixture into the coexistence region. We find that phase ordering dramatically affects morphology, giving rise, for example, to interconnected networks or elongated domains depending on whether phase ordering or phase separation is the initially dominant process.

We study two-dimensional, incompressible mixtures of chain molecules made up of monomers of the same size. In RC, we have short rods that are $`N_A=10`$ monomers long, and coils that are $`N_B=100`$ monomers long. The phase behavior of the system is governed by a bulk free energy $`F_{\mathrm{RC}}`$ that couples the area fraction of rods, $`\varphi `$, to the orientational density of the rods, $`\stackrel{}{S}`$. This free energy consists of two parts: the Flory-Huggins free energy, which governs phase separation, and the Landau-de Gennes free energy, which governs the isotropic/nematic transition. The free energy was calculated within the random phase approximation. It depends on the rod and coil lengths, and contains only two free parameters. These are the two interaction parameters, namely the Flory parameter, $`\chi `$, and the Maier-Saupe parameter, $`w`$, which control the isotropic and anisotropic monomer-monomer interactions, respectively. Both of these parameters depend on temperature with entropic and enthalpic contributions: $`\chi =\chi _0+\chi _1/T`$ and $`w=w_0+w_1/T`$. We have chosen the parameters $`\chi _i`$ and $`w_i`$ so that the critical temperature for phase separation according to the Flory-Huggins free energy, $`T_c`$, and the isotropic/nematic transition temperature of the pure rod system, $`T_{ni}`$, are both of order unity in our (arbitrary) units, with $`T_{ni}`$ higher than $`T_c`$. We use $`\chi _0=0.055`$, $`\chi _1=0.036`$, $`w_0=0.55`$, and $`w_1=0.26`$, which yield $`T_c=1.14`$ and $`T_{ni}=1.3`$. The resulting RC phase diagram is shown in Fig. 1.

Below a triple point, the system demixes into an isotropic phase rich in coils and a nematic phase rich in rods. Above the triple point, there is an isotropic-isotropic coexistence region and an isotropic-nematic (IN) coexistence region. The IN coexistence region ends in a critical point that is connected to the IN transition of a pure rod system by a second-order transition line. Note that in three dimensions, the IN transition is first order, so the phase diagram would be different. Below the triple point, however, we find that the IN coexistence curves are qualitatively identical in two and three dimensions. The dashed line represents the spinodal for phase separation (PS), while the dotted line is the spinodal for phase ordering (PO).

In the CC system, we also use $`N_A=10`$ and $`N_B=100`$ monomers. Because the “rods” are now flexible, the free energy $`F_{\mathrm{CC}}`$ is given by the Flory-Huggins free energy only, without the Maier-Saupe contribution . The parameter $`\chi `$ is exactly the same as in the RC system. Thus, CC is identical to RC except that there is no phase ordering.

We study the morphology following four quenches from the isotropic, homogeneous phase into the IN coexistence region below the triple point, to the four points marked A-D in the RC phase diagram. We use a simplified version of the equations of motion derived within the dynamical random phase approximation

$`{\displaystyle \frac{\varphi }{t}}`$ $`=`$ $`\mathrm{\Gamma }_{\varphi \varphi }^2{\displaystyle \frac{\delta F(\varphi ,\stackrel{}{S})}{\delta \varphi }}`$ (1)   
$`{\displaystyle \frac{S^{ij}}{t}}`$ $`=`$ $`\mathrm{\Gamma }_{SS}^{ijkl}{\displaystyle \frac{\delta F(\varphi ,\stackrel{}{S})}{\delta S^{kl}}}`$ (2)   
where $`\mathrm{\Gamma }_{\varphi \varphi }`$ and $`\mathrm{\Gamma }_{SS}^{ijkl}`$ are calculated Onsager coefficients that depend on the single chain and single rod diffusion coefficients; expressions for these coefficients are provided in Ref. . The free energy functional $`F(\varphi ,\stackrel{}{S})`$ consists of the bulk free energy and a nonlocal free energy that controls the cost of gradients in composition and orientational density. Note that the cost of gradients in orientational density are determined by the Frank elastic constants that characterize nematic elasticity. For CC, the time evolution is given by Eq. 1 alone, since $`\stackrel{}{S}=0`$ and $`\delta F_{\mathrm{CC}}/\delta S^{ij}=0`$. We emphasize that for both systems, the equations of motion are not phenomenological; they are derived from microscopic models. We solve the discretized equations on a square lattice of size $`150^2`$ using a variable timestep Runge-Kutta numerical integration scheme. We have also varied the number of lattice points and the size of the mesh to verify that our observations do not depend on system size or discretization.

Quench A: Here we quench to a point where RC is initially unstable with respect to PS, but metastable with respect to PO. Thus, the point marked A in Fig. 1 lies below the spinodal for PS and above the one for PO. For CC, where phase ordering is absent, this quench leads to circular droplets rich in the shorter coils, in a matrix rich in the longer coils. RC initially displays almost identical behavior with circular droplets rich in rods. Once the concentration of rods in the droplets is comparable to the concentration at the IN spinodal, however, the rods in the droplets begin to order. At this time, the droplets abruptly expel more coils because the coils are less soluble when the rods are ordered. In addition, the droplets must develop defects because the rods want to be parallel to each other and parallel to the droplet interface. As the rods order, a pair of defects forms inside each droplet and separates, with the two defects moving along the director in opposite directions towards the edge of the droplet. The magnitude of orientational order is lower at the edges than in the center; thus, the defects migrate towards the edges to lower their energy. Since the overall system is isotropic, the long axis of each droplet is randomly oriented. Note that it is essential to retain the tensorial nature of the orientational order parameter in order to obtain randomly-oriented elongated domains. Fig. 2 shows a snapshot of the RC system at a time at which there is significant phase separation and ordering.

Quench B: For this quench, CC is metastable with respect to PS, so isolated droplets rich in the long coils would form by nucleation if we had included thermal noise. Since we have not included thermal noise, the CC system does not evolve. In this region RC is also initially metastable with respect to PS, but it is unstable with respect to PO. The instability towards orientational ordering eventually drives the system to phase separate because the two order parameters are coupled. This makes physical sense: once the rods are strongly aligned, they expel the coils into isolated droplets. Although there is no orientational order within the coil-rich droplets, the droplets are anisotropic because of the nematic elasticity in the surrounding rod-rich matrix.

The appearance of droplets even when the system is only metastable to phase separation is reminiscent of recent theoretical work on protein and polymer crystallization, which shows that a quench below the spinodal for one order parameter (density) can promote domain growth in another order parameter (crystallization). The advantage of our system is that we can calculate the coupled equations of motion for our two order parameters ¿from a microscopic model of rods and coils.

Quench C: In this quench, RC is initially unstable both to PS and to PO, but is more unstable with respect to PS. In both RC and CC, the system forms a bicontinuous network that rapidly breaks up into droplets rich in long coils. In RC, however, defects in the surrounding rod-rich domains give rise to droplets that are noncircular, as shown in Fig. 3. Furthermore, the coupling of PS and PO leads to a faster onset of phase separation in RC than in CC, because the rod-rich regions tend to expel coils as the rods order.

Quench D: As in Quench C, RC is initially unstable both to PS and to PO. However, in this quench it is more unstable with respect to PO. Once the degree of order is significant, then phase separation begins. Because of PO, PS begins much earlier in RC than in CC; by the time CC displays any noticeable phase separation, the concentration difference between the two phases in RC has already reached its equilibrium value. Fig. 4 presents snapshots of the systems as they evolve in time. In CC, an interconnected network rich in the longer coils initially appears. However, it quickly breaks up into droplets that become increasingly circular over time. In RC, on the other hand, small highly-ordered rod-rich droplets initially form in a coil-rich matrix. As these rod-rich droplets grow, the surrounding coil-rich region shrinks into a network of interconnected domains that are strikingly fibrillar, despite the fact that the coil-rich phase is the minority phase. This is in contrast to systems with only a compositional order parameter (Model B ), where only the majority phase can form networks. Eventually, this network breaks up to form coil-rich droplets; again, these are noncircular because of defects in the surrounding rod-rich regions. However, in experiments the crosslinking of the polymer network may arrest the phase separation at the fibrillar network stage.

In summary, we find that phase ordering can significantly influence domain morphology, especially when (1) the system is unstable to both phase separation and phase ordering and (2) orientational order is significant at the onset of phase separation. This is consistent with morphologies observed in PSLC’s, where fibrillar networks of the minority polymer-rich domains form when the system is initially ordered. Our results show that we can learn much about domain morphology from the phase diagram and spinodal lines, and that the coupling of phase separation and ordering kinetics leads to rich phenomena that warrant further study.

We thank Abdullah Al Sunaidi, Rashmi Desai, Weinan E, Peter Palffy-Muhoray, and Rebecca M. Nyquist for stimulating and instructive discussions that led to this research. This work was supported by NIST through the Center for Theoretical and Computational Materials Science and by the NSF through Grant No. CHE-9624090 (AJL).