# Diffusional growth of wetting droplets

## Abstract

The diffusional growth of wetting droplets on the boundary wall of a semi-infinite system is considered in different regions of a first-order wetting phase diagram. In a quasistationary approximation of the concentration field, a general growth equation is established on the basis of a generalized Gibbs-Thomson relation which includes the van der Waals interaction between the droplet and the wall. Asymptotic scaling solutions of these equations are found in the partial-, complete- and pre-wetting regimes.

The physics of wetting phenomena has attracted much interest in recent years, both from experimental  and from theoretical  points of view. Whereas initially static properties dominated the discussion, the interest has shifted more recently to the dynamics of wetting . In many experimental situations the formation of a wetting layer starts with the nucleation of droplets on the boundary wall of the system. The central question therefore is the temporal evolution of the droplet profile.

There are essentially two different types of dynamic behavior of a liquid surface droplet. The first is a spreading process which e.g. dominates, if a droplet of a non-volatile liquid is overheated from below to above a wetting transition point. Such processes are driven by hydrodynamic modes of the liquid, and they have extensively been discussed in the literature . The second mechanism is the phase transformation (condensation or evaporation) between the liquid and the vapor phase of the droplet. This is driven by particle diffusion in the vapor, and e.g. is the dominating process in the growth of supercritical droplets in a metastable situation.

Whereas the diffusional growth of a homogeneous wetting layer has been discussed in the literature , this seems not to be the case for surface droplets. The present paper deals with the diffusional growth of a supercritical droplet from a super-saturated vapor. This process is accompanied by the creation of latent heat, and it will be assumed that heat transport as well as other hydrodynamic modes are fast compared to the diffusion. As a consequence the droplet is isothermal and always has a shape which minimizes its free energy at a given volume. The time dependence of this shape is the main object of interest in this paper.

The excess free energy of a wetting film of local thickness $`f(x)`$ on a planar boundary wall of a semi-infinite system can be written in the form 

$$_h[f]=d^2x\left[\frac{\gamma }{2}\left(f\right)^2+V(f)hf\right],$$
(1)   
where $`\gamma `$ is the interface stiffness, $`h`$ is the difference of the chemical potential from that of the saturated vapor and $`V(f)`$ is an effective interface potential. The field $`h`$ can be expressed by the difference between the vapor concentration $`c`$ and its value $`c_0`$ at saturation, so that in linear order

$$c=c_0\left(1+\mathrm{\Gamma }h\right).$$
(2)   
The form of the potential $`V(f)`$ corresponding to a first-order wetting transition is sketched in Fig. 1. There, for temperatures $`T`$ less than the wetting temperature $`T_w`$, the global minimum of $`V(f)`$ is at $`f=f_0`$, whereas for $`T>T_w`$ this minimum becomes metastable in favor of the global minimum at diverging film thickness. For $`f\mathrm{}`$ we assume $`Vf^{1\sigma }`$, where $`\sigma =3`$ for nonretarded and $`\sigma =4`$ for retarded van der Waals interactions .

Homogeneous (i.e. $`f(x)=const`$) minima of the excess free energy $`_h[f]`$ (i.e. the global minima of $`V(f)hf`$) determine the phase diagram, shown in Fig. 2. In the region $`h>0`$, where the liquid bulk phase is stable, a film of infinite thickness forms on the wall in thermal equilibrium. On the line $`h=0`$, which means bulk coexistence of the liquid and vapor phases, the first-order wetting transition occurs at $`T=T_w`$, where $`f=f_0`$ for $`h=0`$, $`T<T_w`$ (partial wetting), and $`f=\mathrm{}`$ for $`T>T_w`$ (complete wetting). From the transition point a prewetting line $`h_p(T)`$ extends into the region $`h<0`$ where the vapor phase is stable in the bulk. This line separates a region (below $`h_p(T)`$) where the wall is covered by a thin film from a region ($`h>h_p(T)`$) where the wall is covered by a thick film. The jump in film thickness along the prewetting line vanishes at the prewetting critical point $`T_{pw}`$. The partial wetting line $`h=0`$, $`T<T_w`$ and the prewetting line $`h_p(T)`$ together form a first order line concerning the wetting properties of the system .

If the system is quenched from below to above the first order line (for example by increasing the pressure), the phase transition is initialized by the formation of critical droplets on the wall (provided, one stays within the surface spinodal lines, shown in Fig. 2). The shape of these droplets is qualitatively different in different regions of the phase diagram . Axisymmetric profiles $`f(r)`$ can be calculated via the saddle point equation

$$\delta _h/\delta f(r)=0$$
(3)   
with the natural boundary conditions of a droplet profile

$$f^{}(0)=0,\underset{r\mathrm{}}{lim}f(r)=f_0.$$
(4)   
As illustrated in Fig. 2, this leads to spherical (in the squared gradient approximation of Eq. (1) parabolic) caps in the partial wetting regime, to flat cylindrical droplets (pancakes) in the prewetting regime  and to ellipsoid-like droplets in the complete wetting regime . The saddle point $`\delta _h/\delta f(r)=0`$ has an unstable growth mode but the volume preserving shape fluctuations are stable .

Assuming that the volume growth of the droplet is slow, the diffusion in the surrounding concentration field $`c`$ becomes quasistationary and can be approximated by the Laplace equation

$$D\mathrm{\Delta }c=0,$$
(5)   
where $`D`$ is the diffusion constant. At far distances from the droplet the concentration field is given by the system concentration $`c_{\mathrm{}}(t)`$ which is time-dependent in a supersaturated system ($`h>0`$) because of the phase-separation process in the metastable bulk phase. The normal derivative of the concentration field on the boundary wall of the system vanishes because there is no diffusion flux into the wall, i.e. the Neumann boundary condition

$$D_{}c|_{\text{wall}}=0$$
(6)   
has to be fulfilled.

To obtain a well defined diffusion problem the boundary condition on the surface as well as the actual shape of the supercritical droplet need to be specified. Motivated by the slow diffusional growth of the droplet the concentration field close to the droplet surface is assumed to be in local thermal equilibrium. Therefore the local chemical potential $`h(x)`$ at the droplet surface is given by $`h(x)=\delta _0/\delta f(x)`$ which due to (2) corresponds to a concentration

$$c_s(x)=c_0\left(1+\mathrm{\Gamma }\frac{\delta _0}{\delta f(x)}\right),$$
(7)   
which can be denoted as a generalized Gibbs-Thomson relation for wetting droplets. The expression $`\delta _0/\delta f`$ consists of a term $`\gamma `$ times the local curvature $`K`$ of the droplet interface plus an interaction term $`V/f`$. Neglect of the interaction term reduces (7) to the classical Gibbs-Thomson relation $`c_s=c_0(1+\mathrm{\Lambda }K)`$ with the capillary length $`\mathrm{\Lambda }\mathrm{\Gamma }\gamma `$. It identifies the concentration at a curved interface as the concentration $`c_0`$ for a flat interface modified by a linear curvature correction.

The assumption of fast hydrodynamic modes (compared with the diffusional growth) implies that the shape of a growing droplet can be calculated by minimizing its free energy under the constraint of a fixed droplet volume $`\mathrm{\Omega }(t)`$. Technically, this variational calculation leads again to Eq. (3) with the boundary conditions (4) but now with $`h`$ in (3) replaced by a function $`h_{\mathrm{\Omega }(t)}`$ which includes a Lagrange parameter corresponding to $`\mathrm{\Omega }(t)`$. Consequently the growing supercritical droplet always looks like a critical droplet at a different time-dependent chemical potential. With increasing volume $`\mathrm{\Omega }(t)`$ the corresponding field $`h_{\mathrm{\Omega }(t)}`$ approaches the first order line, where eventually the volume of the droplet diverges. In this sense wetting droplets grow along isotherms towards the first order line, as illustrated in Fig. 2.

The saddle point equation (3) with the fixed volume constraint is equivalent to $`\delta _0/\delta f=h_{\mathrm{\Omega }(t)}`$. Via Eq. (7) this implies that the Dirichlet boundary condition of the constrained equilibrium droplet is given by

$$c_s(t)=c_0\left(1+\mathrm{\Gamma }h_{\mathrm{\Omega }(t)}\right)$$
(8)   
and therefore independent of $`x`$. Especially in the complete wetting or prewetting case, where the droplets are not spherical, one would expect a non trivial boundary condition having the classical Gibbs-Thomson condition in mind. Additionally corrections due to the potential $`V(f)`$, which determine the shape of the droplets in these regions, have to be taken into account. Nevertheless both effects add up in such a way that Eq. (7) can be written as Eq. (8) for a droplet in a volume-constraint equilibrium showing that $`c_s`$ is constant along the droplets surface!

Now, the $`x`$-independent Dirichlet boundary condition (8) allows to use an electrostatic analogy to solve the quasistationary diffusion problem (5)–(7) for the growing droplet . To fulfill the Neumann condition (6), the system (including the droplet) is mirrored at the boundary wall of the system. Then the field $`4\pi Dc`$ is identified with an electric potential which also obeys the Laplace equation. The normal derivative of the field, i.e. the diffusion flux density on the droplet surface field, corresponds to the charge density of a conductor with the shape of the droplet including its mirror image. Consequently, the total volume growth of the droplet corresponds to the total charge, which is given by the capacity $`C`$ of the conductor times the potential difference between the surface and infinity. This ultimately leads to the droplet growth equation

$$\dot{\mathrm{\Omega }}=4\pi DC(t)\left[c_{\mathrm{}}(t)c_s(t)\right]=4\pi D\mathrm{\Gamma }C(t)\left[h(t)h_{\mathrm{\Omega }(t)}\right]$$
(9)   
where $`C`$ depends on the droplets profile and therefore is implicitly time-dependent . The difference $`\left[h(t)h_{\mathrm{\Omega }(t)}\right]`$ may be interpreted as the supersaturation of the system with respect to the droplet.

Eq. (9) together with Eqs. (1), (3) and (4) allow to determine selfconsistently the growing droplet profile if $`h(t)`$ is known. For a given volume $`\mathrm{\Omega }`$, the droplet profile can be calculated from by Eqs. (1), (3) and (4) with a conveniently chosen Lagrange multiplier $`h_\mathrm{\Omega }`$. Then the capacity $`C`$ of the conductor represented by the droplet plus its mirror image is calculated. Insertion of $`C`$, $`h_\mathrm{\Omega }`$ and the chemical potential $`h`$ into Eq. (9) yields the droplet growth rate $`\dot{\mathrm{\Omega }}(t)`$ and integration of (9) eventually determines $`\mathrm{\Omega }(t)`$.

In practice, for large droplets, the calculation can be facilitated by the use of scaling properties of critical droplets close to the first-order transition line . At temperatures $`T>T_w`$ the wetting droplets on the wall nucleate either as ellipsoid-like droplets at $`h0`$ (complete wetting) or as pancake like droplets at $`h_p(T)<h<0`$ (prewetting). In both cases the droplets grow along an isotherm towards the prewetting line ($`h_{\mathrm{\Omega }(t\mathrm{})}h_p(T)`$). This means that they eventually become pancake-like droplets with a constant height but diverging radius $`R(t)`$ so that the capacity of large droplets is given by the capacity of a flat disk $`C(t)R(t)`$. In the case where the initial quench leads to a supersaturated bulk system ($`h>0`$) the volume will phase separate until it reaches $`h=0`$ whereas for initial values $`h<0`$ the vapor bulk phase is stable and $`h`$ remains constant in time. In either situation the difference $`[hh_\mathrm{\Omega }]`$ approaches a non-vanishing constant so that Eq. (9) yields $`\dot{\mathrm{\Omega }}\mathrm{\Omega }^{1/2}`$ or $`\mathrm{\Omega }t^2`$ which implies

$$Rt,$$
(10)   
and only is determined by the time dependent capacity, i.e. the increasing diffusive coupling to the environment.

Wetting droplets at $`T=T_w`$ in a supersaturated system ($`h>0`$) also are not spherical. Their radius $`R`$ scales as $`Rh_{\mathrm{\Omega }}^{}{}_{}{}^{(\sigma +1)/\mathrm{\hspace{0.17em}2}\sigma }`$, their central height $`F`$ as $`Fh_{\mathrm{\Omega }}^{}{}_{}{}^{1/\sigma }`$, and consequently their volume as $`\mathrm{\Omega }h_{\mathrm{\Omega }}^{}{}_{}{}^{(\sigma +2)/\sigma }`$ . Therefore, the profile of a growing wetting droplet becomes flatter and approaches a disk with capacity $`CRh_{\mathrm{\Omega }}^{}{}_{}{}^{(\sigma +1)/\mathrm{\hspace{0.17em}2}\sigma }`$. In a supersaturated system (i.e. $`h>0`$) there are not only wetting droplets on the wall, but also droplets in the bulk. The set of growing bulk droplets reduces the supersaturation in a Lifshitz-Slyozov-Wagner type way as $`ht^{1/3}`$ . With this input the wetting droplet growth equation (9) can be written as

$$\dot{h}_\mathrm{\Omega }h_{\mathrm{\Omega }}^{}{}_{}{}^{\frac{2(\sigma +1)}{\sigma }}h_{\mathrm{\Omega }}^{}{}_{}{}^{\frac{\sigma +1}{2\sigma }}\left[At^{1/3}h_\mathrm{\Omega }\right]$$
(11)   
for large droplets. This leads to the asymptotic growth law $`h_\mathrm{\Omega }t^{\frac{4\sigma }{3(\sigma +3)}}`$ which due to the above scaling properties for $`R`$ and $`F`$ implies

$$Rt^{\frac{2(\sigma +1)}{3(\sigma +3)}},Ft^{\frac{4}{3(\sigma +3)}}.$$
(12)   
Finally, in the partial wetting regime $`T<T_w,h>0`$, the wetting droplets are spherical caps, and therefore their growth properties are similar to those of bulk droplets, i.e.

$$Rt^{1/3}$$
(13)   
The evaluation of the difference $`[hh_\mathrm{\Omega }]`$ in Eq. (9) can only be done in a theory where diffusional interactions between surface and bulk droplets are taken into account . At late stages partial wetting droplets in systems with a temperature corresponding to a contact angle $`\mathrm{\Theta }>\pi /2`$ will shrink because $`[hh_\mathrm{\Omega }]`$ turns negative for each droplet, whereas droplets at a temperature with $`\mathrm{\Theta }<\pi /2`$ will grow.

One of the basic ingredients of the present calculation is the Neumann boundary condition (6). It derives from the fact that there is no diffusion flux through the wall. Even if the wall locally is in a non-wet state it always is covered by a film of microscopic thickness $`f_0`$. If somewhere in such a region Eq. (6) were not valid, the film would thicken there and the interface would run out of the microscopic minimum of the interface potential shown in Fig. 1. Due to the generalized Gibbs-Thomson relation (7), which includes a term $`V/f`$, the local concentration on top of the surface would then increase and the film would evaporize until it again reaches the former height $`f_0`$. Thus, up to fluctuations, Eq. (6) will be valid.

The calculation of the supercritical droplet shape is based on the assumption of fast hydrodynamic modes compared to the droplets diffusional growth. This assumption may become questionable, if a prewetting droplet becomes very large. However at this very late stage the coalescence of different droplets will be dominant anyway.

I like to thank R. Bausch and R. Blossey for stimulating discussions and the Deutsche Forschungsgemeinschaft via SFB 237 “Unordnung und große Fluktuationen” and “Benetzung und Strukturbildung an Grenzflächen” as well as the EU via FMRX-CT 98-0171 “Foam Stability and Wetting Transitions” for financial support.