# Untitled Document

Diffusional Growth of Colloids

Dima Mozyrsky and Vladimir Privman

Department of Physics, Clarkson University

Potsdam, New York 13699–5820, USA

Abstract

We consider incorporation of particle detachment in Smoluchowski model of colloidal growth. Two approaches are considered, utilizing phenomenological rate equation and exact large-time results. Our main conclusion is that the value of the large-time diffusing particle concentration at the aggregate surface is the only parameter needed to describe the added effect of detachment. Explicit expression is given for the particle intake rate.

Electronic mail: privman@clarkson.edu

1. Introduction

In this work we address aspects of the theory of growth of aggregates by capture of small diffusing particles (singlets), such as atoms, molecules, etc., with focus on processes relevant in colloidal growth. The celebrated work of Smoluchowski , reviewed, e.g., in , considered the process of diffusional capture of particles as follows. The growing aggregate is modeled “adiabatically” as a sphere of radius $`R`$. The concentration of particles is initially $`c_p`$ ($`p`$ stands for particles). Next, the radially symmetric concentration of particles at time $`t`$, $`c(r,t)`$, is calculated by solving the diffusion equation with the absorbing boundary condition at $`r=R`$, i.e., $`c(R,t>0)=0`$. The resulting particle intake $`\mathrm{\Phi }`$ (number per unit time) into the sphere is usually taken as the large-time (steady-state) limit of the following expression obtained from this solution:

$$\mathrm{\Phi }(t)=4\pi DRc_p\left(1+\frac{R}{\sqrt{\pi Dt}}\right),$$
$`(1.1)`$   
where $`D`$ is the singlet diffusion constant. The value of $`\mathrm{\Phi }(\mathrm{})`$ is then used to estimate the growth rate of the spherical aggregate.

In colloidal growth, a popular model has been that of “burst nucleation” by LaMer and Dinegar \[3-4\]. In this model, one adopts concepts from the classical nucleation theory to colloidal aggregation. Specifically, for sufficiently small aggregate radii $`R`$, it is assumed that the aggregate sizes are distributed according to the equilibrium condition with the Boltzmann factor determined by the aggregate free energy $`G(R)`$. This equilibrium distribution is usually assumed to apply for $`R<R_c`$, where the critical radius $`R_c`$ corresponds to the maximum of the free energy.

Larger aggregates, those with $`R>R_c`$, are assumed to grow irreversibly by the diffusional mechanism (1.1) and possibly by cluster-cluster aggregation, depending on the precise nature of forces between aggregates. The whole picture is “adiabatic” in that many of the quantities involved, specifically, $`G`$, $`R_c`$, $`c_p`$, evolve in time, presumably on the time scales much larger than the times needed to establish the asymptotic large-time diffusional flux; see (1.1). Thus, for the diffusion part of the description, the steady state results nearly always suffice.

For clusters with $`R<R_c`$, there must be dynamical mechanisms that lead to equilibration, if the “nucleation” droplet-model concept is indeed applicable to colloids. In addition to the mechanisms that correspond to internal rearrangement and restructuring, there must be also $`\underset{¯}{\text{detachment}}`$ of particles. Indeed, the aggregates cannot only grow, by capturing singlets, while at the same time achieve equilibrium distribution. Since the critical cluster size $`R_c`$ can be actually quite large, it follows “by continuity” that detachment will also occur for clusters with $`R>R_c`$ which are not in equilibrium.

The main goal of the present work is to incorporate detachment process in Smoluchowski model. Thus, we focus on the diffusion problem. We assume that the aggregates are large, $`R>R_c`$, and that their radii vary slowly with time so that the time scales of singlet diffusional processes are fast in comparison. Furthermore, by focusing on the diffusion problem we avoid discussion of cluster-cluster aggregation and of detachment of multiplets, as well as of internal restructuring processes. The latter are present not only for small clusters but also for large clusters because without internal restructuring, diffusion-limited colloidal growth would result in fractals, e.g. . Under properly chosen experimental conditions, e.g.  and references therein, the aggregates are as dense as the bulk material and have definite shapes, frequently spherical as assumed here, and semicrystalline structure.

Our second goal is to emphasize a difference between the colloidal growth and classical nucleation. Specifically, we note that the intake expression (1.1) for $`t=\mathrm{}`$ is proportional to $`R`$ rather than to the surface area of the collector aggregate $`4\pi R^2`$. In ordinary metastable-to-stable two-phase nucleation, when the transport mechanisms are not diffusional, for large clusters one can assume that each unit of the surface area captures and emits equal amounts of atoms or molecules. The net intake rate is then proportional to the surface area . We would like to explore failure of this “surface extensivity” argument for colloids and include detachment in this discussion. A related matter is the mere existence of the “surface layer” since intuitively it seems to be connected with the “per-unit-area” adsorption and detachment.

Finally, we would like to have few-parameter approaches that retain the simplicity and exact solvability of Smoluchowski model. We note that numerous modifications of Smoluchowski model have been proposed in the literature; see  for reviews. The most studied case in the field of colloids has been deposition of particles in a low- or intermediate-density monolayer on a solid substrate, without incorporation of the deposited particle into the material of the collector by internal restructuring. Detachment from such monolayers is approximately proportional to the amount of matter deposited. It is modeled by phenomenological rate equations for the surface coverage coupled with expressions for the diffusional or convective-diffusional flux . A detailed mathematical study of one such boundary condition was published by Agmon . Experimental results have been reviewed in .

Another application of Smoluchowski approach has been in the field of chemical reaction rates in the diffusion-limited regime, reviewed in . Here $`R`$ is no longer large. Instead of detachment one has partial reaction, i.e., some particles may not react on encountering a collector. This is mathematically described by the radiation boundary condition .

The outline of the rest of this article is as follows. In Section 2, we consider a phenomenological model for the boundary condition at the aggregate surface that allows for detachment in Smoluchowski model. In Section 3, we derive a generalized radiation boundary condition which is exact in the large-time limit. The diffusion problem with the latter boundary condition is solved in Section 4. Finally, in Section 5 we compare the two approaches and conclude that for all practical purposes one can actually use a simpler boundary condition which only involves one new parameter: the concentration of the diffusing particles right at the aggregate surface.

2. Phenomenological Rate Equation Model

In the original Smoluchowski model , the radially symmetric version of the diffusion equation,

$$\frac{c}{t}=r^2\frac{}{r}\left(r^2D\frac{c}{r}\right)$$
$`(2.1)`$   
is solved for $`rR`$, with the initial condition

$$c(r,t=0)=c_p$$
$`(2.2)`$   
and boundary condition

$$c(r=R,t>0)=0.$$
$`(2.3)`$   
The discontinuity in the value of the concentration at $`r=R`$ (at $`t=0`$ as compared to that at $`t>0`$), shared by many modifications of the problem, leads to singular behavior at $`t=0`$, see (1.1), that has been of some concern in the literature on chemical reaction applications .

One can consider various modifications of the relations (2.1)-(2.3) to improve the model and incorporate effects other than the irreversible adsorption at $`r=R`$ expressed by (2.3). In this section we consider a phenomenological modification of the boundary condition (2.3) to allow for detachment. We use Langmuir-type mean-field rate equation approach popular in applications of this sort in colloid literature, e.g. . Thus, we propose the relation

$$\frac{c}{t}=Kc+k,\mathrm{at}r=R,$$
$`(2.4)`$   
to replace (2.3). Here we assume that diffusing particles that reach the surface are incorporated in the aggregate structure at the rate $`Kc`$ proportional to their concentration at $`R`$. The second term corresponds to detachment, and we assume that this rate only depends on the internal processes so there is no dependence on the external diffuser concentration.

In order to solve (2.1) with (2.2), (2.4), we define Laplace Transform of the concentration,

$$n(r,s)=_0^{\mathrm{}}𝑑te^{st}c(r,t),$$
$`(2.5)`$   
which satisfies the equation

$$snc_p=r^2\frac{}{r}\left(r^2D\frac{n}{r}\right).$$
$`(2.6)`$   
Here we already used the initial condition. The general solution of this equation is given by

$$n=\frac{c_p}{s}+\frac{A(s)}{r}e^{\sqrt{s/D}r}+\frac{B(s)}{r}e^{\sqrt{s/D}r},$$
$`(2.7)`$   
where we set $`B=0`$ to have a bounded solution as $`r\mathrm{}`$. The boundary condition at $`R`$ becomes

$$snc_p=Kn+ks^1,\mathrm{at}r=R.$$
$`(2.8)`$   
The final result for the concentration is

$$n=\frac{c_p}{s}\left(\frac{R}{r}\right)\frac{c_pKk}{s(s+K)}e^{\sqrt{s/D}(rR)},$$
$`(2.9)`$   
The full time-dependence of the concentration can be expressed in terms of error functions, etc., by using the tables of Inverse Laplace Transform. However, the result is quite cumbersome and unilluminating. We present a simpler limiting expression shortly.

For Laplace Transform of the intake rate $`\mathrm{\Phi }(t)`$, denoted $`\varphi (s)`$, we get

$$\varphi =4\pi DR\frac{c_pKk}{s(s+K)}\left(1+R\sqrt{s/D}\right),$$
$`(2.10)`$   
where we used

$$\mathrm{\Phi }(t)=4\pi R^2D\left(\frac{c}{r}\right)_{r=R}.$$
$`(2.11)`$   
The time-dependence of the intake rate is then

$$\mathrm{\Phi }(t)=4\pi DR\left(c_pKk\right)\left(\frac{1e^{Kt}}{K}+\frac{2R}{\sqrt{\pi DK}}e^{Kt}_0^{\sqrt{KT}}𝑑xe^{x^2}\right).$$
$`(2.12)`$   
We note that this rate expression is actually regular for small times. However, for colloid applications we are interested in large times. For $`t1/K`$, the limiting form of (2.12) is quite similar to Smoluchowski result (1.1). Keeping only the leading time-dependent term, we have

$$\mathrm{\Phi }(t)4\pi DR\left(c_p\frac{k}{K}\right)\left(1+\frac{R}{\sqrt{\pi Dt}}\right).$$
$`(2.13)`$   
The only change is the reduction of the rate due to detachment, proportional to the ratio $`k/K`$ (the intake rate can actually become negative if the detachment is fast enough).

We now turn to the concentration and present its leading time dependence in the limit $`t1/K`$,

$$c(r,t)c_p\left(\frac{R}{r}\right)\left(c_p\frac{k}{K}\right)\mathrm{Erfc}\left(\frac{rR}{2\sqrt{Dt}}\right).$$
$`(2.14)`$   
As $`t\mathrm{}`$, the concentration profile develops a long-range tail $`R/r`$ that has no length scale of order 1 associated with it. In fact, the perturbation of the diffuser particle concentration extends for distances comparable to $`R`$. The vanishing of the term $`R^2`$ in (2.13), so that only the “nonextensive” contribution $`R`$ survives as $`t\mathrm{}`$, is associated with this property. Obviously, it is dependent on the transport mechanism being diffusional. Note that the terms retained in (2.13), (2.14) vary on the time scales set by $`R^2/D`$. Since we are interested in large $`R`$ values, this quantity is much larger than the “transient” time scale $`1/K`$ present in the exact expressions.

3. Model with Boundary Layer

In this section we address the question of whether the boundary condition at $`r=R`$ can be derived from a diffusional model. We will keep the assumption that the diffusion is free for $`r>R`$ in the sense that there is no external potential. However, let us assume that in a certain boundary region from $`R\mathrm{}`$ to $`R`$, where $`\mathrm{}R`$, the particles move in the potential energy $`U(r)`$ owning to their interaction with the aggregate. As $`rR\mathrm{}`$ from above, the diffusional picture breaks down as the particles are subject to the internal restructuring mechanisms in the aggregate. We will assume that this dense aggregate structure can be represented by the boundary condition

$$c(Rl,t)=c_0.$$
$`(3.1)`$   
In fact, the diffusion constant $`D`$ will be affected by the increased particle concentration, proximity to the semicrystalline aggregate, and external potential which itself can be partly functionally $`c`$-dependent. We ignore all these complications and keep $`D`$ constant.

Thus, our model is presented in Figure 1. We assume that $`c_0c_p`$ is a fixed quantity that only depends on the aggregate material. We also put

$$V(r)=U(r)/k_BT$$
$`(3.2)`$   
and assume that $`V(r)`$ is a fixed function of the difference $`rR`$, vanishing for $`rR`$. This potential energy (in units of $`k_BT`$) may represent a truncated version of the full interaction energy at $`r`$. For “free” diffusional aggregation, we can assume that the interactions for $`r>R`$ are weak. However, in the boundary layer of size $`\mathrm{}`$, large negative energy is expected, as sketched in Figure 1. Thus, we denote

$$V(R\mathrm{})V_0,$$
$`(3.3)`$   
with $`V_01`$. Furthermore, we expect that $`|V(r)|1`$ in most of the boundary layer.

The diffusion equation is replaced by one with the potential energy term:

$$\frac{c}{t}=r^2\frac{}{r}\left[r^2D\left(\frac{c}{r}+c\frac{dV}{dr}\right)\right].$$
$`(3.4)`$   
We now offer exact considerations which are valid only in the steady-state $`t\mathrm{}`$ limit. Then the diffusion equation can be integrated as follows:

$$D\left(\frac{dc}{dr}+c\frac{dV}{dr}\right)=\frac{\mathrm{\Phi }}{4\pi r^2}.$$
$`(3.5)`$   
Here $`c(r)`$ denotes $`c(r,\mathrm{})`$, and $`\mathrm{\Phi }=\mathrm{\Phi }(\mathrm{})`$ is the (constant) intake rate into a sphere of radius $`r`$ at time $`t=\mathrm{}`$.

Now the potential $`V(r)`$ is continuous but its derivative is likely discontinuous; see Figure 1. It then follows from (3.5) that the concentration $`c(r)`$ is continuous but the derivative $`dc/dr`$ is not. Consider the limit $`rR`$ from above, denoted by + here. We have the following expression involving the derivative:

$$\mathrm{\Phi }=4\pi R^2D\left(\frac{dc}{dr}\right)_{rR+}.$$
$`(3.6)`$   
Next, we solve the steady-state diffusion equation for $`r<R`$ for the concentration $`c(r)`$ by direct integration and use of the boundary values (3.1) and (3.3). We also use $`V(R)=0`$ to get, for the the concentration at $`R`$,

$$c(R)=c_0e^{V_0}+\frac{\mathrm{\Phi }}{4\pi D}_R\mathrm{}^R𝑑r\frac{e^{V(r)}}{r^2}.$$
$`(3.7)`$   
Finally, we utilize (3.6) to obtain the following relation:

$$c(R)=\alpha \left(\frac{dc}{dr}\right)_{rR+}+\beta ,$$
$`(3.8)`$   
where

$$\alpha =R^2_R\mathrm{}^R𝑑r\frac{e^{V(r)}}{r^2},$$
$`(3.9)`$   
$$\beta =c_0e^{V_0}.$$
$`(3.10)`$   
Since relation (3.8) applies with the derivative at $`R+`$, it can be used as the boundary condition for the free diffusion at $`rR`$. We can thus lump all the effects of the boundary layer in two parameters $`\alpha `$ and $`\beta `$. Such boundary condition resembles the radiation boundary condition used in the chemical reaction applications , which assumes that the concentration is proportional to its derivative. However, there are two important differences. Firstly, there is the additional constant term $`\beta `$. Secondly, the coefficient $`\alpha `$ in our case is only weakly dependent on $`R`$. The integral in (3.9) is obviously of order

$$\alpha \mathrm{}e^{V_0}.$$
$`(3.11)`$   
Thus, the main result of this section is that the problem with the boundary layer can be replaced, at least for large times, by an equivalent problem of free diffusion at $`rR`$, as long as we use our generalized radiation boundary condition at $`R`$,

$$c=\alpha \frac{c}{r}+\beta ,\mathrm{at}r=R.$$
$`(3.12)`$   
4. Generalized Radiation Boundary Condition

Before comparing, in the next section, the two choices of the boundary condition: phenomenological (2.4) and radiation (3.12), let us work out, in this section, what would be the time dependence of the free diffusion problem at $`rR`$ if the boundary condition (3.12) were used for all times. We go through steps similar to Section 2 and only emphasize the final expressions. In Laplace Transform version, the boundary condition becomes

$$n=\alpha \frac{n}{r}+\beta s^1,\mathrm{at}r=R.$$
$`(4.1)`$   
For the concentration and intake rate, we get

$$n=\frac{c_p}{s}\left(\frac{R}{r}\right)\frac{c_p\beta }{s\left(1+\alpha R^1+\alpha \sqrt{s/D}\right)}e^{\sqrt{s/D}(rR)},$$
$`(4.2)`$   
$$\varphi =4\pi DR\frac{c_p\beta }{s\left(1+\alpha R^1+\alpha \sqrt{s/D}\right)}\left(1+R\sqrt{s/D}\right).$$
$`(4.3)`$   
These results can be inverted to get the time dependence since they only involve tabulated functions. For instance,

$$\mathrm{\Phi }(t)=4\pi DR(c_p\beta )\frac{R}{\alpha +R}\left[1+\frac{R}{\alpha }e^{(\alpha +R)^2\alpha ^2R^2Dt}\mathrm{Erfc}\left(\frac{\alpha +R}{\alpha R}\sqrt{Dt}\right)\right].$$
$`(4.4)`$   
This expression is well-behaved at $`t=0`$. As in Section 2, though, it is more useful to analyze limiting results for large $`R`$ and large times. We note that $`\beta `$ is the product of a large quantity ($`c_0c_p`$) and a small Boltzmann factor ($`e^{V_0}1`$); see (3.10). However, $`\alpha `$ is the product of two small quantities: $`\mathrm{}R`$ and the Boltzmann factor; see (3.11). Therefore, we can always assume that $`R\alpha `$. Given this assumption, one then identifies the transient time scale via the condition

$$t\alpha ^2/D.$$
$`(4.5)`$   
The asymptotic expression for the intake rate becomes

$$\mathrm{\Phi }(t)4\pi DR\left(c_p\beta \right)\left(1+\frac{R}{\sqrt{\pi Dt}}\right),$$
$`(4.6)`$   
which is the same as (2.13) provided we identify

$$\beta =\frac{k}{K}.$$
$`(4.7)`$   
Similarly, with (4.7), the concentration is given by (2.14).

5. Constant Boundary Condition. Discussion

In view of the above discussion it is tempting to combine the phenomenological model which was introduced for all $`t`$-values with the exact expression for the boundary condition at $`t=\mathrm{}`$. We could write something like

$$K^1\frac{c}{t}=c+\beta +\alpha \frac{c}{r},\mathrm{at}r=R.$$
$`(5.1)`$   
Here $`\beta `$ is given by (3.10), $`\alpha `$ by (3.9) and (3.11), and it is also tempting to assume that there is only one transient time scale so that

$$KD/\alpha ^2.$$
$`(5.2)`$   
However, as long as we are interested only in the large $`R`$ and large time behavior, for all practical purposes we can use instead the boundary condition

$$c=\beta ,\mathrm{at}r=R.$$
$`(5.3)`$   
Indeed, the value of the concentration at $`R`$ for large times, which is exactly $`\beta =k/K`$, independent of $`R`$, in both models, see (2.9) and (4.2), is the only parameter needed to calculate the modification of the asymptotic intake rate due to detachment. With this boundary condition for all times, the results (2.13) or (4.6), and (2.14), become exact. The price paid is that the singularity at $`t=0`$ is back. However, only large $`t`$ results are of interest in colloidal growth applications.

In summary, a combination of phenomenological and exact considerations yields expressions for the diffusional intake rate of particles in Smoluchowski model with added detachment. The intake rate is reduced (it can become negative) and its value can be calculated from the large-time concentration at the collector surface ($`\beta `$) and the value far away from the surface ($`c_p`$). The only added parameter is thus $`\beta `$. At large times, the concentration profile develops a slowly varying contribution $`R/r`$ and the perturbation of the concentration due to the collector surface extends on length scales $`R`$, far beyond the dimension of the “boundary layer” $`\mathrm{}R`$. This added concentration variation is not present in classical nucleation models with nondiffusional transport. The main result is the nonextensive ($`R`$ instead of $`R^2`$) behavior of the intake rate in the $`t\mathrm{}`$ limit in the diffusional model.

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Figure Caption

Figure 1: Schematic representation of the truncated dimensionless Figure 1: potential energy $`V(r)`$, defined in Section 3.