A CELLULAR AUTOMATA SIMULATION OF THE PIT GROWTH

1
B. Malki, 1,2B. Baroux
1
Institut National Polytechnique de Grenoble, LTPCM/GEDAI, France
2
Usinor Recherches, CMDI
Ugine Research Center, 73400 Ugine, France

ABSTRACT

This paper is devoted to a numerical simulation of the corrosion pit growth using a cellular
automata technique (1). So as to develop the technique, the work begins by defining the simulation-
transition rules of a so-called automaton constituted by the metal/passive film/solution system.
After that, a parametric study is performed focusing on the role of the mass transport mechanism in
the electrolyte on the pit growth morphology. Some transport modes are then found to be related to
a particular morphology. Also, pit repassivation susceptibility was analyzed and its specific effect
on the corresponding growth kinetics is qualitatively described.

KEYWORDS: Pitting Corrosion, Cellular automata Simulation, Growth kinetics

INTRODUCTION

The idea of the existence of a universal pattern in the pitting process, which doesn’t necessarily
depend on the mechanistic details at microscopic scale, opens the possibility of modeling this
process by using phenomenological approach at mesoscopic scale such as the limited diffusion
aggregation and/or the cellular automata. These techniques are based mainly on the diffusion
growth mechanism, nevertheless, they allow easily to conduct simulations of a pit growth dynamic,
which means the time evolution of a constituted electrochemical system inside a pit,
As the evolution of the corrosion pit morphology and the metastable-stable pit transition are of
the stimulating pitting problems, the simulation of a pit growth dynamic through these techniques,
is helpful way to investigate these mentioned aspects, which are not necessarily accessible by
experimental studies.
The very few work (2) developed in this direction, and based on the assumption of kinetics
controlled by diffusion of a corrosive agent, puts well obviousness the stages of metastable-stable
pitting and the current transients growth laws. The metastable-stable transition was then found to be
closely associated to a particular morphology (3, 4). Obviously, the investigation of a list of
physical parameters can be envisaged, but one of those that seems more interesting to go thoroughly
into is the repassivation phenomena and its specific effect on metastable-stable pit transition.

The purpose of this work is to use the cellular automata technique in order to simulate on a two-
dimensional lattice the dynamic of a pit growth. For the elementary process (mass transport, metal
dissolution passivation and depassivation), it is assumed simple interaction rules between the cells
of the automaton of a corrosion pit system.
Given that, the study is focused on the effect of the local pit repassivation, while changing the
dynamics of the dissolution process, on the growth kinetics and pit morphology. Morphological
analysis of a simulated corrosion patterns is the main purpose of this work.
 COMPUTER MODEL

The basic assumption of the model is to suppose that corrosion kinetics are based on a diffusion
mechanism. In a second step, the transport mechanism is extended to the electromigration of the
charged species in the aqueous solution. Also, the passive layer acts like a perfect barrier and the pit
initiation step is supposed to be done.
Such modeling system can be built by dividing the Solution/Film/Metal system into a regular
discrete lattice of cells, where each cell is characterized by a couple {x, y}of states, taken from a
finite set of states (see fig.1). During the time evolution of this automaton , each cell can change its
states according to rules known as transition rules which depend only on the state of the cell and a
finite number of neighboring cells. The latter should reflect the dynamic of the pit growth assuming
a diffusion control of the mass transport, a dissolution process at the "metal/solution” interface and
disregarding any chemical changes in the solution.

B Local
Repassivation
A
F
M

Fig.1: the constructed cellular automaton of a corrosion pit: built by dividing the system
“Solution/Film/Metal” into elementary cells with random orientations: A is a corrosive cell; B a non
corrosive cell, F a passive film cell and M metallic substrate cell. Each electrolyte cell has an initial
orientation with intent to diffuse randomly.

The {x, y} set of states for the above a pit system is defined as following:
x represents the type of a cell:
- A is a corrosive cell which can dissolve the non protected metallic cells
- B a non corrosive cell having no interaction with the metallic cells;
- F a passive film cell;
- M a metallic substrate cell.
y is an number which varies between 0 and 4 which states:
-0 the cell of the network is not occupied, a free cell
-1 the cell is oriented towards North
-2 the cell is oriented towards East
-3 the cell is oriented towards south
-4 the cell is oriented towards the West.
During a transition, all the cells are moved towards the direction of their initial orientation, and
then new random orientations are selected for the moved cells. When two or several cells meet, they
change their states according to whether a corrosive cell meets or not a metallic cell or a passive
film cell. In the first case, metallic cells are transformed into free or passive film cells depending on
whether we want to simulate the dissolution and/or the repassivation. Therefore, probability laws
are built allowing a control of the dissolution and the repassivation process. Periodic boundaries are
applied in this system.
 RESULTS AND DISCUSSION

Analysis of the electrolyte concentration effect

The first result to present concerns the effect of the concentration of corrosive cells on pit growth
and on the macroscopic morphology. This parameter was varied by choosing different values of the
A/B ratio of in the initial configuration of the automaton. Fig.2 clearly show that the resulting
pattern has rather a spherical morphology and a high dissolution current considering the large
removed pixels when the concentration is taken higher.

Fig.2: Corrosion patterns obtained by varying the concentration of the corrosive cells: left picture
for the high concentrated case: A/B~0.2, the pattern has rather a spherical morphology with
significant dissolved matter and the right picture for the low concentrated case: A/B~0.8, low
metallic dissolution is observed

Influence of the dissolution rate

Following the parametric study, “dissolution probability” called s of the non protected metallic
cells is now varied. It appears that for low dissolution rates the limiting stage of the mass transport
is not diffusion but dissolution step through the metal/electrolyte interface (see left pattern in fig.3).
On the other hand, when the dissolution rate is taken high the diffusion becomes again the limiting
stage. Here is therefore a suitable way to distinguish between the role of the dissolution and
diffusion transport in the growth processes.
Fig.3: Corrosion patterns obtained using various dissolution rates: a) left side low dissolution rate
(s=0.2); b) right side high dissolution probability (s=0.8). We note a ramified morphology in the
latter case.
Role of the mass transport mechanism on the pit growth dynamic

Finally, by including the electro-migration in the transport process, achieved by imposing a

preferential orientation f of the cells towards south, we observe a drastic change in the resulting pit
morphology, a perforating pattern is obtained after a only few iterations, although, dimixion
problem of the electrically charged species is to rise because of the no fulfilling electro-neutrality
conditions. However that may be, this indicates the critical and the crucial role of an established
electric field.

Fig.4: Strong perforating morphology obtained using driving diffusion due to the electro-migration
part of the mass transport. Note the directional propagation growth of the pit for f=0.8.

Effect of a local repassivation on the pit growth

 The following fig.4 show the effect of a repassivation probability p on the morphology of the pit.
This probability is introduced by allowing some of the metallic cells to become passive film cells
after each transition. One can note the progressively inhibited propagation pit and ramified
morphology for intermediate values of the repassivation probability (p ~ 0.2).

Fig.5: A net tendency to a ramified morphology resulting from the simulation for various
repassivation probability; a) very low repassivation probability, p=0.01, b) medium repassivation
probability (p=0.2).

CONCLUDING REMARKS

It was proposed in this work to introduce the cellular automata as a simulation tool to study of
the dynamic of a pit growth. In a first step, the technique was successfully implemented by
developing transition rules for the local interactions laws between the cells of the so-called
automaton , reproducing the observable macroscopic phenomena.
As a matter of fact, anodic dissolution as well as local repassivation were properly simulated,
showing significant changes in the morphology of the pitting process. A growing pit exhibit an
isotropic morphology for low repassivation probability and it ramifies for intermediate values of the
probability parameter (p~0.2) until a definitive arrest of the growth for higher probabilities. Also,
significant effect of the electrolyte concentration was obtained when raising the ratio of corrosive
cells in the automaton .
On the whole, these preliminary and qualitative results are presented to show the feasibility of
the cellular automata technique as a suitable tool to study the pitting kinetics. Further coming work
will be presented with quantitative kinetics analysis deduced from the simulation and discussed in
the light of the various models dedicated to the effect of repassivation on the metastable-stable
transition.
This work joined the effort agreed in a second article published in this proceedings that deals
with another simulation approach using the Monte Carlo technique (4). The main purpose is the
investigation of a pit growth focusing only in the dissolution step. Pit repassivation is then
simulated and its effect on a transient current growth is analyzed. This work is in keeping with a
new approach to regard the growth pitting process.

REFERENCES
1) S. Wolfram, Cellular Automata and Complexity, Addison-Wesley, (1994).
2) P. Meakin, Physical Rev. E, 48, (1993), p 2906.
3) N. Sato, J. Electrochem. Soc., 129, (1982), p 261.
4) D. Landolt, Electrochem. Acta., 25, (1980), p 1255.