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Modelling of Corrosion Processes - A Brief Overview

Corrosion is the wearing away of metals due to a chemical reaction. It is diffusion controlled process and occurs on exposed surfaces. The corrosion is a self-inhibiting process,
whereby as corrosion proceeds, the protective properties of its products, generally the ion oxides, improve. As a result of this, the corrosion rate slows over time. There are different types of corrosion and this makes the modelling of the process a challenging task. The most commonly observed forms of corrosion are:

Uniform or general corrosion Uniform corrosion is characterized by corrosive attack proceeding evenly over the entire surface area, or a large fraction of the total area. General thinning takes place until failure

Pitting corrosion Pitting corrosion is a localized form of corrosion by which cavities or "holes" are produced in the material and pitting is considered to be more dangerous than uniform corrosion damage because it is more difficult to detect, predict and design against)

Galvanic corrosion Corrosion damage induced when two dissimilar materials are coupled in a corrosive electrolyte

Fretting corrosion Contact surfaces exposed to vibration during transportation are exposed to the risk of fretting corrosion

Intergranular corrosion The microstructure of metals and alloys is made up of grains, separated by grain boundaries and intergranular corrosion is localized attack along the grain boundaries, or immediately adjacent to grain boundaries, while the bulk of the grains remain largely unaffected

Graphitic Corrosion Cast iron loosing iron in salt water or acids and leaves the graphite in place, resulting in a soft weak metal

The review of the potential of using finite element analysis for modelling the corrosion process has focused primarily on the atmospheric related types of corrosion. In this case the electrolyte is moisture from precipitation, fog or dew, sea spray, or other sources. The main factors that have the most influence on the corrosivity of the atmosphere at a given site are the amount of time that the exposed surfaces remain wet at the site, the amount of chloride that may be presented on the surfaces, the amount of industrial pollutants (mainly acids) that may reach the surfaces, and the temperature and the relative humidity. In terms of corrosion modelling, it is typically based on explicit mathematical models of the corrosion rates are widely reported in the literature. Examples of this type of models include the Erying-Peck model and Power-law model [1]. The Erying-Peck model is an empirical model based on extensive test data for mainly plastic packages (printed circuit boards) of failure by corrosion mainly controlled by temperature and humidity of the environment. The Power-law model [2, 3, 4] is also another explicit model for the corrosion process controlled by time of exposure and two coefficients which depend on the exposure condition such as d (t ) = a.t b , where d(t) is the thickness of

corrosion wastage at exposure time t and both coefficients a and b are obtained from the explicit model to the experiment data. In [2] a slightly modified version of Power-law was used for corrosion depth such as
d (t ) = t a + 10 ( b ( SO2 ) +c ( Cl )+d ( TOW ) ) ,

where a, b, c, and d are constants, (SO2) as concentration of sulphur oxide in mg/ (m2 day), (Cl-) as the concentration of chlorides in mg/ (m2 day) and TOW as time of wetness (h/year). Other explicit models are

The two phase corrosion model [5] This model consists of two phase (in the first phase rapid exponential corrosion growth and in the second a slow linear growth) such as

d (t ) = a.t +b.(1 e c.t ) .


where a = constant (typical value: 0.009mm/yr), b = corrosion depth scaling constant (typical value: 6.27 mm) and c = corrosion rate inhibition factor (typical value: 0.14yr -1

The linear corrosion model [5] This simple model mostly suited to pitting type corrosion is defined as

d * (t ) =

d (t ) d (t0 ) (t t0 )

Where d * (t ) =corrosion rate, d (t) = pit depth at time t and d(t0) = pit depth at time t0

The non-linear time variant model [6,12]

t c governing parameters that include, d = long term thickness of corrosion wastages, = t transition time and = coating thickness, which is equal to the time interval between the c
painting and the time when its effectiveness is lost.

d ( t c ) / t e This model for marine atmosphere is defined as d (t ) = t 0

t > c

the

The damage function model [13] This is an explicit model developed based on the extensive experiment data specifically for aluminium such as d(t)=0.206 t 0.987[0.099 +0.139 f90 SO2 + 0.0925 Cl + 0.0164 H+ - 0.0013 DUST] where SO2 = the average SO2 concentration (g m-3) , Cl = chloride deposition rate (mg m-2 day), H+ = hydrogen ion deposition rate in precipitation (Eq m-2 day), f90 = the fraction of time where relative humidity is >90% and temperature >0o C and DUST = the dustfall deposition rate (mg m-2 day).

Up to now we summarised various explicit models in the literature. To model corrosion behaviour in finite element modelling we need to understand the actual process of corrosion. Corrosion mechanism or process in large particle porous media is investigated in [7] with particular reference to bulk carriers (ship) and a mathematical model of the corrosion process for that scenario is developed to estimate the corrosion rate. The overall rate of corrosion in [7] is determined by the rate of charge transfer of either anodic or cathodic reactions, or by the rate of mass transfer of the cathodic reactant (oxygen) to corroding surface or anodic product away from the corroding surface. With this the corrosion rate can be determined using electrochemical equation. Another analytical (mathematical) model of long term corrosion of metals embedded in concrete is described in [8]. This

corrosion rate model [8] is expressed from oxygen reduction rate. Corrosion product thickness estimated with the analytical model is then compared to test results and verified. The mechanism occurring inside the rust layer and the characteristics of the rust layer during the wet-dry cycle in the long term atmospheric corrosion behaviour of metallic containers of nuclear waste are formulated in [9].The atmospheric corrosion behaviour of iron based materials such as carbon or low alloy steels has generally been well predicted for periods of few ten years by above mentioned explicit models such as power-law model. The mechanistic model in [9] is for long term predictions of corrosion behaviour. Atmospheric corrosion (AC) can be summarised by the stoichiometric equilibrium [9] Iron substrate Atmosphere Electrolyte Rust 4Fe + 3O2 + 2H20 = 4FeOOH Wet dry cycle in long term corrosion is divided into three periods such as wetting, wet stage and dry stage. During wetting stage the corrosion depth is defined as
d wetting = N .S .n VFe 2 N Av

And during the wet stage corrosion depth is defined as

d wet stage =

2 D0CO VFe t w 0

Where N = density of FeOOH surface site, S = area of the pores per surface site, n = number of reduced monolayer of FeOOH ( one type of FeOOH), VFe = molar volume of iron, NAv = Avogadro constant, = porosity of layer, D0 = O2 diffusion coefficient in the electrolyte, C0 = O2 concentration at atmosphere, 0 = diffusion length of O2, tw = duration of wet stage and = tortuosity of rust layer. During dry cycle no electrolyte are present which reduces corrosion. The development of mathematical model for pitting corrosion, based on the mass conservation law for dissolving moving electrode boundary and the adjacent electrolytic solution, combined with diffusion type transport law and chemical kinetics laws for the dissolution process is discussed in [10]. Corresponding mathematical solution (time dependent fields of concentration) are obtained by means of finite volume method. For experimentally supported model input values the influence of overpotential on the corrosion characteristics is shown in 2D simulation. For the 2D case the governing partial differential equation is defined as c ( x, t ) [ D(c)c ]( x, t ) = 0 . t where D(c) = concentration dependent diffusion coefficients, c = molar concentration, t = time Generally it is possible to define a crude mathematical model representing corrosion process rate [11].

References
[1] Hall, P.L., and Strutt, J. E., Probabilistic physics of failure models for component reliabilities using Monte Carlo simulation and Weibull analysis: a parametric study, Reliability Engineering and System Safety 80 (2003) 233-242 [2] Gonzalez, J. E. G., et al, The effect of environmental and meteorological variables on atmospheric corrosion of carbon steel, copper, zinc and aluminium in a limited geographic zone with different types of environment , Corrosion Science 45 (2003) 799-815 [3] Yuantai Ma, Ying Li and Fuhui Wang, Corrosion of low carbon steel in atmospheric environments of different chloride content, Corrosion Science 51 (2009) 997-1006 [4] Alamilla J. L., Espinosa-Medina, M. A. and Sosa, E., Modelling steel corrosion damage in soil environment, Corrosion Science 51 (2009) 2628-2638 [5] Rehan Sadiq, Balvant Rajani and Yehuda Kleiner, Probabilistic risk analysis of corrosion associated failures in cast iron water mains, Reliability engineering and system safety 86 (2004) 110 [6] Soares, C. G., Garbatov, Y., Zayed, A. and Wang, G., Influence of environmental factors on corrosion of ship structures in marine atmosphere, Corrosion Science 51 (2009) 2014-2026 [7] Gardiner, C.P. and Melchers, R. E., Corrosion of mild steel in porous media, Corrosion Science 44 (2002) 2459-2478 [8] Walter-John Chitty, Philippe Dillmann, Valerie LHostis and Alain Millard, Long-term corrosion of rebars embedded in aerial and hydraulic binders- Parametric study and first step modelling, Corrosion Science 50 (2008), 3047-3055 [9] Hrl, S., Mazaudier, F., Dillmann, Ph. and Santarini G., Advances in understanding atmospheric corrosion of iron. II. Mechanistic modelling of wet-dry cycles, Corrosion Science 46 (2004) 1431-1465 [10] Stefan Scheiner and Christian Hellmich, Finite volume model for diffusion and activation controlled pitting corrosion of steel, Comput.Methods Appl. Mech. Engrg. 198 (2009) 2898-2910 [11] Kenneth Richard and John Chamberlain, Corrosion: for science and engineering, Harlow: Longman press, 1995. [12] Soares, C. G., Garbatov, Y., Zayed, A. and Wang, G., Corrosion wastage model for ship crude oil tanks, Corrosion Science 50 (2008) 3095-3106 [13] Roberge, P. R., Klassen, R. D. and Haberecht, P. W., Atmospheric corrosivity modelling a review , Materials and design 23 (2002) 321 - 330

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