Atmospheric and Marine Corrosion: Influential

Environmental Factors and Models

Y K Cai

, Y Zhao

, Z K Zhang

, X B Ma

1,*

and B Cheng

School of Reliability and Systems Engineering, Beihang University, No.37

Xueyuan Road, Haidian District, Beijing, China

Science and Technology on Reactor System Design Technology Laboratory,

Chengdu, China

Corresponding author and e-mail: X B Ma, maxiaobing@buaa.edu.cn

Abstract. The corrosion of metals exposed to the atmosphere and marine environments is

expensive to our societies in terms of structure safety and durability. In this paper, the effects

of environmental factors on atmospheric and marine corrosion are reviewed as well as the

accelerating models. It is revealed that relative humidity, temperature, sulfur dioxide, and

chloride are the major influential factors to atmospheric corrosion. Generally, the increase of

these factors would cause the increase of corrosion rate and the accelerating effects are

nonlinear in most cases. Interactive effects exist between different factors and the

mechanisms are complicated. In marine environment, salinity, temperature, dissolved dioxide,

pH, oxidation reduction potential and water velocity can influence the corrosion process

simultaneously in even more sophisticated mechanisms. Meanwhile, as the marine

environmental factors that mentioned above are strongly dependent on each other, it is

difficult to analyse the marine environmental factors and the corrosion rate.

1. Introduction

Corrosion has been reported to account for more failures in terms of cost and tonnage than any other

type of material degradation process. The components and structures corrosion are inseparable from

the environmental factors. At present, the more extensive research is corrosion in the atmosphere and

the marine. Under each environment, there are some models about the environmental sensitive

factors on corrosion rate, and each environmental factor has different influence on the corrosion rate.

So, it is difficult to analyze the influence of a single factor due to the existence of complex

interactions between them. In addition, there is also a correlation between different environmental

factors. Therefore, environmental factors have a long and complex impact on the corrosion process.

Many works have been done to derive accurate models to estimate corrosion under different

environmental conditions.

This paper summarizes the commonly used corrosion rate - environmental factors models for

atmospheric and marine environment, and gives the parameter meaning and applicable conditions of

each model. The interaction between different environmental factors is also briefly discussed.

178

Cai, Y., Zhao, Y., Zhang, Z., Ma, X. and Cheng, B.

Atmospheric and Marine Corrosion: Inﬂuential Environmental Factors and Models.

In Proceedings of the International Workshop on Environmental Management, Science and Engineering (IWEMSE 2018), pages 178-186

ISBN: 978-989-758-344-5

2. Effects of environmental factors on atmospheric corrosion

Atmospheric corrosion is simultaneously influenced by various environmental factors. In this paper,

only the effects of relative humidity, temperature, sulphur dioxide, and chloride on corrosion are

studied. Effects of wind and other factors on atmospheric corrosion are discussed in Ref. [1-4]. The

acceleration model is a link that relates the corrosion parameters to the environmental variables.

General discussions about which model is useful for different environmental factors in practice can

be found in Ref. [5].

2.1. Relative humidity

The increase of relative humidity has been found to increase the corrosion rate [2, 6-8]. Studies have

demonstrated that the corrosion current increases following an exponential law when RH increases

from 53% to 92% [7] and from 40% to 90% [8]. However, when the relative humidity is below 80%–

85%, nearly no atmospheric corrosion of carbon steel was observed in many studies [9, 10]. This is

because that the presence of a film electrolyte formed on metallic surfaces is the fundamental basis to

proceed atmospheric corrosion with anodic and cathodic reactions. This threshold is denoted as the

critical relative humidity (CRH). Studies have also found that the thickness of the electrolyte film can

influence the corrosion rate. Corrosion rates increase with the thickness of the electrolyte film. When

the electrolyte film exceeds a finite thickness, corrosion reaction will slow down due to limited

oxygen diffusion [11].

In atmospheric conditions, there are many factors that can influence the critical relative humidity

level and the thickness of the electrolyte film. These factors include material, corrosion products

composition, pollutants concentration, and hygroscopic salts [4]. For instance, N. Van den Steen, et

al. [12] have found that sample thickness, heat transfer and changing rates, and relative humidity

influence the electrolyte film thickness. When metallic surfaces are contaminated by hygroscopic

salts, the surface can be wetted at lower RH [4].

In most applications where relative humidity is used as an accelerating variable, the Peck

accelerating model is employed, which is expressed as

 

r RH A RH

(1)

where

is a proportion denoting relative humidity and

are constants. An alternative relative

humidity relationship suggested by Klinger [13] on the basis of a simple corrosion kinetic model,

uses the term

 

1RH RH

instead of

in Eq. (1). Thus, the Peck accelerating relation comes to

   

r RH A RH RH    



(2)

Note that as

1RH 

, Eq. (2) is singular, and so it is not valid if

is sufficiently close to 1. The

exponential relation proposed by Vernon (Eq. (3)) [14] can be introduced to correlate the corrosion

rate with relative humidity, which is

 

B RH

r RH A e





(3)

2.2. Temperature

The complicated effect of temperature on corrosion is reflected in two aspects: the influence on

corrosion reaction rate directly and influence on electrolyte film formation.

Atmospheric corrosion is an electrochemical process controlled by anodic and cathodic reactions. In

theory, the corrosion rate can be correlated to the ambient temperature with the Arrhenius law [5]. It

has been suggested that a 2

increase in temperature can increase the corrosion rate by 15% [15]. C.

Lin [16]

studies three kinds of steel in accelerated corrosion tests and develops a corrosion model

Atmospheric and Marine Corrosion: Inﬂuential Environmental Factors and Models

179

deduced from the Arrhenius law. There is also a strong positive correlation between corrosion rate

and temperature for magnesium [6, 17] and zinc [7].

In reality, the atmospheric corrosion is a complex discontinuous electrochemical process due to

the evaporation and condensation of moisture in highly dynamic environments. Generally, metal

surfaces undergoes daily wet-dry cycles. Electrolyte film forms on the metal surface at night when

temperature decreases and RH increases, proceeding the corrosion reactions. Corrosion reactions halt

after sunrise when temperature increases and the electrolyte film evaporates. In the winter, when the

temperature is lower than the freezing point, corrosion reactions cannot proceed due to constrained

transport of oxygen to the metal surface.

Theoretically, the effect of temperature on atmospheric corrosion rate is typically described with

the Arrhenius relation [5], which follows

 

r T D e





(4)

In Eq. (4),

 

is the corrosion reaction rate,

is a constant.

is the thermodynamic

temperature in Kelvin.

E E K

, where

is the activation energy which can be estimated from

experimental data, and

is the Boltzmann constant.

2.3. Sulfur Dioxide and Chloride

Many researchers have demonstrated the accelerating effect of sulfur dioxide on atmospheric

corrosion [18-20]. The corrosion rates for metal pieces (bronze, copper, marble and steel) exposed in

outdoor environment are found generally proportional to the sulfur dioxide concentration [21], while

some researchers [19, 22, 23] used the power function to model the accelerating effect. G. W. Walter

[24] indicated that sulfur dioxide will be oxidized to sulfate ion (



) in the water. During the

process, hydrogen ions (



) are produced, which results in the increase of the corrosion rate and

causes the dissolution of corrosion products. X. Cao [3] elucidates the reasons of the accelerating

effect as following: (a) the cathodic reactant is more effective than the dissolved oxygen because the

solubility of sulfur dioxide is about 1,300 times higher than oxygen in the water; (b) the CRH level

reduces due to the presence of sulfur dioxide; (c) sulfur dioxide acts as a catalyst and one sulfate ion

can catalyze the dissolution of more than 100 atoms of iron.

It has also been reported that the presence of chloride can obviously accelerate the atmospheric

corrosion for steel [16], zinc [18], and magnesium alloys [6, 16-18]. When chloride deposits on the

metal surface, the electrolyte conductivity increases [6] as well as the time of wetness of the metal

surface. The power function [19, 22, 23, 25] and the quadratic function [16, 18] is used to correlate

the corrosion loss rate with the chloride deposition rate by some researchers. I.S. Cole [26] has

discussed that the chloride deposition is primarily controlled by the wind turbulence, the distance

from the coast and also influenced by rain and surface temperature.

J Tidblad [22] and A. A. Mikhailov [23] analyzed the metal exposure investigation of the ISO

CORRAG program [27] and derived the dose-response function which follows

 

r SO F SO

(5)

 

r Cl H Cl

(6)

where

is the sulphur dioxide concentration,

is the chloride deposition rate.

, and

are constants estimated from experimental data. However, Eqs. (5)-(6) are not appropriate because

in practice, the corrosion rate does not equal zero when the sulfur dioxide concentration or the

chloride deposition rate equals zero. Instead, Eqs. (5)-(6) are modified to the following Eqs. (7)-(8)

[19]

IWEMSE 2018 - International Workshop on Environmental Management, Science and Engineering

180

   

r SO F SO  

(7)

   

r Cl H Cl  

(8)

2.4. Discussion

In the field environment, there are interactive effects between different environmental factors. For

example, it is showed that the zinc corrosion rate did not show dependence on temperature in the

presence of carbon dioxide [28]. Similar results were also reported for copper corrosion in the

presence of nitric acid [2]. Moreover, the nitrogen oxides (NO

) are also important factors that can

promote the atmospheric corrosion. J. G. Castano [29] summarizes the effect of NO

on atmospheric

corrosion of different metals (copper, aluminum, nickel, carbon steel and zinc), but no coincident

conclusion is drawn. Some authors believe to be of little influence [30, 31], some detected it an

inhibitive effect [32, 33], while others consider the effect is dependent on other factors such as

humidity [34, 35], the type of the metal [29], and SO

concentrations [20, 29]. With such complex

mechanisms, the interactive effect between different factors is hard to be fully quantified. In this

paper, the effect of SO

is included and the interactions between different pollutants are not

considered.

Except from the environmental factors discussed above, carbon dioxide, ozone, solar radiation,

wind, and rain are also important for different materials. For example, carbonation is the major cause

for the failure of concrete structure due to the erosion of carbon dioxide [15]. The corrosion of silver

can be accelerated by the presence of ozone and ultraviolet [36]. Solar radiation, wind, and rain can

influence the deposition rate of chloride and the time of wetness [4]. When materials are subject to

more complex ambient environmental conditions with multiple atmospheric corrosive factors,

interactive effect occurs and the effect of each factor should be analyzed carefully.

3. Effects of environmental factors on marine corrosion

Marine environment contains plenty of corrosive media like seawater temperature, dissolved oxygen,

water velocity, pH, oxidation reduction potential (ORP) and various dissolved salts, so the influence

of marine environment on corrosion is more complex than atmosphere. When components and

structures operate in such a complex marine environment, all kinds of corrosion forms are inevitable.

Marine corrosion can take different forms, for example: general corrosion, pitting corrosion, stress

corrosion cracking, weld corrosion, bimetallic corrosion, filiform corrosion, corrosion fatigue,

fretting corrosion and bacterial corrosion [37-39, 51]. In general marine corrosion, which is the most

common form of corrosion, the wastage is spread over the surface of the materials [40]. Through the

different forms of corrosion, the uniform general corrosion is the type that is considered here.

3.1. Salinity

Seawater is extremely corrosive due to its high salt content. The salinity of seawater generally is 35

ppt and far higher than river water which is only 0.02 ppt. Thus, marine corrosion occurs easily and

accelerates the corrosion rates. But the corrosion rates do not rise all the time with the salinity rising.

Test shows that corrosion rates reach the maximum when the salinity is 32 to 35 ppt, namely the

salinity of natural seawater [45, 49].

This is due to the effect of salinity on the corrosion reaction. On one hand, the transfer speed of

the charge is accelerated with the increase of the salinity of the seawater. So, the corrosion rates

accelerate obviously. On the other side, with the salt concentration increasing, the solubility of

oxygen in the seawater is decreasing so that the corrosion rate will be reduced. When the salinity is

less than the natural sea, the influence of electrical conductivity is dominated. When the salinity

exceeds the natural sea water salinity, the increase of salinity causes the decrease of oxygen content

Atmospheric and Marine Corrosion: Inﬂuential Environmental Factors and Models

181

to exceed the increase of electrical conductivity. In this case, the corrosion rate decreases with the

increase of salinity.

The relation between the corrosion rate correction factors for salinity and salinity ratio, based on

the results presented by Uhlig and Revie [42], can be modeled by a truncated log-normal function as

 

exp







  















(9)

In Eq. (9),

 

is the corrosion rate correction factor for salinity (corrosion rate at actual salinity

/ corrosion rate at nominal conditions),

is the salinity ratio (actual salinity / nominal salinity).



a constant introduced as a magnification factor to adjust the values of the corrosion rate correction

factor (







is a constant introduced to adjust the truncated portion (







, and



are

constants corresponding to mean value and standard deviation of the distribution. It must be stressed

that this function has been chosen just to represent the form of the curve and not as a probability

density function.

3.2. Temperature

Temperature is also an important parameter in seawater corrosion because it usually accelerates

corrosion by increasing the temperature [43-45, 50]. However, as the temperature rises, the solubility

of oxygen decreases, which also weakens the temperature effect [48].

Based on the experimental evidence, a correlation factor is proposed to adjust for the effect of

temperature. It is assumed that corrosion rate is a linear function of temperature for seawater

temperatures below 80 ºC

 

R T cT d

(10)

In Eq. (10),

 

is the corrosion rate correction factor for temperature (corrosion rate at actual

temperature / corrosion rate at nominal conditions),

is the temperature ratio (actual temperature /

nominal temperature),

is the constant representing the slope of the

 

-R T T

relationship and

the constant represents the

 

value at zero

3.3. Dissolved oxygen

Because the corrosion of most metals in seawater is oxygen depolarization corrosion, the content of

dissolved oxygen in seawater is an important factor affecting the corrosivity of seawater. The

solubility of oxygen in sea water mainly depends on the salinity and temperature of the sea water.

With the increase of salinity or temperature, the solubility of oxygen is reduced [45].

Melchers [46] has shown that there is a linear relationship between dissolved oxygen and rate of

corrosion. Fontana [43] has proposed a schematic diagram showing the effect of oxygen and

oxidizers on the corrosion rate.

Based on the mentioned results, the relation between the corrosion rate correction factor for

dissolved oxygen and the dissolved oxygen concentration ratio is proposed as a linear relationship:

 

R O aO b

(11)

In Eq. (11), where

 

is the corrosion rate correction factor for dissolved oxygen

concentration (corrosion rate at actual oxygen concentration / corrosion rate at nominal conditions),

is the dissolved oxygen concentration ratio (actual oxygen concentration / nominal oxygen

IWEMSE 2018 - International Workshop on Environmental Management, Science and Engineering

182

concentration),

is a constant representing the slope of the

 

-R O O

relationship and

is a

constant representing the corrosion rate correction factor

 

at zero

3.4. pH

In the range of near neutral pH, the corrosion rate of metals decreases with the increase of pH. After

the reduction of pH, the corrosion rate of metals increased significantly, which is not only due to the

increase of hydrogen evolution, but also the metal surface dissolved by the surface oxide film has

greater affinity for oxygen and is conducive to the depolarization of oxygen. However, the pH of

seawater is always stabilized at 7.6 to 8.3. That is to say, the difference of corrosion rate in this range

is very small.

A relation between corrosion rate and pH can be derived [37, 48] as

 

n pH

R pH k





(12)

In Eq. (12),

 

R pH

is corrosion rate correction factor for Ph (corrosion rate at actual Ph /

corrosion rate at nominal conditions).

and

are constants.

3.5. Water velocity

Flowing water can result in an increase in the amount of dissolved oxygen that reaches the material

surface. Meanwhile, flowing water can remove protective films over the material surface. Higher

velocity of seawater particles will lead to an increase in corrosion rate. The corrosion rate may

double when water moves at 1m/s [47].

These results suggest that the relation between the corrosion rate correction factor for velocity and

velocity ratio can be modeled as an exponential relation:

 

R v e









(13)

In Eq. (13),

 

is the corrosion rate correction factor for velocity,

is the flow velocity ratio,



is a magnification factor to adjust the value of the corrosion rate correction factor (



≥0),



is a

constant introduced to adjust the truncated portion from the distribution (



≥0) and



is a factor to

adjust the curvature and the slop of the curve (



≥0).

3.6. Discussion

The marine environmental factors that mentioned above do not vary independently and they have a

strong correlation. For instance, temperature can make great difference to other parameters and the

increase of dissolved oxygen can rise the ORP. Therefore, it is difficult to analyze the marine

environment factors and the correlation of corrosion rate.

Generally, temperature is the independent variable which is not changed by other factors. Except

salinity, pH, dissolved oxygen and ORP are affected with temperature variation. In addition,

dissolved oxygen is negatively correlated with temperature and salinity. And temperature, dissolved

oxygen and pH have varying degrees of effect on ORP.

4. Conclusions

This paper presented a review of the influential environmental factors on atmospheric and marine

corrosion processes and the accelerating models. Relative humidity, temperature, sulfur dioxide, and

chloride are the major influential factors to atmospheric corrosion while in marine environment, the

factors include salinity, temperature, dissolved dioxide, pH, oxidation reduction potential and water

velocity. Generally, the change of these factors would change the corrosion rate. However, the

Atmospheric and Marine Corrosion: Inﬂuential Environmental Factors and Models

183

accelerating effects are different for each environmental factors. Interactive effects exist between

these factors and the mechanisms are complicated. Care should been taken when these models are

applied in practice for different materials and in different environments.

Acknowledgement

This work is supported by the National Natural Science Foundation of China (No: 61473014).

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