Corrosion Science 137 (2018) 163–175

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Influence of environmental factors on atmospheric corrosion in dynamic T

environment
⁎
Yikun Caia, Yu Zhaob, Xiaobing Maa,b, , Kun Zhouc, Yuan Chenc
a
School of Reliability and Systems Engineering, Beihang University, Beijing, China
b
The Key Laboratory of Reliability and Environmental Engineering Technology, Beijing, China
c
Southwest Institute of Technology and Engineering, Chongqing, China

A R T I C LE I N FO A B S T R A C T

Keywords: This paper studies the effects of relative humidity, temperature, sulphur dioxide, and chlorides on the short-term
Atmospheric corrosion corrosion behavior in the dynamic environment. A multi-parameter method is developed to characterize the
Modeling statistical distributions of the environmental factors with high accuracy. The results suggest that TOW (time-of-
Mass loss wetness) should be replaced by temperature and relative humidity distributions. A corrosion model which is
Environmental factors
combined with physical and empirical knowledge of corrosion is presented and gives more accurate corrosion
estimation than using the mean values of the environmental factors and fitting them independently. It is also
demonstrated that relative humidity is the most influential factor on corrosion and temperature is secondary.
The nonlinearity of their accelerating effects on corrosion rate are remarkable and should be considered in the
daily dynamic environment. Sulphur dioxide and chlorides are important accelerating variables and their
nonlinear accelerating effects are less significant.

1. Introduction atmospheric corrosion model considering the integrated effects of the

Atmospheric corrosion is a complex process that depends on the
interactions of multiple environmental factors like relative humidity,
temperature, pollutants and wind. It is difficult to analyze the influence
of a single factor due to the existence of complex interactions between
them. Many works have been done to derive accurate models to esti-
mate corrosion under different environmental conditions.
The short-term corrosion models [1–4] have long been studied by
multiple researchers. They correlate the corrosion loss or corrosion rate
with environmental factors like time-of-wetness (TOW), sulphur di-
oxide concentration, and chlorides deposition rate. In these studies, the
environment is assumed to be constant and equal to the averaged
quantities. The corrosion damage is calculated with the yearly average
values of these environmental factors. And the majority of the models
account for only one or two environmental factors and the exposure
period is not included as a predictor variable except for the models in
the publications from the ICP materials [5,6].
However, the actual environmental corrosive condition for field
exposed materials is dynamic and with multiple environmental factors.
The yearly average values cannot capture the complexity of the dy-
namic environmental conditions. The influence of the environmental
factors variation has not been considered. Therefore, a new
dynamic corrosive environment is needed. In this paper, when con-
sidering the actual environmental condition, four main influential fac-
tors of outdoor environment are included: dynamic temperature, re-
lative humidity, sulphur dioxide concentration and chlorides deposition
rate.
In order to build the atmospheric corrosion model in dynamic en-
vironments, firstly a corrosion kinetic model is needed to estimate
corrosion process over time. Then a parametric method is necessary to
describe the dynamic environmental factors. And finally an accelerating
model which describes the effects of environmental factors on corrosion
rate is essential to correlate the corrosion parameters with the en-
vironmental factors.
The power law relation C = A⋅t n is the most commonly studied ki-
netic model which correlates long-term corrosive damage C with ex-
posure time t . S. W. Dean [7] analyzed the long-term field exposure
result of the ISO CORRAG program and found that coefficient A and
expoment n are influenced by the environmental factors. D. E. Kline-
smith [3] proposed a model that considers effects of four environmental
variables on atmospheric corrosion: time-of-wetness, sulphur dioxide,
salinity and temperature. The model has a rational structure and the
author has demonstrated the fundamentals for each of the environment
adjustment factors.

⁎
Corresponding author at: School of Reliability and Systems Engineering, Beihang University, Beijing, China.
E-mail address: maxiaobing@buaa.edu.cn (X. Ma).

https://doi.org/10.1016/j.corsci.2018.03.042
Received 25 July 2017; Received in revised form 21 March 2018; Accepted 25 March 2018
Available online 28 March 2018
0010-938X/ © 2018 Elsevier Ltd. All rights reserved.
Y. Cai et al.
However, these models have some limitations. Some of these models
are not realistic from a physical standpoint because of the erroneous
effects they yield [3]. For example, the corrosion loss does not equal
zero even when the sulphur dioxide pollution, the TOW, and the salinity
equal zero. Therefore, the model structure is not an accurate re-
presentation of the corrosion process [3]. Tidblad [8] and Mikhailov
[9] also suggested that it is necessary to include temperature T , or
substitute T and RH for TOW to describe situations beyond the tem-
perature region. And the current ISO 9223 standard [10] which is re-
vised and published in 2012 ha s replaced TOW with T and RH in the
dose-response function.
Moreover, when used in highly dynamic atmospheric environment,
these models will generate inaccurate result due to the non-uniformity
of environmental factor distributions and the nonlinear effects of en-
vironmental factors on the corrosion rate.
Environmental factors distributions are often skewed and multi-
modal. Based on the analysis of the environmental data at multiple
locations, it is found that most of the temperature distributions are
bimodal and relative humidity distributions are the mix of multiple
normal distributions. The sulphur dioxide concentration and the
chlorides deposition rate can be described by log-normal distributions.
The influence of temperature on corrosion rate usually follows an
exponential law which is known as the Arrhenius relation [11]. The
influence of relative humidity on the corrosion rate is usually captured
by a power law function which is called the Peck relation [11]. The
effects of sulphur dioxide and chlorides are also nonlinear following the
power law dose-response functions [7–9]. The corrosion rate is much
higher in highly corrosive environments. Thus, the average corrosion
rate do not equal to the corrosion rate calculated with the average value
of each environmental factor.
In addition, the dependence of relative humidity on temperature
must be considered because the relative humidity distribution is sig-
nificantly influenced by the ambient temperature. The relative hu-
midity fluctuates with the change of temperature, which is mainly
controlled by the evaporation and condensation of water vapor. The
temperature of the air dictates how much kilogram of water vapor a
kilogram of air can contain. If the absolute humidity stays constant and
the temperature increases, the relative humidity will drop. On the other
hand, more water will evaporate, increasing the absolute humidity. The
relationship between the measured temperature and relative humidity
is thus very complex in the field environment.
Starting in the next section, the effects of relative humidity, tem-
perature, sulphur dioxide, and chlorides on atmospheric corrosion
process are discussed. Then the mathematical foundation is laid for the
construction of the atmospheric corrosion model and the procedure of
extracting model parameters is presented in detail. Corrosion estima-
tion results and discussions are also presented. The temperature and
relative humidity data are from the National Oceanic and Atmospheric
Administration (NOAA) website. The sulphur dioxide concentration
data are from the online database of China National Environmental
Monitoring Center (CNEMC). Chlorides deposition rates are provided
by the Southwest Institute of Technology and Engineering. Laboratory
and field experimental results for the calibration of the accelerating
model are from references [12–14].
2. Effects of atmospheric factors on corrosion
Atmospheric corrosion is influenced by various environmental fac-
tors simultaneously. It has been demonstrated that the atmospheric
corrosion effect of environment on metals consists of three component
parts [9,15]: the effect of dry deposition of sulphur dioxide, the effect of
dry deposition of chloride, and the effect of wet deposition of hydrogen
ions (acid rain). There are a couple of exposure programs like the
MICAT project [16], the OSD program [17], and the UN/ECE program
[18], that have measured the amount of rainfall and the acidity of the
precipitation. However, the data are far from enough for developing
164
Corrosion Science 137 (2018) 163–175
quantitative models. In the acting ISO 9223 standard [10], hydrogen
ions are not included due to the lack of experimental data. Thus, in this
paper, only the effects of relative humidity, temperature, sulphur di-
oxide, and chlorides on corrosion are studied. Discussions about the
effects of wind, rain, carbon dioxide, ozone, and other particles on at-
mospheric corrosion can be found in Refs. [19–23].
2.1. Effect of relative humidity
The relative humidity of the ambient environment has great influ-
ence on atmospheric corrosion. In many works, the corrosion rate is
found increasing when the relative humidity increases [12,13,20,24].
For example, an increase of the RH from 75% to 95% results in an
increase of the corrosion rate, whatever the temperature is [12].
Quantified studies have demonstrated that the corrosion current in-
creases following an exponential law when RH increases in a range of
53%–92% [13] and 40%–90% [24]. However, many works have re-
ported that nearly no atmospheric corrosion of carbon steel was ob-
served below relative humidity of 80%–85% under some specific en-
vironmental conditions [25,26]. Because a fundamental requirement
for atmospheric corrosion is the presence of a film electrolyte formed on
metallic surfaces, to proceed atmospheric corrosion with anodic and
cathodic reactions. This threshold is denoted as the critical relative
humidity (CRH). Normally, it is accepted that for iron, the CRH is
around 60% in unpolluted atmospheres. CRH can be much less when
the presence of hygroscopic salts on a surface stabilize the surface
wetness even more.
Studies have also found that the thickness of the electrolyte film on
a zinc surface increases with RH and that corrosion rates increase with
the thickness of the electrolyte film [27]. However, there also seems to
be a finite thickness of the electrolyte film that, when exceeded, can
control the corrosion reaction due to limited oxygen diffusion [27].
In atmospheric conditions, there are many factors that can influence
the critical relative humidity level and the thickness of the electrolyte
film, such as the nature of the material, the composition of the formed
corrosion products, the concentration of atmospheric pollutants, and
the presence of hygroscopic salts [22]. For instance, Van den Steen
et al. [28] have concluded that sample thickness, heat transfer, salts,
and changing rates of T and RH influence the electrolyte film thickness.
When metallic surfaces are contaminated by hygroscopic salts, the
surface can be wetted at lower RH. The presence of Magnesium chloride
hexahydrate on a metallic surface can make a surface apparently wet at
34% RH while sodium chloride requires 77% RH to create the same
effect [22]. Moreover, the hysteresis phenomenon of CRH during wet-
ting and drying process of the wet-dry cycles is unavoidable in the
presence of hygroscopic salts [28].
2.2. Effect of temperature
Temperature is another important influential environmental factor
on atmospheric corrosion. The complicated effect of temperature is
reflected in two aspects: the influence on corrosion reaction rate di-
rectly and influence on electrolyte film formation.
Atmospheric corrosion is an electrochemical process controlled by
anodic and cathodic reactions. In most of the practical applications, the
corrosion rate can be correlated to the ambient temperature with the
Arrhenius law [11] which is based on the Van’t Hoff’s equation [29].
Based on the Arrhenius equation, it has been suggested that corrosion
rates will increase by up to 15% if temperature increases by 2 ∘C [30].
Lin [31] has studied three kinds of steel in accelerated corrosion tests
and develops a corrosion model deduced from the Arrhenius law. Ex-
perimental observations have also found the increase of temperature
will increase the corrosion rate of different materials. M. Esmaily [32]
has reported that AM50 alloy corrosion has a strong positive correlation
with temperature, which coincides with the result LeBozec [12] has
reported. Corrosion current for zinc is also found increasing with
Y. Cai et al.
temperature increasing from 285 K to 308 K [13].
In reality, the corrosion reaction only happens when there is an
electrolyte film formed on the metal surface. Thus the atmospheric
corrosion becomes a complex discontinuous electrochemical process
due to evaporation and condensation of moisture in highly variable
environmental conditions. The relative humidity is a function of the
absolute humidity (water vapor content in the air) and temperature.
Generally, it is inversely proportional to the temperature when the
absolute humidity stays constant. Metal surfaces will undergo daily
wet-dry cycles. Temperature decreases and RH increases at night. Metal
surface cools down, allowing condensation to occur. Electrolyte film
forms on the metal surface and corrosion reactions become active. After
sunrise, temperature increases and the electrolyte film evaporates, thus
the corrosion reactions halt. 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. With such a
complex mechanism, the effect of temperature on atmospheric corro-
sion is perceived to be secondary [33].
Moreover, Lindstroem [34] showed that in the presence of carbon
dioxide, the zinc corrosion rate did not show dependence on tempera-
ture. Similar results of copper corrosion in the presence of nitric acid
were also reported [20]. When materials are subject to more complex
ambient environmental conditions with multiple atmospheric corrosive
factors, coupling effect occurs and the effect of temperature should also
be analyzed.
2.3. Effect of sulphur dioxide
Many researchers have demonstrated that there exists an accel-
erating effect of sulphur dioxide on atmospheric corrosion process
[3,35,36]. Kim [37] has found that the corrosion rates for metal pieces
(bronze, copper, marble and steel) exposed in outdoor environment is
generally proportional to the sulphur dioxide concentration, while
some researchers [3,8,9] used the power function to model the accel-
erating effect. G. W. Walter [38] conducted laboratory simulation of
atmospheric corrosion by sulphur dioxide and indicates that sulphur
dioxide will be oxidized to sulfate ion (SO24−) in the water. During the
process, hydrogen ions (H+) are produced and the acidity of the elec-
trolyte rises, which increases the corrosion rate and causes the dis-
solution of corrosion products. Cao [21] also finds that sulphur dioxide
can accelerate atmospheric corrosion of carbon steel and elucidates the
reasons as following: (a) The solubility of sulphur dioxide is about 1300
times more soluble than oxygen in the water, which will make the
cathodic reactant more effective than the dissolved oxygen; (b) The
hygroscopicity of sulfate causes a reduction in the CRH level of carbon
steel, prolonging the duration of electrochemical corrosion process; (c)
Sulphur dioxide acts as a catalyst such that one sulfate ion can catalyze
the dissolution of more than 100 atoms of iron.
2.4. Effect of chlorides
It has been reported that the deposition of chlorides can obviously
accelerate the atmospheric corrosion for steel [31], zinc [35], and
magnesium alloys [12,31,32,35]. When chlorides deposite on the metal
surface, the electrolyte conductivity increases [12] as well as the TOW
of metal surface. And the power function [3,8,9,39] and the quadratic
function [31,35] is used to correlate the corrosion loss rate and the
chlorides deposition rate by some researchers. Cole [40] has discussed
that the chlorides deposition is primarily controlled by the wind tur-
bulence, the distance from the coast and also influenced by rain and
surface temperature.
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Corrosion Science 137 (2018) 163–175
3. Atmospheric corrosion model in dynamic environment
3.1. The model incorporating dynamic environmental factors
The most commonly used model for long-term atmospheric corro-
sion is expressed in a power-law relation
C = A⋅t n (1)
where C is the corrosion loss, t is exposure time (years). A is a pro-
portionality constant, n is the mass loss exponent and both are esti-
mated from experimental data.
Eq. (1) predicts corrosion loss as a function of exposure time only.
The coefficients A and n represent the effects of all the factors that
affect the corrosion process, including environmental conditions. It has
been proved that the parameter A is significantly influenced by the
environmental factors for different metals from field exposure ob-
servations [7]. Thus, it is not accurate to estimate corrosion loss in
environments that are different from the environment where the model
is calibrated.
To quantify the effect of dynamic environments on atmospheric
corrosion, a model that estimates the corrosion loss as a function of
environmental parameters and exposure time is needed. The new model
should: (i) has a rational structure allowing variation of the environ-
ment, (ii) incorporates the effects of multiple environmental factors
with appropriate accelerating models, (iii) describes the dynamic en-
vironment with proper parameters and functions, and (iv) be able to be
extrapolated to other locations with different environmental conditions.
As most previous models are empirical and lack theoretical basis of
how these environmental factors affect the corrosion process, an en-
vironmental correction factor R (T , RH , S, Cl) is introduced to correct
the coefficient A in Eq. (1). The correction factor incorporates the effect
of temperature, relative humidity, sulphur dioxide, and chlorides on the
corrosion process. The Arrhenius relation, which is based on the Van’t
Hoff’s equation [29] for the temperature dependence on the reaction
rate, is used in conjunction with the Peck relation to correlate the ef-
fects of temperature and relative humidity on the corrosion process.
The dose-response functions are the relations between corrosion para-
meters (response) and the environmental parameters (dose). In this
paper, the dose-response functions in the ISO 9223 standard [10] are
used to describe the effects of sulphur dioxide and chlorides.
Besides, using TOW as the parameter to estimate the corrosion rate
has some problems. It is usually approximated as the time when RH is
greater than the CRH (80% for steel) and the temperature is greater
than 0 ∘C. But three conditions (rain, dew and water adsorption) con-
tribute to TOW and it is difficult to distinguish between these categories
because there is no sharp boundary between them. Furthermore, TOW
is a function of RH and T . In the new model, TOW is replaced by T and
RH as the environmental factors.
In addition, if all the environmental parameters are monthly or
yearly averaged value, the nonlinearity of atmospheric factors on cor-
rosion and the non-uniformity of environmental factors distributions
cannot be considered. In the new model, statistical distributions are
employed to describe each environmental factor.
At last, considering the dependence of relative humidity on tem-
perature, a parametric method is developed to characterize the condi-
tional relative humidity distribution at each value of temperature.
And the corrosion loss for the new model can be expressed as
C = A0 ⋅R (T , RH , S, Cl)⋅t n (2)
R (T , RH , S, Cl) = R (T )⋅R (RH )⋅R (S )⋅R (Cl) (3)
where A0 is the value of A at the average level of the environmental
factors. R (T ) , R (RH ) , R (S ) , and R (Cl) are the correction factors for
temperature, relative humidity, sulphur dioxide, and chlorides and they
are calculated through the following equation
Y. Cai et al. Corrosion Science 137 (2018) 163–175

T by Klinger [42] on the basis of a simple corrosion kinetic model, uses

R (T ) = ∫T U r (T )⋅f (T )dT
L
RHU
the term RH (1 − RH ) instead of RH in Eq. (6). Thus, the Arrhenius-
R (RH ) = ∫ RHL
r (RH )⋅g (RH |T )dRH Peck temperature-humidity accelerating relation comes to
SU
R (S ) = ∫ SL
r (S )⋅h (S )dS α
RH (1 − RH0 ) ⎤ −E 1 1
r (T , RH ) = ⎡ ⋅exp ⎧ a ⋅⎛ − ⎞ ⎫
⎜ ⎟
Cl
R (Cl) = ∫Cl U r (Cl)⋅k (Cl)dCl ⎢
⎣ RH0 (1 − RH ) ⎥
⎦ ⎨
⎩ K ⎝ T T0 ⎠⎬
⎭ (7)
L (4)
Note that as RH → 1, Eq. (7) is singular, and so it is not valid if RH
where
is sufficiently close to 1. However, the relative humidity of the field
r (T ) , r (RH ) , r (S ) , and r (Cl) are the accelerating factors for tem-
environments can be very close to 1 and even reaches 1, especially in
perature, relative humidity, sulphur dioxide, and chlorides, respec-
wet environment. Thus an exponential relation suggested by Vernon
tively.
[43] is introduced to correlate the corrosion rate with relative hu-
f (T ) , h (S ) and k (Cl) are the probability distribution functions
midity, and a more conservative temperature-humidity accelerating
(PDF) of temperature, sulphur dioxide concentration, and chlorides
relation is shown as following
deposition rate, respectively. g (RH |T ) is the conditional PDF of re-
lative humidity at each value of temperature. The construction of both −E 1 1
the accelerating factors and the probability distribution functions will r (T , RH ) = ⋅exp {α⋅(RH − RH0 )}⋅exp ⎧ a ⋅⎛ − ⎞ ⎫
⎜ ⎟

⎨
⎩ K ⎝ T T0 ⎠⎬
⎭ (8)
be detailed in the following section.
(TL, TU ) , (RHL , RHU ) , (SL, SU ) , and (ClL , ClU ) are the lower and upper From Eqs. (6)–(8) it is shown that the effects of both temperature
E
bound for the distributions of temperature, relative humidity, sulphur and relative humidity on corrosion are nonlinear. Let β = − Ka , para-
dioxide concentration, and chlorides deposition rate, respectively. meters α , β of Eqs. (6)–(8) will all be estimated with experimental data,
It has also been reported that the exponent n for mild steel is a and their accuracy will also be examined.
function of the type of atmosphere (rural, urban, industrial, and The accelerating effects of sulphur dioxide and chlorides are usually
marine) where it is exposed [41] However, Dean [5] has analyzed the captured by the dose-response functions. Tidblad [8] and Mikhailov [9]
influence of the environmental factors (TOW, S, Cl) on the exponent n analyzed the outdoor exposure observations of the ISO CORRAG pro-
for the four metals from the ISO CORRAG program. It is found that, gram and derived the dose-response function for different metals. And
from a statistical point of view, the exponent n is barely or not all the accelerating factor for sulphur dioxide and chlorides follows
significantly influenced by the environmental factors for different me- γ
S
tals [7]. And there has no agreement on the quantitative model corre- r (S ) = ⎛ ⎞
⎜ ⎟

lating the exponent n with environmental factors with such complex ⎝ S0 ⎠ (9)
mechanisms. In this paper, the correction of the exponent n is not υ
Cl ⎞
considered. r (Cl) = ⎛⎜ ⎟

Cl
⎝ 0⎠ (10)
Eq. (2) is the basic structure to incorporate effects of dynamic en-
vironmental factors. Other influential variables on atmospheric corro- where γ and υ are constants estimated from experimental data. S0 and
sion like wind and nitrogen dioxide can also be included with proper Cl 0 are the reference sulphur dioxide concentration and chlorides de-
accelerating models and quantitative description of them. position rate, respectively. They are also the average value of sulphur
dioxide concentration and chlorides deposition rate in the calculation.
3.2. The accelerating factor
3.3. Atmospheric factors parameterization
The environmental correction factor is a link that relates laboratory
models to dynamic field conditions. General discussions about which An accurate parameterization method of atmospheric factors is very
model is useful for the construction of the correction factor in practice important. The effects of these factors on corrosion are nonlinear as
can be found in Ref. [11]. There are some statistical models derived stated above and a small bias of parameter may lead to serious in-
from experimental data and some physical models based on the un- accuracy of the correction factor. In this section, a parametric method is
derstanding of the failure mechanism, physical and chemical theories. presented to describe the dynamic temperature, relative humidity,
The accelerating effect caused by temperature T is usually modeled sulphur dioxide concentration, and chlorides deposition rate, which can
by the Arrhenius relation on the first order chemical reaction with the also be employed to describe other atmospheric factors.
following express [11] To state the different characteristic of environmental factors dis-
tributions, the weather observation data of seven cities are selected to
−E 1 1
r (T ) = exp ⎧ a ⋅⎛ − ⎞ ⎫ ⎜ ⎟
represent different climate and atmosphere types as listed in Table 1.
⎨
⎩ K ⎝T T0 ⎠ ⎬
⎭ (5) The selected cities locate from hot and wet coastal areas to cold and dry
inland regions and include different kinds of atmosphere.
where T is the thermodynamic temperature in Kelvin. T0 is the reference
The weather data is from the National Oceanic and Atmospheric
temperature, which is also the average temperature in this paper. Ea is
Administration (NOAA) website. Temperature and relative humidity
the activation energy which can be estimated from experimental data.
are recorded every one or three hours with 0.1 ∘C and 1% precision for
And K is the Boltzmann constant.
temperature and relative humidity respectively. An entire 10-year
Relative humidity is a fundamental accelerating variable for cor-
period (from 2007 to 2016) of NOAA climate data is used for parameter
rosion. In most applications where relative humidity is used as an ac-
extraction to avoid year-to-year effects. The sulphur dioxide con-
celerating variable, it is used in conjunction with temperature and the
centration data are from the online database of China National
Arrhenius-Peck temperature-humidity accelerating model is employed,
Environmental Monitoring Center (CNEMC). Chlorides deposition rate
which is expressed as
is provided by the Southwest Institute of Technology and Engineering.
α Sulphur dioxide concentration and chlorides deposition rate are mea-
RH ⎞ −E 1 1
r (T , RH ) = ⎛ ⎜ ⋅exp ⎧ a ⋅⎛ − ⎞ ⎫
⎟ ⎜ ⎟
sured according to the ISO 9224-2012 Standard. The SO2 concentration
⎝ RH0 ⎠ ⎨
⎩ K ⎝ T T0 ⎠⎬
⎭ (6)
is measured every three hours and the chlorides deposition rate is
where RH is a proportion denoting relative humidity and α is a con- measured monthly. The results from concentration measurements are
stant. RH0 is the reference relative humidity, and also the average re- typically given in micrograms per cubic meter (μg m−3) and, for de-
lative humidity. An alternative relative humidity relationship suggested position measurements, in milligrams per square meter per day

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Y. Cai et al. Corrosion Science 137 (2018) 163–175

Table 1
Information about the environmental factors of the seven cities.
City T (∘C ) RH (%) S (μg m−3) Cl (mg m−2 day−1)

Range Average Range Average Range Average Range Average

Haikou 7–38 24.9 25–100 80.6 2–50 3.2 0.1–16.8 3.98

Kunming 5–39 23.2 15–100 74.3 3–90 17.0 – –
Chongqing 0–41 18.9 15–100 75.7 3–65 14.7 – –
Beijing −18–42 12.2 5–100 54.1 2–115 13.2 – –
Lanzhou −25–41 10.8 2–100 39.5 2–120 16.4 – –
Lhasa −12–27 9.4 0–97 34.8 2–60 8.8 – –
Harbin −44–35 −2.4 0–100 69.1 8–218 27.5 – –

(mg m−2 day−1).

3.3.1. Temperature parameterization

In outdoor exposure circumstances, the temperature is usually dis-
tributed asymmetrically within a wide range. But in many previous
studies, the temperature is usually considered constant and is averaged
during the entire exposure period. This will lead to the loss of tem-
perature variation information and estimation results become in-
accurate.
In this paper, the temperature is parameterized with probability
distribution functions (PDF). The PDF of the NOAA temperature data
for different cities is examined and reveals different modalities. The
shapes of the temperature distribution were observed to be unimodal,
bimodal, as well as multimodal as shown in Fig. 1. Thus, the tem-
perature is modeled by a mixture of multiple normal distributions
Fig. 2. Relative humidity PDF fitted by the mixture of multiple normal dis-
n tributions at the seven cities.
f (T ) = ∑ ωi⋅fi (T )
i=1 (11)
distribution of the seven cities. The relative humidity distributions are
1 )2
(T − μi ⎫ observed to be skewed and multimodal. For example, the relative hu-
fi (T ) = exp ⎧−
2πσi2 ⎨
⎩ 2σi2 ⎬
⎭ (12) midity distribution of Chongqing is unimodal and skewed right, while
the relative humidity of Beijing distributes in triple peak pattern. Thus,
n
the mixed normal distribution can also be used to describe the PDF of
∑ ωi = 1 relative humidity at different cities.
i=1 (13)
Dividing the relative humidity data into subgroups corresponding to
where n is the number of normal distributions, fi (T ) is the PDF of each value of ambient temperature, the mean and variance are found
distribution i (i = 1, 2, …, n ) and ωi is the proportion (weight), and μi varying along with ambient temperature (as shown in Fig. 3). As the
and σi2 are the mean and variance. Parameters (μi , σi2, ωi ) can be esti- relative humidity distribution must fall in the range of 0 ≤ RH ≤ 100
mated by the maximum likelihood estimation (MLE) and the EM al- and the relative humidity PDF is depending on ambient temperature,
gorithm. thus the conditional PDF of the relative humidity, given each ambient
temperature T , is described with the mixture of truncated normal dis-
3.3.2. Relative humidity parameterization tributions
Unlike the TOW in previously mentioned models, the relative hu-
midity raw data from weather observation are analyzed directly and
described with distributions. Fig. 2 shows the relative humidity

Fig. 1. Temperature PDF fitted by the mixture of multiple normal distributions Fig. 3. Conditional relative humidity PDF of different temperature fitted by
(Eqs. (11)–(13)) at the seven cities. Eqs. (14)–(17) at Lanzhou.

167
Y. Cai et al. Corrosion Science 137 (2018) 163–175

m gj (RH |T )
g (RH |T ) = ∑ wj (T )⋅ G (RH |T )
j=1 j (14)

2
gj (RH |T ) =
1 ⎧ [RH − uj (T )] ⎫
exp − 2
2πs j2 (T ) ⎨ 2s j (T ) ⎬
⎩ ⎭ (15)
100
Gj (RH |T ) = ∫0 gj (RH |T )dRH

=Φ ( 100 − uj (T )
sj (T ) ) − Φ( )
−uj (T )
sj (T ) (16)
m
∑ wj (T ) = 1
j=1 (17)
where m is the number of normal distribution, gj (RH |T ) is the PDF of Fig. 4. Sulphur dioxide concentration PDF fitted by the three-parameter log-
distribution j ( j = 1, 2, …, m ) and Gj (RH |T ) is the normalization factor. normal distribution (Eq. (23)) at the seven cities.
uj (T ) and s j2 (T ) are the mean and variance, and wj (T ) is the proportion
(weight) of given value of temperature T . This supports the observation variance of ln S , and η is the location parameter which denotes the
that the relative humidity distribution varies with temperature. minimum value of the sulphur dioxide concentration. Parameters can
uj (T ) , s j2 (T ) , wj (T ) are estimated at each value of temperature T be estimated by the MLE method or the generalized least squares
with relative humidity observations. It is found that the mean and method.
variance of the relative humidity can be expressed as a function of
temperature T . In different cities, the mean and variance of relative
3.3.4. Chlorides parameterization
humidity change with temperature in different patterns and can be
The chlorides is mainly from the sea salts and when the distance
described with piecewise functions. To find a model with the lowest
from the coast increases, the salinity of the air decreases. The salinity is
order and good accuracy, parameters are fitted to a polynomial equa-
very low and barely changes over time in inland regions. Thus the
tion as shown in the following
chlorides deposition rate is only recorded at coastal cities. The PDF of
p
uj (T ) = ∑hj=0 ajh T h the chlorides deposition rate data for Haikou is examined. It reveals
(18)
that it follows the log-normal distribution with density function
q
sj (T ) = ∑kj=0 bjk T k (19) 1 ( ln Cl − λ )2 ⎫
k (Cl) = exp ⎧−
rj 2πδ 2 ⋅Cl ⎨
⎩ 2δ 2 ⎬
⎭ (24)
wj (T ) = ∑l=0 cjl T l (20)
where Cl is the chlorides deposition rate, λ and δ2
are the mean and
where pj , qj , r j are the number of coefficients in the polynomial rela- variance of ln Cl . Parameters can be estimated by the MLE method or
tions for the mean, standard deviation and weight of the jth distribu- the generalized least squares method.
tion. For some cities, a linear relation can fit uj (T ) , s j2 (T ) , wj (T ) and T
very well, Eqs. (18)–(20) are degraded to a linear relation to avoid
4. Study cases
overfitting.
To show the accuracy of this multi-parameter method, the overall
4.1. Calibration of the accelerating models
relative humidity PDF and TOW of the city can also be generated, by the
integration of the relative humidity PDF at each value of temperature
Laboratory experiment observations are needed to examine the ac-
and the temperature PDF with the following express (21) and (22). And
celerating effect of environmental factors on corrosion. Two cases re-
the results of relative humidity distribution and TOW obtained by these
ported in previous studies [12,13] are selected to calibrate the accel-
two equations can be compared to the actual observation results for the
erating models of temperature and relative humidity. And the dose-
seven cities.
response functions of sulphur dioxide and chlorides are calibrated with
TU
field exposure results of the ISO CORRAG program [14].
g (RH ) = ∫T L
g (RH |T )⋅f (T )dT
(21) In case one, laboratory tests for zinc are conducted at constant
TU RHU temperatures of 285 K, 300 K and 308 K and the relative humidity is set
TOW = ttot⋅ ∫T ∫CRH
0
f (T )⋅g (RH |T )dRH dT
(22) to be 53%, 84% and 92% [13] in the test chamber. Corrosion current is
investigated continuously for 18–32 h by Zn–Graphite coupling type
where T0 and CRH are the critical temperature and critical relative atmospheric corrosion monitor (ACM) sensor. The structure of the ACM
humidity that an electrolyte film can form on the metal surface. ttot is sensor is in the sandwich form, and there is a porous insulating film
the total exposure time in hours. (0.02 mm thick) between the tested Zn specimen and conductive gra-
Therefore, (ajh , bjk , cjl ) are calculated for each city. This parametric phite film. This galvanic current has been found to show a good re-
method can help to describe the dependence of relative humidity on lationship with the corrosion rate of metals [44]. The detailed in-
temperature. formation of the experimental procedure can be found in Ref. [13] and
the monitored data are presented in Fig. 5 (a) and (b).
3.3.3. Sulphur dioxide parameterization In case two, magnesium alloys are exposed at 75%, 85%, and 95%
The PDF of the CNEMC sulphur dioxide concentration data for relative humidity and at 298 K and 308 K [12]. Metal corrosion loss rate
different cities are examined as shown in Fig. 4. It reveals that it follows was calculated and the data are presented in Fig. 5 (c). The details of
the three-parameter log-normal distribution with density function the experiment can be found in Ref. [12]. The least squares method is
1 [ ln (S − η) − θ]2 ⎫ used to fit the data for both of the two cases. The estimated parameters
h (S ) = exp ⎧− (α , β ) are listed in Tables 2 and 3.
2πe 2 ⋅S ⎨
⎩ 2e 2 ⎬
⎭ (23)
To show the performance of each accelerating model, the Akaike
where S is the sulphur dioxide concentration, θ and e2 are the mean and information criterion (AIC), the correct Akaike information criterion

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Y. Cai et al. Corrosion Science 137 (2018) 163–175

Table 3
AIC, AICC, and BIC of different accelerated models calculated by Eqs. (25)–(28)
for case two.
Model Eq. (6) Eq. (7) Eq. (8)

α 3.115 0.371 0.0366

β −2640.4 −2640.4 −2640.4
R-square 0.9533 0.8679 0.9438
AIC Eq. (25) −25.28 −19.04 −24.17
AICC Eq. (26) −13.28 −7.04 −12.17
BIC Eq. (27) −25.91 −19.66 −24.79

RSS
AIC = 2M + N ⋅ln( )
N (25)

2N RSS
AICC = ⋅M + N ⋅ln( )
N−M−1 N (26)

RSS
BIC = ln(N )⋅M + N ⋅ln( )
N (27)
N
RSS = ∑I =1 (lgSI − lgS′I )2 (28)
where M is the number of parameters in the model, N is the sample size
and RSS is the residual sum of square. SI and S′I are the Ith point ob-
tained by experimental measurement and model prediction respec-
tively.
AIC, AICC and BIC consider the complexity of the model as a se-
lection criterion and essentially penalize the likelihood, based on the
number of variables in the model and the sample size. When applying
these criteria to several proposed models, the best model is the one with
the lowest value of the AIC, AICC or BIC.
For case one, it is seen (in Table 2) that Eq. (8) has the highest R-
square and lowest AIC, AICC and BIC, which suggests that it is the most
successful one in correlating the galvanic current obtained under dif-
ferent test conditions. Therefore, in the rest of this study, Eq. (8) is used
to calculate the accelerating factor of temperature and relative hu-
midity for case one, which is expressed as

1 1
r (T , RH ) = exp {0.128⋅(RH − RH0)}⋅exp ⎧−5009.6 ⎛ − ⎞ ⎫⎜ ⎟

⎨
⎩ ⎝ T T0 ⎠⎬
⎭ (29)
For case two, as can be seen in Table 3, Eq. (6) is the best one with
the highest R-square and lowest AIC, AICC and BIC. Thus, in the rest of
this study, Eq. (6) is used to calculate the accelerating factors of tem-
perature and relative humidity for case two, which follows
3.115
RH ⎞ 1 1
r (T , RH ) = ⎛ ⎜ ⎟ ⋅exp ⎧-2640.4 ⎛ − ⎞ ⎫
⎜ ⎟

⎝ RH0 ⎠ ⎨
⎩ ⎝T T0 ⎠ ⎬
⎭ (30)

Fig. 5. Corrosion data under different experimental conditions for case one Generally, relative humidity is thought to be the most influential
[13] and case two [12]. factor of corrosion rate and temperature is secondary. Assume that the
average temperature T0 = 293K and the average relative humidity
RH0 = 75%, The nonlinear relations of the accelerating factor with re-
Table 2
AIC, AICC, and BIC of different accelerated models calculated by Eqs. (25)–(28) lative humidity and temperature for case one are shown in Fig. 6. As
for case one. can be seen, corrosion is nearly inactive when RH is lower than 60%.
When RH is higher than this level, the accelerating factor increases
Model Eq. (6) Eq. (7) Eq. (8)
rapidly.
α 6.815 2.439 0.128 The accelerating models for sulphur dioxide and chlorides are ca-
β −5011.4 −4870.9 −5009.6 librated using the 1-year exposure data of flat specimens from the ISO
R-square 0.9201 0.9663 0.9831 CORRAG program. The parameters for zinc are estimated with the least
AIC Eq. (25) −18.03 −54.25 −83.26
square method and listed in Table 4. Magnesium is not included in the
AICC Eq. (26) −16.95 −53.17 −82.18
BIC Eq. (27) −11.08 −47.30 −76.31
ISO CORRAG program. The accelerating factors of sulphur dioxide and
chlorides for magnesium are based on the dose-response function, fol-
lowing the same functional form as carbon steel, zinc, copper, and
(AICC) and the Bayesian information criterion (BIC) are introduced as a aluminum. The parameters in Eqs. (9) and (10) are assumed to be 0.87
criterion for model selection. All of these criteria are balance between and 0.49 as listed in Table 4. They are smaller than 1.0. This is because
fitness and model complexity with the following form that: (i) the growth trend of the accelerating factor slows down as
sulphur dioxide concentration and chlorides deposition rate increase

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Y. Cai et al. Corrosion Science 137 (2018) 163–175

Fig. 6. Accelerating factor as a function of temperature and relative humidity for case one, and as a function of sulphur dioxide concentration and chlorides
deposition rate for zinc and magnesium.

Table 4
The parameters of the dose-response function for sulphur dioxide and
chlorides (Eqs. (9) and (10)).
Metal type Parameter

γ υ

Zinc 0.43 0.68

Magnesium 0.87 0.49

due to the saturation of the electrolyte film on metal surface; (ii) the
parameters for carbon steel, zinc, copper, and aluminum are also
smaller than 1.0.
Assume that S0 = 15μg/m3 and Cl 0 = 8mg⋅m-2⋅day -1, the correlation
of the accelerating factor with the sulphur dioxide concentration and Fig. 7. Relative humidity PDF generated from independent and dependent fit-
the chlorides deposition rate are also illustrated in Fig. 6. It is shown ting at Chongqing and Lhasa. “Dependent fitting” curves are obtained by Eq.
that both the two relations are nonlinear. The growth trend of the ac- (21) which considers the dependency of relative humidity on temperature while
celerating factor slows down as sulphur dioxide concentration and “Independent fitting” curves does not consider.
chlorides deposition rate increase, which is different from that of
temperature and relative humidity.

4.2. Parameters extraction of the dynamic environmental factors

Parameters of temperature, relative humidity, and sulphur dioxide

concentration for all the seven cities are estimated with the parametric
method. And two of them are illustrated as examples in the following.
Parameters of chlorides deposition rate are estimated only for Haikou
due to the lack of source data.
City I: Chongqing
The temperature at Chongqing have a mean value of 18.9 ∘C and
ranges from 0 to 41 ∘C. The temperature PDF is well fitted with a bi-
modal normal distribution and parameters are μ1 = 9.3, σ1 = 2.9,
ω1 = 0.24 , μ 2 = 21.7 , σ2 = 6.9, ω2 = 0.76. The relative humidity data has
a mean value of 75.7% and ranges from 15% to 100% with a left Fig. 8. Relative humidity PDF of different temperature fitted by Eqs. (14)–(17)
skewed tail. It can be fitted with truncated normal distribution as at Chongqing and Lhasa.
shown in Fig. 7, and the parameters are u1 = 89, s1 = 16, w1 = 0.83,
u2 = 53, s2 = 14 , w2 = 0.17 . (18)–(20) and piecewise linear relations are obtained as shown in
The relative humidity distribution at each value of temperature is Fig. 9. Applying these equations to calculate uj (T ) , s j2 (T ) , wj (T ) at given
unimodal and varies with temperature as shown in Fig. 8. The mean value of temperature T and integrate them together, the overall relative
and standard deviation of relative humidity can be fitted to Eqs.

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Y. Cai et al. Corrosion Science 137 (2018) 163–175

Fig. 9. Relative humidity distribution parameters (u and s) as a function of

temperature obtained by Eqs. (18)–(20) at Chongqing.

humidity distribution is obtained through Eq. (21) and is also shown in

Fig. 7. We can see that the integrated distribution agrees well with the
raw data.
The sulphur dioxide concentration data ranges from 3 to 65 μg m−3
and has a mean value of 14.7 μg m−3. It is right skewed and well fitted
by the three-parameter log-normal distribution with θ = 2.35, e = 0.72,
and η = 2.7.
City II: Lhasa
The temperature at Lhasa has a mean value of 9.4 ∘C and ranges
from −12 to 27 ∘C. The temperature PDF is well fitted with a bimodal
normal distribution and parameters are μ1 = 13.1, σ1 = 5.8, ω1 = 0.71,
μ 2 = 0.3, σ2 = 4.5, ω2 = 0.29. The relative humidity data have a mean
value of 34.8% and ranges from 0 to 97% with a right skewed tail. It can
be fitted with truncated normal distribution as shown in Fig. 7, and the
parameters are u1 = 15, s1 = 12 , w1 = 0.31, u2 = 38, s2 = 30 , w2 = 0.69.
The relative humidity distribution at each value of temperature is
also bimodal and varies with temperature as shown in Fig. 8. The mean,
standard deviation and weight of the relative humidity distribution can
be fitted to Eqs. (18)–(20) and parameters are shown in Fig. 10. Ap-
plying these equations to calculate uj (T ) , s j2 (T ) , wj (T ) at given value of
temperature T , the overall relative humidity distribution obtained by
Fig. 10. Relative humidity distribution parameters (u, s and w) as a function of
g (RH |T ) and f (T ) is also shown in Fig. 7. We can see that the in-
temperature obtained by Eqs. (18)–(20) at Lhasa.
tegrated distribution is very close to the actual relative humidity data.
The sulphur dioxide concentration data ranges from 2 to 52 μg m−3
and has a mean value of 8.8 μg m−3. It is right skewed and well fitted by Table 5
the three-parameter log-normal distribution with θ = 1.74 , e = 0.55, Calculated TOW (hours/year) with Eq. (22) and the bias.
and η = 2.5. City TOWR TOWD Bias
For all the seven cities, the real time-of-wetness TOWR is calculated
from the weather observation raw data and TOWD through Eq. (22). Haikou 8127 8441 3.9%
Kunming 6554 6715 2.4%
The critical temperature is 0 ∘C and critical relative humidity equals Chongqing 7134 7618 6.8%
60%. Then the bias of TOWD relative to TOWR are calculated by Beijing 3168 3127 −1.3%
(TOWR − TOWD)/ TOWR × 100%. As can be seen in Table 5, all the biases Lanzhou 856 830 −3.2%
are within ± 10%. This indicates a good accuracy of the multi-para- Lhasa 1366 1239 −9.3%
Harbin 2690 2511 −6.7%
meter method for different types of environmental conditions.
The chlorides deposition observation is only available at Haikou.
The chlorides deposition rate ranges between 0.1–16.8 mg m−2 day−1
and equal to 1.0 by definition as the reference value equals to the
and the average value is 3.9 mg m−2 day−1. It is right skewed and well
average value of each environmental factor. Rd are the correction
fitted by the log-normal distribution with λ = 1.12 and δ = 0.71.
factors calculated with environmental factors distributions. Considering
the dependence of relative humidity on temperature, the correction
factors calculated with conditional relative humidity distributions are
4.3. Corrosion in dynamic environment
denoted as Rcd . The average bias for the seven cities is the mean of
their bias absolute value with respect to Rr .
In this section, three calculated results are compared to the real
The corrosion process is thought to be active only when the tem-
correction factors for temperature, relative humidity, sulphur dioxide
perature is higher than 0 ∘C. Thus the lower bound of the temperature
and chlorides as listed in Tables 6 and 7. The real correction factors Rr
TL = 0∘C, while the upper bound TU is set to be the highest observed
are calculated directly with the environmental observation data. Rm
temperature at each city. And the lower and upper bounds of relative
are calculated with the yearly average value of environmental factors

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Y. Cai et al. Corrosion Science 137 (2018) 163–175

Table 6
Correction factors of the seven weather observation cities for case one.
Correction factor Haikou Kunming Chongqing Beijing Lanzhou Lhasa Harbin Average

Rr(T ) 1.03 1.05 1.11 1.18 1.23 1.05 1.52 1.17

Rd(T ) 0.98 1.04 1.08 1.17 1.22 1.02 1.52 1.15

Rr(RH ) 2.15 5.28 3.97 22.5 15.0 40.8 5.60 13.6

Rd(RH ) 2.45 5.62 4.18 26.7 39.0 76.2 8.72 23.2
Rcd(RH ) 2.90 4.15 3.67 23.6 12.4 65.0 6.19 16.8

Rr(S ) 0.98 0.97 0.97 0.87 0.90 0.98 0.97 0.95

Rd(S ) 0.98 0.96 1.00 0.90 0.90 1.00 1.00 0.96

Rr(Cl) 0.91 – – – – – – 0.91

Rd(Cl) 0.94 – – – – – – 0.94

Rr(T , RH , S, Cl) 1.97 5.34 4.25 23.0 16.7 41.9 8.28 15.1
Rd(T , RH , S, Cl) 2.21 5.61 4.50 28.2 24.9 57.4 13.2 25.7
Rcd(T , RH , S, Cl) 2.62 4.14 3.95 24.9 13.6 45.9 9.34 18.6

humidity (RHL and RHU ) correspond to the range of the observed re-
lative humidity at each city. Sulphur dioxide and chlorides are accel-
erating variables and they range between the lowest and highest value
observed in the field environment.
For case one, as shown in Figs. 11 and 12, all Rm results under-
estimate the correction factor and are an order of magnitude smaller
than Rr . The average bias of the seven cities is 83%. This is primarily
because of the nonlinearity of the accelerating effect and the non-uni-
formity of environmental factors distributions in dynamic environ-
ments. Corrosion rate in highly corrosive environments is much higher
than that in slightly corrosive environments. It is seen that all the
temperature and relative humidity correction factors are greater than
1.0 for the seven cities. As the relative humidity accelerating effect is
highly nonlinear, gross error appears when the average relative hu-
midity is low under which the corrosion is nearly negligible, Beijing, Fig. 11. Correction factors calculated with different methods for case one.
Lanzhou, and Lhasa for example.
Rd results show better performance in correction factor calculation well reflected in the model. And that is more representative of the ac-
and the average bias is 27%. Some of them are very close to the real tual dynamic corrosive environment.
value. However, most of them overestimate the correction factor and For case two, the calculated correction factors are shown in Table 7.
some of their bias are higher than 50%. This is because that the method As shown in Figs. 13 and 14, four Rm results underestimate the cor-
assumes temperature and relative humidity distribution are in- rection factor and three results slightly overestimate it with the average
dependent, which is not true in the actual field environments. Relative bias of 27% for the seven cities. Rd results show better performance, but
humidity will decrease when temperature increases. As a consequence, all of them overestimate the correction factor with bias ranges from 1%
the relative humidity distribution is changed. The corrosion process to 53% and the average bias is 21%. Rcd results have the best accuracy
slows down as well. with an average bias of 12%, ranging from −8% to 23%.
Rcd results have good accuracy with an average bias of 16%, ran-
ging from −23% to 33%. It is also the most robust method, giving no 4.4. Discussion
significantly erroneous results. This is because that the nonlinear ac-
celerating effects of environmental factors on the corrosion process and Theoretically, relative humidity is the main factor that influences
the dependence of relative humidity distribution on temperature are the correction factor and the temperature is secondary. From Tables 6

Table 7
Correction factors of the seven weather observation cities for case two.
Correction factor Haikou Kunming Chongqing Beijing Lanzhou Lhasa Harbin Average

Rr(T ) 1.01 1.01 1.03 0.96 0.94 0.93 0.87 0.96

Rd(T ) 0.98 1.01 1.01 0.94 0.93 0.91 0.86 0.95

Rr(RH ) 1.07 1.22 1.15 1.44 1.10 2.33 0.68 1.28

Rd(RH ) 1.10 1.24 1.17 1.76 2.13 2.75 1.11 1.61
Rcd(RH ) 1.14 1.15 1.17 1.42 1.26 2.71 0.80 1.38

Rr(S ) 0.99 0.98 0.99 0.94 0.95 0.99 0.99 0.97

Rd(S ) 1.03 0.97 1.07 0.92 0.92 1.02 1.04 1.00

Rr(Cl) 0.90 – – – – – – 0.90

Rd(Cl) 0.93 – – – – – – 0.93

Rr(T , RH , S, Cl) 0.95 1.22 1.17 1.29 0.98 2.15 0.58 1.21
Rd(T , RH , S, Cl) 1.04 1.22 1.27 1.52 1.83 2.57 0.99 1.52
Rcd(T , RH , S, Cl) 1.08 1.13 1.27 1.22 1.08 2.53 0.72 1.30

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Y. Cai et al.
Fig. 12. Bias of correction factors calculated with different methods for case one.
Fig. 13. Correction factors calculated with different methods for case two.
and 7, it is seen that the environmental correction factor is mainly
contributed by the relative humidity. Rcd(RH ) are greater than 1.0
except at Harbin in case two (Rcd(RH ) = 0.68). This is because the
relative humidity accelerating relations (Eqs. (29) and (30)) are convex
and the overall accelerating effect is higher than that at the average
relative humidity level. But in Harbin, the temperature is lower than
0∘C for nearly half of the year and hence corrosion is not active. The
value of R (RH ) for case two is smaller than that for case one at the same
city. This is caused by the difference in the parameters and functional
form of the accelerating relation for the two cases.
Fig. 14. Bias of correction factors calculated with different methods for case two.
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Corrosion Science 137 (2018) 163–175
The temperature correction factor is also influenced by both the
convex Arrhenius accelerating relation and the non-uniform tempera-
ture distribution. In case one, the temperature correction factors are
greater than 1.0 even though the corrosion process halts under 0∘C at
Beijing, Lanzhou, Lhasa, and Harbin. But in case two, the temperature
correction factor of these four cities are less than 1.0. This is because
the parameter β is smaller than that in case one (2640.4 vs 5009.6), and
the corrosion rate is less sensitive to temperature variation. As a con-
sequence, the contribution in the high temperature region is eliminated
when no corrosion happens under 0∘C. As the temperature distribution
is approximately symmetric in most cases, when temperature is higher
than 0∘C all over the year, the temperature correction factor is expected
to be greater than 1.0.
The sulphur dioxide correction factor for the both cases are all less
than 1.0 and ranges between 0.87 and 0.99. The dose-response accel-
erating relation is concave and the overall accelerating effect is smaller
than that at the average sulphur dioxide concentration level. But most
of them are very close to 1.0. For chlorides, although only one site has
measured chloride level, the discussion about its accelerating effect is
still included in the manuscript because: (i) the accelerating effect of
chloride is significant at marine sites and chlorides-rich locations; (ii)
the functional form of the accelerating model of sulphur dioxide and
chloride (Eqs. (9) and (10)) is the same. When use the dose-response
function as the accelerating relation for chlorides correction factor, si-
milar conclusions can also be drawn.
There are some other interesting findings to be noticed. If TOW is
Y. Cai et al.
use as the parameter, some erroneous results will appear. For example,
TOW of Kunming (65,542 h) is smaller than TOW of Chongqing
(71,341 h). However, the average corrosion loss of Kunming is higher
than that of Chongqing in both cases. This is because the temperature
and relative humidity distributions for these two cities are significantly
different, but TOW cannot distinguish the difference. Thus it is rea-
sonable to replace TOW with temperature and relative humidity dis-
tributions. Van den Steen et al. [28] has also highlighted the conclusion
that TOW is not a real measure for corrosion rate.
It is also found that the bias of the calculated correction factors is
larger than the bias of the environmental factors distributions for most
cities. This is because the error of fitting the environmental factors
distributions is magnified by the nonlinear accelerating relation. When
dealing with temperature and relative humidity parameterization, the
lower bound of relative humidity and temperature can be set as the
critical relative humidity level and the lowest temperature that an
electrolyte can form on the metal surface. The relative humidity and
temperature data out of the valid region can be filtered out. Thus the
integrated model is able to obtain more accurate results, with less
amount of calculation at the same time, especially in cold and arid
climate with low temperature and relative humidity. For example, in
the case of Lhasa, if TL = 0∘C and RHL = 60%, the temperature can be
fitted with a single truncated normal distribution. The relative humidity
distribution becomes unimodal and uj (T ) , s j2 (T ) , wj (T ) can be fitted
with much fewer parameters and higher accuracy.
The correction factors for temperature, relative humidity, sulphur
dioxide, and chlorides provide measurements of how these environ-
mental factors influence the corrosion process in field dynamic en-
vironment. The method estimates a better set of environmental para-
meters and can be extrapolated to environments different from where
the model is calibrated. It may also be helpful to estimate the corro-
sivity category of the atmosphere and improve the ISO 9223 classifi-
cation system.
However, there are gaps between the laboratory test results and the
field corrosion observations. Actually, to make the comparison between
the proposed modeling results and the field corrosion data, three types
of data and a model are needed: the accelerating corrosion test data, the
field corrosion data, the field environment data, and the accelerating
model. It would be better to use the design of experiment (DOE)
methodology for conducting the laboratory accelerating corrosion ex-
periments under controlled temperature, relative humidity, sulphur
dioxide concentration, and chloride deposition rate. Then a rational
accelerating model that captures the effect of all these environmental
factors on corrosion is possible to be built. At the same time, the field
corrosion exposure should be conducted in different cities for the same
material and the environmental data should be recorded. It would be a
huge complicated project to have all these work done. The authors are
now still working on this and the results are expected to be reported in
future publications.
In addition, the laboratory tests are conducted under controlled
conditions while the filed environmental condition includes all the
environmental factors. In this paper, only the influences of relative
humidity, temperature, sulphur dioxide, and chlorides on corrosion are
studied. The influence of solar radiation, wind, cloud, various kinds of
pollutant and other unknown variables also requires further research
effort. Moreover, although SO2 concentration in China is higher than in
Europe and is still the most important pollutant, it has been going down
in the recent decades. It would be very important to consider the re-
ducing of SO2 in the future and the influence of other pollutants (ni-
trogen dioxide, ozone, carbon dioxide, ammonia, et al.) on corrosion.
Theoretically, the accelerating factors should be derived from the
laboratory data under controlled environmental conditions, rather than
the field data under dynamic environmental conditions. In this paper,
the accelerating factors are derived from the mix of laboratory data and
field data. This is because that there is no such data that studied the
corrosion process of one material under combined conditions of
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Corrosion Science 137 (2018) 163–175
temperature, relative humidity, sulphur dioxide concentration, and
chlorides deposition rate. For sulphur dioxide and chlorides, the ac-
celerating factors are derived from the field corrosion data from the ISO
CORRAG program. It is an alternative of the laboratory data, though
not completely appropriate. Although the deriving of the accelerating
factors of sulphur dioxide and chlorides are difficult, they are still in-
cluded in this paper because they are very important influential en-
vironmental factors on corrosion. The deriving of the accelerating fac-
tors will be more reasonable using the laboratory data under combined
environmental conditions. The results are also expected to be reported
in future publications.
On the other hand, the study of the long-term effects of the dynamic
environmental factors on corrosion is still challenging. In this paper, the
influence of the environmental factors on the exponent n is not con-
sidered in the long-term kinetic model. In fact, the long-term corrosion
of metals undergoes three periods: the incubation, transition, and
steady-state periods. Starting from the steady-state period, corrosion
loss increases linearly with time. The time to reach a steady state de-
pends on the environmental conditions of the atmosphere [2] and the
nature of the metal. The stabilization time for wreathing steel amounts
to 6–8 years in less corrosive environments (categories C2–C3) or
4–6 year in more corrosive environments (categories C4–C5) [45]. For
mild steels exposed in all types of atmospheres, the stabilization time is
observed to be 4–6 years [41]. Morcillo [2] also finds that the stabili-
zation time decreases as the corrosivity category of the atmosphere
rises. The steady-state corrosion rate rises with the corrosivity in both
rural, urban, industrial and marine atmospheres [2]. Panchenko have
used the power function [46] and the power-linear function [47] to
predict the long-term corrosion losses. In his paper, a quadratic function
n = a (bA − c )2 + d is used to describe the dependence of exponent n on
A . The steady-state corrosion rate is also found in good linear relation
with A . As A is an integral parameter of the atmosphere corrosivity
including all the effects of influential environmental factors on corro-
sion, it is possible to estimate the long-term corrosion losses in different
field environments based on these important findings.
For the multi-parameter method, the environmental factors should
be recorded at least 6–8 times per day to describe their daily fluctua-
tion. This could be satisfied by the climate data recorded by the weather
observation stations and it is sufficient to estimate the model para-
meters with good accuracy. For the parameterization of the conditional
relative humidity distributions, a total number of 10–15 groups of re-
lative humidity data corresponding to different value of temperature
would be sufficient to estimate the parameters with good accuracy.
Thus in this paper, the width of each group is approximately 3–6 °C for
different cities depending on the range of the temperature distribution.
And the groups should be symmetrically selected around the average
temperature.
5. Conclusions
This paper presents the method of modeling the effects of tem-
perature, relative humidity, sulphur dioxide, and chlorides on atmo-
spheric corrosion in dynamic environment. A multi-parameter method
is developed to characterize the environmental factors distributions and
the dependence of relative humidity on temperature. The effects of each
environmental factor are analyzed and represented by the correction
factors. The following conclusions are drawn.
• The presented method significantly improves the accuracy of cor-
rosion estimation for all the seven cities. The average bias is 16%
and 12% for the two cases comparing with the results calculated
with the actual environmental data.
• The parametric method is accurate to describe the dynamic en-
vironment and the conditional relative humidity distribution fits the
real relative humidity data well, within ± 10% deviation from the
real value.
Y. Cai et al.
• It is better to replace TOW with T and RH and describe them with
distributions considering the dependence of relative humidity on
temperature.
• Relative humidity is the most influential factor and temperature is
secondary. They have remarkable nonlinear accelerating effects on
the corrosion process which must be considered in the dynamic
environment. Their integral correction factors are usually greater
than 1.0.
• Sulphur dioxide and chlorides are important accelerating variables.
The nonlinearity of their accelerating effects on the corrosion pro-
cess is less significant. The integral correction factors are slightly
smaller than 1.0.
•
Both the accelerating relation and the distribution parameters of the
environmental factors can influence their total effects on the cor-
rosion process.
•
This paper shows the way to quantify the effects of dynamic en-
vironmental factors on the corrosion behavior. It is extensible to
include more kind of influential factors of atmospheric corrosion for
different materials as long as there is clear understanding of how
they affect the corrosion process and describe these factors cor-
rectly.
Acknowledgement
This work is supported by the National Natural Science Foundation
of China (No: 61473014).
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