Corrosion Science 51 (2009) 2055–2062

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Corrosion Science
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Atmospheric corrosion of zinc induced by runoff

L. Veleva a,*, M. Acosta b, E. Meraz c
a
Applied Physics Department, CINVESTAV-Merida, Carr. Ant. a Progreso, Km. 6, 97310 Merida, Yucatan, Mexico
b
Universidad Juárez Autónoma de Tabasco, DACB, Km. 1 Carr. Cunduacán-Jalpa de M., 86690 Cunduacán, Tabasco, Mexico
c
Universidad Juárez Autónoma de Tabasco, DAIA, Km. 1 Carr. Cunduacán-Jalpa de M., 86690 Cunduacán, Tabasco, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: Atmospheric corrosion and runoff of zinc were investigated during two years in humid tropical climate
Received 9 March 2009 on hot dip galvanized steel and zinc samples. The high zinc mass loss (14.70 g m2) is induced by the
Accepted 24 May 2009 intensive zinc release (12.40 g m2). No corrosion phase containing chloride was detected on the zinc sur-
Available online 28 May 2009
face, while a variety of sulfates not dissolved by rains reveals the sensitivity of zinc to SO2 pollutant. How-
ever, two chloride-containing corrosion products were detected on the galvanized steel. Exponential
Keywords: equation is proposed that fits well the experimental data for zinc mass loss induced by runoff process
A. Zinc
as a function of the time of wetness. The formula gives possibility to predict the mass loss even before
A. Galvanized steel
B. Mass loss
a steady state in the corrosion process has been reached. This equation can converge to a Benarie lineal
B. Damage function function (C = Atw), when the coefficient b = 1 for the corrosion which is accelerated with the partial
C. Atmospheric corrosion removal of the corrosion layer during the runoff phenomena.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction
The ability of zinc to galvanically protect steel has made this
metal important from an industrial point of view [1–2]. Zinc is rel-
atively resistant to corrosion in neutral environments [3], increas-
ing its localized corrosion degradation in marine-coastal
atmospheres due to the presence of airborne particles [4]; it is very
sensitive to any change of atmosphere acidity, e.g., SO2 presence.
Although zinc is available in many forms, such as sheet, plate, strip,
and pressure die castings, its principal uses are for corrosion con-
trol as a coating on steel and as Zn anodes for cathodic protection
of steel (underground pipelines, oil rigs, offshore structures, and
bridges).
Zinc, in particularly as galvanized hot dip steel is a common me-
tal used for effective corrosion protection of steels (laminated
roofs, fences, containers and tubes for water transport, etc.), often
exposed to outdoor atmospheres with different corrosive aggres-
sivity. Worldwide the use of zinc for galvanization results in an an-
nual consumption of more than three million tones of zinc,
constituting nearly one-half of the world zinc production [5]. Zinc
sheet has been used over 200 years as a roofing material easily
adapting to various design styles and having a long lifetime. It
was reported by the Mexican INEGY (Anuario 2002) that approxi-
mately 67% of the consumption of zinc is used for an elaboration of
galvanized steel (hot dip zinc). Its production in Mexico is gener-
* Corresponding author. Tel.: +52 999 9429447; fax: +52 999 9812917.
E-mail addresses: veleva@mda.cinvestav.mx, lucienveleva@yahoo.com.mx (L.
Veleva).
ally 80,000 tons year1: 56% steel sheet, 9% tubes, 9% wire, and
26% others. In southeastern Mexico, in humid tropical climate,
the housing statistics reported that 63% of roofs and walls are
made from galvanized hot dip steel.
1.1. Atmospheric corrosion of zinc
Because of its negative standard redox potential (0.76 V/SHE),
Zn is very active metal and tends to corrode in contact with oxygen
and moisture. For zinc the atmospheric corrosion goes to the for-
mation of oxides/hydroxides layer, which acts as a physical barrier
between the metal and environment [1,2,6,7]. However, the zinc
mass loss increases with time, until reaching a steady state, due
to the fact that zinc corrosion products do not form protective
films. In atmospheric corrosion conditions metal rapidly corrodes
forming initially a thin film of zinc oxide (ZnO), that is an n-type
semiconductor and its electronic conductivity promotes the com-
mon cathodic corrosion reaction of oxygen reduction [8]:
½O2 + H2O + 2e ) 2OH (1). In posterior stages the formed film
of ZnO is transformed to various zinc hydroxides, consuming the
liberated hydroxide ions in the reaction (1). Thick corrosion prod-
ucts are mainly composed of ZnO, zinc hydroxycarbonate
Zn5(CO3)2(OH)6, and hydroxychloride Zn5(OH)8Cl2. Approximately
1 nm of the outermost layer of the zinc corroded surface is rich
in surface contaminants, such as chloride and sulfate ions, and
the composition of the corrosion layer is not constant with depth
[9]. One study focused on the role of zinc corrosion products
suggests that their electronic properties can be insulating, n- or
p-type ZnO semiconductors, depending on the environmental

0010-938X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.05.030
2056 L. Veleva et al. / Corrosion Science 51 (2009) 2055–2062
contamination and alloying elements [8]. When p-type semicon-
ductor products are formed on Zn-55Al coating, these prevented
the cathodic reaction because of a deplete zone formation at the
surface of products [10]. Moreover, experimental measurements
of Zeta-potential and isoelectric point, as a function of pH 6–8,
indicate that the likelihood of zinc corrosion products possessing
a negative surface charge decreases in the order of: zinc hydroxy-
carbonate > zinc hydroxysulfate > zinc hydroxide > zinc hydroxy-
chloride > zinc oxide [11]. Thus, negatively charged zinc
corrosion products have the ability to aid in the repulsion of chlo-
ride ions and prevent the zinc attack.
1.1.1. Specific corrosion products of zinc
Zinc is the only one of the commonly used industrial metals
with an abundant corrosion product containing carbonate, proba-
bly as a function of the aqueous solubility of the formed hydroxy-
mixed salts in the presence of carbon dioxide in humid air, and this
product plays an important role in zinc atmospheric corrosion [12].
One study suggests that the corrosive effect of CO2 is caused by the
acidification of the surface electrolyte, giving rise to higher surface
conductivity and an enhanced dissolution of metal surface films
[13]. The main corrosion products in the presence of CO2 have been
zinc hydroxycarbonate Zn4CO3(OH)6H2O and hydrozincite
Zn5(CO3)2(OH)6, the last one identified after exposure to high CO2
concentration; in the absence of carbon dioxide ZnO was formed.
Zinc hydroxycarbonate was completely converted into hydroxysul-
fate Zn4SO4(OH)64H2O by traces of SO2. It was shown that the for-
mation of zinc hydroxysulfate, the main corrosion product in
humid SO2 polluted air, does not necessarily proceed from a reac-
tion with zinc hydroxycarbonate. In situ spectroscopy (IRAS) stud-
ies of atmospheric corrosion of zinc, in CO2 polluted atmosphere
and in presence of NaCl, reveal that when the CO2 concentration
is high (>350 ppm), a neutralization of the surface electrolyte by
CO2 occurs and the amount of precipitated insoluble
Zn5(OH)8Cl2H2O and Zn5(OH)6(CO3)2 increases [14]. However, in
highly polluted acidic industrial atmospheres no protective corro-
sion films should form on zinc, leading to significantly rapid zinc
dissolution.
A basic assumption in the metal corrosion analyses is that the
rate of consumption of corrodents on a metal surface is small with
respect to the rate of their delivery [15]. This assumption may be
valid for surfaces having minimal interaction with the corrodents,
but is not valid for surfaces which consume the ions as fast as they
are delivered: for example, SO2 will never saturate an aqueous
layer on a zinc surface, because SO2 reacts readily to form ZnSO4.
1.1.2. Relative humidity and time of wetness influence
The electrochemical nature of atmospheric corrosion requires a
wet metal surface, i.e., the presence of electrolytic solution, created
by water condensation, dew, rainfall, mist, or melting snow. Raman
spectroscopy analysis of zinc corrosion products formed in atmo-
spheric environment in the presence of NaCl particles, reveals that
when the air RH was <80%, zinc was covered by ZnO [16]. However,
when the RH was >80%, the initial corrosion products changed to
aqueous ZnCl2 layer formed on the surface, that increased and
reached saturation during the zinc corrosion process, followed by
the precipitation of simonkolleite Zn5(OH)8Cl2. The protective nat-
ure of passivation on zinc has been discussed in terms of the ability
of zinc oxidation products to retain moisture, by correlating wet-
ting data with the criteria for droplet retention on planar surfaces
[17]. The energetic properties of the oxide surfaces have been de-
scribed from measurements of the contact angle with water and
the results show that zinc hydroxychlorides possess the lowest
contact angle while naturally formed zinc oxide–hydroxide coat-
ings are the most hydrophobic. The response of the various oxides
to rain washing events and water adsorption processes is discussed,
and mass gain data indicate that corrosion rates decrease with
decreasing contact angle, suggesting that hydrophobic surfaces
are not necessarily advantageous for improving corrosion
performance.
The period during which a metallic surface is covered by
adsorptive and/or liquid film of electrolyte, necessary for initiation
and progress of the atmospheric corrosion, is defined as time of
wetness (TOW) of the metal surface, according to ISO 9223:92
[18], which can be measured or calculated [18,19]. Therefore,
TOW as a fraction of the total exposure time, determines the dura-
tion of the electrochemical corrosion process and denotes explic-
itly when the mass transport and charge transfer occur during
the electrochemical corrosion, and usually TOW does not coincide
with the exposure time of metal. Due to this fact, the study of the
wetting of metal surfaces in order to understand the process con-
trolling atmospheric corrosion has been gaining attention [7,20–
24]. The time of wetness of zinc surface, under wet–dry cyclic con-
ditions with different drying periods, is a controlling parameter for
the corrosion process kinetic and specifics: the shorter drying per-
iod in each cycle leads to higher amount of corrosion products on
the metal, because the surface has been under wet conditions for
longer periods, necessary for the development of the corrosion pro-
cess [25]. It is highly recommendable to calculate the distribution
of TOW in different temperature ranges, in order to explain metal
corrosion process and its rate [7,26–28].
1.2. Precipitation runoff from zinc
The formed corrosion layer on zinc surface can be transformed
by removing physically (winds and sand erosion) or by dissolution
of soluble corrosion products during pluvial precipitations or water
condensation on the metal surface. When zinc corrosion products
are dissolved by dew and rains, zinc ions are liberated from the
corroded surface and dispersed to the environment. This phenom-
enon is recognized today as a metal runoff process [29–36].
Although zinc is an element essential for all live forms, long term
presence of elevated concentrations of dissolved zinc in natural
systems can damage ecosystem. The runoff process is related to
the characteristics of precipitations (volume, pH, intensity, flow
rate, prevailing pollutant level of atmosphere, etc.) and corrosion
process prior to and during a rain event. Among the factors which
must be considered are the type and frequency of precipitation, the
time-varying concentration and solubility of atmospheric aggres-
sive gases within that precipitation, and other environmental
parameters such as the relative humidity. During the dry period
neutral zinc salts with high solubility constants are frequently
formed, e.g., ZnSO4 or Zn(NO3)2, and they are easily dissolved dur-
ing the first flush release, whereby less soluble zinc salts are
formed, including zinc hydrosulfates and zinc hydrocarbonates.
Their solubility properties govern the posterior dissolution rate
during the steady-state runoff. The concentration of zinc ions re-
leased during the first flushes varies significantly, according to
the aggressivity of the environment and have been reported to
be 2.6, 1.6, and 3.7 Zn g m2 year1, for samples exposed to urban,
rural, and marine atmospheres, respectively, considering annual
pluvial precipitations of 500 mm year1 [31]. The rate of zinc run-
off is considerable lower than its atmospheric corrosion rate, 50–
90% for zinc exposed during 5 and 2 years, respectively. Thus, the
zinc runoff process makes the atmospheric corrosion mechanism
and kinetics more complicated. As a consequence of metal runoff,
in different countries in EU and in the USA traces of different met-
als (zinc, iron, copper, and lead) have been detected in soils, water,
and biosphere, which are originated from the corroded surface of
metal structures, and are dangerous from an environmental point
of view. The analysis of the literature shows that since 1990 in Eur-
ope and USA the attention to the metal runoff is enormous. For
 L. Veleva et al. / Corrosion Science 51 (2009) 2055–2062
example, in Germany [38], a runoff rate of 3.73 g m2 and a volume
weighted mean zinc concentration of 4.9 mg L1 were determined
(868 mm year1 precipitations on 238 m2 of a 14-year-old real
roof). Low rain intensities are correlating with higher zinc concen-
trations in runoff, whereas the duration of preceding dry periods
could not be correlated with initial zinc concentration. It is also re-
ported [30] that roofs made from galvanized hot dip steel can gen-
erate zinc runoff precipitations of 1–44 g m3, while roofs made
from zinc generate zinc concentrations between 0.01 and
2.6 g m3. The zinc retention capacity of the soil proved to be be-
tween 80% and 99%, hence allowing a small portion of introduced
zinc in the rain or the natural zinc content of the soil to pass
through the soil core during a continuous rain event [31]. It is
noted also that 34% of the total zinc concentration (1000 lg L1)
is bioavailable. Zinc is natural chemical element, which is essential
for the existence of life. However, zinc in high ionic concentration
in water can cause toxic effect for the aquatic life, for example.
According to the requirements of the standard for water quality,
the highest permitted zinc concentration level is 1000 lg L1. For
residual industrial waters the maximum level of zinc ions the
USA standard establishes 5000 lg L1 (EPA 200.7) and in Mexico
this level is higher – 9000 lg L1 (NOM-0001-ECOL, 1996; NOM-
002-ECOL, 1996).
1.3. Runoff from zinc in humid tropical climate
The humid tropical climate is recognized as an aggressive envi-
ronment for metals, due to the very high annual values of time of
wetness for the metal structures, which provides conditions for
higher corrosion rates, even in the presence of low level of contam-
inants, compared to different temperate climates [12,39,40]. The
tropical humid climate of Southeaster Mexico and Gulf of Mexico
creates large annual time of wetness about 8400 h for the mar-
ine-coastal regions and between 3000 and 4500 h for the rural
ones [27]. In rural sites (more than 30 km from the sea shore)
the air relative humidity is above the critical value (80%) for mois-
ture formation on the metal surface only during the night and,
therefore, corrosion does not occur during the day: it fol1ows that
the metal and corrosion scale encounters both dry and wet cycles,
while that formed at marine-coastal sites are wet throughout the
day. Moreover, it is very important to recognize that in tropical hu-
mid climates the TOW coincides with high temperature ranges. For
example, at marine-coastal sites 64–73% of TOW is spent in the
temperature range 25–30 °C; in rural sites 54–64% of the time of
wetness occurs in the lower temperature range 20–25 °C (this
determines different rates of metal corrosion in each site). These
specifics of humid tropical climate determine its high aggressivity
for metal structures especially in the marine-coastal regions, with
accelerated degradation of the principal metals, such as low carbon
steel, zinc, copper, and aluminium [28,39–41], compared to the
aggressivity of different temperate climates in Europe and USA
[42–46].
The first study of runoff metal process in humid tropical climate
has been carried out in the Gulf of Mexico, in the state of Tabasco
[47–49]. The reported results cover the initial stages of metal loss
Table 1
Annual environmental parameters of rural and urban test sites of humid tropical climate, Gulf of Mexico, Tabasco State, during the period of test of two years (February 2004 –
February 2006).
Environment Tav (°C) RHav (%) TOW (h)
Rural 26 84 3003
3195
Urban 27 82 3007
3060
2057
of zinc and galvanized hot dip steel samples and runoff release dur-
ing two years. In order to extend the available experimental data,
integrating the previous works of these authors, the present paper
point to the kinetics of the atmospheric corrosion of zinc induced
by the runoff process and its specifics, including a review of the
damage functions reported in the scientific literature.
2. Materials and methods
2.1. Sampling and field exposure
Flat sheet specimens of commercial electrolytic zinc
(100  150  1 mm, 99.95% purity, % wt composition: Cu 0.064;
Cd 0.002; Fe 0.003; Ti 0.006; Sn, Pb, Al 0.001) and commercial gal-
vanized steel (100  150  0.95 mm, 10 lm of hot dip zinc: Zn
0.83–1; Al 0.4) where exposed in open air in two test sites, in
accordance to the procedures of ISO [18] and ASTM [50] standards:
rural environment of Cunduacán – 50 km from the coast, and urban
atmosphere of Villahermosa – 68 km from the sea coast. In both
test sites during the exposure period (February 2004–February
2006), the analysis of temperature–relative humidity (T/RH) daily
complex was used for calculation of time of wetness, as an effective
time of corrosion [18]. The statistic analysis showed that the an-
nual TOW, that occurs at night time and during rains, is 34% of an-
nual exposure time, and moreover, 90% of TOW is done in
temperature range of 20–25 °C; the last fact contributes to the
acceleration of zinc corrosion, compared to that in temperate cli-
mates. The monthly deposition rates of sulfur dioxide and airborne
chloride salinity were continuously measured in both test sites
[51]. The pluvial precipitations were registered, as important infor-
mation for the runoff zinc process. Table 1 presents the measured
environmental factors.
During the period of test in the rural atmosphere there were 152
rainy days and 582 dry days (1:4 ratio), with total amount of
3332 mm, while in the urban environment have been 184 rainy
days and 550 dry days (1:3 ratio), with a total amount of
3456 mm. The acidity of precipitation varies between events as
well as during them, and it was often greatest at the start (pH
4.7) of rainy event, with decreasing acidity later (pH 5.5).
2.2. Corrosion and runoff measurements
The progress in zinc and galvanized steel corrosion processes
where studied by a gravimetry. Periodically (10, 60, 152, 227,
306, 456, 487, 517, 540, 600, 660, and 720 days) the mass loss, as
an average of three samples in each exposure period, was deter-
mined removing the zinc corrosion products in solution of ammo-
nium hydroxide at 20–25 °C [52].
It is necessary to note, that the corrosion attack on zinc surface
is not a uniform in the initial stages and due to this fact the mass
loss presented as mass per unit area (g m2) involves a certain er-
ror. Semiquantitative XRD, SEM-EDX analysis of the corrosion
products revealed information about the progress in the corrosion
process. Part of the exposed samples was connected to recipients
for collection of runoff solutions released from the metal surface
SO2 (mg m2 day1) Chloride (mg m2 day1) Rains (mm)
1.50–3.80 (min–max) 6.00–25.30 (min–max) 1179 (1st year) 2153 (2nd year)
2.90–5.80 (min–max) 3.80–10.00 (min–max) 1406 (1st year) 2050 (2nd year)
2058
140
120 galvanized steel
zinc
100 rains
CO32- (mg L-1)
80
60
40
20
0
Feb Mar
Fig. 1. Cumulative monthly concentration of carbonate ions in rains and runoff solutions collected from galvanized steel and zinc samples, during their exposure in urban
environment of humid tropical climate (Tabasco, Gulf of Mexico).
during each pluvial precipitation, in order to determine their pH,
conductivity and the zinc mass loss, as a part of soluble corrosion
products, liberated during the runoff process. Atomic absorption
spectroscopy with direct aspirator in flame of air-acetylene was
applied for analysis of zinc ions (Zn2+) as a part of the runoff solu-
tions, according to the standard NMXX AA-051 SCFI 2004. Addi-
tionally, different chemical analysis was used for measurement of
several ions, which characterize the composition of the collected
runoff solutions and rains.
3. Results and discussion
3.1. Runoff precipitation analysis
The chemical analysis of collected runoff solutions, after each
pluvial precipitation, indicate that the majority and significant
concentration corresponds to CO32 ions (Fig. 1), followed by Cl,
NO3, and SO42 ones, while with minority presence are NH4+,
K+, Mg2+, Na+, and Ca2+. Some of them are originated from the mar-
ine breeze in the Gulf of Mexico and another one come from spe-
cific source of contamination in this area (e.g., calcareous soils).
The ions of Mg2+ and Ca2+ are considered as inhibitors of the catho-
dic corrosion reaction that effectively suppress the oxygen reduc-
tion rate in the presence of sodium chloride [53,54].
The concentration of carbonate ions CO32 detected in zinc run-
off solutions reached concentrations 1.2–1.3 times higher than
those measured in rains (Fig. 1), due to the dissolved zinc carbon-
ate corrosion product, hydroxycarbonate Zn5(OH)6(CO3)2 – hydro-
zincite, by weakly acid rains, as it is suggested by several authors
[12,55,56]. The acidity of the collected runoff solutions was higher
(pH 5.5–7.6) than that of rains (pH 3.7–5.5) and varies between
events, as well as during them, and it was often greatest at the start
of rainy event, with decreasing acidity later. The amount of liber-
ated carbonate ions depended on the rain pH, its periodicity and
intensity. It is considered that the growth and amount of hydro-
zincite is determined by the concentration of CO2 in the water
solution in contact with the zinc surface [57]. Soluble and poorly
adhesive corrosion products as zinc hydroxide carbonate formed
in more aggressive environment will primarily be released during
first flush and result in higher runoff rate.
3.2. Zinc corrosion products
Several not soluble corrosion products, remained on the zinc
surface, were detected by XRD on zinc samples during the expo-
L. Veleva et al. / Corrosion Science 51 (2009) 2055–2062
Urban environment
Apr May Jun Jul Ago Sep Oct Nov Dec Jan Feb
Exposure period (2004-2006)
sure to humid tropical climate and the sequence of their likely
transformation has been previously reported [47]. In different
stages of zinc atmospheric corrosion progress, which is competing
always with the runoff process during rainy events, in rural and ur-
ban environments on zinc metal surface were maintained (not dis-
solved) zinc sulfates crystalline phases: (Zn(OH)2)3(ZnSO4)5(H2O) –
hydroxysulfate as the majority phase and several minorities at later
stages, as Zn4O3(SO4)7H2O, Zn(HSO4)2.(HSO4)2, Zn4SO4(OH)6
4H2O, and ZnSO43Zn(OH)2. Zinc oxide, zincite (ZnO) was detected
later at 24 months of exposure in very low content, which in fact
could be attributed to its very fast transformation to other corro-
sion products or dissolution of the porous zinc oxide formed in
the range of pH 3.8–5.8 [58]. As it is suggested, this oxide is ther-
modynamically stable in the pH range between 6 and 12. In gen-
eral, the wet/dry situation is very different from a fully immersed
condition, and different compositions of the corrosion products
can be expected in the two cases.
The variety of sulfates as corrosion products reveals the sensi-
tivity of zinc to SO2 acid pollutant. Even in the presence of chloride
contamination, coming from the Gulf of Mexico, no corrosion
phase containing chloride was detected on the zinc surface. How-
ever, two chloride-containing corrosion products were registered
on the galvanized steel: hydroxylchlorosulfates NaZn4Cl(OH)6-
SO46H2O as majority phase in the rural site (at 50 km from the
coast, which has higher chloride contamination) and hydroxychlo-
ride (Zn5(OH)8Cl2H2O) – simonkolleite, in both test sites as minor-
ity phase. The only sulfate found on the galvanized steel was
Zn(HSO4)2(HSO4)2 and at later stages (24 months) zinc hydroxide
(Zn(OH)2) was detected in very low content. These results reveal
that galvanized steel is more sensitive to chloride aggressivity,
while the zinc is to SO2 contamination.
3.3. Zinc losses by corrosion and runoff
Fig. 2a–b compares the cumulative mass loss and the released
zinc mass from samples of both materials, as a consequence of plu-
vial events, that occurred in the urban test site. The zinc mass dis-
solved during the runoff process has smaller values than the
cumulative mass of metal turned to corrosion products: the annual
mass loss of zinc has increased in 47% in the second year of test
(from 10.00 to 14.70 ± 0.30 g m2), while the zinc runoff mass in
50% (from 8.20 to 12.40 g m2 ± 0.30 g m2).
Both processes (of corrosion and runoff) tend to lower increas-
ing values in the time during the second year of experiment. The
rate of zinc runoff is 16% to 18% smaller than the total zinc corro-
sion rate of both zinc samples. The difference between the values
 L. Veleva et al. / Corrosion Science 51 (2009) 2055–2062 2059

Urban environment (b)

Urban environment (a) 14 Galvanized steel
zinc
14
12
Mass loss of Zn (g m )
-2

12

Mass loss of Zn (g m-2 )

10
10
8
8
6
6

4 4

2 2

0 0
0 100 200 300 400 500 600 700 0 100 200 300 400 500 600 700
Period of exposure (days) Period of exposure (days)

Fig. 2. Cumulative mass loss of zinc due to atmospheric corrosion compared to released zinc mass during runoff phenomenon, as a function of the period of exposure of zinc
(a) and galvanized steel (b) samples in urban humid tropical climate.

of cumulative zinc corrosion and zinc runoff gives the mass of
those zinc corrosion products that are not dissolved and have re-
mained on the zinc surface as a protective layer. The results also
confirm the smaller mass loss of zinc by runoff, measured in galva-
nized steel runoff solutions (Fig. 2b), than that of zinc released
from zinc samples (Fig. 2a). These differences suggest that zinc sur-
face forms more soluble corrosion products, than that of the galva-
nized hot dip steel. The described behavior is similar to that
observed in the rural environment.
The data of the dependent variable mass loss of zinc, due to
atmospheric corrosion and zinc release (runoff), have been related
to several independent parameters and a linear equation has been
obtained [47]:

C ¼ C 0 þ x1 ½TOW þ x2 ½SO2  þ x3 ½Cl 
2
where C is the zinc mass loss (g m ); TOW – the calculated time of
wetness (h) of the metal surface, as an effective time for the corro-
sion progress; C0 – the zinc mass loss in absence of contaminants
(only wetness on the metal surface); [SO2] and [Cl] – the amount
(g m2) of sulfur dioxide and chloride contaminants, respectively,
deposited on the metal surface; x1, x2, and x3 – regression coeffi-
cients (Table 2).
The regression analysis shows that the sulfur dioxide exerts the
major influence on the zinc mass loss (x2 highest coefficient value,
Table 2): SO2 determines the pH of rains and of the humid layer
formed on the metal surface, and these factors are directly related
to the partial or complete dissolution of soluble zinc corrosion
products and their release to the surrounded environment. The
time of wetness of the metal surface is the second most important
independent variable, which controls the corrosion development
with the time of exposure of zinc samples. The minor factor for
the zinc corrosion is the chloride contamination: its coefficient x3
is at least one order of magnitude smaller. While different relation-
ships between zinc corrosion rates and environmental parameters
have been proposed in the literature [32,59,60], we found our
experimental data obtained in humid tropical climate to fit quite
well (R2 > 0.95) for this simple linear model.
3.4. Damage functions for atmospheric corrosion
During the last three decades different functions have been pro-
posed to represent the atmospheric corrosion behavior of zinc and
galvanized steel. For example, Haynie and Upham [61], studied the
effects of atmospheric sulfur dioxide on the corrosion of zinc and
proposed the following expression for the corrosion rate (R, in
lm year1):
ð1Þ R ¼ 3:92  104 ðRH  48:8Þ½SO2  ð2Þ
where 48.8 represents the relative humidity below which no exten-
sive surface wetting is expected and SO2 concentration is given in
parts per billion (ppb).
A general corrosion function in terms of atmospheric pollutant
concentrations, time of wetness (TOW) and rain pH has been de-
scribed by Benarie and Lipfer [62], based on critical review and sta-
tistical analysis of available reported data by corrosion test
programs. The authors consider that the kinetics of metal atmo-
spheric corrosion can be described by the well-known exponential
expression [63,64], called also linear bilogarithmic relationship:
M ¼ at b ð3Þ
log M ¼ log a þ b log t ð4Þ
where M is the metal loss (g m2) during the exposure time t
(years).
If the multiplicative factor a is expressed in terms of tw (time of
wetness), which is a fraction of the total exposure time t(tw = f  t),
then

M ¼ Aðtw =tÞb ð5Þ

Table 2
Mass loss of zinc (C, g m2) as a function of time of wetness (TOW, h) of metal surface
where A is the metal loss per 1 year of wetness (g m2).
and contaminants (SO2 and Cl, g m2). The exponent b, which characterizes the diffusivity of the corro-
sion product layer, could be considered as a function of the average
Zinc (environment) R2 Regression analyses equations
rain pH and as an index of the physical–chemical behavior of the
Galvanized steel (urban) 0.99 C = 0.32 + 2.12 [TOW] + 4.91 [SO2] + 0.28 [Cl ] corrosion product layer, including the reactions of this layer with
Zinc (urban) 0.99 C = 0.19 + 3.05 [TOW] + 5.08 [SO2] + 0.13 [Cl ]
Galvanized steel (rural) 0.99 C = 0.07 + 2.20 [TOW] + 5.28 [SO2] + 0.03 [Cl ]
such environmental factors as acid rain:
Zinc (rural) 0.99 C = 0.22 + 3.00 [TOW] + 7.57 [SO2] + 0.06 [Cl ] b ¼ 1:55  0:142ðpHav-rain Þ ð6Þ
2060 L. Veleva et al. / Corrosion Science 51 (2009) 2055–2062

16 Table 3
Urban enviroment Values of Cf and tw calculated using the exponential fit (Eq. (7)) on the experimental
14 galvanized steel data for corrosion mass loss of zinc samples exposed at humid tropical climate.
Corrosion mass loss (g m )
-2

Metal sample (test site) Cf (g m2) te (weeks) R2

12
Galvanized steel (rural) 16.8 21 0.97
Galvanized steel (urban) 18.2 20 0.97
10
Zinc (rural) 16.2 17 0.97
Zinc (urban) 18.6 18 0.97
8

6
samples indicate that zinc is less resistive in both environments,
Experiment
4 compared to galvanized steel.
Exponential Fit
The corrosion mass loss (C) as a function of time of wetness (tw)
2 (a) determines the corrosion rate dtdCw as follows from equation (7):
 
0 dC C f ttw
0 5 10 15 20 25 30 35 40 ¼ e e ð8Þ
dtw te
Time of wetness (weeks)
Fig. 4 shows, as an example, the calculated corrosion rates (Eq.
16 (8)) and the experimental mass loss for galvanized steel samples
Rural environment exposed at rural environment (less polluted in SO2). As can be seen,
14 the corrosion rate decreases significantly, starting at
Zinc
Corrosion mass loss (g m )
-2

14 g m2 year1 and reaching 2.5 g m2 year1, approaching its

12
steady state value, when the mass loss Cf will be approximately
10 of 16.8 g m2 (Table 3).
We applied Eq. (7) for reported experimental data for copper
8 runoff [72], registered during one year in marine atmosphere and
as can be seen in Fig. 5, these data fit very well. Thus, we can pre-
6 dict in this case that the steady state corrosion mass loss value (Cf)
Experiment for those copper samples will be in the order of Cf = 19.4 g m2 and
4
Exponential Fit te = 14 weeks. This last fact can indicate that the marine environ-
2 ment is aggressive for copper, comparing the values of te for zinc,
(b) for example, reported in Table 3.
0 The mechanism of atmospheric corrosion runoff metal process,
0 5 10 15 20 25 30 35 40 presented by Eqs. (7) and (8), can be seen as a solution of the fol-
Time of wetness (weeks) lowing differential equation:

Fig. 3. Corrosion mass loss for galvanized (a) and zinc (b) samples versus time of
dC
¼ a  kC ð9Þ
wetness of metal surface, during the exposure in urban and rural environments in dtw
the Gulf of Mexico. (Exponential fit according to Eq. (7).)
where a ¼ Ctef and k ¼ t1e .
tw
If we expand e te (8) in power series:
with range of validity covered by the data for rains with pH 3.5–7.7 !
[62]. tw t w ðt w =te Þ2 ðtw =t e Þ3 ðt w =t e Þ4
e te ¼ 1  þ þ þ þ 
te 2! 3! 4!
The galvanized steel behaves very similarly to pure zinc, until no
tw
exposed free steel surface appears. In this approach, mathematical C ¼ C f ð1  e te Þ
!!
functions have been empirically formulated for the atmospheric cor- t w ðt w =t e Þ2 ðt w =te Þ3 ðtw =t e Þ4
¼ Cf 1  1  þ þ þ þ  ð10Þ
rosion rate [11,29,42,65,67–71], based on the statistical analysis of te 2! 3! 4!
historical data with respect to the different relevant environmental
factors, contributing to the atmospheric corrosion of galvanized
steel structures.
14 14
Corrosion rate (g m -2 year )
Corrosion mass loss (g m-2 )

-1

3.5. Atmospheric corrosion induced by runoff of metal 12 12

Mass loss
The fitting of the reported experimental data in our study (Fig. 3) 10 10
indicates the following exponential relationship between C (metal
8 8
mass loss per area, in g m2) and tw (time of wetness, in h):
 tw
 Corrosion rate
6 6
C ¼ C f 1  e te ð7Þ
4 4
where Cf is the mass loss reached in a very long period of time (stea-
dy state); te is a value of the TOW for which 63% of Cf is reached. 2 2
(When tw = te, C = Cf(1  e1) = 0.63Cf). Thus, the te value can indi-
cate how fast the corrosion process will arrive at the value of Cf. 0 0
0 5 10 15 20 25 30 35 40
The calculated values for Cf and te, using the exponential fitting
(7), are shown in Table 3.
Time of wetness (weeks)
The values of Cf (Table 3) show that zinc and galvanized steel Fig. 4. Calculated corrosion rate (Eq. (8)) and experimental mass loss data for
samples tend to corrode faster when they are exposed at urban galvanized zinc steel samples versus time of wetness, during their exposure at rural
environment. On the other hand, the lower values of te for zinc environment in the Gulf of Mexico.
 L. Veleva et al. / Corrosion Science 51 (2009) 2055–2062 2061

20 sion and runoff tend to increase at a slower rate during the second
year of experiment. The concentration of carbonate ions CO32 de-
tected in zinc runoff solutions reached concentrations 1.6–1.7
Corrosion mass loss (g m-2)

times higher than those measured in rains, due to the dissolved

15
zinc carbonate corrosion product.
2. Several corrosion products, no released by rain events, were
detected by XRD on zinc samples. The variety of sulfates as corro-
10 sion products reveals the sensitivity of zinc to SO2 acid pollutant.
Experiment Even in the presence of chloride contamination, coming from the
Exponential fit Gulf of Mexico, no corrosion phase containing chloride was de-
5 tected on the zinc surface. However, two chloride-containing cor-
rosion products were registered on the zinc galvanized hot dip
steel. These results reveal that galvanized steel (hot dip) is more
sensitive to chloride aggressivity.
0
0 10 20 30 40 50 60 3. Reported damage functions for metal atmospheric corrosion
Exposure period (weeks) in mass loss rates have been reviewed and an exponential equation
is proposed that fits well the experimental data for zinc corrosion
Fig. 5. Fitting (Eq. (7)) of experimental reported data [72] for copper corrosion mass mass loss (C) induced by runoff process, as a function of time of
of samples exposed during one year at marine environment. wetness (tw):
tw
C ¼ C f ð1  e te Þ;
and simplifying then, we will obtain:
! where Cf is the mass loss reached in a very long period of time (stea-
t w ðt w =te Þ2 ðt w =t e Þ3 ðtw =t e Þ4 dy state). The formula gives possibility to predict the metal mass
C ¼ Cf  þ  þ  ð11Þ
te 2! 3! 4! loss when steady state has not been reached. Its application to
experimental data reported for another metal (copper) also fits well.
If we suppose that te, as a part of time of wetness, has large val- This function can converge to Benarie lineal one (C = Atw), when
ues, then Eq. (11) can be approximated as a linear function (12): coefficient b = 1, for metal corrosion process accelerated by the par-
Cf tial removal of the corrosion layer, e.g., runoff phenomena.
C¼ tw ð12Þ
te
Acknowledgments
as it is reported for the corrosion kinetics of many metals. If we
compared the Eq. (12) to Eqs. (3)–(5), we can see that:
The authors thank the CINVESTAV-Merida and the UJAT – Ta-
Cf 1 basco in Mexico for financial support of this project. They are also
¼ A ¼ c1 ½SO2  þ c2 ½Cl  ð13Þ
te grateful to M.Sc. D. Aguilar for his technical assistance in XRD
analysis.
Redefining variable in (13) we will obtain the Benarie equation [62]
for b = 1, when the corrosion is accelerated due to partial removal of
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