Corrosion Science 52 (2010) 216223

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

Atmospheric corrosion of carbon steel in Colombia

J.G. Castao *, C.A. Botero, A.H. Restrepo, E.A. Agudelo, E. Correa, F. Echeverra
Corrosion and Protection Group, University of Antioquia, P.O. Box 1226, Medellin, Colombia

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

Article history: The corrosion behaviour of carbon steel at six test sites in Colombia and its relationship with exposure
Received 24 April 2009 time and environmental characteristics of each site were investigated. The corrosion products were char-
Accepted 2 September 2009 acterized by XRD, SEM and EDS. It was found that in Barranquilla, the most aggressive site, corrosion
Available online 9 September 2009
depends mainly on chlorides. Furthermore, in the more aggressive environments there was a greater ten-
dency to formation of protective corrosion products. Lepidocrocite and goethite were found as major con-
Keywords: stituents of rust. A structure not reported in the literature was found, corresponding to strings of several
A. Steel
hundred micrometers long and consisting of lepidocrocite plates.
B. Weight loss
B. SEM
2009 Elsevier Ltd. All rights reserved.
B. XRD
C. Atmospheric corrosion

1. Introduction The aim of this research is to investigate, in various atmo-

Atmospheric corrosion of steel is inuenced principally by the
time of wetness (TOW), which depends on climatic factors such
as temperature and relative humidity, and the presence of atmo-
spheric constituents such as SO2 and chlorides, which accelerate
the process [14]. In tropical climates it is common to have a com-
bination of high temperature, high humidity and considerable pre-
cipitation, so the time of wetness is often very high [58].
The rust layer formed on carbon steels has a complex morphol-
ogy. It is generally porous, with poor adherence, and cracked in its
outer part. This structure gives a poor protection to steel against
atmospheric corrosion, because it is not a barrier to the passage
of electrolyte and corrosive species towards the metallic substrate
[1,9,10]. The rust is mainly composed of lepidocrocite (c-FeOOH),
which is usually the rst oxyhydroxide formed, and goethite (a-
FeOOH) [11,12]. Often, there is also maghemite (c-Fe2O3) [13]. In
marine atmospheres is common to nd magnetite (Fe3O4) and
akaganeite (b-FeOOH) [13,14].
Although Colombia is located near the equator, its territory is
crossed by the Andes mountain range and has a wide geographical
diversity, ranging from tropical and jungle regions to moorlands
and snowy peaks. Despite this diversity, in the country it had not
been performed until now atmospheric corrosion studies of carbon
steel including environments of different aggressiveness. The only
reference is the project Atmospheric Corrosion Map of Ibero-
America (MICAT), in which Colombia participated only with a rur-
al and a marine station [15].
* Corresponding author. Tel.: +57 42196679; fax: +57 42196565.
E-mail address: jcasta@udea.edu.co (J.G. Castao).
spheres of Colombia, the inuence of the amounts of chloride ions
and SO2, as well as TOW, on the atmospheric corrosion of carbon
steel, with regard to its evolution in time and characteristics of cor-
rosion products formed. For this purpose, carbon steel plates were
exposed during 14 months, at six sites with different environmen-
tal characteristics, which are indicated in Fig. 1. In Barranquilla, a
city located near the Caribbean Sea, the atmospheric corrosion sta-
tion was installed at 7 km from the coast. Cartagena station was
also located in an area close to the sea with industrial activity.
The rural station of Chinu was located in the Caribbean region,
about 40 km from the coast. Bogota and Medellin stations were in-
stalled in semi-industrial areas of both cities, which are located in
the central Andean region. Finally, the rural station of San Bernar-
dino was located in the southern Andean region.
2. Experimental procedure
Commercial AISI-SAE 1016 carbon steel plates, with the
dimensions of 100 mm  150 mm  2 mm, were used for the eld
tests. The composition of the steel is given in Table 1. Surface
preparation of the carbon steel plates consisted of degreasing
with acetone and washing with detergent, cleaning with ethanol
during 15 min and drying in a hot air jet. Following their prepa-
ration, the specimens were stored for 24 h in a desiccator. Imme-
diately before testing, they were weighed on an analytical balance
of 0.01 g of sensitivity. Plates were exposed in the six sites shown
in Fig. 1, at an angle of 45 from horizontal and with skyward sur-
face facing south, except for the two coastal stations (Barranquilla
and Cartagena), where the plates were exposed facing the sea,
according to ASTM G-50 [16]. The study was carried out over a

0010-938X/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.09.006
 J.G. Castao et al. / Corrosion Science 52 (2010) 216223 217

3. Results and discussion

3.1. Environmental characteristics at exposure sites

The environmental characteristics measured at the six exposure

sites are included in Table 2, as well as atmosphere classication
according to ISO 9223 for the rst year of exposure [19]. In ISO
standard the environments are classied in terms of SO2 (class P)
and chloride (class S), whereas S0 and S1 correspond to chloride
deposition rate of <3 and 360 mg/m2 day, respectively, and P0,
and P1 correspond to SO2 deposition rates of <10 and 1035 mg/
m2 day, respectively. Using this classication, San Bernardino and
Chinu stations presented rural characteristics and were designated
as S0P0 atmospheres. Medellin and Bogota stations exhibited mod-
erate industrial characteristics, with medium contents of SO2 and
Fig. 1. Location of Colombia and the atmospheric corrosion stations. low deposition of Cl, and were designated as S0P1 atmospheres.
Barranquilla and Cartagena were essentially marine stations. Bar-
ranquilla was classied into the subgroup S2P0, and Cartagena into
the subgroup S1P0.
14-month period between September 2006 and November 2007.
In all sites, TOW was in the highest categories (f4 and f5),
Test specimens were retrieved each 2 months. During every sam-
according to ISO 9223 standard. Temperatures did not exhibit ma-
pling period, three samples were picked up from each site for
jor variations during the year. The three stations with higher tem-
weight loss test. After 14 months, four samples were picked up,
peratures (Barranquilla, Cartagena and Chinu) had at the same
one sample for rust characterization and the other three for
time the highest TOW.
weight loss test.
Figs. 2 and 3 show the average deposition rates of Cl and SO2 at
The deposition rate of SO2 in each station was determined using
the six test sites for various exposure periods. Signicant variations
the lead dioxide sulfation candle, according to ASTM D-2010 [17].
in the deposition of chlorides were found throughout the test per-
The deposition rate of chlorides was determined using the wet can-
iod, especially in Barranquilla and Cartagena. Regarding to SO2,
dle method described in ASTM G-140 [18]. The analyses of chlo-
some variations in semi-industrial stations (Bogota and Medellin)
rides and SO2 were carried out bimonthly over the 14-month
were found.
period of exposure. In addition, temperature and relative humidity
When comparing the deposition rates of chlorides, it was found
were recorded continuously for determining TOW.
that Barranquilla showed signicantly greater rates for all exposure
For weight loss measurements, corrosion products on the
periods due to its proximity to the seashore (Fig. 2). In Cartagena, de-
specimen surfaces were removed chemically by immersion in
spite being located 2 km from the sea, deposition of chloride was rel-
a specic solution (500 ml HCl + 500 ml distilled water + 3.5 g
atively low, which could be explained by the prevailing wind
hexamethylenetetramine) that was vigorously stirred for about
direction. In both cities, the prevailing winds direction is NNE. In Bar-
10 min at 25 C. After corrosion products had been completely
ranquilla station, the sea is located to the north, thus favouring the
removed, the specimens were rinsed with distilled water,
deposition of chlorides. On the other hand, in Cartagena station the
dried with blower, and then weighed to determine their mass
sea is located to the west, so the wind blows from land to sea. The
loss.
inuence of wind patterns at each specic site on the atmospheric
The corrosion products were characterized by XDR using a PAN-
salinity has been highlighted by some researchers [2022].
alytical XPert PRO MPD diffractometer with Cu anode radiation
In Barranquilla, there was a remarkable increase between
and a scanning rate of 0.04/min and 2h was from 10 to 70. The
months 6 and 8, in which the chloride content was almost 4 times
SEM studies were performed using a JEOL JSM 6490LV unit with
higher than in other periods. This increase, although at a substan-
an OXFORD INCAPentaFET-x3 electron microprobe for energy dis-
tially lower magnitude, was also observed in Cartagena. This
persive X-ray (EDS) analysis.

Table 1
Chemical composition of carbon steel.

Element Fe C Si Mn S P Ni Cr Mo Al Cu
Composition (wt.%) 99.368 0.063 0.016 0.360 0.008 0.016 0.026 0.062 0.007 0.034 0.03

Table 2
Anual environmental data at six exposure sites.

Site Altitude, m Average temperature, C TOW Cl SO2 CA

% f mg/m2 day S mg/m2 day P
San Bernardino 1735 20.3 48.3 f4 0.21 S0 2.02 P0 C3
Chinu 100 28.7 75.7 f5 2.66 S0 0.91 P0 C3C4
Medellin 1400 23.3 39.0 f4 2.12 S0 19.75 P1 C3
Bogota 2600 14.9 58.3 f4 1.42 S0 21.90 P1 C3
Cartagena 1 28.8 66.1 f5 5.69 S1 9.28 P0 C3C4
Barranquilla 2 29.3 69.5 f5 96.59 S2 5.16 P0 C5

f, S, P: Categories obtained for TOW, Cl and SO2, respectively, using the ISO 9223 standard. CA: Category of corrosivity in accordance with ISO 9223 (medioambiental
parameters).
218 J.G. Castao et al. / Corrosion Science 52 (2010) 216223

Cartagena 1600
200 Barranquilla Bogot
Chinu 1400 Cartagena
150 San Bernardino Barranquilla
Bogot
1200 Medelln
Medelln
Cl (mg / m2 day)

100

Mass loss (g / m )
San Bernardino

2
1000 Chin
50

0 800

15 600
10
400
5
0 200
2 4 6 8 10 12 14
Exposure time (months) 0
0 2 4 6 8 10 12 14
Fig. 2. Chloride deposition at six test sites for various exposure periods. Exposure time (months)

Fig. 4. Mass loss versus exposure time at six test sites.

Cartagena
Barranquilla
exposure was in this order: Barranquilla > Bogota > Cartagena >
Chinu
50 Medellin > Chinu > San Bernardino.
San Bernardino
Bogota The highest mass loss in Barranquilla was associated with its
40 Medellin high content of Cl. The greatest increase in mass loss coincided
with a marked increase in the deposition of chlorides (>150 mg/
SO2 (mg / m2 day)

m2 day), between months 6 and 8. In the same period, deposition

30
20
10
0 with these characteristics has been corroborated by other studies
2 4 6 8 10 12 14
Exposure time (months)
Fig. 3. SO2 deposition at six test sites for various exposure periods.
variation could be related to the rainy season in the Caribbean
coast. In this season, stormy rains are frequent, and they could de-
posit high amounts of chlorides particles in few hours [22]. In non-
coastal stations there was little variation in the deposition rate, as
observed by other researchers [8].
The deposition of SO2 in the two semi-industrial stations (Fig. 3)
showed different trends: In Medellin tended to increase, while in
Bogota to decrease. In Medellin, a peak concentration was observed
at month 12 (the highest of all stations evaluated), while in Bogota
the highest concentration was observed in the fourth month. In
Barranquilla and Cartagena, annual average deposition of SO2
was not greater than 10 mg/m2 day. However, in some periods
(Fig. 3), values of SO2 deposition higher than 10 mg/m2 day were
registered.
3.2. Mass loss of the specimens
Fig. 4 shows the variation in the mass loss at the six test sites dur-
ing 14 months of exposure. In all cases, an increase in the mass loss
was observed, which tended to stabilize over time. In the rst
6 months the highest mass loss was observed in Bogota. However,
after 6 months there was a notable increase of the mass loss in
Barranquilla. The magnitude of mass losses at the 14th month of
of SO2 was relatively low (between 4 and 5 mg/m2 day). A ten-
dency to attenuation was observed in the mass loss curve at the
end of exposure time. In the last period, the lowest deposition of
Cl was registered (14.21 mg/m2 day), as well as the highest deposi-
tion of SO2 (near 15 mg/m2 day). Hence, attenuation on the mass
loss is more related with chlorides rather than SO2. The inuence
of the Cl deposition on steel atmospheric corrosion in marine sites
in the Caribbean Sea [8,15,23,24].
In Cartagena, high mass loss was observed in the beginning of
exposure. This behaviour seems to be more related with the con-
tent of SO2, since in the rst period the deposition rate measured
was higher than 20 mg/m2 day (similar to deposition rate in
semi-industrial station of Bogota), while the deposition rate of Cl
measured in the same period was relatively low (near 4 mg/
m2 day). From the fourth month, the deposition of SO2 showed
some uctuations, but remained between 5 and 10 mg/m2 day.
The deposition rate of Cl showed a rising trend until month 8,
when it reaches the maximum value of 15 mg/m2 day. However,
from the fourth month the mass loss had a tendency to attenua-
tion. It seems that in this type of environment the corrosion is
more dependent on SO2 content. According to data from MICAT
project [15], it was found that in S1P0 marine atmospheres from La-
tin America with deposition rates of SO2 between 4 and 10 mg/
m2 day, it seems to have an inhibitory effect between sulphur diox-
ide and chlorides, since the sites with higher Cl contents have a
lower corrosion rate [8,15,24]. In Cartagena, the results obtained
seem to conrm this effect.
In Bogota, mass loss was associated with its SO2 content. The
largest increase in the mass loss was presented at the beginning
of exposure, coinciding with the peak observed in the deposition
of SO2. In Medellin, despite its SO2 content was similar to that of
Bogota, there was a minor mass loss, probably due to its lower
TOW.
The mass losses found in Chinu, which are similar to those of
two stations with higher deposition of pollutants (Cartagena and
Medellin), could be explained by its high TOW, the highest of all
the sites studied. Other researchers have found that for carbon
steel the singularities of the tropical climate (high average
 J.G. Castao et al. / Corrosion Science 52 (2010) 216223
temperature, RH and pluviosity) promoting a high TOW, would
lead to high atmospheric corrosion rates [25,26]. It seems to be
that the effect of evaporation on the temperature is insufcient,
because the metal surface remains moist in three quarters of the
year, which favours the electrochemical reactions of corrosion.
The deposition rate of chlorides could have some incidence on
the TOW and the corrosion rate in Chinu, because although located
in the category ISO S0, is very close to the threshold between S0 and
S1 (3 mg/m2 day).
ISO 9223 standard classies the corrosivity category of different
environments under class C, where C1, C2, C3, C4 and C5 correspond
to very low, low, medium, high and very high corrosivity, respec-
tively. The corrosivity category can be obtained either from envi-
ronmental data (Table 2) or from determination of the corrosion
rates after one year exposure. Table 3 shows the corrosion rates
calculated at the six stations for the rst exposure year and the cat-
egories of corrosivity according to ISO 9223 standard. Barranquilla
reached the highest category of corrosivity (C5). Although the cor-
rosion rate in Chinu was almost equal to that in Medellin and
Cartagena, this station did not have the same category of corrosiv-
ity, because corrosion rate was lower than the 25 lm/year limit.
The categories of corrosivity obtained according to the environ-
mental parameters (Table 2) coincided with the data obtained
using actually measured corrosion rates in marine stations (Carta-
gena and Barranquilla), as well as Medellin. However, in Bogota the
category found from environmental data was lower, which could
be attributed to high deposition of SO2 in the rst months of expo-
sure, resulting in the high mass loss measured in this period, that
had a great inuence on the corrosion rate measured at 12 months.
In the following months the deposition of SO2 decreased signi-
cantly and the value of annual deposition had little variation.
In rural sites (San Bernardino and Chinu) the categories of cor-
rosivity found from environmental characteristics was higher than
that obtained from corrosion rates. This discrepancy in rural atmo-
spheres of Latin America had already been reported in the MICAT
Project [15], where it was found that in the rural stations the cat-
egories of corrosivity based on the corrosion rates were lower,
which is attributed to an inadequate criterion for estimating the
category from environmental data in atmospheres with high
TOW. For this reason, some modications to the standard have
proposed in order to obtain the category of corrosivity in rural
atmospheres where the TOW is f4 and f5.
The mass losses at the sites tested, except for Barranquilla
(Fig. 4), showed a behaviour over time that ts perfectly into the
bi-logarithmic equation DW = atn, proposed by several researchers
[1], where DW is the mass loss (g/m2), t is the exposure time, while
a and n are constants. The power n can be considered as a measure
of the growth law of the corrosion products: parabolic or linear. If
the value of n is between 0.5 and 1, the corrosion products are not
sufciently protective. On the other hand, values lower than 0.5
indicate a parabolic growth of the layer by formation of protective
corrosion products that decrease the corrosion rate by acting as a
barrier to the passage of aggressive agents (water, oxygen and
pollutants).
Table 3
Corrosion rate and category of corrosivity of the test sites.
Site Corrosion rate (lm/year) Category -ISO 9223-
San Bernardino 6.40 C2
Chinu 22.92 C2
Medelln 25.93 C3
Bogota 64.28 C4
Cartagena 26.52 C3
Barranquilla 168.67 C5
219
Table 4
Values of n and correlation coefcient of the tted curves.
Site n R2
San Bernardino 0.883 0.106 0.96311
Chinu 0.855 0.122 0.91138
Medellin 0.440 0.067 0.91435
Bogota 0.354 0.022 0.98449
Cartagena 0.549 0.035 0.9861
Although bi-logarithmic expression was dened for exposure
times over one year, t procedure allows the observation of trends
in the value of n. Table 4 shows the estimated values for n and the
correlation coefcient of the tted curves shown in Fig. 4 for the
different sites, with the exception of Barranquilla. It was noted that
in the rural stations (San Bernardino and Chinu) the values of n
were close to 1, indicating that the rust layer had a linear growth
and therefore the corrosion products were not sufciently protec-
tive. In Cartagena, the value of n corresponded to a non-protective
layer of rust, but it was close to the threshold that determines the
protective behaviour.
At the moderate industrial stations (Bogota and Medellin), the
value of n indicated a parabolic growth of corrosion products,
which were becoming more protective with time during the period
evaluated. In Barranquilla, the curve exhibited an S shape and,
towards the end of the exposure period, attenuation in the mass
loss was observed, which would correspond to the formation of
protective corrosion products.
The higher the amount of SO2 deposited, the greater the protec-
tive character of corrosion products layer, according to Tables 2
and 4. It is possible that the presence of SO2 inuences the forma-
tion of protective rust layers, although the initial rate of corrosion
had been high. The differences between the mass losses found in
Bogota and Medellin could be explained because in the rst period
the deposition rate of SO2 is much higher in Bogota and protective
rust have not yet formed. However, over time there is an attenua-
tion in the mass loss in both cities, probably due to the rust be-
comes more compact and protective, although the mass loss is
still higher in Bogota that in Medellin for the corrosion in the rst
two months. Other researchers have reported the inuence of low
and medium contents of SO2 in the compaction of the corrosion
products layer [11,15,23]. The higher compaction of rust after the
fourth month of exposure could be related to the formation of
nano-sized goethite, which reduced the porosity of the coating
and decreased the amount of oxygen and water reaching the steel
substrate [24]. In environments with low pollution, by contrast, the
rust formed were not protective.
3.3. Characterization of corrosion products
3.3.1. XRD
Fig. 5 shows XRD spectra of corrosion products obtained after
14-month exposure in San Bernardino (rural), Barranquilla (mar-
ine) and Bogota (semi-industrial).
In the three stations lepidocrocite (c-FeOOH) and goethite
(a-FeOOH), the most common rust constituents in natural environ-
ments, were found. Also, in Barranquilla, constituents that are com-
mon in marine environments were found: akaganeite (b-FeOOH)
and spinel-type oxides, which were referenced as magnetite (Fe3O4).
3.3.2. SEM/EDS
Figs. 611 show the analysis of the corrosion products per-
formed by SEM and EDS after 14-month exposure.
At the rural station of San Bernardino, the SEM analysis show
cotton-ball type structures, no larger than 5 lm, characteristic of
goethite (Fig. 6(a) and (b)), as well as owery and plate crystals,
220
-FeOOH
-FeOOH
Intensity (arbitrary unit)
O of this type of structure in the literature.
O
O O
10 20 30 40
2 (degrees)
Fig. 5. XRD spectra obtained after 14-month exposure. (a) San Bernardino, (b)
Barranquilla and (c) Bogota.
characteristic of lepidocrocite [13,25,27]. EDS spectra (Fig. 6(c)) re-
veal no more than iron and oxygen from these hydroxides. In non-
polluted environments is common to nd very small lepidocrocite
crystals, whereas in polluted environments crystals are generally
larger [15].
The cross-section analysis of a specimen exposed in San Bernar-
dino (Fig. 6(d)) indicates an early stage of corrosion process and an
irregular layer of corrosion products. This layer has a low thickness
and shows some sites with localized corrosion, which probably act
as anodes in the rst steps of atmospheric corrosion. A two-layer
structure is observed, formed on a point of localized corrosion of
the substrate. The outer layer, of about 10 lm, which is more com-
pact, is crossed by a crack just above the area that presents local-
ized corrosion. The inner layer is less compact and exhibits
Fig. 6. Morphology of corrosion products found in San Bernardino: (a) goethite, (b) lepidocrocite, (c) EDS spectrum from area with goethite, (d) cross-section of a two-layer
structure of corrosion products.
J.G. Castao et al. / Corrosion Science 52 (2010) 216223
-FeOOH horizontal and longitudinal cracking, and appears to be composed
Fe3O4 of corrosion products from the area with localized corrosion.
O
In Chinu station, goethite crystals and lepidocrocite plates
(somewhat larger than those seen in San Bernardino) are observed.
Very particular structures were found, in the form of strings
(Fig. 7), some of which have several hundred micrometers long.
(a)
Strings are composed of lepidocrocite crystals. There are no reports
The cross-section (Fig. 7(d)) shows a thicker layer of corrosion
products than that found in San Bernardino, as well as some sites
(b)
with deep localized corrosion. The thickness of the layer of corro-
sion products is 2570 lm. Inside the cavities, the corrosion prod-
ucts are more compact, while in the outer zone are less compact
and cracked.
In Bogota and Medellin, very similar morphologies were found.
(c) The more abundant constituent in the external surface of rust was
lepidocrocite (Fig. 8(a)). Goethite was also observed. The cross-sec-
50 60 tion of corrosion products layer in Bogota (Fig. 8(b)) shows a thick-
ness between 60 and 100 lm, and despite some cracks observed, it
is the most compact and homogeneous among the layers evalu-
ated. The SEM analysis conrms the relatively protective character
of this rust layer in the presence of SO2.
In Cartagena, also goethite and lepidocrocite were found
(Fig. 9(a)). Acicular crystals of lepidocrocite, as well as larger ow-
ery and plate crystals (to about 10 lm) were observed (Fig. 9(b)).
The cross-section shows a serrate prole in the substrate
(Fig. 9(c)), with a corrosion products layer with little variation in
thickness (between 80 and 90 lm) and low compactness. The map-
ping of chlorine through the cross-section shows a uniform distri-
bution and there is no accumulation in the cavities of the substrate
(Fig. 9(d)).
In Barranquilla, acicular lepidocrocite was found in the external
surface (Fig. 10(a)). EDS spectrum corresponding to the area shown
in Fig. 10 (a) indicates the presence of chlorine (Fig. 10(b)). Akag-
aneite was also found (Fig. 10(c)). This constituent exhibits a very
porous structure and is more common in the inner layer of rust
 J.G. Castao et al. / Corrosion Science 52 (2010) 216223 221

Fig. 7. (a) Morphology of corrosion products found in Chinu, including string type structures (b) string type lepidocrocite structure, (c) detail of the central area in previous
image, (d) cross-section of rust layer.

Fig. 8. Morphology of corrosion products found in Bogota, (a) lepidocrocite, (b) cross-section of rust layer.

[13]. In some areas, lepidocrocite crystals formed acicular aggre-
gates of about 10 lm long (Fig. 10 (d)).
The metal surface in Barranquilla presents zones with depth
localized corrosion and the thickness of the corrosion products var-
ies between 100 and 180 lm (Fig. 11(a)).The cross-section of the
corrosion products layer shows the existence of more cracks in
the outer zone. The corrosion products near the cavities of sub-
strate seem to be more compact. The presence of transverse cracks,
which cause the easy exfoliation of the corrosion products, is com-
mon in environments with high salinity [25]. The mapping of chlo-
rine shows a uniform distribution as in Cartagena (Fig. 11(b)).
In general, there are no changes in morphology or size of goe-
thite in the different stations. With regard to the lepidocrocite,
larger and more acicular crystals are observed in coastal environ-
ments, which has been observed by other researchers [15].
In most cases a good correlation was found between the protec-
tive characteristics of rust calculated from mass loss data and
observations made by SEM. The more compact layer of corrosion
products was found in Bogota, which is in agreement with the va-
lue of n (Table 4), that corresponds to a protective rust. In other
stations, including rural atmospheres, the rust layers are not com-
pact and show many cracks, which is consistent with the high val-
ues of n.
In Barranquilla, a marked increase in mass loss from 4 months
was observed (Fig. 4(a)), while at the end of the exposure the curve
tends to stabilize. The increased deposition of chloride in this sta-
tion plays a primary role on the high mass loss. The akaganeite
structure can provide the tunnels for the penetration of corrosive
species such as chlorides. Chloride ions can easily penetrate into
corrosion products and deposit on the rust-steel interface to form
the intermediate containing chloride, which cause the breakdown
of rust layer. This rust structure cannot prevent the penetration of
the chloride ions and accelerate the corrosion of steel [13]. The
breakdown of rust in chloride-rich environments has been linked
with the presence of akaganeite [13,21,28,29]. So, the existence
of akaganeite accelerates the corrosion of steel and deteriorates
the protective effect of rust layer.
With the process of the corrosion, some intermediate phase
close to the inner layer gradually transformed to the other stable
and dense oxides phase, which resulted in the outer layer growing
thicker. The penetration of chloride ion through the outer layer be-
comes more difcult. On the other hand, the chlorides deposited
222 J.G. Castao et al. / Corrosion Science 52 (2010) 216223

Fig. 9. Morphology of corrosion products found in Cartagena: goethite (left) and lepidocrocite (right), (b) lepidocrocite, (c) cross-section of rust layer, (d) Cl mapping of
window in Fig. 9(c).

during the initial stage exposure are used up. These two effects
promote the formation of a dense and adherent inner layer, which
enhances the protective effect of rust layer and decreases the cor-
rosion rate of steel [13].
This two-layer structure was evidenced in Chinu, although
the inner layer was observed only inside the substrate cavities.
The greater compaction of this sublayer could be associated
with magnetite. In marine environments, magnetite is common
to nd in the most internal layer of corrosion products, near
the metal surface. In addition, this type of environments tends
to produce depth penetrations due to the existence of localized
corrosion phenomena caused by chlorides [25]. Despite being
located far from the coast, the rate of deposition of chloride
is this station is near to ISO category S1, and the depth of
the cavities observed (Fig. 7(d)) suggests the action of
chlorides.
Mappings performed in Cartagena and Barranquilla samples
showed no evidence about accumulation of chloride in the bottom
of cavities after 14-month exposure. The low retention of chlorides
may be related to high TOW at the two stations, because lixiviation

Fig. 10. Morphology of corrosion products found in Barranquilla: (a) lepidocrocite, (b) EDS spectra of (a), (c) akaganeite, (d) acicular aggregates of lepidocrocite.
 J.G. Castao et al. / Corrosion Science 52 (2010) 216223
Fig. 11. (a) Cross-section of corrosion products layer in Barranquilla, (b) mapping of Cl.
of chlorides is easier in humid environments due to its high solu-
bility in water [15,30].
4. Conclusions
In more aggressive environments, there was a greater tendency
to the formation of protective corrosion products after 14-month
exposure. This protective behaviour was most evident in atmo-
spheres with medium SO2 amounts.
The most abundant constituent in all samples was lepidocro-
cite, which exhibited a more acicular morphology in environments
with high chlorine amounts. Goethite was also found in all sta-
tions, as well as magnetite and akaganeite in coastal environments.
In Chinu a structure not reported in the literature was found, cor-
responding to strings of several hundred micrometers long, consti-
tuted by lepidocrocite crystals.
The more aggressive station was Barranquilla, where the chlo-
rides were the predominant corrosive specie, followed by Bogota,
where the SO2 was the major pollutant.
The low initial protection of the rust layer in Barranquilla could
be related to the presence of akaganeite. Its porous structure could
facilitate the penetration of corrosive species such as chloride ions.
However, chloride ions are not retained in the metal-rust interface,
probably due to its high TOW.
The classication of corrosivity of the test stations based on
environmental data, according to ISO 9223, is not in agreement
with that based on the corrosion rates in rural stations.
Acknowledgements
The authors gratefully acknowledge to University of Antioquia
by the nancial support through the program Estrategia de
Sostenibilidad.
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