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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
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
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.
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)
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)
(a)
Strings are composed of lepidocrocite crystals. There are no reports
O of this type of structure in the literature.
The cross-section (Fig. 7(d)) shows a thicker layer of corrosion
O
O O 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-
10 20 30 40 50 60 tion of corrosion products layer in Bogota (Fig. 8(b)) shows a thick-
2 (degrees) ness between 60 and 100 lm, and despite some cracks observed, it
is the most compact and homogeneous among the layers evalu-
Fig. 5. XRD spectra obtained after 14-month exposure. (a) San Bernardino, (b)
Barranquilla and (c) Bogota.
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
characteristic of lepidocrocite [13,25,27]. EDS spectra (Fig. 6(c)) re- (Fig. 9(a)). Acicular crystals of lepidocrocite, as well as larger ow-
veal no more than iron and oxygen from these hydroxides. In non- ery and plate crystals (to about 10 lm) were observed (Fig. 9(b)).
polluted environments is common to nd very small lepidocrocite The cross-section shows a serrate prole in the substrate
crystals, whereas in polluted environments crystals are generally (Fig. 9(c)), with a corrosion products layer with little variation in
larger [15]. thickness (between 80 and 90 lm) and low compactness. The map-
The cross-section analysis of a specimen exposed in San Bernar- ping of chlorine through the cross-section shows a uniform distri-
dino (Fig. 6(d)) indicates an early stage of corrosion process and an bution and there is no accumulation in the cavities of the substrate
irregular layer of corrosion products. This layer has a low thickness (Fig. 9(d)).
and shows some sites with localized corrosion, which probably act In Barranquilla, acicular lepidocrocite was found in the external
as anodes in the rst steps of atmospheric corrosion. A two-layer surface (Fig. 10(a)). EDS spectrum corresponding to the area shown
structure is observed, formed on a point of localized corrosion of in Fig. 10 (a) indicates the presence of chlorine (Fig. 10(b)). Akag-
the substrate. The outer layer, of about 10 lm, which is more com- aneite was also found (Fig. 10(c)). This constituent exhibits a very
pact, is crossed by a crack just above the area that presents local- porous structure and is more common in the inner layer of rust
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 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- pact and show many cracks, which is consistent with the high val-
gates of about 10 lm long (Fig. 10 (d)). ues of n.
The metal surface in Barranquilla presents zones with depth In Barranquilla, a marked increase in mass loss from 4 months
localized corrosion and the thickness of the corrosion products var- was observed (Fig. 4(a)), while at the end of the exposure the curve
ies between 100 and 180 lm (Fig. 11(a)).The cross-section of the tends to stabilize. The increased deposition of chloride in this sta-
corrosion products layer shows the existence of more cracks in tion plays a primary role on the high mass loss. The akaganeite
the outer zone. The corrosion products near the cavities of sub- structure can provide the tunnels for the penetration of corrosive
strate seem to be more compact. The presence of transverse cracks, species such as chlorides. Chloride ions can easily penetrate into
which cause the easy exfoliation of the corrosion products, is com- corrosion products and deposit on the rust-steel interface to form
mon in environments with high salinity [25]. The mapping of chlo- the intermediate containing chloride, which cause the breakdown
rine shows a uniform distribution as in Cartagena (Fig. 11(b)). of rust layer. This rust structure cannot prevent the penetration of
In general, there are no changes in morphology or size of goe- the chloride ions and accelerate the corrosion of steel [13]. The
thite in the different stations. With regard to the lepidocrocite, breakdown of rust in chloride-rich environments has been linked
larger and more acicular crystals are observed in coastal environ- with the presence of akaganeite [13,21,28,29]. So, the existence
ments, which has been observed by other researchers [15]. of akaganeite accelerates the corrosion of steel and deteriorates
In most cases a good correlation was found between the protec- the protective effect of rust layer.
tive characteristics of rust calculated from mass loss data and With the process of the corrosion, some intermediate phase
observations made by SEM. The more compact layer of corrosion close to the inner layer gradually transformed to the other stable
products was found in Bogota, which is in agreement with the va- and dense oxides phase, which resulted in the outer layer growing
lue of n (Table 4), that corresponds to a protective rust. In other thicker. The penetration of chloride ion through the outer layer be-
stations, including rural atmospheres, the rust layers are not com- 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 to produce depth penetrations due to the existence of localized
promote the formation of a dense and adherent inner layer, which corrosion phenomena caused by chlorides [25]. Despite being
enhances the protective effect of rust layer and decreases the cor- located far from the coast, the rate of deposition of chloride
rosion rate of steel [13]. is this station is near to ISO category S1, and the depth of
This two-layer structure was evidenced in Chinu, although the cavities observed (Fig. 7(d)) suggests the action of
the inner layer was observed only inside the substrate cavities. chlorides.
The greater compaction of this sublayer could be associated Mappings performed in Cartagena and Barranquilla samples
with magnetite. In marine environments, magnetite is common showed no evidence about accumulation of chloride in the bottom
to nd in the most internal layer of corrosion products, near of cavities after 14-month exposure. The low retention of chlorides
the metal surface. In addition, this type of environments tends 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 223
Fig. 11. (a) Cross-section of corrosion products layer in Barranquilla, (b) mapping of Cl.
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