Corrosion Science 49 (2007) 1420–1436

www.elsevier.com/locate/corsci

Long-term atmospheric corrosion of zinc

D. de la Fuente a, J.G. Castaño b, M. Morcillo a,*

a
National Centre for Metallurgical Research (CENIM-CSIC), Avda. Gregorio del Amo 8, 28040 Madrid, Spain
b
University of Antioquia, Engineering School, Ciudad Universitaria, Calle 67 No. 53 108 Medellı́n, Colombia

Received 25 April 2006; accepted 2 August 2006

Available online 4 October 2006

Abstract

A great deal of information is available on the short- and mid-term atmospheric corrosion of zinc:
corrosion rate data as a function of atmosphere type, corrosion mechanisms, effect of environmental
variables, effect of surface orientation, damage functions, etc. However, very little information has
been published on the atmospheric corrosion of zinc over long time periods (10–20 years), despite
its great usefulness. On the other hand, many studies have analyzed the nature of corrosion products
formed on zinc in a wide range of atmospheric environments, using different experimental tech-
niques, but few have focused on the morphology of corrosion product layers. This paper reports
the characteristics—mainly composition and morphology—of corrosion products formed on zinc
panels after long-term exposure (13–16 years) in various types of atmospheres in Spain: rural, urban,
industrial, mild marine and severe marine.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: A. Zinc; B. SEM, XRD, weight loss; C. Atmospheric corrosion

1. Introduction

Zinc is one of the most widely used metals. Its most important commercial application
is in the corrosion protection of steel, for which it is extensively employed to coat or gal-
vanise ferrous metallic products. Likewise, zinc roofs are common in buildings and have
provided satisfactory service lives in excess of 100 years in urban atmospheres.

*
Corresponding author. Tel.: +34 91 5538900; fax: +34 91 5347425.
E-mail address: director@cenim.csic.es (M. Morcillo).

0010-938X/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2006.08.003
 D. de la Fuente et al. / Corrosion Science 49 (2007) 1420–1436 1421

Much information is available on the atmospheric corrosion of zinc and the formation
mechanisms of zinc corrosion products in the short and mid term, based on tests of a dura-
tion not usually exceeding 10 years; from the earliest studies by Anderson (1956) [1],
Schikorr (1964) [2], Guttman (1968) [3], Haynie and Upham (1970) [4], Rozenfeld
(1972) [5] and Barton (1976) [6], to more recent studies by Biestek (1982) [7], Legault
(1982) [8], Dunbar and Showak (1982) [9] and Odnevall and Leygraf (1995) [10].
The general picture of the atmospheric corrosion of zinc has been summarised in several
review articles [11–15]. A prerequisite for atmospheric corrosion to occur is that a moisture
layer be present on the zinc surface. This layer acts as a solvent for atmospheric constit-
uents and a medium for electrochemical reactions. The atmospheric corrosion of zinc is
influenced principally by the time of wetness and the presence of atmospheric constituents
such as CO2, SOx and Cl. When the moisture layer evaporates, a film of corrosion
products precipitates. The nature of the precipitates is dependent on the environmental
characteristics of the atmosphere.
Although a good knowledge of what happens in the short and mid term has been
obtained, little is known about the long-term evolution of the atmospheric corrosion of
zinc, i.e., for times of more than 10 years. In a previous study [16] the authors analysed
the corrosion kinetics of zinc and other metals exposed for 13–16 years in different Spanish
atmospheres, comparing the results with other long-term studies reported in the literature.
A great deal of effort has also been dedicated to identifying corrosion products and to
quantifying corrosion effects in terms of mass loss, and several models have been devel-
oped to describe the influence of various environmental parameters on the corrosion rate,
particularly the sulphur dioxide and chloride concentration [17]. However, studies of the
morphology of corrosion product films are often lacking. For this reason, the present
study places emphasis on the morphology of the corrosion product films formed on zinc
after long-term atmospheric exposure (13–16 years) in five Spanish atmospheres of differ-
ent types: rural, urban, industrial, mild marine and severe marine. The characterisation
was performed by scanning electron microscopy (SEM)/energy dispersive X-ray spectros-

copy (EDS), X-ray diffraction (XRD), and extractable ion (SO2 4 , Cl ) analysis.

2. Experimental

The study involved the exposure of zinc panels to the atmosphere for various lengths of
time. The composition of the zinc was as follows (wt.%): 0.36% Pb, 0.015% Fe, 0.0007%
Cu, 0.007% Cd and <0.001% Sn.

2.1. Test sites network

The test sites network comprised several types of atmospheres, viz. rural (El Escorial),
urban (Madrid), industrial (Bilbao) and marine (Barcelona and Alicante, 30 m from the
shore). Table 1 summarises the environmental characteristics of the test sites.
The rural site of El Escorial is characterised by low sulphur pollutant levels and insig-
nificant chlorine levels. The surrounding area is mainly forested with some residential
(holiday home) areas. The urban atmosphere is represented by the Madrid test site, which
is characterised by moderate SO2 levels and insignificant chlorine levels. The test site is sit-
uated on the CENIM roof terrace. The proximity of a road with considerable traffic
accounts for the SO2 levels encountered. The industrial atmosphere is represented by
1422 D. de la Fuente et al. / Corrosion Science 49 (2007) 1420–1436

Table 1
Atmospheric corrosion stations. Environmental characteristics and corrosivity. Data corresponding to the first
year of exposure (1976–1977) [18]
Atmosphere Test site Time of Deposition rate (mg/m2 d) Zinc
(code) wetness 
SO2 Cl First year ISO [19],
(h/year) corrosion corrosivity
(lm) category
Rural El Escorial 3900 8 Negligible 0.9 C3
Urban Madrid 2100 56 Negligible 1.4 C3
Industrial Bilbao 3000 81 41 5.2 C5
Marine
Light Barcelona 3200 52 27 2.2 C4
Severe Alicante 4300 126 219 5.8 C5

the Bilbao test site, situated in the industrial setting of a shipyard at Sestao; specifically on
the roof terrace of the chemistry laboratories. The atmosphere at the test site is of an acid
nature, while Bilbao is characterised by a high number of rainy days and a high annual
rainfall rate. Both of these factors are important when it comes to interpreting the results
obtained at this test site. The two marine atmospheres in this study are represented by the
test sites of Barcelona and Alicante, both situated within 30 m of the seashore; the former
in the city of Barcelona (urban character) and the latter in an aluminium plant (industrial
character). The Alicante test site is characterised by high chlorine levels (mainly NaCl) and
relatively high sulphur levels (mainly SO2, Na2SO4).
All the sites were equipped with temperature and humidity recorders and the instru-
mentation necessary to measure atmospheric pollution in terms of SO2 [20] and Cl
[21]. The time of wetness was estimated from the number of hours per year that the relative
humidity was equal to or above 85% and the temperature exceeded 0 °C.
The panels were exposed in triplicate on open-air racks at an angle of 45o from the
horizontal plane. Specimen batches were withdrawn after 1–6, 8, 10, 13 and 16 years of
exposure. The corrosion data obtained after 1, 6, 8 and 13–16 years of exposure has been
published elsewhere [16,22–24]. After their final withdrawal, one of the specimens was used
to carry out studies of the composition and morphology of the corrosion products formed
on zinc during long exposure times in the atmosphere.
The techniques used to characterise the corrosion products were XRD (for the identifi-
cation of crystalline phases), SEM/EDS (for morphological studies and for qualitative
elemental studies on the surface and in cross-sections of the corrosion product film) and
the extraction and quantification of soluble salts. XRD analysis was performed using a
SIEMENS D5000 diffractometer with monochromatised copper anode radiation (Cu Ka,
k = 1.5406 Å).For the SEM/EDS studies, use was made of a JEOL JXA-840 electron
microscope equipped with a LINK SYSTEM electron microprobe. Analyses were
performed in cross-sections and on the surface of the specimens, considering both the sky-
ward and groundward sides. For the extraction and quantification of soluble salts the spec-
imens were placed (separately) in deaerated distilled water at boiling point for 30 minutes,
following the method established by Mayne [25]. The solutions obtained were subse-
quently filtered and made up to a constant volume for the analysis of chlorides and sul-
phates. The chlorides present in each filtrate were determined using an ORION 94-17B
 D. de la Fuente et al. / Corrosion Science 49 (2007) 1420–1436 1423

chloride-selective electrode in combination with an ORION 901 ion analyser. Sulphates

were determined by the turbidimetric method, according to ASTM standard D516 [26].

3. Results

3.1. Corrosion versus exposure time

A matter of great practical importance is to know whether or not the zinc atmospheric
corrosion rate decreases with exposure time. Some papers [27,28] have reported a reduc-
tion in the zinc corrosion rate. This slowing of the corrosion rate with exposure time is
probably due to the formation of adherent corrosion products on the surface. The corro-
sion product film becomes denser with continued exposure, thus affording a thicker, more
protective coating.
However, it is often assumed that the zinc atmospheric corrosion rate does not undergo
any marked change with exposure time. In this sense, a linear behaviour of the corrosion
rate has been verified more or less precisely by a number of researchers [1,3,4,6]. Legault
and Pearson [29] found that skyward-facing surfaces tend to corrode much more rapidly
than groundward-facing surfaces. The corrosion rate on the skyward side is linear with
time, while corrosion on the groundward side is parabolic in shape.
This is more or less the situation found in the five test sites where the study was carried
out (Fig. 1). Closer analysis of the average corrosion rates recorded during the first
10 years of exposure, and their evolution in time, indicates that the behaviour of zinc in
the two marine atmospheres of Barcelona and Alicante deviated from the usual behaviour
(constant corrosion rate) found in the other three atmospheres. In particular, the plot of
the curve for Alicante test site, following a serrated pattern, suggests the occurrence of cor-
rosion product layer formation–compaction–detachment processes.
Therefore, long-term atmospheric corrosion data for zinc conforms to the general
equation

C ¼ Atn ð1Þ

where A and C are the corrosion losses after 1 and t years of exposure, respectively, and n
is a constant. The corrosion data for zinc at the different test sites reasonably fits a linear
log–log plot with correlation coefficients close to unity, as is frequently reported in the lite-
rature [16,30–34].

3.2. The corrosion product layer

Unlike in the atmospheric corrosion of iron, the corrosion products formed on zinc
include the respective characteristic anion of the environment where the metal is exposed:

CO2 2
3 , SO4 , Cl , etc., giving rise to different basic chemical compounds: carbonates, sul-
phates, chlorides, etc. Zinc exposed to the atmosphere is particularly sensitive to wetting
and drying cycles, which are largely dependent on the climatology. These alternating peri-
ods have a considerable influence on certain characteristics of the corrosion products, such
as their amount and compactness. Many zinc compounds can form in each generic type of
atmosphere (rural, urban, industrial and marine), but only a few major components are
found in each specific atmosphere [9,15].
1424 D. de la Fuente et al. / Corrosion Science 49 (2007) 1420–1436

Zinc corrosion rate, μm/year

Zinc corrosion rate, μm/year
Alicante Barcelona
7
Alicante
6 3 ρ= 0.988
5

100 4

3 2

2 Bilbao
80
2 4 6 8 10
2 4 6 8 10 ρ= 0.996
Time, years Time, years
Zinc corrosion, µm

60

Barcelona
ρ= 0.992
40

Madrid
ρ = 0.995
20

El Escorial
ρ = 0.964
0
0 2 4 6 8 10 12 14 16 18
Time, years

Fig. 1. Variation of zinc corrosion with time of exposure in different Spanish atmospheric test sites
(q = correlation coefficient).

The presence of sulphur in zinc corrosion product layers is a usual occurrence, partic-
ularly in long-term exposure. Friel [35] identified ZnSO4 (zincosite) and Biestek et al. [36]
reported the presence of zinc hydroxysulphate [Zn4SO4(OH)6 Æ nH2O]. In marine environ-
ments it is very common to find basic chlorides, such as simonkolleite [Zn5(OH)8-
Cl2 Æ H2O]. The zinc chloride (ZnCl2) that may form tends to be washed away rather than
be available for incorporation in more complex corrosion products.
The chemical composition of the corrosion product layers changes with exposure time.
Some phases appear after short exposure times while others are found only after longer
exposures. Moreover, the layers are not uniform in terms of composition throughout their
thickness.
The corrosion product film is very sensitive to environmental conditions, such as dry
and rainy seasons and atmospheric pollutant levels. Thus, stable corrosion product films
are favoured in neutral or near-neutral environments, while acid or basic environments
tend to dissolve these films, leading to further corrosion. Being highly specific to the envi-
ronment where they are formed, the composition of the corrosion product layers has a
direct influence on zinc corrosion resistance. On the contrary, the microscopy morpholo-
gies of corrosion products formed in many different atmospheres appear to be rather sim-
ilar [37].
The protectiveness of the corrosion products formed on exposed metals depends on
their chemical composition, conductivity, adhesion, compactness, solubility, hygroscopic-
ity, and morphology. These properties are mainly determined by the metal composition,
surface sheltering and orientation, and by environmental variables such as atmospheric
conditions, type and level of pollutants, and wet–dry cycles.
 D. de la Fuente et al. / Corrosion Science 49 (2007) 1420–1436 1425

The compounds identified in the corrosion product film (Table 2) include well known
phases such as ZnO (zincite), ZnCO3 (smithsonite), Zn4SO4(OH)6 Æ H2O (zinc hydroxysul-
phate), Zn5(OH)8Cl2 Æ H2O (simonkolleite) and NaZn4Cl(OH)6SO4 Æ 6H2O (sodium zinc
chlorohydroxysulphate); the latter thanks to the interpretation of the diffractogram
performed by Odnevall [37]. Insolubility is a common characteristic of the compounds that
are detected, and are thus considered to be the major compounds in the corrosion
products.
The formation of corrosion products in an atmospheric environment is a complex and
continuously changing process. The degree of complexity and the rate of change depend
on the type of atmosphere and the various factors involved. In a review article on atmo-
spheric corrosion mechanisms, Graedel [15] proposed formation reactions for the zinc
compounds commonly found in atmospheric corrosion products based on the stability
domain of each compound. Furthermore, Odnevall and Leygraf [10] investigated the for-
mation sequence of various zinc compounds in corrosion products obtained in different
types of atmospheric environments.
Zhang, in his book [38], compiles the information that has been obtained on the com-
position, structure and morphology, and properties of zinc corrosion products according
to the atmospheric environments in which they form.
The amount of solid corrosion products formed on a zinc surface depends on many fac-
tors, among which rain is particularly important. Schikorr [39] found that the amount of
corrosion products washed away by rain is comparable to that remaining on the surface.
The runoff of corrosion products was found by Flinn et al. [40] to be mainly due to the
effect of the hydrogen concentration in rainwater. This is the situation found in the Bilbao
testing station.
Due to their great solubility the relative amounts of chlorides and sulphates in the
corrosion products are usually low, especially in the outer surface layer, due to the
wash-off action promoted by the rain. For this reason it is common for these ions to
accumulate at the zinc/corrosion product layer interface. The soluble salt ions may also
penetrate through to the interior of the corrosion product film via cracks and defects
[15]. The remaining proportion of soluble salts is at times so small that it may not be
detected by conventional analysis techniques [41]. The chloride is present mainly as
zinc chloride because zinc is a good scavenger for chloride-containing species. The
sulphate and nitrate are present as a mixture of ammonium, sodium, calcium, and zinc
salts [42].
Table 2 also indicates the soluble salt contents (sulphates and chlorides) extracted from
the corrosion product films formed in the five Spanish atmospheres. With regard to solu-
ble salts extracted from the corrosion product layers, the chloride and sulphate contents
found in the films formed in the rural and urban atmospheres were low, of the order of
those found by Munier et al. [42] in long-term exposure in various urban atmospheres.
In the case of Bilbao the amount of soluble salts detected was smaller than expected, prob-
ably due to washing by rainwater. As has been mentioned before, the climatology of this
city presents abundant rainfall [43].
The technique used to determine soluble pollutant contents in the corrosion products
(boiling in distilled water) not only releases the soluble salts dispersed among the corrosion
products but also produces the hydrolysis of zinc sulphates and chlorides, releasing SO2 4
and Cl ions. This explains the high soluble Cl and SO2 4 levels found in the marine
atmospheres.
 1426
D. de la Fuente et al. / Corrosion Science 49 (2007) 1420–1436
Table 2
Phase identifications and extracted soluble salts contents from the film of corrosion products
Atmosphere Test site Phases Sulphate (mg/m2) Chloride (mg/m2)
Rural El Escorial ZnO (zincite) 267 143
Urban Madrid ZnO (zincite) 609 106
Industrial Bilbao ZnO (zincite) 1057 194
Zn4SO4(OH)6 Æ H2O
(zinc hydroxysulphate)
Marine Barcelona ZnO (zincite) 2592 5663
ZnCO3 (smithsonite)
Zn5(OH)8Cl2 Æ H2O (simonkolleite)
NaZn4Cl(OH)6SO4 Æ 6H2O (sodium
zinc chlorohydroxysulphate)
Marine Alicante ZnO (zincite) 3941 15261
ZnCO3(Smithsonite)
Zn5(OH)8Cl2 Æ H2O (simonkolleite)
NaZn4Cl(OH)6SO4 Æ 6H2O (sodium
zinc chlorohydroxysulphate)
 D. de la Fuente et al. / Corrosion Science 49 (2007) 1420–1436 1427

4. Discussion

4.1. Overview of the atmospheric corrosion of zinc

As other metals zinc corrodes in the atmosphere in a discontinuous process, electro-

chemical in nature, each time the metallic surface is wet. Previous studies have noted that
temperature plays only a secondary role in the process [43], however Quintana et al.[44]
point out the importance of the temperature–humidity complex in the atmospheric corro-
sion of zinc. Both, metal temperature and time of wetness, influence the morphology of the
corrosion products formed.
SO2 concentration in the atmosphere is a major factor in controlling the rate of corro-
sion of zinc; the zinc corrosion film has been shown to strongly absorb SO2 during dry
deposition. Likewise, deposition of acidic condensates produces a fall in pH and the rate
of zinc attack again increases [45]. Chloride in marine atmospheres also increases the
atmospheric corrosion of zinc. There is an approximately linear relationship between
the corrosion rate and salinity [27] or sulphur dioxide concentration [3] in the atmosphere.
A ZnO (zincite) film is the first thin layer to form from the reaction of zinc with
atmospheric oxygen [10]. According to Schikorr [2] these films have a relatively minor
protective effect. Zincite is the most commonly detected corrosion product. SEM photo-
micrographs reveal a crystalline material spread uniformly over the zinc surface. In the
presence of water, zincite is promptly transformed into hydroxides. Many studies agree
that upon initial exposure zinc rapidly forms a thin film of zinc hydroxide. In continued
exposure this film is transformed into various other atmospheric corrosion products [15].
Carbonates are formed as a result of the reaction of zinc hydroxide with atmospheric
CO2. Carbonates are second only to hydroxides in abundance in most natural layers on
zinc [39]. Although several compounds have been detected, the most common are ZnCO3
(smithsonite) and Zn5(CO3)2(OH)6 (hydrozincite). As noted by Odnevall and Leygraf [10],
the latter compound is formed almost instantaneously on zinc surfaces exposed to the
atmosphere, and its formation is promoted by the presence of water. However, hydrozin-
cite is sometimes difficult to detect by XRD. In neutral media the rainwater do not dissolve
the layer of basic carbonates.
Under slow zinc corrosion conditions (less aggressive atmospheres) the corrosion prod-
uct film is uniform, somewhat nodular, and fine grained. According to Odnevall [37], small
islands of thin platelets are initially formed, followed by larger islands with thicker, longer
and more rounded platelets. These islands or patches gradually increase in size and merge
to cover the whole surface.
When faster corrosion takes place (aggressive atmospheres), massive dissolution and pre-
cipitation features are superimposed on the underlying nodular material. In the case of pure
marine atmospheres, the protective hydrozincite is attacked by chlorides, leading to its trans-
formation into zinc hydroxychloride (simonkolleite). In a study performed by Almeida et al.
[46] it was seen that an atmospheric chloride level of close to 25 mg/m2 d is necessary for this
phase to be integrated in the corrosion product layer. Basic chlorides are scarcely soluble
and are not washed off by the rainwater, remaining in the layer of corrosion products.
In the case of atmospheres with SO2 pollution, the formation of basic zinc sulphates
and zinc hydroxysulphate takes place. Different compounds may be formed (6Zn(OH)2 Æ
ZnSO4 Æ 4H2O, Zn7(OH)12 Æ SO4 Æ 4H2O, Zn2(OH)2 Æ ZnSO4, Zn2(OH)2SO4, 3Zn(OH)2 Æ
ZnSO4 Æ 4H2O, Zn4(OH)6SO4 Æ 4H2O, etc.) whose precipitation contributes [47] to the
1428 D. de la Fuente et al. / Corrosion Science 49 (2007) 1420–1436

inhibition of the atmospheric corrosion of zinc. However, in this type of atmospheres the
condensed moisture is acidic and corrodes zinc at a rapid rate. The corrosion products are
dissolved and washed off by the acid rain.
When SO2 is also present in marine atmospheres, Svenson and Johansson [47] note that
an inhibiting effect is sometimes observed due to the formation of sodium zinc chlorohydr-
oxysulphate [NaZn4Cl(OH)6SO4 Æ 6H2O] or zinc chlorohydroxysulphate [Zn4Cl2(OH)4-
SO4 Æ 5H2O].

4.2. Long-term atmospheric corrosion

As has been noted above, the atmospheric corrosion of zinc obeys a potential law
(Eq. (1)) in which the exponent n is close to unity, which, according to Benarie [34], indi-
cates that the diffusion process through the corrosion product layer is accelerated by its
removal due to erosion, dissolution, flaking, cracking or other similar processes. In fact,
as will be seen below, the corrosion product layers that form on zinc are highly cracked.
In low acidity environments (rainwater pH values close to 6), rainwater was not capable
of dissolving the basic carbonates integrated in the corrosion product. In environments of
weak acidity (atmosphere of El Escorial) some corrosion products stay on the surface and
the access of corrodents to the zinc surface becomes diffusive. As a consequence, the expo-
nent n tends to drop towards 0.5.
This is not the case in environments heavily polluted with SO2. In these atmospheres,
condensed moisture and rainwater are of an acid nature and can dissolve the corrosion
product layers. In industrial environments the dissolution of corrosion product films
can reach the point where practically no corrosion products are found on the metal sur-
face. In the observation of SEM cross-section views it is possible to see the removal of
the outer zones of the corrosion product layers. The films are thinner than expected due
to partial dissolution of the corrosion products by rainwater. Flinn et al. [40] have
described in some detail the morphology of corrosion films on zinc exposed to the atmo-
sphere in acidic conditions, in an interesting paper which analyses the modification of cor-
rosion films through a dissolution and reprecipitation process, considering the chemistry
of the corrosion films and the effects of particulate and acidic deposition.
It is proposed that these features are evidence for a process of sequential dissolution,
concentration, redistribution and precipitation that builds large structures on the metal
surface, and that these processes probably occur when the surface is drying. Alternate
destruction and rebuilding of a protective film can easily produce an excellent approxima-
tion of linear corrosion kinetics in atmospheric exposure.
The sheltering effect is enormously important in the case of zinc. Groundward-facing
surfaces do not exhibit linearity like skyward-facing surfaces generally do, even in aggres-
sive industrial environments. The groundward exponent n is always lower, albeit slightly,
indicating a somewhat more diffusive protection behaviour of the groundward side, nearer
to 0.5, while on the skyward side the exponent is 0.5 < b < 1.0.
Zinc corrodes substantially more on the skyward side than on the groundward side [48].
Corrosion on the skyward side is uniform and a dense layer of corrosion products is
formed, being strongly adhered to the metal surface. In contrast, corrosion on the ground-
ward side is more localised.
SEM examination of skyward sides reveals substantial amounts of particulate matter
[44,49]. On the other hand, greater pitting is observed on the skyward side due to dust
 D. de la Fuente et al. / Corrosion Science 49 (2007) 1420–1436 1429

particles settled on the surface. This effect is particularly appreciable in rural atmospheres,
where corrosion product layers are very thin. Askey et al. [50] demonstrated that in rela-
tively unpolluted atmospheres inert particulate matter can cause an increase in atmo-
spheric corrosion rates of zinc owing to differential aeration.

4.3. Rural atmosphere (El Escorial)

At El Escorial test site (Fig. 2) the corrosion products present a morphology of very
small rounded agglomerates of a diameter less than 5 lm. EDS analysis of this layer
reveals the presence of S and particulate matter (Al and Si).
Pitting corrosion is observed (Fig. 3), possibly as a consequence of particulate settle-
ment causing corrosion attack on zinc due to differential aeration. This feature was also
observed by Askey [50], and by Almeida [51] in the Iberoamerican MICAT project on
atmospheric corrosion [52].
Dunbar and Showak [9] reported a similar surface aspect, with the presence of pitting,
in long-term exposure (20 years) in rural atmospheres. The thickness of the remaining cor-
rosion product layer is 7–8 lm. A wash-off effect due to the action of rainwater is seen,
since the corrosion products inside the pits are less voluminous than the corroded metal,
when normally the reverse would be true.
No important morphological differences are seen between the skyward side and the
groundward side, although the latter presents a lesser degree of attack. This corroborates
the effect of deposited dust, since it is more difficult for particles to be deposited on the
groundward side.
XRD analysis (Table 2) only detects zincite (ZnO), although probably, in view of the
presence of S in the EDS spectra, zincite may coexist with a certain zinc hydroxysulphate
content in the corrosion products. Biestek [7] reports the presence of this phase in rural

5000

4000
counts x 103

3000
Zn
10 μm
2000
Zn

1000
Si
Al S
Zn
0
1 2 3 4 5 6 7 8 9 10
Energy / KeV

Fig. 2. SEM/EDS results obtained on the surface of a zinc specimen exposed for 13 years in the rural atmosphere
of El Escorial.
1430 D. de la Fuente et al. / Corrosion Science 49 (2007) 1420–1436

5000
Zn
4000

counts x 103
3000
Zn
2000
10 μm
1000
Si S Cl
10 μm Zn
0
1 2 3 4 5 6 7 8 9 10
Energy / KeV

Fig. 3. Cross-section SEM/EDS results obtained on the zinc corrosion product layer formed in the rural
atmosphere of El Escorial. Pitting corrosion is observed.

atmospheres after long exposure times. On the other hand, Graedel [15], Grauer [13], and
Almeida [51] all refer to ZnO as a frequently predominant phase in unpolluted atmo-
spheres, and Friel [35] reported that during exposure ZnO becomes increasingly abundant.
Moderate amounts of soluble salts have been extracted from corrosion products formed
in this type of atmosphere [51]. According to the EDS spectrum in Fig. 3, the salts accu-
mulate in the bottom of the pits.

4.4. Urban atmosphere (Madrid)

Corrosion is slightly greater in this atmosphere, with higher sulphur dioxide contents
than the rural atmosphere (Table 1), although the corrosion product layer does not exceed
a thickness of 10 lm, as in the case of El Escorial.
The morphology of the aged surfaces, on both the skyward and groundward sides, is
very similar to that seen in the rural atmosphere: presence of rounded shape corrosion
products (Fig. 4, left). The EDS spectrum reveals a greater S content than in the rural
atmosphere, in consonance with a higher soluble sulphate content (Table 2), and the pres-
ence of particulate matter (Al, Si).
The cross-sections of the corrosion layers (Fig. 4, right) reveal the existence of abundant
cracking, as in the rural atmosphere, confirming the lack of protective properties of the
layers of zinc corrosion products.

4.5. Industrial atmosphere (Bilbao)

No great morphological differences were observed between the groundward side and
the skyward side; the corrosion products (Fig. 5) have the flattened rounded appearance
corresponding to zinc hydroxysulphate. The EDS spectrum indicates the presence of S
and of abundant particulate matter (Si, Al, K, Ca and Fe).
The skyward side shows a serrated attack profile with peaks and valleys, denoting a
notable solubility of the corrosion product layer due to the washing action of the
 D. de la Fuente et al. / Corrosion Science 49 (2007) 1420–1436 1431

5000

4000
counts x 103

3000
Zn
10 μm
2000
Zn
S
1000 10 μm
Si
Al Fe Zn
0
1 2 3 4 5 6 7 8 9 10
Energy / KeV

Fig. 4. Left: SEM/EDS results obtained on the surface of a zinc specimen exposed for 16 years in the urban
atmosphere of Madrid. Right: Cross-section SEM view of the zinc corrosion product layer. Abundant cracking is
observed.

4000
counts x 103

10 μm
Zn Fe

2000 Zn
Si
Al S

K Fe
Ca Zn
0
3 6 9
Energy / KeV

Fig. 5. SEM/EDS results obtained on the surface of a zinc specimen exposed for 16 years in the industrial
atmosphere of Bilbao.

somewhat acidic rainwater (Fig. 6, left). This attack profile contrasts with that correspond-
ing to the groundward side, where the attack is more uniform (Fig. 6, right).
A more magnified view of this serrated profile (Fig. 7) shows a clear stratification of the
corrosion products in sublayers. In the peaks the corrosion products are lighter and more
compact, while in the valleys their appearance is darker and more porous. EDS in both
cases reveals the presence of S and some Fe. The appearance of pitting in this case may
indicate an important action of chlorides. Cl and S were found in the bottom of these
1432 D. de la Fuente et al. / Corrosion Science 49 (2007) 1420–1436

Fig. 6. Cross-section SEM micrographs of the zinc corrosion product layers formed skyward (left) and
groundward (right) in the industrial atmosphere of Bilbao.

5000

4000
Zn
counts x 103

3000

2000
Zn
1000 S
Si Fe Zn
0
1 2 3 4 5 6 7 8 9 10
Energy / KeV
5000
Zn
10 μm 4000
counts x 103

3000
Zn
2000
S
1000
Cl
Fe Zn
0
1 2 3 4 5 6 7 8 9 10
Energy / KeV

Fig. 7. Cross-section SEM/EDS results obtained in the zinc corrosion product layer formed groundward in the
industrial atmosphere of Bilbao.

pits. This peak and valley morphology has been found in other long-term tests in industrial
atmospheres [9]. It is common for sulphates and chlorides to be located in inner zones of
the corrosion product layer. This explains why, despite there being important amounts of
soluble sulphates and moderate amounts of soluble chlorides (Table 2), less Cl and S is
found in the surface analysis than would be expectable.

4.6. Marine atmospheres (Barcelona and Alicante)

The corrosion product layers of the greatest thickness were found in this type of
atmosphere (Fig. 8), which indicates that, apart from the high aggressivity of these
 D. de la Fuente et al. / Corrosion Science 49 (2007) 1420–1436 1433

5000
Zn
4000 S
Zn

counts x 103
3000

2000
Cl
1000
Si Zn
0
1 2 3 4 5 6 7 8 9 10 10 μm
10 μm Energy / KeV

Fig. 8. Cross-section SEM/EDS results obtained in the zinc corrosion product layers formed groundward in the
marine atmosphere of Alicante (left) and Barcelona (right).

atmospheres, the washing action of rainwater has been considerably lesser than in the indus-
trial atmosphere of Bilbao. This is corroborated by the large amount of soluble salts (sul-
phates and chlorides) found in both stations; the greatest amounts of all the study (Table 2).
The corrosion product layer is thick, heterogeneous and cracked. The cross-sections of
the corrosion product layers formed in these marine atmospheres show the existence of
two clearly differentiated subzones: an inner sublayer, crossed by cracks, and an outer sub-
layer, completely microcracked and thus exhibiting many extremely fine microscopic chan-
nels. Observation of the outer sublayer at a high magnification (Fig. 8) shows with greater
clarity the ‘‘spongy’’ microstructure formed by an extremely fine interlinked network of
microcracks, having pores of less than 1 lm diameter. The spongy structure of the outer
sublayer facilitates the entry of oxygen, water and pollutants, for which reason this sub-
layer is in continuous growth. This type of structure has previously been identified in mar-
ine atmospheres, although in different conditions [53]. The inner sublayer is compact and
stable, impeding the passage of water and pollutants, making it that which controls the
kinetics of the corrosion process.
The total layer thickness in Barcelona varied between 70 and 130 lm, with an inner sub-
layer thickness of around 10 lm (Fig. 8, left). In Alicante a similar appearance was found
(Fig. 8, right). In this case the total thickness (180–200 lm) of the layer is greater than that
found in Barcelona, as is the inner sublayer thickness (around 30 lm). The EDS spectrum
of the layer shows the abundant presence of S throughout its thickness and a lesser pres-
ence of Cl.
XRD analysis (Table 2) reveals the presence of sodium zinc chlorohydroxysulphate in
both stations. In view of its poor solubility, this compound is relatively protective. In mar-
ine atmospheres it has been identified as one of the last to form, and reflects the incorpo-
ration of sulphate ions and sodium atoms in the zinc hydroxychloride structure, the
compound that forms previously [10], as can be seen in lamellar shape, as platelets, in
the micrograph of Fig. 9.
In both stations the morphology of the corrosion products is similar on both sides of
the specimens. Corrosion products with elongated globular and leaf-shaped morphologies
were seen on the surface views (Fig. 9), containing important amounts of S, Cl and par-
ticulate matter (Al, Si, Mg, K, Fe and Ca).
1434 D. de la Fuente et al. / Corrosion Science 49 (2007) 1420–1436

5000 5000
4500 Zn 4500
4000 4000
3500 3500 Si

counts x 103
counts x 103

3000 3000
2500 Zn 2500
2000 10∝
m 2000 10∝m
1500 Si
1500 Al
1000 Mg S 1000 Zn S Zn
Al Zn Cl
500 Cl K Ca 500 Mg K Ca Fe
Fe Fe Fe Zn
0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
Energy / KeV Energy / KeV

Fig. 9. SEM/EDS results obtained in the zinc corrosion product layer formed skyward in Barcelona (left) and
Alicante (right) after 13 and 16 years of atmospheric exposure, respectively.

5. Conclusions

The conclusions obtained in this study are as follows:

1. A linearly increasing amount of zinc corrosion with time has been found in long-term
exposures at the different test sites.
2. However, the behaviour of zinc in the two marine atmospheres deviated from the usual
behaviour (constant corrosion rate) found in the rest of atmospheres. The serrated pat-
tern of the zinc corrosion rate versus time graph found in severe marine atmosphere of
Alicante suggests the occurrence of a corrosion product layer formation-compaction-
detachment processes.
3. Very thin films of corrosion products (zincite) were found in rural and urban atmo-
spheres of El Escorial and Madrid respectively. Abundant cracking of the zinc corro-
sion layers and pitting corrosion due to particulate settlement were found.
4. The low thickness of the remaining corrosion product layer formed in the industrial
atmosphere of Bilbao denotes its notable solubility due to the washing action of the
somewhat acidic rainwater. Zinc hydroxysulphate was detected in the layer of corrosion
products.
5. Simonkolleite and sodium zinc chlorohydroxysulphate were found in the thick layers of
corrosion products formed in the marine atmospheres of Barcelona and Alicante.

Acknowledgements

The authors acknowledge to the following companies for the facilities allowed and the
help provided to carry out this study: AESA, Telefónica, ENDASA, Instituto de Ciencias
del Mar de Barcelona (CSIC).

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