CORROSION SCIENCE SECTION
Atmospheric Corrosion of Copper in Ibero-America
M. Morcillo,* E. Almeida,** M. Marrocos,*** and B. Rosales****
ABSTRACT
Within the framework of the American Map of Atmospheric
Corrosiveness (MICAT) project, 4 years of field research on
atmospheric corrosion carried out in 14 countries of Ibero-
America, this paper reports atmospheric copper corrosion
in 21 unpolluted rural atmospheres and 45 marine atmo-
spheres covering a broad interval of climatic conditions.
High temperatures and relative humidities seem to promote
greater copper corrosion in rural atmospheres; attack rates
are found in the range of 0.1 µ m/y to 2 µ m/y, and corrosion
product layers, generally comprising only cuprite (Cu2O), are
discontinuous and have open structures with patinas acquir-
ing increasingly darker colors (from salmon pink to dull
brown) with exposure time. From the results obtained at ma-
rine sites, a critical deposition rate threshold is inferred for
atmospheric salinity (20 mgCl–/m2 per day), after which the
atmospheric corrosion of this material is intensified.
KEY WORDS: copper, atmospheric corrosion, patina, rural,
marine, Ibero-America
INTRODUCTION
Copper and its alloys are important functional mate-
rials widely used in indoor and outdoor environments.
Submitted for publication August 2000; in revised form, August
2001.
* Departamento de Ingeniería de Materiales, Degradación y
Durabilidad, Centro Nacional de Investigaciones Metalúrgicas,
CSIC. Avda. Gregorio del Amo 8, 28040 Madrid, Spain.
** LTR/IMP, Instituto Nacional de Engenharia e Tecnologia
Industrial, Estrada do Paço do Lumiar, 1649-038 Lisboa, Portugal.
*** Centro de Pesquisas de Energia Electrica, Avd. Um s/n, Ilha do
Fundao, 21941-590 Rio de Janeiro, Brasil.
**** Departamento de Investigaciones en Corrosion, CITEFA,
Zufriategui 4380, 1603-Villa Martelli, Argentina.
0010-9312/01/000193/$5.00+$0.50/0
CORROSION–Vol. 57, No. 11 © 2001, NACE International
There is a long tradition of their use as architectural
materials, and it is common to find copper roofs in
castles and other monumental buildings, frontages,
flashings, statues, and ornamental objects many hun-
dreds of years old. Several traits have promoted the
widespread use of copper as an architectural mate-
rial, such as its good resistance to atmospheric cor-
rosion and the pleasant colors (patinas) that develop
on its surface during its exposure to the atmosphere.
Because of its high electrical conductivity, cop-
per has also been profusely used in electrical con-
ductors of different kinds. Presently, copper is a
basic material in the electromechanical and electron-
ics and communications industries (as electrical con-
tacts, terminals, printed circuits, etc.), and these new
applications have recently encouraged in-depth stud-
ies of the interaction of copper with atmospheres.
Copper corrosion in high-tech equipment, though
insignificant from the point of view of material wear,
can impede operation by causing current leakages,
increasing contact resistances, etc., leading to short
circuits and other faults in printed circuits.
There is abundant literature covering the atmo-
spheric corrosion of copper and its alloys,1-10 in Euro-
pean and North American countries in particular.
However, information about tropical atmospheres is
comparatively scarce.11 The information obtained in
the American Map of Atmospheric Corrosiveness
(MICAT) project,12 4 years of field research on atmo-
spheric corrosion carried out in 14 countries of
Ibero-America (including a considerable number of
tropical atmospheres), can help narrow this gap in
the literature.
967
CORROSION SCIENCE SECTION
FIGURE 1. Network of MICAT atmospheric corrosion test sites.
EXPERIMENTAL PROCEDURES
Despite its own peculiarities, the MICAT project12
basically followed the outline of an international pro-
gram about atmospheric corrosion launched by the
International Organization for Standardization’s
(ISO)(1) ISO/TC 156/WG 4.13
Figure 1 shows the location of the Ibero-Ameri-
can network of atmospheric corrosion testing sta-
tions. The MICAT project considered 21 test sites
located in rural atmospheres of the 14 Ibero-Ameri-
can countries involved in the project.12 All corre-
sponded to the category S0P0, which ISO 922314
defines as rural atmospheres with sulfur dioxide
(SO2) and chloride deposition rates of <10 mg/m2 per
day and 3 mg/m2 per day, respectively. The project
also considered 45 marine atmospheres. Of these,
25 were classified as pure marine atmospheres and
the remaining 20 were classified as mixed atmo-
spheres. Three Antarctic atmospheres were included
in the first group, though with a special consider-
ation because of their climatic singularity.
(1)
International Organization for Standardization, 1 rue de Varembe,
Case Postale 56, CH-1121 Geneve 20, Switzerland.
968
According to ISO 9223,14 the marine atmo-
spheres considered in this study were classified in
the following groups:
—Pure marine atmospheres (SxPo), where Po indi-
cates that SO2 contamination remains <10 mg/m2
per day. S refers to the chloride content (airborne s
alinity) of the atmosphere, and the subindex “x” can
be 1, 2, or 3, depending on whether the salinity is
between 3 mg/m2 per day and 60 mg/m2 per day (1),
between 60 mg/m2 per day and 300 mg/m2 per day
(2), or >300 mg/m2 per day (3).
—Mixed atmospheres (SxPy) are simultaneously
contaminated by chlorides and SO2. P refers to the
degree of SO2 contamination in the atmosphere, and
the subindex “y” depends on whether the SO2 content
is between 10 mg/m2 per day and 35 mg/m2 per day
(1), 35 mg/m2 per day and 80 mg/m2 per day (2), or
80 mg/m2 per day and 200 mg/m2 per day (3).
The general experimental methodology for con-
ducting the MICAT project has been explained else-
where.12 Climatological and pollution characterization
of the atmospheres was carried out according to ISO
methodology.14-15
The test specimens (10 cm by 15 cm) were pre-
pared from 1-mm thick sheets of copper (99.5% min.)
and installed in the racks according to ISO 8565.16
After 1, 2, 3, and 4 years of exposure, the specimens,
once withdrawn from the test rack, were subjected to
a pickling treatment to remove the corrosion prod-
ucts,17 and mass losses were determined.18 The cat-
egories of atmospheric corrosivity were assigned
according to ISO 9223.14
Morphological evaluation of the corrosion prod-
uct layers formed on copper was carried out by scan-
ning electron microscopy (SEM) and energy-disper-
sion spectrometry (EDS), and chemical characteriza-
tion of the patinas was performed by x-ray diffraction
(XRD) and Fourier transform infrared spectroscopy
(FTIR). Table 1 shows the different corrosion prod-
ucts identified on the copper specimens. Soluble
salt contents (chlorides and sulfates) retained in
corrosion products were determined by the Mayne
method.20
Determination of the coloring presented by cop-
per specimens weathered in the different atmo-
spheres was done visually with the naked eye and by
trichromatic colorimetry21 using a Dr. Lange reflec-
tion apparatus. The colors formed on both upward
and downward sides of the specimens were exam-
ined. At least three measurements were taken for
each specimen.
RESULTS
Tables 2 through 10 display in summarized form
much of the information generated for each of the
test sites during the MICAT project.12 The test sites
are grouped according to their SxPy categories defined
CORROSION–NOVEMBER 2001
 CORROSION SCIENCE SECTION

TABLE 1
Corrosion Products Identified on the Copper Specimens Exposed in Atmospheres of MICAT Project

Substance Formula Crystal System19 Symbol

Oxides
Cuprite Cu2O Cubic Cu

Carbonates
Azurite Cu3(CO3)2(OH)2 Monoclinic Az

Sulfates
Copper (II) sulfate CuSO4·H2O Monoclinic Sc
Antlerite Cu3(SO4)(OH)4 Orthogonal An
Brochantite Cu4(SO4)(OH)6 Monoclinic Br
Langite Cu4(SO4)(OH)6·2H2O Orthogonal La
Posnjakite Cu4(SO4)(OH)6·2H2O Monoclinic Po

Chlorides
Tolbachite CuCl2 Monoclinic To
Copper (II) chloride CuCl(OH) Monoclinic Cc
Atacamite Cu2Cl(OH)3 Orthogonal At
Paratacamite Cu2Cl(OH)3 Trigonal Pa

Sulfides
Chalcocite Cu2S Monoclinic Ca
Covellite CuS Hexagonal Co

by ISO 9223.14 The values shown for environmental
factors, time of wetness (TOW) and pollutant deposi-
tion rates, are average values for the first 3 years of
atmospheric exposure.
Tables 2 through 10 also display the copper cor-
rosion rates recorded for the first year of exposure
and after the 4-year duration of the research, the
former being the average of the three 1-year exposure
values. Where corrosion data for 4 years of exposure
was not available, the data corresponding to 3 years
is shown in order to give a certain indication of the
evolution of the corrosion rate with exposure time.
The tables also display the corrosivity categories of
the atmospheres defined by ISO 922314 on the basis
of corrosion data obtained in the first year of atmo-
spheric exposure.
The final columns of Tables 2 through 10 show
information about the corrosion products (Table 1)
identified on the specimens withdrawn after the dif-
ferent exposure times and the soluble salt contents
(chlorides and sulfates) of the corrosion products
formed during the first year of exposure.
Nature of Corrosion Products
Rural Atmospheres (Table 2) — Columns 9
through 11 of Table 2 suggest that cuprite (Cu2O) is
the most common corrosion product found on all the
specimens. Cuprite is responsible for the dark red
color initially formed. The formation of brochantite
(Cu4SO4[OH]6) and its isomorphic form posnjakite
(Cu4SO4[OH]6·2H2O) was also fairly frequent. These
insoluble sulfates are the principal components of
copper patinas that present a greenish color, but in
this case the concentrations existing on the speci-
mens were not sufficient to change the general color-
ing of the specimen. Even in atmospheres where
chloride concentrations were very low, atacamite
(Cu2Cl[OH]3) formations could also be observed in
some sites (Belem and V.Martelli test sites).
Marine Atmospheres (Tables 3 through 10) —
Atacamite is the corrosion product most commonly
found in marine atmospheres. In some cases,
paratacamite (Cu2Cl[OH]3), an isomorphic compound
of atacamite, is also found. Both products present a
blue-greenish coloring, characteristic of the copper
patinas formed in marine atmospheres.
It is also common to find brochantite and
posnjakite, even when the atmosphere presents low
SO2 deposition rates (Tables 3 through 5), because of
the easy retention of background atmospheric pollu-
tion in the copper corrosion product layers. These
two basic sulfates can be the only corrosion products
detected when the marine atmosphere presents low
salinity values (test sites in the upper part of Tables
3 and 7).
Coloring of the Patinas
The color of copper and copper alloys exposed
outdoors is known to change very quickly. These col-
orings are the result of not only the corrosion prod-
ucts formed but also the deposition of atmospheric
particulate material on the surface of the specimens.
Rural Atmospheres — In rural atmospheres, the
corrosion products darken with time, changing from
salmon-pink to brown and then black, or nearly so.
After 3 years of exposure, practically all the speci-
mens already have dark surfaces, the downward side
being always lighter in color than the upward side.

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TABLE 2
SoPo MICAT Test Site Characteristics
Deposition Rate Corrosion Rate Corrosion Products Soluble Salts
In (mg/m2 per day) (µm/y) Corrosivity (Table 1) (mg/m2)
Figure 1 Test Site Cl– SO2 TOW14,(A) 1st Year 4 Years Category14,(B) 1 Year 2 Years 3 Years Cl– SO42–

60 Cuzco (C) (C)

τ4 0.09 0.18 C1 Cu (D) (D)
249 387
4 San Juan (C) (C)
τ3 0.17 0.20 C2 Cu Cu Cu,Po 187 361
59 Arequipa (C) (C)
τ2 0.20 0.15 C2 Cu (D) (D)
305 441
44 Granada (C)
6.2 τ3 0.22 0.16 C2 Cu Cu Cu 246 420
49 Cuernavaca (C)
7.9 τ3 0.30 0.27(E) C2 Cu (D) (D)
155 338
36 Riobamba 1.1 1.2 τ4 0.43 (D)
C2 Cu (D) (D) (D) (D)

61 Pucallpa (C) (C)

τ5 0.56 0.44 C2 Cu (D) (D)
198 420
47 Arties 1.7 9.0 τ3 0.62 0.38 C3 Cu Cu,Br,Po Cu,Br,Po 12 19
14 Belem (C) (C)
τ5 0.64 (D)
C3 Cu,At Cu,At,Ca (D)
229 432
35 Guayaquil 1.5 3.0 τ4 0.71 0.86(E) C3 Cu (D) (D)
198 389
21 Cotove (C)
0.3 τ4 0.73 0.47 C3 Cu Cu Cu 17 0
3 Iguazu (C) (C)
τ5 0.77 0.83 C3 Cu Cu Cu,Po,An 30 84
2 V.Martelli (C)
9.0 τ4 0.79 0.47 C3 Cu,Po, Cu,Po, Cu,Po, 86 108
Br,At Br,At Br,At
40 Leon (C) (C)
τ3 0.81 0.65 C3 Cu Cu Cu 191 379
43 Tortosa (C)
5.3 τ4 0.81 0.36 C3 Cu Cu Cu 224 365
65 Trinidad 1.5 0.7 τ4 0.83 0.57 C3 (D) (D) (D)
39 137
20 San Pedro (C)
0.6 τ5 1.05 0.90 C3 Cu (D) (D)
226 300
16 Brasilia (C) (C)
τ4 1.12 0.78(E) C3 Cu,Po Cu,Br,Po (D) (D) (D)

6 La Plata (C)
6.9 τ4 1.57 1.22 C4 Cu (D) (D)
219 381
17 P.Afonso (C) (C)
τ3 1.86 (D)
C4 (D) (D) (D) (D) (D)

(C) (C) (D) (D) (D) (D) (D) (D) (D)

18 Porto Velho 1.94 C4
(A)
Time of wetness (h/y): 10 < τ2 ≤ 250; 250 < τ3 ≤ 2,500; 2,500 < τ4 ≤ 5,500; τ5 > 5,500.
(B)
C(µm/y): C1 ≤ 0.1; 0.1 < C2 ≤ 0.6; 0.6 < C3 ≤ 1.3; 1.3 < C4 ≤ 2.8.
(C)
Apparently uncontaminated atmosphere (≤3 mg Cl–/m2 per day and ≤10 mg SO2/m2 per day).
(D)
Not available.
(E)
Three years of exposure.

Figure 2 shows, for some test sites, the regions
for which the calculated coordinates were plotted. As
can be seen, after the first year of exposure the chro-
matic values recorded have moved very far away from
the initial color of copper, but with time (2 years and
3 years) the spread of results hardly varies.
Marine Atmospheres — In marine atmospheres,
greenish spots, corresponding basically to copper
chlorides, can be observed on copper surfaces after
1 year of exposure, increasing in intensity with time
and atmospheric salinity. This occurs mainly on the
upward side of the specimens where chloride depos-
its are greater. Under these greenish spots, the cop-
per surface has a coloring that changes from red to
brown and then to black. This coloring is principally
a function of the pollutant quantities and dust par-
ticles, and consequently the downward side is gener-
ally lighter in color.
In the Río de Janeiro atmosphere (Table 8),
where a high concentration of hydrogen sulfide (H2S)
was found, the surface became black after the sec-
ond year of exposure and remained black for the
subsequent years as a result of the presence of cop-
per sulfides (chalcocite).
In summary, the coloring presented by patinas
formed on copper in marine atmospheres can be said
to be characterized by the following:
—The blue-turquoise coloring shown by corro-
sion products formed in Antarctic atmospheres,
resulting from the presence of only basic chlorides
(atacamite) in the corrosion product layers, occurs
in the atmospheres of Marsh, Artigas, and Jubany,
where SO2 levels must be extraordinarily low.
—The presence of greenish tones, as exposure
time increases, occurs in mixed atmospheres where
there is a preponderance of the chloride ion deposi-
tion rate.
—The dark brown, almost black tones, as expo-
sure time increases, occur in mixed atmospheres
where there is a preponderance of the SO2 deposition
rate.
Figure 3 shows the variation with exposure time
of the chromaticity coordinates of copper surfaces
weathered in some marine atmospheres. As can be
seen, after the first year of exposure, the chromatic
values recorded diverge from the initial color of new
copper, but, as exposure time increases (2 years and
3 years of exposure), this spread of results does not
increase significantly.
DISCUSSION
First, it is interesting to note the state of copper
surfaces at the start of their atmospheric exposure,

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TABLE 3
S1P0 MICAT Test Site Characteristics
Deposition Rate Corrosion Rate
In (mg/m2 per day) (µm/y) Corrosivity
Figure 1 Test Site Cl– SO2 TOW14,(A) 1st Year 4 Years Category14, (B)

67 Melo 3.8 0.7 τ5 1.27 0.72 C3

41 El Pardo 3.9 6.4 τ4 0.81 0.54 C3
7 Caratinga 5.8 1.3 τ4 0.99 0.59 C3
64 Pego 6.0 7.9 τ4 1.43 0.66 C4
46 Labastida 9.8 3.6 τ4 0.95 0.47 C3
25 Sabanilla 11.3 4.9 τ5 1.23 1.10 C3
73 Matanzas 15.9 9.3 τ4 0.95 (C)
C3
74 Barcelona,V 21.8 1.5 τ4 0.35 0.41(E) C2
51 Acapulco 23.8 9.6 τ4 1.23 0.95 C3
(C) (C)
39 S.Cristóbal 25.0 1.1 1.52 C4
72 Coro 27.5 6.5 τ4 2.35 1.17 C4
71 Punto Fijo 31.0 5.0 τ4 3.19 2.51 C5
22 Puntarenas 33.4 7.1 τ4 2.98 1.96 C5
37 Salinas 47.3 2.3 τ4 2.33 1.21(E) C4
1 Camet 55.1 (F)
τ5 2.23 0.65 C4
In Corrosion Products (Table 1) Soluble Salts (mg/m2)
Figure 1 1 Year 2 Years 3 Years 4 Years Cl– SO42–
(C) (C) (C) (C)
67 207 376
(C)
41 Cu,Po Cu,Po Cu,Po,Br 26 146
7 Cu,Po Cu,Po,Br Cu,Po,Br Cu,Po,Br 34 90
64 Cu,Po(D) Cu,Po,Br Cu,Po,Br,La(D) Cu,Po,Br,La(D) 157 24
(C)
46 Cu Cu Cu 360 310
(C)
25 Cu Cu Cu,Br 189 351
(C) (C) (C) (C)
73 269 355
(C) (C) (C) (C)
74 218 328
(C) (C)
51 Cu,At Cu,At 303 404
(C) (C) (C) (C) (C) (C)
39
(C) (C) (C) (C)
72 351 347
(C) (C) (C) (C)
71 600 382
(C)
22 Cu,At Cu,At,Po Br 323 362
(C) (C) (C) (C) (C) (C)
37
(C)
1 Cu Cu,At,Br Cu,At,Br 492 7
(A)
Time of wetness (h/y): 2,500 < τ4 ≤ 5,500; τ5 > 5,500.
(B)
C(µm/y): 0.1 < C2 ≤ 0.6; 0.6 < C3 ≤ 1.3; 1.3 < C4 ≤ 2.8; 2.8 < C5 ≤ 5.6.
(C)
Not available.
(D)
Traces.
(E)
Three years of exposure.
(F)
Apparently non-SO2-polluted atmosphere (≤10 mg SO2/m2 per day).

as well as some general considerations of the atmo-
spheric corrosion of this metal.
At room temperature, copper in contact with
clean air becomes instantaneously coated by a thin,
invisible film of cuprous oxide (cuprite) through a
direct oxidation mechanism.2 This natural cuprite
film, of ≈1.6 nm thickness, grows with exposure time
following a parabolic law or an oxidation kinetics
of a greater order,22 becoming more compact and
impeding the diffusion of Cu+ ions through it. Subse-
quently, the oxidation rate decreases with time, prac-
tically stopping at 50 Å (5 nm).
Before their atmospheric exposure, copper sur-
faces present a salmon-pink coloring. X-ray photo-
electron spectroscopy (XPS) analysis of a copper
surface prior to atmospheric exposure (Figure 4)
shows that the initial patina consists mainly of cuprite.
Atmospheric corrosion of copper obeys an elec-
trochemical mechanism by which the metal dissolves
anodically, forming cuprous or cupric ions. Oxygen
diffused through the aqueous film that wets the
metal acts as cathodic reagent. As a consequence of
these reactions, oxides and hydroxides are formed
on the metallic surface. Cu+ and Cu2+ ions can also
interact with other atmospheric species (CO2, Cl–,
SO42–, etc.) to form carbonates, chlorides, sulfates,
sulfides, etc.23
Natural patinas present a porous structure and
adhere strongly to copper, particularly in the case
of cuprite films. Graedel23 and Muller and McCrory-
Joy24 suggest that polar organic species anchor the
patina to the copper surface. This porous structure
facilitates the growth of the corrosion products
layers.

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TABLE 4
S2P0 MICAT Test Site Characteristics

In Deposition Rate (mg/m2 per day) Corrosion Rate (µm/y) Corrosivity

Figure 1 Test Site Cl– SO2 TOW14,(A) 1st Year 4 Years Category14,(B)

11 Ubatuba 113 2.6 τ4 3.29 1.79 C5

69 P.del Este 144 4.0 τ4 2.51 (C)
C4
23 Limón 220 3.5 τ5 3.68 2.18 C5
9 A.do Cabo 229 6.7 τ4 4.12 2.50 C5
75 P.Cabello (C) (D)
τ5 4.50 2.13 C5
70 El Tablazo 63.3 6.0 τ4 5.80 2.26 >C5
In Corrosion Products (Table 1) Soluble Salts (mg/m2)
Figure 1 1 Year 2 Years 3 Years 4 Years Cl– SO42–

11 Cu,At Cu,At Cu,At Cu,At 231 370

(C) (C) (C) (C) (C) (C)
69
(C)
23 Cu,At Cu,At Cu,At 317 270
9 Cu,At Cu,At,Br Cu,At,Br Cu,At,Br 270 56
(C) (C) (C) (C)
75 300 336
(C) (C) (C) (C)
70 561 430
(A)
Time of wetness (h/y): 2,500 < τ4 ≤ 5,500; τ5 > 5,500.
(B)
C(µm/y): 0.1 < C2 ≤ 0.6; 0.6 < C3 ≤ 1.3; 1.3 < C4 ≤ 2.8; 2.8 < C5 ≤ 5.6; > C5 ≥ 5.6.
(C)
Not available.
(D)
Apparently non-SO2-polluted atmosphere (≤10 mg SO2/m2 per day).

TABLE 5
S3P0 MICAT Test Site Characteristics
In Deposition Rate (mg/m2 per day) Corrosion Rate (µm/y) Corrosivity
Figure 1 Test Site Cl– SO2 TOW14,(A) 1st Year 4 Years Category14,(B)

15 Fortaleza >300 (C)

τ4 3.80 (D)
C5
In Corrosion Products (Table 1) Soluble Salts (mg/m2)
Figure 1 1 Year 2 Years 3 Years 4 Years Cl– SO42–
(D) (D)
15 Cu,Co,At,Po Cu,Co,At,Po 389 318
(A)
Time of wetness (h/y): 2,500 < τ4 ≤ 5,500; τ5 > 5,500.
(B)
C(µm/y): 0.1 < C2 ≤ 0.6; 0.6 < C3 ≤ 1.3; 1.3 < C4 ≤ 2.8; 2.8 < C5 ≤ 5.6.
(C)
Apparently non-SO2-polluted atmosphere (≤10 mg SO2/m2 per day).
(D)
Not available.

Rural Atmospheres atmospheric exposure in the same atmosphere. EDS

From a preliminary analysis of Table 2, there is
an enormous variation in the corrosion values found
during the first year of exposure (from 0.09 µm/y in
Cuzco to 1.94 µm/y in Porto Velho), which seems to
indicate the importance of climatic conditions on the
corrosion of this material in rural atmospheres; and,
corrosion products present high soluble chloride and
sulfate contents. Levels on the order of 200 mg/m2
are frequent for soluble chlorides and 400 mg/m2
for soluble sulfates, probably due to retention of
background pollution from the atmosphere by the
open structure of the corrosion product layers, as
noted by Graedel.19
Figure 5(a) shows a SEM micrograph for a cop-
per surface after 1 year of exposure in the Arties at-
mosphere, in which the granular and discontinuous
formation of cuprite can be seen. Figure 5(b) shows
the appearance of a copper surface after 3 years of
analysis shows the aforementioned capacity of cu-
prite to retain all types of pollutants, including those
with which copper forms no compounds (silicon, alu-
minum, etc.) but which are included in its thin films.
The low TOW of this atmosphere means that solid
pollutants are not prevented from becoming inte-
grated, resulting in apparently high thicknesses for
the low corrosion rates measured. Since the pollut-
ants are not uniformly distributed, the resulting
films have heterogeneous thicknesses with variable
concentrations of soluble salts and solid pollutants,
meaning that behaviors are more strongly dependent
on the region of the specimen selected for analysis
than on any other parameter.
The granular and discontinuous morphology of
the weathered copper surfaces is similar in all the
atmospheres of this group, though grain size can
vary somewhat from one atmosphere to another. The

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TABLE 6
Antarctic MICAT Test Site Characteristics
In Deposition Rate (mg/m2 per day) Corrosion Rate (µm/y) Corrosivity
Figure 1 Test Site Cl– SO2 TOW14,(A) 1st Year 4 Years Category14,(B)

33 Marsh (C) (D)

τ4 8.22 (C)
>C5
5 Jubany (C) (D)
τ4 2.00 0.73 C4
68 Artigas 159 (D)
τ4 2.16 0.84 C4
In Corrosion Products (Table 1) Soluble Salts (mg/m2)
Figure 1 1 Year 2 Years 3 Years 4 Years Cl– SO42–
(C) (C) (C) (C)
33 947 373
(C)
5 Cu,At Cu,At Cu,At 1,031 71
(C) (C) (C) (C) (C) (C)
68
(A)
Time of wetness (h/y): 2,500 < τ4 ≤ 5,500; τ5 > 5,500.
(B)
C(µm/y): 0.1 < C2 ≤ 0.6; 0.6 < C3 ≤ 1.3; 1.3 < C4 ≤ 2.8; 2.8 < C5 ≤ 5.6; > C5 ≥ 5.6.
(C)
Not available.
(D)
Apparently non-SO2-polluted atmosphere (≤10 mg SO2/m2 per day).

TABLE 7
S1P1 MICAT Test Site Characteristics

In Deposition Rate (mg/m2 per day) Corrosion Rate (µm/y) Corrosivity

– 14,(A)
Figure 1 Test Site Cl SO2 TOW 1st Year 4 Years Category14,(B)

42 Barcelona,E 4.4 16.7 τ3 0.71 0.46 C3

29 Cerrillos 4.5 20.0 τ4 0.73 0.48 C3
30 Valparaíso 10.0 23.6 τ5 0.87 0.46(D) C3
8 Ipatinga 6.8 23.0 τ4 1.21 0.78 C3
52 Panamá 9.8 21.7 τ4 1.24 0.75 C3
66 Prado 10.8 12.1 τ4 1.38 0.82 C4
26 Ciq 12.0 31.6 τ4 1.45 0.86 C4
58 San Borja 20.0 29.0 τ5 1.62 0.56 C4
28 Bauta 6.4 16.4 τ4 1.80 0.85 C4
57 V.Salvador 38.0 18.0 τ5 1.98 0.94 C4
In Corrosion Products (Table 1) Soluble Salts (mg/m2)
Figure 1 1 Year 2 Years 3 Years 4 Years Cl– SO42–
(C)
42 Cu,Po Cu,Po Cu,Po 307 150
(C) (C) (C)
29 Cu 236 517
(C) (C) (C) (C) (C) (C)
30
8 Cu Cu Cu Cu 304 501
(C) (C) (C) (C)
52 246 336
(C) (C) (C) (C)
66 740 363
26 Cu C,At Cu,At Cu,At,Br 159 193
(C) (C) (C)
58 Cu 384 638
28 Cu,At,An,Br,Po Cu,At,An,Br,Po Cu,Br,Po,At Cu,Br,Po,At 133 131
(C) (C) (C)
57 Cu 343 499
(A)
Time of wetness (h/y): 2,500 < τ4 ≤ 5,500; τ5 > 5,500.
(B)
C(µm/y): 0.1 < C2 ≤ 0.6; 0.6 < C3 ≤ 1.3; 1.3 < C4 ≤ 2.8; 2.8 < C5 ≤ 5.6.
(C)
Not available.
(D)
Three years of exposure.

discontinuous formation of cuprite configures open
structures of low compactness. This rugged topogra-
phy makes the leaching of soluble salts difficult, im-
peding the washing effect of rain water.19 After longer
exposure times, the density of globular particles on
the copper surface increases and the corrosion prod-
uct layers become more compact, but with very low
internal cohesion, so that corrosion films formed are
of low compactness and great fragility.
The coloring of the patinas in these types of
atmospheres tends toward darker brown-red shades,
which become even darker as exposure time in-
creases. This darkening is attributable not only to
the formation of corrosion products but also in a
large part to the deposition of particles sedimented
from the atmosphere, which are trapped on the rug-
ged cuprite surface, and possibly to the photoelectro-
chemical behavior of cuprite.

CORROSION–Vol. 57, No. 11 973

CORROSION SCIENCE SECTION

TABLE 8
S1P2 MICAT Test Site Characteristics
In Deposition Rate (mg/m2 per day) Corrosion Rate (µm/y) Corrosivity
Figure 1 Test Site Cl– SO2 TOW14,(A) 1st Year 4 Years Category14,(B)

45 Lagoas 16.7 39.5 τ4 1.23 0.56 C3

10 Cubatao 8.1 54.5 τ4 2.86 2.12 C5
31 Idiem 16.8 43.3 τ5 4.79 2.48 C5
32 Petrox 12.8 65.2 τ5 5.35 (C)
C5
13 Río Janeiro 16.4 43.5 τ4 7.01 4.30 >C5
In Corrosion Products (Table 1) Soluble Salts (mg/m2)
Figure 1 1 Year 2 Years 3 Years 4 Years Cl– SO42–
(C)
45 Cu Cu,Po Cu,Po 57 134
10 Cu,Br,Ca Cu,Br,At,Ca Cu,Br,At,Ca Cu,Br,At,Ca 206 493
(C) (C)
31 Cu Cu 247 567
(C) (C) (C)
32 Cu,Br 277 690
13 Cu,Br Cu,Br Cu,Br Cu,Br,Ca 229 312
(A)
Time of wetness (h/y): 2,500 < τ4 ≤ 5,500; τ5 > 5,500.
(B)
C(µm/y): 0.1 < C2 ≤ 0.6; 0.6 < C3 ≤ 1.3; 1.3 < C4 ≤ 2.8; 2.8 < C5 ≤ 5.6; > C5 ≥ 5.6.
(C)
Not available.

TABLE 9
S2P1 MICAT Test Site Characteristics
In Deposition Rate (mg/m2 per day) Corrosion Rate (µm/y) Corrosivity
Figure 1 Test Site Cl– SO2 TOW14,(A) 1st Year 4 Years Category14,(B)

63 Sines 203 27.0 τ4 3.61 5.19 C5

19 Isla Naval 60.7 10.3 τ5 4.72 3.07 C5
27 Cojímar 104 22.5 τ4 4.89 2.43 C5
In Corrosion Products (Table 1) Soluble Salts (mg/m2)
Figure 1 1 Year 2 Years 3 Years 4 Years Cl– SO42–

63 Cu,At,La(C) Cu,At,La(C) Cu,At,Sc Cu,At,Sc 57 23

(D)
19 Cu Cu,At Cu,At 1,070 253
27 Cu,At Cu,At Cu,At Cu,At 414 129
(A)
Time of wetness (h/y): 2,500 < τ4 ≤ 5,500; τ5 > 5,500.
(B)
C(µm/y): 0.1 < C2 ≤ 0.6; 0.6 < C3 ≤ 1.3; 1.3 < C4 ≤ 2.8; 2.8 < C5 ≤ 5.6.
(C)
Traces.
(D)
Not available.

As mentioned above, the notable variability of
1-year copper corrosion in these types of atmo-
spheres, with very low Cl– or SO2 pollution, could be
a result of the climatic characteristics of the different
atmospheres. To consider this question, an analysis
was made of the annual average temperatures (T)
and relative humidities (RH) recorded at the test
sites. To this end, Figures 6 and 7 display the varia-
tion of first-year corrosion rates with the average
annual T and RH values. The figures seem to suggest
that low T and low RH tend to promote low copper
corrosion rates, while high RH and high T (provided
there is sufficient TOW of the metallic surface)
tend to intensify copper corrosion in these types
of atmospheres. This is in agreement with the obser-
vations of Kucera and Mattsson, who note that
low temperatures and dryness of the atmosphere
considerably delay the time of formation of patinas
on copper.25
During the first year of exposure, cuprite is the
only corrosion product formed in practically all the
rural atmospheres that is in the form of a porous film
which does not completely cover the copper surface
and therefore presents a scant protective power. As
time passes, the porous and open structure of cuprite
enables the accumulation of soluble salts (mainly
chlorides and sulfates) among the corrosion prod-
ucts, with the formation and precipitation of basic
salts. Nevertheless, there is insufficient time to com-
pletely pack the initial open structure of the cuprite
film, and thus, its protective capacity increases only
slightly. Examination of the evolution of corrosion
rates in these types of atmospheres (columns 6 and 7
in Table 2) confirms this observation.
Marine Atmospheres
The discussion corresponding to copper corro-
sion in this type of atmosphere is divided into two

974 CORROSION–NOVEMBER 2001

 CORROSION SCIENCE SECTION

TABLE 10
S2P2 MICAT Test Site Characteristics
In Deposition Rate (mg/m2 per day) Corrosion Rate (µm/y) Corrosivity
Figure 1 Test Site Cl– SO2 TOW14,(A) 1st Year 4 Years Category14,(B)

62 Leixões 97.6 69.2 τ4 4.32 2.30 C5

In Corrosion Products (Table 1) Soluble Salts (mg/m2)
Figure 1 1 Year 2 Years 3 Years 4 Years Cl– SO42–

62 Cu,Pa,At(C), Cu,Pa,Po, Cu,Pa,Sc,To(C) Cu,Pa,Sc,To(C) 281 150

Sc(C),Cc(C) Sc,To(C)
(A)
Time of wetness (h/y): 2,500 < τ4 ≤ 5,500; τ5 > 5,500.
(B)
C(µm/y): 0.1 < C2 ≤ 0.6; 0.6 < C3 ≤ 1.3; 1.3 < C4 ≤ 2.8; 2.8 < C5 ≤ 5.6.
(C)
Traces.

FIGURE 3. Chromaticity coordinates of patinas formed on copper

FIGURE 2. Chromaticity coordinates of patinas formed on copper
exposed to MICAT rural atmospheres and its evolution with time of
exposure: M new copper, v 1 year, ▲ 2 years, and m 3 years. Test
sites: (47) Arties, (2) V.Martelli, and (3) Iguazu.
exposed to MICAT marine atmospheres and its evolution with time
of exposure: M new copper, v 1 year, ▲ 2 years, and m 3 years. (1)
Camet, (7) Caratinga, (9) Arraial do Cabo, (10) Cubatao, (26) Ciq,
(27) Cojimar, (28) Bauta, (42) Barcelona,E, (45) Lagoas, (62)
Leixões, (63) Sines, (64) Pego, and (41) El Pardo.

major blocks, separately considering pure marine at-
mospheres (≤10 mg SO2/m2 per day) and mixed ma-
rine atmospheres, which also present SO2 pollution.
Pure Marine Atmospheres — In these types of at-
mospheres, characterized by the presence of only
chloride pollution, four groups can be differentiated.
The first three are distinguished according to their
atmospheric salinity level, from lesser to greater S1P0,
S2P0, and S3P0, in accordance with ISO 9223;14 and
the fourth group is reserved for Antarctic atmospheres,
in view of their singular climatic characteristics.
Group S1P0, in which atmospheric salinity re-
mains <60 mg Cl–/m2 per day, comprises 15 test
sites. Table 3 orders them on the basis of increasing
atmospheric salinity. Observation of the table shows
the existence of two classes of atmospheres:
—Inland marine atmospheres are those whose
atmospheric salinity remains below a threshold
value, ~20 mg Cl–/m2 per day, and which geographi-
cally cannot be catalogued as marine because of their
long distance from the sea, even though they present
a certain chloride content (Melo, El Pardo, Caratinga,
Pego, Labastida, Sabanilla, and Matanzas).
—Coastal marine atmospheres have salinities of
>20 mg Cl–/m2 per day and correspond to test sites
located closer to the shoreline (Barcelona,V, Acapulco,
San Cristóbal, Coro, Punto Fijo, Puntarenas, Salinas,
and Camet).
In inland marine atmospheres, the species
formed as corrosion products are basic sulfates—
posnjakite, brochantite, and langite
(Cu4SO4[OH]6·2H2O)—as well as cuprite, as in the
rural atmospheres, while the predominant species in
the latter is atacamite (copper-basic chloride), which
may coexist with copper-basic sulfates.
The corrosion rate for the first year of exposure
in inland marine atmospheres is similar to that noted
for rural atmospheres (i.e., <2 µm/y), while copper
attack slightly increases in the coastal marine atmo-
spheres with corrosion rates generally between
2 µm/y and 3 µm/y. In both types of atmospheres,
the soluble salt contents (chlorides and sulfates) re-

CORROSION–Vol. 57, No. 11 975

CORROSION SCIENCE SECTION
FIGURE 4. XPS corresponding to copper surface before atmospheric
exposure.
main generally high because of the porous structures
of the corrosion products formed in these atmospheres,
thus facilitating retention of atmospheric pollutants
and impeding their being washed off by rainwater.
As exposure time increases, copper surfaces be-
come covered with corrosion products, which grow in
a disorderly manner, apparently closing the structure
of the layer, though with numerous imperfections
that impede the development of compact and thus
protective films (the ratio between the corrosion rates
after 4 years and after 1 year of atmospheric expo-
sure is of the order of 0.7). This packing of the struc-
ture occurs first in the coastal marine atmospheres
because of the greater formation of corrosion prod-
ucts in these types of atmospheres. However, the cor-
rosion product layers are liable to crack and become
detached as a result of their poor internal adhesion.
In S2P0 and S3P0 marine atmospheres, where
atmospheric salinity levels are within the range of
60 mg Cl–/m2 per day to 300 mg Cl–/m2 per day and
300 mg Cl–/m2 per day to 1,500 mg Cl–/m2 per day,
respectively (Tables 4 and 5), the observations made
for S1P0 coastal marine atmospheres are fully con-
firmed, the only difference being that the copper at-
tack increases even more (corrosion rates of >3 µm/y).
In Figure 8, the variation of the first-year copper
corrosion rate with salinity in pure marine atmo-
spheres is shown. It must be pointed out that copper
corrosion in atmospheres with salinities of <20 mg
Cl–/m2 per day is close to copper corrosion in rural
atmospheres (an average of 0.77 µm/y). Salinities
>20 mg Cl–/m2 per day notably accelerate copper
attack.
The greater formation of atacamite in these at-
mospheres, in the form of cotton balls with some-
what amorphous textures growing on the underlying
cuprite film and becoming coarser in size as expo-
sure time increases (Figure 9[b]), leads the copper
surface to become totally covered, forming layers of
976
(a)
(b)
FIGURE 5. (a) SEM micrograph showing the discontinuous formation
of cuprite on the copper surface after 1 year of exposure in the Arties
atmosphere and (b) SEM/EDS of the copper surface after 3 years of
exposure in the Arties atmosphere.
great thickness (Figure 9[c]). These corrosion product
layers, even when highly imperfect and with great
internal porosity, provide a certain protective effect
for the base copper, with attack decay ratios close
to 0.6.
Antarctic atmospheres (Table 6) present singular
characteristics that distinguish them from the
marine atmospheres previously considered. These
singular characteristics are related to the purity of
the air, the absence of rainfall in these frozen cli-
matic conditions, and the formation of ice on the
metallic surface during an important part of the
exposure time.
Because of air purity, only basic copper chlorides
are formed (basically atacamite), without the coexist-
ence of basic copper sulfates (brochantite and
posnjakite) as would occur in other atmospheres
somewhat impurified by SO2, giving rise to the forma-
tion of patinas of a pleasant blue-turquoise coloring.
On the other hand, the absence of rainfall to wash off
the salts from the marine aerosol deposited on the
metallic surface favors the rapid precipitation of ba-
sic chlorides, and the surface soon becomes covered
CORROSION–NOVEMBER 2001

FIGURE 6. First-year copper corrosion rate vs air temperature in
rural (S0P0) atmospheres.
with corrosion products. During the first year of
exposure, a large percentage of the copper surface
already becomes covered with atacamite.
In principle, it seems surprising to find a rela-
tively low copper corrosion rate (≈2 µm/y) in these
atmospheres, in comparison with other atmospheres
of similar atmospheric salinity. However, considering
that electrochemical activity on the copper surface is
impeded (or at least reduced) by the formation of ice
during a considerable part of the exposure time, the
lower corrosivity of these atmospheres for copper
could be justified.
Mixed Marine Atmospheres — These are marine
atmospheres that present both chloride and SO2 pol-
lution. They are presented in Tables 7 through 10 in
order of lesser to greater copper corrosivity.
In the case of S1P1 atmospheres, with a low con-
centration of both pollutants (Table 7), most are situ-
ated in the lower zone of atmospheric salinity,
catalogued previously as inland marine atmospheres
because of their distance from the sea. Only the
Peruvian test sites of San Borja and V.Salvador
(S > 20 mg Cl–/m2 per day) can be described as
coastal marine atmospheres.
The S1P1 inland marine atmospheres present
a copper corrosivity in the interval 0.7 µm/y to
1.4 µm/y, similar to the equivalent atmospheres
polluted only by chlorides (S1P0) or sulfates (S0P1),
CORROSION–Vol. 57, No. 11
CORROSION SCIENCE SECTION
FIGURE 7. First-year copper corrosion rate vs air relative humidity
in rural (S0P0) atmospheres.
while the S1P1 coastal marine atmospheres present a
somewhat higher copper corrosivity (1.5 µm/y to
2.0 µm/y). In both types of atmospheres, the first
species to form as corrosion products are basic chlo-
rides rather than basic sulfates. With exposure time,
both species (basic chlorides and sulfates) coexist,
helping to more rapidly close the initially open struc-
ture of the corrosion product layers, and low decay
ratios (close to 0.5) are found.
In the case of S1P2 atmospheres (Table 8), with a
low chloride content but considerable SO2 pollution,
the copper corrosion rate increases notably (1 µm/y
to 7 µm/y). The presence of both pollutants (Cl– and
SO2) leads to the abundant formation of basic salts,
both sulfates (brochantite) and chlorides (atacamite),
which noticeably compact the corrosion product
layers (decay ratios close to 0.6).
Within this group of atmospheres, special men-
tion is made of the Río de Janeiro test site, which, in
addition to SO2 pollution, presents non-negligible
concentrations of H2S because of its proximity to a
swamp area. As is known, this compound promotes
significant copper attack, and thus it is not surpris-
ing that copper in this atmosphere shows a corrosion
rate of 7 µm/y in the first year of exposure. The col-
oring of the patina also reflects the presence of the
sulfide ion (S2–), acquiring blackish tones after the
second year of exposure as a result of the black color
977
CORROSION SCIENCE SECTION

(a)

FIGURE 8. First-year copper corrosion rate vs Cl– deposition rate in

marine (S1P0, S2P0, S3P0, and S4P0) atmospheres. In the graph, the
average value of corrosion rate in rural atmospheres (V ) is shown. (b)

of copper sulfides; chalcocite (Cu2S) is detected

among the corrosion products. This simultaneous
presence of H2S reinforces the sulfur peak (Figure
10[b]), minimizing to a certain extent the action of
Cl– and preventing it from forming corrosion prod-
ucts, which never include basic chlorides. In the
micrographs shown in Figure 10, it is possible to see
the great formation of brochantite in the first year of
exposure, growing from the new surface created by
the cuprite layer. This strong growth of brochantite
causes some cracking and detachment of the layer, (c)
as can be seen in the surface and cross-sectional
micrographs shown in Figures 10(a) and (c).
The S2P1 atmospheres (Table 9) include the
marine test sites of Sines, Isla Naval, and Cojimar,
which also present some SO2 pollution. The corrosion
rate in the first year of exposure is high, 2 µm/y to
5 µm/y, of the order of that found in S2P0 atmo-
spheres. The presence among the corrosion products
of basic chlorides (atacamite and tolbachite) and ba-
sic sulfates (langite and copper [II] sulfate) promotes
the formation of patinas with emerald green color-
ings. The formation of atacamite needles can be
clearly observed in the corrosion product layers
formed on copper in the atmosphere of Sines, along
with the preponderance of the chlorine peak over the
sulfur peak in the corrosion products formed, which
(d)
leads to significant pitting of the base metal resulting
from the presence of chlorides at the copper surface/ FIGURE 9. SEM/EDS results obtained on copper exposed in S2P0
corrosion product interface. MICAT atmospheres: (a) Arraial do Cabo (3 years), (b) Ubatuba
(4 years), (c) Tablazo (3 years), and (d) x-ray mapping for Cl
In the case of S2P2 atmospheres, the only test
corresponding to (c).
site considered in the MICAT project is Leixões (Table

978 CORROSION–NOVEMBER 2001


(a)
(c)
FIGURE 10. SEM/EDS results obtained on copper after 1 year of exposure in the Río de Janeiro S1P2 atmosphere:
(a) surface view, (b) EDS spectrum corresponding to (a), (c) cross-sectional view, and (d) x-ray mapping for S corresponding
to (c).
10). This is an atmosphere with notable Cl– and SO2
pollution, and which presents high copper corrosivity
(4.32 µm/y). After the first year of exposure, there is
a significant formation of corrosion products on the
copper surface, preferentially basic chlorides
(paratacamite), and, with exposure time, the forma-
tion of basic sulfates (posnjakite) is also detected,
which subsequently evolve to copper (II) sulfate. The
abundant initial formation of corrosion products,
covering all of the copper surface, provides a certain
protective effect, and the corrosion rate is reduced to
half after the second year of exposure (decay ratio
close to 0.5).
Figure 11 shows a three-dimensional diagram
on first-year copper corrosion as a function of the
atmospheric pollution by Cl– and SO2, built with the
results obtained in the MICAT project by means of a
commercial computer software.
CORROSION–Vol. 57, No. 11
CORROSION SCIENCE SECTION
(b)
(d)
CONCLUSIONS
Rural Atmospheres
❖ In rural atmospheres, annual copper corrosion can
vary greatly. This research shows values ranging
from 0.09 µm/y (Cuzco) to 1.94 µm/y (Porto Velho).
High T and RH of the atmospheric air seem to inten-
sify copper corrosion in these atmospheres.
❖ Cuprite forms discontinuously on the copper sur-
face, giving rise to open structures that do not close
completely after 4 years of exposure. The corrosion
product layers present low compactness and high
fragility. The open structures facilitate retaining
background atmospheric pollution and sedimentable
particles, and detecting copper hydroxysulfates and
hydroxychlorides among the corrosion products is
common in the first years of exposure.
❖ Patinas formed on copper change very quickly and
979
CORROSION SCIENCE SECTION
FIGURE 11. Three-dimensional diagram of first-year copper
corrosion as a function of atmospheric chloride and SO2 pollution.
vary from almost salmon-pink (atmospheres with low
aggressiveness to copper) to dull brown and black, or
nearly so, darkening with exposure time.
Pure Marine Atmospheres
❖ A critical threshold for atmospheric salinity, ~20 mg
Cl–/m2 per day, seems to differentiate copper behavior
in these types of atmospheres. Below the threshold,
copper behaves as in rural atmospheres with corrosion
rates of <2 µm/y. Above the threshold, copper corro-
sion accelerates notably with atmospheric salinity.
❖ Copper hydroxysulfates are frequently detected in
the corrosion product layers, accompanying the basic
copper chlorides typical of these types of atmospheres.
❖ The coloring of patinas ranges from brown (as in
the case of rural atmospheres) to turquoise-blue
(Antarctic atmospheres with no SO2 pollution) and
emerald-green (conditions of high atmospheric salin-
ity and SO2 background contamination levels).
Mixed Marine Atmospheres
❖ Copper corrosion also accelerates in these types of
atmospheres after a critical threshold of 20 mg Cl–/m2
per day, increasing with Cl– and SO2 contents in the
atmosphere.
❖ Basic chlorides and sulfates coexist in the atmo-
spheric corrosion products. The threshold of 20 mg
Cl–/m2-d defines what will be the main constituent of
the patinas; below this value the predominant phase
is basic sulfates and above it basic chlorides.
❖ Patina color ranges from greenish shades (low
levels of atmospheric SO2) to dark brown-blackish or
almost black shades (high levels of atmospheric SO2).
980
ACKNOWLEDGMENTS
The authors acknowledge their colleagues in the
MICAT Working Group, namely L. Uller (Brazil), A.
Valencia (Colombia), J.F. Alvarez (Costa Rica), A.
Cabezas (Cuba), G. Joseph (Chile), J. Peña (Ecuador),
J. Uruchurtu (Mexico), A. Bosquez (Panama), G. Salas
(Peru), M. Ferreira (Portugal), S. Rivero (Uruguay),
and M.R. Prato and O.T. de Rincón (Venezuela). They
also wish to thank the CYTED Programme, CSIC
(Spain), and JNICT (Portugal) for financial support.
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