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Effect of Relative Humidity on Copper Corrosion by Acetic and Formic Acid

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 327

Canadian Metallurgical Quarterly, Vol 41, No 3 pp 327-336, 2002

© Canadian Institute of Mining, Metallurgy and Petroleum
Published by Canadian Institute of Mining, Metallurgy and Petroleum
Printed in Canada. All rights reserved

EFFECT OF RELATIVE HUMIDITY ON COPPER CORROSION

BY ACETIC AND FORMIC ACID VAPOURS
E. CANO and J. M. BASTIDAS

CENIM-National Centre for Metallurgical Research (CSIC),

Avda. Gregorio del Amo 8, 28040 Madrid, Spain

(Received February, 2001; in revised form February, 2002)

Abstract — A comparative study is made of the copper corrosion rate and corrosion products origi-
nated by acetic and formic acid vapours at 40%, 80% and 100% relative humidity (RH) using gravi-
metric, scanning electron microscopy, X-ray powder diffraction and X-ray photoelectron spec-
troscopy techniques. Five acetic and formic acid vapour concentration levels (10, 50, 100, 200 and
300 ppm) were tested for a period of 21 days at 30 °C. The copper corrosion rate in the presence of
acetic acid vapour was up to ~0.002 mg/cm2 day (mcd) for 40% RH, ~0.07 mcd for 80% RH and
~0.23 mcd for 100% RH. Formic acid vapours yielded a copper corrosion rate of up to ~0.005 mcd
for 40% RH, ~0.03 mcd for 80% RH and ~0.13 mcd for 100% RH. The main compounds found were
cuprite (Cu2O), copper hydroxide (Cu(OH)2), copper acetate (Cu(CH3COO)2) and copper formate
(Cu(HCOO)2).

Résumé — On fait une étude comparative du taux de corrosion du cuivre ainsi que des produits de
corrosion provenant des vapeurs d’acide acétique et formique à 40%, 80% et 100% d’humidité relative
(HR), utilisant des techniques gravimétriques, la microscopie électronique à balayage, la diffraction
aux rayons x de la poudre et la spectroscopie de photoélectron à rayons x. On a évalué cinq niveaux de
concentration de vapeur d’acide acétique et formique (10, 50, 100, 200 et 300 ppm) pendant 21 jours,
à 30 °C. Le taux de corrosion du cuivre en présence de vapeur d’acide acétique atteignait ~0.002
mg/cm2 jour (mcj) à 40% HR, ~0.07 mcj à 80% HR et ~0.23 mcj à 100% HR. Les vapeurs d’acide
formique ont résulté en un taux de corrosion du cuivre atteignant ~0.005 mcj à 40% HR, ~0.03 mcj à
80% HR et ~0.13 mcj à 100% HR. Les principaux composés obtenus incluaient le cuprite (Cu2O),
l’hydroxyde de cuivre (Cu(OH)2), l’acétate de cuivre (Cu(CH3COO)2) et le formate de cuivre
(Cu(HCOO)2).

INTRODUCTION Organic acids from synthetic lubricant oils are a source

Corrosion of copper can be caused by volatile organic sub-
stances such as acetic and formic acids. The severity of
this type of corrosion increases as the number of carbon
atoms in the alkyl chain (acid strength) decreases in the
order C4 < C3 < C2 < C1 [1-4]. Volatile organic substances
are produced by many everyday substances such as vinegar
containing seasonings like vegetable oil dressing and grain
vinegar, cosmetics such as eau de cologne, adhesives from
synthetic building materials, woods and certain paints,
plastics, rubbers and resins which can cause the deteriora-
tion of metallic materials [5-7]. Insecticides are also sus-
pected to be corrosive agents [2]. Organic acid anions con-
stitute about 0.1 to 1% of the total ion concentration in the
corrosion products (patina) on copper exposed to outdoor
atmospheres for long periods of time [8].
of failure in the manufacturing or joining of copper tubes
used in air conditioning, evaporating, refrigerating, heat
exchanger and solar systems where pitting corrosion has
been detected early in service and even during leakage tests
after installation and during degreasing and stamping
processes [5,9].
Controversy exists about the role played by relative
humidity (RH) in atmospheric copper corrosion. Vernon
reported 60% as the critical RH value below which copper
corrosion does not take place [10]. However, other authors
have reported copper corrosion at 35% and 50% RH
[11,12] and have shown copper mass loss values of 26.2 ¥
10–4, 23.4 ¥ 10–4 and 21.4 ¥ 10–4 mg/cm2 for 50, 70 and
90% RH, respectively [13]. On the other hand, some
authors indicate that copper loss at 70% RH (0.005

CANADIAN METALLURGICAL QUARTERLY

328 E. CANO and J. M. BASTIDAS
mg/cm2) was about half the value obtained at 90% RH
(0.012 mg/cm2) [14].
The aim of this work is to compare the corrosion rate and
the chemical composition of corrosion products generated
by copper exposure for a short period of time, 21 days, to
acetic and formic acid vapours in laboratory experiments at
40%, 80% and 100% RH. The corrosion rate was studied
using a gravimetric method at a controlled vapour pressure
of acid. The copper surfaces were analyzed using X-ray
photoelectron spectroscopy (XPS), scanning electron
microscopy (SEM) and X-ray powder diffraction (XRD)
techniques to elucidate the influence of acetic and formic
acid vapour contamination levels on the atmospheric cop-
per corrosion mechanism at 30 °C.
EXPERIMENTAL
The copper used had the following chemical composi-
tion (% mass): 0.009 Sn, < 0.001 As, < 0.001 Bi, 0.003
Ni, < 0.001 Fe, 0.015 Pb, < 0.001 Mn, 0.019 P, < 0.0005
Ag, < 0.001 S, < 0.005 C, < 0.002 Sb, < 0.001 Al with
the balance being Cu. The copper was phosphorus
deoxidized and had a low residual phosphorus content
(type Cu-DLP, ISO/R Standard 1337).
The specimens were mechanically cut from a sheet 1.0
mm thick and their surfaces were hand polished with emery
paper down to grade 600, degreased with acetone, rubbed
with cotton wool soaked in ethanol, dried at room temper-
ature and tested immediately. The morphological aspect of
the copper surface after cleaning is shown in Figure 1.
The experimental procedure has already been described
elsewhere [4,15,16]. Corrosive environments were gener-
ated in an airtight 2.4 L glass vessel. The concentration of
the acids in vapour phase was considered to be proportion-
10 mm
Fig. 1. General morphology of the copper surface after cleaning.
CANADIAN METALLURGICAL QUARTERLY
al to the concentration in an aqueous solution of the acid
according to Raoult’s law. Five aqueous solutions were
prepared for each acid: from 0.58 g/L to 17.65 g/L for
acetic acid and from 0.23 g/L to 6.95 g/L for formic acid to
obtain vapour concentration from 10 to 300 ppm.
The RH was achieved by placing 350 mL of a satu-
rated aqueous salt solution, according to ASTM Standard
E-104, in the bottom of an airtight 2.4 L glass vessel. A
dihydrated potassium carbonate (K2CO3◊2H2O) solution
was used for ~43% RH and an ammonium chloride
(NH4Cl) solution for ~78% RH [17]. The RH of ~100%
was obtained by placing 350 mL of distilled water in the
bottom of the airtight glass vessel.
The copper specimens were placed on a perforated
ceramic grill situated above the saturated aqueous salt solu-
tion or distilled water used for humidity control.
Five vapour concentrations (10, 50, 100, 200 and 300
ppm) were studied for both acetic and formic acids. The
vapour concentration of acetic or formic acid was obtained
by placing a glass vessel with 100 mL of a solution con-
taining the appropriate amount of glacial acetic acid
(Merck) or 85% formic acid (Merck) on the perforated
ceramic grill. The temperature was maintained at 30 ± 1 °C
during the experiments by immersing the airtight glass ves-
sel in a thermostatically controlled water bath. After 21
days, the specimens were analyzed using gravimetric, XPS,
SEM and XRD methods.
Gravimetric studies were carried out using specimens
of 50 cm2 surface area and taking measurements at the
beginning of the experiments and at the end following the
removal of the corrosion products using an undeaerated
10% H2SO4 aqueous solution for 3 minutes at room tem-
perature in accordance with ASTM Standard G-1. All the
experiments were performed in triplicate; the gravimetric
corrosion rate is listed as an average value of three speci-
mens studied under identical experimental conditions. The
reproducibility of the experimental gravimetric results was
higher than 95%. An electronic analytical balance with a
precision of ± 0.1 ¥ 10–3 g was used.
XRD analysis was conducted on solid phases formed
on the copper surface employing a Siemens D-500 diffrac-
tometer with monochromatic Cu Ka1.2 radiation. XRD
analyses were performed on the copper specimens exposed
to 100% RH.
XPS analysis was carried out using a VG Microtech
model MT 500 spectrophotometer with an Mg Ka1.2 anode
X-ray source (hn = 1253.6 eV) with a primary beam energy
of 1.5 kV and an electron current of 20 mA. The pressure in
the analysis chamber was maintained at 1 ¥ 10–9 Torr
throughout the measurements. The regions of interest were
C 1s, O 1s and Cu 2p3/2. The instrumentation was calibrated
 EFFECT OF RELATIVE HUMIDITY ON COPPER CORROSION BY ACETIC AND FORMIC ACID VAPOURS 329

periodically using Ag 3d5/2 (368.3 eV) and Au 4f7/2 (84.0 eV)

substrates. The spectra were integrated for 20 scans. The
XPS spectra were analysed by a least squares fit in order to
obtain more information about the chemical states. The
peaks were fitted using a Gaussian/Lorentzian product func-
tion. XPS analyses were carried out on the copper specimens
exposed to 40% and 80% RH, where the amount of corro-
sion products was not enough to conduct XRD analysis.

SEM morphological observation was recorded using a

JEOL JXA-840 unit. Conducting specimens for SEM were
prepared by gold sputtering the copper plates.

RESULTS

Figure 2 reports the corrosion rate estimated from gravimet-

ric data, expressed as mg/cm2 day (mcd), for copper speci-
mens exposed to the action of acetic or formic acid vapour
(10, 50, 100, 200 and 300 ppm) for 21 days experimentation
at 40%, 80% and 100% RH and 30 ºC temperature. The cop-
per corrosion rate in the presence of acetic acid vapour was
in the range of 8 ¥ 10–4 to 17 ¥ 10–4 mcd at 40% RH, of
11 ¥ 10–4 to 653 ¥ 10–4 mcd at 80% RH and of 82 ¥ 10–4 to
2250 ¥ 10–4 mcd at 100% RH. Formic acid vapour yielded a
higher copper corrosion rate than acetic acid vapour at 40%
RH for the five contamination levels studied and at 80% RH
for the 10, 50, 100 and 200 ppm levels which showed val-
ues in the range of 12 ¥ 10–4 to 55 ¥ 10–4 mcd for 40% RH
and of 44 ¥ 10–4 to 160 ¥ 10–4 mcd for 80% RH. Conversely,
the 300 ppm formic acid vapour level caused a copper cor-
rosion rate of 310 ¥ 10–4 mcd at 80% RH (653 ¥ 10–4 mcd
for acetic acid vapour) (Figure 2). Finally, at 100% RH,
formic acid vapour originated a copper corrosion rate in the Fig. 2. Copper corrosion rate estimated from gravimetric method
range of 56 ¥ 10–4 to 1290 ¥ 10–4 mcd. against acetic or formic acid content in the air and RH after 21
days exposure at 30 °C.
It can be observed (Figure 2) that for 40% RH, the pres-
ence of 10, 50 and 100 ppm acetic acid vapour contamina-
tion occasioned a similar copper corrosion rate of the order 300 ppm acetic acid vapour are dihydrate copper acetate
of 10 ¥ 10–4 mg/cm2 day, but in the presence of 200 and 300 (Cu(CH3COO)2◊2H2O) as the main component and cuprite
ppm acetic acid vapour, the copper corrosion rate increased (Cu2O). For 50 and 100 ppm acetic acid vapour, a third
slowly. At 80% and 100% RH, it can be seen that the cop- phase can be observed which may be attributed to copper
per corrosion rate increased with the increase in acetic acid hydroxide acetate (Cu(OH)(CH3COO)2◊2H2O) [15]. The
vapour concentration. At 100% RH, there seems to be an XRD patterns for specimens exposed to 50 and 100 ppm
acetic acid vapour contamination threshold (200 ppm) formic acid vapour show the presence of copper hydroxide
above which the copper corrosion rate stabilizes. In the hydrate (Cu(OH)2◊H2O) and cuprite. As can be observed, a
case of formic acid vapour, the copper corrosion rate third, not well crystallised phase started to form at these
increased with the increase in formic acid vapour content in formic acid vapour levels. This phase might consist of cop-
the air at 40%, 80% and 100% RH. As with acetic acid per hydroxyformate (Cu(OH)(HCOO)) formed as an inter-
vapour, at 100% RH, formic acid vapour originated the sta- mediate reaction product (see discussion below). The main
bilization of copper corrosion above the 200 ppm value. component of the 300 ppm specimen is copper formate.
Peaks corresponding to a cuprite decrease as the formic
Figure 3 shows representative XRD patterns recorded acid vapour level increases from 100 to 300 ppm. A similar
from 10 to 60 2q degrees for copper specimens exposed to evolution is observed with copper hydroxide, in the pattern
the action of acetic or formic acid vapour (50, 100 and 300 corresponding to a copper specimen exposed to 300 ppm
ppm) at 100% RH for 21 days experimentation. The crys- formic acid vapour, in which diffraction maxima for that
talline phases observed on the copper specimens exposed to phase are hardly observed.

CANADIAN METALLURGICAL QUARTERLY

330 E. CANO and J. M. BASTIDAS
Fig. 3. XRD patterns for copper exposed to acetic and formic acid
vapours at 100% RH after 21 days exposure; c = cuprite, h = cop-
per hydroxyacetate and y = copper hydroxide. Unlabelled peaks
correspond to copper acetate in the acetic patterns and to copper
formate in the formic patterns.
Since the amount of corrosion products originated at
40% and 80% RH was not enough to conduct XRD analy-
ses, XPS experiments were carried out at these RH levels.
Table I depicts XPS results recorded for copper specimens
exposed to 10, 100 and 300 ppm at 40% RH and 10 and
300 ppm at 80% RH acetic acid vapour and 10, 100 and
300 ppm formic acid vapour at 80% RH for 21 days of
exposure. XPS spectra identified copper acetate, cuprite,
copper hydroxide and copper formate as the main com-
pounds.
Copper specimens exposed to 100 ppm acetic acid
vapour at 40% RH show an important peak corresponding
to copper acetate. Besides copper acetate, the copper spec-
trum shows the presence of copper hydroxide and cuprite.
Corrosion products found in copper specimens exposed to
300 ppm acetic acid vapour at 40% RH are similar to the
CANADIAN METALLURGICAL QUARTERLY
previous specimens (100 ppm) except for the absence of
copper hydroxide. Copper specimens exposed to 10 ppm
acetic acid vapour at 80% RH show some differences com-
pared with 40% RH [18]. Both specimens present only a
very small amount of acetate. Nevertheless, the main com-
pound in the 80% RH specimen is cuprite with a smaller
contribution from copper hydroxide. For 100 ppm acetic
acid vapour the XPS spectra show a widening in the low
binding energy (BE) region due to differential charging
phenomena. For this reason, 100 ppm at 80% RH spectrum
was not fitted [19].
The patina on copper specimens exposed to 10, 100 and
300 ppm formic acid vapours at 40% RH is constituted by
a thin layer of cuprite, which is not charged by the action of
X-rays. On some local zones voluminous corrosion prod-
ucts, principally copper hydroxide and copper formate, are
formed. The compounds are charged by the action of X-rays
which cause a splitting of the peaks in the XPS spectra and
for this reason were not included in Table I.
In general, the results obtained at 80% RH show that
cuprite, copper hydroxide and copper formate constituted
the corrosion products. As the formic acid vapour contam-
ination level increases, the amount of copper hydroxide
decreases and the amount of cuprite and copper formate
increases. This behaviour is similar to that of copper spec-
imens at 40% RH. However, unlike at 80% RH, the corro-
sion products are formed by a uniform layer and charging
processes were not observed.
Figures 4, 5 and 6 show typical SEM morphological
aspects for copper specimens exposed to 10, 100 and 300
ppm acetic acid vapour, respectively, at a) 40%, b) 80%
and c) 100% RH. For 10 ppm acetic acid vapour, Figure 4a
shows small corroded dark areas without a defined struc-
ture surrounded by larger clean areas of a light colour.
Figure 4b shows that the corrosion process increases as the
RH increases presenting an agglomerate of cuprite crys-
tals. Corrosion starts in the deepest polished lines where
water is more easily retained. Finally, Figure 4c shows that
at 100% RH, the corrosion products cover all the surface
and follow the orientation of the polished surface. For 100
ppm acetic acid vapour, Figure 5a shows that the corrosion
process increases as the acetic acid vapour concentration
rises as compared with Figure 4a and cuprite crystals can
be observed on the copper surface. Figure 5b shows small
uncorroded areas surrounded by bulky corrosion products
consisting of cuprite and copper acetate crystals. Figure 5c
shows an agglomerate of corrosion products with plate-
like crystals of copper acetate developed over prisms of
copper hydroxide acetate. For 300 ppm acetic acid vapour,
Figure 6a shows small corroded white areas surrounded by
larger uncorroded areas. Figure 6b shows that corrosion
products cover all the copper surface. Figure 6c shows cor-
rosion products (copper acetate) covering all the copper
surface. In some zones, it is possible to observe large
 EFFECT OF RELATIVE HUMIDITY ON COPPER CORROSION BY ACETIC AND FORMIC ACID VAPOURS 331

Table I – XPS results for copper exposed to acetic and formic acid vapours (ppm) at 40% and 80% RH for
21 days: main peak (element), position (binding energy) and compound.

RH,% ppm Element Position, eV Compound

Acetic acid vapour

C 1s 284.6, 286.1, 287.6m, 288.4m Cuprite, copper hydroxide,

10 O 1s 531.5, 533.0, 529.9 hydrocarbon contamination,
Cu 2p3/2 933.9, 934.2, 934.4m copper acetatem

C 1s 284.6, 288.4, 286.1m, 287.6m Cuprite, copper hydroxide,

40 100 O 1s 531.5, 533.0, 529,8 copper acetate, hydrocarbon
Cu 2p3/2 934.4, 933.9, 935.5 contamination

C 1s 284.6, 288.4, 286.1 Copper acetate, cupritem,

300 O 1s 531.5, 533.0m, 529.8m
hydrocarbon contamination
Cu 2p3/2 934.2, 932.4

C 1s 284.6, 286.1m, 287.6m, 288.4m Cuprite, copper hydroxide,

10 O 1s 531.5, 529.7, 533m copper acetatem, hydrocarbon
Cu 2p3/2 932.4, 933.8, 934.4m contamination
80
C 1s 284.6, 286.1, 287.6m, 288.4m
Copper acetate, cuprite,
300 O 1s 531.4, 529.4, 533.0m.
hydrocarbon contamination
Cu 2p 3/2 934.2, 933.7, 932.5

Formic acid vapour

C 1s 284.6, 288.3, 286.1m, 287.6m Copper hydroxide, copper

10 O 1s 531.6, 529.9, 533m formate, cuprite, hydrocarbon
Cu 2p3/2 934.4, 933.9, 932.4 contamination

C 1s 284.6, 288.3, 286.1m, 287.6m Copper formate, copper

80 100 O 1s 531.6, 529.8, 533m hydroxide, cuprite, hydrocarbon
Cu 2p3/2 934.3, 933.8, 932.3 contamination

C 1s 284.6, 288.4, 286.1m Cuprite, copper formate,

300 O 1s 531.6, 529.4, 533.0m copper hydroxidem, hydrocarbon
Cu 2p3/2 932.3, 934.2, 933.7m contamination

m: minor component

cuprite crystals (see arrow) arising between the copper
acetate crystals.
Figures 7, 8 and 9 show representative SEM morpholog-
ical aspects for copper specimens exposed to 10, 100 and
300 ppm formic acid vapour, respectively, at a) 40%, b) 80%
and c) 100% RH. For 10 ppm formic acid vapour, Figure 7a
shows the general appearance of the copper surface. It can be
observed that blisters of corrosion products appear on the
copper surface. Figure 7b shows that the corrosion process
increases as the RH increases covering all the surface with a
layer of corrosion products without a defined structure.

CANADIAN METALLURGICAL QUARTERLY

332 E. CANO and J. M. BASTIDAS

Finally, Figure 7c shows that the corrosion process has covered with corrosion products following surface polishing
spread farther over the copper surface. Corrosion products lines. Figure 8b shows that the corrosion process increases
have grown on certain local areas. For 100 ppm formic acid as the RH increases (Figure 8a). Figure 8c shows that corro-
vapour, Figure 8a shows that the copper surface is totally sion products, consisting of well formed crystals cover all

(a) (a)

10 mm 1 mm

(b) (b)

10 mm 10 mm

(c) (c)

10 mm 10 mm
Fig. 4. SEM micrographs for copper exposed to 10 ppm acetic Fig. 5. SEM micrographs for copper exposed to 100 ppm acetic
acid vapour at a) 40%, b) 80% and c) 100% RH, after 21 days acid vapour at a) 40%, b) 80% and c) 100% RH, after 21 days
exposure at 30 °C. exposure at 30 °C.

CANADIAN METALLURGICAL QUARTERLY

 EFFECT OF RELATIVE HUMIDITY ON COPPER CORROSION BY ACETIC AND FORMIC ACID VAPOURS 333

the copper surface. For 300 ppm formic acid vapour, Figure arrow) seems to develop from cuprite deposition (see the
9a shows corrosion products spreading over all the surface. dissolution precipitation mechanism below). Finally, Figure
Figure 9b shows that as the RH increases, layers of different 9c shows corrosion products consisting of a bubble-like and
corrosion products cover the surface. Copper formate (see smooth surface layer.

(a) (a)

10 mm 100 mm

(b) (b)

1 mm 10 mm

(c) (c)

10 mm 10 mm
Fig. 6. SEM micrographs for copper exposed to 300 ppm acetic Fig. 7. SEM micrographs for copper exposed to 10 ppm formic
acid vapour at a) 40%, b) 80% and c) 100% RH after 21 days acid vapour at a) 40%, b) 80% and c) 100% RH, after 21 days
exposure at 30 °C. exposure at 30 °C.

CANADIAN METALLURGICAL QUARTERLY

334 E. CANO and J. M. BASTIDAS

(a) (a)

10 mm 10 mm

(b) (b)

10 mm 10 mm

(c) (c)

1 mm 10 mm

Fig. 8. SEM micrographs for copper exposed to 100 ppm formic Fig. 9. SEM micrographs for copper exposed to 300 ppm formic
acid vapour at a) 40%, b) 80% and c) 100% RH, after 21 days acid vapour at a) 40%, b) 80% and c) 100% RH, after 21 days
exposure at 30 °C. exposure at 30 °C.

CANADIAN METALLURGICAL QUARTERLY

 EFFECT OF RELATIVE HUMIDITY ON COPPER CORROSION BY ACETIC AND FORMIC ACID VAPOURS
DISCUSSION
The copper corrosion rate depends on the acetic or formic
acid vapour concentration level and on the RH (Figure 2).
Thus, for 40% RH with 10, 50, 100, 200 and 300 ppm of
formic acid vapour concentrations the copper corrosion rate
is higher than with acetic acid vapour. Similar behaviour
can be observed for 10, 50, 100 and 200 ppm formic acid
vapour at 80% RH as compared with acetic acid vapour
(Figure 2). Conversely, 300 ppm acetic acid vapour at 80%
RH yielded a higher copper corrosion rate than formic acid.
At 100% RH formic vapour occasioned a lower copper cor-
rosion rate than acetic vapour.
The higher corrosion rate originated by formic acid
vapour at the lower RH and pollution levels (40% RH and
80% RH with 10, 50, 100 and 200 ppm contamination) as
compared with acetic acid vapour may be explained on the
grounds of their dissociation constants in aqueous solution:
1.77 ¥ 10–4 at 25 °C for formic acid and 1.76 ¥ 10–5 at 25 °C
for acetic acid [16].
On the other hand, with high RH and pollution levels
(300 ppm acetic acid vapour at 80% RH and with 10, 50,
100, 200 and 300 ppm at 100% RH), the corrosion rate was
influenced by the nature of the corrosion products of acetic
or formic acid. In the presence of formic acid vapour, the
corrosion product layer was very compact and adherent.
However, in the presence of acetic acid vapour the corro-
sion product layer was non-uniform and porous (Figures 5
and 6). This may explain why formic acid vapour gave a
lower copper corrosion rate than acetic acid vapour. These
results agree with the literature for the case of mild steel
vapour phase corrosion [4,7].
Patina formed at different depths shows a stratified
structure from the inner interface to the outermost interface
with Cu2O/CuO/Cu(OH)2 or CuO·xH2O in the inner layer
[15,19-22].
When copper is exposed to 40%, 80% and 100% RH,
the water vapour adsorbed causes a corrosion process start-
ing at local surface defects and this process may be cat-
alyzed by acetic or formic acid. The first reaction taking
place is
4Cu + O2 + 4H+ Æ 4Cu+ + 2H2O (1)
The copper (I) must be oxidized to form copper hydroxide
hydrate (Cu(OH)2◊2H2O),
4Cu+ + O2 + 4H+ Æ 4Cu2+ + 2H2O (2)
Copper acetic acid vapour corrosion products may be
explained by the following mechanism where copper
acetate is formed from copper hydroxide present on the sur-
face.
335
The presence of hydroxide or hydrated oxide on the
copper surface provides a building block for the formation
of basic copper acetate. The formation of copper acetate
may be preceded by copper hydroxide acetate
4Cu(OH)2
+ 7CH3COOH Æ Cu4(OH)(CH3COO)7◊2H2O (3)
+ 5H2O
This copper hydroxide acetate evolves to form copper
acetate under the atmospheric conditions of high concen-
tration of acetic acid by the reaction
Cu4(OH)(CH3COO)7◊2H2O
+ CH3COOH Æ 4Cu(CH3COO)2·2H2O + H2O (4)
the final constituents of the corrosion products being
cuprite and copper acetate [15].
For the case of formic acid vapour, as for acetic acid
vapour, the presence of hydroxide or hydrated oxide on the
initially exposed copper surface provides a building block
for the formation of copper formate. The formation of cop-
per formate may be as follows [16].
On local surface areas from Cu(OH)2◊H2O
Cu(OH)2 + 2HCOOH
(5)
+ H2O Æ Cu(HCOO)2 + 3H2O
However, at low formic acid concentrations, the formation
of copper hydroxyformate as intermediate reaction prod-
ucts may be considered according to reaction
Cu(OH)2◊H2O
(6)
+ HCOOH Æ Cu(OH)(HCOO) + 2H2O
An alternative mechanism in the presence of formic
acid vapour may be as follows. Copper formate spreads
across the copper surface from copper (I) ions, Equation 2
8Cu+ + 8HCOOH
(7)
+ O2 Æ 4Cu(HCOO)2 + 2Cu2O + 8H+
In summary, copper dissolution in the presence of acetic
acid vapour generates a patina through cuprite paths and in
the presence of formic acid vapour, the patina is formed via
an ion complex mechanism.
CONCLUSIONS
The copper corrosion rate in the presence of acetic acid
vapour (10, 50, 100, 200 and 300 ppm) was in the range of
8 ¥ 10–4 to 17 ¥ 10–4 mcd at 40% RH, of 11 ¥ 10–4 to 653
¥ 10–4 mcd at 80% RH and of 82 ¥ 10–4 to 2250 ¥ 10–4 mcd
at 100% RH for a period of 21 days at a temperature of 30 °C.
CANADIAN METALLURGICAL QUARTERLY
 336 E. CANO and J. M. BASTIDAS
Formic acid vapour, in the same experimental conditions
as acetic acid vapour, originated a copper corrosion rate
of 12 ¥ 10–4 to 55 ¥ 10–4 mcd at 40% RH, of 44 ¥ 10–4 to
310 ¥ 10–4 mcd at 80% RH and of 56 ¥ 10–4 to 1290 ¥ 10–4
mcd at 100% RH.
The main components of the patina were cuprite
(Cu2O), copper hydroxide (Cu(OH)2), copper acetate
(Cu(CH3COO)2) and copper formate (Cu(HCOO)2). At low
acetic or formic acid vapour concentration (10 ppm), the
corrosion process takes place on the adsorbed film and the
corrosion products are initially developed in a uniform
manner. As the acetic or formic acid concentration increas-
es (100-300 ppm), the copper hydroxide and copper acetate
or formate start to develop on local zones of the surface. In
the presence of acetic acid vapour, the copper dissolution
process generates a patina through porous cuprite paths.
Formic acid vapour generates the patina via an ion complex
mechanism involving copper hydroxide and/or formic acid
cuprous compounds.
ACKNOWLEDGEMENT
The authors express their gratitude to the Regional
Government of Madrid for financial support under Project
No. 07N/0043/1999.
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