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Corrosion of Copper and Lead by Formaldehyde, Formic and Acetic Acid

Vapours

Article  in  Studies in Conservation · December 2003

DOI: 10.1179/sic.2003.48.4.237

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 CORROSION OF COPPER AND LEAD BY FORMALDEHYDE, FORMIC AND ACETIC ACID VAPOURS 1

Corrosion of Copper and Lead by

Formaldehyde, Formic and Acetic
Acid Vapours
Jean Tétreault, Emilio Cano, Maarten van Bommel, David Scott, Megan Dennis,
Marie-Geneviève Barthés-Labrousse, Léa Minel and Luc Robbiola

The formation of corrosion products and the corrosion sensitivity of copper and lead were studied under experimental
conditions in which formaldehyde (methanal), formic (methanoic) and acetic (ethanoic) acid concentration, relative humidity
(RH) and duration of exposure were varied. Levels of formic acid above 0.4 parts per million based on volume (ppmv)
affect the appearance of copper at 75% RH, and at levels above 4 ppmv the copper gains weight at both 54 and 75%
RH. The main compound found on copper was cuprite, copper(I) oxide. Lead has a higher sensitivity to formic acid: at
levels as low as 0.04 ppmv lead becomes darker, and at above 0.1 ppmv weight gains were measurable at both 54 and
75% RH. In the presence of different levels of mixed carbonyl vapours at 75% RH, copper reacted mainly with formic
acid. On the other hand, the reaction of lead was more complex. Acetic acid tends to form a thick white layer (composed
mainly of plumbonacrite and possibly lead acetate compounds) on the lead surface, while formic acid tends to form a rather
thin and darker layer of lead formate hydroxide. In the presence of formic acid, the action of acetic acid on lead was
inhibited. At levels of formaldehyde up to 3 ppmv, no significant contribution of formaldehyde to the corrosion process on
lead and copper was observed.

INTRODUCTION investigated. The formation of corrosion products and

For the last two decades, there has been an increasing
interest in indoor air quality in museums and archives.
Reliable, sensitive monitoring techniques have been
developed for some carbonyls and better information
is available on the typical off-gassing of construction
products [1]. However, some pollutant–object inter-
actions have not yet been fully investigated. Many data
refer to the effect of carbonyls on metals, but few of
them were collected in conditions comparable to
museum and archive environments [2, 3].
The aim of this project was to gain a better
understanding of the tendency of copper and lead
to corrode within a few months in carbonyl-rich
environments — containing formaldehyde (meth-
anal), formic (methanoic) and acetic (ethanoic) acids
— frequently found in display or storage settings [1].
The ‘no observable adverse effect level’ (NOAEL) of
formic acid for these metals, the rate of film formation
above the NOAEL, and the nature of the film were
Received April 2003
the corrosion sensitivity of metals were studied at
different concentrations of carbonyls, relative humid-
ity (RH) and exposure duration. Humid carbonyl
environments were generated by carbonyl–water–salt
mixtures in glass jars. Metal coupons were suspended
above the mixtures for up to 135 days. The corrosion
of the metals was investigated by weight gain measure-
ment, colour measurement, scanning electron
microscopy (SEM), X-ray diffraction (XRD) and
X-ray photoelectron spectroscopy (XPS). Based on
the results, strategies for controlling the adverse effects
of carbonyls on copper and lead in enclosures can be
optimized.
EXPERIMENTAL METHODS
Two experiments were conducted to investigate the
corrosion behaviour of untarnished copper and lead
coupons in a humid carbonyl environment containing
formic acid alone (experiment 1) or mixtures of
formaldehyde, formic and acetic acids (experiment 2).
A third experiment was also conducted on lead in

S T U D I E S I N C O N S E R V A T I O N 4 8 ( 2 0 0 3 ) P A G E S 1– 6
2 J. TETRÉAULT, E. CANO, M. VAN BOMMEL, D. SCOTT, M. DENNIS, M.-C. BARTHÉS-LABROUSSE, L. MINEL AND L. ROBBIOLA

contact with a piece of particleboard to simulate the
conditions in a wooden display case or storage cabinet.
The methods used for sample preparation, generation
of the humid carbonyl environment and the analytical
method used to characterize the vapours are explained
in Appendices 1, 2 and 3 respectively. The exposure
conditions are summarized in Table 1.
exposure to a carbonyl mixture or a piece of particleboard
for 33 days. The comparison between exposure to a
synthetic atmosphere and the environment generated
by particleboard at a RH of 54, 75 or 100% was
investigated by weight measurement and by XRD.
Sample examination

Experiment 1: Effect of formic acid vapour concentration
The corrosion of copper and lead was conducted at
54 or 75% RH for 135 days with different concentra-
tions of formic acid. The exposed samples were
characterized every 28 days by weight and colour
measurements. Mineralized corrosion products were
also characterized by XRD after 108 days of exposure.
Experiment 2: Effect of different carbonyl pollutants
The atmospheric corrosion behaviour of copper and
lead was investigated at 75% RH for up to 135 days
using different mixtures of formic acid with formalde-
hyde and acetic acid. Weight measurements and XRD
were conducted as for experiment 1. Surface investi-
gations after 27 days of exposure were also performed,
using optical microscopy, SEM, XRD and XPS.
Experiment 3: Corrosion of lead in a synthetic carbonyl
environment or with particleboard
The formation of corrosion products on untarnished
and previously tarnished lead samples was studied by
For all the experiments, the corrosion products were
not powdery enough to fall off during handling. The
weight gain of the metal samples was obtained with a
Mettler balance (model AE163) with a measurement
accuracy of ±0.1 mg. The lightness (L*) of the samples
was measured every month with a Minolta chroma
meter (model CR-200) using the CIE L*, a*, b* colour
system. Three colour measurements were made for
each sample, but only the lightness parameter (L*)
is presented; the measurements have an accuracy of
±0.5 L*. To evaluate the nature of the corrosion films
after 27 days of exposure in experiment 2, the SEM
observations of the metal surface were conducted on
a Hitachi (model S-2500). The surface of these samples
was also analysed by small angle X-ray diffraction and
by XPS. XRD was conducted with an incidence of
0.5° at room temperature, using a Philips apparatus
with a Co source (Ka = 0.17902 nm), running at 30 mA
and 40 kV with a step of 0.035° (90 seconds per
step). X-ray photoelectron spectra were recorded at
normal angle with a CLAM 2 apparatus (Thermo VG
Scientific) using monochromatic Al Ka radiation (1486.6
eV); an ellipse of around 0.5 cm2 on the surface of the
sample was irradiated. The photoelectron spectra

Table 1 Summary of the experiments

Experiment Metal Na RH (%) Concentration range (ppmv)b Method of analysis

(exposure time prior to
analysis) c
1 copper 3 54 FA 0.6 - 40 W(p), C(p), XRD(108d)
75 FA 0.2 - 140
lead 3 54 FA 0.04 - 20
75 FA 0.04 - 40
2 copper 2 75 FA : AA : F 0 : 0.2 : 8 W(p), XRD(27d and 108d),
lead 2 0 : 0.2 : 11 XPS(27d), OM(27d),
0 : 0.6 : 3 SEM(27d)
d
3 lead 3 54, 75, 100 particleboard (FA: 0.2, AA: W(33d), XRD(33d)
<0.07, F: 0.9), carbonyl mix
(FA: 0.2, AA: 0.3, F: 0.6)

(a) Number of samples.

(b) Parts per million based on volume. FA: formic acid, AA: acetic acid, F: formaldehyde.
(c) W: weight measurement; C: colour measurement; OM: optical microscopy; p: periodic measurement, every 28 days up to 135 days; (27d,
33d, 108d): numbers of days of exposure in the dark and at 21.3 ± 0.7°C prior to sample analysis.
(d) Each vessel contains a sample of newly sanded lead, lead tarnished for five years, and lead tarnished for five years then scratched with a knife.

S T U D I E S I N C O N S E R V A T I O N 4 8 ( 2 0 0 3) P A G E S 1– 6
 CORROSION OF COPPER AND LEAD BY FORMALDEHYDE, FORMIC AND ACETIC ACID VAPOURS 3
were recorded using a step of 0.1 eV, looking at the
1s signal for carbon, the 1s and Auger KLL signals for
oxygen, the 3p, 3s, 2p and Auger LMM signals for
copper, and the 4f, 4d, and 5d signals for lead. The
binding energies of the photoelectron peaks were
referenced with respect to the carbon 1s level, which
was set at 285.0 eV. For experiments 1 and 2, other
metal surfaces were analysed, after exposure for 108
days, by XRD using a Siemens D5005 with Gobels
mirror in detection scan mode, running at 40 mA and
40 kV.
RESULTS
Experiment 1
Figures 1, 2 and 3 illustrate the formation of corrosion
layers on copper and lead at various concentrations of
formic acid. Figure 1 shows that an increase in the
Figure 1 Weight gain for copper exposed to different formic acid
concentrations over a period of 135 days at 54 or 75% RH, and
lightness changes measured at 75% RH.
S T U D I E S I N C O N S E R V A T I O N 4 8 ( 2 0 0 3 ) P A G E S 1– 6
concentration of formic acid has a strong effect on
the corrosion of copper. A significant weight gain
for copper samples is seen when the formic acid
concentration is higher than 2 ppmv. This behaviour
is observed after 27 days exposure at both 54 and 75%
RH. The film formation is accompanied by a surface
colour change, based on the lightness (L*) measure-
ment at 75% RH, confirming that at a concentration
above 0.4 ppmv the copper begins to react signifi-
cantly with formic acid. A thin brown/green layer is
formed on the copper surfaces. According to the
XRD analysis, this is possibly due to the presence of
a small amount of cuprite, copper(I) oxide; some grey
patches were also present. Above 14 ppmv, the copper
samples show whitish surface colours. Corrosion
compounds found on copper exposed at 14 and 140
ppmv were identified respectively as copper formate
and copper formate dihydrate; formulae for these
corrosion compounds are provided in Table 2.
Figure 2 Weight gain and lightness changes for lead exposed to
different formic acid concentrations over a period of 135 days at
54% RH.
4 J. TETRÉAULT, E. CANO, M. VAN BOMMEL, D. SCOTT, M. DENNIS, M.-C. BARTHÉS-LABROUSSE, L. MINEL AND L. ROBBIOLA
Figure 3 Weight gain and lightness changes for lead exposed to
different formic acid concentrations over a period of 135 days at
75% RH.
Figures 2 and 3 show the weight gain and lightness
change of lead samples exposed to various concentra-
tions of formic acid, at 54 and 75% RH respectively. At
54% RH (Figure 2), a significant weight gain for lead
samples occurs when the formic acid concentration
exceeds 0.1 ppmv. The rate of weight increase is
greatest over the first 27 days. After that, the rate of
formation of compounds slows down. The colour
measurement shows a change of lightness at the lowest
concentration studied (0.035 ppmv). At 1.5 and 8.8
ppmv, lead formate and lead hydroxide formate were
identified by XRD. At 75% RH (Figure 3), lead
showed a significant weight gain only above 0.35
ppmv. At 0.35 ppmv, mainly lead formate hydroxide
was identified. A maximum weight gain was achieved
after 54 days, with little or no further gain as exposure
was prolonged. Above 0.35 ppmv, most colour change
occurred in the first 27 days and the lead surface
showed greyish and bluish colours with a matt appear-
ance. It should be noted that the weight gain due to
S T U D I E S I N C O N S E R V A T I O N 4 8 ( 2 0 0 3) P A G E S 1– 6
the corrosion products does not strictly increase with
the concentration of formic acid: a maximum weight
gain occurs at about 1.5 ppmv of formic acid at either
54 or 75% RH.
Experiment 2
Tables 3 and 4 show the weight gain for lead and
copper after 135 days exposure to different mixtures of
formaldehyde, formic and acetic acids at 75% RH. The
nature of the corrosion products on some samples,
determined by XRD (including small angle), is also
included in the tables.
Table 3 shows that formaldehyde and acetic acid,
alone or present together with formic acid, are not
significantly involved in the corrosion of copper.
Copper appears visually untarnished in the absence of
formic acid or when a low concentration (0.2 ppmv)
is present, even though a thin film of cuprite was
identified for all the samples by both XRD and XPS
after 27 days of exposure. Furthermore a strong oxygen
1s signal at 531.8 eV was observed in the XPS spectra
in both cases, suggesting the presence of some
hydroxy–copper compounds normally formed in clean
indoor air. This type of compound has been detected
by XPS on copper exposed to an unpolluted environ-
ment at relative humidities between 40 and 80% [10].
After 135 days there were some areas of grey corrosion,
identified as tenorite, copper(II) oxide. At 8 ppmv of
formic acid, with or without other carbonyls, the
copper samples are covered by a thin layer of a matt,
dull green to grey film with some darker grey patches.
Cuprite was the most common corrosion compound
identified, as well as a trace of copper formate dihy-
drate. Copper acetate dihydrate was identified on a
sample exposed to high levels of carbonyls.
For lead, formaldehyde alone, or mixed with formic
and acetic acids, does not contribute significantly to
corrosion at 75% RH, as shown in Table 4. This is also
confirmed by the lead sample exposed for 27 days at
0.2 ppmv of formic acid; both XPS and XRD results
are similar with and without formaldehyde present in
the vapour phase. SEM examination (Figures 4b with
4c and 4d with 4e) further confirmed that formalde-
hyde has no significant effect on the corrosion process.
On the other hand, acetic acid plays a major role in the
formation of corrosion compounds on lead. Acetic
acid alone forms more corrosion than formic acid.
As shown in Figure 4f, after 27 days of exposure,
localized corrosion is well established in the
presence of 0.2 ppmv of acetic acid vapour, and the
 CORROSION OF COPPER AND LEAD BY FORMALDEHYDE, FORMIC AND ACETIC ACID VAPOURS 5

Table 2 Characteristics of copper and lead compounds found in this study

Name (synonyms) Formula ICDD No. Colour Water solubility Ref.

(g per 100 ml)a
Copper acetate hydrate Cu(CH 3CO 2) 2·H 2O 27–0145 dark green 7.2 4
Copper formate Cu(CHO 2) 2 14–0708 blue 12.5 4
Copper formate dihydrate Cu(CHO 2) 2·2H 2O 16–0954 - - -
Copper(I) oxide Cu 2 O 05–0667 red i 4, 5
(cuprite, cuprous oxide)
Copper(II) oxide CuO 02–1040 black i 4, 5
(tenorite, cupric oxide)
Lead acetate Pb(CH 3CO 2) 2 43–0743 white 44.3 4
Lead acetate trihydrate Pb(CH 3CO 2) 2·3H 2O 14–0829 white 45.6 4
(sugar of lead)
Lead acetate hydroxide Pb(CH 3CO 2) 2·Pb(OH) 2·H 2O 14–0737 white vs 4
hydrate
Lead acetate oxide Pb(CH 3 CO 2) 2·2PbO·H 2 O 18–1740 white i 6
hydrate
Lead formate Pb(CHO 2) 2 14–0825 white 1.6 4
Lead formate hydroxide Pb(CHO 2)(OH) 14–0831 - - -
(lead hydroxyformate)
Lead 2,2’-oxydiacetate Pb(C 4H 4O 5)·H 2O 31–0688 - - 7
hydrate
Lead oxide carbonate 6PbCO 3·3Pb(OH) 2·PbO 19–0680 white - 8, 9
hydroxide (plumbonacrite)
Lead(II) oxide a-PbO 05–0561 red 0.0017 4
(litharge, lead monoxide)

(a) ‘i’ indicates insoluble and ‘vs’, very soluble.

Table 3 Weight gain measurements and some XRD analysis on copper samples after 135 days exposure to carbonyl vapour mixtures at
75% RH

Weight gain (g.m-2) and XRD analysisb

Carbonyls (ppmv) a Mix with formic acid (ppmv)c
0 0.2 ± 0.1 8 ± 1
Formic acid alone 0.07 ± 0.05 0.22 ± 0.01 1.4 ± 0.3
cuprite: T c cuprite: T c cuprite
grey areas: tenorite
Acetic acid 0.2 ± 0.1 0.08 ± 0.01 0.19 ± 0.01 1.2 ± 0.6
cuprite: T c cuprite
copper formate dihydrate: T
Acetic acid 11 ± 2 0.30 ± 0.04 0.30 ± 0.01 1.42 ± 0.03
cuprite
copper formate dihydrate: T
Formaldehyde 0.6 ± 0.1 0.16 ± 0.01 0.33 ± 0.06 1.8 ± 0.5
cuprite: T c cuprite
copper formate dihydrate: PT
Formaldehyde 3 ± 1 0.13 ± 0.01 0.21 ± 0.01 1.03 ± 0.03
cuprite
copper formate dihydrate: T
Acetic acid Formaldehyde 0.2 ± 0.1 0.6 ± 0.1 0.21 ± 0.01 0.16 ± 0.01 0.97 ± 0.03
cuprite: T c cuprite
copper formate dihydrate: T
Acetic acid Formaldehyde 11 ± 2 0.26 ± 0.02 0.27 ± 0.04 1.73 ± 0.03
3 ± 1 cuprite
copper acetate hydrate

(a) With increasing level of formic acid, the level of acetic acid increases (see Appendix 3).
(b) T indicates trace amounts and P, possible presence of this component.
(c) Analysed by small angle XRD analysis after 27 days of exposure.

S T U D I E S I N C O N S E R V A T I O N 4 8 ( 2 0 0 3 ) P A G E S 1– 6
6 J. TETRÉAULT, E. CANO, M. VAN BOMMEL, D. SCOTT, M. DENNIS, M.-C. BARTHÉS-LABROUSSE, L. MINEL AND L. ROBBIOLA

Table 4 Weight gain measurements and some XRD analysis on lead samples after 135 days exposure to carbonyl vapour mixtures at 75% RH

Weight gain (g.m-2) and XRD analysisb

Carbonyls (ppmv) a Mix with formic acid (ppmv)
0 0.2 ± 0.1 8 ± 1
Formic acid alone 0.1 ± 0.2 1.2 ± 0.9 2.25 ± 0.02
c c
litharge: T lead formate hydroxide lead formate

Acetic acid 0.2 ± 0.1 23 ± 5 4.9 ± 0.9 2.5 ± 0.3

plumbonacrite plumbonacrite c lead formate
c
lead oxide acetate lead formate hydroxide: T
compound: PT lead formate hydroxide
lead oxide acetate
compound: P
Acetic acid 11 ± 2 47 ± 11 29.60 ± 0.01 3.8 ± 0.3
c
plumbonacrite
Formaldehyde 0.6 ± 0.1 0.2 ± 0.1 1.24 ± 0.04 1.6 ± 0.1
c
lead formate hydroxide
Formaldehyde 3 ± 1 0.08 ± 0.03 1.5 ± 0.4 1.6 ± 0.1
Acetic acid 0.2 ± 0.1 0.6 ± 0.1 37 ± 5 6.4 ± 0.4 2.13 ± 0.01
Formaldehyde plumbonacrite plumbonacrite c lead acetate oxide
hydrate
lead formate hydroxide lead formate
lead acetate trihydrate
Acetic acid 11 ± 2 46.6 ± 0.8 34 ± 3 4.0 ± 0.2
Formaldehyde 3 ± 1 lead acetate trihydrate: P lead acetate trihydrate: P lead acetate
lead acetate: P lead acetate: P hydroxide hydrate
lead formate hydroxide: P lead formate hydroxide: P lead formate

For (a), (b), (c), see Table 3.

Figure 4 SEM photomicrographs of lead samples after 27 days exposure to various carbonyl mixtures (FA: formic acid, F:
formaldehyde, AA: acetic acid).

S T U D I E S I N C O N S E R V A T I O N 4 8 ( 2 0 0 3) P A G E S 1– 6
 CORROSION OF COPPER AND LEAD BY FORMALDEHYDE, FORMIC AND ACETIC ACID VAPOURS 7
crystalline product is mainly plumbonacrite,
6PbCO3·3Pb(OH)2·PbO. As seen in Table 4, in the
presence of formic acid, the capacity of acetic acid to
produce corrosion products is highly inhibited. This
can be attributed to a modification of the chemical
nature of the corrosion layer, which gives increasing
protective properties that were confirmed by XPS
measurements made after 27 days. This effect can also
be correlated to a decrease in the electronic conductiv-
ity of the surface layer, manifest in an increase of the
charge effect in the course of XPS. This charge effect
(positive charge on the surface) is due to the X-ray
induced removal of electrons from the surface during
XPS analysis. In an isolating surface, the electronic
conductivity is low and cannot compensate for
this charge. Spectra obtained from these surfaces are
displaced towards higher binding energies, i.e., lower
kinetic energies for the detected electrons. Therefore,
a greater displacement of the spectra indicates a lower
electronic conductivity in the layer analysed.
Figure 5 Weight gain for lead exposed for varying periods of time
to different formic and acetic acid concentrations at 75% RH.
S T U D I E S I N C O N S E R V A T I O N 4 8 ( 2 0 0 3 ) P A G E S 1– 6
This inhibition effect is well illustrated in Figure 5,
which shows the kinetics for the formation of
compounds over 135 days at different concentrations
of formic and acetic acids. A uniform thin layer,
composed mainly of lead formate hydroxide, is formed
on lead exposed to 0.2 ppmv of formic acid (Figure
4b). When acetic acid is added to formic acid, the
weight gain increases due to the formation of lead
acetate compounds, which coalesce into tiny white
grains (a few microns in diameter) spread uniformly
across the surface. However, the corrosion is retarded
by lead formate compounds as the concentration of
formic acid increases. The visual appearance of the
corrosion layer on lead exposed to acetic acid alone
(either 0.2 or 11 ppmv) changes from a thick white film
to a darker thin film as the formic acid concentration
changes from 0 to 0.2, and to 8 ppmv.
It should be noted that apart from the increase
of acetic acid with an increasing level of formic acid
as described in Appendix 3, the measurement of
carbonyl levels generated by the three carbonyl–salt
solutions did not show any changes in the levels of
formaldehyde or formic acid. No significant oxidation
of formaldehyde into formic acid occurred in the
vapour phase in the presence of weak oxidants such
as acetic or formic acids or in the presence of the
copper or lead metal surfaces.
Experiment 3
The results of experiment 3 are given in Table 5. In
general, the corrosion layer formed on lead is heavier
as the RH increases in a carbonyl environment. There
is less corrosion produced if there is already a corrosion
layer present, either a continuous (T) or partial (TS)
layer. But this increase varies with the surface state of
the lead. The presence of an initial corrosion film on
lead has an important effect on the evolution of
further corrosion. The freshly exposed lead surface
(N) has a reactivity higher than a surface with a
naturally formed patina. At 54% RH, no corrosion is
observed on lead with a natural patina. The vapours
emitted by the particleboard tend to contribute to a
higher weight gain than observed with the vapours
from the carbonyl–salt solution. This trend was
surprising, since the level of carbonyls from the board
was similar or less (mainly in acetic acid) than that from
the carbonyl–salt solution. Unfortunately, due to lack
of time, the level of carbonyls was measured for only
one jar containing a sample of particleboard and one
jar of carbonyl–salt solution. In addition, the weight
8 J. TETRÉAULT, E. CANO, M. VAN BOMMEL, D. SCOTT, M. DENNIS, M.-C. BARTHÉS-LABROUSSE, L. MINEL AND L. ROBBIOLA

Table 5 Weight gain (g.m-2) and some XRD analyses of lead samples after 33 days exposure to particleboard or to a carbonyl environment

Sources and levels (ppmv)a 54% RH 75% RH 100% RH

N TS T N TS T N TS T
Particleboard 0.73 0.69 < 0.01 3.99 1.41 0.38 4.22 3.09 1.84
FA: 0.2, AA: <0.07, F: 0.9 b XRD1 XRD2
Carbonyl–water–salt system 0.55 0.31 < 0.01 1.40 0.87 0.37 0.94 1.93 0.75
FA: 0.2, AA: 0.3 F: 0.6 b XRD3 XRD4

XRD1: plumbonacrite, XRD2: lead formate hydroxide, XRD3: lead acetate hydroxide hydrate (possible) and lead formate (possible), XRD4:
lead acetate hydroxide hydrate and lead formate hydroxide.
(a) FA: formic acid, AA: acetic acid, F: formaldehyde. N: newly sanded lead sample, TS: five-year-old tarnished and scratched, T: five-year-
old tarnished.
(b) The carbonyl levels were measured only at 100% and 75% RH respectively.

gains were measured for only one sample of each type
of lead (untarnished, tarnished and scratched,
tarnished) per vessel. These factors may limit the
confidence level for these interpretations.
DISCUSSION
Copper
Formic acid reacted with copper at 54 or 75% RH,
forming mainly cuprite, while acetic acid and formal-
dehyde did not contribute significantly to the
corrosion in the range of vapour concentrations
studied. In general, copper(II) compounds are always
formed on copper exposed to polluted or unpolluted
environments for a long time. The typical structure of
the patina formed on copper comprises an inner layer
of copper(I) oxide (cuprite) and an outer layer of
copper(II) oxide (tenorite) and/or copper(II) hydrox-
ide. The presence of these copper(II) compounds
seems to provide the building blocks for the formation
of acetates or formates [11].
The ‘no observable adverse effect level’ (NOAEL)
is defined as the highest level of a pollutant that does
not produce an adverse effect on a specific chemical
or physical characteristic of a material in a particular
experimental set-up [1]. In this research, the NOAEL
of formic acid on copper was found to be 0.4 ppmv
at 75% RH based on change of lightness (L*) and about
3 ppmv based on the weight gain at both the relative
humidities studied. For acetic acid, previous work has
established a NOAEL (based on weight gain) above
the maximum level studied, 50 ppmv at 54% RH [12].
Independent research has demonstrated that copper
samples change colour when exposed to 5 ppmv of
acetic acid or 5 ppmv of formaldehyde at 50% RH [2].
It is important to note that in the presence of high
concentrations of formic acid, there is more corrosion
at the lower RH. A similar behaviour has been
observed for other corrosive environments, and has
been attributed to the different protective effects of
the corrosion products formed at different relative
humidities [10]. As shown in Table 6, there is a low
probability of carbonyls damaging copper inside
enclosures such as display cases or storage cabinets, as
long as any coatings formed by oxidative polymeriza-
tion, including oils, oil-based urethanes, alkyds and
epoxy esters, are avoided, or as long as the copper is not
exposed to these coatings before an extended drying
period [13]. Most copper objects will still be better
preserved in an enclosure containing low levels of
carbonyls than if they were left exposed to an ambient
environment containing more aggressive pollutants
such as hydrogen sulphide, carbonyl sulphide or
sulphur dioxide (unless there is an unexpected source
of a sulphur compound from a product or an object
inside the enclosure [1]).
Lead
The research shows that formic acid has a significant
reactivity with lead until a stable film is formed. The
NOAEL of formic acid on lead is roughly 0.1 ppmv at
both 54 and 75% RH based on weight gain, and below
0.04 ppmv based on lightness change. Similar NOAELs
for acetic acid on lead were previously determined at
54% RH [3]. Above the NOAEL of the two acids, the
rate of corrosion of lead with acetic acid is higher than
that for formic acid. In contrast to the reaction of
acetic acid with lead, formic acid tends to form a stable
film, composed mainly of lead formate and lead
formate hydroxide. From Table 6 it can be seen that
most wooden enclosures, coated or not, can generate
levels of acetic acid above the NOAEL (0.1 ppmv).
This may result in a significant risk of corrosion of lead
objects displayed or stored in such enclosures. How-
ever, if a stable film already covers the lead, or if formic
acid is present, the risk, or the rate of corrosion, can be

S T U D I E S I N C O N S E R V A T I O N 4 8 ( 2 0 0 3) P A G E S 1– 6
 CORROSION OF COPPER AND LEAD BY FORMALDEHYDE, FORMIC AND ACETIC ACID VAPOURS 9

Table 6 Sources and typical range levels of carbonyls [11]

Carbonyls Sources Typical range levels (ppmv)a

Acetic acid Rooms 0.02 – 0.04
Outdoor: clean to polluted sites 0.0001 – 0.1
Silicone sealant: 7 and 29 days cured 0.04 – 0.4
Wooden enclosures (new and old) 0.03 – 1
Oak (old) 0.01 – 3
Emulsion or two-part epoxy paint; 5 weeks dried 1 – 8
Paints formed by oxidative polymerization; 5 weeks dried 8 – 30
Cellulose acetate based film (smelly collection) 0.4 – 40
Formic acid Outdoor: clean to polluted sites 0.00005 – 0.01
Rooms 0.00005 – 0.02
Wooden enclosures (new and old) 0.001 – 1
Formaldehyde Outdoor: clean to polluted sites 0.004 – 0.02
Rooms 0.008 – 0.06
Wooden enclosures (new and old) 0.04 – 0.4
Wood products with urea formaldehyde (new and old) 0.4 – 5

(a) The levels generated by these products were measured in airtight enclosures.

reduced. Scratches and cracks caused by handling and
transportation can produce new unprotected lead
surfaces vulnerable to corrosion. The high probability
of lead corrosion in enclosures reinforces the need for
the proper selection of products with little or no acid
emission. Guidelines for the optimum preservation of
lead objects, and the factors influencing the deteriora-
tion of lead, are covered in more detail elsewhere [1, 3].
Formaldehyde showed no significant effect on lead
in the experimental conditions covered. Although, in
the museum context, corrosion of lead objects in the
presence of formaldehyde-containing wood products
has been observed [14], it is hard to reproduce this
phenomenon in the laboratory without extreme
environmental conditions. The oxidation of formal-
dehyde to formic acid is negligible in the atmosphere
in the absence of oxidants such as peroxide [15].
However, potentially high levels of peroxide can
occur inside an enclosure during the curing of a
newly-applied coating formed by oxidative polymeri-
zation [16, 17].
Monitoring methods and deterioration
Two methods have been used to quantify the NOAEL
for formic acid on copper or lead in this research. In
a well-controlled environment, lightness measure-
ments L* are around 10 times more sensitive than
weight gain measurements. The single measurement
of L* in this experiment, in situ using metal coupons in
display cases or on the object itself, will not fully
explain the kinetics of the deterioration; the lightness
of the metal may not change over months, but
deterioration may still continue as the corrosion film
grows. However, in a museum context, visual com-
parisons of metal objects or coupons with a control
sample can be a very simple monitoring tool to detect
early signs of deterioration. For metal objects or
coupons that must remain shiny or for metals that are
plated or fragile, gloss or colour change observations
are an appropriate method. Otherwise, weight gain
and full spectral measurements will provide more
comprehensive information related to the effects of
indoor and outdoor pollutants, while XRD and XPS
analyses remain important to identify the film compo-
sition.
CONCLUSIONS
In the presence of different levels of mixed carbonyl
vapours, copper reacted mainly with formic acid while
the reaction of lead proved to be more complex. On
lead, there was a competition between acetic and
formic acids, where acetic acid tended to form a thick
white layer compared to formic acid which tended to
form a rather thin and darker layer of lead formate
compounds. The latter film was able to inhibit the
action of acetic acid on lead. No significant contribu-
tion of formaldehyde to the corrosion process on lead
or copper was observed.
Display, storage or transportation cases made of
wood products can cause corrosion of lead and
copper, particularly if the interior of the cases is
covered by coatings formed by oxidative polymeriza-
tion. The selection of products with little or no acid
emission is recommended.

S T U D I E S I N C O N S E R V A T I O N 4 8 ( 2 0 0 3 ) P A G E S 1– 6
10 J. TETRÉAULT, E. CANO, M. VAN BOMMEL, D. SCOTT, M. DENNIS, M.-C. BARTHÉS-LABROUSSE, L. MINEL AND L. ROBBIOLA
ACKNOWLEDGEMENTS
The authors are grateful to Jean-Pierre Dallas of the
Centre d’études de chimie métallurgique (Centre
national de la recherche scientifique), Vitry, France,
for providing extra data on small angle XRD analysis.
We also would like to thank Carole Dignard, Lyndsie
Selwyn and R. Scott Williams from CCI for reviewing
this article and offering their comments. David Thickett,
formerly of the British Museum, is thanked for his
technical advice. Emilio Cano’s internship in Canada
was made possible by funding from the Spanish
Ministry of Education and Culture.
APPENDIX 1: MATERIAL PREPARATION
Copper foil 1.0 mm thick (composition, by weight
percent: 0.015 Pb, 0.009 Sn, <0.001 Al, <0.002 Sb,
<0.001 As, <0.001 Bi, <0.001 Fe, 0.003 Ni, 0.019 P,
<0.001 Mn, balance Cu; type Cu-DLP Standard ISO
1337 [18]) was cut into 2.5 × 5 cm pieces and lead foil
0.2 mm thick (purified grade) was cut into 2 × 5 cm
strips. The samples were cleaned with propanone
(acetone), then sanded. Metal samples used for experi-
ments 1, 2, and part of 3 were rubbed with grade P500
(based on the scale of the Federation of European
Producers Association) sandpaper to produce a rough
surface. Other metal samples for experiment 2 were
sanded and polished with different grades of paper up
to P2500 to provide a very flat and glossy surface
suitable for small angle XRD analysis. A hole was
pierced through each sample in order to suspend it in
the glass jar. For experiment 3, lead samples were used
in three different states: newly sanded, after tarnishing
for five years in indoor air, and scratched with a sharp
knife after tarnishing for five years in indoor air.
APPENDIX 2: GENERATION OF THE HUMID
CARBONYL ENVIRONMENT
In order to generate a humid carbonyl environment in
glass jars at room temperature (21.3 ± 0.7°C), a three-
component system of carbonyl–water–salt was used.
This system was based on different equilibria: water
vapour in equilibrium with a saturated salt mixture and
a carbonyl vapour in equilibrium with its solution.
Magnesium nitrate (MgNO3·6H2O) or sodium chlo-
ride (NaCl) was used to generate relative humidities of
54 or 75% respectively [19]. Solutions without a salt
were used to generate a RH of 100%. The relative
humidities were checked with a data-logger and were
verified as correct.
S T U D I E S I N C O N S E R V A T I O N 4 8 ( 2 0 0 3) P A G E S 1– 6
For experiment 1, a small plastic container contain-
ing 15 g of salt and 3 ml of one of the formic acid
solutions was placed in a 0.45 l glass jar with a hard
plastic screw-cap lid. The formic acid levels in the
vapour phase were calculated using the relationship
between the vapour phase and salt–acid solution for
each RH value (see Appendix 3).
To generate the carbonyl levels desired for experi-
ments 2 and 3, the following relationships between
the solution concentration and the vapour phase
were used as an estimate. These relationships were
established by experimental work conducted by
Thickett for the acids [2], and preliminary vapour
measurements for formaldehyde:
Formic acid, vapour phase: ppmv = 33 × content
of salt solution in % (v/v)
Acetic acid, vapour phase: ppmv = 23 × content
of salt solution in % (v/v)
Formaldehyde, vapour phase: ppmv = 25 ×
content of salt solution in % (v/v)
Three carbonyl–water–salt systems (one for each
carbonyl) were placed in a 0.90 l glass jar. It was
observed that the tarnishing layer formed on the metal
surfaces was more uniform in this larger jar. Each
carbonyl solution was three times more concentrated
than in the experiment using only one carbonyl–
water–salt system, in order to compensate for absorp-
tion by the other two solutions. The carbonyl vapour
levels were measured in each jar to check that the
appropriate levels had been achieved, and to identify
any possible interactions between the solutions.
For experiments 1 and 2, the carbonyl–water–salt
mixtures were replaced every 27 days. During the
replacement of the mixtures, the metal samples were
removed from their glass jars for measurement and put
back the following day. For experiment 3, some lead
samples were exposed to carbonyl vapours for 33 days
in the same way as experiment 2. The other lead
samples were exposed to vapour released by a 30 g
piece of five-year-old particleboard containing a urea
formaldehyde adhesive, in an atmosphere conditioned
by a salt solution (54 and 75% RH) or water alone
(100%).
APPENDIX 3: ANALYTICAL METHODS TO
DETERMINE CARBONYL LEVELS IN THE VESSELS
The concentration of carbonyls in the vessels was
determined by a previously developed method using
 CORROSION OF COPPER AND LEAD BY FORMALDEHYDE, FORMIC AND ACETIC ACID VAPOURS 11
sorbents in diffusion tubes and high performance
liquid chromatography (HPLC) [20, 21]. The sorbent
for the acids was potassium hydroxide at a concentra-
tion of 1 mole per litre in water mixed with 10%
ethylene glycol dimethyl ether. 40 µl of this solution
were transferred to a stainless steel frit, which was
placed in a diffusion tube. For formaldehyde,
dinitrophenylhydrazine (DNPH) was used as the
sorbent, at a concentration of 0.137 moles per litre in
acetonitrile (ethanenitrile). A solution was made by
dissolving 150 mg DNPH in 4.75 ml acetonitrile, 0.5 ml
ethylene glycol dimethyl ether and 0.25 ml phosphoric
acid (85% v/v). 60 µl of this solution were added to a
paper filter (Whatman, 13 mm). The ethylene glycol
dimethyl ether was used as a wetting agent, and the
phosphoric acid was added to decrease the pH,
because the reaction of formaldehyde with DNPH is
faster at a lower pH.
Carbonyl vapours were collected during a period of
27 days, by hanging diffusion tubes in the space above
the carbonyl solution. For each vessel, the measure-
ments of formic and acetic acids were made in
triplicate and that of formaldehyde in duplicate. Levels
of carbonyls were obtained by the analysis of two sets
of measurements. Overall, the limits of detection were
0.08 ppmv for formic acid, 0.07 ppmv for acetic acid
and 0.01 ppmv for formaldehyde.
In experiment 1, the concentration of formic acid
was not measured directly for each vessel. Instead, the
levels were calculated after determining experimen-
tally the relationship between the vapour phase and
the acid content in the salt–acid solution for 54, 75 and
100% RH. The results showed that the level of formic
acid in the vapour phase was directly proportional to
its content in the solution over the range 0.0042–
0.422% (v/v) at 23 ± 0.1°C according to the following
relationships:
At 54% RH: formic acid, vapour phase: ppmv =
8.3 ± 0.7 × acid content of salt acid solution in
% (v/v)
At 75% RH: formic acid, vapour phase: ppmv =
32.6 ± 0.6 × acid content of salt acid solution in
% (v/v)
At 100% RH: formic acid, vapour phase: ppmv
= 23.7 ± 0.5 × acid content of salt acid solution
in % (v/v)
In experiment 2, the levels of carbonyls for each vessel
were measured. It was observed that the level of acetic
S T U D I E S I N C O N S E R V A T I O N 4 8 ( 2 0 0 3 ) P A G E S 1– 6
acid increased in the presence of formic acid with or
without formaldehyde. The level of acetic acid in the
jar increased from 0.2 ppmv to 0.3 and 0.6 in presence
of 0.2 and 8ppmv of formic acid respectively. Similarly,
with the most concentrated solution of acetic acid, the
level of acetic acid moved from 11 to 13 and 16 ppmv
with increasing levels of formic acid.
In experiment 3, the levels of carbonyls were
measured for only two jars: those containing the
particleboard at 100% RH and the carbonyl mixture at
75% RH.
SUPPLIERS
Acetic acid, reagent grade, 80%; lead foil, purified; magnesium
nitrate, certified ACS; sodium chloride, certified ACS: Fisher
Scientific, 112 Colonnade Road, Nepean, Ontario, Canada K2E
7L6.
Copper: Subero, Fuercarral 25, 28004 Madrid, Spain.
Particleboard: Pilon Ltee, 5 Montclair, Hull, Québec, Canada
J8Y 2E3.
REFERENCES
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Archives: Risk Assessment, Control Strategies and Preservation
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2 Thickett, D., ‘Relative effects of formaldehyde, formic and
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corrosion in acetic acid environment’, Studies in Conservation
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12 J. TETRÉAULT, E. CANO, M. VAN BOMMEL, D. SCOTT, M. DENNIS, M.-C. BARTHÉS-LABROUSSE, L. MINEL AND L. ROBBIOLA
ray photoelectron spectroscopy study on the chemical
composition of copper tarnish products formed at low
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E26–E30.
11 Cano, E., and Bastidas, J.M., ‘Effect of relative humidity on
copper corrosion by acetic and formic acid vapours’, Canadian
Metallurgical Quarterly 41 (2002) 327–336.
12 Tétreault, J., ‘Corrosion of zinc and copper by acetic acid
vapour at 54% RH’, Canadian Conservation Institute, Ottawa,
unpublished results (1992).
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Technical Bulletin No. 21, Canadian Conservation Institute,
Ottawa (1999) 4–6.
14 Leveque, M.A., ‘The problem of formaldehyde – a case
study’ in Preprints of papers presented at the fourteenth annual
meeting, Chicago, Illinois, 21–25 May 1986, American Institute
for Conservation of Historic and Artistic Works, Washington
DC (1986) 56–65.
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‘Formaldehyde oxidation and lead corrosion’, Studies in
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F.A., ‘A laboratory study of the effect of acetic acid vapor on
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21 Gibson, L.T., and Brokerhof, A.W., ‘A passive tube-type
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AUTHORS
JEAN TÉTREAULT graduated from the University of
Montreal with a MSc in analytical chemistry. In 1989,
he joined the Canadian Conservation Institute. He
was president of the Canadian Association for Conser-
vation of Cultural Property from 1995 to 1997. He
serves as an advisor and researcher on general environ-
mental guidelines, pollutants, display and storage prod-
ucts, and light issues. Address: Canadian Conservation
Institute, 1030 Innes Road, Ottawa, Ontario, Canada K1A
0M5. Email: jean_tetreault@pch.gc.ca
S T U D I E S I N C O N S E R V A T I O N 4 8 ( 2 0 0 3) P A G E S 1– 6
EMILIO CANO obtained a PhD in conservation from the
Complutense University of Madrid in 2001. He works
as scientific researcher at the Spanish National Centre
for Metallurgical Research (CENIM-CSIC), where he
studies the deterioration (corrosion) and conservation
of metallic objects of historic and artistic interest.
Address: Departamento de Ingeniería de Materiales, Degradación
y Durabilidad, Centro Nacional de Investigaciones Metalúrgicas
(CENIM), Avda Gregorio del Amo 8, 28040 Madrid,
Spain. Email: ecano@cenim.csic.es
MAARTEN VAN BOMMEL studied analytical chemistry at
the University of Amsterdam, followed by a PhD at
Leiden University, which involved the coupling of
enzyme-amplified biochemical detection to continu-
ous-flow systems. In 1999, he joined the Netherlands
Institute for Cultural Heritage in Amsterdam. His main
interests are in the analysis of dyestuffs and organic
pigments by HPLC and the analysis of volatile organic
acids and formaldehyde with solid phase micro extrac-
tion combined with gas chromatography-mass
spectrometry. Address: Netherlands Institute for Cultural
Heritage, Conservation Research, PO Box 76709, 1070
KA Amsterdam, The Netherlands. Email:
maarten.van.bommel@icn.nl
DAVID SCOTT obtained a BSc in chemistry from the
University of Reading (England) in 1971, a BA in
archaeological conservation in 1978 and a PhD in
ancient metallurgy from University College London in
1982. He lectured in conservation at the Institute of
Archaeology, London University, 1981–87, before
joining the Getty Conservation Institute as head of the
Museum Research Laboratory in 1987. He is now a
professor in art history and archaeology at UCLA and
director of the UCLA/Getty MA program in archaeo-
logical and ethnographic conservation, scheduled to
start in 2005. Address: Department of Art History, Dodd
Hall-100, UCLA, Los Angeles, CA 90095, USA.
Email: dascott@ucla.edu
MEGAN DENNIS studied archaeological sciences at the
University of Bradford. She has worked within the
technology section of the Centre for Archaeology,
English Heritage, and at the Getty Conservation
Institute. Her main research interests are the study
of ancient technologies, specifically metallurgy; the
application of science to archaeological collections;
and the incorporation of the scientific work
of museums into education and display. Address:
Queen’s College, Oxford OX1 4AW, UK. Email:
megan.dennis@archaeology.oxford.ac.uk
 CORROSION OF COPPER AND LEAD BY FORMALDEHYDE, FORMIC AND ACETIC ACID VAPOURS 13

MARIE-GENEVIÈVE BARTHES-LABROUSSE, PhD, is research
director at the Centre national de la recherche
scientifique (CNRS), France, specializing in surface
science. Her work mainly concerns metallic surfaces
and polymer–metal adhesion mechanisms. Address:
Centre d’études de chimie métallurgique, CNRS UPR 280,
15 rue Georges Urbain, 94407 Vitry Cedex, France. Email:
marie-genevieve.barthes@glvt-cnrs.fr
LUC ROBBIOLA obtained his MSc in conservation-
restoration (Université Paris I–Sorbonne, 1985) and a
PhD in chemistry in 1990; since 1990 he has been head
of the electron microscopy unit at the National School
of Chemistry, Paris. Address: Service commun des microscopies
électroniques, Laboratoire de métallurgie, École nationale
supérieure de chimie de Paris, 11 rue P et M Curie, 75231
Paris Cedex 5, France. Email: robbiola@ext.jussieu.fr

LÉA MINEL is an engineer specializing in surface analysis

at the CNRS. Address: as for Barthes-Labrousse. Email:
lea.minel@glvt-cnrs.fr

Résumé — La formation des produits de corrosion du cuivre et du plomb, ainsi que la sensibilité de ces deux métaux à se
corroder, ont été étudiées en présence de formaldéhyde et d’acides formique et acétique, et ce, à différents temps d’exposition
et différents taux hygrométriques (HR). Dans le cas du cuivre, l’acide formique affecte son apparence lorsque ce gaz est à
des concentrations supérieures à 0,4 ppmv et en présence de 75% HR. D’autre part, le gain en poids fut décelable lorsque
les niveaux d’acide formique étaient supérieurs à 4 ppmv à 54 et 75% HR. Le principal composé trouvé sur le cuivre fut
la cuprite. Par contre, le plomb a une plus grande sensibilité face à l’acide formique. A 54% et à 75% HR, avec une
concentration d’acide formique aussi basse que 0,04 ppmv, le plomb se noircit, et au-delà de 0,1 ppmv, il y a un gain de
poids observable. En présence de différentes concentrations de vapeur des trois carbonyles sous étude, le cuivre à 75% HR
réagit principalement avec l’acide formique. Par contre, la réactivité du plomb est plus complexe. L’acide acétique tend à
former une épaisse couche blanche (composée principalement de plumbonacrite et possiblement de composés acétates) sur la
surface du plomb. Pour sa part, l’acide formique tend plutôt à former une couche sombre et mince de hydroxy-formate de
plomb. En présence d’acide formique, l’action de l’acide acétique sur le plomb fut inhibée. Avec des concentrations allant
jusqu’à 3 ppmv, le formaldéhyde n’a montré aucune contribution au processus de corrosion du cuivre et du plomb à 75%
HR.

Zusammenfassung — to follow

Resumen — Se ha estudiado la sensibilidad a la corrosión del cobre y del plomo, y los productos de corrosión formados
sobre ambos metales, en distintas condiciones experimentales en las que se han variado las concentraciones de formaldehído,
ácido fórmico y ácido acético, la humedad relativa (HR) y el tiempo de exposición. El aspecto del cobre se altera en
presencia de ácido fórmico en concentraciones iguales o superiores a 0,04 ppmv al 75% de HR, y se produce incremento
de masa a partir de 0.4 ppmv, tanto al 54% como al 75% de HR. El principal producto de corrosión formado sobre el
cobre es cuprita. El plomo muestra una mayor sensibilidad al ácido fórmico. Desde 0,04 ppmv el plomo se oscurece, y el
aumento de masa es apreciable desde 0,1 ppmv en ambas humedades, 54% y 75% RH. En presencia de distintas
combinaciones de los vapores orgánicos estudiados, el cobre reacciona principalmente con el ácido fórmico. Por otro lado, la
reacción del plomo es más compleja. El ácido acético tiende a formar sobre la superficie del plomo una gruesa capa
blanquecina (compuesta fundamentalmente por plumbonacrita y probablemente acetato de plomo), mientras que el ácido
fórmico produce una capa fina y oscura de hidroxiformiato de plomo. En presencia de ácido fórmico, la acción del ácido
acético sobre el plomo queda inhibida. No se ha observado un efecto apreciable del formaldehído en la corrosión del plomo ni
del cobre en concentraciones de hasta 3 ppmv y humedad relativa del 75%.

S T U D I E S I N C O N S E R V A T I O N 4 8 ( 2 0 0 3 ) P A G E S 1– 6

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