An in-situ spectroelectrochemistry study of

the response of artificial chloride corrosion

layers on copper to remedial treatment

Mieke Adriaens1, Mark Dowsett2

1 Ghent University, Belgium

2 University of Warwick, UK
Christian Degrigny

Mieke Adriaens
Mark Dowsett
Photo © Western Austrialia’s Maritime Museum

archaeological copper artefacts recovered from wet saline

environments corrode at accelerated rate in oxygen-rich air

storage in a solution

tap water sodium

sesquicarbonate
solution
Photo © Western Austrialia’s Maritime Museum

artefacts often show a certain instability

(e.g. chemical transformation of the natural patina
and development of active corrosion)

monitoring the treatment remains necessary

Present monitoring method

 determination of the chloride

concentration in solution using volumetric
analyses
– change of solution when
predetermined value is
exceeded
– repetition until value low enough

 disadvantages
– time consuming
– indirect monitoring method
– no idea of potential side reactions
Objective

 investigate the use of corrosion potential measurements

(Ecorr) to monitor the behaviour of copper based alloys
during their storage and stabilization

 benefits
– simple tool
– inexpensive to conservators
– direct monitoring method of the metal surface
– more complete reaction profile when combined with the
analysis of the solution
Corrosion potential

 potential difference between metal object and reference electrode

 depends on reference
electrode
– metal composition
– solution
– interface metal – solution object
(porthole)

Photo © EVTEK

 hypothesis: surface composition is stable when the corrosion

potential measurements do not change as a function of time
Strategy

 Corrosion simulation
 Evaluate corrosion products
 Immerse sample into sodium sesquicarbonate solution
 Perform corrosion potential measurements as a function
of time and monitor the surface of the electrode
simultaneously
Corrosion simulation
electrical connection

 Electrodes
– reference materials with known composition
• copper
• copper-tin alloy
• copper-tin-lead alloy epoxy resin
metal surface
(12 mm diameter)

 Corrosion products

cuprite nantokite atacamite atacamite and

paratacamite
 detector
webcam

incoming X-rays

eCell

SRS 6.2
 Nantokite (CuCl) protocol*

 Immersing pure copper

samples for one hour in a
saturated CuCl2.2H2O
solution
 Rinsing with deionised water
 Exposure to atmosphere
over night

1 mm

C. Lamy (1997) Stabilisation d’Objects Archéologiques Chlorurés en Alliage Cuivreux – Définition des Conditions d’une Polarisation
Cathodique à Potentiel Constant en Solution de Sesquicarbonate de Sodium 1%, Rapport du Stage, Université de Nantes ISITEM.
 XRD data – nantokite coated copper in 1% sodium sesquicarbonate

Copper
Nantokite

Cuprite

Cuprite
K. Leyssens et al., Electrochemistry Communications 7 (2005) 1265.
 XRD
Ecorr data

100 -0.04

-0.06
80 -0.08
Relative peak area / percent

-0.10
60
-0.12

Ecorr/V
(29.6oo))
Nantokite (29.6
Nantokite
(37.7oo))
Cuprite (37.7
Cuprite -0.14
40
Cuprite (43.8o)
Copper -0.16
Copper
Nantokite (49.3oo)
Nantokite (49.3 )
Cuprite (43.8oo) corrected for Cu -0.18
20 Cuprite (43.8 ) corrected for Cu
Corrosion Potential (Ecorr)
-0.20

0 -0.22
0 50 100 150 200
Elapsed time / minutes

K. Leyssens et al., Electrochemistry Communications 7 (2005) 1265.

XRD conclusions

 Corrosion potential measurements need to be treated with

caution

 Further investigations needed

• E.g. which reactions take place?
– CuCl -> Cu2O
– CuCl -> Cu -> Cu2O
Can XAS data provide additional information?

 An independent means of surface characterization which

is sensitive to the presence and evolution of amorphous
compounds
XAS data New
fromfig powder samples (references)
2 (slightly renormalized) Reference powders and copper

1.2 Atacamite
Copper

1.0 CuCl
normalized (E)

0.8 Cuprite

1.2
0.6
1.0

0.8
0.4 0.6

0.4

0.2 0.2

0.0
8.97 8.98 8.99 9.00
0.0
8.96 8.98 9.00 9.02 9.04 9.06 9.08 9.10

Energy / keV
XAS data from corroded copper samples
New fig 3 - Dry corrosion products on copper

1.2
Atacamite
Copper

1.0
Nantokite
normalized 

0.8
Cuprite
1.2
0.6
1.0

0.8
0.4 0.6

0.4

0.2 0.2

0.0
8.97 8.98 8.99 9.00
0.0
8.96 8.98 9.00 9.02 9.04 9.06 9.08 9.10

Energy / keV
XAS data from corroded copper samples in solution
New fig 4
Corrosion products on copper-first wetting

1.2
Atacamite

1.0
Nantokite
normalized (E)

0.8 Cuprite

1.2
0.6 Copper
1.0

0.8
0.4 0.6

0.4

0.2 0.2

0.0
8.97 8.98 8.99 9.00
0.0
8.96 8.98 9.00 9.02 9.04 9.06 9.08 9.10

Energy / keV
 “atacamite” (Cu2(OH)3Cl isomers ) protocol*

 prepare a solution of 15.07

g (NH4)2CO3.NH3 and 10.02 g
NH4Cl in 100 mL deionised
water
 wet coupons twice a day
with this solution
 repeat procudere for 5 days
 between each application,
the samples were left to dry
to the air

C. Lamy (1997) Stabilisation d’Objects Archéologiques Chlorurés en Alliage Cuivreux – Définition des Conditions d’une Polarisation
Cathodique à Potentiel Constant en Solution de Sesquicarbonate de Sodium 1%, Rapport du Stage, Université de Nantes ISITEM.
Time dependence – “atacamite” on copper in 1% sodium sesquicarbonate

(E) normalized to the first scan 40 12

30
11

20
10

10 9

8
1
0
8.9 9.0 9.1 9.2 9.3 9.4 9.5 9.6

Energy (keV)
 CuCO3
atacamite *
CuCl2.2H20
our sample
B

8.90 8.95 9.00 9.05 9.10

Energy (keV)

* Add 50 mL 0.1 M Na2CO3 solution dropwise to a stirred solution of 100 mL 0.1 M CuCl2.2H2O. Boil at reflux. After 5 h filter the slurry,
wash and dry at 333 K. Crush the samples to a very fine powder.
C. Lamy (1997) Rapport du Stage, Université de Nantes ISITEM.
Time dependence

 “atacamite” coated copper in 1% w/w sodium

sesquicarbonate
 "Atacamite" before and after rinse/centrifuge

12000

10000
“atacamite” as obtained from protocol

8000
Intensity

6000

4000

2000

0
20 40 60 80
Two theta
 "Atacamite" before and after rinse/centrifuge

12000

10000
“atacamite” as obtained from protocol

after rinsing
8000
Intensity

6000

4000

2000

0
20 40 60 80
Two theta
 12000

“atacamite” as obtained from protocol

10000

after rinsing
8000
XRD reference of atacamite
Intensity

6000

4000

2000

0
20 40 60 80
Two theta
 Time dependence – “atacamite” on copper in 1% sodium sesquicarbonate

40 12
(E) normalized to the first scan

30
11

20
10

10 9

8
1
0
8.9 9.0 9.1 9.2 9.3 9.4 9.5 9.6

Energy (keV)
 Simulaneous Ecorr measurement

0.00
Corrosion potential / V

-0.02
Fluid
change
(vs Ag/AgCl ref)

Fluid
-0.04 change

-0.06

-0.08
0 10 20 30 40
time/hours
Overall reaction

 Cuprite forms at the chloride/copper interface

 The insoluble chlorides fall off or remain physically but not

chemically attached

 The corrosion potential becomes

characteristic of a passive cuprite
covered surface but chlorides may
remain to cause further problems

 Corrosion potential measurements

need to be treated with caution!
Summary simulated chloride species

 Nantokite
– Converts to cuprite
 “Atacamite”
– Surface converts to cuprite
– “Atacamite” becomes detached
 Paratacamite/atacamite
– Protocol also produces nantokite
– Nantokite converts to cuprite and can coat the hydroxychlorides
Future

 Address the suitability of simulated alloys/corrosion

products

 More complex systems

– Bronzes
– Multi-layers

Photo: Paola Letardi

 Long term experiments in portable cells

Acknowledgments

 Karen Leyssens, Bart Schotte and Gareth Jones

 Pieter Van Hoe, Derrick Richards, Adrian Lovejoy

 Dr. Manolis Pantos, Dr. Tony Bell, Dr. Chris Martin, SRS
 Dr. Laurence Bouchenoire, Dr. Sergey Nikitenko, ESRF
 Dr. Christian Degrigny, SARL Germolles

 COST Action G8 - http://srs.dl.ac.uk/arch/cost-g8/

Further reading

 K. Leyssens, A. Adriaens, M. Dowsett, B. Schotte, I. Oloff, E. Pantos, A. Bell and

S. Thompson, Simultaneous In-situ time Resolved SR-XRD and Corrosion
Potential Analyses to Monitor the Corrosion on Copper, Electrochemistry
Communications 7 (2005) 1265-1270.
 K. Leyssens, A. Adriaens, C. Degrigny, E. Pantos, Study of Corrosion Potential
Measurements as a Means to Monitor the Storage and Stabilization Processes
of archaeological Copper Artefacts, Analytical Chemistry 78(8) (2006) 2794-
280.
 M. Dowsett, A. Adriaens, Cell for Simultaneous Synchrotron Radiation X-ray and
Electrochemical Corrosion Measurements on Cultural Heritage Metals and Other
Materials, Analytical Chemistry 78(10) (2006) 3360-3365.
 A. Adriaens, M. Dowsett, K. Leyssens, B. Van Gasse, Insights into electrolytic
stabilization with weak polarization as treatment for archaeological copper
objects, Analytical Bioanalytical Chemistry 387(3) (2007) 861-868.
 A. Adriaens, M. Dowsett, G.K.C. Jones, K. Leyssens, S. Nikitenko, An in-situ X-ray
absorption spectroelectrochemistry study of the response of artificial chloride
corrosion layers on copper to remedial treatment, J. Anal. At. Spectrom. 24(1)
(2009) 62-68.