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Mieke Adriaens
Mark Dowsett
Photo © Western Austrialia’s Maritime Museum
storage in a solution
disadvantages
– time consuming
– indirect monitoring method
– no idea of potential side reactions
Objective
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
depends on reference
electrode
– metal composition
– solution
– interface metal – solution object
(porthole)
Photo © EVTEK
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
incoming X-rays
eCell
SRS 6.2
Nantokite (CuCl) protocol*
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
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*
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
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
* 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
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
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
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
Dr. Manolis Pantos, Dr. Tony Bell, Dr. Chris Martin, SRS
Dr. Laurence Bouchenoire, Dr. Sergey Nikitenko, ESRF
Dr. Christian Degrigny, SARL Germolles