Beruflich Dokumente
Kultur Dokumente
An overview
Christian Degrigny
Leiden, 11-15 January 2010
A bit of history…
End of 19th c. 1950s
Plenderleith (UK)
- use of constant
current I to clean &
stabilise iron & copper
artefacts
F. Rathgen - otherwise cleaning by
electrochemical
reduction (Zn/NaOH)
- Berlin: cleaning of
encrusted coin treasures I -
+ V
by electrochemical
reduction
X X
X X
X X
Leiden, 11-15 January 2010
1970s 1980s
EVTEK Aqueous
solution
Artefact + -
M
All reactions
taking place at M Î Mn+ + ne-: oxidation
the metal
surface 2H2O + O2d + 4e- Î 4OH-: reduction
without external
current
Reference
Local measurement electrode V
V
Ecorr/SHE= V + Eref/SHE
Artefact
Artefact
Ag/AgCl: 0.2V/SHE
Ref
Calomel: 0.242V/SHE
Leiden, 11-15 January 2010
Monitoring of Ecorr with time… in a
certain solution
Ecorr
Passivation
No reaction
time
Corrosion
E/SHE 7 14 E/SHE 7 14
C P
1 1 C
I C
0 0
Au Cu
-1 -1 I
pH pH
E/SHE 7 14 E/SHE 7 14
1 1
P C
C P
0 0 C
Fe -1 Al
I -1
I
pH pH
Leiden, 11-15 January 2010
Electrolytic cleaning
Battery
MAH, Genève
Arc’Antique
Power supply
Potentiostat
Leiden, 11-15 January 2010
Definition of experimental conditions:
voltammetric curves
CE
RE
PC
WE
X X
X X Potentiostat
X X
X X
Cathode
X X
I (A)
EH2 Ecp Ecorr
E (V)
Mn+ + ne- Î M
Oxygen dissolved
2H2O + 2e- Î 2OH- + H2
I (A)
M ÎMn+ + ne-
Real artefacts
Arc’Antique
Arc’
Antique
Steel oxidised I (A)
Ecorr
Arc’Antique
E (V)
Silver tarnish
A
+
_
V
X X
X X • Application of specific potentials
X X (given in the literature)
HECR Arc
X Cathode X • Measurement of the
X X corresponding I
anodes but
• Monitoring is difficult (with basic
equipment)
E/SHE
Ag2O3
1 Ag+
Ag2O
0
Ag
? -1
Ag
Ag2S
pH
7 10
Daguerreotype
Sodium sesquicarbonate
Leiden, 11-15 January 2010
Determination of the parameters
Ecorr
E (V)
Ag Ag+ + e- Î Ag
Ag2S
Ag
Ag
2H2O + 2e- Î 2OH- + H2 Red. Ag
I (A)
1
Cathodic reduction
Epmax
at Epmax
3
4
t (min)
Saxophone in
HECR Arc silvered brass, Musée
de la Musique, Paris
Silver vase,
private collection, Art-Métal
CH
Art-Métal
After mechanical
cleaning…
I (A)
Ecorr E (V)
Cu2S Cu2O
Red. Ag
Ag-Cu Red. Cu
Ag2S ÎAg
Gilt silver
MAH, Genève
MAH, Genève
Ag2S ÎAg
Ag
reduced
AgCl
Ag Ag2S Ag
Before During
Leiden, 11-15 January 2010
Results on several plates
Validation of heterogeneities
detected from visual observation
Leiden, 11-15 January 2010
2nd step: anodic polarisation
I (A) Epmax
Ag+ E (V)
Ag
GCI
+ -
J. Paul Getty Museum
V
M
J. Paul Getty Museum
EVTEK
Arc’Antique
Arc’Antique
Provoking the
bubbling of H2
KOH
Cleaning Stabilisation
Fe2+←Fe3+
Fe←Fe2+
H 2 0 → H2
Gourbeyre 1999
-1.0V/SHE
Leiden, 11-15 January 2010
Monitoring of the voltage and current
At -1V/SHE in KOH solution
1,8
1,6 2
1,4
1,2 voltage 1,5
1
0,8 1
0,6 I
0,4 0,5
0,2
0 0
0 200 400 600 800 1000 1200 1400 1600
time (h)
Stainless steel
mesh (anode)
Electrolyte (KOH
1%)
Plastic board
Plastic support
Arc’Antique
-
cracks
Remaining
material
EDF
Arc’Antique
marine crust
Arc’Antique
In KOH solutions
E (V/HSE)
EDF-Valectra
-1.3V
Pb2+ Î Pb
I (mA)
Needed?
E
Arc’Antique
2
4
3 1
Natural Arc’Antique
patina
Leiden, 11-15 January 2010 destroyed
Limitations: composite artefacts
Arc’Antique
Arc’Antique Documentation
Investigation:
Waterlogged?
Arc’Antique
Arc’Antique
Arc’Antique
Pneumatic… …ultrasonic
Arc’Antique
Arc’Antique
-0.6 Hostacor 1%
Hostacor 1.5%
-0.7
Hostacor 2%
-0.8
Pre-storage with
a corrosion inhibitor…
Ecorr (V/HSE)
EVTEK
EVTEK
before
To clean
Leiden, 11-15 January 2010
EVTEK
EVTEK