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Cleaning of CH artefacts

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

Hamilton (USA) Pearson and


MacLeod (Australia)
« Techniques »
applied to marine
Use of constant V (voltage)
metal artefacts
for the treatment of marine
metal artefacts

Leiden, 11-15 January 2010


Since 1990s…
-better control of the reactions taking
place on the metal surface (systematic use
of reference electrodes when establishing
electrochemical parameters);
- more research on conservation
protocols and determination of treatment
parameters;
- development of new approaches and
design of new tools.
Corrosion scientists
Ù
Leiden, 11-15 January 2010 Conservators
An alternative to other
treatments?

- mechanical (superficial damage:


tarnished silver, marine cast iron, lead
artefacts…)

- heat treatment (modification of the


Arc’Antique
microstructure due to overheating)

Often applied in combination


with other treatments

Leiden, 11-15 January 2010


Choice of the electrolyte:
behaviour of metals in solution

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

Ecorr (corrosion potential)


Leiden, 11-15 January 2010
Ecorr measurement

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

Leiden, 11-15 January 2010


Influence of the pH of the solution

Several results from


Fe Pourbaix diagrams:
-Prediction of possible
reactions within the field of
stability of the aqueous
solution (normally no cleaning);
-Choice of the appropriate
electrolyte (pH) to favour the
passivation effect;

Pourbaix diagrams are


calculated from
Field of stability of
the aqueous thermodynamics
solution
Leiden, 11-15 January 2010
From gold to aluminium…

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

Modification of electrochemical parameters


with external current

Battery
MAH, Genève

Arc’Antique

Power supply

Potentiostat
Leiden, 11-15 January 2010
Definition of experimental conditions:
voltammetric curves

Pourbaix diagrams cannot be used

CE
RE
PC
WE
X X
X X Potentiostat
X X
X X
Cathode
X X

• Scanning of potentials in the cathodic


and anodic regions
• Determination of treatments parameters
• Follow up of treatments (I=f(t))
Leiden, 11-15 January 2010
Cathodic scanning: reduction reactions

I (A)
EH2 Ecp Ecorr
E (V)

2H2O + O2 + 4e- Î 4OH-

Mn+ + ne- Î M

Oxygen dissolved
2H2O + 2e- Î 2OH- + H2

Leiden, 11-15 January 2010


Anodic scanning: oxidation reactions

2H2O Î O2 + 4H+ + 4e-

I (A)
M ÎMn+ + ne-

Ecorr Eap EO2 E (V)

Leiden, 11-15 January 2010


Coupons to be used for the definition
of parameters ?

Real artefacts

Arc’Antique

Leiden, 11-15 January 2010


Use of artificial coupons

Arc’
Antique
Steel oxidised I (A)

Ecorr
Arc’Antique
E (V)

Silver tarnish

Leiden, 11-15 January 2010


Practically… use of a generator

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)

Leiden, 11-15 January 2010


CS1: cleaning of tarnished silver
Art-Métal Saxophone in silvered
brass, Musée de la
Musique, Paris

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

Potential range I (A)

Ecorr
E (V)

H2 2H2O + O2 + 4e- Î 4OH-

Ag Ag+ + e- Î Ag
Ag2S
Ag
Ag
2H2O + 2e- Î 2OH- + H2 Red. Ag

Leiden, 11-15 January 2010


Monitoring of tarnish removal

I (A)
1
Cathodic reduction
Epmax
at Epmax

3
4

t (min)

Leiden, 11-15 January 2010


In practice
(in 1% (w/v) sodium sesquicarbonate, pH=10)

Saxophone in
HECR Arc silvered brass, Musée
de la Musique, Paris
Silver vase,
private collection, Art-Métal
CH

Art-Métal

After mechanical
cleaning…

Leiden, 11-15 January 2010


Problem of silver alloys Ag-Cu

I (A)

Ecorr E (V)

Cu2S Cu2O
Red. Ag
Ag-Cu Red. Cu
Ag2S ÎAg

Heterogeneous surface after treatment


Leiden, 11-15 January 2010
Cleaning of tarnished gilt silver

MAH, Genève Silver

Gilt silver
MAH, Genève

Leiden, 11-15 January 2010


Ag Î Ag+
I (A) 2 steps
• 1. Reduction
(Ag on Ag and Au)
Ecorr E (V) • 2. Oxidation

MAH, Genève

Ag2S ÎAg

In buffered NaNO3 solution


Leiden, 11-15 January 2010
1st step: cathodic polarisation

Reduction of Ag2S and AgCl in


buffered NaNO3, vb=1mV/s

Ag
reduced
AgCl
Ag Ag2S Ag

Leiden, 11-15 January 2010


Au
Arc’Antique Arc’Antique

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

Leiden, 11-15 January 2010


…when the metal cannot be immersed

GCI

© J. Paul Getty Museum


Definition of the parameters of
Tarnished gilt silver J. Paul Getty Museum the treatment with a potentiostat
stags (17th c.)

+ -
J. Paul Getty Museum
V

M
J. Paul Getty Museum

Use of the electrolytic pen with a


power supply to clean the
tarnishing Collaboration with GCI
Leiden, 11-15 January 2010
CS2: Cleaning of marine objects
…Iron-based objects

EVTEK

Arc’Antique

Arc’Antique

Provoking the
bubbling of H2

KOH

Leiden, 11-15 January 2010


Cleaning or stabilisation?

in 1% (w/v) KOH solution

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

2 Voltage (V) Intensity (A)


I 2,5

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)

Leiden, 11-15 January 2010


Device

Mild steel rod


covered by a Insulated copper wires
PVC tube
− DC power
+ supply

Stainless steel tank

Stainless steel
mesh (anode)

Electrolyte (KOH
1%)

Plastic board

Plastic support

Leiden, 11-15 January 2010


In practice

Arc’Antique
-

cracks
Remaining
material
EDF
Arc’Antique

marine crust

Leiden, 11-15 January 2010


Limiting the bubbling of H2 to the minimum

Arc’Antique

Leiden, 11-15 January 2010


EDF-Valectra
…lead objects

In KOH solutions

E (V/HSE)
EDF-Valectra

-1.3V
Pb2+ Î Pb

I (mA)

Needed?

Leiden, 11-15 January 2010


…copper-based objects
In sodium sesquicarbonate
I
EVTEK

E
Arc’Antique

2
4
3 1

Natural Arc’Antique

patina
Leiden, 11-15 January 2010 destroyed
Limitations: composite artefacts

A collection of rifles (17th c.),


Mediterranean Sea

Arc’Antique

Arc’Antique Documentation

Rifles at their arrival

Investigation:
Waterlogged?
Arc’Antique

Leiden, 11-15 January 2010


When mechanical cleaning is the only
way…

Arc’Antique
Arc’Antique

Pneumatic… …ultrasonic

Arc’Antique

Leiden, 11-15 January 2010


Storage in Hostacor + H2O solution

Arc’Antique

100 300 t (hours)

-0.6 Hostacor 1%

Hostacor 1.5%
-0.7
Hostacor 2%

-0.8
Pre-storage with
a corrosion inhibitor…
Ecorr (V/HSE)

Leiden, 11-15 January 2010


Other applications of the electrolytic
pen…

Porthole with wooden frame


19th c. Finnish wreck
EDF-Valectra

EVTEK

EVTEK
before
To clean
Leiden, 11-15 January 2010
EVTEK

EVTEK

Electrolyte: mixture of triammonium after


citrate. Voltage: 4,6 V and Current: 45 mA
Leiden, 11-15 January 2010