Stabilisation of CH artefacts

An overview

Christian Degrigny

Leiden, 11-15 January 2010

 A bit of history, choice of solution…

The same as for the

cleaning overview could be
said here

Leiden, 11-15 January 2010

 Why a stabilisation treatment?

Ingots left to dry

DRASSM in storage area

Arc’Antique Arc’Antique

Iron ingots from the

1st century
BC – Mediterranean
Sea –
DRASSM site

Part of the cargo

left to dry outdoor
Leiden, 11-15 January 2010
 Exposure to the atmosphere

• Rupture of the equilibrium

Droplets (Fe2+,
Fe3+, Cl-) • ÔHR and ÒO2
- Drying of corrosion products and
- Crystallisation of salts
- Oxidation of some salts
- If the artefact contains chlorides:
development of active corrosion

- Formation of akaganeite (β-FeOOH ):

mechanical effect
on the corrosion layer, unstable,
- Weeping phenomenon, droplets
Leiden, 11-15 January 2010
 Stabilisation without polarisation

Arc’Antique

Uncleaned Cleaned

Storage in KOH solution

Leiden, 11-15 January 2010

 On clean iron-based alloys…

Passivation observed

Leiden, 11-15 January 2010

 On corroded iron-based alloys

Ecorr

bare
Passivation

corroded

time

Transformation
of the oxide layer
Leiden, 11-15 January 2010
 … confirmation in practice

Arc’Antique

Artificial steel coupon

Max. extraction
= solution reach M
Leiden, 11-15 January 2010
 Marine wrought iron

EVTEK

stock
shackle
shank
fluke
arm

Finnish, 19th c. Active or not?

Leiden, 11-15 January 2010

 FeOOH
Fe3O4
Cl- ?
Fe
EVTEK

EVTEK

EVTEK

EVTEK

Humid chamber
Leiden, 11-15 January 2010
 EVTEK

Set-up of the
electrical contact

EVTEK

EVTEK

Immersion of
the anchor

Checking of the good

electrical contact
Leiden, 11-15 January 2010
 Monitoring Ecorr vs time

E corr m e a s u r e m e n t a n c h o r w it h s to c k
in 1 % ( w /v ) K O H
0 10 20 30 40 50 60 70 80 90 1
0

-5 0
Quick diffusion of KOH
E (mV/Ag-Ag-Cl)

-1 0 0

-1 5 0
through thin corrosion layers
-2 0 0

-2 5 0

-3 0 0

-3 5 0
T im e ( h o u r s )

Transformation of Passivation
the corrosion layer

And no extraction of chloride: stable artefact

Leiden, 11-15 January 2010

 Metals with thick corrosion layers?

KOH KOH
thin corrosion layers
Remaining
metal
CL CL
KOH
CL KOH
thick corrosion layers
CL
KOH
KOH CL

Corroded Fe in KOH solution

Leiden, 11-15 January 2010

 Iron ingots (Mediterranean sea)

Arc’Antique
Weeping on the surface of ingots

Arc’Antique

Arc’Antique Arc’Antique

High reactivity of the inside

of one ingot in the atmosphere

Leiden, 11-15 January 2010

 Stabilisation in KOH

Slow diffusion of KOH

Questions
• slow re-increase of
Ecorr after III step?
-Cl- compete with
Quick diffusion OH-?
of chlorides - KOH still diffuses
within the cracks of
the ingot and cannot
passivate the whole
metal surface?

Leiden, 11-15 January 2010

 How chlorides interfere with the behaviour
of iron in KOH solutions?

E (V) Passivation of Fe in KOH solution

Interference with Cl-

Further perturbations t (time)

Leiden, 11-15 January 2010

 Marine iron-based swivel gun

Multimeter
in NaOH

Ref. electrode HM

Swivel gun recovered from Maltese waters

Leiden, 11-15 January 2010

 Full monitoring of the stabilisation

Ecorr pH

Λ
CCl-

Leiden, 11-15 January 2010

 Cathodic polarisation
speed up of stabilisation
processes

Leiden, 11-15 January 2010

 Voltage (V) Intensity (A) I
2 2,5

1,8

1,6 2
0.95V/Ag-AgCl
1,4
voltage
1,2 1,5

0,8 1
I Arc’Antique
0,6

0,4 0,5

0,2
Chlorides (ppm)
1100

0 1000 1st wash (14 samples)

0 2nd wash (26 samples)
0 200 400 600 800 1000 1200 1400 1600
900 First
time (h) wash
800

700
Electrolyte changed Second
wash
600

500 Linear
(First
400
wash)
300 Linear
(Second
200
wash)
100

0
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00

Square root of time (hours)

Leiden, 11-15 January 2010
 Use of pulsed currents

Ec=-0.75V/SHE -preventing hydrogen bubbling

-accelerating the stabilisation
process by favouring rapid
processes

Q Cl
= 0 , 29
Qtotal

Q
= 0,17
Cl

Q total

Leiden, 11-15 January 2010

 Application

Mass treatment: 23 iron bullets

from a grape shot

EVTEK
EVTEK

EVTEK

Leiden, 11-15 January 2010

 EVTEK
EVTEK

Cathodic polarisation in 1% KOH at –0.95V/Ag-AgCl

Leiden, 11-15 January 2010

Leiden, 11-15 January 2010
Leiden, 11-15 January 2010
 Stabilisation of copper-based
Pitting corrosion of copper
alloys

Cl-
Cu2(OH)3Cl, atacamite
EDF-Valectra

Cu CuCl, nantokite

Pitting corrosion: autocatalytic corrosion process

- metal dissolved inside the pit : excess of positive
copper ions.
- chlorides migrate from the environment or the metal
bulk inside the pit to maintain electroneutrality, and
nantokite (CuCl) is formed.
- Inside the pit, the metal is hydrolysed, resulting in low
pH inside the pit.
- Low pH and high concentration of chlorides:
Leiden, 11-15 January 2010 acceleration of corrosion
 In sodium sesquicarbonate

Bell - Ecorr and Cl- with time in sodium sesquicarbonate 1%

Ecorr CCl-
0 70
0 100 200 300 400 500 600 700
4
1
60
-0.005
3
5
2 CCl- 50
-0.01

40
-0.015
Ecorr 30
0
EVTEK
-0.02
20

-0.025
10

-0.03 0
time (h)

Leiden, 11-15 January 2010

 Stabilisation of aluminium-
based alloys
AWM

Pitting corrosion sensitivity

according to the alloys

[NaCl]=10-3M

Leiden, 11-15 January 2010

 Risk of pitting corrosion

pH=5.4, [NaCl]=10-3M

Leiden, 11-15 January 2010

 Cathodic corrosion on aluminium alloys in
NaCl solutions

2H2O + 2e- Î H2 + 2OH- Î pH Ò

e-
Al2O3 is dissolved preferably above
Al active sites (Al3Fe and Al2Cu)

Al2O3 + 2OH- Î AlO2- + H2O

pH Ò: Al is dissolved
Under the H2 bubble
H2

Leiden, 11-15 January 2010

 Optical monitoring

Leiden, 11-15 January 2010

 Modification of the Pourbaix diagram

Field of
6082 alloy with the stability
fields of pitting
corrosion and
cathodic corrosion
in neutral pH
added.
[NaCl]=10-3M

Leiden, 11-15 January 2010

Leiden, 11-15 January 2010
 Marine composite objects

Cleaning of the wood:

soaking in 1% EDTA
disodique followed by
electrophoresis in tapwater
(2 times): appearance of
the wood more natural
Porthole, Finnish
wreck, 19th c.

EVTEK

Impregnation of the wood iIn PEG 400 and

Leiden, 11-15 January 2010 PEG 4000
 Leather/wooden clog

Day Solution Iron conc. Iron Content

(mg/L) (mg)

1 1 % Na2EDTA 0.2 1.7

2 61 529

3 200 1736
EVTEK

3 1 % triammonium 1.2 10
citrate
4 11 95

5 23 200

5 – 18 Stored in tap water and treated with electrophoresis

19 - 25 1 % Na2EDTA

Leiden, 11-15 January 2010

 EVTEK

250 16

14
In tap water
200
12

10
Current (mA)

150

Voltage
current
8
voltage
100
6
1st side 2nd side
4
50
2

0 0
0 10 20 30 40 50 60
tim e (hours)
Leiden, 11-15 January 2010
 …with metal left
- +
Arc’Antique

XX XX
X
X
X
X X
XCl- X
XX X
X XXX
Rifles, 17th c.

… stabilisation of the barrels

in un-buffered KNO3 (+ addition
of HNO3 to keep the pH neutral)

Leiden, 11-15 January 2010

 Further treatment of the wood…

Protection

Loss of protection
Arc’Antique

-400

-450
Stabilisation of the 4. New PEG 400

wooden part: 2. Protection

Potential (mV) / ESS

-500 5. PEG
Impregnation in 4000

PEG 400 + -550

Hostacor
-600

-650

3. Contamination
-700
1. +Hostacor

-750
0 5 10 15 20 Weeks 25

Leiden, 11-15 January 2010

 Better monitoring of the cathodic potential
EVTEK

Stabilisation in a neutral
EVTEK
unbuffered solution
(1% (w/v) NaNO3)
Dry porthole, 19th c., Glass
Finnish waters

Stabilility of the pH?

EVTEK

rubber

Leiden, 11-15 January 2010

 Preparation of the artefact

EVTEK

Preliminary mechanical
cleaning

EVTEK
Electrical contact

Leiden, 11-15 January 2010

 Simulating the treatment in NaNO3

Corroded Bare nail

nails

EVTEK
Slightly
polished nails

Leiden, 11-15 January 2010

 Bare iron nails

Potential
corresponding
to the highest
extraction
of chlorides

The following reaction is favoured:

Leiden, 11-15 January 2010
2 H2O+ O2d + 4 e- Æ 4 OH-
 Slightly polished iron nails

The following reaction is favoured:

2 H2O+ O2d + 4 e- Æ 4 OH-
x FeO(OH) + x e- Æ x Fe + x OH-
Leiden, 11-15 January 2010
 Corroded iron nails

Opposite behaviour than before:

with corrosion layers and an increase of the
cathodic potential,
the pH tends to decrease
Leiden, 11-15 January 2010
 Application on the porthole

Monitoring of all electrochemical parameters

Anodic
potential

Cathodic
potential
pH

Leiden, 11-15 January 2010

 Low!

Decrease
of pH

Night
Addition of NaOH
(day)
Leiden, 11-15 January 2010
 Conditions modified
During the 5 first days.
Same conditions
Afterwards: anodic
Control and
Ea=1.1V/Ag-AgCl and
Ec=-0.5V/Ag-AgCl

Leiden, 11-15 January 2010

 Stabilisation of corroded Pb
artefacts
Arc’Antique

E (V/HSE)

Jacquard
looms
(Musée
des Arts
et
Métiers,
-1.3V
Paris) Pb2+ Î Pb

Arc’Antique
I (mA)

Cathodic polarisation of a lead coupon

Arc’Antique
carbonated artificially in Na2SO4 0.5M
(objective: treatment of composite artefacts),
vb= 1mV/s
Leiden, 11-15 January 2010
 Chronoamperometric curve at –1.3V/HSE in Na2SO4
0.5M. Counter-electrode: Pb

Arc’Antique

Leiden, 11-15 January 2010

 Application
Conservation of corroded lead seals still
attached to parchments with silk threads

Original
surface lost
Arc’Antique

Arc’Antique

Arc’Antique

Leiden, 11-15 January 2010

 Simulation of the treatment
of real composite artefacts:
-lead: fragments from lead
seals
-silk threads: naturally died
silk coupons
- counter-electrode: lead
plates

Dissolution of the dies

Arc’Antique without any protection

Leiden, 11-15 January 2010

 Protection of the textile threads

Loss of
Arc’Antique
adherence

Arc’Antique

Cathodic reduction

Paper impregnated with paraffine

Arc’Antique

Leiden, 11-15 January 2010

 Simulation of a treatment on artificial
materials

Immersion
test
Arc’Antique Arc’Antique

Arc’Antique

Enveloppe +
CDD
after
immersion
test

Leiden, 11-15 January 2010

 Preparation of a simulated composite

Absorbing paper

Arc’Antique
Arc’Antique
Arc’Antique

Lead
hemp
silk

Leiden, 11-15 January 2010

 Arc’Antique
Simulation
of the Arc’Antique

protection
of both
the silk and
Arc’Antique
the
Arc’Antique parchment

Arc’Antique
Leiden, 11-15 January 2010
 Design of a special support for the artefact
once protected

Arc’Antique

Arc’Antique

Arc’Antique

Arc’Antique

Leiden, 11-15 January 2010

 Arc’Antique

Arc’Antique
Leiden, 11-15 January 2010
 Arc’Antique

Optimisation: use of
Perspex rods to give
a better strength Arc’Antique

Leiden, 11-15 January 2010

 Packing the organic materials in PE
envelops sealed with cyclododecane

Arc’Antique

Arc’Antique Reinforcing of the protected

composite with Perspex rods
Parchment from the
Arc’Antique
French National Archives

Leiden, 11-15 January 2010