Local Investigation of Corrosion Processes by

Coupled Electrochemical and Spectroscopic

Techniques

M-C. Bernard, S. Joiret, V. Vivier

Laboratoire Interfaces et Systèmes Électrochimiques

CNRS – UPR 15 (Paris – France)
suzanne.joiret@upmc.fr
vincent.vivier@upmc.fr

Electrochemistry in Historical and Archaeological Conservation – Leiden 11-15 January 2010

 Objectives

Coin of post-Roman Empire Vth – IIIrd A.D.

found in Morocco

- Characterization of corrosion products (Raman

spectroscopy, SEM, X-Ray diffraction,
electrochemical techniques …)

- Characterization of corrosion processes:

electrochemical techniques coupled with
spectroscopy
Monument to Francis Garnier, Paris
 Outline

How to perform electrochemistry on tiny amount of

powder materials?

1. Electrochemical tools for studying powder materials

2. Cavity microelectrode – Interest of decreasing
electrode size
3. Coupling with Raman spectroscopy
4. Analysis of corrosion products
- iron
- bronze
5. Conclusion
Electrochemical tools for powder materials

Composite or carbon paste electrode

Electrode dimension

diameter ~ 5 - 10 mm
mass ~ 5 – 100 mg

Use of graphite for electrical conductivity

and a binder (Teflon) for mechanical properties
 Electrochemical tools for powder materials

micromanipulator / abrasive electrode

1 mm

scratches

I. Uchida, H. Fujiyoshi and S. Waki, J. Power sources, 68 (1997) 139.

M. Perdicakis, N. Grosselin and J. Bessière, Electrochim. Acta, 42 (1997) 3351 D.A. Fiedler, J. Solid State Electrochem., 2 (1998) 315
 Cavity microelectrode

Electrode dimension

diameter ~ 50 µm
depth ~ 25 µm

volume ~ 5 10-8 cm3

half of the cavity is filled

V ~ 2.5 10-8 cm3

density of the material 1-10

mass ~ 25 – 250 ng
C. S. Cha, C. M Li, H. X. Yang, and P. F. Liu, J. Electroanal Chem., 368 (1994) 47
V. Vivier, C. Cachet-Vivier, C.S. Cha, J-Y. Nedelec, L.T. Yu, Electrochem. Comm. 2 (2000) 180.
C. Cachet-Vivier, V. Vivier, C.S. Cha, J-Y. Nedelec, L.T. Yu, Electrochim. Acta. 47 (2001) 181
 Cavity microelectrode

Let us assume m = 100 ng

and a specific surface area of

10 – 1000 cm2g-1

 Select = 100 µm2 – 0.01 mm2

Ohmic drop: E=U-R ei tot

Capacitive current:
 Ei   -t 
ic =vC0 +  -vC0  exp  
 e
R   e 0
R C
 Interest of decreasing electrode dimension

● reversible electrochemical system

D = 10-5 cm2s-1
k0 = 1 a = 0.5
Cox = 10 mM
r0 = 5 mm
V = 100 Vs-1
Re = 2 W
Cdl = 50 µF
 Interest of decreasing electrode dimension

Significant parameters : Re and Cdl

For a usual working electrode (disk-electrode) smaller than the counter electrode
the current is then forced to flow through a conical volume delimited by the two
electrodes.


Re  Cdl   r02 itot   r02
4r0

counter electrode
working electrode
Ohmic drop Reitot  r0

Time constant ReCdl  r0

 Interest of decreasing electrode dimension

Significant parameters : Re and Cdl

For a very small working electrode (microelectrode), edge effects and non planar
diffusion control the mass transport to the electrode interface.


Re  Cdl   r02 itot  r0
4r0

Ohmic drop Reitot independent of the electrode size

Time constant ReCdl  r0

 Interest of decreasing electrode dimension

C. Amatore in Electrochemistry at Ultramicroelectrodes, Physcal Electrochemistry 1995 Chap. 4

 Cavity microelectrode
Pani powder as an example (0.5 M H2SO4)
5 5
(a) (b) 100 (c)
4 4

3 3 50

2 2

I / mA
I / µA

I / µA
1 1 0

0 0

-50
-1 -1

-2 -2
-100
-0.2 0.0 0.2 0.4 -0.2 0.0 0.2 0.4 -0.4 0.0 0.4 0.8
E / VSCE E / VSCE E / VSCE

10 cycles 1 cycle 1 cycle

at 2 Vs-1 at 0.5 mVs-1 at 0.02 Vs-1
 Outline

How to perform electrochemistry on tiny amount of

powder materials?

1. Electrochemical tools for studying powder materials

2. Cavity microelectrode – Interest of decreasing
electrode size
3. Coupling with Raman spectroscopy
4. Analysis of corrosion products
- iron
- bronze
5. Conclusion
 Coupling with Raman spectroscopy

Notch
Filter
Intensity
Laser
250
Lens
200
(x80)
150

100

50

0
200 400 600 800
Wavenumber (cm-1)

Wavenumber

potentiostat CCD Energy of vibration
detector

The Raman spectra is
a material signature
 Analysis of corrosion products

Iron: nail from Bois l’Abbé – Gallo Roman site in France

Layered structure
Outer layer

Inner layer

Massive iron

Is this structure is protective? How does Iron corrode?

What can we say about the model of iron dissolution?
M.C. Bernard, S. Joiret, Electrochim. Acta. 54 (2009) 5199
 Analysis of corrosion products

Layered structure
Outer layer

Inner layer

Massive iron

The process of metallic corrosion associates dissolution of the metal as

anodic reaction and a counter part the cathodic reaction. In moisture air this
can be the reduction of oxygen into hydroxyle anions, in water this can be the
reduction of water to hydrogen gas. For long duration buried artefacts,
oxygen is supposed to be absent close to the object and iron cannot
spontaneously reduce water in soils.

One hypothesis have been proposed: the reduction of already formed iron
oxides, which can take place and allowed further corrosion process without
any oxygen intervention.
 Analysis of corrosion products

Maghemite
-Fe2O3
50
Length Y (µm)

60

500 1000
70 Wavenumber (cm-1)

Ferrihydrite
80 (Fe2O3,5H2O)
60 80 100
carbonate
Length X (µm)

Goethite 500 1000

Magnetite
a-FeOOH Wavenumber (cm-1)
Fe3O4

200 400 600 800 200 400 600 800

Wavenumber (cm-1) Wavenumber (cm-1)

M.C. Bernard, S. Joiret, Electrochim. Acta. 54 (2009) 5199

 Analysis of corrosion products

in situ Lepidocrocite
300s
-FeOOH
ex situ
30s
200 400 600 800
Wavenumber (cm-1)
Fe3O4
-1µA 2hrs
Fe3O4 60’ E=-1.1
E=-1.3
40’ E=-1.1
SO42-
-1µA 1hr 30’ E=-1.1
E=-1.3
15’ E=-1.05
-0.5µA 1hr 2’ E=-1.02
E=-1.1
400 600 800 i=-500nA
200 400 600 800
Wavenumber (cm-1)
Wavenumber (cm-1)

Borate buffer Sulphate solution

-500nA/ 1heure = 20 x the theoretical charge for the whole reduction

M.C. Bernard, S. Joiret, Electrochim. Acta. 54 (2009) 5199

 Analysis of corrosion products

Goethite
a-FeOOH
-0.5µa 4 heures
v=-1.35
-0.3µa 2heures
v=-1.21
Maghemite / Magnetite
200 400 600 800 1000
-Fe2O3 / Fe3O4
Wavenumber (cm-1)
50nA 3hrs
V=+1
500 50nA 1hr
V=+1
-50nA 3hrs
V=-1.2
0 départ

500
Wavenumber (cm-1)

M.C. Bernard, S. Joiret, Electrochim. Acta. 54 (2009) 5199

 Analysis of corrosion products

-50 nA
150 1heure E = -0.96 V

100 -50 nA
10 minutes E = -0.93 V

50

Taking (ex situ)

0

400 600 800 1000

Wavenumber (cm-1)

Reduction of synthetic lepidocrocite to magnetite and of goethite from patina

(easier than pure goethite) is taking place only during hydrogen evolution from
water reduction. This mecanism is not responsible of ferrous objects
corrosion.
M.C. Bernard, S. Joiret, Electrochim. Acta. 54 (2009) 5199
 Analysis of corrosion products

Alloy composition of the Roman coin bronze

Cu Sn Pb Fe Al
at.% 80.0 7.75 10.9 0.74 0.54
wt.% 61.1 11.1 27.2 0.24 0.36
M. Serghini-Idrissi et al., Electrochim. Acta. 50 (2005) 4699
 Analysis of corrosion products

a-PbO
F F 2PbCO3·Pb(OH)2

PbClOH G
F b-PbO
Sn02

Cu20

M. Serghini-Idrissi et al., Electrochim. Acta. 50 (2005) 4699

 Analysis of corrosion products

10 cycles
in 10 g/L K2B4O7
10 mV s-1

M. Serghini-Idrissi et al., Electrochim. Acta. 50 (2005) 4699

 Analysis of corrosion products

Raman spectra collected during CV experiments

Cu20 ; Sn02
a-PbO2
SnO2

Chemical dissolution
Cupric form
Cu(II)

Reduction to
metallic species

Cu20
but lost of
cristallinity

M. Serghini-Idrissi et al., Electrochim. Acta. 54 (2005) 4699

 Analysis of corrosion products

Cu(II)/Cu(0)
Cu(I)/Cu(0) PbO2/Pb

10 cycles
in 10 g/L K2B4O7
Cu(II)/Cu(I)
10 mV s-1

M. Serghini-Idrissi et al., Electrochim. Acta. 50 (2005) 4699

 Analysis of corrosion products

Electrochemical impedance at the corrosion potential

Diffusion of dissolved oxygen cannot be neglected

M. Serghini-Idrissi et al., Electrochim. Acta. 50 (2005) 4699
 Analysis of corrosion products

Reactivity of the patina:

oxygen reduction at the patina
redox couple formed by patina products

M. Serghini-Idrissi et al., Electrochim. Acta. 50 (2005) 4699

 Analysis of corrosion products

Possibility of performing “layer by layer” analysis

C. Chiavari et al., Electrochim. Acta. 52 (2007) 7760

 Analysis of corrosion products

Possibility of performing “layer by layer” analysis

C. Chiavari et al., Electrochim. Acta. 52 (2007) 7760

 Analysis of corrosion products

Possibility of performing “layer by layer” analysis

- No electrochemical reactivity at pH = 5.6

- Same behavior for sample FG1 & FG2 (same layer)
- Copper dissolution during the first cycle
- Fluorescence for Raman spectroscopy
C. Chiavari et al., Electrochim. Acta. 52 (2007) 7760
 Analysis of corrosion products

Possibility of performing “layer by layer” analysis

Same model than for the bronze coin

Oxygen reduction + diffusion
Patina = redox couple

the inner layer (with Cu/Zn) exhibits a similar behavior than the bronze coin

C. Chiavari et al., Electrochim. Acta. 52 (2007) 7760

 Conclusion

- Cavity microelectrode allows studying few amount of material (~100 ng)

- Possibility to perform Raman spectroscopy and electrochemistry

simultaneously

- We can scrap off corrosion product layer by layer

M. Serghini-Idrissi et al., Electrochim. Acta. 54 (2005) 4699

 Acknowledgments

M-C. Bernard, S. Joiret (LISE)

H. Takenouti (LISE)
L. Robbiola (ENSCP  Toulouse)