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Local Investigation of Corrosion Processes by Coupled Electrochemical and Spectroscopic Techniques M-C. Bernard, S.
Local Investigation of Corrosion Processes by Coupled Electrochemical and Spectroscopic Techniques M-C. Bernard, S.

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 Monument to Francis Garnier, Paris Coin of post-Roman Empire V t h – III

Objectives

Objectives Monument to Francis Garnier, Paris Coin of post-Roman Empire V t h – III r

Monument to Francis Garnier, Paris

Coin of post-Roman Empire V th III rd A.D. found in Morocco

Empire V t h – III r d A.D. found in Morocco - Characterization of corrosion

- Characterization of corrosion products (Raman

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

- Characterization of corrosion processes:

electrochemical techniques coupled with

spectroscopy

Outline How to perform electrochemistry on tiny amount of powder materials? 1. Electrochemical tools for

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

Electrochemical tools for powder materials

Composite or carbon paste electrode

for powder materials Composite or carbon paste electrode Electrode dimension diameter ~ 5 - 10 mm

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 I. Uchida, H. Fujiyoshi and S.

Electrochemical tools for powder materials

micromanipulator / abrasive electrode

for powder materials micromanipulator / abrasive electrode I. Uchida, H. Fujiyoshi and S. Waki, J. Power

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

and J. Bessière, Electrochim. Acta , 42 (1997) 3351 1 mm scratches D.A. Fiedler, J. Solid

1 mm

and J. Bessière, Electrochim. Acta , 42 (1997) 3351 1 mm scratches D.A. Fiedler, J. Solid
and J. Bessière, Electrochim. Acta , 42 (1997) 3351 1 mm scratches D.A. Fiedler, J. Solid

scratches

D.A. Fiedler, J. Solid State Electrochem., 2 (1998) 315

Cavity microelectrode Electrode dimension diameter ~ 50 µm depth ~ 25 µm volume ~ 5

Cavity microelectrode

Electrode dimension

diameter ~ 50 µm depth ~ 25 µm

volume ~ 5 10 -8 cm 3

half of the cavity is filled V ~ 2.5 10 -8 cm 3

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

Cavity microelectrode

Let us assume m = 100 ng and a specific surface area of 10 –
Let us assume m = 100 ng
and a specific surface area of
10 – 1000 cm 2 g -1
 S elect = 100 µm 2 – 0.01 mm 2
E=U-R i
Ohmic drop:
e
tot
Capacitive current:
 -vC
E
-t
i
i =vC +
exp
c
0
0
R
R C
e
e
0
Interest of decreasing electrode dimension ● reversible electrochemical system D = 10 - 5 cm

Interest of decreasing electrode dimension

reversible electrochemical system

electrode dimension ● reversible electrochemical system D = 10 - 5 cm 2 s - 1

D = 10 -5 cm 2 s -1

k 0 = 1

C ox = 10 mM r 0 = 5 mm

V = 100 Vs -1

R e = 2 W C dl = 50 µF

a = 0.5

Interest of decreasing electrode dimension Significant parameters : R e and C d l For

Interest of decreasing electrode dimension

Significant parameters : R e and C dl

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.

working electrode counter electrode
working electrode
counter electrode

4 r

0

2

r

0

2

r

0

R

e

C

i

tot

dl

Ohmic drop

R i r

e tot

0

Time constant

R C r

e

dl

0

Interest of decreasing electrode dimension Significant parameters : R e and C d l For

Interest of decreasing electrode dimension

Significant parameters : R e and C dl

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

R

e

4 r

0

Ohmic drop

Time constant

C

dl

R i

e tot

2

r

0

i  r tot 0
i
 r
tot
0

independent of the electrode size

R C r

e

dl

0

Interest of decreasing electrode dimension C. Amatore in Electrochemistry at Ultramicroelectrodes , Physcal

Interest of decreasing electrode dimension

Interest of decreasing electrode dimension C. Amatore in Electrochemistry at Ultramicroelectrodes , Physcal
Cavity microelectrode Pani powder as an example (0.5 M H 2 SO 4 ) 5

Cavity microelectrode

Pani powder as an example (0.5 M H 2 SO 4 ) 5 5 100
Pani powder as an example (0.5 M H 2 SO 4 )
5
5
100
(a)
(b)
(c)
4
4
3
3
50
2
2
0
1
1
0
0
-50
-1
-1
-2
-2
-100
µ
I
/ µA
I
/ mA

-0.2

0.0

0.2

E / V SCE

0.4

-0.2

0.0

0.2

0.4

E / V SCE

-0.4

0.0

0.4

E / V SCE

0.8

0.4 -0.2 0.0 0.2 0.4 E / V SCE -0.4 0.0 0.4 E / V SCE

10 cycles at 2 Vs -1

1 cycle at 0.5 mVs -1

1 cycle at 0.02 Vs -1

Outline How to perform electrochemistry on tiny amount of powder materials? 1. Electrochemical tools for

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 Laser Lens (x80) potentiostat CCD detector Intensity 250 200

Coupling with Raman spectroscopy

Notch

Filter Laser Lens (x80) potentiostat CCD detector
Filter
Laser
Lens
(x80)
potentiostat
CCD
detector

Intensity

250

200

150

100

50

0

250 200 150 100 50 0 200 400 600 800 Wavenumber (cm-1)
250 200 150 100 50 0 200 400 600 800 Wavenumber (cm-1)

200

400

600

800

Wavenumber (cm-1)

Wavenumber

Energy of vibration

The Raman spectra is a material signature

Analysis of corrosion products Iron: nail from Bois l’Abbé – Gallo Roman site in France

Analysis of corrosion products

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

nail from Bois l’Abbé – Gallo Roman site in France Layered structure Outer layer Inner layer
nail from Bois l’Abbé – Gallo Roman site in France Layered structure Outer layer Inner layer

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

Analysis of corrosion products

Analysis of corrosion products Layered structure Outer layer Inner layer Massive iron The process of metallic

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 -Fe 2 O 3 50 60 500 1000 Wavenumber (cm-1)

Analysis of corrosion products

Maghemite -Fe 2 O 3 50 60 500 1000 Wavenumber (cm-1) 70 Ferrihydrite (Fe 2
Maghemite
-Fe 2 O 3
50
60
500
1000
Wavenumber (cm-1)
70
Ferrihydrite
(Fe 2 O 3 ,5H 2 O)
80
60
80
100
carbonate
Length X (µm)
Goethite
500
1000
a-FeOOH
Magnetite
Fe 3 O 4
Wavenumber (cm-1)
Length Y (µm)

00

400

600

800

Wavenumber (cm-1)

00

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

400

600

800

Wavenumber (cm-1)

Analysis of corrosion products in situ 300s ex situ 30s Lepidocrocite  -FeOOH 200 400

Analysis of corrosion products

Analysis of corrosion products in situ 300s ex situ 30s Lepidocrocite  -FeOOH 200 400 600
Analysis of corrosion products in situ 300s ex situ 30s Lepidocrocite  -FeOOH 200 400 600
Analysis of corrosion products in situ 300s ex situ 30s Lepidocrocite  -FeOOH 200 400 600
Analysis of corrosion products in situ 300s ex situ 30s Lepidocrocite  -FeOOH 200 400 600
Analysis of corrosion products in situ 300s ex situ 30s Lepidocrocite  -FeOOH 200 400 600

in situ

300s

ex situ

30s

Lepidocrocite

-FeOOH

200

400

600

800

-1µA 2hrs

E=-1.3

-1µA 1hr

E=-1.3

-0.5µA 1hr

E=-1.1

Wavenumber (cm-1)

Fe 3 O 4
Fe 3 O 4
1hr E=-1.3 -0.5µA 1hr E=-1.1 Wavenumber (cm-1) Fe 3 O 4 400 600 800 Wavenumber (cm-1)
1hr E=-1.3 -0.5µA 1hr E=-1.1 Wavenumber (cm-1) Fe 3 O 4 400 600 800 Wavenumber (cm-1)
1hr E=-1.3 -0.5µA 1hr E=-1.1 Wavenumber (cm-1) Fe 3 O 4 400 600 800 Wavenumber (cm-1)
1hr E=-1.3 -0.5µA 1hr E=-1.1 Wavenumber (cm-1) Fe 3 O 4 400 600 800 Wavenumber (cm-1)

400

600

800

Wavenumber (cm-1)

Fe 3 O 4 SO 4 2-
Fe 3 O 4
SO 4 2-
Fe 3 O 4 400 600 800 Wavenumber (cm-1) Fe 3 O 4 SO 4 2-
Fe 3 O 4 400 600 800 Wavenumber (cm-1) Fe 3 O 4 SO 4 2-

00

400

600

800

Wavenumber (cm-1)

60’ E=-1.1

40’ E=-1.1

30’ E=-1.1

15’ E=-1.05

2’ E=-1.02

i=-500nA

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 00 400 600 800 1000 Wavenumber (cm-1) M.C. Bernard,

Analysis of corrosion products

Goethite a-FeOOH
Goethite
a-FeOOH
Analysis of corrosion products Goethite a-FeOOH 00 400 600 800 1000 Wavenumber (cm-1) M.C. Bernard, S.
Analysis of corrosion products Goethite a-FeOOH 00 400 600 800 1000 Wavenumber (cm-1) M.C. Bernard, S.

00

400

600

800

1000

Wavenumber (cm-1)

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

-0.5µa 4 heures

v=-1.35

-0.3µa 2heures

v=-1.21

Maghemite / Magnetite -Fe 2 O 3 / Fe 3 O 4

500

0

/ Magnetite  -Fe 2 O 3 / Fe 3 O 4 500 0 500 50nA
/ Magnetite  -Fe 2 O 3 / Fe 3 O 4 500 0 500 50nA
/ Magnetite  -Fe 2 O 3 / Fe 3 O 4 500 0 500 50nA
/ Magnetite  -Fe 2 O 3 / Fe 3 O 4 500 0 500 50nA
/ Magnetite  -Fe 2 O 3 / Fe 3 O 4 500 0 500 50nA

500

50nA 3hrs

V=+1

50nA 1hr

V=+1

-50nA 3hrs

V=-1.2

départ

Wavenumber (cm-1)

Analysis of corrosion products 150 100 50 0 400 600 800 1000 Wavenumber (cm-1) -50

Analysis of corrosion products

150

100

50

0

400 600 800 1000
400
600
800
1000

Wavenumber (cm-1)

-50 nA 1heure E = -0.96 V

-50 nA 10 minutes E = -0.93 V

Taking (ex situ)

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

Analysis of corrosion products

Analysis of corrosion products Alloy composition of the Roman coin bronze   Cu Sn Pb Fe
Analysis of corrosion products Alloy composition of the Roman coin bronze   Cu Sn Pb Fe

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

F a-PbO F PbClOH G F b-PbO
F a-PbO
F
PbClOH
G
F b-PbO

Analysis of corrosion products

2PbCO 3 ·Pb(OH) 2

b-PbO Analysis of corrosion products 2PbCO 3 ·Pb(OH) 2 B Sn0 2 Cu 2 0 M.
B Sn0 2 Cu 2 0
B
Sn0 2
Cu 2 0

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

Analysis of corrosion products 10 cycles in 10 g/L K 2 B 4 O 7

Analysis of corrosion products

Analysis of corrosion products 10 cycles in 10 g/L K 2 B 4 O 7 10

10 cycles in 10 g/L K 2 B 4 O 7

10 mV s -1

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

Analysis of corrosion products Raman spectra collected during CV experiments Chemical dissolution Cu 2 0

Analysis of corrosion products

Raman spectra collected during CV experiments

Chemical dissolution Cu 2 0 ; Sn0 2 a-PbO 2 SnO 2 Cupric form Cu(II)
Chemical dissolution
Cu 2 0 ; Sn0 2
a-PbO 2
SnO 2
Cupric form
Cu(II)
Reduction to
metallic species
Cu 2 0
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) PbO 2 /Pb Cu(II)/Cu(I) 10 cycles in 10 g/L

Analysis of corrosion products

Cu(II)/Cu(0) Cu(I)/Cu(0) PbO 2 /Pb Cu(II)/Cu(I)
Cu(II)/Cu(0)
Cu(I)/Cu(0)
PbO 2 /Pb
Cu(II)/Cu(I)

10 cycles in 10 g/L K 2 B 4 O 7

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

Analysis of corrosion products

Electrochemical impedance at the corrosion potential

Electrochemical impedance at the corrosion potential Diffusion of dissolved oxygen cannot be neglected M.
Electrochemical impedance at the corrosion potential Diffusion of dissolved oxygen cannot be neglected M.

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

Analysis of corrosion products

Analysis of corrosion products Reactivity of the patina: oxygen reduction at the patina redox couple formed

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.,

Analysis of corrosion products

Possibility of performing “layer by layer” analysis

products Possibility of performing “layer by layer” analysis C. Chiavari et al., Electrochim. Acta. 52 (2007)

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

products Possibility of performing “layer by layer” analysis C. Chiavari et al., Electrochim. Acta. 52 (2007)
Analysis of corrosion products Possibility of performing “layer by layer” analysis C. Chiavari et al.,

Analysis of corrosion products

Possibility of performing “layer by layer” analysis

products Possibility of performing “layer by layer” analysis C. Chiavari et al., Electrochim. Acta. 52 (2007)

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

products Possibility of performing “layer by layer” analysis C. Chiavari et al., Electrochim. Acta. 52 (2007)
products Possibility of performing “layer by layer” analysis C. Chiavari et al., Electrochim. Acta. 52 (2007)
Analysis of corrosion products Possibility of performing “layer by layer” analysis - No electrochemical reactivity

Analysis of corrosion products

Possibility of performing “layer by layer” analysis

Possibility of performing “layer by layer” analysis - No electrochemical reactivity at pH = 5.6 -

- 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

Analysis of corrosion products

Possibility of performing “layer by layer” analysis

Possibility of performing “layer by layer” analysis Same model than for the bronze coin Oxygen reduction

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

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)

Acknowledgments

M-C. Bernard, S. Joiret (LISE) H. Takenouti (LISE) L. Robbiola (ENSCP Toulouse)

Acknowledgments M-C. Bernard, S. Joiret (LISE) H. Takenouti (LISE) L. Robbiola (ENSCP  Toulouse)