Electrochemical

assessment of protection
systems for metal
artefacts

Dr. Emilio Cano Díaz

Centro Nacional de Investigaciones Metalúrgicas
(CENIM)
Consejo Superior de Investigaciones Científicas
(CSIC)
 Outline
• New protection systems for heritage?
• Pros and cons of electrochemical techniques
• Rp: fundamentals and applications
• EIS: fundamentals and applications
• Evaluation of innovative coatings in the
PROMET project.

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 Need of new protection systems
• Improved efficiency
• Lower toxicity
• Specific needs for cultural heritage
conservation:
– Reversibility/re-tratability
– Respect to original object and surface
– Transparency, good visual aspect
– Reproducibility issues

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 Testing new protection systems
• Tests in laboratory coupons
– Difficult (impossible?) to reproduce composition
and corrosion layers
• Tests in real objects:
– Not uniform in composition, microstructure and
patina/corrosion products
– Unique value of each object
• Combination of both, specific protocols and
non-destructive and highly sensitive
techniques
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 Testing new protection systems
• Natural exposure
– Very reliable, but very slow
• Accelerated tests in climatic chambers
– Fast, but too accelerated
– Well established for industrial applications (for
instance, salt fog test)
– Better for comparison purposes
– Not applicable to real objects
• Electrochemical tests

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 Electrochemical tests
• Advantages
– Very high sensibility
1 nA/cm2
Fe → Fe2+ 1,04 · 10-8 g
1 hour

– Measure instantaneous corrosion rate and are not

destructive: evolution of protection/corrosion with
time
– Measure in real conditions: even on real objects!
– Relatively simple and inexpensive equipment

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 Electrochemical tests
• Disadvantages
– Usually need a bulk electrolyte: not real
atmospheric conditions
– Interpretation might be not easy in some cases
(EIS)

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 Polarization resistance (Rp)
• At Ecorr, the slope of the V/I curve is
proportional to the corrosion rate
• Stern and Geary (1957):

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 Polarization resistance (Rp)
• Potential sweep from +- 10 mV vs. Ecorr
• Usually not employed for coatings due to the
very high resistance of the coating
• Fast and easy to intrepret

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 Electrochemical Impedance
Spectroscopy (EIS)

• Based on the application of a AC low

amplitude (typically 10 mV) potential signal

• Perturbation: E(t)=E0 cos(ω t)

• System response : I(t)=I0 cos(ω t-ϕ )
• Response function: Z (ω) = E/I

• Frequency swept from 100 kHz to 1 mHz

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 Electrochemical Impedance
Spectroscopy (EIS)

• The most important technique for evaluation

of corrosion protection coatings in the last 30
years
• Allows for the measurement of the properties
of high resistance coatings
• Can obtain information of different
processes/parts of your system: electrolyte,
coating, corrosion processes, etc.

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 History of use of EIS for CH
• Pioneer work: Price, Hallam et al., Metal 95
• In situ evaluation of CH objects (Letardi, Metal
98)
• Very important increase of the use of EIS in
CH in the last years

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 PROMET project

• PROMET:
“Innovative conservation approaches for monitoring
and protecting ancient and historic metals collections
from the Mediterranean basin”
– 6º Framework Program E.U. INCO-MED
– November 2004 - April 2008
– 21 partners from 11 mediterranean countries
– Spain: CENIM-CSIC & UAM

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 Protocol to study new protection
systems

Artificially
Study of real Laboratory
corroded
objects tests
coupons

New Naturally
Laboratory
products corroded
tests
selection coupons

Real exposure

Final list of
products
Application in real
heritage objects
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 Experimental

• Material: low carbon steel (0,14%)

• Coatings
– New: Poligen ES91009 (BASF)
• Ready to use liquid poliethylene wax emulsion
• Dries in24 h.
• Non toxic and environmentally safe
– Traditional: Paraloid B-72 and Renaissance
• With and without corrosion inhibitor additives
• Electrochemical tests (Rp and EIS)

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 Coatings tested

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 Experimental setup

• Polarization resistance (Rp)

– -10→+10 mV vs. OCP
– 0,16 mV/s
• Electrochemical Impedance(EIS)
– 64 kHz → 1mHz, 10 mV, 0 V vs. OCP
• PAR 273A
Solartron 1250

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 Experimental setup

Reference Platinum
electrode mesh
(counter
electrode)

4.15 cm2
working
electrode

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 Rp tests
ID Coating

• Clean samples 0 No coating (Blank)

1 Renaissance wax
16
2 Poligen ES 91009
14
Thickness, micrometers

2a Poligen ES 91009 + M435 inhibitor

12

10 2b Poligen ES 91009 + M370 inhibitor

8 3 Paralloid B-72 (15% Acetonae
6
3a Paralloid B-72 + M435 inhibitor
4
3b Paralloid B-72 + M109 inhibitor
2
3c Paralloid B-72 + Alkaterge-T
0
1 2 2a 2b 3 3a 3b 3c
-2

Sample

7
10

2
resistance, cm
6
10

5
10
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10 19
 Rp tests
ID Coating

• Pre-corroded and NC
TC1
No coating (Blank)
15% Paraloid B-72 in acetone

aged samples TC2

C1
Renaissance wax
Poligen ES 91009
C2 Poligen ES 91009 + M370
C3 Poligen ES 91009 +M435
C4 15% Paraloid B-72 in acetone + Alkaterge-T
C5 15% Paraloid B-72 in acetone + M109
140
Reference
120 Accelerated aged

100
Thickness, μm

1.0E+08
80
1.0E+07 Reference **
Accelerated aged
60 1.0E+06

40 1.0E+05

2
Rp, Ω cm
1.0E+04
20
1.0E+03
0
NC TC1 TC2 C1 C2 C3 C4 C5 1.0E+02
Coating
1.0E+01

1.0E+00
NC TC1 TC2 C1 C2 C3 C4 C5
Coating
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 EIS results
107
106
105
Sin recubrimiento
104
|Z|

Cdl
103
102 RS
101
R1
100
10-1 100 101 102 103 104
Frequency (Hz) No coating
Coating 1
Coating 2
Coating 2a
Coating 2b
-90
theta

-45

0
10-1 100 101 102 103 104
Frequency (Hz)

21
 EIS results
107
106
105
Sin recubrimiento
104
|Z|

103
102 RS CPE1
101
R1
100
10-1 100 101 102 103 104
Frequency (Hz) No coating
Coating 1
Coating 2
1
Coating 2a
Z CPE 
Y0  j 
Coating 2b 
-90
theta

-45 CPE1
Y0 α R1
2 (1-α)
F /cm s Ω cm2
2.8 × 10-3 0.74 2681
0
10-1 100 101 102 103 104
Frequency (Hz)

22
 EIS results
107
106
105
Rennaissance wax
104
|Z|

103 CPE1
102 RS
101
100 R1 CPE2
-1 0 1 2 3 4
10 10 10 10 10 10
No coating
R2
Frequency (Hz)
Coating 1
Coating 2
Coating 2a
Coating 2b CPE1 CPE2
-90 Y0 α R1 Y0 α R2
2
2 (1-α)
F /cm s Ω cm 2 (1-α)
F /cm s Ω cm2
0.4 × 10-3 0.8 22.86 0.3 × 10-3 0.79 2960
theta

-45

0
10-1 100 101 102 103 104
Frequency (Hz)

23
 EIS results
107
106
105
Poligen ES 91009
104
|Z|

103
CPE1
102
RS
101
100 R1
10-1 100 101 102 103 104
CPE2
Frequency (Hz) No coating
Coating 1
Coating 2 CPE1 CPE2
Coating 2a
Coating 2b Y0 α R1 Y0 α
2 (1-α) 2 2 (1-α)
-90 F /cm s Ω cm F /cm s
-3
0.4 × 10 0.76 2162 59 × 10-3 0.51
-6 -5
1.17 × 10 0.76 82442 2.7 × 10 0.58
theta

-9 -7
-45 8.89 × 10 0.96 280810 8.3 × 10 0.47

0
10-1 100 101 102 103 104
Frequency (Hz)

24
 EIS results
107 Paraloid B72
106
CPE1
105
RS
104
|Z|

103 R1 CPE2
102
101 R2
100
10-1 100 101 102 103 104
CPE1 CPE2
Frequency (Hz) No coating Y0 α R1 Y0 α R2
Coating 3 2
Coating 3a
2 (1-α)
F /cm s Ω cm 2 (1-α)
F /cm s Ω cm2
Coating 3b 2.95 × 10-7 0.56 16725 4.6 × 10-6 0.5 34825
Coating 3c -3 -3
-90 0.39 × 10 0.5 407 1.2 × 10 0.82 1395
-7 -6
4.53 × 10 0.65 32228 1.0 × 10 0.63 1.29 × 106
2.14 × 10-7 0.65 8031 7.6 × 10-6 0.54 28949
theta

-45

0
10-1 100 101 102 103 104
Frequency (Hz)

25
 Conclusions

• Electrochemical tests give a quantitative

information of the protection provided by
different coatings in a short time
– Rp provide quick and easy to interpret results
– EIS provide in-depth information on the corrosion
and protection mechanisms

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 Conclusions

• The addition of corrosion inhibitor additives

did not provide and improvement of the
protection, and in some cases have a
negative effect.
• Poligen ES91009 provides better protection
than Paraloid B72 when applied in thick layers
• Rennaissance provides very little protection

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 PROMET: additional information

– CSSIM conference proceedings “Strategies for

saving our cultural heritage”
– Book “Metals and Museums in the Mediterranean.
Protecting, preserving and interpreting”

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 Further reading
• Cano E, Bastidas DM, Argyropoulos V, Fajardo S, Siatou A, Bastidas JM, Degrigny C (2009) Electrochemical
characterization of organic coatings for protection of historic steel artefacts. Journal of Solid State Electrochemistry, 1-
11.
• Cano E, Lafuente D, Bastidas DM (2009) Use of EIS for the evaluation of the protective properties of coatings for
metallic cultural heritage: a review. Journal of Solid State Electrochemistry, 1-11.
• Ellingson LA, Shedlosky TJ, Bierwagen GP, de la Rie ER, Brostoff LB (2004) The use of electrochemical impedance
spectroscopy in the evaluation of coatings for outdoor bronze. Studies in Conservation 49, 53-62.
• Letardi P, Beccaria A, Marabelli M, D'Ercoli G (1998) Application of electrochemical impedance mesurements as a tool
for the characterization of the conservation and protection state of bronze works of art. In 'Metal 98. International
Conference on Metal Conservation '. Draguignan-Figanières (France). (Eds J Ashton and D Hallam) pp. 303-308.
(James & James)
• Loveday D, Peterspm P, Rodgers B (2004) Evalution of organic coatings with electrochemical impedance spectroscopy
part 2: Application of EIS to coatings. JCT CoatingsTech 1, 88-93.
• Mansfeld F (1995) Use of electrochemical impedance spectroscopy for the study of corrosion protection by polymer
coatings. Journal of Applied Electrochemistry 25, 187-202.
• Mansfeld F (2008) Fundamental aspects of the polarization resistance technique-the early days. Journal of Solid State
Electrochemistry, 1-6.
• Murray JN (1997) Electrochemical test methods for evaluating organic coatings on metals: An update. Part III: Multiple
test parameter measurements. Progress in Organic Coatings 31, 375-391.
• Price C, Hallam D, Heath G, Creagh D, Ashton J (1995) An electrochemical study of waxes for bronze sculpture. In
'Metal 95. International Conference on Metal Conservation '. Semur-en-Auxois (France). (Eds ID MacLeod, SL Pennec
and L Robbiola) pp. 233-241. (James & James)

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 Acknowledments

• Organizers of the workshop

• PROMET project E.U.
• Colleagues in the PROMET
• Prof. José María Bastidas

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