Letardi, P. y Cano, E. Electrochemical Protection Systems Metal Artefacts. 2010

Electrochemical Assessment of
Electrochemistry in Historical and Archaeological Conservation

Workshop January 11 - 15 2010, Leiden, The Netherlands
Protection Systems on Metal

Artefacts
P. Letardi
CNR - ISMAR, Genoa, Italy
E.Cano
CENIM-CSIC, Madrid, Spain
Introduction
Basic of EIS
Electrochemical cell and electrolyte
Overview of commercially available

instruments
Data acquisition, representation and

analysis
Test of coatings for cultural heritage

Basic of EIS
The fundamental approach of

Energy level (Potential E) all impedance methods is to

+ + + + apply a small amplitude
sinusoidal excitation signal to
the system under investigation
and measure the response.
Charge flow (Current I) Theoretical Electrochemical
systems are usually
Ref characterised by non-linear I-E
curve .
- - - -
A low amplitude sine wave
DEsin(wt), of a particular
frequency, is superimposed on
the dc polarization voltage E0.
This results in a current
response of a sine wave
DIsin(wt+f) superimposed on
the dc current I0. The current
response is shifted with
respect to the applied
potential.
• Perturbation:
• System response :
• Response function:
Basic of EIS
Z (w) = E/I
E(t)=E0 cos(w t)
I(t)=I0 cos(w t-f )
Basic of EIS
Z(w) is a complex quantity with a magnitude and a

phase shift which depends on the frequency of the

signal. Therefore by varying the frequency of the
applied signal one can get the impedance of the
system as a function of frequency.
Typically in electrochemistry, a frequency range of
100kHz – 0.1Hz is used.
The plot of the real part of impedance on the X-axis Bode Plot
and the imaginary part on the Y-axis gives a 105
Nyquist Plot. While plotting data in the Nyquist 104

Nyquist Plot
format the real axis must be equal to the imaginary
|Z|
103
axis so as not to distort the shape of the curve. The 102
advantage of Nyquist representation is that it gives 101

-90
a quick overview of the data and by the shape of
Zim
the curve one can make some qualitative -60

interpretations of the data. The disadvantage is that -30
|Z|
one loses the frequency dimension of the data. w

w0
0
10-2 10-1 100 101 102 103 104 105
The absolute value of impedance (|Z|=Z0) and the frequency [Hz] Zre
phase shifts are plotted on the Y-axis with log
frequency on the X-axis in two different plots giving
a Bode plot. This is the more complete way of
presenting the data.
The EIS technique
Basic of EIS
(Electrochemical Impedance Spectroscopy)
…and interface
properties
EIS spectrum can provide

information about
electrochemical processes...
C.Gabrielli “Identification of Electrochemical Processes by Frequency

Response Analysis”, (1998)
http://accessimpedance.iusi.bas.bg/vlab2/e-school/tech04.pdf
A.Amirudin, D.Thierry “Application of electrochemical impedance

spectroscopy to study the degradation of polymer-coated metals”,
Prog. Org. Coat. 26 (1995) 1-28
Basic of EIS
Electrochemical Impedance Spectroscopy (EIS): 1. Basic Principles

http://www.ecochemie.nl/download/content/Appl011.pdf
Electrochemical Impedance Spectroscopy (EIS): 2. Experimental Setup
http://www.ecochemie.nl/download/content/Appl012.pdf
Basics of Electrochemical Impedance Spectroscopy

http://www.gamry.com/App_Notes/EIS_Primer/EIS_Primer_2007.pdf
Basics of Electrochemical Impedance Spectroscopy

http://new.ametek.com/content-manager/files/PAR/078.pdf
Electrochemical Impedance Measurements: Instruments and Techniques
http://new.ametek.com/content-manager/files/PAR/079c.pdf
http://www.solartronanalytical.com/Pages/Electrochemistry.htm
Instruments and methods
WE REF CE
Potentiostat
E I 
FRA
Electrolyte
Personal
Computer
WE – Working Electrode:
Commercially available instruments
the electrode under investigation
Potentiostat: it is used to fix the DC value and to CE – Counter Electrode:

apply a sinusoidal perturbation over it the electrode necessary to close the electrical circuit
REF – Reference Electrode:
Frequency Response Analyzer (FRA): controls
the EIS scan and impedance evaluation the electrode used to determine the potential of the
working electrode precisely
Acquisition Software: controls Potentiostat and Electrolyte:
FRA, and store data file It ensures electrical conductivity between WE and CE
• 3 electrode
flat plate cell
– WE: coated metal
– RE: Usually SCE or
Ag/AgCl
– CE: platinum,
graphite or
stainless steel
mesh, wire or rod
Workshop January 11 - 15 2010, Leiden, The Netherlands Electrochemical cell and electrolyte
• Immersion cell
– Testing of wax
coatings
C. Price et al, Proceedings of Metal 95,

James&James, London (1997) 233-241
• Immersion cell
– Testing of oil
coatings
D. Hallam et al, Proceedings of Metal 04, National

Museum of Australia, Canberra (2004) 388-399
REF
Contact
CE
probe
WE
Cloth soaked with mineral water
a contact probe setup

measurement method
has been developed to
make measurements on
art object also
Electrochemical
Instrumentscell
andand
methods
electrolyte
ST Contact Probe
CE cable
CE: Stainless Steel
AISI 316
CE
REF: Stainless Steel
AISI 316
REF cable
inserted in PTFE
 = 1.5 cm
REF
A= 1.77 cm2
Letardi P., in: P.A.Vigato (Ed.), The Science of Art, Outdoor bronze protective coatings: characterisation by a new contact-probe
Electrochemical Impedance measurements technique, Libreria Progetto di Padova, 2002, pp. 173-178
• Integrated cell+EIS electronics
E. Angelini et al, IEEE Transactions on Instrumentation and Measurement 55 (2006) 436-441

• Electrolyte: as close as possible to the

real environment of the object or
specially aggressive towards de
metal/coating
– NaCl 0.1M
– Harrison (0.35% (NH4)2SO4+0.05% NaCl)
– Mineral water (Letardi)
– K2SO4 0.25M (Hallam)
– Acetic acid (Dowsett)
P. Letardi et al., Proceedings of Metal 98, James&James, London (2001) 303-308
D. Hallam et al, Proceedings of Metal 04, National Museum of Australia, Canberra (2004) 388-399
M. Dowsett et al., Proceedings of Metal 07, Rijkmuseum Amsterdam (2007) 26-31
Overview of commercially available instruments
http://www.solartronanalytical.com/Pages/Electrochemistry.htm
http://www.ecochemie.nl/?pag=7
http://www.gamry.com/Products/Potentiostats.htm
http://www.princetonappliedresearch.com/products/potentiostats.cfm
Overview of commercially available instruments
• Transportable instrumentation
•Gamry FAS1 Femtostat
•Portable instrumentation
•Gamry Ref600
Data acquisition and representation
Bode plot Nyquist plot
Same scale!
Do not miss phase angle graph!
E. Cano, D. Lafuente, D.M. Bastidas, J. Solid State Electrochem. 14

(2010) 381-391
Bode vs. Nyquist
C. Gabrieli, “Use and Application of Electrochemical Impedance

Techniques TECHNICAL REPORT NUMBER 24. Solartron Analytical (1997)
Data analysis
• Physio-chemical model from first principles

• Equivalent circuits (EC)
• Evaluation of single parameters (|Z| at low
frequency, C coating, etc.)
Equivalent circuits
• EC= analogues that reproduce the

electrical properties of our system
• Pasive elements: resistors, capacitors,
inductances, and other special elements
(CPE, Warburg Impedance, etc.)
• Many circuits can be used to model the
same data
Equivalent circuits
A good fitting does not mean you choosed a good model!
Gamry Instruments (2007) “Basics of electrochemical impedance spectroscopy”

http://www.gamry.com/App_Notes/EIS_Primer/EIS_Primer_2007.pdf
The basic EC
• Intact coating
2
Impedande Modulus |Z| /  cm
10
10 (a)
9
10
8
-100 10
7
10
6
10
5
10
4
-80 10
3
10
2
10
1
10
0
-60 10
2
-Z" / M cm
(b)
0
-10
-40
-20
Phase Angle f -30
-40
-50
-20
-60
-70
-80
-90
-3 -2 -1 0 1 2 3 4 5
20 40 60 80 100 10 10 10 10 10 10 10 10 10
2
Z' / M cm Frequency / Hz
The basic EC
• Damaged coating
2
10
10 (a)
9
10
8
-100 10
7
-4 10
6
10
5
10
4
-80 -2 10
3
10
2
10
1
10
0
-60 10
2
2 4
-Z" / k cm
(b)
0
-10
-40
-20
Phase Angle f -30
-40
-50
-20
-60
-70
-80
-90
-3 -2 -1 0 1 2 3 4 5
20 40 60 80 100 10 10 10 10 10 10 10 10 10
2
Z' / k cm Frequency / Hz
The basic EC
• Damaged coating
(CPE)
2
10
10 (a)
9
10
8
10
7
10
-100 6
10
-4 10
5
4
10
3
-80 10
-2 2
10
1
10
0
10
-60
2
2 4 (b)
-Z" / k cm
0
-10
-40 -20
Phase Angle f
-30
-40
-50
-20 -60
-70
-80
-90
-3 -2 -1 0 1 2 3 4 5
20 40 60 80 100 10 10 10 10 10 10 10 10 10
2
Z' / k cm Frequency / Hz
The basic EC
• Damaged coating
(CPE)
α =1 CPE=C
1 α =0 CPE=R
Z CPE 
Y0  jw 

α =-1 CPE=L
α =0.5 CPE=W
Usually, CPE is interpreted as an imperfect capacitor

The basic EC
• Difussion
(Warburg Imped.)
2
10
10 (a)
9
10
8
10
7
10
-100 6
10
5
10
4
10
3
-80 10
2
10
1
10
0
10
-60
2
(b)
-Z" / M cm
0
-10
-40 -20
Phase Angle f
-30
-40
-50
-20 -60
-70
-80
-90
-3 -2 -1 0 1 2 3 4 5
20 40 60 80 100 10 10 10 10 10 10 10 10 10
2
Z' / M cm Frequency / Hz
829-839
• Multiple paralel R-C
S-J. Lee and S-I Pyun, J Solid State Electrochem 11 (2007)

Other EC
Acta 49 (2004) 2937-2943

• Multiple nested R-C
M. Evesque, M. Keddam and H. Takenouti, Electrochim.

Other EC
•
•
•
•
•
f min
C DL
C coat
Θ high f
|Z| max or |Z| low f
Single EIS parameters
EIS analysis software
• Zview (Scribner)
• EIS300 (Gamry)
• PowerSine (PAR)
• EIS Spectrum
Analyser (freeware!!!)
– http://www.abc.chemistry.bsu.by/vi/analyser/
UN MN UA Patina plays a
relevant role
◊ Natural ◊ Natural ◊ Artificial
◊ 80 years ◊ 1 year ◊ Pichler on coating
urban marine process behaviour
◊ 20 µm ◊ 30 µm ◊ 80 µm
◊ brochantite ◊ Atacamite ◊ brochantite
|Z|10mHz = 5 ± 2 K |Z|10mHz = 29 ± 4 K
• composition
|Z|10mHz = 69 ± 18 K
105
Urban Natural UN Substrate
105
Marine natural MN Substrate
105
Urban artificial UA Substrate • thickness
UN substrate
UN substate (1)
MN substrate UA substrate
• texture
104 104 104 • porosity
•…
|Z|10mHz [K]
|Z|10mHz [K]
103 103
|Z|10mHz [K]
103
102 102 102
101 101 101
100 100 100

none Tref T1S T2S T3S I1S Iref none Tref T1S T2S T3S I1S Iref none Tref T1S T2S T3S
Treatment Treatment Treatment

[A] - Soter 201LC

[B] - R21
[C] - Tromm TeCe 3534F
[D] - Incralac
[E] - Incralac+Soter
[A] [C] [F]
[F] - Incralac+R21
[E] [D]
[B
]
Test on monuments could be prone to several limitations:

• accessibility
• outdoor measurements
• variables out of control
• authorisations
•…
Test on monuments could be prone to several limitations:

•…
• previous restoration treatments are also to be considered carefully
Coupons for testing:

• alloy composition
• dimension
• patina
• natural (new)
• natural (old)
• artificial
• characterisation
Coating application:
• method
• thickness
• characterisation
wheatering:
Multiple coupons for statistical reasons
• natural
EN ISO 8565 – Metals and alloys – Atmospheric
corrosion testing – General requirements for field
tests.
• artificial
EN ISO 11341 - Paints and varnishes. Artificial
weathering and exposure to artificial radiation.
Exposure to filtered xenon-arc radiation
EN ISO 9227 - Corrosion tests in artificial
atmospheres. Salt spray tests
Because of the large number of variables

involved, one need several coupons in order
to check the behaviour
Statistical methods such as Experimental
Design could be of great help in order to
reduce the number of experiments required
http://www.itl.nist.gov/div898/handbook/pri/section3/pri3.htm
http://www.chemometrics.se/images/stories/pdf/aug2002.pdf
J. A. Bishopp, M. J. Parker and T. A. O’Reilly, The use of statistical experimental design procedures in
the development and “robust” manufacture of a water-based, corrosion-inhibiting adhesive primer,
International Journal of Adhesion and Adhesives 21,(2001), 473-480
M.J. Anderson, P.J. Whitcomb, Design of experiments for coatings, in A.A. Tracton, Coatings
Technology Handbook, Third Edition, 3rd ed., CRC Press, 2005
Further references
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.
Loveday D, Peterson P, Rodgers B (2004) Evaluation of organic coatings with electrochemical
impedance spectroscopy: Part 1: Fundamentals of electrochemical impedance spectroscopy. JCT
CoatingsTech 1, 46-52.
Loveday D, Peterson P, Rodgers B (2005) Evaluation of organic coatings with electrochemical
impedance spectroscopy. JCT CoatingsTech 2, 22-27.
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.
Letardi P., Laboratory and field test on patinas and protective coating systems for outdoor bronze
monuments, in: Ashton J., Hallam D.(Eds.), Proceedings of Metal2004, National Museum of Australia,
Canberra, 2004, pp. 379-387
Joseph E., Letardi P., Mazzeo R., Prati S., Vandini M., Innovative treatments for the protection of
outdoor bronze monuments, in: C.Degrigny, R. van Langh, I. Joosten, B.Ankersmit (Eds.), Proceedings
of Metal07, Amsterdam 2007, v5 pp. 71-77

Letardi, P. y Cano, E. Electrochemical Protection Systems Metal Artefacts. 2010

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Letardi, P. y Cano, E. Electrochemical Protection Systems Metal Artefacts. 2010

Hochgeladen von

Copyright:

Verfügbare Formate

Electrochemical Assessment of

Electrochemistry in Historical and Archaeological Conservation

Protection Systems on Metal

Electrochemical cell and electrolyte

Overview of commercially available

Data acquisition, representation and

Test of coatings for cultural heritage

The fundamental approach of

Energy level (Potential E) all impedance methods is to

Z(w) is a complex quantity with a magnitude and a

phase shift which depends on the frequency of the

Nyquist Plot. While plotting data in the Nyquist 104

axis so as not to distort the shape of the curve. The 102

advantage of Nyquist representation is that it gives 101

a quick overview of the data and by the shape of

EIS spectrum can provide

C.Gabrielli “Identification of Electrochemical Processes by Frequency

A.Amirudin, D.Thierry “Application of electrochemical impedance

Electrochemical Impedance Spectroscopy (EIS): 1. Basic Principles

Basics of Electrochemical Impedance Spectroscopy

Basics of Electrochemical Impedance Spectroscopy

Electrochemical cell and electrolyte

Potentiostat: it is used to fix the DC value and to CE – Counter Electrode:

C. Price et al, Proceedings of Metal 95,

D. Hallam et al, Proceedings of Metal 04, National

Cloth soaked with mineral water

a contact probe setup

• Integrated cell+EIS electronics

E. Angelini et al, IEEE Transactions on Instrumentation and Measurement 55 (2006) 436-441

• Electrolyte: as close as possible to the

•Gamry FAS1 Femtostat

Bode plot Nyquist plot

Do not miss phase angle graph!

E. Cano, D. Lafuente, D.M. Bastidas, J. Solid State Electrochem. 14

C. Gabrieli, “Use and Application of Electrochemical Impedance

• Physio-chemical model from first principles

• EC= analogues that reproduce the

A good fitting does not mean you choosed a good model!

Gamry Instruments (2007) “Basics of electrochemical impedance spectroscopy”

Usually, CPE is interpreted as an imperfect capacitor

S-J. Lee and S-I Pyun, J Solid State Electrochem 11 (2007)

Acta 49 (2004) 2937-2943

M. Evesque, M. Keddam and H. Takenouti, Electrochim.

102 102 102

101 101 101

100 100 100

Treatment Treatment Treatment

[A] - Soter 201LC

Test on monuments could be prone to several limitations:

Test on monuments could be prone to several limitations:

Coupons for testing:

Multiple coupons for statistical reasons

Because of the large number of variables

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