1st training school – mCBEEs network,

Delft 15-20 July 2018

Localized techniques:
Electrochemical micro-cell and
scanning Kelvin probe force microscopy

F. Andreatta

University of Udine
Polytechnic Department of Engineering and Architecture
Udine, Italy
Outline
 Why local electrochemical techniques?
Main local techniques

 Scanning Kelvin probe force microscopy (SKPFM) and

electrochemical micro-cell
 Working principle
 Equipment
 Examples
 Advantages and drawbacks
Why local electrochemical techniques?

MACRO LOCAL
electrochemical techniques electrochemical techniques
(open circuit potential and (scanning Kelvin probe force
potentiodynamic polarization) microscope, SVET, micro-cell)

Overall Local
electrochemical electrochemical
behaviour behaviour

Microstructure
Localized attack at intermetallics in AA7075
As received After attack
Main local electrochemical techniques
 Main local electrochemical techniques

Micro-Reference
electrode immersed
in the electrolyte
 Main local electrochemical techniques

Micro-Reference
electrode immersed
in the electrolyte

Non immersion
techniques
 Main local electrochemical techniques

Selective
characterization of
different areas of
Micro-Reference
the sample surface
electrode immersed
in the electrolyte

Non immersion
techniques
SRET, SVET and LEIS
 Scanning vibrating electrode technique (SVET)
Ø 2 mm

Mouanga, M., Andreatta, F., Druart, M. -., Marin, E., Fedrizzi, L., & Olivier, M. -G. (2015). A localized approach
to study the effect of cerium salts as cathodic inhibitor on iron/aluminum galvanic coupling. Corrosion
Science, 90, 491-502.
 Scanning Kelvin probe (SKP)
(Vreference el.– Vsample) is the Volta
potential difference or contact
potential difference.

Interpretation of Volta potential difference

De Wit, J. H. W. (2004). Local potential measurements with the SKPFM on aluminium alloys. Electrochimica
Acta, 49(17-18), 2841-2850.
 Scanning Kelvin probe (SKP)
Inhomogeneities at a metal surface: Volta potential difference

Zn Fe

DRIVING FORCE
FOR CORROSION

Tahara, A., & Kodama, T. (2000). Potential distribution measurement in galvanic corrosion of Zn/Fe couple
by means of kelvin probe. Corrosion Science, 42(4), 655-673.
Electrochemical micro-cell

Suter, T., & Böhni, H. (2001). Microelectrodes for corrosion

studies in microsystems. Electrochimica Acta, 47(1), 191-199.
In this presentation
1. Scanning Kelvin probe force microscopy (SKPFM)
 Volta potential maps

2. Eletcrochemical micro-cell
 Localized potentiodynamic polarization curves
Scanning Kelvin probe force microscopy (SKPFM)

AFM (Atomic Force Microscope), Nanoscope IIIa

(Digital Instruments VEECO), Bruker
Scanning Kelvin probe force microscopy (SKPFM)
 Implementation of the working principle of the SKP in an
atomic force microscope (AFM)
 Surface potential (Volta potential) imaging

 Two-step method:
 Topographic map
 Volta potential map
Atomic force microscope (AFM)
 Scanning probe method (SPM)
 The AFM scans a sharp probe on the the surface of a material
 3D topographic image with resolution in the nm range (atomic
resolution)
Atomic force microscope (AFM)
Atomic force microscope (AFM)
 Interaction (force) between probe (tip) and the sample:
 Long-range forces – 100 nm:
• Electrostatic force in air
• Magneto-electrostatic forces
• Electrostatic forces in double layer in fluid

 Short-range forces:
• Van der Waals – 10 nm
• Surface-induced solvent ordering – 5 nm
• Hydrogen-bonding – 0.2 nm
• Contact – 0.1 nm
Atomic force microscope (AFM)
 Interaction (force) between probe (tip) and the sample:
 The deflection of the cantilever is measured by a photodiode
detector
Atomic force microscope (AFM)
Atomic force microscope (AFM)

a scanner base
b cantilever holder
c optical head
d scanner
Atomic force microscope (AFM)
Head of the AFM
Atomic force microscope (AFM)
Tip holder
Atomic force microscope (AFM)
Tip with straight shape cantilever

 Tip:
• Si3N4
• With or without conductive coating (PtIr5)
Atomic force microscope (AFM)
 Main operation modes of the AFM:
 Contact mode (tip –sample distance < 0.5 nm)
 Tapping mode (distance between 0.5 and 2 nm)
Atomic force microscope (AFM)
Contact mode
Atomic force microscope (AFM)
Tapping mode
Scanning Kelvin probe force microscopy (SKPFM)
 Surface potential imaging
 1st pass: topography (tapping mode)
 2nd pass: Volta potential map (lift mode)
Scanning Kelvin probe force microscopy (SKPFM)

Vac: AC voltage applied to the tip

Vdc: DC voltage applied to the tip
F = dC/dz Vac[Vdc - (Vtip-Vsample)]
Vdc F=0 Vdc = Vtip - Vsample
Scanning Kelvin probe force microscopy (SKPFM)
 Advantages
 High spatial resolution

 Drawbacks
 Interpretation of Volta potential differences
 Measurements in air and not in an electrolyte
 Example: Intermetallics in AA7075

AA7075 Zn Mg Cu Fe Si Al
wt% 5.48 2.44 1.55 0.28 0.07 balance

Intermetallics:
 Al7Cu2Fe
 (Al,Cu)6(Fe,Cu)
 Mg2Si

Affect the resistance to

localized corrosion of the
alloy

Andreatta, F., Terryn, H., & de Wit, J. H. W. (2003). Effect of solution heat treatment on galvanic coupling
between intermetallics and matrix in AA7075-T6. Corrosion Science, 45(8), 1733-1746.
Example: Intermetallics in AA7075
Example: Intermetallics in AA7075
Example: Intermetallics in AA7075
Example: Intermetallics in AA7075
SW60 T76

Temper Al7Cu2Fe (Al,Cu)6(Fe,Cu)

As rec. T6 396 ± 65 341 ± 38
SW60 604 ± 84 500 ± 114
T6 374 ± 41 322 ± 45
T76 431 ± 55 377 ± 58
 Example: Zr-Ti conversion coating on AA6016
As received alloy
Al(Fe,Mn)Si intermetallic
Second phase particles:
• Al(Fe,Mn)Si
• Al(Fe,Mn)Si + Cr
• Si

Size:
• 10÷20 μm
• 1÷3 μm

Volta potential:
• Al(Fe,Mn)Si 450÷550 mV
• Si 550÷650 mV
• cathodic behaviour

Andreatta, F., Turco, A., de Graeve, I., Terryn, H., de Wit, J. H. W., & Fedrizzi, L. (2007). SKPFM and SEM study
of the deposition mechanism of Zr/Ti based pre-treatment on AA6016 aluminum alloy. Surface and Coatings
Technology, 201(18), 7668-7685.
Example: Zr-Ti conversion coating on AA6016
Open circuit potential during coating deposition

OCP:
• Initial decrease (40 sec)
• Increase (40÷180 sec)
• Plateau region
180 sec 300 sec
120 sec

60 sec • Initial decrease:

removal of natural
oxide layer-surface
activation (fluorides in
the bath)
• Increase: deposition
of Zr and Ti layer?
• Plateau region:
complete coverage?
Example: Zr-Ti conversion coating on AA6016
Deposition of conversion layer – 60 sec

Al(Fe,Mn)Si intermetallic

EDXS analysis: Volta potential:

• Deposition on intermetallics • Intermetallics
(cathodic behaviour of retain cathodic
intermetallics) behaviour
• Limited deposition on the matrix
Example: Zr-Ti conversion coating on AA6016
Deposition of conversion layer – 60 sec

Al(Fe,Mn)Si intermetallic

Volta potential:
• 60 sec dipping partially reduces Volta potential of the
intermetallic relative to matrix as compared to sample after
surface preparation
• Still rather high
• Similar results for 90 sec dipping
Example: Zr-Ti conversion coating on AA6016
Deposition of conversion layer – 180 sec
Al(Fe,Mn)Si intermetallic Volta potential:
• Large areas with
positive and uniform
Volta potential
• Reduction of Volta
potential
• Extensive
deposition with some
areas still not covered
(OCP)

180 sec
Example: Zr-Ti conversion coating on AA6016
Deposition of conversion layer – 300 sec
Al(Fe,Mn)Si intermetallic [1]

EDS analysis:
• Surface completely covered
• Thicker Zr and Ti layer on the large
intermetallics than on the matrix
• Cracks on intermetallics
Example: Zr-Ti conversion coating on AA6016
Deposition of conversion layer – 300 sec
Al(Fe,Mn)Si intermetallic
Volta potential:
• Uniform Volta
potential over the
entire surface
• No Volta potential
difference between
intermetallic and
matrix
• Plateau region
(OCP)

300 sec
Example: Zr-Ti conversion coating on AA6016
Deposition mechanism of the conversion layer
Activation Complete coverage

Initiation + lateral growth

300 sec
180 sec
120 sec

60 sec

30 sec
Electrochemical micro-cell
Electrochemical micro-cell
Electrochemical micro-cell Electrochemical micro-cell
with free droplet with silicone gasket

Picture from T. Suter

Miniaturization of the electrochemical cell

Electrochemical micro-cell

T. Suter, H. Böhni, Electrochimica Acta 47 (2001) 191-199.

Electrochemical micro-cell

3-electrode setup:
 working electrode
 counter electrode
 reference electrode
Electrochemical micro-cell
1. Electrochemical micro-cell mounted on
the rotating head
of an optical microscope
2. Potentiostat/Galvanostat
3. Faraday cage
Electrochemical micro-cell
Electrochemical micro-cell
 Glass capillary
 Electrolyte supply
 Connection for RE
 Connection for CE
Electrochemical micro-cell
T. Suter, H. Böhni,
Glass capillary
Electrochimica Acta
47 (2001) 191-199.
 Diameter: 1μm – 800μm
 Silicone gasket

M.M. Lohrengel, A. Moehring, M. Pilanski, Electrochimica Acta 47 (2001) 137-141.

Electrochemical micro-cell
Potentiostat/Galvanostat
 10 fA current resolution

IPS potentiostat
by Elektroniklabor Peter Schrems

M.M. Lohrengel, A. Moehring, M. Pilanski, Electrochimica Acta 47 (2001) 137-141.

 Example: Intermetallics in AA7075

Breakdown: localized attack

at the intermetallic particle

Andreatta, F., Lohrengel, M. M., Terryn, H., & De Wit, J. H.

W. (2003). Electrochemical characterisation of aluminium
AA7075-T6 and solution heat treated AA7075 using a
micro-capillary cell. Electrochimica Acta, 48(20-22), 3239-
3247.
Electrochemical micro-cell
 Advantages
 Only the area investigated is wetted by the electrolyte
 Possibility to use aggressive solutions
 Sample does not need to be flat
 High spatial resolution (size of the glass capillary)
 Possibility to perform standard DC (and AC) electrochemical
measurements
 Electrochemical micro-cell
 Critical aspects
 Silicone gasket
• Crevice corrosion
• Differential aeration

 IR drop
 Sweep rate
 Shape of the glass micro-capillary
 Results reproducibility
• Type of material under investigation
• Statistical effect
Andreatta, F., & Fedrizzi, L. (2015). The use of the electrochemical micro-cell for the investigation of corrosion
phenomena. Electrochimica Acta, 203, 337-349.
Electrochemical micro-cell
Silicone gasket

T. Suter, H. Böhni, Electrochimica Acta 47 (2001) 191-199

Electrochemical micro-cell
IR drop
Stainless steel in 0.1M NaCl

Galvanostatic RΩ resistance
pulse of 1 nA
between WE and CE

N. Birbilis, B.N. Padgett, R.G. Buchheit,

Electrochimica Acta 50 (2005) 3536-3544.

IR drop is about 10 mV for a 20 µm glass micro-capillary

Electrochemical micro-cell
IR drop
Stainless steel in 0.1M NaCl

RΩ is geometry dependent

N. Birbilis, B.N. Padgett, R.G. Buchheit,

Electrochimica Acta 50 (2005) 3536-3544.

IR drop is important only at high anodic or cathodic currents

Electrochemical micro-cell
Sweep rate
Pure Aluminium in 0.1M NaCl

 Cell leakeage
 Corrosion products
 Minimize test duration

N. Birbilis, B.N. Padgett, R.G. Buchheit,

Electrochimica Acta 50 (2005) 3536-3544.

Sweep rate must be selected carefully in order to avoid misleading kinetic data
Electrochemical micro-cell
Shape of the glass capillary
316L stainless steel in 1.7 M NaCl

H. Krawiec, V. Vignal, R. Akid, Electrochimica Acta 53 (2008) 5252–5259.

The angle at the tip of the Si gasket (shape) affects the electrochemical
behaviour of the substrate (current density)
Electrochemical micro-cell
Results reproducibility

 It depends on:
1. Type of material under investigation
 active or passive behaviour

2. Statistical effect
 related to the small area under investigation
Electrochemical micro-cell
Type of material under investigation

 Active material
 High current density
 Reproducible results
 Passive material
 Low current density
 Breakdown of passivity related to weak spots
Electrochemical micro-cell
Statistical effect

T. Suter, R.C. Alkire, Journal of the Electrochemical Society 148 (2001) B36-B42.
Different behaviour than conventional large scale measurements
 reduction of the probability that weak spots are present in the area under
investigation
Electrochemical micro-cell
Statistical effect
Pitting potential in NaCl
Intrinsic behaviour due to the increased
resolution of the micro-cell as compared
to large scale electrochemical
techniques
 electrolyte
 microstructure

T. Suter, R.C. Alkire, Journal of the Electrochemical

Society 148 (2001) B36-B42.
Electrochemical micro-cell
Statistical effect
AA2024 in 1M NaCl

T. Suter, R.C. Alkire, Journal of the Electrochemical Society 148 (2001) B36-B42.

The electrochemical micro-cell enables to establish a hierarchy between the

different intermetallic particles
 multiple experiments are required
 Example: Inhibition by Ce species in AA1050
Bare substrate Immersion step in After Immersion in
Cerium Chloride Cerium Chloride

Microstructure Microstructure
characterization characterization
and and
24 h immersion
Electrochemical Electrochemical
in 2.5 10-3M CeCl3
measurements measurements
in 0.05M NaCl in 0.05M NaCl
solution solution

Andreatta, F., Druart, M. -., Lanzutti, A., Lekka, M., Cossement, D., Olivier, M. -., & Fedrizzi, L. (2012). Localized
corrosion inhibition by cerium species on clad AA2024 aluminium alloy investigated by means of electrochemical
micro-cell. Corrosion Science, 65, 376-386.
Example: Inhibition by Ce species in AA1050
Microstructure after immersion in CeCl3 solution
Example: Inhibition by Ce species in AA1050
Electrochemical behaviour of the bare substrate
Measurements carried out on areas containing intermetallics
Potentiodynamic polarization in 0.05M NaCl solution

Ecorr/V
av. st. dev.
-0.555 0.098

Eb/V
av. st. dev.
-0.016 0.275
Example: Inhibition by Ce species in AA1050
Electrochemical behaviour after immersion in in CeCl3 solution
Measurements carried out on areas containing intermetallics
Potentiodynamic polarization in 0.05M NaCl solution
Before polarization

After
Example: Inhibition by Ce species in AA1050
Area containing an Fe-rich intermetallic

Eb
Example: Inhibition by Ce species in AA2024
Fe-rich intermetallics
After immersion in 0.05M NaCl solution containing 5g/L Ce(NO3)3

Paussa, L., Andreatta, F., De Felicis, D.,

Bemporad, E., & Fedrizzi, L. (2014).
Investigation of AA2024-T3 surfaces
modified by cerium compounds: A localized
approach. Corrosion Science, 78, 215-222.
Example: Inhibition by Ce species in AA2024
Matrix
After immersion in 0.05M NaCl solution containing 5g/L Ce(NO3)3
Matrix
Example: Inhibition by Ce species in AA2024
Electrochemical behaviour before and after immersion
in 0.05M NaCl solution containing 5g/L Ce(NO3)3

Before immersion After immersion

Example: Active surface layers in AA8009
GDOES composition profile
Sn

Mg

4 mm
Example: Active surface layers in AA8009
Potentiodynamic polarization in 0.05 M NaCl
Active behaviour
of the surface

 Anodic activation
 Related to enrichment of
alloying elements at the
surface

Passive behaviour
of the bulk

 New oxide on the surface

without segregation
Conclusions

 Local electrochemical techniques (SKPFM and micro-cell)

 Effective methods to study localized electrochemical processes
 Link between microstructure and electrochemical behaviour
 Complementary techniques

 Critical aspect
 Support of surface analysis techniques for validation of the results
Bibliography
 Local electrochemical methods
 Roland Oltra, Vincent Maurice, Robert Akid, Philippe Marcus, Local Probe Techniques
for Corrosion Research, 2007, Woodhead Publishing, ISBN: 9781845692360.

 SKPFM
 Ernst Meyer, Hans J. Hug, Roland Bennewitz, Scanning Probe Microscopy, 2004,
Springer-Verlag Berlin Heidelberg, DOI 10.1007/978-3-662-09801-1.
 De Wit, J. H. W. (2004). Local potential measurements with the SKPFM on aluminium
alloys. Electrochimica Acta, 49(17-18), 2841-2850.

 Micro-cell
 Suter, T., & Böhni, H. (2001). Microelectrodes for corrosion studies in
microsystems. Electrochimica Acta, 47(1), 191-199.
 Andreatta, F., & Fedrizzi, L. (2015). The use of the electrochemical micro-cell for the
investigation of corrosion phenomena. Electrochimica Acta, 203, 337-349.