Experimental techniques in tribocorrosion

S. Mischler, A. Igual Muñoz,

Ecole Polytechnique Fédérale de Lausanne (EPFL) Lausanne,
Switzerland
 Outline
• Definition of a tribocorrosion system

• Tribo-electrochemical techniques
– Open Circuit measurements

– Potentiostatic tests

– Potentiodynamic tests

• Characterization of worn surfaces

 MECHANICAL
Load
Kinematics
Geometry
Vibrations
…
SOLUTION
ELECTROCHEMICAL Viscosity
Potential Conductivity
Ohmic resistance pH
Tribocorrosion
Passivation Oxidants
Active dissolution system Complexing agents
Kinetics Aggressive ions
Oxidation valence Adsorbing species
Mass transport Temperature
… MATERIAL …
Hardness, elasticity
Microstructure
Roughness
Surface properties
Debris, transfer
…

D. Landolt et al. Electrochimica Acta 46 (2001) 3913-3929

 Definition of a tribocorrosion system

Material Mechanics Environment

• Chemical • Type of motion • Oxidizing agents
composition • Type of contact • Agressive ions
• Hardness • Type of load • Adsorbing species
• Microstructure • Sliding velocity • Complexing species
• Surface chemistry • Sliding distance • Electrode potential
• Roughness • Geometry • pH, T
• Lubrication
 Material-chemical interactions
• Material: Composition, Hardness, Microstructure, Surface
chemistry, Roughness
T1 T2 T3

200 µm 200 µm 200 µm

35

30
Wear Volume (10-3 mm3)

Microstructure and 25

wear volume of a HC 20 T1

CoCrMo alloy with 15

T2

different thermal T3
10
treatments
5
Casabán et al. Tribology
0 International (2011) 44, 318-329
NaCl NaCl+BSA BS
 Material-chemical interactions
• Material: Composition, Hardness, Microstructure, Surface
chemistry, Roughness
T1, NaCl T1, T1, BS
NaCl+BSA

35

SEM images of the wear 30

track of T1
Wear Volume (10-3 mm3)

25

20 T1
T2
15
T3
10

5
Casabán et al. Tribology
0 International (2011) 44, 318-329
NaCl NaCl+BSA BS
 Influence of roughness

Wear track
Rough
ball Wear volume
(mm
0.04 3)

0.03
Rough ball
0.02

0.01
Smooth Smooth ball

Wear track
ball
0.00
0 2 4 6 8 10 12
Normal force (N)

Wear tracks (SEM images) of AISI430

rubbed against rough and smooth Al2O3
ball in 0.5M H2SO4

Stemp et al. Wear (2003) 255, 466-475

 Defining the mechanics of the system
1. Type of contact

Conformal Non-conformal
(flat on flat) Aj = Fn / n Aj = Fn / n (ball on flat)

2. Type of motion

Aj = Fn / n Aj = Fn / n Aj = Fn / n Aj = Fn / n

Sliding Impact Spin Rolling

 Defining the mechanics of the system
3. Type of load: continuous, cyclic
Fn Fn

4. Geometry: ball-on-flat, cylinder-on-cylinder, block-on-ring,

pin-on-disk

5. Lubrication: boundary, mixed and hydrodynamic

 Defining the environment
• Oxidizing agents: oxygen, protons
• Aggressive ions: Cl-
• Adsorbing species
• Complexing species
• Electrode potential
• pH, T

Acidity Ecor (H2SO4 0.05 M) = -0.55 V Ag/AgCl

Ti CP Ecor (H2SO4 0.5 M) = -0.89 V Ag/AgCl

Chemistry Ecor (PBS) = -0.38 V Ag/AgCl

Ti6Al4V Ecor (PBS +albumin) = -0.52 V Ag/AgCl
Ecor (PBS + collagen) = -0.61 V Ag/AgCl

Oxidising agents Ecor (Calf serum) = -0.006 V Ag/AgCl

Ti6Al4V Ecor (Calf serum + 0.1% H2O2) = +0.101 V Ag/AgCl
 Rationalizing results from different
solution chemistries using the potential
0.07

Wear Coefficient [10-3 mm3 / N m]

Applied
0.06 potential
OCP
0.05

0.04

0.03

0.02

0.01

0
-1 -0.5 0 0.5 1
Potential [VSHE]
 Choice of set-up
In-vivo tests Simulators Laboratory model
tests

Test of Systems Components Materials

Situation Real Realistic Idealized

Conditions Partially undefined Controlled Best controlled

Response time Very long Long Short

 Experimental configuration
• Tribocorrosion: Material degradation process which
results from simultaneous mechanical (wear) and
chemical or electrochemical (corrosion) material
removal mechanisms.

Prerequisite for tribocorrosion experiments is

therefore the possibility to control not only
the mechanical but also the chemical test
conditions
 Outcomes and interpretation

Inputs Outputs
Friction
Wear and debris particles
Operating variables
Tribocorrosion Appearance of worn surfaces
Bodies in contact
Test Noise, vibrations
Corrosion environnent
Changes in properties of the
bodies in contact and the
environment
 Outline
• Definition of a tribocorrosion system

• Tribo-electrochemical techniques
– Open Circuit measurements

– Potentiostatic tests

– Potentiodynamic tests

• Characterization of worn surfaces

 Tribo-electrochemical techniques
• Electrochemical techniques control in-situ and in real time
surface reactivity.
Current I
Active domain Passive domain Transpassive domain
I

0 Potential E
Ecor,a Ecor,b
At Ecor Ianodic = - Icathodic
Polarisation curve
of the cathodic
reaction, for example
a) Low oxidizing b) High oxidising reduction of oxygen
power of the solution power of the solution
Polarisation curve
of the anodic reaction,
i.e. metal oxidation.
 Tribo-electrochemical experiment
• Electrochemical techniques control in-situ and in
real time surface reactivity

• Triboelectrochemical experiment: A tribological

experiment carried out in an ionic conductor under
controlled electrochemical conditions

Interaction wear and corrosion

 History
• 1887-1949: Early observations of the effect of polarisation on friction (
Bowden & Tabor 1950).

• Late 1970s: First published papers using potentiostatic control in wear

experiments.

• 1995: ASTM G119-04 Standard guide for determining synergism

between wear and corrosion.

• 1998: First quantitative model of tribocorrosion.

• 2001: Inter-laboratory study on tribo-electrochemical methods.

• 2011: “Tribocorrosion of passive metals and coatings” Ed. Woodhead.

Editors S. Mischler, D. Landolt.

• 2020: “Tribocorrosion” Ed. Springer. A. Igual, N. Espallargas, S. Mischler

 Electrochemical techniques in
tribocorrosion

• Basic techniques: Open circuit potential

measurements and anodic current measurements.

• Other techniques: Non-steady-state techniques

(impedance measurements and potentiodynamic
curves).
 Electrochemical tribometer
Photodiode for
displacement
monitoring
Reference
electrode
Laser
Working
electrode (Metal Moving arm
disk)
Counter
electrode
(Platinum wire)

Force Sliding partner Force

transducer for (alumina ball) transducer for
frictional force normal force
 Potentiostat
•An electronic instrument that automatically maintains an electrode
at a controlled potential (V) relative to a suitable reference
electrode by imposing a proper current (A).
 Tribo-electrochemical techniques for studying
tribocorrosion
Tribometers Open circuit potential technique
Reference
Fn electrode
Fn

Ball on disk

Potentiostatic technique Current I

Counter
Fn electrode

Potentiostat
Reference
electrode
Fn

Reciprocating
ball on disk
 Outline
• Definition of a tribocorrosion system

• Tribo-electrochemical techniques
– Open Circuit measurements

– Potentiostatic tests

– Potentiodynamic tests

• Characterization of worn surfaces

 Tribo-electrochemical techniques for
studying tribocorrosion
Can we QUANTIFY tribocorrosion under “equilibrium”
conditions (no-polarization)??

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 Monitoring of corrosion potential
5N
2 Hz, 5 mm

• Ecor mesasurement 9% NaCl

Al2O3 ball

with time : Ti6Al4V

Indicates corrosion Indicates rubbing

situation situation

Rubbing
 Galvanic coupling between passive
and depassivated areas

Wear track completely

depassivated

Wear track partially

depassivated

+ Cathode potential Ec (Ec>Ea)

- Anode potential Ea (Ea<Ec)
2
6
Tribocorrosion as galvanic coupling of 2 mixed
electrodes (depassivated and passive metal)
log i log i M -> Mn+ + ne
O2 + 2H2O + 4e -> 4OH- (Depassivated metal)

M -> Mn+ + ne M -> Mn+ + ne

log icor
Passive metal (Passive metal)

Ecor E’cor Ecor E

E
Ecor
E’cor
Rubbing
log i

Passive metal De-passivated metal

log ia

Ec
Ea RI
Galvanic
coupling Ea Ec E
Monitoring of corrosion potential
0.1
Wear starts

DLC
Electrode potential (VSCE)

-0.1

CrSiN

-0.3
301 SS

316L SS
-0.5
0 1000 2000 3000

Time (s)

from Marwan Landolt, D., Mischler, S. (2011) Tribocorrosion of Passive Metals and Coatings
Formalism for galvanic coupling between passive and
depassivated areas
•Electroneutrality: Ia = - Ic <=> ia Aa = - ic Ac

•Cathodic Tafel kinetics: Ec = Ecorr + ac – bc log |ic|

Ec = Ecorr + ac – bc log ia – bc log (Aa/Ac)

Ea = Ec – Rsolution Ia
Ia , ia : anodic current , anodic current density
Ic , ic : cathodic current , cathodic current density
ac, bc : Tafel coefficients
Aa : surface area of anode (depassivated area)
Ac : surface area of cathode (passive area)
Rsolution : electrical resistance between anode and cathode
Vieira et al, Corrosion Science (2012) 54, 26-35
Formalism for the electrode potential evolution
during wear (ball on plate configuration)

With :
Ec = Ecorr + ac – bc log ia – bc log (Aa/Ac ) V(t): Wear volume
Aa = Awt (wear track area) k: wear coefficient
Awt = L R (V(t)/0.003)0.333 L: stroke length
V(t) = k Fn vs t R: ball radius
Ac = Aowt (area outside wear track) Fn: normal load
vs: sliding velocity
t: rubbing time
Formalism for the electrode potential evolution
during wear (ball on plate configuration)

Ec = Ecorr + ac – bc log ia – bc log (Aa/Ac )

Aa = Awt (wear track area)
Awt = L R (V(t)/0.003)0.333
V(t) = k Fn vs t
Ac = Aowt (area outside wear track)

Ec = Ecor+ ac – bc log ia – bc log [(1/Aowt) (L2RCwt / 0.0833)0.333]

Quantification of wear accelerated corrosion

η = E – Ecor = ac + bc log i
Simulation of the evolution of sample potential
Ec during tribocorrosion of a AlSiCuMg alloy
Potential [V SCE]

ia=11 mA/cm2

ia=7.5 mA/cm2

ia=13 mA/cm2

Vieira et al, Corrosion Science (2012) 54, 26-35

 Consequences on corrosion of a
decrease in potential

Actively corroding metal: Passive metal:

Corrosion rate decreases Corrosion rate increases
Potential measurements in simulators

Evolution with time of potential in

a hip joint simulator

100000 300000 500000 700000

0

E (VAg/AgCl) -0.3

400
-0.6 0
Time (s)
Yan et al. Proceedings of the Institution of Mechanical Engineers (2010)
Hesketh et al. Tribology International (2013)332–338
 Monitoring of corrosion potential
•Quantification of wear accelerated corrosion :

log ia = (Ecorr - Ec + ac - bc log (Aa/Ac)) / bc

ia ~ 10-4
A/cm2
VWAC = Vchem = Q Mmol / n F ρ

Q= Ia trub

Mischler et al, Wear (2013) 297, 1081-1094

Predicting the evolution of potential with time
Ec = Ecor + ac - bc · log (ia · Aa / Ac)

OCP evolution during

0.5 N
rubbing Titanium in
0.14M NaCl at different
loads
3N 7N

Papageorgioiu et al, Tribology Letters (2012) 48, 271-283

 Corrosion cells
• Monitoring of current Icell due to tribological induced differences in
potential between CE and WE.

Current I

Counter
electrode / CE

Fn

Same metal
Working
electrode/ WE

Mischler Tribology International (2008) 41, 573-583

 Zero-Resistance ammeter
• Monitoring of current Icell due to tribological induced
differences in potential between two WEs.

Sliding'+'Load'
RE$

epoxy'

WEA$ WEB$

ZRA'

E and I versus time

 Zero-Resistance ammeter
• Monitoring of current Icell due to tribological induced differences
in potential between two WEs.

Espallargas et al. Wear 307 (2013) 190-197

 Zero-Resistance ammeter
• Current and potential evolution with time by ZRA.

Current (A)
Potential (V)

Time (seconds)
Cast Ti6Al4V rubbed against SiC pin 10N
 Zero-Resistance ammeter
• Monitoring of current Icell due to tribological induced differences
in potential between two WEs.

EG with (red lines) with the IG with (green line) with the
galvanic coupling model (blue galvanic coupling model (blue
line) line)
Espallargas et al. Wear 307 (2013) 190-197
 Zero-Resistance ammeter
• Monitoring of current Icell due to tribological induced differences
in potential between two WEs.

EG with time with a cathode of 5.6 cm2 (black lines) along with the galvanic coupling
model (blue line) and cathode surface area of 2.8 cm2 (red lines).
 Outline
• Definition of a tribocorrosion system

• Tribo-electrochemical techniques
– Open Circuit measurements

– Potentiostatic tests

– Potentiodynamic tests

• Characterization of worn surfaces

 Potentiostatic set-up
• Monitoring of current I under constant applied potential E.

• POTENTIOSTAT: electronic device

that maintains a selected potential E
between RE and WE by passing an
appropriate current I between WE
and CE.

With:
RE: reference electrode
CE: counter electrode
WE: working electrode
Advantages:

• The applied potential E (driving force for reactions) imposes a well defined
surface chemistry.
• In-situ and real time measurement of corrosion kinetics (current I).
 Electrode potential vs reaction rate
The electrode potential, E determines the nature and
I the rate of the electrochemical reactions

MÞM n++n e- M+nH2OÞMO n/2+nH++n e-

Epassive Etranspassive
n+ n+
M M
Oxide ~ 1 nm
Metal Metal Metal
Active
Passivity
dissolution
Potentiostatic set-up
Wear accelerated corrosion
Current density (corrosion rate):

Guadalupe et al. Wear 308 (2013) 213–221

 Quantification of material loss components
Wear accelerated corrosion Vchem/Vwac : integration of the current
during rubbing and use of Faraday’s law.
0.14
0.12
Vchem = Q M / n F r
Current (mA)

0.10
0.08 M: atomic weight (g/mol)
0.06
0.04
Q n: oxidation valence
F: Faraday constant (C/mol)
0.02 r: metal density (g/cm3)
0.00
0 1000 2000 3000
Time (s)

Mechanical wear Vmech : difference between Vchem

+
wear track volume and chemical wear.
Vmech
 Potentiostatic set-up: Vchem
•Quantification of wear accelerated corrosion :

M ⇒ M n+ + n e-

M + nH2O ⇒ MO + 2nH+ + 2n e-
With:
Ir current excess (A)

Critical points: n charge number

trub rubbing time (s)

• Value of n Mmol (g·mol-1)

ρ mass density (g·cm-3)
F 96500 (C·mol-1)
• Involved reactions

• Ohmic drop
 Influence of valence oxidation on Vchem
• Influence of the valence of oxidation of an AISI 430 SS on the calculations of
mechanical and chemical wear at different applied potentials on the wear rates.

n=2 n=3

n=2 n=3

n=2 n=3

Landolt, et al. (2001) Electrochimica Acta, 46, 3913-3929.

Influence of secondary reactions on Vchem

•Critical points —> involved reactions:

i = ic + ia
Anodic:
M ⇒ M n+ + n e-
M + nH2O ⇒ MO n/2+ nH+ + n e-

Cathodic:
2H+ + 2e- ⇒ H2
O2 + 2H2O + 4e- ⇒ 4OH-
Influence of secondary reactions on Vchem
•Critical points: Fretting of stainless steel against PMMA in
Ringer’s solution.

Geringer et al. Wear (2006) 261:971–9.

 Influence of ohmic drop on Vchem
•Critical points: Ohmic drop ΔΦΩ Ereal = Eappl + ΔΦΩ
ΔΦΩ = iRohm= iL/κ

κ = electrolyte conductivity
 Influence of ohmic drop on Vchem
•Critical points: Ohmic drop ΔΦΩ

• Instantaneous current during

one stroke length measured in
0.5 and 0.005 M H2SO4 for AISI
430 SS pin against Al2O3 plate.

Stemp et al. Corrosion Science (2006) 45:625–640.

Influence of electrochemical conditions on
the wear volume
• Electrochemical conditions determine surface chemistry.

• Effect of the applied potential on the volume of removed material and on

the ruthenium surface chemistry :

Stojadinovic et al, Wear (2009), 267, 186-194

 How electrode potential influences wear
No passive Passive film
film

11 N
Guadalupe et al. Wear 308 (2013) 213–221 1 Hz, 5mm
0.5 M H2SO4

Al2O3 ball
Stellite21
FIB cross section of a wear track formed on a CoCrMo
alloy at (-1.5 and 0 VMSE)
Guadalupe et al. Wear 308
(2013) 213–221

Rubbing
direction

-1.5 V/MSE 0 V/MSE

5.8 N normal force, dwell time 0.25s 5.8 N normal force, dwell time 0.25s
2µm 2µm
 How electrode potential influences wear
4.5"
CoCrMo"
4"
Nitrided)I"
3.5"
Should we think in non-
V"loss"[10)2"mm3]"

Nitrided)II"
3"
2.5" passive materials for
2" tribocorrosion?
1.5"
1"
0.5"
0"
)1.5" )1" )0.5" 0" 0.5" 1"
Poten2al"[VSHE]"

A.Bazzoni et al. Tribology Letters 49(1) (2013) 157-167

 Potentiostatic set-up

•Potentiostatic tribo-electrochemical tests allows to evaluate

Vchem and Vmech under imposed potential.

•Quantification of Vchem requires precise knowledge of n and the

absence of secondary reactions.

•Vmech quantification depends on the presence or not of third

bodies.

•Has allowed mechanistic interpretation.

 Outline
• Definition of a tribocorrosion system

• Tribo-electrochemical techniques
– Open Circuit measurements

– Potentiostatic tests

– Potentiodynamic tests

• Characterization of worn surfaces

 Potentiodynamic set-up
• Monitoring of current I under variable applied potential E.
• Influence of applied potential on the friction coefficient and current of AISI430 SS
rubbing against alumina in 0.5M H2SO4.
Friction coefficient

20
0.4 µ

Current (mA)
10

Function generator
0.3
0
0.2
I -10

0.1
-20

-1000 -500 0 500 1000

Potential (mV SME)

Landolt et al. Electrochimica Acta (2001) 46, 3913–3929

 Potentiodynamic set-up
•Monitoring of current I under variable applied potential E.

• Potentiodynamic polarization curves of AISI 316L in 0.5 M H2SO4 measured in

absence (a) and with simultaneous rubbing (b) against alumina pin.
102

Current density (mA/cm 2)

101

10-1

10-2

10-3
-1.5 -1.0 -0.5 0.0 05 1.0
Potential (VMSE)
Mischler, S. (2008), Tribology International, 41, 573-583.
 Potentiodynamic set-up

Advantages:
• Allows characterizing the effect of rubbing on the electrochemical
behavior of materials (i.e. passivity).

Critical points:
• The effect of rubbing on polarization curves depends on the ratio
between worn and unworn areas.

• Non-stationary conditions.
 Polarization resistance measurements
• DC measurements: ASTM G119-09: Standard Guide for Determining
Synergism Between Wear and Corrosion
• AC measurements: OCP and EIS evolution, before, during, and after
sliding tests

Function generator
Critical points :
• Macroscopic techniques in which the whole depassivated-passive
areas are characterized (not takes into account galvanic coupling).

• Models for ac response of pseudo-steady-state regime under

continuous sliding.
 Tribo-electrochemical techniques

What do we measure ?

• Potential: quantification of Vchem and Vmech at OCP galvanic coupling

model.

• Current: Vchem and Vmech at constant potential mechanical depassivation

model.

• Rp: ? (no physical model available).

 Outline
• Definition of a tribocorrosion system

• Tribo-electrochemical techniques
– Open Circuit measurements

– Potentiostatic tests

– Potentiodynamic tests

• Characterization of worn surfaces

 Wear track volume
• Geometry of the wear track
• Wear track volume (Vtot)
 Wear track geometry
• Cross sections measured using 2D laser scanning
profilometer or confocal microscopy

-2
z (μm)

-4

-6 T1 Bovine serum
T2 Bovine serum
T3 Bovine serum
-8
0 100 200 300 400 500
x (μm)

Casabán, Igual Tribology International (2011) 44, 318–329

 Morphology of worn surfaces
• Optical microscopy
• Scanning electron microscopy
• AFM
CoCrMo alloys in 0.14M NaCl at applied passive potential sliding against alumina

Igual et al. J Mater Sci: Mater Med (2011) 22:437–450

 Surface chemistry modification
• AES Auger electron spectroscopy
• XPS X-ray photoelectron spectroscopy
• SIMS Secondary ion mass spectroscopy

AES depth profiling on

carbon steel after
tribocorrosion in neutral
borate solutions

S. Mischler et al. Wear (2001) 251, 1295–1307

 Surface composition
• Principles of different surface analysis methods
 Surface composition
AES or XPS depth profile analysis

electrons analyser
photons ion beam

electrons

crater

film

substrate
 Surface composition
AES depth profiling on
carbon steel after Borate pH8.4
tribocorrosion in neutral
borate solutions

AES Intensity [counts] Borate pH8.4

+ chromate
Passivity determines
chemical degradation
of metal and particles
and also plays a role NaOH 1 M
on the mechanical
properties

Depth [nm]
S. Mischler et al. Wear (2001) 251, 1295–1307
 Subsurface characterization
• Matallographic cross sections
• Micro-nano hardness
• XRD
• TEM
• FIB

TEM bright-field images and

electron diffraction patterns of
the wear track cross section.
Ti6Al4V after fretting in 0.9%
NaCl.
Subsurface characterization
Perret et al., Wear, (2010) 269, 383-393

FIB transversal cross section of

wear track formed in 304
stainless steel at (a) passive
potential and (b) cathodic
potential in 0.5 M H2SO4.
!
Take-home messages
ü Electrochemical techniques are available and give insight into
the tribocorrosion mechanisms and quantification (allows
distinguished interaction between wear and corrosion)

ü Potentiostatic tests allow to evaluate WAC and Vmech under

imposed potential (requires precise knowledge of n, third bodies
and no secondary reactions).

ü Potential measurements allow quantify WAC and Vmech at OCP.

ü Ex-situ methods complement the quantification and

understanding of tribocorrosion mechanisms