Tribocorrosion: Third body model

S. Mischler, A. Igual Muñoz,

Ecole Polytechnique Fédérale de Lausanne (EPFL) Lausanne,
Switzerland
 2 and 3 body tribocorrosion contacts
316L surface after wear against alumina ball in
sulfuric acid.
2 body contact
Mechanical wear
Wear activated (detachment of metal
corrosion indenter particles)

Passive metal

Ti6Al4V surface after fretting against alumina ball in

3 body contact sodium chloride.

Friction film Mixed Ti-TiOx

(third body) friction film
Indenter

Ti6Al4V
alloy
Passive metal
3
Corrosion of 304L steel in PWR
Build-up of a 1-3 µm thick oxide film on stainless steel by exposure to PWR conditions

Outer oxide
layer
(Magnetite)

304L
Inner oxide
layer
(Chromite) Plane view of a 304L steel after
exposure to PWR conditions, at pH
7.9
Thesis Perret, 2014

Ziemniak, Corr. Sc. 2002

4
Wear of rod/guide contact

Guidance
card

tub
Sliding
e

Tube

Metallographic
cross section of a
worn tube from a
reactor.
Thesis Kaczorowski
2002

10µm
5
Build-up of friction film on 304L steel in PWR

io n
ic t
Fr Metal
film
6
Possible build up mechanism of friction film

Mechanical mixing of metal and oxide during repeated scratching of the surface

Before rubbing First stroke Subsequent strokes Subsequent strokes

(Oxide film formation) (Formation of ridges) (Flattening of ridges) (Breaking and smearing
of ridges)
7
Physical view of the mass flows in the friction film
8
Model of mass flows within the friction film

Mass compartments Ci Mass flows !i [g/s]

Mn

Water
!4: particles re-
deposition C4
M+n
!3: particle
detachment from !4 !3
friction film
Friction
film !5: oxidation of metal
!5 particles within the
C2 C3
M+n M0 friction film

!2 !1
!2: oxidized metal
C1 entering friction film
M0
!1: metal particles
Metal
entering friction film
9
Physical laws describing the flows

51: metal particles entering the friction film

Archard approach
Water

C4
M
n
+
1
!" = $%& ' ()*+,- ' . ' /0 ' 12 '
54 53
4)*+
Friction
film
C2 55
C3
M
KΦ1: constant
+
n M0

52 51 ρ: metal density
C1 a: Normal force attenuation factor (friction film
M0
Metal reduces
force acting onto the metal)
FN: normal force [N]
vs: sliding velocity [cm/s]
Hmet: hardness of the metal [N/cm2]
10
Physical laws describing the flows

!2: oxidized metal entering the friction

film
Water Adapting established tribocorrosion model
C4
M +
7.9
n
'()* -2
!4 !3 Tribocorrosion model"# = %∅# , ./ , 01 ,
+ , - 3456
Friction
film
C2 !5
C3 Introducing oxidation +,- <⁄# <⁄#
M+
M 01 = 2%1 6=>=*?
'()*
0

parabolic kinetics
n

!2 !1

C1
M0
7.9
Metal <⁄# <⁄# @ , -2
"# = %∅# , 2%1 , 6=>=*? , ./ ,
3456

KΦ2: constant Qp= passivation charge density

Kp: parabolic tcycle= stroke time
constant [s]
11
Physical laws describing the flows

!3: particle detachment from friction film

Water
Archard approach
C4
M +
n

!4 !3 "# = %&' ( )*+,-. ( /0 ( 12 ( 3*+

Friction
film
C2 !5
C3
M
4566*7 8566*7 ( 9:,*+,-.
+
n M0
3*+ = =
!2 !1 4*+,-. 9:,566*7 ( 8*+,-.
C1 KΦ3: constant
M0
Metal
M: molar mass of the alloy or of the oxide

n = molar fraction of metal X in alloy or in the oxide

12
Physical laws describing the flows

!4: particles re-deposition on friction film

Water Sedimentation model: flow proportional to
C4
M +
settling velocity, surface area and particle
concentration.
n

!4 !3
Friction
film
2 DE − DG / H / I J
C2 !5 :;<==>?@A = /
M
n
+
C3
M0
9 K
3° #
!2 !1
"# = %&'()),)+&,-(. / 0)+,,1-.2 /
C1 56#
M0
Metal
"# = 789 / 3° #

KΦ4: constant VC4: volume of C4

|M|4: metal mass in R : radius of
C4
g : gravit. constant µ : viscosity
particles
13
Physical laws describing the flows

!5: oxidation of metal particles in the friction film

Water First order chemical kinetics:
C4 Oxidation rate proportional to metal content in C3
M +
n

!4 !3
Friction "# = %&' ( )* +
film
C2 !5
C3
M +
M0
n

KΦ5: constant
!2 !1
|M|3: metal mass in
C1
M0 C3
Metal
14
Mass balance within compartments

Generality* !!!"#"$%&'() = !"#$% − !"#$"#*

Accumulation Water

!p !q
Schema* !"
∆
C C4
Cni M+n
INPUT OUTPUT
*
!!!
= !! − !! *
!4 !3
Differential*equation* !"
* Friction
* film
!5
Compartment* Differential*equations* C2 C3
M+n M0
C1* !!!
= −!! − !! !
!"
!2 !1
C2* !!!
= !! − !! + !! + !! !
!" C1
M0
C3* !!!
= !! − !! !
!" Metal
C4* !!!
= !! − !! !
!"

!
15
Mass balance within compartments

Initial(
C! Equations(solved!
conditions!

1! !! 0 = 0! !! ! = −! !! + !! !

−1 + ! !!!! −1 + ! !!!!
2! !! 0 = 0! !! ! = ! + !! + !!! + !! !
!! !!

1 − ! !!!! !!
3! !! 0 = 0! !! ! = !
!!

1 − ! !!!! !!
4! !! 0 = 0! !! ! = !
!!

!
16
The Aurore PWR tribometer

Experimental conditions:
Reference • Sleeve: 304L SS
electrode
Counter Tube • Tube: 304L SS
electrod support • FN: 15 N
e • vs: 0.3 m s-1
Mast
• Orbital frequency: 10 Hz
• tcycle: 0.1 s
• 70 hours sliding
• Water 300 C, 150 bar
tube
Sleeve
• Open circuit potential

Measured mass loss (ΔC4)

pH Sleeve Tube
7 0.78mg 1.72mg
5 4.15mg 13.3mg
17
Thickness and chemical composition of friction film (C2)

Auger Electron Spectroscopy sputter depth profiling

Outside wear track Outside wear track

pH 7
AES Intensity [a.u.]

pH 5

Inside wear track Inside wear track

0
0 0.8 1.6 0 0.8 1.6
Depth [µm]
18
Calibration of flow constants

1
!" = $%& ' ()*+,- ' . ' /0 ' 12 '
4)*+
?.A
"⁄5 ⁄
" 5 . ' /0
!5 = $∅5 ' 2$8 ' :;<;-* ' 12 '
4=>:

B∅C DEF B∅G can be determined from tribo-electrochemical test at

room temperature where no friction film forms (thus a = 1).

Attenuation factor “a” is theoretically comprised between 0 and 1.

Computer simulations for stainless steel covered by a 1µm thick
oxide film indicate that a ≈ 0.5 (Kermouche 2007).
19
Calibration of variables

!" = $%& ' ()*+,- ' ./ ' 01 ' 2)*

345 corresponds roughly to the wear rate of oxide ceramics in water and
can thus be estimated from literature data.

Reference Couple Environme Load Speed

nt
345
Hsu 2001 Al2O3 / Water, room 10 N 0.3 m/s 4 10-16 m2 *N-1
Al2O3 temperature
Hsu 2001 ZrO2/ Water, room 10 N 0.3 m/s 2 *10-16 m2 *N-1
ZrO2 temperature
Wei 1996 Cr2O3 / Water, room 1 *10-16 m2 *N-1
steel temperature
Liu 1966 ZrO2/steel Water, room 60N 0.4 m/s 2 *10-13 m2 *N-1
temperature
Lancaster Al2O3 / Water, 10N 0.1m/s 1.5 *10-14 m2 *N-1
1990 Al2O3
20
Calibration of variables

!" = $%& ' (° "

$%& can be estimated using two different approaches:

Approach 1:
• Assuming sedimentation of iron oxide particles one obtains *+, = 5.3*10-4
s-1
• Values expected to be much lower because of strong convection in
Approach
reactors 2:
• Comparing experimental results on total wear and friction film thickness
one obtains *+, = 3.3*10-7 s-1

!- = $%. ' ( / 0

$%. is supposed to be very fast and thus an arbitrary value of 1 was considered.
21
Wear (mass variation in C4) vs KΦ3 and KΦ4

KΦ3

∆Mass in C4
[mg]

The blue horizontal

plane corresponds
to experimental
observable. KΦ4

FN15N, vs 0.3m/s, rox=1.04, ρoxide= 5240kg/m3.

22
Friction film mass variation (C2) vs KΦ3 and KΦ4

KΦ3

∆Mass in C2

KΦ4
FN 15N, vs 0.3 m*s-1, rox=1.04, ρ oxide= 5240 kg*m-3, a=0.5, K!1=
12.9*10-5 [-], K!2=0.86, Kp=1.28*10-12 kg2 m-4 s-1
23
Friction film mass variation (C2) vs H and a

∆Mass in C2

H
FN 15N, vs 0.3m*s-1, rox=1.04, ρ oxide= 5240 kg*m-3, a=0.5,
K!1= 12.9*10-5, K!2=0.86, K!3= 1*10-14 m2*N, Kp=1.28*10-12 kg2 m-4 s-1
24
Influence of the parabolic constant Kp on compartments

200$

C1$ C2$ C4$

150$

Kp range of
100$
typical PWR
50$ materials
mass$[mg]$

0$

!50$

!100$

!150$

!200$
1E!18$ 1E!16$ 1E!14$ 1E!12$ 1E!10$ 1E!08$ 1E!06$
Kp$[kg2*m-4*s-1]$

FN 15N, vs 0.3m*s-1, rox=1.04, ρ oxide= 5240 kg*m-3, a=0.5, K!1= 12.9*10-5, K!2=0.86.
 Concluding remarks

Modeling tribocorrosion systems as a set of material flows

according to the third body approach constitutes a valuable
tool:
• To rationalize and understand experimental observations even of
complex systems
• To assess relevance of specific parameters
• To improve design of experiments

The approach indicates that the mechanical properties of the

friction film play a key role. They still need to be assessed.