ELSEVIER Wear 186-187 (1995) 284-290

WEAR
Modelling the influence of surface oxidation on high temperature erosion
D.J. Stephenson, J.R. Nicholls
School of I ndustrial and Manufacturing Science, Cranjeld University, Cranjeld, Bedford MK43 OAL, UK
Abstract
The interaction between a growing surface oxide and impacting particles is of importance in many high temperature applications such as
gas turbines and combined cycle power generation systems and may often result in accelerated rates of metal wastage. In this paper the
interaction between a growing oxide film and an impacting particle is considered. The impact conditions are analysed to predict the impact
damage morphology and the importance of parameters such as oxidation rate, oxide mechanical properties, impact velocity and particle size
and distribution, highlighted. The analysis has been used to extend the range of application of predictive erosion models using a Monte Carlo
simulation approach.
The modelling has been used to produce high temperature erosion mechanism maps which define the conditions over which a particular
material removal mechanism will predominate. For many of the high temperature erosion conditions encountered in practice, this modelling
approach suggests that several material removal mechanisms may co-exist locally across a surface and it is therefore essential that these factors
are included when life-prediction models are developed.
Keywords: Oxidation; Erosion; High temperature studies; Monte Carlo method; Particle impact
1. Introduction
Solid particle erosion processes are a potential problem in
many high temperature systems ranging from the gas turbine
through to fluidised beds. Within these high temperature sys-
tems material degradation occurs through both oxidation/
corrosion and erosive wear, with metal recession rates often
enhanced as a result of the synergistic interaction between
the two processes. The prediction of material behaviour under
such complex high temperature erosion conditions is essential
if reliable life prediction models for critical components are
to be produced.
The erosion of metals operating at elevated temperatures
will clearly be influenced by the formation of surface scales
such as oxides. Based on bulk properties, the metal substrate
will respond in a ductile manner whereas the oxide scale may
exhibit a brittle response. Thus in the first instance, high
temperature erosion can be considered as material removal
from a composite system, consisting of a ductile substrate
and a brittle surface oxide.
Several studies reported in the literature have investigated
the interaction between erosion and a surface oxide film [ l-
71. Mechanisms of material removal have been proposed
which include oxide fracture and chipping, oxide spallation
at the metal-oxide interface and plastic deformation of metal
substrate resulting in both oxide and metal loss.
0043-1648/95/$09.50 0 1995 Elsevier Science S.A. All rights reserved
SSDIOO43-1648(95)07157-l
I METALLIC
PARTICLE
ENERGY
+
1.--,,l,,,,il
I
OXIDATION
i
OXIDATION
SCALE GROWTH RATE
Fig. 1. Schematic diagram showing the types of degradation that can occur
under conditions of combined oxidation-erosion (after Ref. [ 1 ] )
Such interactions have been summarised by Barkalow and
Pettit [ I] using schematic diagrams typical of Fig. 1. For
low energy particles, scale fracture does not occur and there-
fore metal recession rates will be determined by the oxidation
process only. As the impact energy is increased and damage
to the oxide scale occurs, an interaction between erosion and
oxidation will result in accelerated metal loss. At still higher
D.J . Stephenson, J.R. Nicholls/ Wear 186187 (1995) 286290 285
impact energies, deformation of the substrate produces metal-
lic erosion.
For materials to operate successfully at high temperatures
a key requirement is the formation and maintenance of a
protective oxide scale. The particle impingement conditions
for which oxide failure occurs must therefore be quantified if
material behaviour is to be predicted.
280
In this paper, high temperature erosion mechanism maps
are developed which predict the conditions under which var-
ious material removal mechanism predominate.
E
\ 200
;
:
"
t;
160

2
t
:
120
2. Material properties at high temperatures
80
There are two important factors which differentiate the
high temperature erosion of metals from their low tempera-
ture behaviour:
(i) the surface properties of the metal may change signifi-
cantly with time due to the growth of a surface oxide.
The rate of growth of the oxide is a function of the
temperature.
0 1.0 2.0 30 4.0 50 60 7.0 8.0
Thickness Ipml
(ii) the mechanical properties of oxide and metal may
change with temperature and time.
It can be assumed in the first instance that oxide scales
respond in a brittle manner and therefore their fracture behav-
iour must be quantified whereas erosion of the metallic sub-
strate is controlled by localised plastic deformation and
therefore high temperature strength must be considered.
Cracked Unrracked Temp' C K, HPJ rn
950C . 0 700 20
800' C . A 800 2. 1
7OOY . I I I 900 37
950 4s
, 000 62
Fig. 2. Change in fracture stress of chromium oxide scales with temperature
and oxide thickness (from Ref. [ 51)
The fracture stress of oxides can be determined using
acoustic emission or resonant frequency techniques and work
to date has demonstrated the importance of both temperature
and scale thickness [ 81. Fig. 2 [ 51 illustrates the fracture
stress of chromic oxide scales as a function of oxide thickness
and temperature and shows how the fracture stress increases
as the temperature is raised and the oxide thickness reduced.
The fracture stress can be evaluated using linear elastic frac-
ture mechanics and a knowledge of the fracture toughness
and defect distribution within the scale as discussed in Ref.
[81.
The localised deformation behaviour of the metallic sub-
strate can be estimated from hot hardness testing. Structural,
high temperature alloys such as the nickel base superalloys,
maintain their strength up to temperatures in the region of
700 C, but at higher temperatures a sharp reduction in
strength is observed. A typical example for IN738 is shown
inFig. 3 [5].
oxidation kinetics. If the erosion damage is highly localised
at the surface such that only loss of oxide occurs, for example
by localised fracture and chipping (Fig. 4(b) ) , but the scale
remains protective, then metal loss can be expected to
increase due to enhanced oxidation. In this oxide dominated
regime the boundary conditions for the on-set of damage
require that the fracture stress of the oxide is exceeded and
that the oxide behaves as though it were of infinite thickness.
The latter requirement can be estimated from the modelling
work of Halling and Arnell [ 121 as discussed elsewhere [ 51
and is estimated from the ratio of the particle-target contact
radius a and oxide thickness z. From Hallings and Amells
analysis the substrate will have no influence on the scale
surface properties when z/a > 0.23.
3. Erosion regjmes and failure criteria
The oxide modified regime, (Fig. 4(c) ) occurs when the
fracture strength of the oxide is exceeded and z/a is below
0.23, i.e. for relatively thin oxide scales. Damage morphol-
ogies vary from through thickness scale fracture to oxide
spallation, although damage to the substrate is not observed.
In this regime metal loss rates are likely to be high since the
surface oxide is non-protective and linear kinetics will pre-
vail.
The approach used previously to model erosion processes As the relative thickness of oxide is reduced, the maximum
by the authors [ 9, lo] has centred around the four regimes normal force at the oxide-metal interface will increase and if
which are summarised in Fig. 4 and form the basis of the the particle velocity is sufficiently high, plastic deformation
Monte Carlo simulation model of erosion corrosion [ 111. of the substrate will occur. In this substrate dominated regime
When the impact conditions are such that no damage results, (Fig. 4 (d) ) material removal is primarily from the substrate
(Fig. 4(a) ) , metal loss will be predicted from the standard with a contribution from the surface oxide. Metal loss rate is
286 D.J. Stephenson, J.R. Nicholls/Wear 186-187 (1995) 284-290
450
400
350
300
T:
E
y
L0 250
Ln
aI
&
k
r 200
150
100
50 J
0 100 400 SO0 600 700 BOO 900 1000 1100
Temperature ICI
Fig. 3. Change in hardness of IN738 with temperature (from Ref. [ 51)
determined by the erosion resistance of the metal substrate
and oxidation makes only a minor contribution to the degra-
dation process. It should be noted that an interesting condition
can exist where the oxide film does not fracture and its effect
is to reduce the force applied to the substrate. Thus, when
this applies the erosion rate will be reduced. Examples of the
various erosion damage morphologies on oxide films are
shown in Fig. 5.
From a knowledge of the particle, oxide and substrate
properties and the impact dynamics, the boundary conditions
between each regime can be quantified by considering the
contact conditions at the oxide surface and how these change
with oxide thickness.
The conditions for scale fracture can be determined by
calculating the maximum radial tensile stress at the oxide
scale surface for a given impact event and comparing this
with the fracture stress values shown in Fig. 2. The contact
radius is estimated assuming Hertzian behaviour with the
effective elastic properties of the surface determined using
the Halling and Amell analysis, as detailed in Ref. [ 111. This
enables both the oxide dominated and oxide modified regimes
to be evaluated.
The substrate dominated regime is assumed to be dominant
when a state of full plasticity is reached at the metal surface.
The impact conditions associated with the metal-oxide inter-
face are correlated with the critical conditions for the on-set
of plastic damage using expressions given by Tabor [ 131 and
Mamoun [ 141, which enable a critical velocity to be esti-
mated.
NO EROSION
i Oxldaflon only
OXIDE
METAL
i
Am
NO impact damage
Protective oxide
L--_.
t
2a OXIDE DOMINATED
I-----!
&
Oxide fracture
xkl>0.23
Oxide chlpping
OXIDE MODIFIED
Am
Oxide fracture
Oxide spallalion
Non-protectwe oxide
Enhanced
oxldatlon
t
T
Catastrophic
oxldatmn
LL
t
SUBSTRATE DOMINATED
?I
Am
I/
Substrate deformabon
Metal and Oxide removal
1 Erosion co,nlrolled
t
Fig. 4. Summary of erosion regimes observed at high temperatures.
D. J. Stephenson, J.R. Nicholls/Wear 186187 (1995) 284-290
(cl (d)
Fig. 5. Typical damage morphologies produced at elevated temperature illustrating erosion regimes: ( a) oxide dominated showing Hertzian core cracks in
NiO; (h) oxide modified showing scale fracture on CrzOs; (c) oxide modified demonstrating spallation of a thin CrzOs scale; (d) substrate dominated showing
gross plastic damage to nickel, the generation of metallic wear debris and disruption of the surface oxide.
4. Erosion mechanism maps
Fig. 6 illustrates an erosion mechanism map for the impact
of 25 pm alumina particles on IN738 at 700 C and a 90
impact angle. The boundary conditions for the different ero-
sion regimes identified in Fig. 4 are highlighted as a function
of impact velocity and oxide thickness.
The map indicates that for this particular erosion system
the oxide modified regime exists only over a limited range of
velocities and oxide thicknesses. At velocities less than about
0.2 m s - an increase in oxide thickness results in a direct
transition from no erosion to oxide dominated. The sub-
strate dominated regime occurs when a critical velocity is
exceeded, about ,12 m s- for very thin oxides. As expected,
this velocity increases as the oxide thickness increases and
higher impact energies are required to deform the substrate
plastically.
In terms of metal recession rates, the conditions within the
substrate dominated and oxide modified regimes are likely to
be the most severe which means that velocities should be
maintained below 0.2 m s-. Even though the erosion map
predicts that low velocities and thin oxides will result in no
erosion, oxide growth is a dynamic process and therefore the
no erosion-oxide modified boundary will eventually be
crossed and scale failure will result. The time to achieve this
100 i-
/
..j
: : .SCiSTh7ATE DOivifLiiE~ .:. i : :;
OXlOk
DdMINATED
0.1 1
Oxide Thickness (urn)
Fig. 6. Erosion mechanism map for IN738 impacted by 25 pm A1203 at 90
impingement angle and 700 C.
288 D.J . Stephenson, J.R. Nicholls/ Wear 186-187 (1995) 284-290

..-,.:.. ,, ,,
L:-:
7
,..
-..__ __.._r._i_f__._..l___._.l.l.L__~ : : : Ii _ - . _ L _ . . . , _ -
0.01 0.1 1
Oxide Thickness (urn)
10
Fig. 7. Erosion mechanism map for IN738 impacted by 250 km sea salt
particles at 90 impingement angle and 700 C.
.j
. ._.,
,. ..-
1.:. :
:.. f : :j
: : ::
.DOMINATED
0.1 1
Oxide Thickness (urn)
Fig. 8. Erosion mechanism map for IN738 impacted by 250 km sea salt
particles at 90 impingement angle and 850 C.
therefore there will be a higher probability of scale failure
and removal.
The effect of changing the temperature and erodent prop-
erties are shown in Figs. 7 and 8 for the impact of 250 pm
sea salt on IN738 at 700 and 850 C respectively. For the sea
salt particles which exhibit a reduced elastic modulus and
lower density compared to alumina, the oxide modified
regime is much larger at 700 C, with the substrate dominated
response only observed for velocities in excess of 500 m s- .
The minimum velocity for oxide modified behaviour is pre-
dicted to be about 1 m s- .
At 850 C, Fig. 8, the oxide fracture strength is increased
and the IN738 substrate yield strength is decreased. This
results in a shift in the boundary conditions, with the oxide
modified regime becoming more restricted. The minimum
velocity for oxide removal increases to over 2 m s- and the
on-set of substrate deformation is reduced to around
180 m s- . The enhanced plasticity of the oxide is reflected
in the thicker oxides required before fracture occurs.
Examples of impact damage morphologies on IN738 pro-
duced at 700 C and 850 C under simulated sea salt shedding
conditions are illustrated in Figs. 9 and 10. The sea salt par-
ticles (200-300 pm) were entrained within a 250 m s - gas
stream. Packets of particles were fired at the IN738 surface
at either 5 min (high flux) or 1 h (low flux) intervals. There
will depend on the oxidation kinetics and the particle fiux.
As the number of particles is increased, the time between
impacts at a given point on the surface will be decreased and
Fig. 9. Impact damage morphologies observed on IN738 following simulated
sea salt compressor shedding at 700 C: (a) low particle flux; (b) high
particle flux illustrating oxide modified erosion.
D.J . Stephenson, J.R. Nicholls/Wear 186187 (1995) 284290 289
Fig. 10. Impact damage morphologies observed on IN738 following simu-
lated sea salt compressor shedding at 850 C: (a) low particle flux showing
oxide modified behaviour; (b) high particle flux illustrating substrate dom-
inated response in areas of t!iin oxide scale.
was therefore a range of particle sizes, impact velocities (typ-
ically 150-200 m s-l) and time between impacts and this
was reflected in the type of damage observed at each test
temperature.
At 700 C, when oxidation rates are relatively low, the
erosion maps, Fig. 7, predict that erosion proceeds by oxide
fracture and removal only, principally within the oxide mod-
ified regime (oxides thickness less than 3-4 pm). Fig. 9
shows that the damage morphologies for both the high and
low particle flux conditions are consistent with this predic-
tion.
At 850 C, Fig. 8 predicts that oxide fracture and/or sub-
strate deformation will result depending on the oxide thick-
ness and impact velocity. The erosion damage shown in Fig.
10 indicates that for thicker oxides (low particle flux) the
oxide modified regime applies (e.g. 2.5 p.m oxide impacted
at 200 m s-) but when the probability of impact increases
(high particle flux) substrate deformation may occur in areas
where the oxide film is thin enough (e.g. oxides less than
2 km thick impacted at 200 m s-l).
This general approach to modelling high temperature ero-
sion has been included in the predictive Monte Carlo com-
puter simulations developed in recent years at Cranfield
[ 10,111. Since impact velocity and particle size are often
considered to be of particular importance in erosion studies,
the computer simulation has been used to predict material
behaviour for IN738 impacted by silica at 700 C and a 90
impact angle as a function of particle size and velocity.
Fig. 11 illustrates an erosion map which highlights the ero-
sion mechanism regimes and also includes predicted levels
of metal recession. The substrate dominated regime in this
example has been divided into two regions, oxide + substrate
and substrate dominated. In this case substrate deformation
occurs as soon as the oxide modified-oxide+ substrate
boundary is crossed, but metal loss remains principally a
result of oxide removal. In the substrate dominated region
metal loss is predominantly through loss of metal with oxide
removal providing only a minor contribution to the surface
recession.
The erosion map shown in Fig. 11 has been constructed
assuming a constant particle loading of 1 X 1O-4 g
rnmV2 h- . It can be seen that particle size influences both
the dominant material removal mechanism and metal loss
1,000
r
.
_x
Yl.
,-_ _-_--
,
/
/
,,, z
10um,1000h
I I
1 10 100
Particle size (urn)
Fig. 11. High temperature erosion map for IN738 impacted by silica particles
at 90 impingement angle and 700C at a particle loading of 1 X 10e4 g
mm- h- illustrating damage regimes and metal recession rates predicted
by Monte Carlo modelling.
290 D.J . Stephenson, J.R. Nicholls/ Wear 186187 (1995) 284-290
rate. This is a result of both the change in impact dynamics
and the number of particles arriving at the surface. As particle
size increases the velocity for the onset of substrate removal
decreases. Within the substrate dominated region the metal
recession rate changes little with particle size except when
particles size is reduced below the 10-100 pm range. Within
the oxide modified range the metal loss rate is more sensitive
to particle size as a result of the change in the frequency of
impact events and the subsequent oxide thickness (i.e. effec-
tive surface properties) at any given time. In reality a range
of particle sizes will impact the metal surface and therefore
the impact damage morphology produced for a given impact
event will be a function of the size distribution of the erodent,
the particle flux and how these variables interact with the
dynamically growing oxide film. Thus, it should be expected
that for many high temperature erosion situations, more than
one erosion mechanism may be operating across a surface
and that the principal erosion mechanism may change with
time as observed in practice [ 151. Any life prediction model
must therefore take account of this factor if a high degree of
reliability is to be assumed. This is a principal factor behind
the success of using Monte Carlo methods to model erosion
processes [ 111.
Conclusions
Several material response regimes have been identified
which describe high temperature erosion, namely sub-
strate dominated, oxide modified and oxide dominated.
Which erosion regime applies to a given impact event
depends on a complex interaction between the impact
dynamics, the thickness of oxide and the temperature.
Erosion mechanism maps have been produced which
identify the dominant material removal mechanisms
depending on velocity and scale thickness.
4. For erosion conditions which involve a wide distribution
in particle sizes and impact velocities or variations in
particle flux, the principal erosion mechanism may change
from one regime to another, or several erosion mecha-
nisms may coexist across a surface. The ability to predict
this behaviour is essential for life prediction modelling
and highlights the necessity of using a statistical approach.
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