Escolar Documentos
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09
Erosion/Corrosion
R. J. K. WOOD
University of Southampton, Southampton, UK
6.09.1 INTRODUCTION AND DEFINITIONS 397
6.09.1.1 High-Temperature ErosionCorrosion 398
6.09.1.2 General Models 399
6.09.2 EROSIONCORROSION FUNDAMENTALS 399
6.09.2.1 Factors Affecting ErosionCorrosion 399
6.09.2.1.1 Material parameters 399
6.09.2.1.2 Coatings 401
6.09.2.1.3 Environment factors 401
6.09.2.1.4 Geometry factors 403
6.09.2.1.5 Galvanic interactions 405
6.09.2.2 Electrochemical Reaction Kinetics 406
6.09.2.2.1 Kinetics under polarization 406
6.09.2.2.2 Mass-transfer coefficient 408
6.09.2.3 Fluid Flow Fields 408
6.09.2.3.1 Turbulence 408
6.09.2.3.2 Wall shear stresses 410
6.09.2.4 Erosion Fundamentals 410
6.09.2.4.1 Solid-particle erosion 410
6.09.3 EROSIONCORROSION MECHANISMS 412
6.09.3.1 Flow-Accelerated Corrosion 412
6.09.3.1.1 KouteckyLevich equation 412
6.09.3.2 ParticleSurface Interactions 413
6.09.3.2.1 Depassivation and repassivation kinetics 413
6.09.3.3 Synergy 415
6.09.3.3.1 Models and mapping 415
6.09.4 EROSIONCORROSION TESTING 419
6.09.4.1 Gravimetric and Coupon Techniques 419
6.09.4.2 Rotating Systems 420
6.09.4.3 Flow Systems 421
6.09.5 EROSIONCORROSION DETECTION 421
6.09.5.1 Advanced Electrochemical Monitoring 421
6.09.5.1.1 Electrochemical noise 421
6.09.6 EROSIONCORROSION-RESISTANT MATERIAL AND SURFACE SELECTION 422
6.09.7 CONCLUSIONS 423
6.09.8 REFERENCES 425
NOMENCLATURE
a scaling constant
A real contact area (m
2
)
A
a
affected area (m
2
)
a
j
jump distance (m)
A
nom
nominal contact area (m
2
)
395
B migration kinetic constant (czFa
j
/
RT)
b
a
anodic Tafel slope (mV decade
1
)
b
c
cathodic Tafel slope (mV decade
1
)
C pure corrosion (mg or mg s
1
)
C9 static corrosion rate (mg or mg s
1
)
C0 corrosion rate under erosioncorro-
sion (mg or mg s
1
)
C
0
concentration of species at electrode
surface (M, mM, mol cm
3
)
C
1
constant
C
C)
U free stream velocity (m s
1
)
U
cr
critical velocity for plastic deforma-
tion (m s
1
)
U
f
velocity component normal to sur-
face (m s
1
)
U
p
particle velocity (m s
1
)
v* friction velocity (=
_
(t
w
/r))
(m s
1
)
V
cr
critical particle impact velocity for
plastic flow (m s
1
)
v
s
volume fraction of abrasives
V
u
erosion rate (mm
3
impact
1
)
W erosion mass loss per unit time
(mg s
1
)
y vertical height (m)
y
dimensionless scale
z number of electrons
z
i
valence
a angle of impact (
)
a
1
symmetry constant
b charge-transfer barrier coefficient
d boundary layer thickness (m)
396 Erosion/Corrosion
DC change in concentration of species
(=(C
b
C
0
)) (M, mM, mol cm
3
)
DC
i
change in concentration of species i
(M, mM, mol cm
3
)
DC
e
enhancement of C due to the pre-
sence of erosion (mg or mg s
1
)
DC9
e
enhancement of C9 due to flow and
erosion (mg or mg s
1
)
DE
c
synergistic effect or enhanced ero-
sion rate due to corrosion (mg or
mg s
1
)
DH change in hardness (Hv or Pa)
Dw mass loss (mg)
Dx change in distance in x direction (m)
Df potential difference across oxide (V)
e
c
critical plastic strain (mm m
1
)
Z turbulent eddy viscosity (Pa s)
Z
c
cathodic overpotential (mV)
Z
a
anodic overpotential (mV)
Z
act
activation overpotential
(mV) = E
applied
E
eq
y surface coverage fraction
l particle flux (impact m
2
s
1
)
l
i
molar conductivity (S m
2
mol
1
)
r
f
density of fluid (kg m
3
)
r
ox
density of oxide (kg m
3
)
r
p
density of particle (kg m
3
)
r
t
density of target material (kg m
3
)
o dynamic plastic flow stress for target
(N m
2
)
o
C
standard deviation of flow corrosion
current (A)
o
T
standard deviation of erosioncor-
rosion current (A)
t passive film recovery time (s)
t
w
wall shear stress (N m
2
)
i kinematic viscosity (m
2
s
1
)
m dynamic viscosity (Pa s)
ABBREVIATIONS
AISI American Iron and Steel Institute
ASTM American Society for Testing and
Materials
CE counter electrode
CFD computation fluid dynamics
CRA corrosion-resistant alloy
CVD chemical vapor deposition
ECN electrochemical current noise
ENA electrochemical noise analysis
EPN electrochemical potential noise
EPS extracellular polymeric substances
FBC fluidized bed combustors
HVOF high-velocity oxy-fuel
KE kinetic energy
MDPE medium-density polyethylene
NAB nickel aluminum bronze
NACE National Association of Corrosion
Engineers
OCP open circuit potential
PEO plasma electrolytic oxidation
RCE rotating cylinder electrodes
RDE rotating disc electrodes
RE reference electrode
SCE saturated calomel electrode
UNS Unified National System
WC tungsten carbide
6.09.1 INTRODUCTION AND
DEFINITIONS
The derivations of both erosion and corro-
sion have similar origins in the Latin verb rodere
and corrodere which mean to gnaw away and
intensely gnaw away, respectively (Oxford
English Dictionary Online, 2006). The term ero-
sion is used in a diverse number of technologies
ranging from geological loss of rock, soil, and
beach to loss of wall thickness in engineering
systems. Corrosion can be defined as the chemi-
cal or electrochemical reaction between a
material, typically electrically conducting (i.e.,
metallic), and its environment which produces
material deterioration and degradation of mate-
rial properties. Corrosion has an equally wide
use, covering electrochemical dissolution of
metal surfaces to staining of metallic architec-
tural fittings on buildings to the degradation of
plastics. In the context of this chapter, the term
relates to surface degradation involving electro-
chemical processes only.
Erosion is a process by which discrete small
solid particles, with inertia, strike the surface of
a material causing damage or material loss to its
surface. Erosion can be a problem for compo-
nents such as turbine blades, propulsors,
pipelines, and fluidized bed combustion sys-
tems. Erosion does have its beneficial
applications, notably for cleaning and prepara-
tion of surfaces for subsequent coating/painting
by grit-blasting, descaling/dewaxing produc-
tion risers in the oil and gas industries, and
cutting through rocks or subsea steel oil struc-
tures using abrasive water jets.
Erosioncorrosion is a combination of erosion
and corrosion processes and has been used to
describe component wall dissolution rates under
flow-assisted corrosion as well as wall loss rates
under solid-particle erosion and corrosion or
cavitation erosion and corrosion conditions.
Within this chapter, the term erosioncorrosion
is restricted to describe conditions where both
mechanical erosion and electrochemical corro-
sion processes are acting together and where
Introduction and Definitions 397
mechanically induced material loss is equal to or
about 10 times greater than the corrosion-
induced material loss. The term corrosion
erosion relates to the opposite condition, where
corrosion-induced material loss is equal to or
about 10 times greater than the erosion-induced
material loss. The chapter uses flow-assisted cor-
rosion to describe enhanced corrosion where
mechanical processes are not involved such as
single-phase flows relative to component wall
surfaces. However, to fully discuss erosioncorro-
sion, the chapter initially sets out to detail some of
the current understanding of flow-assisted or
enhanced corrosion prior to introducing the con-
sequence of adding mechanical erosive processes
on material removal rates. It should be noted that
previous literature has sometimes used a much
more liberal definition of erosioncorrosion.
The need to minimize costs associated with
modern fluid handling and propulsion equip-
ment demands increasing flow rates with the
inherent risk of flow-dependent corrosion and,
if solids are entrained or cavitation occurs, ero-
sioncorrosion. This is especially true for
industries that transport slurries and other par-
ticle-laden fluids in pipes or seawater
propulsion systems such as offshore and marine
technologies. These industries expend the
equivalent of millions of pounds every year on
maintenance costs and on costs associated with
loss of productivity caused by solid-particle
impingement and cavitation erosioncorrosion
damage. Typical examples of this kind of mate-
rial destruction are erosioncorrosion damage
to pump impellers (see Figure 1), propellers,
valves, heat exchanger tubes, pneumatic and
hydrotransport systems, fluidized bed combus-
tors (FBCs), and many other types of fluid-
handling equipment. In a recent survey,
erosioncorrosion was rated in the top five
most prevalent forms of corrosion damage in
the oil and gas industry (McIntyre, 1999). The
erosioncorrosion data and models published
in the open literature aspire to allow informed
surface selection for combined erosion and cor-
rosion resistance. However, this information is
very patchy and incomplete, therefore badly
hampering any improvement in the perfor-
mance of machines in aggressive environments.
This chapter mainly focuses on aqueous-based
examples of erosioncorrosion. An excellent
reviewof solid-particle erosioncorrosion caused
by gas streams at roomtemperature and elevated
temperatures can be found in Levy (1995). A
brief overview of high-gas-temperature solid-
particle erosioncorrosion is given below to
introduce some of the complexities of erosion
corrosion and to highlight some important mate-
rial properties required for resisting erosion
corrosion. The main surface characteristic to
resist erosioncorrosion conditions, not for
high-temperature gassolid flow systems only,
is the ability to form a protection surface layer
or passive film. These surface films can restrict
charge transfer across liquid/solid interfaces,
reduce the contact stresses induced by low-
energy mechanical impacts by erosive processes,
and reform (repassivate or oxidize) after being
damaged to reduce corrosion loss rates.
6.09.1.1 High-Temperature
ErosionCorrosion
High-temperature erosioncorrosion can be
induced in such cases as heat exchanger tubing
in both FBCs and pulverized coal-fired burners,
where surfaces are exposed to impingements by
hot oxidizing gas-particle mixtures. The perfor-
mances of chromium steels under such
environments rely on the formation of a surface
oxide layer. Such oxides are sensitive to the
silicon content of the parent steel, with increas-
ing levels of Si resulting in retardation of oxide
formation under the transition temperature
(,450
C). For temperatures above transition,
a tenacious and ductile oxide scale is formed,
which protects the parent material from ero-
sioncorrosion under low solid-particle
impingement angles (30
m
3
/
i
m
p
a
c
t
)
Figure 2 Erosion rates for a wide range of
engineering materials and coatings under water
sand slurry erosion conditions of 16.5 m s
1
free jet
impingement at 90
impinge-
ment in gassolid flows or between 20
and 30
a
Figure 7 Schematic of Tafel plot (Pletcher, 1991).
From Pletcher, D. 1991. A First Course in Electrode
Processes. The Electrochemical Consultancy, Romsey.
Table 3 Galvanic series in seawater (Trethewey and
Chamberlain, 1995)
Metal
Potential (V vs SCE)
(approximate)
NiCrMo alloy C 0.030 to 0.090
Titanium 0.050 to 0.060
NiCrMoCuSi alloy B 0.020 to 0.040
NiFeCr alloy 825 0.020 to 0.040
Alloy 20 stainless steels,
cast and wrought
0.040 to 0.060
316, 317 stainless steel 0.000 to 0.100
(0.350 to 0.450)
Nickel copper alloys 400
and K-500
0.050 to 0.150
302, 304, 321, 347
stainless steel
0.040 to 0.100
(0.475 to 0.580)
Silver 0.100 to 0.150
Nickel 200 0.100 to 0.200
Silver braze alloys 0.100 to 0.200
Nickel chromium alloy
600
0.125 to 0.175
Nickel aluminum bronze 0.150 to 0.220
70/30 Copper nickel 0.180 to 0.225
Lead 0.200 to 0.240
430 Stainless steel 0.200 to 0.280
80/20 Copper Nickel 0.220 to 0.280
90/10 Copper nickel 0.225 to 0.290
Nickel silver 0.260 to 0.280
416 and 410 stainless steel 0.260 to 0.330
(0.460 to 0.560)
Tin bronze 0.265 to 0.320
Silicon bronze 0.270 to 0.290
Manganese bronze 0.290 to 0.340
Admiralty brass,
aluminum bronze
0.290 to 0.350
Lead tin solder 50/50 0.290 to 0.375
Copper 0.300 to 0.360
Tin 0.300 to 0.320
Naval brass, yellow brass,
and red brass
0.300 to 0.390
Aluminum bronze 0.320 to 0.410
Austenitic nickel cast iron 0.420 to 0.530
Low alloy steel 0.570 to 0.630
Mild steel, cast iron 0.600 to 0.720
Cadmium 0.700 to 0.730
Aluminum alloys 0.750 to 0.990
Beryllium 0.970 to 0.990
Zinc 0.990 to 1.020
Magnesium 1.600 to 1.640
Values in brackets indicate low-velocity or poorly aerated
water, and at shielded/occluded areas.
Reference electrode SCE = saturated calomel electrode.
ErosionCorrosion Fundamentals 407
forces (Pletcher, 1991). However, the
mass-transfer regime within the electrolyte is
not completely diffusion dependent.
(ii) Diffusion-controlled polarization
For diffusion-controlled mass transport, the
flux of species i is described by Ficks first law:
J
i
= D
i
C
i
x
_ _
[10[
where J
i
is the flux of species i (mol s
1
cm
2
),
D
i
is the diffusion coefficient of species i
(cm
2
s
1
), and DC
i
/Dx is the concentration gra-
dient of species i across the interface (mol cm
4
)
(see Figure 8).
The diffusion coefficient of ionic species in
dilute solutions can be estimated by the Nernst
Einstein eqn [11]:
D
i
=
RT
y
l
i
[z
i
[
2
F
2
[11[
where z
i
is the valence of the species, l
i
is the
molar conductivity.
For flowover the surface or moving electrodes,
the concentrationdistance profile at the electrode
surface canbe approximatedby a simple gradient.
Because the concentration gradient DC
i
/Dx is
maximum when the surface concentration of
species i is zero then
J
i
= D
i
C
bulk
i
d
_ _
[12[
where c is the diffusion layer thickness.
Converting the flux of species J
i
into an
equivalent current density with Faradays law
i
c
= i
L
= nFJ
i
= nFD
i
C
bulk
i
d
_ _
[13[
Here, i
L
is also the anodic current density when
cathodically controlled which is the case for
many engineering situations.
(iii) Limiting current density
By considering electrode reactions involving
only one species, the subscript i can be omitted.
Thus
i = nDF
C
x
= nDF
C
b
C
0
d
[14[
C
0
represents the reactant concentration at the
electrode. As the potential is further decreased,
ions are consumed faster by the electrode reac-
tion, resulting in a lower concentration at the
electrode. Because c, the boundary-layer thick-
ness, is determined by the flow, and the bulk
concentration is fixed, the decrease in C
0
brings
about a higher current. Because the concentra-
tion at the electrode cannot be less than zero,
there is a limit; this mass-transport-limiting cur-
rent is determined by setting C
0
= 0 in eqn [14]
to obtain eqn [15]:
I
lim
= zFD
C
b
d
[15[
The limiting current I
lim
is an important
design parameter because it represents the max-
imum rate at which an electrode reaction can
proceed. Moreover, it provides a convenient
way to measure transport rate, because mas-
s-transport coefficients can be readily and
accurately calculated from the experimentally
obtained current plateau.
6.09.2.2.2 Mass-transfer coefficient
Mass transfer can significantly affect the reac-
tions rates and therefore corrosion rates and are
particularly important in erosioncorrosion con-
ditions. A useful parameter used to develop
predictive models for flow-assisted corrosion and
erosioncorrosion is the mass-transfer coefficient.
The mass-transport coefficient, k
m
, is defined by
J = k
m
C = k
m
(C
b
C
0
) [16[
Representing the flux in terms of the current
k
m
=
I
lim
zF(C
b
C
0
)
[17[
The only parameter on the right that cannot be
readily measured is C
0
; however, at the limiting
current, C
0
is zero (Ra cz et al., 1986), providing
k
m
=
I
lim
zFC
b
[18[
6.09.2.3 Fluid Flow Fields
6.09.2.3.1 Turbulence
The relationships between fluid mechanics
and induced flow patterns for both open and
x =
x
C = C
i
Concentration
Distance from electrode surface
x = 0
Electrode
Bulk solution
Figure 8 Concentration profile at the electrode/
solution interface.
408 Erosion/Corrosion
closed fluid systems are covered extensively in
undergraduate text on fluids mechanics such as
Douglas et al. (2005) and therefore will not be
reproduced here. Such textbooks detail the dif-
ferences between laminar and turbulent flow
and their importance on near-solid-wall shear
stresses and near-wall flow structures. It is these
near-wall flow conditions that are important to
understand if erosioncorrosion rates and loca-
tions are to be accurately quantified for
engineering components, in particular, the
development of eddy structures in turbulent
flows through lateral momentum transfer
between fluid elements. These in turn disrupt
the turbulent boundary layers that are devel-
oped within near-wall flows (Cantwell, 1981;
Robinson, 1991; Panton, 1984) and require par-
ticular attention, as these can develop localized
damage patterns on solid surfaces that can lead
to accelerated loss of fluid containment and
thus decrease component life considerably.
Two examples are given below, namely, rip-
pling in pipe flows and turbulent bursting/
jetting flows over flat plates:
(i) Rippling of pipe surfaces by erosion
corrosion induced by near-wall turbulence
In the cases of multiphase flows
(solidliquid), it is assumed that initially the
turbulent eddy pattern in the flow is determined
by the surface roughness generated by the final
machining operation of the pipe (see Figure 3).
The ability of the sand particles to erode is
largely determined by the bulk flow but will
result in the modification of the surface rough-
ness. The initial surface roughness is thus
replaced by the roughness resulting from indi-
vidual erosion events and varying depths of
corrosion driven by the varying flow and
mass-transport conditions near the pipe wall
(Figure 9a). In a ductile material, such as stain-
less steels, and for erosion-dominated erosion
corrosion, this roughness will be in proportion
to the impact scar dimensions (Figure 9b).
These in turn give rise to a new eddy pattern
in the near-wall flow. During the erosion pro-
cess, the sand particles have to pass through
these eddies and are thereby deflected. The
eddy pattern determines the angle of impact
and areas of increased sand-particle impact
and also the flow corrosion rates over the
surface. The concentration of damage at spe-
cific points results in the establishment of a
ripple pattern, reflecting the turbulence pat-
tern. The surface waviness increases until a
steady state is reached at which point the
surface continues to wear but the wavelength
and shape remain constant (Figure 9c). The
final waviness is thus a reflection of the
conditions that the material is exposed to.
The more severe the condition the greater is
the turbulence in the boundary layer and
hence the larger is the surface waviness.
(ii) Turbulent burst and near-wall flow jetting
The near-wall region can be divided into
three distinct regions: (1) the viscous sublayer,
(2) the buffer layer, and (3) the fully turbulent
region (also known simply as the log region).
Turbulent features are often reported with
reference to the dimensionless scale y
= v*y/
i, where v* is the friction velocity (=t
w
/, or
wall shear stress over fluid density), y is the
vertical height above the surface, and i is the
kinematic viscosity of the fluid. The viscous
sublayer extends from the wall out to about
y
units
long and are believed to occur as a result of
elongated regions of alternating low- and
high-speed fluid produced by streamwise vor-
tices close to the wall. The near-wall streaks
slowly lift up into the buffer region, where
they undergo a distinct oscillation and finally
break up violently around y
= 40 (see
Figure 10) (Kim et al., 1971; Blackwelder,
1989). The majority of the turbulence produc-
tion in the entire boundary layer occurs in the
buffer region from y
)
V
u
=
M
p
U
p
sinc U
cr
_ _
2o
U
p
cosc
3
2
U
p
sinc U
cr
_ _
_ _
[24[
For higher angles of impingement
V
u
=
M
p
U
p
sinc U
cr
_ _
2
12o
cos
2
c
sin
2
c
[25[
Bitter (1963) quotes a value of
U
cr
= 0.668 m s
1
for steel. Keating and Nesic
use this value to successfully predict erosion
rates in a sudden expansion and found the ori-
ginal Finnie model to be not so accurate.
However, modeling of erosioncorrosion
damage in a U-bend using the original Finnie
model as the modified version yielded no ero-
sion due to the low particle velocities involved.
Keating and Nesic conclude that their modeling
needs more experimental validation before
further refinements can be made.
Erosion models typically recognize that two
erosion mechanisms act. The Neilson and
Gilchrist erosion model, used for rocket motor
nozzles (Neilson and Gilchrist, 1968), incorpo-
rate cutting and deformation erosion, with
discrete models representing each. Such models
have been successfully used by Forder et al.
(1998) and Wood et al. (2001, 2002a, 2002b)
to predict erosion of internal components
within choke valves and slurry ducts. The cut-
ting erosion model for low impact angles was
(a) (b)
Acc.V Spot Magn Det WD 10 m
SE 16.4 20.0 kV 5.0 2000x
Acc.V Spot Magn Det WD 10m
SE 16.9 20.0 kV 5.0 2000x
Figure 11 SEM micrographs of erosion damage on the surface of samples tested at a, 7 m s
1
and b, 12 m s
1
,
1wt.% silica (296 mm) sand in 0.1 M NaOH at 40
C, test time = 30 min. The eroded region observed was
located approximately normal to the flow and in the center of the sample (Harvey et al., 2006).
ErosionCorrosion Fundamentals 411
first proposed by Finnie (1972) and later mod-
ified by Hashish (1998). The deformation
model was proposed by Bitter (1963) and is
thought applicable at higher impact angles
(30
90
for critical
components such as straights and bends (see
Wood et al., 2001, 2002a, 2002b), the contribu-
tion to the overall wear rate from deformation
mechanisms can be ignored. The volumetric
erosion per impact can therefore be given by
the modified Hashish model only:
V
u
=
100
2
29
_ r
p
3
U
p
C
k
_ _
n
sin2c
sinc
_
_ _
[26[
where n = 2.54 and
C
k
=
3oR
f
0.6
r
p
[27[
6.09.3 EROSIONCORROSION
MECHANISMS
Published research has tried to deal with the
synergistic effects between erosion and corrosion
processes which result in accelerated material
loss and in some cases actually decelerate mate-
rial loss (Wood, 2004a, 1992; Neville and Hu,
2001; Wang and Stack, 2000; Wood and Hutton,
1990). A wide range of corrosion-resistant mate-
rials rely on a relatively thin surface film to
provide a barrier (of high impedance) to charge
transfer (and thus corrosion) between the rela-
tively active bulk material and the corrosive
environment. This film renders the surface pas-
sive, but for fluid machinery handling flows
where solid particles have been entrained or
cavitation is induced; the passive film will be
removed by mechanical wear or bubble col-
lapse/microjet/shock wave impingement
processes. Where the film is mechanically
removed, charge transfer can occur at the inter-
face without retardation from the barrier film
(Stemp et al., 2003). This interaction between
tribological and electrochemical corrosive effects
causes materials to corrode at a substantially
higher rate than those experienced under static
or quiescent conditions. The possible regions of
erosioncorrosion interactions between different
flow regimes and corrosion are illustrated in
Figure 12. The most significant erosioncorro-
sion regions are where turbulent slurry flow and
corrosion overlap in region A, hydrodynami-
cally induced cavitation overlaps with
corrosion in region B, and turbulent flow over-
laps with corrosion causing flow-accelerated
corrosion, although a fourth case can be envi-
saged when solids entrained into laminar flow
could induce erosioncorrosion if their impact
energy is sufficient to cause plastic deformation
of the surface. All of these have loosely been
referred to in the literature as erosioncorrosion
although in this chapter erosioncorrosion refers
to only regions A and B where mechanical and
electrochemical interactions are involved. Thus,
region C is referenced as turbulent flow corro-
sion or flow-accelerated corrosion rather than
erosioncorrosion.
6.09.3.1 Flow-Accelerated Corrosion
Mass transfer of reactants to and from the
electrode surfaces plays an important role during
flow-accelerated corrosion. Typically, dissolved
oxygen or the dissolved metal ions have to dif-
fuse from the solution to the metal or from the
metal to the solution, respectively (Sedamed
et al., 1998). Mass transport has been studied
by several authors in different hydrodynamic
systems that use convection to enhance the rate
of mass transfer to the electrode. Such devices
include free and submerged jet impingement
geometries, rotating disk electrodes (RDEs),
and rotating cylinder electrodes (RCEs).
6.09.3.1.1 KouteckyLevich equation
The standard model used to describe flow cor-
rosion current densities for mixed controlled
reactions (where activation and diffusion pro-
cesses are present) is the modified Koutecky
Levich model (Wood et al., 1990) given in eqn
[28]. In this equation, k
m
(the mass-transport
coefficient) can be derived from eqns [29][31].
Equation [28] is the summation of activation cur-
rent density, i
a
, which is controlled by the charge-
transfer kinetics and the diffusion-controlled
current density, i
d
, which is related to the
Laminar
flow
Corrosion
Turbulent
flow
Slurry erosion
Cavitation erosion
C
B
A
A = slurry erosioncorrosion
B = cavitation erosioncorrosion
C = turbulent flow corrosion
Figure 12 Venn diagram illustrating the possible
regions of erosioncorrosion interactions between
different flow regimes and corrosion: A slurry
erosioncorrosion, B cavitation erosion
corrosion, and C turbulent flow or flow-enhanced
corrosion (Wood et al., 2002c).
412 Erosion/Corrosion
mass-transport conditions of species and ions to
and from the reacting surface:
1
i
corr
=
1
i
a
1
i
d
=
1
nFk
l
k
1
k
l
nFk
m
[28[
where i
corr
= corrosion current density,
n = number of electrons, F = Faradays con-
stant, k
1
= forward reaction rate,
k
1
= backward reaction rate.
The values of k
m
are normally obtained from
nondimensional correlations between the
Sherwood number Sh = (k
m
L/D), the Schmidt
number Sc = (i/D), and the Reynolds number
Re = (UL/i):
Sh = a Re
x
Sc
y
[29[
giving
k
m
= aD
1y
L
x1
i
yx
U
x
[30[
Taking typical values for the exponents as
x = 0.6 and y = 0.33 (Poulson, 1999) gives
k
m
= aU
0.6
D
0.66
i
0.27
L
0.4
_ _
[31[
where D = diffusion coefficient, U = flow velo-
city, i = kinematic viscosity, L = characteristic
length, a = scaling constant.
Flow-enhanced corrosion rates induced by
solids-free flows, as suggested by eqn [28],
have been shown to depend on k
m
n
where n
varies depending on the surface/environment
combinations and the controlling corrosion
mechanism. For example, corrosion rates for
copper alloys in seawater under mixed activa-
tion and diffusion control are shown to have
n < 1. Steels in sulfuric acid and under simple
mass-transfer control have n = 1, whereas for
steels in water, where flow polarizes the cor-
rosion potential and also influences the
oxides solubility, n lies between 1 and 3 (see
Poulson, 1999). Mass-transport processes also
increase with surface roughness creating large
n values until an upper-bound value is
reached given by
Sh = 0.01 Re Sc
0.33
[32[
However, a power-law relationship between
erosioncorrosion rate and k
m
is not always
seen as in the case of steel in nitrates where
surface films are removed above a critical k
m
resulting in a sudden increase in erosioncorro-
sion rate (Poulson, 1999).
6.09.3.2 ParticleSurface Interactions
When corrosion rate is partially or wholly
controlled by mass transfer of reactant to or
product from the surface, local conditions
under erosion may well influence the
mass-transfer kinetics (measured by the mass-
transfer coefficient k
m
). Under such conditions,
the corrosion will be controlled by the mass
transfer (typically diffusion processes) and the
driving concentration gradient (relative concen-
trations of active species near surface compared
to free stream concentrations) (Silverman,
2004). Both the mass transfer and concentra-
tion gradient will be affected by solid-particle
impingement, which influence the local fluid
flow field and increase surface roughness.
Erosion will also increase the surface area
wetted by the corrosive electrolyte and could
establish microgalvanic cells on the surface
with damaged areas being anodic to the passive
and (cathodic) unaffected areas. Erosion will
also increase the dislocation density in affected
surface areas which can lead to potential differ-
ences between eroded and less eroded areas
being established and the formation of anodic
and cathodic sites generating a microgalvanic
effect enhancing material loss from the surface.
It is also likely that the corrosion kinetics will be
altered on eroded areas.
6.09.3.2.1 Depassivation and repassivation
kinetics
As suggested already, depassivation of pas-
sive or film surfaces is associated with flow
velocity. Figure 13 shows the trend for such a
passive system as a function of flow velocity
and its vulnerability to mechanical processes
which accelerate corrosion loss rates due to
depassivation.
(i) Depassivation
Depassivation in erosioncorrosion pro-
cesses is assumed to be rapid and associated
with the mechanical removal or stripping of
the passive surface layers through particle, cavi-
tation bubble, or liquid droplet impact.
Figure 14 illustrates the level of damage to pas-
sive films as a function of solid-particle
impingement angle. Mechanical removal and/
or rupture of the passive layer enables charge
transfer to proceed at varying rates and parent
metal dissolution is likely. Recovery or repas-
sivation aspects of the passive film are therefore
important but are very system dependent.
Figure 15 shows the current response over
time for individual solid-particle impacts on
the naturally passivating system of stainless
steel. Some impacts will only result in partial
passive layer removal or cracking which will
influence repassivation kinetics and possibly
the composition of the regrown layer.
ErosionCorrosion Mechanisms 413
(ii) Repassivation
Surface coverage models for passive film
growth/recovery relate to the number of moles
of oxide formed N
u
as a ratio of the total num-
ber of surface sites available, N
o,u
in units of
mol cm
2
(from Jemmely et al., 2000):
y =
N
u
N
o.u
[33[
The rate of lateral surface coverage, assum-
ing complete oxidation of the parent metal to
oxide, can be given by
dy
dt
= i
a
M
ox
L
ox
r
ox
nF
_ _
[34[
where i
a
is the anodic current density, n is the
charge number, L
ox
is the oxide film thickness,
,
ox
is the oxide density, and M
ox
is the molecu-
lar weight of the oxide.
If Tafel kinetics applies, then the anodic cur-
rent density i
a
can be given by
i
a
= k
a
(1 y)exp
E
applied
b
a
_ _
[35[
where k
a
is the rate constant and b
a
is the Tafel
slope (=dE/dln(i)). This assumes that oxidation
occurs exclusively on bare parent metal.
Film growth models may explain the thicken-
ing of these oxide layers but assume growth
occurs by high field conduction which is
thought to apply over the longer term but not
in the early stages of repassivation of nascent
surface sites:
i = k
B
exp
Bf
L
ox
_ _
[36[
where k
B
is the rate constant and the migration
kinetic constant for a single ionic species
B = czFa
j
/RT. Here c
1
is a symmetry constant,
0
25
50
75
100
125
150
0 2 4 6 8 10 12 14
Velocity (m s
1
)
Intact
passive
film
provides
barrier to
charge
transfer
Depassivation
and/or
transformation
of film and
increased
mass
transport
Complete
depassivation
and rate
limited
Mechanical
enhancement
(cavitation or
sand erosion)
Critical velocity
C
o
r
r
o
s
i
o
n
r
a
t
e
Figure 13 Possible corrosion trends (with arbitrary units) for a passive metallic surface. From Wood, R. J. K.
2004a. Erosioncorrosion interactions and their effects on marine and offshore components. Keynote at EuroCorr
Conference, Nice, France and accepted for publication in the Special Issue on Tribocorrosion, Wear 2006.
Passive layer or film
Substrate
(a)
(b)
(c)
(d)
Figure 14 Schematic showing that the level of passive
layer damage is dependent on particle impact angle.
6
5
4
t (ms)
l
(
A
)
3
2
270 280 290 300 310
Figure 15 Current transients in erosioncorrosion
due to depassivation/repassivation. From Sasaki, K.
and Burstein, G. T. 2000. Observation of a threshold
impact energy required to cause passive film rupture
during slurry erosion of stainless steel. Phil. Mag.
Lett. 80(7), 489493.
414 Erosion/Corrosion
z is the charge on the migrating ionic species,
and a
j
is the jump distance. The term Dc is the
potential difference across the oxide layer and
taken to be the difference between the electrode
potential and the minimum potential for initia-
tion of film growth. The other term in the
equation is the oxide layer thickness, L
ox
.
This can be linked to the currenttime tran-
sients by setting
L
ox
=
M
ox
q
nFr
ox
[37[
where q is the charge passed or
_
i dt.
The use of such models to predict wall loss
rates depends on the above assumptions and
knowing the oxidation process and the asso-
ciated charge number as well as the area of
depassivation due to the erosion processes.
Figure 16 is an attempt to map surface
responses to the whole range of erosion and
corrosion mechanisms from erosion-dominated
through erosioncorrosion, corrosionerosion
zones to corrosion-dominated mechanisms. To
identify what zone a particular application may
be operating under is difficult without some
data on erosion and corrosion performance of
the surface in question. To plot such a map,
three independent tests to determine pure ero-
sion E, pure corrosion C, and combined
erosioncorrosion gravimetric levels T are
required. However, Table 4 shows the possible
sand-particle energy of various applications
that are directly related to the likely mechanical
erosion damage rates E. This will define a posi-
tion on the TC axis of Figure 16 and the rate of
depassivation as this is likely to be linked to E
k
.
Surface repassivation, on the other hand, is
materialelectrolyteflow-field specific, and
this dictates the corrosion rate C. Three systems
are plotted on this mechanical erosion versus
corrosion map. Two are passivating systems
based on cast and coated nickel aluminum
bronze (NAB) surfaces in saline solution and
have a positive slope (increases with increasing
mechanical erosion effects). This increase is
related to repassivation kinetics being unable
to repassivate the eroded surface under increas-
ing erosion. The third is CS in saline solution
which is not passivating and has a slope near to
zero or slightly negative. Here, the corrosion
products formed on the surface are nonadher-
ent and easily removed and the trend is
dominated by erosion rate while the corrosion
rate remains relatively constant. These results
were obtained using a free jet impingement
erosioncorrosion rig (Figure 19).
6.09.3.3 Synergy
Synergism is the enhancement of material
loss encountered when both erosion and corro-
sion processes work together. This synergy
often leads to significant increase in material
loss rates over and above those expected by
adding the separate erosion and corrosion
rates together. Synergy is defined as the differ-
ence between erosioncorrosion and the
summation of its two parts.
6.09.3.3.1 Models and mapping
Ferng et al. (1999, 2000) modeled erosion
corrosion in pipe flow by adding the erosion
and corrosion contributions together. They
assumed erosioncorrosion of piping is a degra-
dation mechanism that is a coupled
phenomenon between chemical corrosion and
mechanical erosion, which is dominated by pip-
ing layout, fitting geometry, and local flow
structure. They used local flow models, includ-
ing the multidimensional, two-phase fluid
models to simulate flow characteristics within
piping. Erosioncorrosion models were used to
predict two-dimensional distributions of
erosioncorrosion locations in steel pipework.
The model showed satisfactory agreement
with distributions of wear sites measured in
practice.
The erosion model was based on droplet
impingement but used an oxide removal based
on eqn [38]:
m = C
s
NF
y
(y)
r
f
U
2
f
H
v
[38[
where C
s
is a system constant, N the frequency
of impingement, F
0
a characteristic function, 0
0.1
1
10
100
0.1 1 10 100
Mechanical erosion TC (mg)
E
l
e
c
t
r
o
c
h
e
m
i
c
a
l
c
o
r
r
o
s
i
o
n
C
(
m
g
)
Electrochemically
controlled zone
Mechanically
controlled zone
Corrosionerosion
zone
Erosioncorrosion
zone
(TC/C) = 10
(TC/C) = 1
(TC/C) = 0.1
Steel 1020
HVOF NAB
Cast NAB
Figure 16 Mapping electrochemical material loss
against mechanical erosion rates for a
nonpassivating surface CS (AISI 1020) along with
two potentally passivating surfaces of NAB, one
that has been thermally sprayed by HVOF
deposition as a coating on CS and the other which
has been cast. The results have been obtained by jet
impingement erosioncorrosion tests.
ErosionCorrosion Mechanisms 415
the impact angle, ,
f
the fluid density, U
f
the
normal velocity, and H
v
the pipe wall hardness.
The corrosion model was based on a mixed
control corrosion process of dissolution of
magnetite and the mass transfer of ferrous
ions Fe
2
giving
i =
C
eq
C
1,2k
a
( ) 1,k
m
( )
[39[
where k
a
is the reaction rate constant, C
eq
is the
soluble ferrous ion concentration at equili-
brium with magnetite, C
is the soluble
ferrous ion concentration in the bulk solution,
k
m
is the mass-transfer coefficient.
Erosion damage by solid-particle impact or
cavitation bubble collapse to an oxide or pas-
sive film will reveal the underlying nascent
surface. This induces a higher activity (higher
corrosion current), for a limited duration, than
for the intact oxide surface. Bozzini et al. (2003)
employed a simple approximate model using a
recovering target concept. This erosioncorro-
sion model has the advantage in that it can be
applied to both passivating and actively corrod-
ing conditions. The impacting particles are
modeled with rigid monodisperse spheres of
radius r
p
. The particle impact process is
assumed to be Poissonian with parameter l
(impacts m
2
s
1
). It is assumed that each
impact gives rise to an alteration of the corro-
sion rate through a localized change in
corrosion current density for a period of time,
relating to a recovery to the unaffected state.
The effective corrosion current density, i
corr
(nA cm
2
), at a given electrode potential (typi-
cally the corrosion potential) can be related to
the mechanically affected corrosion component
of the synergistic damage through a coefficient,
f
a
, (such that 0 _ f
a
_ 1). The fraction of the
corroding surface which is affected by the ero-
sive action of impinging particles is given by
eqn [40]:
i
corr
= f
a
i
a
(1 f
a
)i
u
[40[
where the subscripts a and u stand for
affected and unaffected, respectively. The
current densities i
a
and i
u
are characteristic for
the corroding material in the absence and in the
presence of the erosive action and can be mea-
sured separately by means of suitable
experiments. In general, the coefficient f
a
can
be defined in eqn [41]:
f
a
=
no. of impacts
control area
_ _
damaged area
impact
_ _
recovery time
= lA
a
t [41[
where A
a
is the affected surface area and t is the
passive recovery time.
Equation [40] indicates an accelerating ele-
ment to corrosion caused by film damage or
removal and is one element of the complex
interactions between erosion and corrosion
that needs to be understood.
These interactions can be defined as follows.
The total damage under erosioncorrosion, T,
can be represented as
T = E C S [42a[
where E is the pure erosion material loss, C is
the solids-free flow corrosion rate (possibly
derived from the corrosion current density i in
eqn [40]). The synergistic effect (interactive
term), S, is referred to as DE
c
or (DC
e
DE
c
),
depending on the literature source, where DE
c
is
the enhanced erosion loss due to corrosion and
DC
e
is the enhanced corrosion due to erosion.
The term DC
e
can be partially expressed by eqn
[40] but additional terms are required relating
to the effect of the erodent deforming the sur-
face leading to increased corrosion activity. The
S terms and how they should be measured are
given by the ASTM G119-93 standard which is
a useful guide to evaluate synergy (ASTM
G119-93, 1993). It is also important to note
that the synergistic term S can be positive or
negative. Bozzini et al. (2003) shows that
annealed CS has a more active corrosion poten-
tial before it is work-hardened, resulting in
i
u
> i
a
, and by using eqn [40] shows a reduction
(i.e., a negative synergy) in overall corrosion
rate with erosion present.
Recent literature in the erosioncorrosion
area has defined synergy in different ways and
thus a cautious note is raised here that care be
taken to determine the definition used when
Table 4 Potential particle kinetic energies and flow velocities for marine components
Marine component
Pipe Valve Pump Propulsor
Velocity (m s
1
) 03 5 10 25
Particle diameter (mm) 100 100 100 100
Particle kinetic energy (mJ) 00.007 0.02 0.07 0.44
416 Erosion/Corrosion
comparing synergistic levels from different
sources in the literature. For example, DE
c
in
some cases is defined as the synergy term and
DC
e
as the additive term. Equations [42b][42d]
all relate to erosioncorrosion but generate dif-
ferent synergy values:
T = E C E
c
C
e
[42b[
T = E C9 E
c
C
e
9 [42c[
T = E C0 E
c
[42d[
where C9 is the static corrosion rate, C is the
solids-free flow corrosion rate, C0 is the corro-
sion rate under erosioncorrosion conditions,
DC
e
is the enhancement of C due to the pre-
sence of erosion, DC9
e
is the enhancement of C9
due to the presence of flow and erosion, and
DE
c
is still the effect of corrosion on erosion.
The synergistic effect, S, is therefore referred to
as DE
c
or (DC
e
DE
c
) or (C0 DE
c
), depend-
ing on the literature source, and thus readers
must take care in extracting synergistic levels
for different materials when using multiple
sources of literature.
Neville et al. (2002) have shown that the
corrosion current density increases with
increasing solid loading (200, 400, and
600 mg l
1
) for UNS S31603 under an imping-
ing jet of 3.5% NaCl at 17 m s
1
. It has also
been shown that synergistic effects, which result
in the damage due to separate corrosion and
erosion processes, are normally greater than the
sum of the individual damage processes and can
accelerate material removal significantly (i.e.,
T = 50 (C E); see Wood and Hutton,
1990). Synergistic effects have also been shown
to be a function of impinging solid-particle
energy for various stainless steels (UNS
S31603, UNS S32100, UNS S32250, and UNS
S32760; Wood, 2004a). Such results indicate
that synergy is more pronounced at lower par-
ticles energies. For example, under an erosion
energy of 0.02 mJ per impact, the volume loss
under erosioncorrosion for UNS S32250
(Ferralium 255) is 10 times that for only erosion
(see Figure 17). However, at higher energies
around 7.5 mJ, the erosioncorrosion rate is
only 1.4 times that for only erosion. It is also
clear that the erosion rate is not simply related
to solid-particle impingement energy but has
two regimes dependent on the magnitude of
the energy: for the lower energy range, V
u
_
U
4
, and for the higher energy range, V
u
_ U
2
.
There is also potentially conflicting data
reported in the literature with certain erosion
corrosion test conditions producing negative
synergy whereas others producing a positive
synergy. Wood (1992) reports negative syner-
gies for a superduplex steel UNS S32750 in
3.5% NaCl solutions at E
k
= 0.05 mJ and 90
m
3
/
i
m
p
a
c
t
)
V
u
U
4
V
u
U
2
UNSS32250 + tap water
UNSS32250 + 3%NaCl
UNSS32760 + tap water
UNSS32760 + 3%NaCl
UNSS31603 + 3%NaCl
UNSS32100 + 3%NaCl
Figure 17 Erosion and erosioncorrosion wear rates of duplex and austenitic stainless steels as a function of
sand energy (Wood, 2004). This material has been reproduced from Challenges of living with erosion
corrosion by R. J. K. Woods pp. 113132 of the Second Symposium on Advanced Materials for Fluid
Machinery ISBN 1 86058 441 1 published by Professional Engineering Publishing. Permission is granted by
the Council of the Institution of Mechanical Engineers.
ErosionCorrosion Mechanisms 417
Table 5 Synergy overview of processes that could lead to positive and negative interactive effects between
mechanical and electrochemical processes present under erosioncorrosion conditions
Mechanism factor Positive interaction Negative interaction
Critical impact
energy
Above-critical impact energy to penetrate/
damage passive/product film/coverage.
Results in increased charge transfer at
the liquid/metal interface
Below-critical impact energy. Results in
reduced charge transfer at the liquid/
metal interface as film could be
influenced in composition by impact
Surface roughness,
R
a
Roughening effects on mass-transfer
coefficients unknown but k
m
is likely to
increase with increasing R
a
. (The
Silverman review ( Silverman, 2004)
suggests mass-transfer sensitivities with
Reynolds number are affected by
surface roughness as k
m
_ Re
0.9
with
solids compared to k
m
_ Re
0.65
solids
free flows for rotating cylinder work
due to roughening effects on the
surface. Roughness may promote
microturbulence affecting the local
double layer. Roughness could also
promote local microelectrode behavior
(potential field distortion) at the tips of
impact craters
Roughness influences the contact
mechanics of angular solid-particle
impingement. Increased roughness
could reduce contact stresses and
thereby the near- and far-field stress
distributions
Plastic
deformation/
strain
Plastically deformed and stressed surfaces
enhance corrosion processes. Corrosion
causes premature detachment of
plastically deformed or strain-hardened
impact carter lips
Strain-hardened surface increases
hardness and reduces erosion rate and
could reduce corrosion due to change in
microstructure/grain lattice distortion
Increased or
unsteady
hydrodynamics
or turbulence
Unstable double layers (nonsteady state)
and unsteady driving concentration
gradients of active species
High concentrations of solid particles
could block the surface from incoming
particles. Particleparticle interaction
alters impact conditions
Contact
temperature
Local surface (flash) temperatures could
be significantly higher around and
within impact craters which could
accelerate corrosion rates
Local surface (flash) temperatures could
influence oxide film composition and
microstructure and thus could be more
erosion resistant
Localized corrosion Pitting and microgalvanic corrosion cells
due to localized defects in the passive
layers induced by erosion or exposure of
inclusions or voids. Crack systems would
also be vulnerable to crevice corrosion
attack and accelerate crack propagation.
Microgalvanic corrosion cells could be
formed between erosion craters and
surrounding unaffected areas
Multiphase surfaces Corrosion of interface potential to lose
bond integrity between hard and binder
phases, binder receding due to corrosion
leaves hard phase loose to be removed
by mechanical action. These interactions
could also apply to splat boundaries
which exist after spraying
Substrate corrosion products can eject via
interconnecting pores onto the coating
surface, reducing erosivity
Passive film state Depassivation: removal of air-borne
oxides or oxide layers produced by
passivation. Oxide layer could increase
friction between impacting solid particle
and the bulk substrate material
Repassivation: overall recovery times and
adherent oxide layers formed by
passivation. Oxide layer could decrease
friction between impacting solid particle
and the bulk substrate material.
Alternatively, denser oxide could be
formed that reduce corrosion or erosion
or both
Partly taken from reviews by Wood, R. J. K. 2004a. Erosioncorrosion interactions and their effects on marine and offshore
components. Keynote at EuroCorr Conference, Nice, France and accepted for publication in the Special Issue on
Tribocorrosion, Wear 2006 and Wang, H. W. and Stack, M. M. 2000. The erosive wear of mild steel and stainless steels
under controlled corrosion in alkaline slurries containing alumina particles. J. Mater. Sci. 35, 52635273.
418 Erosion/Corrosion
induced by erosion strain hardening or corro-
sion softening. For example, the hardness of a
metallic electrode will decrease when anodic
dissolution is present on the surface and the
relative hardness degradation, DH/H, can be
correlated approximately to the anodic current
density present at the electrode surface, i
a
, as
follows:
H
H
= Blog
i
a
i
th
_ _
[43[
where DH = H
*
H and is the change of hard-
ness due to anodic dissolution at the surface, H
and H
*
the hardness without and with anodic
current present at the electrode surface, respec-
tively, B (>0) is an experimental constant, and
i
th
is the threshold anodic current density to
induce the synergistic electrochemicalmechan-
ical effect, that is, when i
a
_ i
th
, DH = 0.
The change in surface hardness induced by
erosion or corrosion can also establish micro-
galvanic cells due to work function differences
between erosion-hardened areas or corrosion-
softened areas and unaffected areas (Guo et al.,
2005). This is an additional microgalvanic pro-
cess to that of surface film removal.
(i) Empirical models
Wood and Hutton (1990), summarizing
experimental data published on erosion wear
over a wide range of solid particle and cavita-
tion erosion, found that the data fell within two
groups, the medium- and high-synergistic
systems. The erosioncorrosion enhancement,
S, was found to be closely linked to the pure
erosion component E. Two expressions were
derived by plotting S/C against E/C ratios to
obtain the following expressions.
For the medium-synergy group:
S
C
= exp 1.277 ln
E
C
_ _
1.9125
_ _
= 0.1477
E
C
_ _
1.277
[44[
For the high-synergy group:
S
C
= exp 0.755 ln
E
C
_ _
1.222
_ _
= 3.3940
E
C
_ _
0.755
[45[
By using the two expressions above and
experimental values of erosion and corrosion,
these can be compared to experimental deter-
mined erosioncorrosion values. This will
indicate the level of synergy occurring in the
system under test. The equations can also be
used to predict synergistic levels should pure
erosion and corrosion rates be known.
(ii) Mapping
(Stack and Pungiwiwat (2002) and Stack
et al. (1995, 2003) have used erosion and corro-
sion models with coupling to potential versus
pH (Pourbaix) diagrams and mechanisms asso-
ciated with synergy levels to predict the
performance of various systems using maps.
The maps typically plot particle or slurry velo-
city against potential and show regime regions
and have been presented for several material/
electrolyte systems with electrolytes of various
pHs. Work is underway to develop erosion
corrosion rate maps based on experimental
data and existing mapping approaches.
6.09.4 EROSIONCORROSION TESTING
6.09.4.1 Gravimetric and Coupon Techniques
The manner by which material wastage is
measured in erosioncorrosion is an important
consideration. Experience shows that the use of
weight loss of a tested specimen or coupon is
not a sufficiently accurate way to represent
material wastage. When surfaces are submitted
to both chemically aggressive fluid flows and
solid-particle impingement, several different
weight changes occur, over and above
erosioncorrosion losses. The surfaces of the
specimen, other than the eroded area, can add
or subtract weight from chemical reactions such
as oxidation. Weight can also be added when
erodent particles become embedded into the
surface or become mixed within the surface
oxide layers or scales. The preferred way to
measure erosioncorrosion of gas-particle-
laden flows is by direct depth measurement
using a scribed grid placed onto the ground
surface to be eroded. The grid area thickness
is measured at the grid intersections using a
micrometer before testing. Post testing, the spe-
cimen is cross-sectioned and measured using a
microscope micrometer, relating the thickness
at the location of the deepest penetration to the
pretest grid thickness at the same position. This
process is reproducible to 1 mm (Levy, 1995).
Szyprowski (2003) reviews H
2
S corrosion and
the methods used to determine the efficiency of
inhibitor performance, employed to suppress
such oilfield flow corrosion. Gravimetric techni-
ques based on coupons in pipe flow prepared to
ASTM G4-95 (1995) are reviewed. Gravimetric
techniques should include the rate of deposit for-
mation on the coupons, the corrosion rate, the
depth and rate of formation of corrosion pits, the
presence of hydrogen blowholes, the changes in
mechanical properties of the specimens (the effect
of hydrogen cracking), and investigations on
metal microstructure to find intercrystalline
ErosionCorrosion Testing 419
corrosion. It is also recommended to use electro-
chemical methods that provide information
about the mechanism of inhibition, time of
adsorption, type of adsorption, and so on.
Corrosimetric (resistance) polarization probe
methods for use in refineries are also reviewed.
De Bruyn (Johnston et al., 1996) has reviewed the
modern methods of monitoring corrosion in pet-
rochemical industries, including electrochemical
noise methods.
Mass loss can be assessed using Faradays laws
of electrolysis (eqn [46]), where q is the charge,
F is Faradays constant (96 485 C mol
1
), z is the
number of electrons involved in the reaction, and
Dw is the mass loss (Barik et al., 2004). For
example, for a NAB composition, the calculated
equivalent oxidation state of the cations pro-
duced by dissolution is 2.09 and the equivalent
molar mass (M
m
) is 59.5 g mol
1
:
q = zF
w
M
m
[46[
6.09.4.2 Rotating Systems
A variety of geometries are used with varying
velocity/flow-regime capabilities. Figure 18 illus-
trates some commonly used geometries to study
the flow effects on electrodes of redox reactions.
The working electrode (under polarization
control) here is illustrated by the NAB electrode.
In Figure 18c, the performance of NAB and the
other metal cylindrical electrodes can be exam-
ined. They are used to study corrosion under
controlled hydrodynamic conditions and are
typically designed to simulate pipe flow regimes
and fluid structures. The first three are, however,
unsuitable for solid-particle erosioncorrosion
studies as the solid-particle impingement condi-
tions are difficult to quantify and reproduce. The
wall-jet geometry may lend itself to single-parti-
cle studies of erosioncorrosion, as solution
resistance in such cells inhibits measurement of
large currents induced by slurry erosioncorro-
sion studies. Slurry erosioncorrosion is
therefore studied using a larger-scale free jet or
submerged-jet impingement rig.
Tests carried out using a slurry-jet impinge-
ment rig are typically in kinetic energies ranging
from 0.02 to 0.40 mJ. However, larger facilities
with both free and submerged jets have been
commissioned that operate up to energies of
1 mJ using recirculated slurries. Modifications
to jet impingement rigs can be made to accom-
modate a silver/silver chloride (Ag/AgCl)
reference electrode (RE) and a platinum coun-
ter electrode (CE) (see Figure 19). This design
has a once-through principle for the sand, and
the ejector assembly, used for sand-particle
intake, is located downstream to prevent ero-
sion damage on the counter and reference
electrodes. A valve situated near the ejector
allows the sand intake to be completely isolated
under flow corrosion conditions. Typically,
flow corrosion tests use an electrolyte of a
3.5% NaCl solution, while slurry tests use a
3.5% NaCl solution with a 3% w/w silica sand
concentration. Pure corrosion (C) experiments
were carried out in the absence of slurry,
whereas the erosioncorrosion (T) experiments
Insulating
polymer
sheath
(a)
(c)
(b)
(d)
NAB
electrode
NAB
electrode
NAB
electrode
NAB
electrode
Other metal
(CuNi or Cu)
Jet nozzle
Figure 18 Types of hydrodynamic working
electrodes. Rotating disc electrode (RDE); rotating
cylinder electrode (RCE); bimetallic rotating cylinder
electrode (BRCE); wall-jet disc electrode (WJDE).
From Wharton, J. A., Barik, R. C., Kear, G.,
Wood, R. J. K., Stokes, K. R., and Walsh, F. C.
2005. The corrosion of nickelaluminium bronze in
seawater. A Century of Tafels Equation: A
Commemorative Issue of Corrosion Science 47(12),
33363367.
Computer and
data logging
Electrolyte
Sand suction
Specimen
holder
Ag/AgCl RE
Jet diameter
5.5 mm
Specimen
Pt CE
Figure 19 Erosioncorrosion rig for low-kinetic-
energy-free jet impingements instrumented to make
electrochemical measurements. Exposed specimen
area typically 7 cm
2
. From Tan, K. S., Wharton J. A.,
and Wood, R. J. K. 2005. Solid particle erosion
corrosion behaviour of a novel HVOF nickel
aluminium bronze coating for marine
applications correlation between mass loss and
electrochemical measurements. Wear 258, 629640.
420 Erosion/Corrosion
were carried out with sand. A potentiostat is
used to monitor the sample potential. For pure
erosion (E), a 200 mV cathodic protection
potential was applied, based on the potentials
observed from erosioncorrosion conditions.
6.09.4.3 Flow Systems
Flow systems are typically based on pipe
loop systems with working sections equipped
for electrochemical measurements. Straight
pipe sections aim to reproduce service condi-
tions and can generate a variety of flow
conditions from fully developed laminar to tur-
bulent or can be used to study pipe entry
conditions where the flow is not fully developed
(see Figure 20). Flow loops clearly require asso-
ciated pipework, filters, and pumps, all of
which have to be selected to be inert to the
experiment. Hence, typically nonmetallic
uPVC pipe fittings and components are used.
A typical loop layout is shown in Figure 21.
6.09.5 EROSIONCORROSION
DETECTION
6.09.5.1 Advanced Electrochemical
Monitoring
6.09.5.1.1 Electrochemical noise
As stated before, Sasaki and Burstein (2000)
observed current transients for single-particle
impacts on passive stainless steels, and illu-
strated that monitoring such transients can
provide direct information on the erosion
corrosion processes. Therefore, techniques to
detect the noise level (small perturbations) on
electrochemical corrosion measurements are
being developed. This is called electrochemical
noise analysis or ENA. Noise can be measured
on both current (electrochemical current noise,
ECN) and potential (electrochemical potential
noise, EPN) outputs and subsequent analysis
can yield corrosion resistance details, assuming
both measurements are in phase with each other.
EPN measurements can be made with two elec-
trode cells while current noise typically requires
three electrodes. Further details of this technique
can be found in Cottis and Turgoose (in press).
Such measurements can be made under flow
corrosion and erosioncorrosion and are now
being analyzed by researchers for insight into
synergistic processes and surface performance
indicators. Figure 22 shows a corrosion flow
cell designed for ENA and Figure 23 shows typi-
cal EPNand ECNoutputs for stainless steel pipe
section electrodes seen in Figure 22 subjected to a
flowing NaCl solution at Re = 2000. The
Figure 20 Flow development for laminar and
turbulent flow regimes. From Wharton, J. A. and
Wood, R. J. K. 2004. Influence of flow conditions
on the corrosion of AISI 304L stainless steel. Wear
256, 526536.
Fluid
reservoir
Header
tank
Bypass
loop
Flowmeter
Filter
Test section
60 pipe diameters
Fluid
reservoir
P
P
Figure 21 Recirculating low loop schematic. The
fluid volume of the flow loop was ,180 l. From
Wharton, J. A. and Wood, R. J. K. 2004. Influence
of flow conditions on the corrosion of AISI 304L
stainless steel. Wear 256, 526536.
Working
electrodes
ZRA
ECN
EPN
Reference electrode
2
8
m
m
Data logging
Flow
Spacer
Assembly clamping rods
Figure 22 Schematic of electrochemical flow cell
and measurement setup. From Wharton, J. A. and
Wood, R. J. K. 2004. Influence of flow conditions on
the corrosion of AISI 304L stainless steel. Wear 256,
526536.
ErosionCorrosion Detection 421
features seen relate to metastable and stable pit-
ting activity on the wetted surfaces of the
stainless steel electrodes.
A simple way to analyze noise data is to
take the standard deviation of the current
traces under flow corrosion, o
c
, and under
erosioncorrosion, o
T
. Attempts are currently
being made to link the standard deviation
ratios of the ECN measurements to synergy
to gain a further understanding of the effects
of erosion-enhanced corrosion, DC
E
.
Although individual events are not likely to
be resolved, the result of multiple impacts as
a function of time may be fruitful
(ZRA = zero-resistant ammeter).
However, caution should be applied to any
electrochemical measurement under erosion
corrosion conditions. Other issues make elec-
trochemical analysis and its comparison to
synergy difficult. These include the possibility
of local film currents between anodes/cathodes
(Oltra et al., 1995), which will not be seen by
ECN measurements, and the effects of
charging/recharging double-layer currents due
to fluctuating local events.
Table 6 lists the possible influences on the
depassivation and repassivation kinetics and
thus the sources of electrochemical noise.
6.09.6 EROSIONCORROSION-
RESISTANT MATERIAL AND
SURFACE SELECTION
Material selection for erosioncorrosion
duty tends to be based on the systems of alumi-
num, copper, zinc, and nickel due to their
relative cheapness. More relatively expensive
options are stainless steels or polymers (where
applicable), Co-based alloys (e.g., Stellite), Ni-
based alloys (e.g., Inconel), hardmetals or cer-
mets (e.g., sintered WC), ceramics and coatings
of these systems unto substrates of CS or low-
corrosion-resistant alloys (Neville et al., 2002;
Wood and Speyer, 2004; Puget et al., 1999;
Scrivani et al., 2001; Levin et al., 1995; Gee
et al., 2005; Gant et al., 2004a, 2004b). Surface
degradation control techniques other than sur-
face selection may well include the use of
inhibitors as well as controlling fluid tempera-
ture, pH, and dissolved oxygen levels. For
example, Poulson (1999) suggests a high pH
(>9), and dissolved oxygen levels as low as
10 ppb have been successfully used to control
flow-induced (solids-free) flow corrosion of CS.
Process parameters should also be reviewed to
minimize erosion and the use of sand-removal
(screens and cyclone separators) techniques and
sand-monitoring systems (acoustic) should be
deployed, where practicable, to reduce the poten-
tial for erosioncorrosion (Madge et al., 2004;
Mylvaganam, 2003; Al-Shammaa et al., 2003).
An overview of material selection for ero-
sioncorrosion was presented by the author at
the 2nd International Symposium on Advanced
Materials for Fluid Machinery at the IMechE
in February 2004 (Wood, 2004).
0.09
0.06
0.03
0
0.03
2
0
2
4
5 5.5 6
Time (h)
C
u
r
r
e
n
t
(
A
)
Re 2000
P
o
t
e
n
t
i
a
l
(
V
)
6.5 7
Figure 23 Electrochemical current and potential
noise for AISI 304L in 3.5 wt.% NaCl solution at a
transition Reynolds number of 2000. From
Wharton, J. A. and Wood, R. J. K. 2004. Influence
of flow conditions on the corrosion of AISI 304L
stainless steel. Wear 256, 526536.
Table 6 Possible influences on the depassivation and repassivation kinetics
Environmental Factor Depassivation Repassivation
Solid-particle impact Removes passive film Activates repassivation
Surface/liquid
interface
High velocities/wall shear
stresses
Film growth kinetics (monolayer coverage plus
lateral film growth)
Occluded geometries/
pits
Local environment changes
such as low pH
Metastable pits
Temperature Local temperature Local temperature
Turbulence bulk flow
structure
Turbulent flow features Rougher/larger surface area
Wood, R. J. K. 2004. Challenges of living with erosioncorrosion. Second International Symposium on Advanced Materials
for Fluid Machinery, IMechE Conference Transations (1), paper S965/008/2004, 113132, ISBN 1 86058 441 1. Professional
Engineering Publishing, Bury St Edmunds.
422 Erosion/Corrosion
Recent research into the erosioncorrosion
of polymer coatings and HVOF aluminum
and NAB coatings are reviewed in Moore and
Wood (1992) and Tan et al. (2005). This sug-
gests that medium-density polyethylene
(MDPE) surfaces should be considered, where
appropriate, as erosioncorrosion surfaces.
Figure 24 shows the erosioncorrosion rates
(T) of the cast NAB, 90/10 Cu/Ni, HVOF
NAB, plasma electrolytic oxidation (PEO) alu-
mina coatings, MDPE, and the 4360 steel
substrate plotted against particle energy, E
k
.
For comparison, data for MDPE pipe mate-
rial, taken from (Moore and Wood, 1992), are
also plotted on Figure 24. These results showthat
MDPE outperforms all the other surfaces tested
and is an attractive option for resisting slurry
erosion in corrosive media where fluid tempera-
tures permit selection. However, it has a high
sensitivity to impact energy with an energy expo-
nent over 1.5 (i.e., V
u
c U
3
) (see Table 7).
For low-energy solid-particle flows, materials
selection could be based on the degree of passivity
a surface offers under the design environmental
conditions it will be subjected to. For example,
alloys that strongly passivate with very adherent
films, such as titanium and some Ni/Cr/Mo
alloys, could be considered for some erosion
corrosion duties. Alloys such as steels and some
copper-based alloys that form protective or
semiprotective films that are easily removed by
flow or particle impingement may be selected for
very low-particle-energy flows but will be prone
to severe material wastage as the particle energies
and/or flow velocities are increased. However, it
is not only the dynamic service conditions that
should also be used for material selection.
Shutdown periods can allow solids to sediment
out of suspension, and accumulation of these on
surfaces such as some stainless steels and nickel-
based alloys can promote localized corrosion
such as pitting or crevice corrosion.
6.09.7 CONCLUSIONS
As demonstrated within this chapter, mate-
rial performance is highly system dependent
and modest changes in environmental condi-
tions can have a significant impact on wall
wastage rates. The discussion throughout this
chapter also confirms that our level of under-
standing of the mechanism involved and
controlling parameters is too low to enable
informed material or coating selection for
such aggressive duties. Therefore, selection
must be accompanied by either relevant experi-
ence of good material performance under
similar erosioncorrosion conditions or rele-
vant experimental results from carefully
constructed laboratory testing that has proved
to simulate field conditions to allow material
and coating screening. For a review of flow-
assisted corrosion, the reader is also referred
to a recent National Association of Corrosion
Engineers (NACE) book by Roberge (2004)
and a review chapter by Craig (1991).
This chapter has detailed the fundamental
aspects currently known to be of importance
to erosioncorrosion. The level of understand-
ing is incomplete and some of the complexities
of erosioncorrosion processes have been high-
lighted; there is a need for serious research
effort to gain full understanding. Therefore,
the overall conclusion, at present, is that it is
difficult to give generic statements of how ero-
sioncorrosion impacts upon structural
0.000 1
0.001
0.01
0.1
1
10
0.01 0.1 1
E
k
(J)
V
u
(
m
3
/
i
m
p
a
c
t
)
Vu alumina
Vu PEO
Vu steel
Vu HVOF NAB
Vu NAB
Vu 9010 CuNi
Vu MDPE
Figure 24 Relationship between erosioncorrosion
rate V
u
and kinetic energy E
k
under sand and 3.5%
NaCl solution slurry jet impingement at room
temperature and 90