Back

Erosion-corrosion interactions and their affect on marine and offshore

components
Robert JK Wood
Surface Engineering and Tribology Group, School of Engineering Sciences,
University of Southampton, SO17 1BJ, UK

ABSTRACT

The operation of modern fluid handling systems demands for low costs, reliability, longevity
and no loss of fluid containment. All these can be achieved by minimising the material
damage caused by the combined attack of solid particle or cavitation impingement and
corrosion. This paper will cover the rationale behind the selection of erosion resistance
surfaces for fluid handling equipment and highlight the complexities encountered when these
surfaces are exposed to environments which contain sand particles or cavitation in a corrosive
medium. The erosion and erosion-corrosion performance of a variety of coatings and bulk
surfaces will be discussed using volume loss rate versus sand impact energy maps. Recent
research into the erosion-corrosion of polymer coatings, PEO and HVOF aluminium and
nickel aluminium bronze coatings will be reviewed. Electrochemical techniques designed to
monitor the erosion-corrosion mechanisms and coating integrity will be presented and used to
quantify the synergistic terms present when both erosion and corrosion act concurrently.

Keywords: Erosion-corrosion, synergy, coatings, HVOF, PEO.

1.0 INTRODUCTION

The need to minimise costs associated with modern fluid handling and propulsion equipment
demands increasing flow rates with the inherent risk of flow-dependent corrosion and, if
solids are entrained or cavitation occurs, the erosion-corrosion of the engineering equipment
involved. This is especially true for offshore and marine technologies and other industries
that transport slurries and other particle-laden liquids in pipes or seawater propulsion
systems. These expend the equivalent of millions of pounds every year to repair erosion
damage caused by solid particle impingement or cavitation. Typical examples of this kind of
material destruction are erosion-corrosion damage to pumps, impellers, propellers, valves,
heat exchanger tubes and other fluid handling equipment. In a recent survey erosion-
corrosion was rated as the fifth most prevalent form of corrosion damage in industry [1].

In general, corrosion resistant alloys do not resist erosion well and conversely, nor are the
synergies that exist between corrosion and erosion well understood. Also, cost reduction
considerations favour coatings on mild steel replacing expensive solid alloy components.
Organic coatings tend to perform relatively poorly under these circumstances [2], whereas
ceramic materials are usually too expensive to use, except in particularly critical applications.
Sprayed metallic coatings are a relatively unexplored possibility for this duty. The most likely
metallic coating materials on cost grounds are aluminium, copper, nickel and zinc, their
alloys and possibly composite materials based on them. For highly aggressive (very energetic
flows) WC-CoCr cermets are used either in sintered form or thermally sprayed by detonation
type or HVOF guns.

1
 Back

For corrosion resistance, the important distinction is between anodic and cathodic coatings.
For example, zinc and aluminium are both anodic to mild steel, i.e. they will protect steel
galvanically in seawater, and are indeed used in offshore applications for this purpose [1,3].
Copper and nickel are both cathodic coatings, i.e. they are not protective to steel. Where
defects in the coating occur, exposed steel is likely to be rapidly corroded; adding to erosion-
corrosion attack, it would be a condition for using copper or nickel (or their likely alloys),
either that a situation is guaranteed that the coating is initially defect free, or that a sealant is
used to protect the defects, although this assumes interconnecting defects through the coating
thickness, which is unlikely.

1.1 Pump materials

Thermal spray techniques such as High Velocity Oxy Fuel (HVOF) are increasingly being
used in environments where erosion and corrosion protection is required [4]. Other coating
processes, involving chemical vapour deposition (CVD) have been used to produce ultra-hard
coatings such as Diamond for pump components such as mechanical seals [5-7].

At present the most widely used coatings for wetted fluid machinery parts are ceramic and
tungsten carbide [8]. A particularly effective coating is a sprayed 86WC-10Co-4Cr coating
produced by the detonation gun (D-gun) process. The erosive wear behaviour of this coating
has also previously been investigated by Wood et al [9]. Tungsten carbide coatings produced
by this process have also been used to reduce fluid erosion, wear and corrosion encountered
on other equipment which operate in harsh environments such as drill bits and downhole tool
assemblies used in mining, oil and gas drilling [10]. Other surfaces used include bulk and
sprayed Stellite, cast iron, stainless steel, low alloy steel and carbon steel. This paper looks at
alternative and experimental HVOF coatings for consideration in machine design. It will use
work in progress to illustrate attempts being made to understand the interaction between
erosion-corrosion with the aim to allow robust surface selection for fluid machinery.

1.2 Valve materials

For production of oil and gas, choke valves on each well are used to balance pressure into a
common manifold. The well stream is extremely aggressive, containing a mixture of oil, gas,
water and solid particles. With the large velocities generated in the pressure reduction
erosion can be a major factor which controls the lifetime of the valve. Severe erosion in
corrosive flows can occur in very short periods on an oil-field valves [11] and as illustrated
by Haugen et al. in [12]. Such premature failures lead to inflated operation costs and
increased safety problems. Advances in materials used for valve components have allowed a
certain control of erosion-corrosion. Often valves can consist of over ten different material
and coating systems combined to give optimum performance [13-15].

1.3 Tribo-corrosion
In the tribo-corrosion regime material selection is extremely challenging and is based on
optimising performance against the combined degradation processes. Tribo-corrosion covers
a range of material degradation processes where there is relative motion between contacting
surfaces or abrasives/erosives and a surface in conjunction with electrochemical corrosion.
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 to decelerate
material loss, [16-19]. A wide range of corrosion resistant materials rely on a relatively thin
surface film to provide a barrier (of high impedence) to charge transfer between the relatively

2
 Back
active bulk material and the corrosive environment. This film renders the surface passive, 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
collapse/microjet/shock wave impingement processes. Where the film is mechanically
removed, charge transfer can occur at the interface without retardation from the barrier film
[20]. This interaction between tribological and electrochemical corrosive effects is referred
to as tribo-corrosion and causes materials to corrode at a substantially higher rate than those
experienced under static or quiescent conditions.

Neville has shown the corrosion current density increases with increasing solid loading (200,
400 and 600mg/l) for UNS S31603 under an impinging jet of 3.5% NaCl at 17m/s, [21]. It
has been shown [e.g. 21-22] that synergistic or additive 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 (50 times for
grey cast iron), see reference [17]. Synergistic effects have also been shown to be a function
of impinging solid particle energy for UNS S31603, UNS S32250 and UNS S32760. Such
results as shown in Figure 1, show that the synergistic effects are more pronounced at lower
particles energies. For example, the volume loss under erosion-corrosion for UNS S32250
(Ferralium 255) from 0.02 µJ impingements is ten times that lost under only erosion.
However, at higher energies around 7.5 µJ the erosion-corrosion rate is only 1.4 times that
lost under 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.

The damage under erosion-corrosion can be represented as:-

T =E+C +S (1)

where E is the pure erosion material loss, C is the solids free flow corrosion rate. The
synergistic effect (interactive term), S, is referred to as ∆Ec or (∆Ce + ∆Ec) depending on the
literature source where ∆Ec is the enhanced erosion loss due to corrosion and ∆Ce is the
enhanced corrosion due to erosion. The ASTM G119-93 standard is a useful guide for
researchers wishing to evaluate synergy [23].

2.0 THERMALLY SPRAYED AND PEO COATINGS

Several candidate HVOF (other than 86WC-10Co-4Cr) and PEO (plasma electrolytic oxide)
coatings have been considered for erosion-corrosion applications. In order that these thermal
spray and plasma coatings can be exploited to their full potential, their resistance to combined
erosion and corrosion needs to be quantified. Of particular concern is the level of porosity
within the coatings (especially the PEO coatings) which can accelerate crack propagation and
coating removal under erosion and also can be interconnected such that electrolyte can
permeate into the coating/substrate interface.

2.1 Solid particle erosion

The rig used has been detailed elsewhere [24]. The jet angle was set at either 90° or 30° and
the jet nozzle stand-off distance was 37 mm. The temperature was ambient (plus effects of
heating by the circulating pump) and the test duration was 6 hours. Before and after each test,
specimens were rinsed in tap water, dried and weighed with a precision balance with a range
of 200g and an accuracy of ± 0.2 mg.

3
 Back

2.1.1 Details of coatings tested

Details of the experimental HVOF and PEO coatings that have been tested at Southampton
are given in Table 1 along with details of 4360 steel and hot dipped Zinc coating used for
comparison purposes. Compositions of the AB and NAB surfaces are given in Table 2.

Table 1: Surface Roughness and Hardness data for samples.

Ra (µm)
SAMPLE As Ground Thickness Hv Porosity
(µm) (%)
Received
AISI 4360 Steel N/a 0.13 8000 149 -
PEO Alumina coating 5.0 N/A 20 500-1000 15
(unsealed) 80 900-2000 2-15
HVOF Aluminium Bronze 7.0-9.0 0.01 250 300-330 1.07
HVOF Nickel Aluminium 7.0-9.0 0.01 300 290 2.00
Bronze
HVOF aluminium on steel 9.0 < 0.1 200 83 0.67
HVOF 14.1 < 0.1 200 155 1.25
aluminium/12%silicon on
steel
CAST Nickel Aluminium N/A < 0.1 N/A 235 N/A
Bronze
Hot-dipped zinc on steel 1.3 N/A 80 220 -

Table 2. Standard chemical composition of HVOF AB and NAB coatings

Element Al Ni Fe Cr Mo Si C Cu

AB coating 9.5 - 1.0 - - - - Bal

NAB coating 8.71 5.55 4.50 1.02 0.15 0.06 0.01 Bal

Cast NAB 9 5 4.5 - - - - Bal

2.1.2 Test conditions

A range of test conditions have been studied at 0, 3 and 5% w/w sand loadings in 3.5% NaCl
solutions to measure T rates and in distilled water or 3.5% NaCl solution with cathodic
protection to measure E rates. Solids free flow tests with 3.5% NaCl allowed the C rates to be
measured. Four combinations of jet velocity and sand sizes have been used see Table 3.

Table 3. Slurry erosion-corrosion jet conditions

Velocity Mean Sand Size (µm) Impingement Energy Impingement angle (°)
(m/s) (µJ)
3.1 135 0.016 90
3.1-3.5 235 0.086-0.110 30-90
5.0 235 0.224 90
6.7 235 0.402 90

Figure 2 shows the erosion-corrosion rates (T) of the Cast NAB, HVOF NAB, HVOF AB,
PEO Alumina coatings and the 4360 steel substrate plotted against energy. The carbon steel

4
 Back
was shown to have the highest erosion rate over the range of energies (0.01 to 1 µJ), its
erosion-corrosion rate is up to 4 times that of the NAB coating in the low energy region. This
is possibly due to the NAB coating being a harder material. However, the erosion-corrosion
rate between the steel substrate and the NAB coating appears to converge at higher energies
(0.4 µJ), due to the erosion-corrosion behaviour of the NAB coating being influenced by
cracking at splat boundaries at these energies. The HVOF AB coating was shown to have the
lowest erosion rate. The difference in erosion-corrosion rate between the coatings is possibly
due to the AB coating having a homogeneous microstructure while the more heterogeneous
NAB coating consists of particles of different alloys with different mechanical properties.
Under erosion-corrosion conditions, an erodent kinetic energy of 0.016 µJ was sufficient in
only removing the outer layer asperities of the PEO coating. At a higher Ek of 0.061 µJ,
removal of the outer layer was evident, assisted by crack enhancement as a result of gross
delamination at the PEO coating / Al substrate interface. The HVOF NAB under erosion-
corrosion conditions and at low energy offers similar resistance to the cast with both eroding
by predominately ductile mechanisms of deformation and cutting wear. With increased
energies the coating offers increasingly less resistance relative to the cast NAB due to crack
propagation and splat ejection.

In order to quantify the amount of the synergy, the synergy percentage (S/T %) for cast NAB,
HVOF NAB coating and the steel was plotted against erosion-corrosion rate Vu, see Figure 3.
Negative synergy was found at all kinetic energies for cast NAB and reflecting an ‘in-built’
safety factor. Positive synergy was found for the HVOF NAB coating at high energy,
suggesting a greater sensitivity to energy and/or increased corrosion activity. This is
consistent with the HVOF NAB coating suffering additional damage mechanisms related to
crack propagation at the splat boundary and/or splat ejection at high energy compared to
those seen on the cast NAB. Negative synergy is beneficial and not all engineering surfaces
demonstrate this property. This implies that the contributions of C and ∆Ce towards the total
material loss under erosion-corrosion conditions are minimal. This is especially true when
substantially thick oxide films or corrosion products are formed on erosion-corrosion
surfaces, affecting the contact mechanics and thus the erosivity of the sand and yielding a
negative ∆Ec. However, it is the influence of the NAB coating microstructure that affects
performance at high energy where the mixed mode of microcutting and splat removal allows
increased corrosion resulting in a positive synergy.

In order to gain a further understanding of the effects of erosion enhanced corrosion,

electrochemical current noise (ECN) measurements were taken. These measurements allow
current perturbations about the mean corrosion current to be analysed. These perturbations
are thought to provide valuable information on the extent of passive film rupture and
repassivation during erosion-corrosion. The standard deviation ratios of the ECN
measurements are plotted against synergy (S) in Figure 4. Data from HVOF NAB and
aluminium and aluminium/12%Si coatings are presented. As the standard deviation ratios
indicate the addition of electrochemical activity (corrosion rate) on the surface under solid
particle impingement, its increase will result in a similar increase in the levels of synergy. At
lower kinetic energy conditions, sand particles might not have sufficient energy to cause
surface film rupture. Sasaki et al. reported that the threshold kinetic energy required to cause
passive film rupture for stainless steels is in the order of 0.03 µJ, [25]. The protective layer on
NAB alloys is approximately 800 nm [26], as opposed to 10 nm for stainless steels,
indicating that a higher kinetic energy is required to cause film damage. If protective films
are sustained on the specimen surface under erosion-corrosion, standard deviation values will

5
 Back
be similar to that under flow corrosion conditions. This can result in a negative synergy and
both erosion and corrosion processes are then considered as antagonistic.

The sand particles will have higher damage efficiencies as their kinetic energy increases. This
will result in unsustainable protective films, leading to higher standard deviation ratios and
mass losses. A possible transition region is shown in Figure 4, [27], at the vicinity where the
electrochemical standard deviation ratio values are close to 10; synergy levels were shown to
shift from negative to positive. This transition can be caused by the following processes: a)
Increased surface film removal by higher energy particles, leading to more exposed surfaces
and an increase in corrosion rate. This is a result of erosion enhanced corrosion (∆Ce)
processes; b) Higher kinetic energy sand particles can remove any work hardened and
corroded plastic deformation lips at a higher efficiency, leading to corrosion enhanced
erosion (∆Ec) processes.

The erosion enhanced corrosion (∆Ce) process can be resolved electrochemically by

obtaining the differences between erosion-corrosion standard deviation and flow corrosion
standard deviation (σT - σC). Figure 5 shows the effects of ∆Ce on the percentage of synergy
for the NAB coating within the range of kinetic energy tested. It is clear that ∆Ce increases
with kinetic energy, subsequently leading to a positive synergy.

Figure 6 shows a complex erosion-corrosion performance for the PEO coating under tests at
various fixed potentials. At the low energy and when anodic potentials were applied, the
formation of corrosion products within the PEO coating resulted in a net mass gain. At a
higher energy Ek of 0.061 µJ, removal of the outer layer was evident for all applied
potentials, with the anodic potential resulting in penetration to the Al alloy substrate, assisted
by crack enhancement as a result of delamination at the PEO coating / Al substrate interface.

3.0 CONCLUSIONS

The erosion-corrosion performance of materials for use in fluid handling and propulsion
systems must be well understood if service lives are to be extended. Research into
experimental HVOF aluminium bronze and aluminium alloys coatings and PEO alumina
coatings shows the value of careful experimentation that reproduces service conditions while
allowing electrochemical and gravimetric measurements to quantify wastage rates and thus
increase the prediction accuracy of component life. Electrochemical noise measurements
show promise as a technique for quantifying synergistic levels present under erosion-
corrosion. Synergy between erosion and corrosion processes on the passivating HVOF
coatings is sensitive to sand energy. These coatings show good erosion-corrosion resistance
at low impact energies with surface films formed by coating-electrolyte contact reducing the
contact mechanics (or erosivity) of sand impingement. The PEO alumina coating offered the
highest erosion-corrosion resistance however at high energies the coating delaminated
exposing the aluminium substrate.

REFERENCES
[1] P.McIntyre, Marine Corrosion Club Meeting, Aberdeen, April 1999
[2] R.J.K.Wood, The sand erosion performance of coatings, Materials and Design, 20
(1999) 179-191.
[3] R.J.Percy, The operational performance of BP choke valves, BP Engineering, Risers
and Subsea Equipment group, 1990 BPE.90.ER152. (Unpublished).

6
 Back
[4] A.Scrivani, S.Ianelli, A.Rossi, R.Groppetti, F.Casadei, G.Rizzi, “A contribution to the
surface analysis and characterisation of HVOF coatings for petrochemical
application” Wear, 250 (2001) 107-113
[5] D.W.Wheeler and R.J.K.Wood, Erosion testing of diamond-coated choke valves,
Mechanical Engineering Consultancy Service, School of Engineering Sciences,
University of Southampton, report No 98/EC221, April 1999.
[6] D.W.Wheeler and R.J.K.Wood, Erosive wear behaviour of thick CVD diamond
coatings, Wear 225-229 (1999) 523-536.
[7] D.W.Wheeler and R.J.K.Wood, Solid particle erosion of CVD diamond coatings,
Wear 233-235 (1999) 306-318.
[8] Anon, Pump coatings prove their durability at Brandon station, Power,145 (2001) 19
[9] R.J.K.Wood, B.G.Mellor, M.L.Binfield, “Sand erosion performance of detonation gun
applied tungsten carbide / cobalt-chromium coatings”, Wear, 211 (1997) 70-83.
[10] K.T.Kembaiyan, K.Keshavan, “Combating severe fluid erosion and corrosion of drill
bits using thermal spray coatings”, Wear, 186-187 (1995) 487-492.
[11] http://corrosion.ksc.nasa.gov/html/eroscor.htm, Corrosion technology test bed, forms
of corrosion – erosion-corrosion.
[12] K Haugen, O Kvernvold, A Ronold, R Sandberg, “Sand erosion of wear resistant
material: Erosion in choke valves” Wear, 186-187, 1995, 179-188.
[13] http://www.tycovalves-na.com/ld/184.pdf, Valve Solutions
[14] B. Vivien, “Identifying and evaluating valve problems”, Proc. Eng., Oct (1985), 33-
36.
[15] B Percy, The operational performance of BP choke valves, BP Engineering Report,
BPE.90.ER.152 (1990).
[16] R.J.K.Wood, The synergistic effect of cavitation erosion and corrosion, PhD thesis,
Department of Mechanical Engineering, University of Southampton, February 1987.
[17] R.J.K.Wood and S.P.Hutton, “The synergistic effect of erosion and corrosion: trends
in published results”, Wear 140 (1990), 387-394.
[18] M.M.Stack, S.Zhou and R.C.Newman, “Identification of Transitions in erosion-
corrosion regimes in aqueous environments”, Wear, 186-187, (1995), 523-532.
[19] Y.Naerheim and M.W.Kendig, “The influence of electrochemical potential on wear”,
Wear, 104 (1985), 139-150.
[20] M.Stemp, S.Mischler and D.Landolt, The effect of mechanical and electrochemical
parameters on the tribo-corrosion rate of stainless steel in sulphuric acid, Wear,
Volume 255, Issues 1-6, 2003, Pages 466-475
[21] A.Neville, M.Reyes and H.Xu, Examining corrosion effects and corrosion/erosion
interactions on metallic materials in aqueous slurries, Tribology International,
Volume 35, Issue 10, 2002, Pages 643-650
[22] R.J.K.Wood and A.J.Speyer, Erosion–corrosion of candidate HVOF aluminium-based
marine coatings, Wear, in press
[23] ASTM Standard G 119-93, “Standard Guide for Determining Synergism between
Wear and Corrosion”, (1993).
[24] K.S.Tan, R.J.K.Wood, .JA.Wharton and K.R.Stokes, Electrochemical investigation of
high velocity oxy-fuel (HVOF) aluminum bronze coatings under slurry erosion in
saline environments, NACE Corrosion 2002, Denver, Colorado, USA, April 7-11,
2002, paper 02199
[25] K.Sasaki, and G.T.Burstein, 'Observation of a threshold impact energy required to
cause passive film rupture during slurry erosion of stainless steel', Philosophical
Magazine Letters, 80, (2000), No. 7, pp. 489-493

7
 Back
[26] A.Schussler and H.E.Exner, 'The corrosion of nickel-aluminium bronzes in seawater -
I. Protective layer formation and the passivation mechanism', Corrosion Science, 34,
(1993), No. 11, pp. 1793-1802
[27] KS Tan, Electrochemical analysis of the erosion-corrosion of HVOF aluminium
bronze coatings, PhD Thesis, School of Engineering Sciences, University of
Southampton, July 2003.

ACKNOWLEDGEMENTS

The work presented in this paper was sponsored by [dstl]

10
E ro s io n R a te uV(µ m 3/im p a c t

1
Vu ∝ v2
0 .1

0 .0 1 S D S S Z ero n 1 0 0 + tap w ater

4
0 .0 0 1
Vu ∝ v S D S S Z ero n 1 0 0 + 3 % N aC l
A IS I 3 2 1 + 3 % N aC l
A IS I 3 1 6 + 3 % N aC l
0 .0 0 0 1 FDuplex
2 5 5 + +T Tap
ap WWater
ater
FDuplex
2 5 5 + 3+%3%NaCl
N aC l
0 .0 0 0 0 1
1 .E -0 9 1 .E -0 8 1 .E -0 7 1 .E -0 6 1 .E -0 5 1 .E -0 4
S a n d p a rtic le e n e rg y E k (J )

Figure 1. Erosion and erosion-corrosion wear rates of duplex and austenitic stainless steels as a
function of sand energy.
10

Steel

NAB coat

AB coat
Erosion-corrosion rate, Vu (µm3/impact)

1
Cast NAB

PEO Alimina AB coating

0.1

0.01

PEO Alumina Cast NAB Steel NAB coat

1.4355 0.9278 0.87 1.18
Vu= 2.66Ek Vu= 1.06Ek Vu = 4.06 Ek Vu = 4.11 Ek
2 2 2 2
R = 1.0 R = 0.97 R = 0.93 R = 0.99
0.001
0.01 0.10 1.00
Kinetic energy, Ek (µJ)

Figure 2: Relationship between erosion-corrosion rate and kinetic energy.

8
 Back

20

-20
S/T (%)

-40

-60
Cast NAB
-80
HVOF NAB
-100 Steel
-120
0 0.5 1 1.5 2
3
Erosion-corrosion Vu (µm /impact)
Figure 3: Relationship of synergy percentage with VuT .

14
HVOF aluminium coatings, Ek = Ek = 0.23 µJ
12 0.11 µJ

10
Ek = 0.41 µJ
8
σ T/σ C

Ek = 0.09 µJ
6

2 Ek = 0.02 µJ

0
-60 -50 -40 -30 -20 -10 0 10 20
S%
Figure 4. Relationship between the standard deviation ratio and synergy (S) percentage for
HVOF NAB coatings and for HVOF Aluminium alloy based coatings. [27]

9
 Back

0.3

Ek = 0.41 µJ
0.25

y = 0.3781x + 0.191
0.2 R2 = 0.9204
∆Ce (µA)

0.15

0.1 Ek = 0.23 µJ
Ek = 0.09 µJ

0.05

Ek = 0.02 µJ
0
-0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0 0.1 0.2
S/T

Figure 5. The effects of erosion enhanced corrosion (∆Ce) in affecting the synergy for the
HVOF NAB coating. [27]

a) b)

Figure 6. Mass loss with respect to applied potential for the unsealed PEO Al2O3 coating.
Two erodent impact kinetic energies a) Ek = 0.016 µJ and b) Ek = 0.061 µJ.

10