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Modelling of Pitting Corrosion in Marine and Offshore Steel Structures - A

Technical Review

Article  in  Journal of Loss Prevention in the Process Industries · September 2015

DOI: 10.1016/j.jlp.2015.06.008


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5 authors, including:

Jyoti Bhandari Faisal Khan

Australian Maritime College Memorial University of Newfoundland


Rouzbeh Abbassi Vikram Garaniya

Macquarie University University of Tasmania


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Journal of Loss Prevention in the Process Industries 37 (2015) 39e62

Contents lists available at ScienceDirect

Journal of Loss Prevention in the Process Industries

journal homepage: www.elsevier.com/locate/jlp

Modelling of pitting corrosion in marine and offshore steel

structures e A technical review
Jyoti Bhandari a, Faisal Khan b, *, Rouzbeh Abbassi a, Vikram Garaniya a, Roberto Ojeda a
Australian Maritime College, University of Tasmania, Launceston, TAS 7250, Australia
Safety and Risk Engineering Group (SREG), Faculty of Engineering & Applied Science, Memorial University of Newfoundland, St. John's, Newfoundland A1B
3X5, Canada

a r t i c l e i n f o a b s t r a c t

Article history: Corrosion is a major cause of structural deterioration in marine and offshore structures. It affects the life
Received 27 May 2015 of process equipment and pipelines, and can result in structural failure, leakage, product loss, environ-
Accepted 21 June 2015 mental pollution and the loss of life. Pitting corrosion is regarded as one of the most hazardous forms of
Available online 29 June 2015
corrosion for marine and offshore structures. The total loss of the structure might be very small, but local
rate of attack can be very large and can lead to early catastrophic failure. Pitting corrosion is a localized
accelerated dissolution of metal that occurs as a result of a breakdown in the protective passive film on
Pitting corrosion
the metal surface. It has been studied for many years; however, the structural failure due to pit char-
Offshore structures
acteristics is still not fully understood. Accurate pit depth measurements, precise strength assessment
Corrosion modelling techniques, risk analysis due to pitting, and the mathematical relationship of the environmental factors
Safety assessment that causes pitting failure are also factors, which need further understanding. Hence this paper focuses
Steel on these issues. It reviews and analyses the current understanding of the pitting corrosion mechanism
and investigates all possible factors that can cause pitting corrosion. Furthermore, different techniques
employed by scientists and researchers to identify and model the pitting corrosion are also reviewed and
analysed. Future work should involve an in-depth scientific study of the corrosion mechanism and an
engineering predictive model is recommended in order to assess failure, and thereby attempt to increase
the remaining life of offshore assets.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction 2005a; 2010; Melchers and Jeffrey, 2008a). This material degrada-
tion results in loss of mechanical properties of the structure such as
The scientific exploration and exploitation of the ocean depth is strength, ductility and impact strength. Material degradation leads
now proceeding at a greatly accelerated rate (Schumacher, 1979). to loss of material and, at times, to ultimate failure (Popoola et al.,
Consequently there has been particularly rapid progress in the 2013). Further, corrosion is also of major economic significance. The
development of equipment for deep-ocean investigation and un- World Corrosion Organization (WCO) estimates that the annual
derwater activities. The oil and gas industries have built a large cost of corrosion worldwide is around $US2.4 trillion (3% of the
number of offshore platforms, pipelines, ships, and underwater world's GDP) (Vela zquez et al., 2014). The economic cost for all
storage and shore facilities. However, the structural reliability of forms of corrosion in advanced economies such as the United States
these structures is not fully understood (Stewart and Al-Harthy, of America was recently estimated at around 4% of gross national
2008). These marine and offshore structures are typically con- product (GNP) (Melchers, 2008a). The environmental cost of
structed from steel and have the highest rate of critical incidents corrosion can also be high; according to the Offshore Hydrocarbon
due to corrosion deterioration (Maureen et al., 2013). Corrosion is Release Statistics and Analysis report 2002e2003 (HSR) (HSR,
well defined as the destructive attack on a material by reaction with 2003), a total of 2313 hydrocarbon releases were reported from
its environment (Popoola et al., 2013; Melchers, 2004a; Melchers, offshore facilities in nine and half years. The most common causes
were ‘mechanical failure’ due to corrosion and other related
degradation. A total of 1034 incidents (44.7% of the total incidents)
* Corresponding author.
were caused as a result of corrosion (HSR, 2003; Khan and Howard,
E-mail address: fikhan@mun.ca (F. Khan). 2007).

0950-4230/© 2015 Elsevier Ltd. All rights reserved.
40 J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62

Amongst all types of corrosion, pitting is the most common and piping, tanks, ships and marine structures (Abood, 2008; Melchers,
damaging form of corrosion in marine and offshore structures (Li 1994). Melchers (1994) stressed the importance of pitting corrosion
et al., 2011). Pitting corrosion is very dangerous, widespread, and knowledge as being crucial for the marine and offshore sectors.
difficult to detect; hence, it has been a matter of great concern to They recommended a deep knowledge of pitting corrosion e its
marine and offshore industries for several years (Sidharth, 2009). effects, and the application of preventative methods e as this will
Pitting corrosion is defined by Szklarska (Szklarska-Smialowska, assist in reducing material losses resulting from same (Melchers,
1986) as a localized dissolution of metals that occurs due to the 2009). It will also improve the safety of operating equipment
breakdown of the protective passive film - notably the protective (Abood, 2008).
coating and paint on metal surfaces (Melchers, 2004a, b; Szklarska- Pitting corrosion has been studied for several decades and
Smialowska, 1986; Stewart, 2009). Pitting corrosion can also occur considerable understanding of the pitting phenomenon has been
during active dissolution if certain sections of the sample are more generated. However in depth knowledge of pitting modelling and
susceptible and dissolve faster than the rest of the surface (Frankel, pitting measurement is still lacking (Frankel, 1998). There is also a
1998). Szklarska et al. (Szklarska-Smialowska, 1986) describes limited understanding of why the pitting corrosion rate is not
pitting as a form of localized corrosion in which metal is removed constant over time and why data tends to be scattered. Hence, it is
preferentially from vulnerable areas of the surface. More specif- necessary to review what actually happens when a steel surface is
ically, the dissolutions lead to the formation of cavities in passivated exposed to natural seawater and how this process progresses with
metals or alloys, which are exposed to solutions containing time (Melchers, 2008a).
aggressive anions. Most pitting failures in the offshore sectors are Many researchers have studied factors affecting pitting corro-
caused by chloride and chloride containing ions. It is very likely for sion in marine and offshore environments (Melchers, 2004a, b;
pitting to occur when protective measures such as paint coating, Caines et al., 2013; Soares et al., 2009; Valor et al., 2007, 2010;
galvanizing or cathodic protection are ineffective (Abdel-Ghany Zamaletdinov, 2007; Zaya, 1984); however, the factors investigated
et al., 2008). Pitting is one of the most vicious and insidious are very limited and there is still a potential to study them more
forms of corrosion; the attack is extremely localized resulting in thoroughly. In this study, all possible factors that can cause pitting
holes in the structure and thereby causing failures (Abdel-Ghany corrosion will be discussed and the effects of a number of factors in
et al., 2008). History shows that pitting corrosion is a dominant initiating the pitting corrosion will be summarized. In addition
cause of structural failure in marine and offshore sectors. The different techniques employed by scientists and researchers, to
reason for this is due to the well-known fact that seawater is an identify and model the pitting corrosion, are focused on in subse-
aggressive corrosive environment and the structures are generally quent sections.
fabricated with alloy steel which favours pitting corrosion. The
pitting in these structures is often very severe, not only under 2. General description of pitting corrosion
sustained immersed conditions, but also under general exposure to
atmospheric conditions (Sidharth, 2009). The effects of pitting Pitting corrosion is defined as localized corrosion of a metal
corrosion can be catastrophic, as illustrated by several incidents surface, confined to a point or small area that takes the form of
reported in the offshore oil and gas sectors. In March 1965 a natural cavities (Abood, 2008). Major consequences of pitting are the
gas pipeline exploded in Louisiana, killing 17 people including 9 breakdown of passivity; in general, pitting occurs when there is a
children. The heat from the explosion was very intense; 6 cars and 3 breakdown of surface films exposed to the pitting environment.
trucks melted and 5 houses were scattered over a large area. In July Pitting corrosion occurs when discrete areas of a material undergo
1988 there was a massive leakage of gas condensate on Piper Alpha rapid attack while most of the adjutant surface remains virtually
due to pitting corrosion which, when it ignited, caused an explosion unaffected (Roberge, 2013). The attack leads to characteristic forms
leading to large oil fires. The scale of the disaster was enormous, of cavity, such as pits or crevices in the metal surface (Melchers,
killing 167 people on board, and it is regarded as the deadliest 1994). Research shows the common factors contributing to the
accident in the history of the oil and gas industry (Maureen et al., initiation and propagation of pitting corrosion are (Roberge, 2008):
2013). In April 1992 a sewer explosion in Guadalajara, Mexico kil-
led 215 people. In this incident a series of blasts damaged 1600  Localized chemical or mechanical damage to the protective
buildings and injured 1500 people (Roberge, 2008). Roberge et al. oxide film
(Roberge, 2008) described it as being one of the most catastrophic  Factors that can cause breakdown of a passive film, such as
accidents resulting from a single pit. A recent example of pitting acidity, low dissolved oxygen concentrations and high chloride
corrosion-related failure is the BP ULA accident in Norway. In concentrations; these are likely to turn a protective oxide film
September 2012, an estimated 125 barrels of oil and 1600 kg of gas less stable, and thereby initiate pit
leaked at the North Sea platform due to pit in a valve; despite there  Localized damage to, or poor application of, protective coating
being no injuries, production was stopped for 67 days (Maureen  Presence of non-uniformities in the metal structure of the
et al., 2013). Similarly, in December 2012 a buried, half a metre component such as non-metallic inclusions.
diameter, high-pressure natural gas pipeline operated by Columbia
Gas Transmission ruptured due to pitting corrosion. There were no Pitting corrosion can produce pits with their mouth open (un-
fatalities; however, several houses were damaged and about 2 covered) or be covered with a semi-permeable membrane of
million standard cubic metres of natural gas was released and corrosion products. Pits can be either hemispherical or cup-shaped.
burned. The total cost was expected to be about $9 million dollars In some cases they are flat-walled, revealing the crystal structure of
(Board, 2014). Consequently, significant attention should be given the metal but they may also have a completely irregular shape.
to predict the occurrence of pitting corrosion in offshore structures Fig. 1 shows the common pit shapes divided in two groups namely:
and adequate measures should be taken to prevent and control the trough pits (upper) and sideway pits (lower):
consequences. Pitting cavities may fill with corrosion products and form caps
Pitting corrosion in offshore steel structures has particular over the pit cavities, sometimes creating nodules or tubercles.
importance where containment is critical, such as for pressure While the shapes of the pits vary widely, as evidenced in Fig. 1, they
vessels, boilers, turbine blades and for metallic containers for toxic are usually roughly saucer-shaped, conical, or hemispherical for
materials. It is also significant for localized structural strength in steel and many associated alloys (Roberge, 2008).
J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62 41

Fig. 1. Sketch of common pit shapes.

Pitting corrosion is complicated in nature; according to Abood seen under optical microscope. Pits have a shape of hemisphere or
et al. (Abood, 2008) the oxide films that form on different metals of a polyhedron by stage 3. At the final stage 4 the pits can be seen
vary one from another in electronic conduction, porosity, thickness with the naked eye. The pit can have an irregular shape if partially
and state of hydration (Abood, 2008). Zaya (1984) studied pitting covered around the mouth with solid corrosion products
theory and stages of pit development; the schematic of different (Schumacher, 1979; Szklarska-Smialowska, 1986; Melchers, 1994;
stages for the development of an individual pit can be seen in the Zaya, 1984).
Fig. 2. Zaya (1984) distinguished various stages of the pitting Many researchers, starting with Evens and Bannister in 1931
corrosion process and divided them into four stages (see Fig. 2). (Evans et al., 1931; Evans, 1976), and later Richardson in 1973
Stage 0 represents an un-attacked metallic surface which is (Thompson et al., 1978), claim that local weak spots or defects are
completely covered with the passive films. Stage 1 involves the always present in the passive films. Therefore stage 0 never exists
rupture of the passive layer; the substrate is still protected except and, immediately after immersion, the process starts at stage 1, i.e.
for a small patch in contact with the electrolyte. The dimension of metal and solution are in contact (Evans et al., 1931; Evans, 1976;
the small patch in stage 1 can be smaller or comparable to the Thompson et al., 1978). The induction period only corresponds to
thickness of the passive film. Subsequently, the dissolution of the the rate time necessary for the corrosion to be well developed and
substrate begins. Stage 2 is reached when the conditions for pit detectable. Additionally, the corrosive attack is highly localised and
growth are met and repassivation cannot occur anymore i.e. the pit the precise location of pits appears to be unpredictable (Melchers,
begins to grow. Therefore, in stage 3 the dissolution of the substrate 1994; Zaya, 1984).
begins to grow and the pit becomes about 1e10 mm which can be Steel alloys, such as stainless steel and aluminium alloys, are
commonly used in marine and offshore sectors. These alloys are
comprised of passive films which are thin (nanometre-scale) oxide
layers that can form on the metal surface in marine environments
(Roberge, 2008; Melchers, 1999). However, such passive films are
often susceptible to localized breakdown resulting in accelerated
dissolution of the underlying metal (Schiroky et al., 2009). If the
attack initiates on an open surface it is called pitting corrosion. This
form of localized corrosion can lead to accelerated failure of
structural components by perforation or by acting as an initiation
site of cracking (Melchers, 1994). Fig. 3 shows an example of the
deep pits on a metal surface.

Fig. 2. Schematic stages of pit development (adopted from Zaya (1984)). Fig. 3. Deep pit in the metal (Roberge 2008, 2013).
42 J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62

Roberge et al. (Roberge, 2008) reported that the practical

importance of pitting corrosion depends on the thickness of the
metal and on the penetration rate. In general, it was found that the
rate of penetration decreases if the number of pits increases. This is
attributed to closely spaced pits having to share the available
adjacent cathodic area which controls the corrosion current that
can flow (Szklarska-Smialowska, 1986; Roberge, 2008, 2013).
Abood et al. (Abood, 2008) studied different parameters that in-
fluence pitting corrosion. The parameters investigated were limited
to environment, metal composition, pitting potential, temperature
and the surface conditions. Within these, environmental parame-
ters were found to be the most critical factors. They include
aggressive ion concentration, pH, and inhibitor concentration
(Szklarska-Smialowska, 1986; Roberge, 2008; Abood, 2008). Simi-
larly, Frankel et al. (Frankel, 1998) provided an overview of the
critical factors that influence the pitting corrosion of metals. They
found that the effects of alloy composition, environment, pitting
Fig. 4. Schematic of anodic curve for a metal immersed in a solution containing
potential and temperature are critical for pitting to occur. These aggressive ions (Adopted from Caines et al. (Szklarska-Smialowska, 1986; Frankel,
critical factors are further reviewed in the following section. 1998; Caines et al., 2013).

2.1. Stages of pitting corrosion

greater resistance to pitting (Szklarska-Smialowska, 1986; Caines
Pitting can consist in various stages: passive film breakdown, pit et al., 2013; Strehblow and Marcus, 1995). Similarly, if the poten-
initiation, metastable pitting, pit growth and pit stifling. Any of tial is reduced below Epit, the surface may repassivate and pit
these stages may be considered to be critical (Szklarska- growth can stop. However, if the potential is between Epit and ER,
Smialowska, 1986; Abood, 2008; Alkire and Wong, 1988). Pitting pitting can be expected (Szklarska-Smialowska, 1986; Caines et al.,
corrosion capitalizes on breakdown in the protective layer, either 2013; Strehblow and Marcus, 1995).
natural or applied, and provides a nucleation point for the forma-
tion of pits in the presence of an electrolyte containing an aggres- 2.1.2. Pit initiation
sive anion (Caines et al., 2013). Once the passive film breaks down The initiation stage of pitting is generally agreed to be of very
and a pit initiates, there is a possibility that a single pit will grow. short duration. Melchers (1994) reported that the duration of pit
The passive state is required for pitting to occur; however some initiation can be as short as micro-seconds and that pitting initia-
researchers believe that the minutiae of passive film composition tion is strongly dependent on the surface conditions of the material.
and structure play a minor role in the pitting process (Abood, This is important in setting the overall areal pattern for subsequent
2008). Regardless, pit growth is critical in practical applications of localised corrosion (Melchers, 1994). Caines et al. (Caines et al.,
failure prediction in marine and offshore structures. 2013) postulated that the initiation of pits is influenced by sur-
face defects which may be due to manufacturing issues such as
2.1.1. Passive film breakdown installation problems, improper maintenance procedures and
A passive film breaking theory was originally proposed by Agar environment changes (Caines et al., 2013). Caines et al. (Caines
and Hoar (1947) in 1967 and was later extended on by many re- et al., 2013) also studied different factors that cause the site of pit
searchers (Zaya, 1984). Agar and Hoar (1947) suggested that the initiation. Some of these are:
absorption of the damaging ions on the surface of the passive film
produces mutual repulsion which lowers the interfacial surface  Damage to protective chemical or mechanical oxide layer
tension. It was reported that when the repulsive force is sufficient,  Environmental factors such as low pH, high chloride concen-
the passive film cracks (Zaya, 1984; Agar and Hoar, 1947). The tration causing protective layer breakdown
breakdown of the passive film and the details of pit initiation  Damage to applied protective coating
comprise the least understood aspect of the pitting phenomenon.  Discontinuities in the protective coating
Breakdown is a rare occurrence that happens very rapidly and on a
very small scale, making direct detection of the breakdown difficult Strehblow et al. (Strehblow and Marcus, 1995) and Frankel et al.
(Abood, 2008; Melchers, 1994; Zaya, 1984; Agar and Hoar, 1947). (Frankel, 1998) represented pit initiation by categorizing it in three
Caines et al. (2013) described passive film breakdown in stain- different mechanisms: (a) penetration (b) adsorption and thinning
less steel alloys commonly used in offshore installations. In these and (c) film breaking mechanisms (Frankel, 1998). Penetration
alloys, the breakdown of the passive film provides sites for pit mechanisms for pit initiation involves the transport of the
nucleation and, consequently, these breakdown sites are suscepti- aggressive anions through the passive film to the oxide interface
ble to pitting corrosion. Passive films are present on the surface of where aggressive dissolution is promoted (Frankel, 1998). This
the stainless steels in the presence of oxygen. At low temperatures, mechanism is aided by the induction time for pitting and the
a true oxide layer is not formed; instead a thin passive film is presence of chloride in an electrolyte. An adsorption theory of
formed and acts as a barrier and thereby provides corrosion resis- pitting initiation is based on the material's adsorption of chloride
tance (Caines et al., 2013). and oxygen. Strehblow et al. (Strehblow and Marcus, 1995)
Fig. 4 illustrates the polarization curve (Melchers, 2008a; described an aspect of pit adsorption, based on X-ray Photoelectron
Szklarska-Smialowska, 1986; Frankel, 1998; Abood, 2008; Caines Spectroscopy (XPS) measurements, as being the exposure of Fe to
et al., 2013; Melchers and Ahammed, 1994) to estimate the sus- chloride and other halides which cause the thickening of the pas-
ceptibility of the metal alloy to pitting corrosion (Caines et al., sive films, even under conditions where pit has not formed. This is
2013). The curve is used to find Epit and repassivation potential as a result of the catalytically enhanced transfer of cations from the
(ER). Higher Epit for a material in a given environment indicates oxide to the electrolyte (Frankel, 1998; Strehblow and Marcus,
J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62 43

1995). The film breaking may occur due to mechanical stress at the combinations of these factors. Szklarska-Smialowska (1986)
weak sites, or flaws, causing local breakdown events; however explained how the pit growth at low potential (i.e. below the
these can also rapidly heal in nonaggressive environments (Frankel, range of limiting current densities) is controlled by a combination
1998; Strehblow and Marcus, 1995). of ohmic, charge transfer, and concentration over potential factors
(Szklarska-Smialowska, 1986; Melchers, 1994). They suggested that
2.1.3. Metastable pitting pit growth is nonlinear at higher chloride ion concentration.
Metastable pits are those that initiate and grow for a limited Additionally, nonlinear growth of the high chloride concentration
period before repassivating, or before dying (Frankel, 1998; Wika, tn with n in the range of 0.33e0.5 has been suggested by Melchers
2012a). Pits which cease growing and repassivate in this manner (1994), Szklarska-Smialowska (1986) and Abood (2008).
are described as metastable (Abood, 2008; Wika, 2012a; Pistorius
and Burstein, 1992a). The metastable pits may survive and 3. Mechanism of pitting corrosion
become stable growing pits depending upon the composition of the
material, the critical solution, mass-transport and the pitting po- Pits almost always initiate due to chemical or physical hetero-
tential at the bottom of the pit. Stable pitting corrosion occurs when geneity at the surface such as inclusions, second phase particles,
the corrosion potential, Ecorr, exceeds the pitting potential, Epit solute-segregated grain boundaries, flaws, mechanical damage, or
(Frankel, 1998; Wika, 2012a). The measure of a material's ability to dislocations (Szklarska-Smialowska, 1986). Most engineering alloys
undergo stable pitting corrosion in a certain environment is defined have many or all such defects and a pit tends to form at the most
as the pitting potential (Epit) (Pistorius and Burstein, 1992a). Galvele susceptible sites first. For example, pits in stainless steels are often
et al. (Galvele, 2005) described Epit as a limit where the growth of associated with manganese sulphide (MnS) inclusions which are
pits happens above the surface, however a passive surface is found in most commercial steels. The role of MnS inclusions in
maintained below (Galvele, 2005). promoting the breakdown and localized corrosion of stainless
Wika et al. (Wika, 2012a) described metastable pits as the steels has been recognized for some time (Sidharth, 2009;
incipient growth of initiated pits, and which must survive in order Szklarska-Smialowska, 1986; Frankel, 1998). Abood (2008)
to become stable growing pits. These are small pits, of only few acknowledge that the pitting corrosion caused by passive film
microns in size, which normally last only a few seconds before the breakdown only occurs in the presence of aggressive anionic spe-
surface repassivates (Wika, 2012a). cies, and that chloride ion is usually the cause. The severity of the
Pistorius et al. (Pistorius and Burstein, 1992a) investigated the pitting tends to vary with the amount of chloride concentration.
development of highly aggressive anolyte inside the metastable pit The reason for the aggressiveness of chloride has been considered
which has low pH as a result of hydrolysis of the dissolving metal for some time and a number of investigations and examinations
cations. The anolyte also carries an enhanced concentration of were carried out in marine and offshore installations (Frankel,
anions because these migrate into the pit to maintain analytic 1998). Chloride is an anion of a strong acid and many metal cat-
charge neutrality. Hence, the pit growth becomes self-sustaining ions exhibit considerable solubility in chloride solutions. Hence, the
due to the development of the aggressive anolyte in the pit. presence of the oxidizing agent (oxide) in a chloride-containing
environment is extremely damaging and it can further enhance
2.1.4. Pit propagation (stable pitting) localized corrosion (Schiroky et al., 2009). Szklarska-Smialowska
The pit propagation is the stage where the development of some (1986) presented an experiment by means of ASTM G48, which is
of the initiated pit occurs and, in particular, where its rate of growth a common procedure when testing pitting corrosion, with the
increases (Melchers, 1994; Caines et al., 2013; Wong and Alkire, specimens immersed in 6% of Fecl3. The results showed that the
1990). Caines et al. (Caines et al., 2013) defined this as the stage increase in potential associated with oxidizing agents enhances the
where pits grow and have the potential to increase beyond wall likelihood of pitting corrosion (Szklarska-Smialowska, 1986;
thickness, thereby leading to leaks (Caines et al., 2013). They also Frankel, 1998; Abood, 2008). Refer to Equation (1.1):
reported that certain conditions must be met for pits to propagate:
Me2 þ 2H2 O/MeðOHÞþ þ Hþ (1.1)
 Epit must be exceeded and remain above ER (repassivation
potential) Pitting corrosion normally starts with chloride rapidly pene-
 An aggressive ion must be present trating the protective oxide film which covers the metal surface.
 Localized breakdown of passive or applied film. These points act as initiation sites for pitting corrosion (Melchers,
1994; Schiroky et al., 2009). Selective dissolution is another way
Melchers (1994) reported that the precise mechanics of pit that pitting corrosion can initiate and this occurs when one of the
propagation is not fully understood; however it is known that components dissolves faster than other components (Szklarska-
highly acidic conditions (i.e. low pH) is associated for pit to be Smialowska, 1986).
propagated (Melchers, 1994). Angal (2010) described pit growth in Abood (2008) considered pitting to be autocatalytic in nature;
the marine environment as an autocatalytic process (Angal, 2010). once a pit starts to grow, the local conditions are altered such that
Fe2þ ions attract negative Cl ions and, through the hydrolysis, further pit growth is promoted. Fig. 5 shows that the anodic and
creates a porous Fe(OH)2 cap over the pit. This process creates a cathodic electrochemical reactions that comprise corrosion sepa-
self-propagating system where the increased acidity in the pit rate spatially during pitting. The local pit environment becomes
cavity increases corrosion of the steel walls of the pit (Caines et al., depleted in cathodic reactant (e.g. oxygen) which shifts most of the
2013; Angal, 2010). Some researchers (Frankel, 1998; Abood, 2008; cathodic reaction to the surface outside of the pit cavity. Refer to
Strehblow and Marcus, 1995; Wong and Alkire, 1990; Frankel and Equation (1.2):
Sridhar, 2008) reported that pit propagates at a rate that depends
O2 þ 2H2 O þ 4e /4OH (1.2)
on material compositions, pit electrolyte concentration, and pit-
bottom potential. It was suggested that, in order to understand In Fig. 5 the metal, M, is being pitted by an aerated NaCl solution.
pit growth and stability, it is essential to ascertain the rate- Rapid dissolution occurs in the pit while oxygen reduction takes
determining factors such as electrochemical reactions which place on the adjacent metal surfaces.
include charge-transfer process, ohmic effects, mass transport and The pitting phenomenon can be summarized as the local pit
44 J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62

pitting corrosion occurs (Szklarska-Smialowska, 1986; Wika,

The environment (chemistry) and the material (metallurgy)
factors determine whether an existing pit can be repassivated or
not (Roberge, 2013). Sufficient supply of oxygen to the reaction site
may enhance the formation of oxide at the pitting site and thus
repassivate or heal the damage to the passive film. An existing pit
can also be repassivated if the material contains a sufficient amount
of alloying elements such as Cr, Mo, Ti, W, N, etc. (Nun ~ ez, 2007).
Amongst these elements, Mo can significantly enhance the
enrichment of Cr in the oxide and thus repassivate the pit. A
detailed analysis of the influence of pit chemistry on pit growth and
stability has been provided by Galvele (2005). The concentration of
various ionic species at the bottom of modelled one-dimensional
pit geometry is discussed by many researchers (Frankel, 1998;
Abood, 2008; Wika, 2012a; Galvele, 2005). The concentration of
various ionic species is determined as a function of current density
based on a material balance that considered generation of cations
by dissolution, outward diffusion, and thermodynamic equilibrium
of various reactions such as cation hydrolysis (Frankel, 1998) (refer
to Equation (1)). Galvele (2005) found that a critical value of the
Fig. 5. Autocatalytic process occurring in a corrosion pit (adapted from Abood (2008)).
factor x$i, (where x is pit depth and i is current density), correspond
to a critical pit acidification for sustained pit growth (Frankel, 1998).
Current density in a pit is a measure of the corrosion rate within the
environment depleted in the cathodic reactant, such as dissolved pit and thus a measure of the pit penetration rate. The value “x$i”
oxygen, and enriched in metal cation including anionic species. This can be used to determine the current density required to initiate
acidic chloride environment is aggressive to most metals and tends pitting at a defect of a given size (Abood, 2008). Increasing the pit
to prevent repassivation, thereby promoting continued propaga- density increases the ionic concentration in the pit solution, often
tion of the pit. It was suggested that removal of oxidizing agents, reaching super saturation conditions. Frankel (1998) demonstrated
e.g. removal of dissolved oxygen, is one powerful approach for an example of a solid salt film that may form on the pit surface.
reducing susceptibility to localized corrosion (Szklarska- When the solid salt film is formed on the pit surface, the ionic
Smialowska, 1986; Frankel, 1998; Abood, 2008). concentration drops to the saturation value and the pit growth rate
A number of researchers (Frankel, 1998; Abood, 2008; Melchers, is limited by mass transport out of the pit (Frankel, 1998; Abood,
1994; Zaya, 1984; Galvele, 2005; Wong and Alkire, 1990; Melchers, 2008; Wong and Alkire, 1990).
2001a) have studied the local chemistries that form in pits using a Although many researchers claimed that salt films are required
range of techniques. Wong and Alkire (1990) described a way to for pit stability, Frankel (1998) disagreed. These authors suggest
isolate the pit solution by rapid freezing of the electrode in liquid that salt films will only enhance stability by providing a buffer of
nitrogen, removal of the surface excess, and subsequent thawing ionic species that can dissolve into the pit to reconcentrate the
(Frankel, 1998; Wong and Alkire, 1990). This approach is mainly environment in the event of failures such as the sudden loss of a
used to study the pH in Aluminium pits and the chloride concen- protective pit cover (Frankel, 1998; Abood, 2008). The shape of the
tration in pits for stainless steel. Likewise, Frankel (1998) consid- pit varies on the environmental conditions, and on whether the pit
ered a way to isolate the pit solution by using artificial pit electrode contains a salt film or not. Abood (2008) and Frankel (1998) both
methods. This is also known as one dimensional pit, or leadein- agreed that, under mass-transport-limited growth, pits can be
pencil electrode, which is a wire imbedded in an insulator such as hemispherical with polished surfaces. In the absence of a salt film,
epoxy (Frankel, 1998). This technique allows a considerable volume pits can be crystallographically etched or irregularly shaped
of pit electrolyte to be analysed (Wong and Alkire, 1990). Another (Frankel, 1998; Abood, 2008).
way to isolate the pit solution is by inserting microelectrodes into
pits, cracks and cervices (Frankel, 1998). With this technique, once
the local solution composition is fully characterized, it is possible to 4. Characteristics of pitting corrosion
reassemble the local environment by reconstituting it in bulk form
from reagent grade chemicals, and then determining the electro- In 1984, Zaya (1984) reported the following characteristics of
chemical behaviour of a normal-sized sample extracted from a local metal that should be studied to characterise the pitting corrosion:
Frankel (1998) also studied the electrochemistry of pitting  Existence of a threshold value of the anodic potential below
corrosion and have found that different characteristics potentials which pitting does not occur in the given electrolyte system or
exist within pitting corrosion (Frankel, 1998). It was found that the potential of the metal must exceed a certain threshold (Zaya,
metastable pit formation can occur below the Epit, however this 1984).
cannot be seen as initiation points of pitting (Szklarska-  Some aggressive anion must be present. These ions correspond
Smialowska, 1986; Frankel, 1998; Wika, 2012a). Metastable pits to strong acids and they tend to form complex and very soluble
are those pits that initiate and grow for a limited period before salts with the metal they attack (Dallek and Foley, 1976).
repassivating. Materials exhibiting higher value of pitting potential  Some other ions inhibit the effect of the aggressive ions as
(Epit) and repassivating potential (Erep) are more resistant to pitting pitting agents. The relationship between the potential necessary
corrosion therefore cyclic polarization experiments are generally for pitting and the concentration of aggressive and inhibiting
used to measure the pitting resistance of metals (Frankel, 1998). ions is given in Equation (1.3) (Szklarska-Smialowska, 1986;
The value of Epit can be used to determine under what conditions Zaya, 1984).
J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62 45

In addition to non-metallic inclusions, the following features

can create weak spots in the passive films:
E ¼ E0  a$log½Agg$ þ b$log½Inh$ (1.3)
 Grain boundaries at which some impurities segregate (i.e. not
purely physical defects)
 The delay (induction time), between the fulfilment of the  Various kinds of mechanical damage
necessary conditions for pitting, and the detection of the first  Three phases of metal (solid, liquid and gas)
pit, is due to the detection not taking place until the pit has  Exit point of dislocations.
reached stage 3 (Fig. 2) (Zaya, 1984).
 The corrosive attack is highly localized on the surface but Melchers (1994) and Szklarska-Smialowska (1986) propose
otherwise still passive. The precise location of a pit is unpre- various ways in which the susceptibility of an existing structural
dictable but the probability of occurrence is higher at grain materials to pitting can be assessed under experimental conditions
boundaries, inclusions and other surface discontinuities (Zaya, (Melchers, 1994). Among these, measuring susceptibility to pitting
1984; Ryan et al., 2002). by using pitting potential and/or by temperature is commonly used
 Inside the pit the aggressive ions reach concentrations much ways and is discussed in the following sections.
higher than in the bulk of the solution. This is accompanied by
changes in the concentration of the other components of the 4.1.1. Measuring susceptibility of pitting using pitting potential
solutions e usually a drop in the pH (Zaya, 1984; Wong and Electrochemical studies of pitting corrosion reported that
Alkire, 1990). pitting potential is related to the electrochemical process associ-
ated to corrosion (Frankel, 1998; Melchers, 1994). When the elec-
These properties were selected after extensive observation of tronic potential is measured for a given metal electrolyte system, it
pitting in combinations of several metal-solutions (Szklarska- was observed that there exists a threshold value of the anodic
Smialowska, 1986; Zaya, 1984). potential below which pitting does not occur (Melchers, 1994).
Szklarska-Smialowska (1986) discussed various electrochemical
4.1. Passive films methods used to determine characteristics pitting potentials and a
detailed description is available (Szklarska-Smialowska, 1986).
It is generally acknowledged that the susceptibility of metals, Different methodology used to determine characteristics pitting
and the rate at which the corrosion processes take place, are closely potentials are:
related to the quality of the passive film which normally occurs on
the metal surface (Szklarska-Smialowska, 1986). Many researchers  Measurements of the anodic polarization curve using a poten-
have studied susceptibility of metals for many years. Amongst tiostatic device (Greene, 1962).
these, Szklarska-Smialowska (1986) and Melchers (1994, 2007,  Measurements of the anodic polarization curve by galvanostatic
2003a, 2004c) applied both theoretical and experimental knowl- methods (Frangini and De Cristofaro, 2003).
edge to estimate the susceptibility of metals for pit to initiate in  Measurements of current density vs. time at constant potential
marine and offshore structures. Szklarska-Smialowska (1986) (Comotti et al., 2013).
described different ways to estimate the susceptibility of the  Measurements of potential vs. time at constant current (Malik
metal alloy to pitting: et al., 1992).
 Repassivation time methods (Scratch Methods) (Szklarska-
 Determination of characteristic pitting potential Smialowska, 1986).
 Determinations of a critical temperature of pitting  The pit propagation rate test (Wilde, 1972).
 Measurement of the number of pits per unit area, weight loss €hni, 2000).
 The critical pitting temperature test (Bo
and, if possible, the size and depth of pits formed in a suitable  The scanning reference electrode technique (Power and
standard solution Shirokoff, 2012).
 Determination of the lowest concentration of chloride ions
causing pitting (Szklarska-Smialowska, 1986). Malik et al. (1992) used these methods to conduct electro-
chemical tests to investigate the pitting corrosion behaviour of AISI
Although the nature of the passive films is not fully understood, 316L in Arabian Gulf Seawater and reported that the pitting po-
many researchers acknowledge that pitting susceptibility is related tentials vary for the same materials under identical conditions
to local imperfections or discontinuities (Melchers, 1994; Wika, depending upon the methods used (Malik et al., 1992).
2012a; Moayed et al., 2003). Szklarska-Smialowska (1986) listed
the following understanding on the formation of weak spots in 4.1.2. Measuring susceptibility of pitting using temperature
passive film (Szklarska-Smialowska, 1986; Melchers, 1994): According to DNV-RP-G101 (Veritas, 2002), temperature is the
main reason for pitting corrosion attack on offshore steel structures
 Boundaries between the metal matrix and non-metallic in- (Veritas, 2002). The reported experimental work on temperature
clusions where differences exist in the coefficient of thermal often focused on finding the critical pitting temperature (CPT)
expansion, causing either cracking or localised compression which is defined as the lowest possible temperature where pitting
zones. occurs (Wika, 2012a). Moayed et al. (2003) defines CPT as “the
 Boundaries between the metal matrix and second phase pre- lowest temperature at which the growth of stable pits is possible”
cipitates, as these often have the ability to draw from the alloy (Moayed et al., 2003). ASTM G 150 is a standard test method for
some components responsible for the passive state (e.g. Cr electrochemical CPT testing of stainless steel.
impoverishment of CreNi stainless steels as a result of chro- Several authors (Frankel, 1998; Melchers, 1994; Caines et al.,
mium carbide formation). 2013; Wika, 2012a) reported that, with an increase in tempera-
 Inclusions of greater chemical reactivity than that of the alloy or ture, the Epit decreases and the damage caused by corrosion in-
metal itself. creases. Melchers (1994) reported that, for Carbon Steel, it appears
46 J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62

that the passive film becomes less protective with higher temper- and Ahammed, 1994).
ature and that this is related to the behaviour of chloride ions Table 2 (Melchers, 1998). Not all of these factors are well un-
(Melchers, 1994). Wika (2012a) found that the increasing temper- derstood although some have become clearer through recent in-
ature causes higher current transients and promotes the conversion vestigations (Melchers, 1998). The main factors governing pitting
of metastable pits into stable growing pits (Wika, 2012a). Bo € hni corrosion in a marine and offshore environment are described in
(2000) carried out electrochemical studies in micro and large subsequent sections.
scale e both in chloride free and in chloride solutions. In chloride
free solutions, the increase in temperature caused an increase in 5.1. Physical factors
dissolution of MnS inclusions, while in a chloride environment the
€ hni, 2000).
growth of pits increases (Bo 5.1.1. Temperature
Temperature is one of the critical factors in pitting corrosion,
5. Factors affecting pitting corrosion in marine and offshore because it greatly influences the corrosion behaviour of steels in
steel structures seawater (Melchers, 2004a; Szklarska-Smialowska, 1986; Frankel,
1998; Abood, 2008; Zamaletdinov, 2007; Strehblow and Marcus,
Steel alloys are used in numerous and diverse applications in 1995; Wong and Alkire, 1990; Malik et al., 1999; Ghali et al., 2004).
marine and offshore industries (Ryan et al., 2002). Stainless steel Many materials do not pit at a temperature below a certain value
grade 316 alloys are commonly used in offshore applications which may be extremely high and reoccurring (Nun ~ ez, 2007).
because of their corrosion resistant nature. It is regarded as safe for Pitting potential of stainless steel alloy is measured in the tem-
design life when choosing a material in an aggressive environment perature range of 25e90  C (Malik et al., 1999). The majority of
(Stewart and Al-Harthy, 2008; Ryan et al., 2002; Carpen et al., 2007; chemical and electrochemical reactions proceed more rapidly at
Isaacs and Kissel, 1972). Nevertheless, even though these alloys higher temperature. Therefore it might be anticipated that the rate
offer a better resistance to general corrosion, they are still suscep- of pitting would increase with increasing (rising?) temperature
tible to pitting corrosion (Wika, 2012b). The most common causes (Szklarska-Smialowska, 1986). Almarshad et al. (Nun ~ ez, 2007)
of failure of stainless steel in marine environments is pitting experimentally studied the effect of temperature on pitting by
corrosion because the material can quickly be penetrated despite either varying the temperature at a range of fixed applied poten-
that its general corrosion rate is very low (Malik et al., 1992). tials, or by varying the potential for a range of constant temperature
Several findings on pitting corrosion of steel alloys, accom- experiments. They provided a plot of pitting and repassivation
plished by using numerical and experimental techniques, have potentials for three different stainless steels in 1 M NaCl as a
been published by different investigators. Salh (1990) studied the function of solution temperature (Abood, 2008; Acun ~ a-Gonzalez
pitting corrosion of carbon steel in sodium molybdite solution. et al., 2012). From these experiments it was observed that
They found that the sodium molybdite is a good pitting inhibitor in extremely high breakdown potentials occur at low temperature
solutions of moderate and low concentration of chloride, and that corresponding to transpassive dissolution e but not with localized
the corrosion potentials shifted to more positive value in the corrosion. However, just above the critical pitting temperature
presence of molybdite (Abood, 2008; Salh, 1990). Malik et al. (1992) (CPT), pitting corrosion occurs at a potential that is far below the
investigated the pitting behaviour of 316L stainless steel in Arabian transpassive breakdown potentials (Nun ~ ez, 2007).
Gulf seawater. The immersion test and electrochemical techniques Hadfield et al. (Hadfield, 1922) reported metal losses for ordi-
were utilized to study different factors affecting the pitting corro- nary steels over a 5 year exposure. Fig. 8 shows the pitting depth for
sion (Malik et al., 1992). Similarly, Melchers, (2008a) investigated tidal conditions as a function of annual mean temperature for
the corrosion wastage in aged offshore structural steels. They different experimental cities. It can be seen that pitting is incon-
summarized the progress in the development of the mathematical sistent as a function of temperature for tidal conditions, whereas
models for corrosion loss and maximum pit depth under in-situ there is an increasing trend of pitting with temperature for general
conditions of steel as a function of time (Melchers, 2014a). corrosion conditions (Melchers, 2008a, 1994; Melchers and
Several published materials (Popoola et al., 2013; Darmawan, 2010; Ahammed, 1994).
Darmawan and Stewart, 2007; Davydov, 2008; Guedes Soares et al., The specimens were despatched to testing stations at Auckland,
2011; Nakai et al., 2006) are widely available. Colombo, Halifax (Canada), and Plymouth. Observations suggest
The phenomenological factors which influence pitting corrosion that, despite the differing sea and atmospheric conditions, im-
in marine and offshore environments are generally similar to those mersion corrosion of carbon steel is very similar when comparing
of uniform corrosion. The influence of these factors differ all five locations. The effect of temperature on atmospheric corro-
depending on the types of marine environments, such as atmo- sion was also thoroughly examined and showed that atmospheric
spheric, splash zone, tidal zone and shallow water immersion corrosion was generally consistent with temperature. Melchers
(Melchers, 1994; Melchers and Ahammed, 1994). The different (1994), 2002, Melchers and Ahammed (1994) stated that the re-
types of exposure can be sub-classified as illustrated in Fig. 6. A action process for corrosion becomes faster with higher tempera-
summary of all the possible factors involved in pitting corrosion is tures after the initial phase, suggesting that the corrosion rate
given in Fig. 7. These factors are categorised into four different increases with increase (rise?) in temperature. However, in im-
types: (1) Physical factors (2) Chemical factors (3) Biological factors mersion conditions, oxygen concentration decreases with increase
and (4) Metallurgical factors. in temperature while biological activity increases with increase in
A summary of the different types of exposure in marine envi- temperature (Melchers, 1994; Melchers and Ahammed, 1994;
ronments is shown in Table 1. Factors which can affect pitting Melchers, 2002).
corrosion given in Fig. 7 are composed from all types of exposure
zones. Attention is not limited to just stainless steel; mild steel and 5.1.2. pH
low alloy steels are also considered because literature indicates that The pH of seawater may vary slightly depending on the photo-
the corrosion behaviour is similar to all (Melchers, 2004a, b, 1994; synthetic activity. Plant matter consumes carbon dioxide and af-
Melchers and Ahammed, 1994; Melchers, 2005b). fects the pH during daylight hours (Schumacher, 1979; Younis et al.,
Environmental factors which influence marine immersion 2012). The carbon dioxide content in seawater (close to the surface)
corrosion are shown in Table 1 (Melchers, 2008a, 1994; Melchers is influenced by the exchange with carbon dioxide in the
J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62 47

Fig. 6. Classification of environments encountered by pitting corrosion (Sørensen et al., 2009).

atmosphere (Schumacher, 1979). It is reported that the usual daily dissolved oxygen concentration results in the maximum pitting
fluctuations of pH (of between 8.0 and 8.2) has little direct effect on corrosion rate. The highest oxygen concentration can be achieved at
corrosion rate. However it can be a factor in calcium carbonate 3.5 weight precents sodium chloride (Yari, 2014). Melchers and
deposits which does affect the corrosivity (Schumacher, 1979; Ahammed (1994) reported that, in immersed conditions, the
Melchers, 1994). Comparable conclusions were made by Melchers corrosion rate is expected to increase due to higher dissolved ox-
(1994). Chandler (1985) did not consider pH of seawater to be ygen concentration with reducing salinity (Fig. 9) (Melchers and
one of the main physical factors that influences pitting corrosion Ahammed, 1994). However, some researchers reported that, in
rate on steel (Chandler, 1985). Revie (2008) stated that, within the the longer term, the pitting corrosion rate effect of salinity may be
range of pH of about 4e10, the corrosion rate is independent of pH less because the increased oxygen has a greater tendency to form
and depends only on how rapidly oxygen diffuses to the metal protective deposits (scale) or protective biofouling containing cal-
surface (Guedes Soares et al., 2011; Revie, 2008). cium carbonate (Melchers and Ahammed, 1994).
Many experiments were carried out to understand the effect of Some researchers (Guedes Soares et al., 2011; Melchers, 1998;
pH on pitting corrosion in marine environments. Malik et al. (1999) Chandler, 1985; Mercer and Lumbard, 1995) reported that, for
performed electrochemical tests on metal and found that corrosion seawater conditions, salinity is of little practical importance to
rate increases with increasing acidity of the solution. They stated marine corrosion. This is because corrosion of metals is not
that corrosion rate increases with rising pH between 4 and 9 (Malik appreciably affected due to the salinity variations in open-ocean
et al., 1999). Similarly, Carpen et al. (2007) carried out potentio- surface water range (ranging) from 32,000 to 37,500 ppm per
dynamic experiments with distilled solutions containing chlorides. thousand gram of water (Guedes Soares et al., 2011; Melchers,
They found that a pH of 3 contributes a little lower pitting poten- 1998; Chandler, 1985; Mercer and Lumbard, 1995). According to
tials than solutions of pH 5 with low chloride content. No effect of the experimental work of Mercer et al. (Mercer and Lumbard, 1995),
pH was observed at higher chloride content. It was therefore sug- the effect of change in salinity appears to be marginal for stainless
gested that pH has little effect on pitting potentials in chloride steel in calm conditions. Chandler et al. (Chandler, 1985) also did
solutions and does not much change the susceptibility to pitting not consider seawater salinity as one of the main environmental
corrosion in the pH range 3e7 (Wika, 2012a; Carpen et al., 2007). factors that influences corrosion rate of steel (Chandler, 1985).
The effect of pH on the breakdown potential was not understood
well (Abood, 2008). Pistorius et al. (Pistorius and Burstein, 1992b)
found that the breakdown potential (Eb) value is almost constant 5.1.4. High velocity of water
within a large range of pH values (Abood, 2008; Salh, 1990; Many metals are sensitive to velocity effects in seawater
Pistorius and Burstein, 1992b). (Schumacher, 1979). For metals like iron or copper, there is a critical
velocity beyond which corrosion becomes high. However, for steel
5.1.3. Salinity structures in marine environments, the little effect of water velocity
Seawater Handbook (Schumacher, 1979) defines salinity as the can be ignored (Melchers, 2005c). Melchers (1998) reported that,
total weight in grams of solid matter dissolved in 1000 g of water with the possible exception of the effect on marine biological
(Schumacher, 1979). The effect of seawater salinity is convention- growth and the influence of the continuous supply of oxygen, the
ally considered to be a very important factor with regard to pitting effect of low and moderate water velocity on the rate of corrosion
corrosion (Zakowski et al., 2014). The composition of seawater for can be ignored (Melchers, 1998, 2005c). However Melchers (2004a)
salinity is given in Table 3. It can be appreciated that the salinity of found that water velocity does increase the rate of pitting corrosion
seawater is composed of about 90% sodium chloride (NaCl). The nonlinearly. They indicated that when corrosion products and/or
dissolved salt leads to a low resistivity so that the seawater acts as a marine growth is disrupted or removed (as through erosion or
good electrolyte, thereby enabling pitting corrosion (Melchers and abrasive action) the effect of water velocity on pitting corrosion can
Ahammed, 1994). be more severe (Melchers, 2003a; Guedes Soares et al., 2011).
Variations on salinity in open surface water appears to range The effect of higher water velocity on marine pitting corrosion
from 32,000 to 37,500 ppm (3.2e3.75%) with deep water mean should be considered. Soares et al. (Guedes Soares et al., 2011) re-
around 35,000 ppm (3.5%) (Melchers and Ahammed, 1994). A great ported that the corrosion of steel by seawater increases as the water
variation in salinity is observed in some of the more isolated seas velocity increases. The effect of water velocity at higher levels is
(see Table 3) and, because the salinity variations are accomplished shown in Fig. 10 and illustrates that the rate of corrosion attack is a
by other changes, the total effect on the pitting corrosion has to be direct function of the velocity until critical velocity is reached
established in each case (Schumacher, 1979). (Abood, 2008; Guedes Soares et al., 2011). Special forms of corro-
Fig. 9 shows how the combination of chloride concentration and sion associated with higher seawater velocity are:
48 J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62

Fig. 7. Factors affecting pitting corrosion in marine and offshore environments.

J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62 49

Table 1
Classification of marine environments (Melchers, 2008a, 1994; Melchers and Ahammed, 1994).

Marine Description of environments Characteristics of steel corrosion behaviour


Interior High humidity, higher than ambient temperature, periodic wetting possible. Particularly aggressive in areas where moisture can accumulate.
Atmosphere Minute salt particles present, corrosivity varies with height above water, wind Sheltered surface may deteriorate more rapidly than those boldly exposed.
direction and velocity, dew cycle, rainfall, temperature, pollution etc. Corrosion decreases rapidly with distance from sea.
Splash Wet, well aerated surface, no fouling. Most aggressive zone for steel. Protective coating is difficult to maintain.
Tidal Well oxygenated, marine fouling likely to occur, oil coating from polluted High attack for steel, however oil coating may reduce corrosion attack.
harbour water may be present. Some protection on continuous steel pile.
Immersion Usually saturated with oxygen. Pollution, sediment, fouling, velocity etc. have key Biofouling restricts oxygen supply rate to surface, reducing corrosion.
roles in the degree of corrosion. Protective coatings may be effective for limited corrosion control.

Table 2
Environmental factors as shown in the flowchart Fig. 7 and its effect on the corrosion rate (Schumacher, 1979; Melchers, 1994; Melchers and Ahammed, 1994; Melchers, 1998).

Type Factor Effect on initial state corrosion Effect on steady state corrosion Influenced by

Biological Bacteria Little effect Controls rate Seawater temperature

Biomass NaCl concentration
Pollutants Varies Varies Little known about
Marine growth Little effect Controls rate Pollutant type/level
Chemical O2 Directly proportional None
CO2 Little effect Little effect
NaCl Inversely proportional Uncertain Little effect at sea
Ca Little effect Varies Little known about
Carbonate solubility Little effect Little effect
Physical Temperature Proportional >10  C Proportional Geographical locations
pH Little effect Uncertain Little effect at sea
Pressure Uncertain Not none Oxygen effect
Water velocity Little effect Uncertain Geographical locations
Suspended solids Uncertain Uncertain Geographical locations
Surface wetting and wave action Proportional for tidal/splash zone Proportional Location, weather patterns
Oil in the water Reduces for tidal zone Reduces for tidal zone Industrial development/shipping

 Erosion-corrosion caused by high-velocity silt bearing seawater

 Impingement attack e where air bubbles are present
 Cavitation e where collapsing vapour bubbles cause mechanical
damage and often corrosion damage as well (Schumacher,

5.1.5. Physical size

Pitting corrosion in seawater is influenced by the size of the
sample. The pitting susceptibility depends on marine environments
such as tidal and/or splash zones; however, the size of the specimen
may alter the rate of pitting corrosion. The effect of physical size on
marine pitting is not yet fully understood. Melchers et al. (Melchers,
1994) recommended that consideration be given to the physical
Fig. 8. Pitting depth for tidal conditions as a function of annual mean water temper-
size of specimen in order to model metal loss and pitting for real-
ature (Melchers, 1994). istic structures (Melchers, 1994; Melchers and Ahammed, 1994).
They also advised that a comparative study be performed with the

Table 3
Composition of seawater and ionic constituents and total solids in Ocean waters (Schumacher, 1979).

Constituent g/kg in 1000 g of water Cations, precent Anion, precent Body of water Salinity ppm

Chloride 19.353 Naþþ 1.056 Cl 1.898 Baltic Sea 8000

Sodium 10.76 Mgþþ 0.127 So4 0.265 Black Sea 22,000
Sulphate 2.712 Caþþ 0.040 HCO 3 0.014 Atlantic Sea 37,000
Magnesium 1.294 Kþ 0.038 Br 
0.0065 Mediterranean Sea 41,000
Calcium 0.413 Srþþ 0.001 F
0.0001 Caspian Sea 13,000
Potassium 0.387 Total 1.262 2.184 Irish Sea 32,5000
Bicarbonate 0.142
Bromide 0.067
Strontium 0.08
Boron 0.004
Fluoride 0.001
50 J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62

steel is higher above the water level than when compared to sub-
merged conditions. This is due to the higher oxygen concentration
above the seawater. However it is just the opposite for 304 stainless
steel; the pitting density and pit depth resulted in an increased rate
of corrosion for this alloy when in a submerged location. Conversely
from these experiments, it was found that the pitting corrosion rate
of metals at semi-submerged conditions is higher than for sub-
merged and atmospheric conditions (Al-Fozan and Malik, 2008;
Zamanzadeh et al., 2004).

5.1.7. Atmospheric effects

In atmospheric conditions, the intensity of the corrosive attack
is influenced greatly by the amount of salt particles or mist which
collects on the metal surface (Little et al., 2008). Salt deposition
Fig. 9. Combination of sodium chloride concentration versus the rate of corrosion in
seawater (Yari, 2014). varies with wind and wave conditions, the height above sea level,
and exposure etc. (Schumacher, 1979). Schumacher (1979) reported
that several other factors which affect the atmospheric corrosion
behaviour in marine environments can include solar radiation, the
amount of rainfall and fungi.
Melchers (1994), Melchers and Ahammed (1994) reported that
macro biological activity is basically absent in atmospheric corro-
sion, but that it may have some influence. Additionally, the air
temperature and exposure will have a direct influence on rate of
corrosion (Melchers, 1994; Melchers and Ahammed, 1994). Newton
et al. (Friend, 1940) conducted an experiment to investigate the
variation of atmospheric corrosion as a function of length of
exposure in various locations. They reported difficulties in drawing
conclusions because of the variation in several factors like expo-
sure, humidity and distance from the sea. Additionally, there were
significant differences in air temperature and annual rainfall
Fig. 10. Effects of velocity of seawater on the corrosion rate of steel (Guedes Soares (Melchers, 1994; Melchers and Ahammed, 1994; Friend, 1940).
et al., 2011).
5.1.8. Water current & tidal conditions
Water current may have an effect on marine biological growth
available observations on steel pylons in a marine environment and
through the provision of an adequate rate of food supply. It also has
the results from isolated test specimens (Melchers, 1994).
an influence on the continuous supply of oxygen (Schumacher,
1979; Melchers and Ahammed, 1994). Lewis et al. (Lewis and
5.1.6. Water depth (hydrostatic pressure) Mercer, 1984) reported that the effect of water current is difficult
The water depth (hydrostatic pressure) is also considered to be a to quantify as it doesn't have a direct effect on pitting corrosion;
factor that increases the rate of pitting corrosion in marine envi- however it can be a subsidiary factor for pit initiation. For example,
ronments. The effect of depth of exposure in seawater on the it may increase the marine biological growth by dissolving the
average corrosion rate of steels has been studied by some re- impurities in the ocean which could then lead to pit growth
searchers (Carpen et al., 2007; Melchers, 2005b; A. International, (Melchers and Ahammed, 1994; Lewis and Mercer, 1984). Melchers
2004; Qin and Cui, 2003; Salau et al., 2011; Zatkalíkova  et al., et al. (Melchers, 1994) suggested that the effect of low to moderate
2010). Melchers, (2005b) studied the corrosion rate for mild steel water currents on the rate of pitting corrosion can be ignored
coupons exposed at variable immersion depths and at various (Melchers, 1994).
geographical locations. Analysis of the data showed that there is not The pitting susceptibility is higher in the tidal zone compared to
an obvious effect of water depth on short-term corrosion behav- pitting susceptibility in a fully immersed zone (Melchers and
iour. Nevertheless, oxygen concentration and water temperature Ahammed, 1994; Southwell and Alexander, 1970). Melchers and
are important parameters influencing weight loss as a function of Ahammed (1994) gathered experimental observations and data,
time in different immersion depths. The effects of immersion depth performed in cities such as Halifax, Colombo, Panama, Auckland,
for long-term corrosion behaviour may not be limited to just these and Plymouth, which investigated the extent of corrosion loss as a
parameters however, as it will also be governed by anaerobic function of length of immersion exposure (Melchers and
conditions (Melchers and Ahammed, 1994; Melchers, 2005b, d). Ahammed, 1994; Southwell and Alexander, 1970). The plot for
Fozan et al. (Al-Fozan and Malik, 2008) conducted a laboratory pitting depth in tidal conditions as a function of annual mean
test to evaluate the effect of seawater level on the corrosion temperature for different experimental cities is shown in Fig. 8.
behaviour of different alloys (Al-Fozan and Malik, 2008). Specimens
were fixed at three locations, namely: above seawater surface, 5.1.9. Surface wetting
semi-submerged in seawater and fully submerged in seawater. The The degree and continuity of surface wetting is particularly
experimental results show that, in a splash zone, the stainless steel important for atmospheric, splash and tidal zone corrosion. The
usually has satisfactory performance but that the carbon and low surface wetting depends on the location of the structural specimen
alloy steels do not. The stainless steels are susceptible to pitting relative to the seawater (Melchers and Ahammed, 1994; LaQue,
corrosion in the submerged zone because of factors such as oxygen 1959).
concentration, biological activities, pollution, temperature, salinity In the tidal and splash zone, wetting may be controlled by the
and velocity. Similarly the pitting corrosion rate for 316L stainless local tidal range and climatic conditions such as water, air and
J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62 51

temperature. The effect of surface wetting is still not fully under- Various authors commented that there is a good correlation
stood but the pitting due to surface wetting is believed to be between dissolved oxygen and corrosion mass loss (Frankel, 1998;
minimal. Melchers et al. stated that no general rule exists to Malik et al., 1992; Guedes Soares et al., 2011; Melchers, 2006a).
describe functional relationships between surface wetting and Melchers (2003a) stated that the corrosion rate usually has a linear
climatic conditions (Melchers, 1994; Melchers and Ahammed, relationship with the concentration of dissolved oxygen (Melchers,
1994; LaQue, 1959). 2003a; Guedes Soares et al., 2011). They further stated that the
dissolved oxygen levels in open ocean conditions reduce with
5.1.10. Initiation time depth around 5e7 ml/l at surface, mainly as a result of increased
Initiation time is often called induction time and pertains to the pressure (Melchers, 1994; Melchers and Ahammed, 1994). Hence,
elapsed time before pitting corrosion begins (Vela zquez et al., the oxygen concentration is critical in the immersion corrosion
2014). Schumacher (1979) and Malik (1999) described an experi- process during the early stage of seawater corrosion (Melchers,
ment conducted in different stainless steels at 50  C which were 1994; Melchers and Ahammed, 1994). Schumacher (1979)
immersed in chloride solutions under open circuit potential mea- mentioned that the oxygen level in seawater may range up to
surements (Schumacher, 1979; Wika, 2012a; Malik et al., 1999). It 12 ppm. The factors that increase seawater oxygen could be
was found that pitting potential could be presented as a linear photosynthesis of green plants and wave action etc. Conversely, the
function of initiation time, ti, where A and B are constants that biological oxygen demand of decomposing dead organisms will
depend on temperature. Refer Equation (1.4)): reduce seawater oxygen level (Schumacher, 1979; Melchers, 1994).
Regional variation exists in surface water temperature; hence,
Epit ¼ A þ B$logðti Þ (1.4) salinity and locally mixed conditions occur due to the regional
variations of oxygen level (Melchers and Ahammed, 1994).
Malik et al. (1992a) conducted electrochemical measurements In waters containing high salt concentration, corrosion is pro-
of the open circuit potential and found that the logarithm of the portional to the amount of oxygen dissolved in the water. If the salt
induction time decreases linearly with increasing chloride con- concentration in the water increases, then the solubility of oxygen
tained and at increasing temperatures. These test temperatures decreases and, consequently, the corrosion rate is reduced
were conducted at 30, 50 and 80  C (Malik et al., 1992a). (Zatkalíkova et al., 2010). Therefore, oxygen dissolved in water is
probably the most troublesome corrosion-producing substance. An
5.2. Chemical factors exception to this statement is metals which depend on a passive
film for corrosion protection. Nevertheless, stainless steel often
5.2.1. High chloride ion concentration corrodes rapidly where the oxygen supply to the metal is restricted
The presence of certain aggressive anions, such as chloride (Schumacher, 1979; Melchers and Ahammed, 1994; Ryan et al.,
concentration (Cl), can migrate to the active corroding area and 2002).
stabilize pitting corrosion (Pardo et al., 2000). The influence of Cl
on the susceptibility to pitting corrosion has been studied in 5.2.3. Carbon dioxide
numerous metals and alloys and particularly in stainless steel. The dissolved carbon dioxide in seawater produces carbonic
Pardo et al. (2000) stated that the presence of alloyed elements, acid and, after ionisation, it forms bicarbonate and carbonate ions
such as Cr, Mo, and N, improve the resistance to localized corrosion (Melchers and Ahammed, 1994). Few effects of carbon dioxide are
of the stainless steel. However, the presence of chloride ions can known for pit initiation in marine steel structures. However,
easily penetrate the film due to its high diffusivity (Wika, 2012a; Melchers et al. (Melchers and Ahammed, 1994) did report that the
Pardo et al., 2000). Frankel (1998) explained that pitting corro- presence of undissolved boric acid in oppositely charged ions such
sion will only occur in the presence of aggressive anionic species, as carbon dioxide may provide a constant and fairly high pH level
which are usually chloride ions, and that the severity of pitting (Schumacher, 1979; Melchers and Ahammed, 1994).
corrosion tends to vary with the logarithm of the bulk chloride
concentration (Frankel, 1998). 5.2.4. Effect of halogen ions
Fig. 4 shows the curves plotted for two different chloride con- Pitting corrosion can be caused by different halide anions
centrations. It can be seen that Epit increases with decreasing (Abood, 2008). The anodic process associated with metal passiv-
chloride content. Many researchers (Frankel, 1998; Malik et al., ation is strongly affected by the presence of halide ions in the
1992a, b; Newman, 2001) have published studies describing the electrolyte. With large concentration of halide ions the passive film
relationship between Epit and the chloride content. Different po- on a metal is susceptible to pitting and also suffers local damage;
larization measurements (Frankel, 1998; Malik et al., 1992a, b; however, low concentration produces only an increase of anodic
Newman, 2001) demonstrated that the pitting potential was a current in the passivity range (Szklarska-Smialowska, 1986).
linear function of the logarithm of the chloride concentration. High Szklarska-Smialowska (1986) described chloride as the most
alloyed stainless steels are less affected by increasing chloride aggressive anions to produce pitting in several metals (Szklarska-
content, and therefore Epit changes only slightly for these Smialowska, 1986; Abood, 2008). The three main reasons for the
alloys (Wika, 2012a). specific effect of chloride ions is explained by Abood et al.
(Szklarska-Smialowska, 1986; Abood, 2008) as:
5.2.2. Dissolved oxygen
Dissolved oxygen content is a major factor affecting the corro-  Its ability to increase the activity of hydrogen ions in the pit
sivity of seawater. For many common metals, a higher oxygen electrolyte
content is accomplished commensurate to the increase in the rate  Ability to form complexes with cations and hydroxide
of pitting attack (Schumacher, 1979). The corrosion rate of local  Its ability to form a salt layer at low pH at the bottom of the pit.
anodes is dependent on the cathode reaction and, therefore, de-
polarization is more rapid with the increase of oxygen at the 5.3. Biological factors
cathode. The depolarization is a function of the amount of dissolved
oxygen in the seawater and the velocity of flow at the surface 5.3.1. Bacterial
(Abood, 2008; Zamaletdinov, 2007). The corrosion of metals by sulphateereducing bacteria (SRB) is
52 J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62

well recognized as one of the factors that increase rate of pitting rate of oxygen transfer for the oxidation process. The effects of
corrosion in marine environments (Thomas et al., 1988). Recent pollutants for marine pitting corrosion is not fully understood;
studies show that the hydrogen sulphide produced by these or- however, for coastal and harbour areas, the effect of pollutants for
ganisms can have a serious effect on mechanical failure processes pitting corrosion is expected to be higher than that for uniform
by increasing a metal's susceptibility to corrosion e especially corrosion (Melchers, 2008a, 1994; Melchers and Ahammed, 1994;
pitting corrosion (Thomas et al., 1988). Thomas et al. (Thomas et al., Schiffrin and De Sanchez, 1985).
1988) stated that the effect of bacteria is particularly important for
offshore structures; here it is envisaged that the combination of
5.4. Metallurgical factors
bacteria activity under marine fouling conditions, wave loading and
an aggressive environment can result in the premature failure of
5.4.1. Alloy composition
metal components by pitting corrosion fatigue (Thomas et al.,
The effect of alloy composition acts on the tendency for an alloy
to initiate pit and also affects rate of corrosion (Szklarska-
Melchers and Ahammed (1994) explained that bacteria is most
Smialowska, 1986). This influence appears to be related to the
commonly associated with marine corrosion of steel. Desulfovibrio
quality of the magnetite layers found on the surface of steel and
is one of the most common; it is a genus of gram negative sulphate
appears to be a function of the alloying elements (Melchers and
reducing bacteria. When this bacteria attached to the surface of a
Ahammed, 1994). Schultze and Wekken (1976) provided a sum-
metal with other bacteria, they may not grow when there is a
mary of the effect of steel composition on corrosion loss. It was
presence of oxygen (Melchers, 1994; Melchers and Ahammed,
reported that a particular alloy may have a favourable effect in
1994). However Melchers (1994), Melchers and Ahammed (1994)
corrosion resistance under some exposure conditions but have an
reported that, where anaerobic conditions are more conducive,
unfavourable effect on others (Melchers and Ahammed, 1994;
they can grow well in the temperature range of 25  Ce 44  C and
Schultze and Wekken, 1976).
with pH ranging from 5.5 to 9.0 (Melchers and Ahammed, 1994).
Table 4 summaries the main effects of alloying elements. The
influence of steel composition on pitting corrosion susceptibility
5.3.2. Fouling
and uniform corrosion susceptibility is similar in marine corrosion.
Marine fouling in offshore structures can have serious conse-
However, the pitting resistance of low alloy steel may be less than
quences on their integrity, enhancing both the corrosion and stress
that of carbon steel (Melchers, 1994).
components of corrosion fatigue (Thomas et al., 1988). Fouling is
Ting et al. (2011) reported that the small changes (say <0.5%) in
commonly considered to be growth beyond the bacterial stage.
the alloying elements used in steel composition should have zero or
Algal growth may include seaweeds, coral, aurelias, barnacles,
negligible effect on the degree of corrosion that occurs while oxy-
mussels etc. Melchers and Ahammed (1994) reported that common
gen diffusion controls the corrosion process (Ting et al., 2011). More
fouling can tolerate a range of temperature and light intensities,
specialized steel with larger alloy compositions will have a lower
with growth most productive in the range of 15  Ce 20  C
initial rate of corrosion. This is particularly so for alloying elements
(Melchers, 1998).
such as chromium, molybdenum and aluminium and, to a lesser
extent, for nickel, silicon, titanium and vanadium (Melchers, 2004c;
5.3.3. Marine growths
Ting et al., 2011). Szklarska-Smialowska (1986) studied the effect of
Marine growth can affect the rate of pitting corrosion in im-
small increases in molybdenum in steel composition and it was
mersion conditions (Lewis and Mercer, 1984). Although the amount
found that only a small increase can greatly reduce pitting corro-
of marine growth varies considerably from location to location, it
sion susceptibility. In addition to this, a small increase in elements
does not have an initial effect for short term immersion corrosion. It
such as nitrogen and tungsten also have a strong influence on the
also appears that an initial effect is not reflected in fouling growth
pitting resistance of stainless steels (Szklarska-Smialowska, 1986;
(Melchers, 1994; Lewis and Mercer, 1984). Melchers et al.
Abood, 2008).
(Zamaletdinov, 2007; Melchers and Ahammed, 1994; Lewis and
Mercer, 1984) reported that, despite local and regional geograph-
ical differences, the overall fouling pattern is somewhat similar. 5.4.2. Steel types
Moreover, the presence of local warm currents with adequate food Steels differ in their relative corrosivity under different condi-
supply appears to be the major factors for marine growth. It was tions. ASTM (A. International, 2004) and Melchers and Ahammed
also assumed that marine growth may be affected adversely by (1994) categorised steels as: 1] ordinary steels, such as mild steel,
high currents and suspended solids (Melchers, 1994; Melchers and 2] low alloy steels, or high strength steels and 3] stainless or
Ahammed, 1994; Lewis and Mercer, 1984). chromium steels (Melchers and Ahammed, 1994; A. International,
5.3.4. Pollutants Stainless steels are obtained by the addition of chromium
Water pollution, particularly in harbours, may result in the in- (around 3%) to steel. This alloy is usually used for applications in
crease of corrosion rate. Under these conditions the water may be marine atmospheric conditions for maintaining the passivity pro-
more aggressive because of the greater concentration of ammonia tective surface film. Melchers and Ahammed (1994) stated that,
or sulphide which is also combined with lower oxygen levels when local perforation of the stainless steel passive film occurs,
(Schiffrin and De Sanchez, 1985). Due to the pollutants, water is less active passive cells are formed and heavy local corrosion such as
able to support marine growth of protective bacteria and biofouling pitting occurs. For immersed conditions, the addition of chromium
(Melchers, 1994; Guedes Soares et al., 2011). Harbours and coastal to stainless steel is beneficial for short term exposure (a few years);
regions may be susceptible to nutrient pollution from sewage or however, it is not agreed if this is also the case for long term
agriculture run-off. Offshore oilfields are also known to provide exposure. The resistance to corrosion of low alloy steels may range
sources of nutrient pollution (Melchers, 1994; Guedes Soares et al., from two to ten times that of ordinary carbon steel. This is because,
2011). Schiffrin et al. (Melchers, 1994; Schiffrin and De Sanchez, due to the formation of basic salts on the surface, low alloy steels
1985) reported the effect of nutrient-based pollution on the form a tighter rust coating at a faster rate than that of coronary
corrosion of mild steel coupons. It was found that pollutants like carbon steels (Melchers and Ahammed, 1994; Melchers, 2002,
oils and grease lower the corrosion rate due to their inhibiting the 2003b).
J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62 53

Table 4
Effects of alloying elements on corrosion resistance of steels (Melchers and Ahammed, 1994; Schultze and Wekken, 1976).

Alloy Immersion zone Tidal zone

Aluminium Not conclusive, but perhaps beneficial long term effect Not conclusive, but perhaps beneficial long term effect
Chromium Favourable initially (<5 years) therefore undesirable
Copper Probably detrimental long term e
Manganese Slight beneficial effect Probably detrimental
Molybdenum Unfavourable short-term, however favourable long term e
Nickel Little effect Beneficial effect
Phosphorus Very detrimental long term, low concentration in steels e
Silicon Not important
Sulphur May be detrimental even in small quantities

5.4.3. Surface conditions & surface roughness from corrosion and to ensure good adhesion to the substrate
The state of the metal surface is known to affect pitting sus- (Sørensen et al., 2009).
ceptibility (Szklarska-Smialowska, 1986; Zamaletdinov, 2007). The Fig. 11 shows the factors that affect the durability of an anti-
more homogenous the surface is, both chemically and physically, corrosive coating system (Sørensen et al., 2009). Sørensen et al.
the higher is the potential for pitting. Consequently the number of (2009) stated that the coating provides the required colour and
pit is expected to be lower and metal resistance to pitting will in- gloss for surfaces exposed to external marine environment. The
crease (Szklarska-Smialowska, 1986; Abood, 2008; Malik et al., protective coating should have a high resistance to ultraviolet ra-
1992). Surface roughness is caused by local ‘weak’ points in the diation (Sørensen et al., 2009) as well as adequate resistance to
protective oxide film where a critical Cl concentration can attend, altering weather conditions and impact from objects. Bayer and
or by homogeneities resulting from surface preparation; either can Zamanzadeh (2004) reported that environmental degradation
increase the number of active sites for pit nucleation (Szklarska- caused by moisture, temperature and ultraviolet radiation will
Smialowska, 1986). Isaacs and Kissel (1972) studied the effect of reduce the lifetime of the coating. These authors reported six pri-
exposure time on active pit propagation on AISI 304 stainless steel mary causes of the majority of paint and coating-related failures: 1]
in 0.4 M FeCl3 solution of pH 0.9, using a scanning reference elec- Improper surface preparation, 2] Improper coating selection, 3]
trode to measure the number of active pits. Both the number of Improper application, 4] Improper drying, curing and over-coating
active pits and the rate at which their growth was decreased times, 5] Lack of protection against water and aqueous systems, and
(because of passivation) depended on the steel surface treatment 6] Mechanical damage (Bayer and Zamanzadeh, 2004).
(Szklarska-Smialowska, 1986; Isaacs and Kissel, 1972).
The roughness of a material's surface depends on the surface 5.4.5. Mill scale
preparation. This preparation is done to ensure proper adhesion of The presence of mill scale on structure's appears to lead to
the coating. The coating is used to protect the materials from the greater pitting corrosion (Melchers and Ahammed, 1994). The ef-
environment by making a smoother surface and, thereby, reducing fect appears to be most significant for atmospheric corrosion and
the possibility of localized corrosion occurring (Wika, 2012a). less for tidal and immersed corrosion conditions. Melchers and
Moayed et al. (2003) reported, and it is well established, that at Ahammed (1994) stated that the intensification of rate of pitting
temperature above the CPT, the pitting potentials tend to decrease attack caused by mill scale is thought to occur due to electro-
as the sample surface roughness increases. The surface roughness chemical action between the mill scale and the undecorated metal.
offers advantages to change the characteristic of sites for pit initi- Generally, mill scale tends to protect the metal underneath, except
ation. Pits initiate at specific sites on the surface and a rougher at cracks. At these points the scale becomes anodic and, because of
surface generally provides the site with more passage geometry the relatively large cathodic area, the rate of attack caused by
(Szklarska-Smialowska, 1986; Wika, 2012a; Moayed et al., 2003). electrochemical action between mill scale and the bare metal at
Moayed et al. (2003) and Malik et al. (1995) studied the relationship local anodes is instantaneous (Melchers, 1994; Melchers and
between CPT and surface roughness. They found that, with an in- Ahammed, 1994).
crease in surface roughness, the CPT decreases and standard devi-
ation of the test result increases. The higher chance of stable pitting
in rough surfaces is attributed to the longer length of diffusion and 5.4.6. Effect of PREN value
Pitting Resistance Equivalent (PREN) is the capacity of an alloy to
larger micro-crevices surrounding the inclusions (Moayed et al.,
2003; Malik et al., 1995). Manning et al. (1980) established a resist pitting. A higher potential is needed to initiate pitting in al-
loys with large PREN values than with alloys which have low values
similar correlation on the effect of surface roughness on pitting
potential for single-phase and duplex stainless steel. (Wika, 2012a; Malik et al., 1999). PREN is represented by the
Equation (1.6):

PREN ¼ %Cr þ 3%Mo þ 16%N (1.6)

5.4.4. Protective coating
Protective coating systems, also known as anticorrosive coating, PREN is mentioned in several studies when assessing whether
is one of the methods developed to protect external surfaces an alloy can resist pitting corrosion (Frankel, 1998; Abood, 2008;
against corrosion (Wika, 2012a). The protective coating systems is Caines et al., 2013; Melchers, 1999; Wika, 2012a; Malik et al.,
highly recommended by classifications society rules such as DNV- 1999; Xiong et al., 2012; Jargelius-Pettersson, 1998). Lorenz and
RP-G101 (Veritas, 2009) and NORSOK M-501 (Norsok, 2004). Pro- Medawar (1969) initially established a good correlation between
tective coatings are critical for marine structures mainly because the pitting potential of a wide range of stainless steels. It was found
the environment is very aggressive and corrosive (Veritas, 2002; that the sum of %Cr þ 3.3  (%Mo), indicating molybdenum addi-
Sørensen et al., 2009; Norsok, 2004). Marine structures require tions, were three times more effective than chromium additions in
applications consisting of primer, one or several intermediate coats, increasing pitting resistance (Jargelius-Pettersson, 1998; Lorenz
and a topcoat. The function of the primer is to protect the substrate and Medawar, 1969). Malik et al. (1999) reported that, PREN >38
54 J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62

Fig. 11. Factors affecting the durability of an anticorrosive coating system (Sørensen et al., 2009).

conditions should be satisfied to provide pitting corrosion resis- 7.2. Metallographic examination
tance to seawater-immersed conditions (Wika, 2012a; Malik et al.,
1999). Johansen (2011) studied CPT as a function of PREN. His Metallographic examination is an investigative technique that
research demonstrated that the CPT increases almost linearly with can be used to determine the size, shape and density of corrosion
increasing PREN. The experiment involved testing of stainless steel pits (Caines et al., 2013). Jana (1995) stated that metallographic
alloy samples in seawater at 50  C with the corrosion rate depen- examination is typically a destructive analysis technique as the
dent on the PREN value. The results showed that the PREN value specimen must be cut from the component and examined with a
decreases with an increase in temperature (Wika, 2012a; Lorenz microscope (Jana, 1995). Power and Shirokoff (2012) studied the
and Medawar, 1969; Johansen, 2011). Malik et al.( 1992b) sug- simultaneous electrochemical analysis and in situ optical micro-
gested that Epit is also a linear function of the PREN value (Wika, scopy for 316L stainless steel samples submerged in sulphuric acid
2012a; Malik et al., 1992b). based solutions. They reported that this technique provides both a
detailed visual account of the corrosion process as well as a stan-
dard electrochemical analysis of the pitting potentials and corro-
6. Corrosion-related accidents in marine and offshore sectors sion rate (Power and Shirokoff, 2012). A brief discussion on the
metallographic examination is provided by Caines et al. (2013).
A summary of the offshore accidents due to pitting reported in
the literature (Maureen et al., 2013; HSR, 2003; A. International,
2004; Zamanzadeh et al., 2004; A. International, 1992; Nesi c, 7.3. Non-destructive testing (NDT)
2007; A. Stand , 2005) is summarised in Table 5.
Non-destructive testing (NDT) is a key technique used in in-
7. Methods of identification of pitting corrosion dustry to evaluate the current state of component and equipment
in service and to aid in maintenance planning. It plays an important
The first stage in understanding pitting corrosion of steel is to role in the continued safe operation of physical assets (Caines et al.,
correctly identify the phenomenon. Pitting corrosion is character- 2013; A. Stand, 2005; Forsyth, 2011). American Society for Non-
ized by small flaws in the surface of a material as shown in Fig. 3 destructive Testing (ASNT) defines NDT as “the determination of
(Caines et al., 2013). There are many techniques that can identify the physical condition of an object without affecting the object's
the presence of pitting (Caines et al., 2013; A. International, 1992): ability to fulfil its intended function. NDT techniques typically use a
probing energy form to determine material properties or to indi-
cate the presence of material discontinuities” (Forsyth, 2011). ASTM
7.1. Visual inspection G46-96 (A. Stand, 2005) stated that NDT technique is applicable to
identify pitting corrosion however, it is not effective at character-
To identify pitting corrosion, visual inspection can be done in izing pitting as a destructive method. Additionally, specialized
ambient light to determine location and severity of pitting. Caines training is required to ensure realistic results (Caines et al., 2013; A.
et al. (2013) stated that photographic imaging is often used to Stand, 2005). A brief description of each NDT method is presented
document the difference in appearance of pits before and after by Forsyth et al. (Forsyth, 2011) and Caines et al. (Caines et al.,
removal of corrosion products (Caines et al., 2013). Roberge (2008) 2013).
describe this technique as easiest to employ as it does not require An NDT method is classified according to its underlying physical
specialized equipment and is relatively economical (Roberge, principle (Caines et al., 2013; Jana, 1995; Forsyth, 2011; Forsyth
2008). Recently, the use of remotely operated vehicles (ROV) and et al., 2006) and common methods are:
autonomous underwater vehicles (AUV) replaces dangerous hu-
man effort for deep water inspection and underwater work. They  Visual and optical Testing (VT) (Forsyth, 2011).
increase safety, reduce costs and increase efficiency. These tech-  Radiographic Testing (RT) (Souza et al., 2008).
nologies utilize visual imaging and produce high resolution pho-  Electrochemical and Electromagnetic Testing (EC, ET)
tographs of the corrosion susceptibility in structures (Kros, 2011). (Szklarska-Smialowska, 1986).
J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62 55

Table 5
Historical offshore accidents reported due to pitting corrosion.

Accident Year Fatalities Cost Descriptions

Umm Said Qatar (weld failure, April 1977 3 killed US$ 179 A tank containing 236,000 barrels of refrigerated propane at 45  F failed at weld. The possible cause
gas processing plant) million of weld failure was corrosion due to the influence of sulphate reducing bacteria that remained inside
the tank after hydro test with seawater. The wave of liquid propane swept over the dikes before
igniting a nearby tank containing 125,000 barrels of buthane. It took eight days to completely
extinguish the fire.
Ekofisk Norway (weld failure, March 123 killed Alexandra L Kielland Platform, a semi-submersible oil-drilling platform located at Ekofisk field North
offshore platform) 1980 Sea, capsized during a storm. The platform was supported by five columns standing on five 22-m
diameter pontoons. The five 8.5 diameter columns on the pontoons were interconnected by a
network of horizontal bracings. A cracked bracing made five other bracings break off due to overload,
and the vertical column connected with the cracked bracings became separated from the platform.
The platform subsequently became unbalanced and capsized. The investigation showed that a
corrosion fatigue crack had propagated from the double fillet near the hydrophone mounted to one
of the horizontal bracings.
Mexico Pipe Leaking (LPG) November 650 killed US$ 29 A 12-inch pipeline between cylinder and sphere storage ruptured. Initial blast caused a series of
1984 64,000 injured million BLEVEs (boiling liquid expanding vapour expansion). The outstanding cause of escalation was the
ineffective gas detection system and, due to this, of lack of emergency isolation. This explosion and
fire is perhaps the most devastating incident ever. The high death toll was due to the proximity of the
LPG terminal to a residential complex. The accident is not fully understood however; researchers
claim that this accident occurred due to the pitting corrosion in the pipe.
Piper Alpha North Sea (UK) July 1998 167 killed US$ 1.27 This was predominantly an operational error. Gas leaked from two blind flanges due to localized
billion corrosion e then the gas ignited and exploded. A pump from two available pumps was tripped, and
an operator accidentally changed the backup pump with a pressure relief valve, which had been
removed, for maintenance. Severity damage of the explosion was due largely to the contribution of
oil and gas pipelines connected to Piper Alpha.
Sinking of the Erika Dec 1999 8 killed Erika broke into two near the coast of France whilst carrying approximately 30,000 tons of heavy
fuel. 19,800 tons of fuel spilt along the coast of Brittany and France. This single oil spill was equal to
the total amount of oil spilt worldwide in 1998. A corrosion problem, which had apparently existed
on the Erika since 1994, led to this devastating accident in 1999.
Roncador Brazil March 2 killed 8 US$ 515 Investigation report of the fire, explosion, and sinking to P-36 (the largest offshore production
2001 missing million facility) revealed a sequence of events started from the failure of the starboard emergency drain tank
(EDT). Excessive pressure in Starboard EDT, due to a mixture of water, oil, and gas, caused a rupture
and leaking of EDT fluids into the fourth level of the column. The leaks were believed to have
occurred due to corrosion.

 Ultrasonic Testing (UT) (Zhu et al., 1998). surface studies and fundamental aspects of ion emission (Williams,
 Liquid Penetrant Testing (PT) (Caines et al., 2013). 1985). Usually, these techniques are associated with ion sputtering
 Magnetic particle Testing (MT) (Caines et al., 2013; Forsyth, (ejecting the atom from a solid) to allow for in-depth analysis of the
2011). sample. However, sputtering has various disadvantages because it
 Acoustic Emission Testing (AET) (Caines et al., 2013; destroys the chemical bonding which may have been present on
Zamanzadeh et al., 2004) and the surface, as well as at the original find topography. It may also
 Infrared and thermal Testing (IRT) (Caines et al., 2013). form a cavity when sputtering is uneven, and some elements may
sputter more slowly than others creating a new distribution in the
removed sample (Zaya, 1984; HSR, 2003; Riviere, 1973; Watts,
7.4. Surface analysis technique 1994).

Methods of surface analysis are increasingly being used to 7.5. Probabilistic approach for pit identification
detect and quantify elements present inside the passive layer (Zaya,
1984; Zatkalíkova  et al., 2010). Auger electrons spectroscopy (AES) Pitting corrosion has long been known to be a particularly
is a common analytical technique used in the study of the inconsistent and unpredictable process (Zaya, 1984; Engelhardt and
composition of the outer 1e5 atomic layer of the surfaces of solids Macdonald, 1998). More precisely, it is challenging to forecast when
(Riviere, 1973). During AES, the sample is attacked with 1e10 KeV a pit will initiate and where this is going to take place, therefore
electrons and the instrument analyses the emitted auger electrons. researchers have tried to extract data from the distributions during
The sensitivity to individual elements is about 0.1%, however the times of pit nucleation events (Valor et al., 2010; Zaya, 1984).
accuracy of the result is fairly poor (Zaya, 1984; Riviere, 1973). Shibata and Takeyama (1977) were the first to postulate that the
X-ray photo-electron spectroscopy (XPS) consists of subjecting a critical potential necessary to induce pitting, and the induction
specimen to X-ray photons and analysing the ejected electrons. The time elapsed before pits become observable, are both statistically
main advantage of this technique is that the energy of these elec- distributed quantities (Henshall, 1992). They asserted that the
trons varies with the chemical state of the sample element. The nucleation of a pit is a statistical process similar to the development
depth sampled, and the sensitivity, is approximately the same as for of a crack in brittle material. They conjectured that the pit gener-
AES. The main disadvantage of XPS is the poor lateral resolution ation process has the Markov property, i.e. that the future proba-
obtained due to the absence of focus by the incoming energy bility of pit nucleation is uniquely determined once the state of the
(Watts, 1994). system at the present stage is known (Zaya, 1984; Shibata and
Secondary ion mass spectrometry (SIMS) is a technique for Takeyama, 1977). Henshall (1992) found that the stochastic model
surface and thin-film analysis. SIMS has been extensively reviewed of pitting corrosion was useful in predicting corrosion damage of
from various instrumental aspects such as analytical applications, high-level radioactive waste containers. They stated that the model
comparison with other surface analytical techniques, application of includes simple phenomenological relationships describing
56 J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62

environmental dependence of stochastic parameters, and that it loss as a function of exposure period. As shown in Fig. 12, the model
can simulate pit initiation and growth under various environments, was developed based on corrosion science philosophy. The model
including those that change during exposure (Henshall, 1992). has several phases, including kinetic, diffusion, transition, and
Similarly, Valor et al. (2007, 2013) used a new stochastic model for anaerobic, and each of these phases is believed to control the
pit initiation and pit growth (Valor et al., 2007, 2010, 2013). corrosion process (Melchers, 2005a, 2003b, 2003c). This model is
Spatial distribution models are commonly used in locational based on theoretical and empirical corrosion mechanics. In Fig. 12,
analysis, including spatial location of activities among the zones of phase 2 indicates the theoretical point at which anaerobic condi-
a region and measure of interaction between zones (Wilson, 1967). tions is reached (Melchers, 2005a, 2010, 2004b, 2009, 2007). This
In the case of pitting corrosion models, spatial distributions is used condition tends to encourage rapid marine growth and, by infer-
when the pits on the sample do not exactly follow a poisson dis- ence, conditions favourable for sulphate-reducing bacteria (SBR)
tribution (Zaya, 1984). Several researchers have modified the including activation and growth (Melchers and Wells, 2006). From
spatial distributions to model pitting corrosion (Vel azquez et al., Fig. 12, the number of sequential phases which correspond to the
2014; Khan and Howard, 2007; Valor et al., 2007, 2013; Wilson, different processes controlling the (instantaneous) rate of corrosion
1967; Aziz, 1956; Chaves and Melchers, 2014; Melchers, 2005e; for ‘at sea’ conditions is summarised as below (Melchers, 2005a,
Melchers et al., 2010; Melchers, 2008b). In addition, Aziz et al. 2003a, 2003b, 2003c, 2006b, 2008c):
(Aziz, 1956) introduced exponential distribution of the pit depth to Phase 0 e a very short period of time during which corrosion is
calculate the maximum depth by the statistic of extreme values under ‘activation’ or kinetic control. This is governed by the rate at
(Aziz, 1956). which local chemical reactions can occur unhindered by external
diffusion or transportation limitations (Melchers, 2005b, d, 2003b).
Phase 1 e a period of ‘oxygen concentration’ control; the
8. Corrosion modelling corrosion rate is governed by the rate of arrival of oxygen through
the water and the corrosion product layer to the corroding surface.
The quantitative understanding (i.e. a model) of how the It can be seen in the multiphase model that this phase can be
corrosion process operates as a function of exposure time and un- modelled, to an approximation, as a linear relationship between
der various environmental influences is necessary. It is also depths of corrosion vs. time (Melchers and Ahammed, 1994;
required to predict the likely amount of corrosion in the future for Melchers, 2014a).
defined conditions (Davydov, 2008). Prediction and identification Phase 2 e in this phase the corrosion rate is controlled by the
of pitting corrosion in marine and offshore structures is a difficult rate of oxygen diffusion to the corroding surface through the
problem for a number of reasons (Frankel and Sridhar, 2008). increasing thickness of the corrosion product. This phase is there-
Firstly, the events take place on a very small scale, with passive film fore a non-linear function of time e the reason being is that, when
nanometres in thickness and with initiation sites of similar sizes. the corrosion products build up, the oxygen flux will decline and
Immediately after initiation, the rate of pit growth can be extremely eventually anaerobic conditions will be established in the zone
high, even tens of A/cm2 (Frankel, 1998; Melchers, 1994; Frankel between the corrosion product and the corroding metal (Melchers
and Sridhar, 2008). Frankel and Sridhar (2008) considered the and Jeffrey, 2011; Melchers and Wells, 2006; Melchers, 2014b).
pitting location as an extremely dynamic one with rapidly moving Phase 3 e in this phase the rate of corrosion is controlled by the
boundaries and rapidly changing chemistries. metabolic rate of sulphate reducing bacteria (SRB) under anaerobic
The modelling of pitting corrosion in marine and offshore con- conditions. Often, this phase 3 is a period of rapid growth of SRB
ditions has been study of interest for some time. The effect of the resulting from the conditions now being suitable for their increased
main factors in pitting corrosion modelling, such as temperature, metabolism and from the plentiful supply of nutrients (Melchers,
bacterial community, oxygen concentration, pH, and velocity, has 2014b). The high rate of metabolite production initially produces
been considered in the past by several researchers (Melchers, a high rate of corrosion, but this reduces to a quasi-steady state
2001a; Moayed et al., 2003; Bo €hni, 2000; Melchers, 2002; Younis situation in equilibrium with the rate of supply of nutrients and
et al., 2012; Malik et al., 1992a; Pardo et al., 2000; Scheers, 1992). energy sources from the bulk water (Melchers, 2009; Melchers and
Researchers (Melchers and Jeffrey, 2008a; Melchers, 2004b, Jeffrey, 2011; Melchers, 2006b, 2014b, 2012).
2001a, 2014a, 1998, 2003b; Melchers et al., 2010; Melchers and Phase 4 e this represents the quasi-steady state situation
Jeffrey, 2008b, 2011; Melchers and Wells, 2006) proposed a reached at the end of phase 3 and is presumed to continue indef-
widely accepted multiphase phenomenological model for corrosion initely. Melchers et al. (Melchers, 2014b) stated that presently there
is insufficient understanding of the precise mechanisms involved in

Fig. 12. General schematic of model for corrosion loss showing the changing behaviour
of the corrosion process as a series of sequential phases (adapted from (Melchers Fig. 13. Corrosion loss model and data fitting for long term corrosion data accessed
(2003b)). from ASTM worldwide corrosion data.
J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62 57

this phase; however, the long term data for pitting corrosion sug- environmental factors included were: temperature, dissolved ox-
gests that it is closely linear with time (Refer Fig. 13). Observations ygen, salinity, calcium carbonate, pH, water velocity and marine
for a variety of steels also suggest that the corrosion rate is largely growth. The probabilistic model divided the corrosion into four
independent of the actual activity levels of SRB and of the type of particular stages: initial corrosion; oxygen diffusion controlled by
steel (Melchers and Jeffrey, 2011; Melchers, 2014b, 2012). corrosion product and micro-organic growth; aerobic activity with
Modelling of the uniform/general corrosion in marine and limited food supply; and anaerobic activity (Melchers, 2003b).
offshore structures is reviewed in the subsequent sections; how- Neither of the previous studies attempted to include the effects
ever, the focus is on modelling the pitting corrosion in marine and of the different operational or environmental factors on the
offshore structures (Melchers, 2004a, 2005a; Vela zquez et al., 2014; corrosion degradation expected through the lifetime of the struc-
Melchers, 2008a; Khan and Howard, 2007; Melchers, 2004b, 2009; tures. Melchers (2005b) stated that in order to improve corrosion
Valor et al., 2007; 2010; Melchers, 2003a; Guedes Soares et al., models it is necessary to not only account for time but also include
2011; Melchers, 2005b, 2006a; Ting et al., 2011; Valor et al., 2013; contributing variables (Melchers, 2005b). They also identified the
Chaves and Melchers, 2014; Melchers et al., 2010; Melchers, main corrosion mechanisms that can be found in steel structures as
2008b, 2003c, 2006b, 2003d, 2006c; Melchers and Jeffrey, 2008c; well as the main environmental factors that affect them (Melchers,
Melchers, 2001b; Rajani and Kleiner, 2001; Katano et al., 2003; 2003a, c). Conversely, other studies tried to extend the previously
Guedes Scares et al., 2005; Mao, 2007; Paul, 2012; Jain et al., developed, time-dependent corrosion models to include the effect
2013; Kolios et al., 2014; Melchers, 2003e). of additional different environmental factors. These studies were
mainly based on statistical analysis of field and experimental data
8.1. Modelling the general corrosion in marine environments (Melchers, 2003a, 2006a, 2003c).
Using literature field data as well as new field observations;
Statistical and stochastic aspects of pitting corrosion were first Melchers (2004a, b, 2003b) calibrated the parameters of multi-
developed in the late 1970s (Mao, 2007). In large-scale engineering phase time-to-corrosion models on mild and low alloy steel under
structures, the measurement of pit depth and frequency is fully aerated immersion conditions. They proposed a phenome-
considered to be time-consuming and expensive. Therefore, only nological model for general corrosion of mild, low alloy steel under
the deepest pits are studied since they are likely to be the cause of near-surface conditions; this was adapted from a model of at-sea
zquez et al., 2014; Valor et al., 2010;
failure in these structures (Vela immersion conditions which had already been proposed
Mao, 2007). The extreme value statistics developed by Gumbel are (Melchers, 2001b). They utilized literature data from the previous
widely used in the application of the maximum pit depth distri- work (Melchers, 2003b, 2001b) and applied a similar probabilistic
butions. Extreme value distributions include three types of framework (refer to Equation (1.7)) (Melchers, 2003d). The cali-
asymptotic distributions for an infinite number of samples: brated parameters were then used to predict the corrosion degra-
dation as a function of time and seawater temperature (Melchers,
Type I : Gumbel distribution FðxÞ  expð  exp½  xÞ (1.7) 2004a, 2004b, 2003b).
Melchers (2006a) proposed examples of mathematical model-
ling for long term general corrosion of structural steels in seawater.
Type II : Cauchy distribution FðxÞ  exp  xK (1.8)
Consideration was given to the early corrosion controlled by oxygen
concentration which then later evolves to anaerobic conditions. The
Type III : Weibull distribution FðxÞ  expð  exp½u  xk Þ model was calibrated using extensive field data received from an
offshore oil platform site located in Haloong Bay, Vietnam, and from
coastal sites along the China Coast (Melchers, 2006a). Furthermore,
where x is a random variable representing the maximum pit depth, Melchers (2006b) proposed the probabilistic model for atmo-
and k and u are constants. spheric corrosion of structural steels in ocean environments
Melchers et al. (Melchers, 2003e) studied the assessment of the (Melchers, 2006b). However, they disagree with some of the as-
remaining safe and serviceable life of deteriorating structures. A sumptions previously made such as that corrosion is the linear
probabilistic model for immersion corrosion loss with time on mild function of time, i.e. that there is a constant corrosion rate and the
and low alloy steels was developed based on the fundamental assumption that the corrosion rate is a monotonically decreasing
physiochemical model (Melchers, 2003a, 2003c). They stated that, function of time (Melchers, 2006b).
for structural reliability assessment using probability theory, the
structural strength at any point in time t can be represented by R(t)
with probability function fR (r,t), where R(t) is a random variable 8.2. Modelling of pitting corrosion in marine environments
and r is a discrete, deterministic value. The generic form of the
proposed model has material loss due to corrosion as a function of Katano et al. (2003) proposed a predictive model for pit growth
time and is expressed by: on underground pipes. They relied on the theory that the pitting
corrosion rate for metal depends on environmental factors. They
cðt; EÞ ¼ bðt; EÞ$f ðt; EÞ þ εðt; EÞ (2.0) established the relationship between pitting depth and environ-
mental factors. This relationship was explored through regression
where c(t, E) is the average depth of penetration from one side of analysis, with pitting depth as dependent variables and on envi-
steel plate (mm); f (t, E) ¼ mean value function; b (t, E) ¼ bias ronmental factors as independent variables. Pitting depth was
function which should be unity when f (t, E) represents c (t, E) expressed as a power of time t.
exactly under all conditions; ε(t,E) ¼ zero mean uncertainty func-
tion; and E ¼ vector of factors which characterize the exposure h ¼ gt a (2.2)
environment, steel composition, and the surface finish factors.
From this analysis Melchers (2003e) stated that the rate of pit where, g and a are constant. From the above relationship, they
growth is not a linear function of time (Melchers, 2003e). Addi- derived a statistical model of pitting depth (y) as a dependent factor
tionally, Melchers (2003c) proposed a similar probabilistic model- and environmental factors (x) as independent factors. A regression
ling based on corrosion mechanics and environmental factors. The model is expressed as:
58 J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62

time, when the super stable pits are introduced the use of extreme
0 1
h  i X
p value distributions (Gumbel distributions) started to become
y ¼ h expðεÞ ε  N 0; s 2
; h ¼ t exp@b0 þ
b j xj A (2.3) doubtful because it was now known that the statistical population
j¼1 of super stable pits are likely to be different from the remaining
pits. Melchers (2005e) recommended the use of normal distribu-
where, a and b are regression coefficient. tions (modelling the probability of occurrences) to represent the
Melchers (2005b) extended the model previously developed extreme pit depth of super stable pitting. Using the structural
(Melchers, 2005e) to include the effect of dissolved oxygen in order reliability system theory, the distributions of the pit depth (for the
to obtain a multiphase, time-dependent pitting corrosion degra- deepest depth) can be expressed as:
dation model incorporating the effect of dissolved oxygen con-
centrations (Melchers, 2005b). Furthermore, Melchers (2005b, c) FXmax ðaÞ ¼ P½Xmax < a ¼ P½all pits xi < a (2.4)
gave consideration to how the previous observations could be used
to represent the effect of water velocity on the previously proposed where, event xi is the pit depth represented as random variable; P
models. They stated that it is essential to investigate the influence [ x i<a] the probability of occurrences; and X is the random vector
of water velocity on early corrosion behaviour; only then could the which hold all component xi. From this analysis, Melchers (2005e)
corrosion rate be correlated with the dissolved oxygen in the early identified that if the probability distributions for the deeper pits are
stages of corrosion. They thereby confirmed that the depth is not an normal, the probability distributions for the extreme pits should
independent factor in marine immersion corrosion of mild steel; also be normal distributions. They further established that these
however, dissolved oxygen, water temperature, and local water probability distributions have more certainty than those estimated
velocity were found to be the main influencing factors (Melchers, by conventional approaches such as Gumbel distributions
2005b, c). (Melchers, 2005e).
Guedes Scares et al. (2005) studied the effects caused by Khan and Howard (2007) proposed statistical methods to
different environmental factors on the pitting corrosion behaviour improve the estimation of degradation rate. They indicated that
of steel plates totally immersed in salt water conditions. They combining the statistical methods with a reliability assessment
proposed a corrosion wastage model based on a non-linear time- would offer a potential for better use of inspection results, and for
dependent function. This model accounts for the effect of various the prediction of the probability of future leaks in offshore pipes as
environmental factors including salinity, temperature, dissolved well as remaining life assessment (Khan and Howard, 2007;
oxygen, pH, and flow velocity (Guedes Scares et al., 2005). Kowaka and Tsuge, 1994). In pitting corrosion, the average degra-
Melchers (2005a) studied the statistical characteristics of pitting dation rate does not represent the real status of material degra-
corrosion, represented by the extreme value distribution ‘Gumbel’. dation due to the nature of pit initiation and to its usually difficult
Since then, considerable progress has been made in the rational location. Hence, for pit corrosion modelling purposes, focus is given
description and mechanistic modelling of individual pit initiation to establishing the relationship between the maximum pit depths
and early pit growth. Regardless, the modelling for growth in pit in the given exposure. Khan et al. (Khan and Howard, 2007) rec-
depth tends to be largely empirical and laboratory observations are ommended a use of extremes value statistics in pitting corrosion to
unlikely to be representative of field conditions. In particular, ex- investigate extreme values and proposed linear, power law and
periments cannot include the precise effect of bacterial activity in logarithmic extreme value models (Khan and Howard, 2007;
pitting corrosion (Melchers, 2005a, 2005b, 2005e). They proposed Kowaka and Tsuge, 1994).
the phenomenological model for pit growth and extreme value of
Linear model : x  x0 ¼ kðT  Ti Þ (2.5)
pit depth using 7 years of field data. From this analysis, they stated
that only those pits that initiate immediately upon exposure, and
then grow as stable pits, can become extreme depth pits. Distri- Power law model : x  x0 ¼ kðT  Ti Þn (2.6)
butions of all pit depths indicate the probability of occurrences of
maximum pit depth for short and long marine immersion condi- Logarithmic law model: x  x0 ¼ k logðT  Ti Þ (2.7)
tions. A Gumble distribution is commonly adopted as extreme valve
distributions because it provides for less conservative probability where, x0 is the threshold depth of degradation (pit depth) at
estimates (Melchers, 2005a, 2005b, 2005e). initiation time Ti; x is the measured depth at time T; and k is the
Melchers (2004a) studied the variability of maximum pit depth pitting corrosion rate. Depths exceeding x0 would grow, whereas
of mild steel specimens subjected to marine immersion. Here the depths lower than the x0 may fail to grow (Khan and Howard, 2007;
authors considered the effect of anaerobic conditions for immer- Kowaka and Tsuge, 1994). Khan and Howard (2007) and Kowaka
sion pitting in mild steel. The data was calibrated and maximum pit and Tsuge (1994) provided a brief list of the applicable distribu-
depth was shown to be a function of seawater temperature tion types for localized degradation.
(Melchers, 2004a, 2005e). When considering the multiphase Melchers (2008b) proposed an extreme value analysis for long
phenomenological model, it was found that pitting was most se- term marine pitting corrosion of steel affected by corrosive agent
vere when widespread anaerobic conditions were established at sulphate reducing bacteria (SRB). They argued that the conven-
the corroding surface. It was acknowledged that the Gumbel dis- tional use of Gumbel distributions is no longer appropriate for
tributions plot that was used previously for expressing pit depth deriving extreme value statistics for maximum depth of pits in
variability was combined with a simple power function. However, pitting corrosion (Melchers, 2008b). They stated that conventional
they reported that the pit growth is a more complex function use of Gumble distribution does not consider either stable or metal
involving several stages such as pit initiation, metastable pit and stable pit growth.
stable pit (Melchers, 2004a, 2005a, 2003b). SRB is the main corrosive agent for longer term pitting corro-
Melchers (2005e) then introduced super stable pit growth sion. Modelling of long term pitting corrosion is rather difficult
which initiates immediately after exposure and grows without because of the lack of sufficient data in one exposure location hence
significant metastable activity (Melchers, 2005e). They reported the use of Frechet extreme value distributions is appropriate as it
that, as a result of super stable pit there is likely to be a high degree combines the data from different exposure times (Melchers,
of dependency among the depths of extreme (deepest) pits. By this 2008b). Melchers (2008b) proposed a statistical model for longer-
J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62 59

term, maximum pit depth which considers the effect of anaerobic 9. Challenges
There are many studies conducted on the mechanism, field-
xðt; TÞ ¼ C½eðt; TÞ=rðtÞt (2.8) testing and laboratory testing in the field of pitting corrosion;
however, there is no development of detailed studies for failures in
where, e(t,T) denotes the rate of supply of nutrients to the corroding offshore structures due to pitting characteristics. One critical
surface; t is the time elapsed since the commencement of overall requirement is the investigation of how pitting characteristics, such
anaerobic activity; and T is the mean water temperature. Also, if r(t) as rate, depth, density and distance, can cause a structural failure.
is the proportion of the surface covered by pits, then the rate of Previously, empirical and statistical degradation models were
supply of nutrient per pit at any time t is proportional to e(t,T)/r(t) developed by either fitting field or laboratory data. However these
(Melchers, 2008b). models, even though useful for specific site or operating conditions,
Mohammad et al. (2012) proposed a prediction model of pitting still carry high uncertainty. Currently, several aspects of current
corrosion characteristics using Artificial Neural Networks (ANNs). knowledge on pitting corrosion are deficient and require further
They used a pre-corroded steel specimen and immersed it in cor- investigation. Some of these challenges have been identified and
rosive ferric chloride solutions in different concentrations. It was listed below:
found that the ANNs results agreed well with those obtained from
laboratory tests. They further stated that, by increasing the corro-  Structural failures due to pitting characteristics such as pit
sive concentration with extended immersion duration, it resulted depth, pit rate, pit density and interfacial distances between pits
in an increase in pitting density and pitting depth (Mohammad is not fully understood; better understanding of these charac-
et al., 2012). teristics is crucial.
Valor et al. (2013) proposed Markov chain models for the sto-  The process of pit propagation and the rate of pit growth are not
chastic modelling of pitting corrosion (Valor et al., 2007, 2010, fully understood.
2013). Two different models of pitting corrosion were proposed:  Precise prediction mechanism of long term anaerobic corrosion
1) a continuous-time, nonhomogeneous linear growth Markov requires essential study in order to develop a failure model.
process was used to model external pitting corrosion in under-  The total depth of pit and its rate of growth are of concern in
ground pipelines, and 2) the distribution of maximum pit depths in marine and offshore structures; the precise mechanics of pit
pitting experiments was modelled combining pit initiation and pit growth mechanism needs to be developed.
growth processes (Valor et al., 2013).  There is still uncertainty in the pit depth measurement; a pre-
Velazquez et al. (2014) proposed a methodology for probabilistic cise pit depth measurement technique needs to be developed.
mathematical modelling of the pit initiation process and its depth-  There is no precise way to observe the depth of deepest pit
of-growth process. Two stochastic models were developed: 1) the without destroying the specimen; this needs to be resolved.
Poisson process which was used to modal pit initiation, and 2) the  Several factors that can affect pitting corrosion in marine envi-
Gamma process to model the pit depth-growth (Vela zquez et al., ronments have been established in this paper; however, the
2014). After obtaining the pit depth, the maximum pit depth was effect of these factors on pit growth is still not fully understood.
studied using Block Maxima (BM) and the Peak-Over-Threshold  Mathematical relationship for the factors that affect pitting rate
(POT) methods. such as surface wetting, humidity, oil in the water, suspended
Velazquez et al. (2014) described the pit initiation as Non- solids etc. is not yet understood.
Homogenous Poisson Process (NHPP). According to NHPP, pit  The influences of pH on pitting corrosion under dynamic con-
initiation time was assumed with intensity function lm(t), where l ditions may also be studied and the role of metal defect on pit
is defined as the mean pit density per area unit and m(t) can be an initiation needs further analysis.
arbitrary function. Hence, the expected number of pits in given  Another possible expansion is the study of the repassivation
time t can be expressed as: mechanisms, including super saturation of the solution, pre-
Zt cipitation of the passivating phase and subsequent increase in
EðNðtÞjl mðsÞ ¼ lðmtÞ (2.9) the electrical resistance of the pore.
 In this paper, several conventional and recent methods for
modelling of pitting corrosion are discussed to evaluate the rate
The pit growth was modelled using the Gamma process which is of corrosion; however, there is a need to find an appropriate
a continuous-time stochastic process with independent gamma method of estimating the corrosion rate and how it develops
increments. The Gamma probability density function can be with time.
expressed by:
Provided that all factors that can cause pitting corrosion are
expðy=qÞ known e as based on the mechanism of corrosion and by using risk
Gað$jk; qÞ ¼ yk1 qk (3.0)
GðkÞ assessment methodologies e a probabilistic risk assessment can be
applied to predict and evaluate future failure due to pitting
where k is shape parameter which controls the rate of the jump; q corrosion.
the inverse of the scale parameters which controls the jump sizes;
Gað$jk; qÞ is the Gamma probability density function; and y > 0 and 10. Conclusion
Z ∞
GðkÞ ¼ t k1 expðtÞdt is the Gamma function.
t¼0 Pitting corrosion is a complex but important problem that is at
zquez et al. (2014) reported that the use of statistical
Finally, Vela the root of many structural and system failures. It has been studied
simulations in the modelling pitting corrosion is significant as to be for many years however crucial phenomena remains unclear. The
familiar with different pit characteristics such as pit depth, pit aim of this paper was to identify and evaluate the parameters that
density and rate of pitting. They ensure that the NHPP process can affect pitting corrosion in marine and offshore environments. This
determine the evolution of the total number of pits and, likewise, paper has reviewed and discussed the mechanisms and charac-
the Gamma process for the pit growth (Vela zquez et al., 2014). teristics of pitting corrosion, several factors that affect its
60 J. Bhandari et al. / Journal of Loss Prevention in the Process Industries 37 (2015) 39e62

development, as well as identification methods and modelling Australian Maritime College (AMC).
techniques. Based on the literature reviewed it is clear that pitting
corrosion is a stochastic, probabilistic phenomenon that requires References
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