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Corrosion Behaviour of Mooring Chain Steel in Seawater
Xiaolong ZHANG1, Nanni NOEL1, Gabriele FERRARI1, Martijn HOOGELAND2
1Endures BV, Bevesierweg 1 DC002, 1781CA Den Helder, The Netherlands,
[email protected], [email protected], [email protected] 2TNO, Van Mourik Broekmanweg 6, 2628 XE Delft, The Netherlands,
Abstract
Failures of mooring lines on floating production, storage and offloading systems (FPSOs) raise
concern to the offshore industry. Localized corrosion of mooring chain is regarded as one of main
failure mechanisms. The project of Localized Mooring Chain Corrosion (LMCC) is aiming at studying
the mechanism of local corrosion on mooring chain steel in seawater and searching for corresponding
mitigation methods. As part of the LMCC project, the corrosion behavior is studied of chain steel in
artificial seawater and artificial seawater containing microorganisms which were collected from the
application site and cultured in the Endures lab.
The corrosion behavior of chain steel was studied using polarization and impedance measurements.
The microstructures of the chain steel and corrosion morphology were investigated using SEM and
epifluorescent methods.
Localized corrosion has been found for the steel in the seawater. Inclusions, such as MnS found in the
chain steel, play an important role in the local corrosion initiation.
Key words: localized corrosion, mooring chain, MIC, SEM
Introduction
Mooring chains are widely used to fix a floating production, storage and offloading (FPSO)
system. Marine corrosion, in particular local corrosion, combined with mechanical loading is
the main reason for mooring chain failures [1-2]. The LMCC project (Localized Mooring
Chain Corrosion) has been set up to investigate the causes of local corrosion, ranging from
electrochemical to microbial behaviour in combination with the chain link surface conditions
and environmental effects.
The aim of this project is to find the mechanism of local corrosion, especially with respect to
the effect of surface condition of the steel and the interaction between microbial and
electrochemical corrosion. In this paper, the description is given of the establishment and
optimization of the electrochemical/microbial test methods to study the corrosion behavior of
mooring chain steels in seawater with and without micro-organisms.
Investigation into the mechanism of local corrosion was carried out by exposing samples of
mooring chain steel R4 in seawater in the laboratory. During and after exposure
electrochemical and microstructure analyses were performed. Since microbial induced
corrosion (MIC) is expected to be one of the main causes of local corrosion, tests were also
run with addition of microorganisms cultured in the laboratory. These Microorganisms,
collected at Makassar Strait (Indonesia) contain different types of corrosive organisms.
The corrosion resistance of the R4 steel was investigated using potentiodynamic polarization
(PDP), linear polarization resistance (LPR) measurements and electrochemical impedance
spectroscopy (EIS).
2
Microbial attachment and biofilm formation were studied using fluorescent dye and
epifluorescent microscopy. The surface microstructures and compositions were analyzed
using SEM and EDS, the corrosion morphology using photo-microscopy.
Experiment description
The experiment is designed to investigate local corrosion and how that is influenced by
micro-organisms. This means that electrochemical measurements and microbial growth
needed to be combined. The set-up managing both aspects is described below. For practical
relevance, chain steel material as served in the North Sea is used and the bacteria culture as
found on a representative offshore site has been used. Various methods having been applied
to measure and analyze the results are described below.
Experimental set-up
In Figure 1 two vessels for test exposure are shown. Each vessel contains 2 identical steel
samples (duplicates) and a counter electrode. A reference electrode (saturated Ag/AgCl) was
inserted in just before electrochemical measurements and taken out after the measurements.
The reference electrode was always cleaned in alcohol before to be inserted in a glass bottle
through the hole in the rubber cover. The vessels were closed during the tests. In Table 1 an
overview of the test set ups, including samples, electrolytes and test period is given.
Description of the abbreviations follows in the next sections.
Figure 1: Exposure vessels.
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Table 1: Experimental conditions
Samples SW SW+ Bacteria (MIC) Test period (day)
P1-2 PDP
B1-2 LPR + EIS 28
B3-4 LPR + EIS 28
BS 5-6 LPR 21
BS 8-9 LPR 7
BS 10 -11 LPR 21
BS 12 -13 LPR 28
BS 14-15 LPR 7
Samples were exposed in stagnant electrolyte (600 ml) at room temperature. The pH of the
solutions at the start was 8.0. Different test periods were designed to study how biofilm and
corrosion develop with time, e.g. tests for samples BS8-9 and BS15-16 were stopped after
exposure for 7 days and they were taken out for analysis.
Materials
Steel samples were cut from a chain link (R4, Φ120 mm) served in North Sea at depth of 85
m for 13 years, provided by a project partner. The dimensions of steel samples were 2.5×2
cm. A copper wire was connected with the steel for electric connection. Steel samples and
connections were embedded in epoxy resin and polished using sand paper up to 1200 grit.
Then the samples were cleaned ultrasonically in alcohol and dried in blowing air.
Electrolyte
In order to be assured that seawater (SW) was free of organism, low-nutrient loaded artificial
seawater was used for exposure of samples without MIC contribution. The artificial seawater
was freshly prepared using chemicals presented in Table 2Table 2.
Table 2: Chemical concentration (g/l) in the artificial seawater. NaCl MgCl2 CaCl2 Na2SO4 KCl NaHCO3 KBr H3BO3 NaF SrCl2 Yeast Lactate
23.93 5.07 1.15 4.01 0.68 0.197 0.099 0. 03 0.01 0.14 0.01 4.2 ml
For investigating the susceptibility to MIC, microorganisms collected at Makassar Strait and
cultured in the laboratory were added to the artificial seawater (SW+bacteria (MIC)).
Bacteria got an additional nutrient supply of 0.004 g FeSO4 ·7H2O, 0.30g Na3C6H5O7 ·2H2O
and 0.10 g C6H8O6 dissolved in 10 ml deionised water which was filter sterilized before and
added through a 0.2 µm pore size filter.
Once a week 250 ml of the medium was exchanged with fresh media to supply enough
nutrients for a continuous microbial growth.
Inoculation of microorganisms
Different groups of corrosion relevant microorganisms have been detected from mooring
chain environment in Makassar Strait and were enriched under laboratory conditions.
Enriched bacteria were grown in specific media to keep them active until the start of the
experiment. A total amount of 6×106 cells/ml were added to the vessel (counted using a
Thoma counting chamber).
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Electrochemical measurements
The PDP measurements were performed in artificial seawater (without containing yeast and
lactate after holding at open circuit potential (OCP) for 1 hour. The cell was open to air and at
20 ˚C. The polarization curves were measured by scanning the potential, started at -0.25 V vs
OCP and ended at 0.35 V vs OCP. The scan rate was 0.167 mV/s.
The LPR and EIS measurements were carried out after 7, 14, 21 and/or 28 days of exposure
with the following experimental procedure:
- OCP measured during 1800 s.
- LPR, ±10 mV vs. OCP; scan rate, 0.167 mV/s.
- EIS was measured using a.c., amplitude 10 mV, frequency range, 0.01 – 100000Hz.
Surface analysis
Epifluorescence microscopy After exposure test, samples were stained by a fluorescent dye to discriminate cells in active
(green) or inactive (red) cells. Stained microbial cells were made visible by exciting the
DNA/stain with ~490 nm blue light and observing the emitted green or red fluorescence under
the microscope. In case of no bacteria, no fluorescence will be detected.
Scanning electron microscopy (SEM)
The sample surfaces were cleaned first in 15% HCl solution with addition of 0.5%
hexamethylenetetramine for 10 minutes, then rinsed in tap water, ultrasonically in alcohol for
2 min. and finally dried in blowing air. The topography for the exposed samples was analysed
using optical microscopy.
Inclusions in the steel and the compositions were analysed using SEM in combination with
Energy-dispersive spectroscopy (EDS). The SEM was executed using a Jeol JSM 5800LV
instrument equipped with a Noran instrument EDS system.
Results
Polarization measurements
Figure 5 show polarization curves in semi-logarithmic plots for both polished samples P1 and
P2. Small (Tafel) slopes in the anodic polarization parts and large slopes in the cathodic
polarization parts are observed, at approximately 50 mV more active than the corrosion
potentials. It means that the corrosion is controlled by the cathodic reactions for the steel in
the seawater.
Corrosion current density icorr can be calculated from the Tafel slopes in the polarization
curves using Stern-Geary equation [3],
icorr = ba×bc / (2.3·Rp·(ba+bc))
where ba and bc are anodic and cathodic slopes, respectively, in the polarization curves; Rp is
the polarization resistance.
The general corrosion rates can be calculated from the corrosion current densities using
equation,
CR = 3267·(icorr · Meq)/ρ (mm/y)
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where icorr is current density (A/cm2), Meq equivalent mass (g), ρ density of the materials
(g/cm3).
The corrosion potentials and corrosion current densities are presented in Table 3. The average
corrosion rate is about 0.3 mm/y. The corresponding corrosion resistance is about 1030
Ω·cm2.
Table 3: Corrosion potentials and corrosion rates for the polished samples in seawater.
Steel Ec (V) ic (µA/cm2) ba (mV/dec) bc (mV/dec) CR (mm/y)
R4 (p1) -0.64 26 68 618 0.30
R4 (p2) -0.63 25 65 676 0.29
10-7 10-6 10-5 10-4 10-3 10-2-1.00
-0.75
-0.50
-0.25
I (Amps/cm2)
E (
V v
s A
g/A
gC
l)
p1.corp2.cor
Figure 2: Polarization curves for the polished samples in artificial seawater (open to air) at
20 ˚C.
Corrosion properties
Figure 3 shows the OCP values as a function of time for the R4 steel in the different
electrolytes. The OCP values for the samples in the seawater without bacteria are around -
0.6 VAg/AgCl. With bacteria, the OCP values moved from -0.67 to -0.6 VAg/AgCl within 7 days.
It suggests that the corrosion systems are not stable within one week.
Figure 3: OCP values as a function of time measured for R4 steel samples in seawater with
and without bacteria.
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Figure 4 shows a typical linear polarization (LP) curve for a sample (BS5) in SW exposed for
14 days. The linear polarization resistance (Rp = ΔE/ΔI) was calculated from the line in ± 5
mV near the corrosion potential (zero current).
Figure 5 shows a typical LP curve for a sample in the SW+bacteria (MIC). The linearity is not
so good near the corrosion potential, indicating that the general corrosion principles are not
valid in these conditions. In the presence of bacteria, biofilms form at the sample surfaces,
which exhibits capacitive behaviour.
Current
Po
ten
tial
Corrosion rate analysis
-40 -20 0 20 40
µA
-0.62
-0.60
-0.58
V
Figure 4: A typical linear polarization curve for a sample (BS5) in SW, exposed for 14 days.
Current
Po
ten
tial
Corrosion rate analysis
-40 -20 0 20
µA
-0.64
-0.62
-0.60
-0.58
V
Figure 5: A typical polarization curve for a sample (BS10) in SW+bacteria (MIC), exposed
for 14 days.
Figure 6 shows the polarization resistance after various exposure times measured for R4 steel
samples in seawater with and without bacteria. The polarization resistance for the samples in
the seawater without bacteria (SW) is increased from 2.4 kΩ·cm2 to 3.6 kΩ·cm2, while for the
samples in the seawater with bacteria (MIC) decreased from 10 kΩ·cm2 to 1 kΩ·cm2 in 21
days. This indicates that the sample surfaces exposed to seawater with bacteria became more
active in 3 weeks, compared to these exposed to seawater only.
7
In order to better study the corrosion resistance, EIS measurements were performed for
samples B1-4. The OCP values for the samples varied around -0.62 V (±0.05 V).
Figure 7 shows the Bode impedance plots for the samples exposed to SW and SW+bacteria
(MIC) for 28 days. The amplitude of the impedance for the samples (B3-4) in SW is higher
than in the SW+bacteria (B1-2 MIC) at low frequency side (0.01 Hz). The phase peaks shifted
to the low frequency side for the samples in the SW with bacteria, which suggests that the
capacitive behaviour is significant or includes diffusion effect at lower frequency side.
Figure 6: Polarization resistance measured by LPR as a function of time measured for R4
steel samples in seawater with and without bacteria.
10-2 10-1 100 101 102 103 104 105100
101
102
103
Frequency (Hz)
|Z| (
Ohm
)
B1 (MIC) day28B2 (MIC) day28B3 (SW) day28B4 (SW) day28
10-2 10-1 100 101 102 103 104 105
-100
-75
-50
-25
0
25
Frequency (Hz)
thet
a
Figure 7: Bode impedance plots for samples B1-4 exposed to SW and SW+bacteria (MIC) for
28 days.
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The impedance data were fit with an equivalent circuit presented in Figure 8. The capacitive
elements are substituted by constant phase elements (CPE) Qc and Qdl. The impedance of a
CPE can be calculated by the equation
ZCPE = Y0-1 (jω)-n
where Y0 is the admittance constant of the CPE, ω the angular frequency and n the CPE
exponent, n = (π/2) ( is the constant phase angle of the CPE). When n = 1, the CPE
becomes a pure capacitor [5].
The fit results are presented in Table 4. The fit results show that the resistance attributed to
the surface layer (Rcp) is very small, compared to the charge transfer resistance Rct. Thus the
polarization resistance is in the same order of the Rct. After exposure for 28 days the
corrosion resistance is approaching the same level (3.6 kΩ·cm2) for the samples in SW and in
SW+bacteria (MIC) (Figure 9).
The steel in SW+bacteria has a larger capacitance (C = Y01/n·R(1-n)/n, [6]) of the double layer
than in SW, which suggests that either its corrosion area is larger, or the double layer
thickness is smaller.
Rel: electrolyte resistance,
Qc: constant phase element for the oxide layer,
Rcp: pore resistance,
Qdl: constant phase element for the double layer,
Rct: charge transfer resistance.
Figure 8: equivalent circuit used for fitting the impedance data.
Table 4: Parameters and fit results of the impedance data using an equivalent circuit, R in
Ω·cm2 and Y in (sn·Ω-1·cm-2).
Sample Time(day) Y1 n1 Rcp Ydl n2 Rct χ2 (x10-4)
B1 (MIC) 14 0.00326 0.893 15 0.00246 0.899 3211 0.6
21 0.00891 0.869 17 0.00211 0.9998 4329 1.2
28 0.01239 1 3 0.01848 0.868 3625 3
B2 (MIC) 14 0.00104 1 3 0.00222 0.808 3654 0.9
21 0.00956 0.931 4 0.01844 0.932 4217 8
28 0.01600 0.997 7 0.01140 0.814 4478 1.8
B3 (SW) 14 0.00036 0.88 39 0.00010 0.965 7826 4.5
21 0.00034 0.932 14 0.00036 0.922 5494 8
28 0.00053 0.94 10 0.00053 0.93 3487 5.9
B4 (SW) 14 0.00033 0.872 12 0.00030 0.943 5513 5.2
21 0.00034 0.922 12 0.00055 0.931 4223 4.4
28 0.00063 0.931 11 0.00066 0.93 3569 3.6
9
Figure 9: Charge transfer resistance values as a function of time measured for R4 steel
samples in seawater with and without bacteria.
Epifluorescence microscopy
After 7 days of incubation microorganisms were regularly found on the metal coupon surface
(Figure 10). Biofilms covered the damaged area. Active cells (green) were mostly found in
and around the pits. The outer part of the biofilm is inactive because the surface was often
covered by red (inactive) cells. This means that microorganisms initially attached to the entire
surface, but could only grow in limited areas where they form a biofilm. These preferred spots
for microbial attachment may contain the right (metallic) nutrients to encourage the growth of
micro-organisms or deliver attractive sites for attachment. In such locations they play a role in
the local corrosion process.
Figure 10: Micrograph of metal coupon (BS9) after 7 days of exposure. Green cells indicate active cells whereas red cells show inactive or damaged cells.
Corrosion morphology
After exposure for 7 days samples BS 8-9 and BS 14-15 were taken out for surface analysis.
Sample BS 15 is shown in Figure 11. Localized corrosion is visible on the up-left corner,
though large area of the sample BS15 showed general corrosion or micro-pits, and little
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corrosion on the up-right corner in the image, where the original polishing pattern can be
recognized.
For the sample BS9 (Figure 12) exposed to SW + bacteria for 7 days, many small pits and a
few big pits (about ϕ 0.6 mm) are found. The maximum depth is about 13 µm.
Figure 13 shows an image for the sample BS6 exposed to seawater for 21 days after cleaning.
Local corrosion spots (macro pits) are visible at the sample surface. The maximum depth of
the pits is 60 µm.
With addition of bacteria in SW, typical localized corrosion due to MIC was observed (Figure
14). The corrosion boundary is in a round shape. The repeated tests showed similar corrosion
morphology for the samples B1-2 exposed to SW+bacteria (MIC) for 28 days. Cross section
view shows that the pit depth is as high as 63 µm (figure 15), which corresponds to 0.82
mm/y.
Figure 11: Sample BS15 exposed to seawater for 7 days (after cleaning the surface). Local corrosion attack was found near the up-left corner and almost no corrosion near the up-right corner in the image.
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Figure 12: Sample BS9 exposed to SW + bacteria for 7 days (after cleaning the surface). Many small pits (diameter <0.1mm)(marked in yellow) and a few big pits (diameter >1 mm) (marked in red) were found.
Figure 13: Sample BS6 exposed to seawater for 21 days. A few big pits were found.
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Figure14: An image for the sample BS13 exposed to seawater with bacteria for 28 days (after cleaning the surface). Half of the surface area was corrosion attacked.
Figure 15: Cross section view at two pits for sample B2 after exposure to the SW + bacteria
for 28 days.
Inclusions in the steel
Inclusions are found in the steel. Figure 16 shows a backscatter image at a cross section and
EDS plots at a particle and nearby area for an exposed sample. This is an MnS particle
determined by the composition analysed using EDS (see Table 5). This particle is about 20µm
in length and 5 µm in width.
TiVCr enriched particles were also found in this steel sample (see Figure 17 and Table 6).
These particles are known for initiating local corrosion due to their potential difference with
regard to that of the surrounding steel matrix.
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Figure 16: An inclusion (backscattering image (a), EDS plots in the position 1 (b) and at position 3 (c) for an exposed sample (R4) after exposure to seawater without bacteria for 1 week.
Table 5: Element percentage (wt. %) measured at positions in Figure 16 (a).
Si S Ca Cr Mn Fe Ni
Position 1 6.2 38.0 0.2 53.2 2.4
Position 3 0.5 0.4 2.0 1.2 95.3 0.6
Figure 17: An inclusion (backscattering image (a), EDS plots in the position 1 (b) and at
position 3 (c) for an exposed sample (R4) after exposure to seawater without bacteria for 1
week.
Table 6: Element percentage (wt.%) measured at positions in figure 17 (a).
Element C Mg Al Si S Ti V Cr Mn Fe
Point 1 9.1 0.1 1.0 75.0 8.6 3.5 2.7
Point 2 0.2 0.3 0.5 24.6 1.7 1.8 1.2 69.7
Discussion
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Several samples have been exposed to seawater and seawater with bacteria to study the local
corrosion and find suitable analysis methods for the local corrosion phenomena associated
with these conditions.
In all cases pits are found in the exposed steel surfaces. Distinction can be made between two
different types of pits:
- Relatively small pits which occur on large areas of the surface. According to the
literature local attacks first occur in places at the boundaries of the matrix because of
inclusions and/or (small) differences in potential. These “micro” pits are formed very
quickly after immersion. Most of these pits reach the depth of 100-200 µm and then
stop to propagate [4]. Pits can continue their growth only under a layer of corrosion
products or biofilms. Corrosion is a combination of anodic and cathodic reactions; the
observed pits are the locations where anodic reactions occur, the rest of the surface
being the cathodic part. Sometime after the start of exposure, corrosion products are
formed in the pits increasing the electrical resistance and inhibiting the access of
oxidizing agents. Then the reactions stop and start elsewhere, but with lower driving
forces.
- A limited number of clearly larger pits is found on the surface of all samples. In
contrast to the small pits described above, these pits are found in limited locations and
cannot be attributed to the normal start of the corrosion process as described above.
Relatively large inclusions are found in the surface of these steel (MnS and TiVCr, 5-
20 µm); inclusions are known to cause local attack. Therefore it is obvious to establish
a link between the inclusions found and the large pits.
The important question is if the “large” pits will propagate because of MIC or other local
causes as for example oxygen depletion (“crevice corrosion”). In this work it is already shown
that active organisms preferentially settle in the neighbourhood of pits indicating their
possible role in the corrosion process. But also exposure of coupons without bacteria
indicated the mentioned formation of pits and the underlying corrosion mechanism needs to
be clarified.
In presence of micro-organisms, OCP shows a large scatter during the first days of exposure.
This has to be attributed to irregular attachment of the organisms at the surface and formation
of biofilm which disturbs the balance of electrochemical reactions. After 2 to 3 weeks all
samples reach a stable value of circa -0.6 VAg/AgCl which is usually measured for this steel in
seawater.
The linear polarization resistance Rp is relatively stable during exposure to SW in absence of
microorganisms. In the closed system the corrosion rate is one third of that in an open system.
The value 3.6 kΩ·cm2 corresponds with circa 0.1 mm/y corrosion rate for this steel in
seawater, in case general corrosion is assumed. On the other hand in presence of
microorganisms the Rp decreases with time. In all cases good reproducibility was found, but
questions were raised about the meaning of the Rp in case of local corrosion, subject of this
study. This parameter and the way to measure it is completely based on the theory of uniform
corrosion. Pits were found in all samples, that means local corrosion. Therefore, the
representative area is not clear, hence the local corrosion rate cannot be established via Rp.
Moreover, in the presence of microorganisms, biofilms are formed on the surface. Results of
epifluorescence microscopy show local concentrations of active organisms (near pits), which
implies also local biofilms. Biofilms can include elements which contribute to the corrosion
mechanism, but can also function as a barrier to oxygen. One mechanism of MIC is the
oxygen differential cell formed under the biofilm.
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The reason of applying OCP and LPR in this investigation is that these techniques are
relatively easy to perform and therefore suitable to be used for in situ monitoring. However,
LPR brings error due to nonlinearity when biofilms are present at steel surface. To better
understand the actual corrosion mechanism it is necessary to use EIS to discriminate the
different corrosion behaviour. The polarization resistance measured by EIS is approaching to
3.5 kΩ·cm2 in 28 days. The capacitance for the steel in the SW with bacteria is larger than in
SW without bacteria. This could be due to a larger corrosion area (see figure 14). Thus EIS
gives more information about the surface conditions, though data fitting needs more
experience. Next to EIS measurements, a detailed pit analysis is also required.
Results of this study, in particular these of the surface investigation after exposure, prove that
surface properties of the steel have an essential role in the start of local corrosion attack. From
SEM analysis, local inclusions have been found. These local corrosion cells are likely onsets
of local corrosion. For future work, it is necessary to continue the investigation with the chain
steel prepared in different stages of the production. Once the underlying mechanisms are
verified, the possible mitigation measures can be postulated.
Conclusions
Preliminary results on the corrosion behaviour of this R4 steel in seawater:
Localized corrosion has been found as well in absence as in presence of bacteria.
Inclusions MnS and TiVCr have been detected in the R4 steel. These inclusions have
influence on the local corrosion attack.
With addition of bacteria already after 7 days of incubation an active biofilm has been
detected on the surface of the coupons with favoured locations in and around the pits.
Localized corrosion rate is as high as 0.82 mm/y in the SW in the presence of bacteria.
Acknowledgements
This work was done under a TKI JIP project LMCC with the partners Bluewater, SBM, Bumi
Armada, SOFEC, Asian Star, Franklin, Boskalis, Corrosion, ABS and DNV-GL. The authors
acknowledge the work partners for the financial support, materials supply and fruitful
discussion.
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