metals
Article
Failure Analysis of Duplex Stainless Steel for Heat Exchanger
Tubes with Seawater Cooling Medium
Husaini Ardy *, Thomas Albatros and Afriyanti Sumboja
Citation: Ardy, H.; Albatros, T.;
Sumboja, A. Failure Analysis of
Duplex Stainless Steel for Heat
Exchanger Tubes with Seawater
Cooling Medium. Metals 2023, 13,
1182. https://doi.org/10.3390/
met13071182
Academic Editors: Yanxin Qiao,
Zhibin Zheng and Lanlan Yang
Received: 20 May 2023
Revised: 22 June 2023
Accepted: 23 June 2023
Published: 25 June 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Metals 2023, 13, 1182. https://doi.org/10.3390/met13071182
Materials Science and Engineering Research Group, Faculty of Mechanical and Aerospace Engineering, Institut
Teknologi Bandung, Bandung 40131, Indonesia; thomasalbatros137@gmail.com (T.A.); sumboja@itb.ac.id (A.S.)
* Correspondence: husaini@itb.ac.id
Abstract: The present paper describes a study case of the failure investigation of duplex stainless steel
(UNS S31803) on the tube and tube sheet sections of BEM TEMA-type shell and tube heat exchanger
with seawater as the cooling medium. The heat exchanger’s shell design pressure was 22.6 MPa at
422 K, and the tube design pressure was 1 MPa at 339 K. Although UNS S31803 offers high strength,
high resistance to chloride-induced SCC, and high resistance to pitting attack in chloride environ-
ments, the heat exchanger in this study experienced some material degradation after 28 months of
use; 102 out of 270 tubes failed, 26 tubes leaked and were plugged on both sides, and scale plugged
76 tubes. The examination in this study case revealed the formation of white-colored biofilm inside
the tubes; XRD examination revealed that the film contained CaCO3 . Using microstructural exami-
nation on the inner surface of the tube, the austenite grains were shown to have been preferentially
attacked; this phenomenon is typical in duplex stainless steel which fails due to crevice corrosion.
According to the examination result, the failure in this case was caused by crevice corrosion between
the substrate and surface deposits that was enhanced by microbiological-induced corrosion (MIC).
Recommendations to avoid similar failures are also suggested in this paper.
Keywords: microbial induced corrosion; failure analysis; heat exchanger failures; crevice corrosion;
seawater corrosion
1. Introduction
Material degradation should be considered in power plants, chemical processing,
and similar industries. Material degradation is a decrease in the ability or properties
of a material, either physically or mechanically, over time due to mechanical, thermal,
or electrochemical loading. Degradation on the material’s surface can take the form of
corrosion and wear. Corrosion is the process of a metal reverting to its thermodynamic state;
for most materials, this means the formation of oxides or sulfides from which they originally
started when extracted from the earth before being refined into valuable engineering
materials. Corrosion in aqueous solutions is the most common of all corrosion processes.
Industry’s water, seawater, and various process streams provide an aqueous medium
where corrosion can occur [1]. Seawater is used for various industrial activities such as
transport, exploration of natural resources, power production, and water supply. Seawater
is a highly corrosive environment and is still challenging for corrosion experts; in some
tests, natural seawater is used as an electrolyte. The main factors that make seawater such a
corrosive fluid are divided into two groups: biochemical (oxygen, carbonate, salts, organic
compounds, biochemical activity, and pollutants) and physical (temperature, flow velocity,
potential, and pressure) [2].
Heat exchangers facilitate heat exchange between two fluids at different temperatures.
They are used in many engineering applications, such as power plants, chemical processing
systems, food processing systems, and waste heat recovery units. Air preheaters, econo-
mizers, evaporators, superheaters, condensers, and cooling towers used in a power plant
https://www.mdpi.com/journal/metals
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Metals 2023, 13, 1182 2 of 15

preheaters, economizers, evaporators, superheaters, condensers, and cooling towers used

in a power plant are a few examples of heat exchangers [3]. The selection of materials for
a are
heat exchanger
a few examples must consider
of heat the operating
exchangers [3]. Theparameters,
selection of cost and reliability,
materials physical
for a heat exchanger
must consider
properties (highthe heatoperating parameters,thermal
transfer coefficient, cost andexpansion
reliability,coefficient),
physical properties
mechanical (high heat
prop-
transfer
erties coefficient,
(tensile strength,thermal
creep expansion
resistance,coefficient),
fatigue limit, mechanical properties (tensile
fracture toughness), strength,
and corrosion
creep resistance,
resistance. Because fatigue
manylimit,
factorsfracture toughness),the
are considered, andmaterial
corrosion resistance.
used for heatBecause
exchangersmany
factors are considered, the material used for heat exchangers
varies, including monel, duplex, super duplex, Hastelloy, and Inconel [4,5]. varies, including monel,
duplex,Typesuper
2205 duplex,
DSS, or Hastelloy,
UNS S31803, andisInconel [4,5]. as a standard duplex stainless steel
categorized
with aType low 2205
carbon DSS, or UNS22%
content, S31803, is categorized
chromium, as a standard
5% nickel, duplex stainless
3% molybdenum, steel with
and controlled
a low carbon
nitrogen content,
additions. 22%
It has chromium,
a reduced 5% nickel,
nickel content3% molybdenum,
compared and controlled
to standard austeniticnitrogen
stain-
additions.
less It hasgives
steels, which a reduced
them nickel
a duplexcontent compared to
microstructure, andstandard austenitic
they contain stainless steels,
molybdenum and
which gives them a duplex microstructure, and they contain
nitrogen for corrosion resistance. These steels are always solution-treated, followed bymolybdenum and nitrogen
for corrosion
quenching, resistance.
to give These steels50%
an approximately areaustenite
always solution-treated, followed
and 50% ferrite duplex by quenching,
microstructure
to give an approximately 50% austenite and 50% ferrite duplex
without deleterious phases, such as sigma. 2205 DSS has a typical PREN of 35 or more. microstructure without
By
deleterious phases, such as sigma. 2205 DSS has a typical PREN
2000, 2205 DSS had become Europe’s third-most widely used grade of stainless steel, afterof 35 or more. By 2000, 2205
DSS had
types 316 L become
and 304 Europe’s third-most
L. It offers widely (approximately
high strength used grade of stainless
twice thatsteel,
ofafter types aus-
standard 316 L
and 304 L. It offers high strength (approximately twice that of standard
tenitic stainless steel grades such as 316 L), good general corrosion resistance in a variety austenitic stainless
ofsteel grades suchhigh
environments, as 316 L), goodto
resistance general corrosion resistance
chloride-induced SCC, and inhigh
a variety of environments,
resistance to pitting
high resistance to chloride-induced SCC,
attack in chloride environments, e.g., seawater [5,6]. and high resistance to pitting attack in chloride
environments,
Even if the e.g., seawater
material [5,6].process has been carried out comprehensively, some-
selection
Even if the material selection
times failures occur due to other factors. process has been
Several carried
failure modes outofcomprehensively,
heat exchangers have some-
times failures occur due to other factors. Several failure modes of heat exchangers have
been identified; the most common modes are fatigue [7,8], creep [9,10], oxidation [11], and
been identified; the most common modes are fatigue [7,8], creep [9,10], oxidation [11],
hydrogen attack [12]. The common causes of heat exchanger failure include weld defects
and hydrogen attack [12]. The common causes of heat exchanger failure include weld
[13,14], vibration [15,16], erosion [17,18], stress corrosion cracking [19–21], and microbial-
defects [13,14], vibration [15,16], erosion [17,18], stress corrosion cracking [19–21], and
induced cracking [22–25]. Considering its numerous failure modes, the failure of the heat
microbial-induced cracking [22–25]. Considering its numerous failure modes, the failure of
exchanger should be analyzed by recognizing the possible root cause, especially the les-
the heat exchanger should be analyzed by recognizing the possible root cause, especially
sons learned from previous studies.
the lessons learned from previous studies.
In this study, a shell and tube heat exchanger used as a discharge cooler at a power
In this study, a shell and tube heat exchanger used as a discharge cooler at a power
plant experienced corrosion. The tube and tube sheet material was 2205 Duplex Stainless
plant experienced corrosion. The tube and tube sheet material was 2205 Duplex Stainless
Steel (DSS), and the cooling medium of the heat exchanger was seawater. Some defects
Steel (DSS), and the cooling medium of the heat exchanger was seawater. Some defects
were found in the tube and tube sheet, such as leaked tubes, deposits under the plug, and
were found in the tube and tube sheet, such as leaked tubes, deposits under the plug, and
the
theformation
formationofofscale.
scale.This
Thisstudy
studywaswas conducted
conducted toto
determine
determine the root
the rootcause
causeofof
the failure.
the failure.
ItItisishoped that by conducting this study, similar failures will not occur
hoped that by conducting this study, similar failures will not occur in the future. in the future.

2.2.Materials
Materialsand andMethods
Methods
The
Thefailed
failedcomponent
componentwas wasa aBEM
BEMTEMA-type
TEMA-typeshell shelland
andtube
tubeheat
heatexchanger
exchangerwithout
without
ananend channel, and it was used as a discharge cooler. According to the Tubular
end channel, and it was used as a discharge cooler. According to the Tubular Exchanger Exchanger
Manufacturers
ManufacturersAssociation,
Association, Inc. (TEMA)
Inc. (TEMA) nomenclature,
nomenclature, BEMBEM is described as a bonnet
is described (in-
as a bonnet
tegral cover)
(integral front-end
cover) stationary
front-end stationaryhead type,
head a one-pass
type, a one-pass shell type,
shell type,and
anda fixed
a fixedtube
tubesheet
sheet
stationary
stationaryhead,
head,rear
rearend
endhead
headtype.
type.AnAnillustration
illustrationofofBEMBEMTEMA-type
TEMA-typeheat heatexchangers
exchangers
isisshown
shownininFigure
Figure1,1,and
andsome
someessential
essentialparts
partstotobebediscussed
discussedininthisthisstudy
studyarearedescribed
described
ininTable
Table1.1.This
Thisheat
heatexchanger
exchangercoolscoolsthe
thedischarge
discharge gas
gasfrom
fromthethethird-stage
third-stagecompressor.
compressor.
The
Thecooling
coolingmedium
mediumfor forthis
thisheat
heatexchanger
exchangerwas wasseawater.
seawater.TheTheshell
shelldesign
designpressure
pressurewaswas
22.6
22.6MPa
MPaatat422422K,K,and
andthe
thetube
tubedesign
designpressure
pressurewas was1 1MPa
MPaatat339339K.K.

Figure 1. Schematic drawing of BEM TEMA-type shell and tube heat exchanger.
Metals 2023, 13, 1182 3 of 15

Table 1. BEM TEMA-type shell and tube heat exchanger parts.

Part Number Part Name

1 Stationary Head-Bonnet
2 Stationary Head Flange-Channel or Bonnet
3 Stationary Head Nozzle
4 Stationary Tube Sheet
5 Tubes
6 Shell
7 Shell Nozzle
8 Expansion Joint
9 Support Plates

This heat exchanger used two types of materials: the shell material was carbon steel,
and the tube and tube sheet material was 2205 duplex stainless steel (UNS S31803). A
hypochlorite solution at two ppm by volume was injected into the running pump caisson
to prevent marine growth in the cooling water; a flow of 15 to 20 US gallons per minute of
hypochlorite solution should be maintained for any running pump. Although 2205 DSS
offers high strength, good general corrosion resistance, high resistance to chloride-induced
SCC, and high resistance to pitting attack in chloride environments, e.g., seawater [5], the
heat exchanger in this study experienced some material degradation after 28 months of
use; 102 out of 270 tubes failed, 26 tubes leaked and were plugged on both sides, and scale
plugged 76 tubes. This study conducted a failure analysis and found the root cause of the
heat exchanger failure.
The failure investigation was conducted on two heat exchangers, one on the platform
and one laid down in the warehouse, due to some defects. Both heat exchangers have
been operating for 28 months. The main steps performed to determine the root cause
of the observed damage are shown in Figure 2. Visual inspections were conducted on
both heat exchangers, including the tube-and-tube-sheet-welded section, and plugged
and unplugged tubes. The chemical composition of the tube and tube sheet material
was examined using a optical emission spectroscopy (Hilger E-9 OA701, Margate, UK)
to confirm the alloy grade. The hardness test was conducted on the tube and tube sheet
material using a Vickers microhardness tester (ZwickRoell ZHV30, Ulm, Germany) with
a load of 200 grams to confirm the alloy grade [26]. The chloride content, water salinity,
sulfate content, and total dissolved solids of the cooling medium were determined by
conducting a seawater examination. Tube deposit scale examination was performed by
using energy dispersive spectrometry (EDS) (JEOL JSM 6510 LA, Tokyo, Japan) and X-ray
diffraction (Rigaku Smart Lab, Tokyo, Japan). A fractography examination was conducted
using a scanning electron microscope (JEOL JSM 6510 LA, Tokyo, Japan) to observe the
corrosion appearance. The microstructure of the tubes was examined by cutting some
samples at the corroded region and mounting them into a cold-setting resin. The samples
were ground with 400, 600, 800, 1000, 1200, 1500, and 2000 grit SiC abrasive paper and
polished with diamond paste to 0.25 µm. The polished samples were swabbed with Beraha
etchant for 15 seconds and observed under an optical microscope [27].
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Figure 2. Schematic drawing of BEM TEMA-type shell and tube heat exchanger.
Figure 2. Flowchart of the failure investigation.
Figure 2. Schematic drawing of BEM TEMA-type shell and tube heat exchanger.
3. Results
3. Results
3. Results
3.1. Visual Examination
3.1.
3.1. VisualVisual
Examination
Visual examinations were
were conducted
conductedon
ontwo
twoheat
heatexchangers.
exchangers.Figure
Figure3a3a
is is
the photo-
the pho-
Visual of
graph
tograph examinations
ofthe
theheat were conducted
heatexchanger
exchanger ononthe on two heat
theplatform;
platform; exchangers.
defects
defects were
were found Figure
found on3atheiswelded
the photo-section
section
graph of the heat
between
between exchanger
the tube and tube on sheet
tube the platform;
sheet (the defects
(the circled
circled were
section
section foundthe
shows
shows theondefects
the welded
defects of thesection
of the tube
tube sheet
sheet
between
under
under thethetube andarea);
gasket
gasket tube further
area); sheet (the
further circled section
examination
examination ofof shows
this
this the
defect
defect isdefects
is shown showninofinthe tube
Figure
Figure sheet
4a,b.4a,b. The
The tube
undertube
thesheet
sheet gasket
of the of area);
the heat
heat exchanger
further
exchanger at the
examination
at the warehouse (Figure
of this defect
warehouse 3b)contained
is shown
(Figure 3b) contained some
in Figuresome leaked
4a,b. leaked
The tubetubes.
tubes.
sheetThe
of circled
The the heatsection
circled shows
exchanger
section showsatthat
the some
that some leaked
warehouse tubes
tubes were
leaked(Figure plugged
pluggedand
3b) contained
were some
and weld-overlayed.
leaked tubes. For
weld-overlayed. For
The further
circled examination,
furthersection shows the
examination, thatheat
some exchanger
leaked tubesat the warehouse
were plugged was and cut into several sections,
weld-overlayed. For
including
further the
the tube
examination,
including the
tube sheet
heatand
sheet gasket
gasket interface,
exchanger
and tube
tube sheet
at the warehouse
interface, inlet
sheetwas cut
inlet sections, and
and the
into several
sections, tube
tube itself.
sections,
the itself.
including the tube sheet and gasket interface, tube sheet inlet sections, and the tube itself.

Figure 3.
Figure 3. Failed
Failed heat
heatexchangers’
exchangers’appearance:
appearance:(a)(a)
tube sheet
tube of of
sheet heat exchanger
heat on on
exchanger thethe
platform; (b)
platform;
tube
Figure 3. sheet
Failed of heat
heat exchanger
exchangers’ at the warehouse.
appearance: (a) tube
(b) tube sheet of heat exchanger at the warehouse. sheet of heat exchanger on the platform; (b)
tube sheet of heat exchanger at the warehouse.
Metals 2023,
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Figure 4.
Figure 4. (a,b) Tube sheet
sheet and
and gasket
gasket interface;
interface; (c,d) tube
tube sheet
sheet inlet
inlet sections;
sections; (e)
(e) lateral
lateral section
section of
of
tubes; (f) tube surface condition.
tubes; (f) tube surface condition.

Figure
Figure 4a,b
4a,bshowshowthe thefurther
furtherexamination
examinationofofFigure
Figure 3a.3a.Pitting defects
Pitting defects under
under thethe
gasket
gas-
can
ket can be seen at the tube sheet interfaces; this defective surface was examined further to
be seen at the tube sheet interfaces; this defective surface was examined further
determine the root cause cause ofof pitting
pitting defects.
defects. Figure 4c,d show the pieces of the the seawater
seawater
inlet tube sheet.
sheet. As practical information, when corrosion was found on the tube sheet, a
plug
plug was
was applied
applied to to the
the corroded
corroded tube,
tube, and
and the
the tube
tube sheet
sheet was
was repaired
repaired by by overlaying
overlaying thethe
tube
tube sheet.
sheet. Figure
Figure 4e 4e shows
shows aa cut
cut and
and plugged
plugged tube
tube on
on the
the outlet
outlet side;
side; white
white scale
scale deposits
deposits
were
were observed
observed inside
inside the
the tubes.
tubes. Two
Two pieces
pieces of
of the
the plugged
plugged tubes
tubes were
were cutcut for
for laboratory
laboratory
examinations
examinations to examine the crack locations. The outer surface of the tube was
to examine the crack locations. The outer surface of the tube was cleaned
cleaned
with
with fine
fine emery
emery paper
paper andand observed
observed visually
visually with
with aa dye penetrant and
dye penetrant and magnifying
magnifying glass.glass.
There
There was no crack observed on the outer surface of the tube. Some shallow pitting was
was no crack observed on the outer surface of the tube. Some shallow pitting was
observed
observed on on the
the outer
outer surface
surface close
close to
to the
the outlet.
outlet. However,
However, this this pitting
pitting started
started from
from the
the
outer surface, and some could be removed with emery paper. Figure
outer surface, and some could be removed with emery paper. Figure 4f shows the defec- 4f shows the defective
tube’s surface
tive tube’s appearance.
surface appearance.For further examination,
For further examination,the tube was cut
the tube waslongitudinally
cut longitudinallyand
the appearance of the tube’s inner surface conditions was assessed; this
and the appearance of the tube’s inner surface conditions was assessed; this examination examination was
conducted
was conducted on the onplugged tube, an
the plugged unplugged
tube, tube, and
an unplugged tube,a standard tube without
and a standard defects.
tube without
The
defects. cross-section of the tube with no defects in Figure 5a shows that a weld overlay
joined the tube and tube sheet; the overlay of the tube sheet protected it from corrosion
The cross-section of the tube with no defects in Figure 5a shows that a weld overlay
and sealed the possible gap between the tube and tube sheet. No defects like corrosion
joined the tube and tube sheet; the overlay of the tube sheet protected it from corrosion
or leak was observed in this tube, and the weld overlay sealed the gap between the tube
and sealed the possible gap between the tube and tube sheet. No defects like corrosion or
and tube sheet well. Figure 5b,c are macro photographs of the plugged tube, and the tube
leak was observed in this tube, and the weld overlay sealed the gap between the tube and
was initially cold expanded on the tube sheet. Corrosion occurred on the tube sheet and
tube sheet well. Figure 5b,c are macro photographs of the plugged tube, and the tube was
has been repaired by weld overlay. Figure 5d,e are pictures of the plugged tube’s inner
initially cold expanded on the tube sheet. Corrosion occurred on the tube sheet and has
surface. Heavy deposits under the plug were observed, and some deposits along the tube
been repaired by weld overlay. Figure 5d,e are pictures of the plugged tube’s inner sur-
indicated the presence of a biofilm that may promote microbiologically induced corrosion.
face. Heavy deposits under the plug were observed, and some deposits along the tube
Figure 5f is the cross-section of the unplugged tube. Heavy deposits on the entrance side
indicated the presence of a biofilm that may promote microbiologically induced corrosion.
were observed, and some deposits along the tube indicated the presence of a biofilm that
Figure 5f is the cross-section of the unplugged tube. Heavy deposits on the entrance side
may promote microbiologically induced corrosion.
were observed, and some deposits along the tube indicated the presence of a biofilm that
may promote microbiologically induced corrosion.
Metals 2023,
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Figure 5.
Figure 5. Longitudinal
Longitudinalcross-section of (a)
cross-section of tube without
(a) tube defects;
without (b–e) (b–e)
defects; plugged tube; (f)
plugged unplugged
tube; (f) un-
tube.
plugged tube.

3.2. Chemical Composition

The chemical
chemicalcomposition
compositionofofthe
thetube
tubeand
andtube sheet
tube sheetmaterial
materialwas examined
was by optical
examined by op-
emission spectrometry. The results are shown in Table 2.
tical emission spectrometry. The results are shown in Table 2.

Table 2. Chemical composition

Table 2. composition of
of tube
tube and
and tube
tube sheet
sheet (weight
(weight %),
%), data
data from
from [28].
[28].

Chemical Chemical
Element Element
Composition Composition
Component C Component
Si S C PSi S Mn P Ni Cr Mn
Ni Cr MoMo Fe
Fe
Tube 0.029 Tube
0.355 0.007 0.029 0.355
0.031 0.007
0.453 0.031
6.781 0.453
6.781
24.602 24.602 3.713
3.713 Balance
Balance
Tube Sheet 0.046 Tube
0.338 Sheet0.001 0.046 0.019
0.338 0.001
1.571 0.019 5.128
5.128 1.571
21.558 21.558 3.226
3.226 Balance
Balance
UNS S31803 ≤0.03 ≤1.00 <0.020 <0.030 ≤2.00 4.50–6.50 21–23 2.50–3.50
2.50– Balance
UNS S31803 ≤0.03 ≤1.00 <0.020 <0.030 ≤2.00 4.50–6.50 21–23 Balance
3.50
Based on optical emission spectrometry results, the tube and tube sheet materials
Based
comply withonduplex
opticalstainless
emission spectrometry
steel results, S31803.
ASTM A-790/UNS the tubeThe
andmechanical
tube sheetproperties
materials
comply with duplex stainless steel
of UNS S31803 are shown in Table 3. ASTM A-790/UNS S31803. The mechanical properties
of UNS S31803 are shown in Table 3.
Table 3. Mechanical properties of UNS S31803, data from [28].
Table 3. Mechanical properties of UNS S31803, data from [28].
Mechanical Properties
Mechanical Properties
Yield Strength ≥450 MPa (65,000 psi)
Yield Strength
Tensile Strength ≥450 MPa
≥620 (65,000
MPa psi)
(90,000 psi)
Tensile Strength
Elongation ≥620 MPa ≥(90,000
25% psi)
Hardness
Elongation ≥290 HBW
≥25%≡ 305 VHN
Hardness ≥290 HBW ≡ 305 VHN
3.3. Hardness Test
3.3. Hardness Test
Besides chemical composition, a hardness test was conducted using a Vickers mi-
crohardness tester (ZwickRoell,
Besides chemical Ulm,
composition, Germany)
a hardness testwith
was aconducted
load of 200 grams
using for material
a Vickers micro-
confirmation
hardness testerpurposes. The survey
(ZwickRoell, was conducted
Ulm, Germany) with aon tube
load and grams
of 200 tube sheet materials,
for material and
confir-
the hardness distribution is shown in Table 4.
mation purposes. The survey was conducted on tube and tube sheet materials, and the
hardness distribution is shown in Table 4.
Table 4. Tube and tube sheet hardness (VHN), data from [28].
Table 4. Tube and tube sheet hardness (VHN),
Component data from [28].
Measurement Average
Tube Component 270,Measurement
256, 256, 256, 270 262Average
± 8.0
Tube sheet
Tube 231, 220,
270, 256,270,
256,220,
256,231
270 ± 21
234262 ± 8.0
Tube sheet 231, 220, 270, 220, 231 234 ± 21
 Metals 2023, 13, x FOR PEER REVIEW 7
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The hardness of the tube and tube sheet is below the ASTM A-790/UNS S31803
The hardness
ificationthe
of andtube
wasand tubescattered
widely sheet is due
below thetorch
to the ASTM A-790/UNS
cutting and the S31803
heating effect, w
specification and
may cause a significant variation in the materials’ hardness. heating effect,
was widely scattered due to the torch cutting and the
which may cause a significant variation in the materials’ hardness.
3.4. Seawater Examination
3.4. Seawater Examination
A seawater examination was conducted to determine the seawater’s salinity,
A seawater examination was conducted to determine the seawater’s salinity, chloride,
ride, sulfate, and total dissolved solids. Samples were taken from the discharge coole
sulfate, and total dissolved solids. Samples were taken from the discharge cooler and the
the discharge cooling pump. The analysis results are shown in Table 5.
discharge cooling pump. The analysis results are shown in Table 5.
Table 5. Seawater examination result.
Table 5. Seawater examination result.
ITEM Unit Discharge Cooler Discharge Cooling Pu
ITEM
P-Alkalinity, Unit
CaCO3 Discharge Cooler
mg/L Discharge Cooling Pump
5 5
P-Alkalinity, CaCO
M-Alkalinity,
3 mg/L
CaCO3 mg/L 5 124 5 129
M-Alkalinity, CaCO3
Chloride, Cl mg/L mg/L124
18130 129
18479
Chloride, Cl mg/L 18130 18479
Sulfate, SO4 Sulfate, SO4 mg/L mg/L
2663 2663 2716 2716
Phosphate, PO4Phosphate, PO mg/L
4 mg/L0.4 0.4 0.8 0.8
pH pH - -8.16 8.16 8.19 8.19
Conductivity Conductivity mS/cm 65.5
mS/cm 65.5 63.9 63.9
Total Dissolved Solid mg/L 32625 31797
Total Dissolved Solid mg/L 32625 31797
Total Suspended
Total mg/LLiquid
Suspended 78.80
mg/L 78.80 62.6 62.6
Liquid

Seawater salinity can be calculated as [29]:

Seawater salinity can be calculated as [29]:
S (%o) = 1.80655 Cl (%o)
S (‰) = 1.80655 Cl (‰) (1)
Based onthe
Based on the equation, thesalinity
equation,
wasthe salinity
33.4%, andwas
the33.4%,
increase andinthe increase
salinity in salinity incr
increased
the rate
the rate of calcium of calcium
carbonate carbonate precipitation
precipitation [30]. The
[30]. The chloride chloride
content wascontent
typicalwas
fortypical fo
seawater (aroundwater (around
19,000 mg/L), 19,000 mg/L),
and the and
sulfate the sulfate
content content
was also was also
considered considered
normal (around normal (ar
2600 mg/L) [29].2600The
mg/L) [29].
total The total
dissolved dissolved
solids were solids were considerably
considerably high (32 g/L)highand
(32 will
g/L) and wil
tribute
contribute to the to theofformation
formation deposits of deposits
and scale inand scale in
stagnant stagnant [31].
conditions conditions [31].

3.5. Scale Examination

3.5. Scale Examination
The tube deposit in Figure
The 3e wasin
tube deposit examined
Figure 3eusing
wasSEM and EDS.
examined Figure
using SEM6aand
is the SEM
EDS. Figure 6a
macrograph of SEMthe tube scale deposit; the particle size was very fine, indicating that
macrograph of the tube scale deposit; the particle size was very fine, it wasindicatin
formed through it awas
chemical
formedreaction.
throughFigure 6b shows
a chemical the results
reaction. Figure from energy
6b shows thedispersive
results from energ
spectrometry ofpersive
the tubespectrometry
deposit, withofa predominance
the tube deposit, with a predominanceand
of calcium, magnesium, of oxygen
calcium, magne
elements. Thisand examination result were
oxygen elements. further examined
This examination usingfurther
result were an XRD analysis,
examined as an XRD
using
illustrated in Figure 7. illustrated in Figure 7.
ysis, as

Figure 6. (a) SEMFigure 6. (a) SEM

examination examination
of tube of tube
scale deposit (b) scale
EDS deposit (b)tube
results of EDSscale
results of tube scale deposit.
deposit.
 (CaCO3) and dolomite (CaMg(CO3)2). The X-ray diffraction results confirmed the energy
dispersive spectrometry data, which showed that calcium, magnesium, and oxygen were
the main components in the tube deposit. According to the shape of the deposit and its
compounds, this scale was formed by microbiologically induced calcium carbonate
Metals 2023, 13, x FOR PEER REVIEW pre-
8 of 15
Metals 2023, 13, 1182
cipitation (MICP) [31–33]. The detailed mechanism of scale formation and the composition
8 of 15
of the scale will be discussed further in the discussion section.

Based on the XRD examination results, the majority of the tube scale was aragonite
(CaCO3) and dolomite (CaMg(CO3)2). The X-ray diffraction results confirmed the energy
dispersive spectrometry data, which showed that calcium, magnesium, and oxygen were
the main components in the tube deposit. According to the shape of the deposit and its
compounds, this scale was formed by microbiologically induced calcium carbonate pre-
cipitation (MICP) [31–33]. The detailed mechanism of scale formation and the composition
of the scale will be discussed further in the discussion section.

XRDexamination
Figure7.7.XRD
Figure examinationof
oftube
tubescale
scaledeposit.
deposit.

Based on the
3.6. Fractography XRD examination results, the majority of the tube scale was aragonite
Examination
(CaCO3 ) and dolomite (CaMg(CO3 )2 ). The X-ray diffraction results confirmed the energy
The surface
dispersive of the tube
spectrometry data,sheet in Figure
which showed4a,b thatwas cleaned
calcium, with Clarkand
magnesium, solution
oxygen before
were
the examination but the dirt on the surface could not be entirely
the main components in the tube deposit. According to the shape of the deposit and its removed by the Clark
solution.
compounds, The this
SEM micrograph
scale was formed of the tube sheet’s defective
by microbiologically induced surface shown
calcium in Figure
carbonate 8a
precipi-
revealed traces of barnacles. The pitting present indicates the
tation (MICP) [31–33]. The detailed mechanism of scale formation and the composition ofeffect of a microbiological
attack
Figure
the on the surface;
7. XRD
scale will examination
be discussedbacterial
tubeactivity
offurther
scale themay
in deposit. changesection.
discussion the structure and properties of the
passivation film on the stainless steel, affecting pitting initiation and growth. Generally,
compact
3.6. microbialExamination
3.6. Fractography biofilms can act as diffusion barriers for reactants such as oxygen, ag-
gressive
The anions, and
The surface ofthe
surface of cations
the tube[34–37].
tube sheet Figure
sheetininFigure 8b4a,b
Figure4a,b iswas
the
was scanning
cleaned
cleaned electron
with Clark
with macrograph
solution
Clark solution of an-
before the
before
other defective
examination
the examination surface.
but the
butdirt A
theondetailed
theon
dirt examination
surface could could
the surface of the
not be not defective
entirely surface
removed
be entirely could not
by the Clark
removed by thebe per-
solution.
Clark
formed
The SEM
solution. because
The a permanent
micrograph
SEM of the deposit
micrograph tube thecovered
of sheet’s the surface.
tubedefective
sheet’s surface shown
defective surfaceinshown
Figurein8aFigure
revealed
8a
traces
revealedof barnacles. The pitting
traces of barnacles. Thepresent
pittingindicates the effectthe
present indicates of aeffect
microbiological attack on
of a microbiological
the surface;
attack on the bacterial
surface;activity
bacterialmay change
activity maythechange
structure theand properties
structure and of the passivation
properties of the
film on the stainless steel, affecting pitting initiation and growth.
passivation film on the stainless steel, affecting pitting initiation and growth. Generally, Generally, compact
microbial biofilms can
compact microbial act as
biofilms diffusion
can barriers barriers
act as diffusion for reactants such assuch
for reactants oxygen, aggressive
as oxygen, ag-
anions, and cations [34–37]. Figure 8b is the scanning electron
gressive anions, and cations [34–37]. Figure 8b is the scanning electron macrograph macrograph of another
of an-
defective surface.
other defective A detailed
surface. examination
A detailed of the of
examination defective surface
the defective could could
surface not benot
performed
be per-
because a permanent
formed because deposit deposit
a permanent coveredcovered
the surface.the surface.

Figure 8. SEM examination of tube sheet (a) pitting appearance (b) defective surface

Figure 8.
Figure 8. SEM examination of tube sheet (a) pitting
pitting appearance
appearance (b)
(b) defective
defective surface
surface.
Metals 2023, 13, 1182Metals 2023, 13, x FOR PEER REVIEW 9 of 15 9

3.7. Microstructural
3.7. Microstructural Examination Examination
Figurethe
Figure 9a represents 9a represents
tube base the tube base
material withmaterial with and
no defects, no defects,
Figureand Figure 9b show
9b shows
basemicrostructure
the base material material microstructure of the
of the tube tube sheet.
sheet. The corroded
The corroded surface
surface of the
of the tubetube sheet
Figure
sheet from Figure 4a was
4a was examined
examined usingusing an optical
an optical micrograph.
micrograph. Figure
Figure 9a,b9a,b
showshowthatthat corr
attacks
corrosion attacks occurred
occurred preferentially
preferentially along
along thethe austenite
austenite grainsand
grains andthere
therewas
was nono attack o
ferritegrain.
attack on the ferrite grain.AApreferential
preferentialattack
attackononthe
theaustenite
austenite grain
grain of
of the
the weld metal phenom
phenomenon was wasobserved
observedduring
duringthethecrevice
crevicecorrosion
corrosiontest.
test.According
Accordingtotoprior
priorstudies,
studies, prefere
dissolution
preferential dissolution occurs
occurs at at
allall morphologies
morphologies ofof austeniticphases:
austenitic phases:grain
grainboundary
boundary (GBA),
manstätten
(GBA), Widmanstätten (WA),(WA),
andand intragranular
intragranular (IGA)
(IGA) [38–40].
[38–40]. TheThe corrosion
corrosion attack
attack on onthethe tube
was caused
tube sheet was caused by crevice
by crevice corrosion
corrosion between
between the surface
the surface deposit
deposit (bacteria
(bacteria product)product) o
tube
on the tube sheet sheetand
surface surface and the substrate.
the substrate.

Figure 9. Optical Figure 9. Optical

micrographs micrographs
of (a) of (a) tube
tube base material base material
without defects,without
(b) tubedefects, (b) tube
sheet base sheet base ma
material,
(c,d) corroded section
(c,d) corroded section of tube sheet 3(a).of tube sheet 3(a).

Figure 10 is an Figure
optical10 is an optical
micrograph of micrograph
the corroded of tube
the corroded tubeother
sheet at the sheetlocation.
at the other loca
The type
The type of attack was of attack was
different fromdifferent
that offrom that9.of The
Figure Figure 9. The corrosion
corrosion attack occurred u
attack occurred
under a deposit a deposit
produced produced by bacteria.
by bacteria. Previous
Previous fractography
fractography data data indicated
indicated thatthat
the the corr
at this site was caused by micro/macro-fouling. However, the corrosion
corrosion at this site was caused by micro/macro-fouling. However, the corrosion occurred occurred u
the gasket; therefore, macro/micro-fouling was formed and attacked
under the gasket; therefore, macro/micro-fouling was formed and attacked the tube sheet the tube shee
face.to
surface. According According
Figure 10,tothe
Figure 10, themechanism
corrosion corrosion mechanism
was crevicewas crevice between
corrosion corrosion betwee
the substrate andsubstrate and surface
surface deposit deposit
that was that was
enhanced by enhanced by microbiologically
microbiologically induced corr
induced corrosion
(MIC) [39–41]. (MIC) [39–41].
Figure 11 is an optical micrograph of the unplugged tube. Corrosion occurred on the
inner surface of the tube, and the austenite grains were attacked by crevice corrosion [39,40].
Corrosion also occurred on the tube sheet overlay.
Figure 12 is an optical micrograph of a plugged tube. Figure 12a shows the inner
surface of the tube attacked by corrosion, with the depth of the austenite grains attacked
being 141 µm. Figure 12b shows the occurrence of corrosion in the crevice between the
plug and the tube. The tube–sheet overlay was also attacked by corrosion (Figure 12c).
 Metals 2023, 13, x FOR PEER REVIEW 10

Metals 2023,
Metals 2023, 13,
13, 1182
x FOR PEER REVIEW 10
10 of 15
of 15

Figure 10. Optical micrograph of a corroded section of tube sheet 3(b).

Figure 11 is an optical micrograph of the unplugged tube. Corrosion occurred o

inner surface of the tube, and the austenite grains were attacked by crevice corr
[39,40]. Corrosion also occurred on the tube sheet overlay.
Figure 10. Optical micrograph of a corroded section of tube sheet 3(b).

Figure 11 is an optical micrograph of the unplugged tube. Corrosion occurred o

inner surface of the tube, and the austenite grains were attacked by crevice corr
10. Optical[39,40].
Figure 10. Corrosion
micrograph of also occurred
of aa corroded
corroded on
section of
section the sheet
of tube
tube tube
sheetsheet
3(b). overlay.
3(b).

Figure 11 is an optical micrograph of the unplugged tube. Corrosion occurred on the

inner surface of the tube, and the austenite grains were attacked by crevice corrosion
[39,40]. Corrosion also occurred on the tube sheet overlay.

Figure 11. Optical micrographs of (a) corrosion on tube sheet overlay of the unplugged tub
corrosion on the inner surface of the unplugged tube.

Figure 12 is an optical micrograph of a plugged tube. Figure 12a shows the

surface of the tube attacked by corrosion, with the depth of the austenite grains atta
Figure 11. OpticalFigure
being 11. Optical
141 ofmicrographs
µm. Figure
micrographs of on
12b shows
(a) corrosion (a)the
corrosion
tube sheeton
occurrence tubeof sheet
overlay overlay
corrosion
of the in of thecrevice
the
unplugged unplugged tub
tube, betwee
corrosion
plug and on the
the innerThe
tube. surface of the unplugged
tube–sheet overlay tube.also attacked by corrosion (Figure 12
was
(b) corrosion on the inner surface of the unplugged tube.

Figure 12 is an optical micrograph of a plugged tube. Figure 12a shows the

surface of the tube attacked by corrosion, with the depth of the austenite grains atta
Figure 11. Optical micrographs of (a) corrosion on tube sheet overlay of the unplugged tube, (b)
being 141 µm. Figure 12b shows the occurrence of corrosion in the crevice betwee
corrosion on the inner surface of the unplugged tube.
plug and the tube. The tube–sheet overlay was also attacked by corrosion (Figure 12
Figure 12 is an optical micrograph of a plugged tube. Figure 12a shows the inner
surface of the tube attacked by corrosion, with the depth of the austenite grains attacked
being 141 µm. Figure 12b shows the occurrence of corrosion in the crevice between the
plug and the tube. The tube–sheet overlay was also attacked by corrosion (Figure 12c).

Figure 12. OpticalFigure 12. Optical

micrographs of (a)micrographs
corrosion onof (a)inner
the corrosion onofthe
surface theinner surface
plugged tube,of(b)
thetube
plugged
and tube, (b
and plug corroded interface, (c) corrosion on tube sheet
plug corroded interface, (c) corrosion on tube sheet overlay of the plugged tube.overlay of the plugged tube.

4. Discussion
The tube and tube sheet materials are made of duplex stainless steel UNS 31803.
Corrosion of theFigure 12. Optical
tube sheet micrographs
may have of (a) by
been caused corrosion on corrosion
galvanic the inner surface
betweenof the
the plugged
gasket tube, (b
and plug corroded interface, (c) corrosion on tube sheet overlay of the plugged tube.
and the tube sheet or between the tube sheet and the carbon steel shell, crevice corrosion,
or microbiologically induced corrosion. The probability of each corrosion mechanism will
be discussed further in Sections 4.1–4.3.
Figure 12. Optical micrographs of (a) corrosion on the inner surface of the plugged tube, (b) tube
and plug corroded interface, (c) corrosion on tube sheet overlay of the plugged tube.
Metals 2023, 13, 1182 11 of 15

4.1. Galvanic Corrosion

Galvanic corrosion occurs when a metal or alloy is electrically coupled to another metal
or conducting non-metal in the same electrolyte. During galvanic coupling, corrosion of
the less corrosion-resistant metal increases while corrosion of the more corrosion-resistant
metal decreases. The driving force for corrosion or current flow is the potential developed
between dissimilar metals. Possible galvanic coupling could occur between the tube sheet
and conductive gasket and between the tube sheet and carbon steel shell. The type of gasket
material is unknown, so the possibility of galvanic coupling cannot be determined [42].
There are two reasons galvanic coupling did not cause tube sheet corrosion: First,
when the galvanic coupling formed between the tube sheet material and carbon steel shell,
carbon steel would corrode because it is less noble than duplex stainless steel. Corrosion
occurred in the tube sheet but not in the shell material. Second, most galvanic corrosion
attacks are similar to general corrosion without surface deposits. If the attack is pitting, the
pitted surface will be shiny, and there will be no surface deposits.

4.2. Crevice Corrosion

Small pits can form on the steel surface under specific conditions, particularly those
involving chlorides (such as sodium chloride in seawater) and exacerbated by elevated
temperatures. Depending on both the environment and the steel itself, these small pits
may continue to grow, and if they do, they can lead to perforation, while most of the
steel surface may still be unaffected. Crevice corrosion can be considered a particular
case of pitting corrosion, where the initial pit is provided by an external feature, such as a
narrow opening or spaces (gaps) between metal-to-metal or nonmetal-to-metal components.
Similarly, unintentional crevices such as cracks, rough surfaces, sheared edges, and other
metallurgical defects can be sites for corrosion initiation. Crevice attack also occurs under
deposits and biofouling growth attached to the metal surface [43].
Stainless steel groups, including duplex stainless steel, a passive alloy, are more prone
to crevice attack in seawater than materials that exhibit more active behavior. The pitting
resistance of duplex stainless steel is defined as resistance to localized corrosion attack and
is expressed as the Pitting Resistance Equivalent Number (PREN) [44]:
PREN = Cr + 3.3 (Mo + 0.5 W) + 16 N (2)
Using PREN as a reference, several duplex stainless steels with different alloy contents
will have different pitting resistance, as shown in Table 6.

Table 6. Pitting resistance of some types of duplex stainless steel data from [28,45].

Material Cr Mo Ni N PREN
UNS S31803 21.00–23.00 2.5–3.5 4.5–6.5 0.08–0.20 38
UNS S32750 24.00–26.00 3.0–5.0 6.0–8.0 0.24–0.32 41
UNS S32760 24.00–26.00 3.0–4.0 6.0–8.0 0.20–0.30 ≥40

According to Table 6, UNS 31803 has a lower pitting resistance than the other grades.
The pitting resistance of duplex stainless steel in seawater can be expressed as the critical
pitting temperature (CPT), below which pitting will not occur. Similar to pitting corrosion,
the susceptibility of duplex stainless steel to crevice corrosion is expressed as the critical
crevice temperature (CCT). Figure 13 shows the critical pitting and crevice temperatures in
a 6% ferric chloride solution for 24 hours of some types of stainless steel [45].
The duplex stainless steel type with the lowest pitting and crevice corrosion resistance
is UNS S31803. The critical crevice temperature of UNS S31803 is about 20 ◦ C; above this,
crevice corrosion will occur. The severity and rate of crevice corrosion will depend on
the crevice’s geometry and the seawater quality. Crevice corrosion of the tube–sheet joint
is likely to occur under the gasket and between the tube and tube–sheet joint. Crevice
corrosion under the gasket is a consequence that cannot be prevented for seawater service
unless a better design and better materials are selected. The expanded joint type is not
Metals 2023, 13, 1182 12 of 15

Metals 2023, 13, x FOR PEER REVIEW 12 of 15

recommended for tubes and tube sheets used in seawater service, as the possibility of
crevice formation is much higher than that of a welded joint. Applying an overlay on
the tube–sheet surface is acceptable, but the overlay material should be selected to avoid
crevice
the corrosion.of
susceptibility The current
duplex overlaysteel
stainless was to
insufficient to prevent
crevice corrosion is crevice corrosion,
expressed as the as some
critical
parts were
crevice attacked. (CCT).
temperature The surface
Figure quality of thethe
13 shows overlay
criticalshould
pittingalso
andbecrevice
considered because a
temperatures
inrough
a 6% surface will create
ferric chloride tiny crevices
solution that can
for 24 hours harmtypes
of some the surface.
of stainless steel [45].

Figure
Figure13.
13.Critical
Criticalpitting
pittingtemperature
temperature(CPT)
(CPT)and
andcritical
criticalcrevice
crevicetemperature
temperature(CCT)
(CCT)ofofsome
somealloys
alloys
reproduced from [45].
reproduced from [45].

4.3. The
Microbially
duplexInduced Corrosion
stainless steel type with the lowest pitting and crevice corrosion re-
sistance is UNScircumstances,
In certain S31803. The critical crevice
microbial temperature
activity of UNS
can influence theS31803 is about
corrosion process20 °C;
and
above this,involves
typically crevice microbes
corrosionthat
willmetabolize
occur. Thesulfur
severity and rate of
compounds, crevice corrosion
producing an aggressive,will
depend on the crevice’s
acidic, hydrogen geometry and localized
sulfide-containing the seawater quality. Crevice
environment corrosion
[46]. When of thesteel
stainless tube–is
sheet joint is
in contact likely
with to occur
natural under athe
seawater, gasketwill
biofilm andgrow
between thesteel
on the tubesurface.
and tube–sheet
Crevice joint.
corro-
Crevice corrosion under the gasket is a consequence that cannot be prevented
sion may also occur because of localized deposits or differential aeration cells caused by for seawater
service unless a bacteria.
slime-forming better design and better materials
The aggregation are selected. of
and inhomogeneity The expanded
biofilms jointlocalized
causes type is
not recommended
differences for tubesand
in the chemical andelectrochemical
tube sheets used in seawater service,
environments as the possibility
at the interface. These gradi-of
ents in formation
crevice pH, sulfide,ischloride, or dissolved
much higher than that oxygen are crucial
of a welded inApplying
joint. the beginning and hastening
an overlay on the
of concentration
tube–sheet surfacecell and galvanic
is acceptable, corrosion.
but the overlay Corrosion due tobemicrobial
material should selected toactivity takes
avoid crev-
thecorrosion.
ice form of aThe pitting attack.
current Sincewas
overlay UNS S31803 is to
insufficient prone to crevice
prevent creviceattack, accumulating
corrosion, as some
microbes
parts were in the crevice
attacked. region will
The surface promote
quality of the pitting
overlaycorrosion
should also under deposit. Localized
be considered because
deposits cause tube corrosion on the inner surface under
a rough surface will create tiny crevices that can harm the surface. the biofilm [32].
The XRD scale examination showed calcium carbonate (CaCO3 ) as the tube deposit.
Calcium
4.3. carbonate
Microbially sediments
Induced Corrosionare prevalent in the ocean. The origin of calcium carbonate is
the result of the following chemical
In certain circumstances, microbial reactions [31,33,47]:
activity can influence the corrosion process and
typically involves microbes that metabolize − → HCO
CO2 + OHsulfur −
compounds, producing an aggressive,
3
acidic, hydrogen sulfide-containing − HCO3 →
OH +localized − −2 When stainless steel is in
H2 O + CO3[46].
environment (3)
CO −2 + Ca+2 → CaCO
contact with natural seawater, a biofilm 3 will grow on the3steel surface. Crevice corrosion
may alsoIn the form of Ca ion, calcium is one oforthe
occur because of
+2 localized deposits differential aerationpositive
major inorganic cells caused by slime-in
ions (cations)
forming bacteria. The aggregation and inhomogeneity of biofilms causes
saltwater and freshwater. It can originate from the dissociation of salts, such as calcium localized differ-
ences in the chemical and electrochemical
chloride or calcium sulfate in water [31,33]. environments at the interface. These gradients
in pH, sulfide, chloride, or dissolved oxygen+2are crucial in− the beginning and hastening of
CaCl2 (s) → Ca (aq) + 2 Cl (aq)
concentration cell and galvanic corrosion. Corrosion due to microbial activity takes the (4)
CaSO4 (s) → Ca+2 (aq) + 2 SO4 −2 (aq)
form of a pitting attack. Since UNS S31803 is prone to crevice attack, accumulating mi-
crobesMost calcium
in the creviceinregion
surfacewill
water comespitting
promote from streams
corrosionflowing
underover limestone
deposit. (CaCO
Localized 3 ),
de-
gypsum
posits (CaSO
cause tube4 ·2H 2 O), and
corrosion onother calcium-containing
the inner surface under rocks and minerals.
the biofilm [32]. Calcium carbon-
ate isThe
relatively insoluble
XRD scale in watershowed
examination but dissolves
calciummore readily in
carbonate water3)containing
(CaCO as the tubesignificant
deposit.
levels of dissolved carbon dioxide [47]. Tube deposits were found only
Calcium carbonate sediments are prevalent in the ocean. The origin of calcium carbonate on plugged tubes.
The tube deposit came from the solid particles
is the result of the following chemical reactions [31,33,47]: in seawater, as the total dissolved solid
content was high. If the outlet ends were not plugged, seawater could enter the plugged
CO2 + OH− → HCO3−
tube from the outlet side. This way, the seawater will remain in the plugged tube, and the
OH− + HCO3− → H2O + CO3−2 (3)
CO3−2 + Ca+2 → CaCO3
Metals 2023, 13, 1182 13 of 15

solid or colloidal particles will be deposited inside the plugged tube. Solid particles will be
accumulated due to the low velocity and almost stagnant seawater inside the plugged tube.

5. Conclusions
UNS S31803 shell and tube heat exchangers that were cooled by seawater experienced
corrosion caused by crevice corrosion enhanced by microbiologically induced corrosion
(MIC). The crevice was between the bacteria’s metabolic products and the substrate material,
as confirmed by the scale’s shape, size, and its compounds that contained CaCO3 . This scale
was formed by microbiologically induced calcium carbonate precipitation (MICP) [31,33].
The microstructural examination revealed that corrosion attack occurred preferentially
along the austenite grains; this phenomenon is common in duplex stainless steel, which
typically fails due to crevice corrosion [39,40]. The use of materials that are inappropriate
for the heat exchangers’ seawater cooling medium conditions is the leading/root cause of
this issue.
Some efforts to prevent similar crevice corrosion enhanced by microbiologically in-
duced corrosion (MIC) in heat exchangers (discharge coolers) include upgrading materials
to ones that can resist crevice corrosion in seawater at the operating temperature, which
can be determined by the critical pitting temperature (CPT) and critical crevice temperature
(CCT). In the design and manufacturing aspects, several efforts should be made to avoid
crevice corrosion, including designing and fabricating to avoid trapped and pooled liquid;
designing and fabricating to avoid crevices; using a weld joint between the tube and tube
sheet instead of a cold expanded joint; preparing surfaces to the best possible finish (mirror
finish resists pitting best); removing all contaminants and weld scale; welding using the
correct consumables and practices; and inspecting to check for inadvertent crevices. The
application of an overlay on the tube–sheet surface is an accepted practice. The current
overlay was insufficient to prevent crevice corrosion, as some parts were attacked. The
surface quality of the overlay should also be considered because a rough surface will create
tiny crevices that can harm the surface.

Author Contributions: Formal analysis, A.S.; investigation, T.A.; writing—review and editing, H.A.
All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: We acknowledged the contribution of an Oil and Gas Company in Indonesia
in providing the material for this work. Any findings or conclusions stated in this paper are of the
Authors and do not represent the Company in any capacity.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Schweitzer, P.A. Fundamentals of Metallic Corrosion: Atmospheric and Media Corrosion of Metals; CRC Press: Boca Raton, FL,
USA, 2006.
2. Shifler, D.A. La Que’s Handbook on Marine Corrosion; Wiley & Sons: Hoboken, NJ, USA, 2021.
3. Balaji, C.; Srinivasan, B.; Gedupudi, S. Chapter 7—Heat Exchangers. In Heat Transfer Engineering; Balaji, C., Srinivasan, B.,
Gedupudi, S., Eds.; Academic Press: Cambridge, MA, USA, 2021; pp. 199–231; ISBN 978-0-12-818503-2.
4. Morales, M.; Chimenos, J.M.; Fernández, A.I.; Segarra, M. Materials Selection for Superheater Tubes in Municipal Solid Waste
Incineration Plants. J. Mater. Eng. Perform. 2014, 23, 3207–3214. [CrossRef]
5. Moura, V.S.; Lima, L.D.; Pardal, J.M.; Kina, A.Y.; Corte, R.R.A.; Tavares, S.S.M. Influence of Microstructure on the Corrosion
Resistance of the Duplex Stainless Steel UNS S31803. Mater. Charact. 2008, 59, 1127–1132. [CrossRef]
6. Farrer, J.C.M. The Alloy Tree, A Guide to Low-Alloy Steels, Stainless Steels and Nickel-Base Alloys; CRC Press: Boca Raton, FL,
USA, 2004.
7. Ravindranath, K.; Tanoli, N.; Gopal, H. Failure Investigation of Brass Heat Exchanger Tube. Eng. Fail. Anal. 2012, 26, 332–336.
[CrossRef]
8. Azevedo, C.R.F.; Alves, G.S. Failure Analysis of a Heat-Exchanger Serpentine. Eng. Fail. Anal. 2005, 12, 193–200. [CrossRef]
Metals 2023, 13, 1182 14 of 15

9. Jones, D.R.H. Creep Failures of Overheated Boiler, Superheater and Reformer Tubes. Eng. Fail. Anal. 2004, 11, 873–893. [CrossRef]
10. Psyllaki, P.P.; Pantazopoulos, G.; Lefakis, H. Metallurgical Evaluation of Creep-Failed Superheater Tubes. Eng. Fail. Anal. 2009, 16,
1420–1431. [CrossRef]
11. Kain, V.; Chandra, K.; Sharma, B.P. Failure of Carbon Steel Tubes in a Fluidized Bed Combustor. Eng. Fail. Anal. 2008, 15, 182–187.
[CrossRef]
12. Al Arada, M.; Al Otaibi, M. Evaluation of High Temperature Hydrogen Attack Effect on Carbon Steel—0.5 Mo Heat Exchanger.
In Proceedings of the NACE—International Corrosion Conference Series, San Antonio, TX, USA, 9–13 March 2014.
13. Otegui, J.L.; Fazzini, P.G. Failure Analysis of Tube–Tubesheet Welds in Cracked Gas Heat Exchangers. Eng. Fail. Anal. 2004, 11,
903–913. [CrossRef]
14. Corleto, C.R.; Argade, G.R. Failure Analysis of Dissimilar Weld in Heat Exchanger. Case Stud. Eng. Fail. Anal. 2017, 9, 27–34.
[CrossRef]
15. Liu, L.; Ding, N.; Shi, J.; Xu, N.; Guo, W.; Wu, C.M.L. Failure Analysis of Tube-to-Tubesheet Welded Joints in a Shell-Tube Heat
Exchanger. Case Stud. Eng. Fail. Anal. 2016, 7, 32–40. [CrossRef]
16. Goyder, H.G.D. Flow-Induced Vibration in Heat Exchangers. Chem. Eng. Res. Des. 2002, 80, 226–232. [CrossRef]
17. Kuźnicka, B. Erosion-Corrosion of Heat Exchanger Tubes. Eng. Fail. Anal. 2009, 16, 2382–2387. [CrossRef]
18. Gong, Y.; Yang, Z.-G.; Yuan, J.-Z. Failure Analysis of Leakage on Titanium Tubes within Heat Exchangers in a Nuclear Power
Plant. Part II: Mechanical Degradation. Mater. Corros. 2012, 63, 18–28. [CrossRef]
19. Xu, S.; Wang, C.; Wang, W. Failure Analysis of Stress Corrosion Cracking in Heat Exchanger Tubes during Start-up Operation.
Eng. Fail. Anal. 2015, 51, 1–8. [CrossRef]
20. Adnyana, D.N. Failure Analysis of Stainless Steel Heat Exchanger Tubes in a Petrochemical Plant. J. Fail. Anal. Prev. 2018, 18,
413–422. [CrossRef]
21. Khodamorad, S.H.; Alinezhad, N.; Fatmehsari, D.H.; Ghahtan, K. Stress Corrosion Cracking in Type.316 Plates of a Heat
Exchanger. Case Stud. Eng. Fail. Anal. 2016, 5, 59–66. [CrossRef]
22. Al-Nabulsi, K.M.; Rizk, T.Y.; Al-Abbas, F.M.; Dias, O.C. Sea Water Cooler Tubes Corrosion and Leaks Due to Microbiologically
Induced Corrosion. In Proceedings of the NACE—International Corrosion Conference Series, Vancouver, BC, Canada, 6–10
March 2016; Volume 1, pp. 141–148.
23. Abraham, G.J.; Kain, V.; Dey, G.K. MIC Failure of Cupronickel Condenser Tube in Fresh Water Application. Eng. Fail. Anal. 2009,
16, 934–943. [CrossRef]
24. Huttunen-Saarivirta, E.; Honkanen, M.; Lepistö, T.; Kuokkala, V.-T.; Koivisto, L.; Berg, C.-G. Microbiologically Influenced
Corrosion (MIC) in Stainless Steel Heat Exchanger. Appl. Surf. Sci. 2012, 258, 6512–6526. [CrossRef]
25. Sharma, P. Microbiological-Influenced Corrosion Failure of a Heat Exchanger Tube of a Fertilizer Plant. J. Fail. Anal. Prev. 2014,
14, 314–317. [CrossRef]
26. ASTM E384-22; Standard Test Method for Microindentation Hardness of Materials. ASTM International: West Conshohocken, PA,
USA, 2022. [CrossRef]
27. ASTM E3-11(2017); Standard Guide for Preparation of Metallographic Specimens. ASTM International: West Conshohocken, PA,
USA, 2017. [CrossRef]
28. ASTM A790/A790M-23; Standard Specification For Seamless And Welded Ferritic/Austenitic Stainless Steel Pipe. ASTM
International: West Conshohocken, PA, USA, 2023. [CrossRef]
29. Millero, F.J.; Huang, F. The Density of Seawater as a Function of Salinity (5 to 70 g Kg−1 ) and Temperature (273.15 to 363.15 K).
Ocean. Sci. 2009, 5, 91–100. [CrossRef]
30. Mortensen, B.M.; Haber, M.J.; Dejong, J.T.; Caslake, L.F.; Nelson, D.C. Effects of Environmental Factors on Microbial Induced
Calcium Carbonate Precipitation. J. Appl. Microbiol. 2011, 111, 338–349. [CrossRef]
31. Liu, Y.; Ali, A.; Su, J.-F.; Li, K.; Hu, R.-Z.; Wang, Z. Microbial-Induced Calcium Carbonate Precipitation: Influencing Factors,
Nucleation Pathways, and Application in Waste Water Remediation. Sci. Total Environ. 2023, 860, 160439. [CrossRef]
32. Chen, X.; Xiao, C.; Wang, X.; Yang, J.; He, C. Corrosion Behaviors of 2205 Duplex Stainless Steel in Biotic and Abiotic NaCl
Solutions. Constr. Build. Mater. 2022, 342, 127699. [CrossRef]
33. Lin, W.; Gao, Y.; Lin, W.; Zhuo, Z.; Wu, W.; Cheng, X. Seawater-Based Bio-Cementation of Natural Sea Sand via Microbially
Induced Carbonate Precipitation. Environ. Technol. Innov. 2023, 29, 103010. [CrossRef]
34. Huttunen-Saarivirta, E.; Rajala, P.; Marja-aho, M.; Maukonen, J.; Sohlberg, E.; Carpén, L. Ennoblement, Corrosion, and Biofouling
in Brackish Seawater: Comparison between Six Stainless Steel Grades. Bioelectrochemistry 2018, 120, 27–42. [CrossRef] [PubMed]
35. Yang, X.; Shao, J.; Liu, Z.; Zhang, D.; Cui, L.; Du, C.; Li, X. Stress-Assisted Microbiologically Influenced Corrosion Mechanism of
2205 Duplex Stainless Steel Caused by Sulfate-Reducing Bacteria. Corros. Sci. 2020, 173, 108746. [CrossRef]
36. Cui, L.Y.; Liu, Z.Y.; Xu, D.K.; Hu, P.; Shao, J.M.; Du, C.W.; Li, X.G. The Study of Microbiologically Influenced Corrosion of 2205
Duplex Stainless Steel Based on High-Resolution Characterization. Corros. Sci. 2020, 174, 108842. [CrossRef]
37. Xu, C.; Zhang, Y.; Cheng, G.; Zhu, W. Pitting Corrosion Behavior of 316L Stainless Steel in the Media of Sulphate-Reducing and
Iron-Oxidizing Bacteria. Mater. Charact. 2008, 59, 245–255. [CrossRef]
38. Aoki, S. Preferential Dissolution Mechanism of α or γ Phase in Crevice Corrosion of Duplex Stainless Steels. Zair. Kankyo/Corros.
Eng. 2016, 65, 45–50. [CrossRef]
39. Azzam, M.; Khalifa, W. Investigation of Duplex Stainless Steel Flow Line Failure. Eng. Fail. Anal. 2023, 143, 106935. [CrossRef]
Metals 2023, 13, 1182 15 of 15

40. Nuñez de la Rosa, Y.E.; Calabokis, O.P.; Pena Uris, G.M.; Borges, P.C. Pitting and Crevice Corrosion Behavior of the Duplex
Stainless Steel UNS S32205 Welded by Using the GTAW Process. Mater. Res. 2022, 25, e20220179. [CrossRef]
41. Machuca, L.L.; Bailey, S.I.; Gubner, R.; Watkin, E.L.J.; Ginige, M.P.; Kaksonen, A.H.; Heidersbach, K. Effect of Oxygen and Biofilms
on Crevice Corrosion of UNS S31803 and UNS N08825 in Natural Seawater. Corros. Sci. 2013, 67, 242–255. [CrossRef]
42. Revie, R.W. Uhlig’s Corrosion Handbook, 3rd ed.; John Wiley & Sons: Hoboken, NJ, USA, 2011.
43. Blackwood, D.J.; Lim, C.S.; Teo, S.L.M.; Hu, X.; Pang, J. Macrofouling Induced Localized Corrosion of Stainless Steel in Singapore
Seawater. Corros. Sci. 2017, 129, 152–160. [CrossRef]
44. Papavinasam, S. Chapter 6—Modeling—Internal Corrosion. In Corrosion Control in the Oil and Gas Industry; Papavinasam, S., Ed.;
Gulf Professional Publishing: Boston, MA, USA, 2014; pp. 301–360; ISBN 978-0-12-397022-0.
45. Gunn, R.N. 1—Developments, Grades and Specifications. In Duplex Stainless Steels; Gunn, R.N., Ed.; Woodhead Publishing:
Cambridge, UK, 1997; pp. 1–13; ISBN 978-1-85573-318-3.
46. Makhlouf, A.S.H.; Botello, M.A. Chapter 1—Failure of the Metallic Structures Due to Microbiologically Induced Corrosion and
the Techniques for Protection. In Handbook of Materials Failure Analysis; Makhlouf, A.S.H., Aliofkhazraei, M., Eds.; Butterworth-
Heinemann: Oxford, UK, 2018; pp. 1–18; ISBN 978-0-08-101928-3.
47. Schütze, M. Corrosion Books: Handbook of Corrosion Engineering. By Pierre R. Roberge—Materials and Corrosion 4/2002.
Mater. Corros. 2002, 53, 284. [CrossRef]

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