Corrosion Engineering, Science and Technology

The International Journal of Corrosion Processes and Corrosion Control

ISSN: 1478-422X (Print) 1743-2782 (Online) Journal homepage: http://www.tandfonline.com/loi/ycst20

FCAW repair welding cycles, HAZ microstructure

and corrosion resistance of 2304 duplex stainless
steel
C. F. Salvador & R. A. Antunes
To cite this article: C. F. Salvador & R. A. Antunes (2016): FCAW repair welding cycles, HAZ
microstructure and corrosion resistance of 2304 duplex stainless steel, Corrosion Engineering,
Science and Technology, DOI: 10.1080/1478422X.2016.1166706
To link to this article: http://dx.doi.org/10.1080/1478422X.2016.1166706

Published online: 19 May 2016.

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FCAW repair welding cycles, HAZ

microstructure and corrosion resistance of
2304 duplex stainless steel

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C. F. Salvador1 and R. A. Antunes 2

Flux-cored arc welding (FCAW) is an automatic welding process widely employed to join duplex
stainless steel (DSS) structures in industrial plants because of its high productivity. However,
when multiple passes are performed, this process can lead to the formation of non-metallic
inclusions originating from the slag in the fusion zone. In this case, the welded joint can be
repaired using the same welding process. Some regions next to the heat-affected zone are not
removed during the repairing operation. Thus, these regions are subjected to repeated welding
cycles and to a high heat input, which can cause microstructural alteration that impairs the
corrosion resistance of the welded material. The aim of this work was to study the corrosion
resistance of 2304 DSS plates joined using the FCAW process and repaired using the same
process. The inuence of the repair procedure on the corrosion resistance of the welded joints
was evaluated using potentiodynamic polarisation and chronoamperometric curves, which allow
the determination of the critical pitting temperature of the samples. The microstructure obtained
after each repair cycle was evaluated using optical microscopy and scanning electron
microscopy. The results showed that the corrosion resistance was depressed as the number of
repair cycles increased.
Keywords: Duplex stainless steel, Repair welding, Flux-cored arc welding, Critical pitting temperature

Introduction
Arc welding processes such as gas metal arc welding
(GMAW) and ux-cored arc welding (FCAW) are promising in the manufacturing of duplex stainless steel (DSS)based pressure vessels, pipelines and industrial equipment
in general.1,2 The FCAW process generates a slag due to
the presence of the ux and, as a result, gaseous species
released when ux melting generates a protective atmosphere, eliminating partially or entirely the need for a protection gas to be used. The process is automated which is
an attractive feature for practical engineering applications. However, the weld bead needs to be cleaned at
each welding pass to remove the slag, thus reducing the
process productivity. If the cleaning procedure is not properly carried out, then non-metallic inclusions will contaminate the weld bead. In this case, it has to be
partially removed and repaired. According to Tuomi
et al.,1 approximately 2% of the welding procedures of
DSS are reproved and need to be repaired. Some regions
1
Department of Materials Engineering, Universidade Estadual de Campinas (UNICAMP), School of Mechanical Engineering, 13083-860 Campinas,
SP, Brazil
2
Universidade Federal do ABC (UFABC), Centro de Engenharia, Modelagem e Cincias Sociais Aplicadas (CECS), 09210-580 Santo Andr, SP,
Brazil

Corresponding author, email renato.antunes@ufabc.edu.br

2016 Institute of Materials, Minerals and Mining

Published by Taylor & Francis on behalf of the Institute
Received 6 January 2016; accepted 13 March 2016
DOI 10.1080/1478422X.2016.1166706

of the heat-affected zone (HAZ) are not removed to execute the repair cycle. Hence, the repaired zones suffer
repeated thermal cycles and this can markedly affect the
corrosion behaviour of the welded joint.3
Welding cycles are likely to produce microstructural
transformations of DSS in the HAZ and fusion zone
(FZ), leading to an unbalanced fraction of the austenite
and ferrite phases.4 In this respect, the corrosion resistance of welded joints can be seriously affected, especially
the pitting corrosion behaviour of the welded DSS.5 Furthermore, partitioning of alloying elements such as chromium, molybdenum and nickel can take place due to
different thermal cycles, giving rise to distinct localised
corrosion behaviours in the weld bead and its surroundings.6 In the same way, the precipitation of undesirable
phases such as chromium nitrides and carbides in the
HAZ or FZ can deteriorate the corrosion properties
too.7 Naghizadeh and Moayed8 showed that secondaryphase precipitation decreases the corrosion resistance of
DSS due to chromium depletion after welding cycles
and this behaviour can be monitored by evaluating the
critical pitting temperature (CPT) of the welded joint.
Garca-Rentera et al.9 showed that resistance to localised
corrosion of DSS joints made by GMAW was impaired
by the presence of detrimental phases such as chromium
carbides. Ferrite-stabilising elements such as molybdenum can give rise to the formation of -phase which,

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in turn, is deleterious to the pitting corrosion resistance of

DSS.10 According to Kang and Lee,11 the onset of pitting
corrosion is associated with the phases in which the pitting
resistance equivalent number (PREN) is the least and this,
in turn, depends on the chemical composition of the corresponding phase.12 According to Sicupira et al.,2 the pitting corrosion resistance of DSS can also be improved in
the FZ due to enrichment of alloying elements after welding. The thermal history of the welded plate has a direct
inuence on its mechanical and corrosion behaviour,13
affecting both the balance between austenite and ferrite
phases and the formation of deleterious phases in
DSS.14,15 The formation of precipitates under specic
heating conditions has been reported to facilitate fatigue
crack growth in DSS and this phenomenon can be further
enhanced by the presence of a corrosive medium.16,17
For welding DSS, heat input should be restricted to
0.52.5 kJ mm1. The lower threshold is imposed due to
the inadequate reformulation of austenite under rapid
cooling rates. The upper limit is established to avoid the
precipitation of intermetallic compounds within the ferrite. Notwithstanding, the number of weld passes also
has an inuence on the deleterious phase formation,
affecting the strength and ductility of DSS.18 According
to Kotecki,19 after welding a 2507 DSS with 10 welding
passes (0.7 kJ mm1) plus 2 repair passes on the backside
(root), some specimens failed to meet specic requirements under the Charpy V-notch test, due to angular precipitates formed in the matrix. The problem was solved by
altering the welding sequence to only four weld passes
from the top and one in the back-gauged root, although
with higher heat input (1.3 kJ mm1). Ling et al.20 showed
that the weld bead overlap during multipass welding of
DSS should be properly controlled to achieve desirable
hardness and impact toughness in the welding joints. Chehuan et al. observed that localised corrosion spots of a
DSS submitted to multipass GMAW were associated
with the formation of undesirable phases in the reheating
zones.21

In spite of the well-known inuence of welding cycles

on the corrosion behaviour of DSS, investigations
focused on the effects of repair welding cycles on the
corrosion resistance of these materials are not found in
the literature. In this context, the aim of the present
work was to study the effect of three different repair
conditions on the corrosion resistance of the 2304
(UNS S32304) DSS. Flux-cored arc welding was
chosen as the welding procedure. The corrosion resistance was evaluated by potentiodynamic polarisation
curves and by determining the CPT. Microstructural
alterations were observed by optical microscopy (OM)
and scanning electron microscopy (SEM) to give support to the observed corrosion properties of the welded
joints.

Experimental
Material and welding procedure
The base metal investigated in this work was a hot rolled
and annealed DSS 2304 (UNS 32304 ArcelorMittal)
sheet with 10-mm thickness. The ller metal was a DSS
2209 ux-cored tubular wire of 1.2-mm diameter (KESTRA 4462 GFP). Compositions of base and ller metals
are shown in Table 1.
The 2304 sheet was cut into four rectangular pieces
with dimensions of 200 100 mm, which were chamfered
in a universal milling machine and welded, in pairs, using
the FCAW process for both root and lling passes. Butt
weld was carried out using reverse polarity in the at
1G position. Even though the weld root was backed
using a ceramic tile, root repair welding was necessary
in the backside of the welded joint. The dimensions of
the welded specimens prior to welding are indicated in
Fig. 1. The protection gas used was a 75%Ar-25%CO2
mixture at a ow of 1619 L min1. Additionally, in the
root pass, 99.9%Ar was used in the backside of the joint
at a ow of 20 L min1. The detailed welding sequence

Table 1 Composition of base (BM) and ller (FM) metals

BM
FM

C (%)

Cr

Cu

Mn

Mo

Ni

Si

0.018
0.028

22.550
22.540

0.424
0.343

1.350
1.370

0.259
3.040

0.001
0.080

3.570
10.000

0.025
0.030

0.001
0.003

0.360
0.540

1 Scheme of the chamfered plate prior to welding

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Electrochemical measurements

2 Dimensions of the welded specimens. Three passes

in the primary welding: (1) root pass; (2) lling; (3)
nishing; (4) root repair; joint repairs; (5) lling and (6)
nishing

is presented in Fig. 2 and the welding parameters are presented in Table 2. For all welding passes, the temperature
in-between was kept below 150C and controlled by
means of type-K contact thermocouple placed on the surface of the weld bead.
The welded sheet was divided into three specimens of
60 mm. The cutting line was perpendicular to the welding
line. The rst and last 10 mm of the weld bead were separated and disposed. One piece was not repaired (R0).
One piece was repaired once (R1) and the last piece was
repaired twice (R2). The repair cycles were carried out
always on the same side of the plate which was backgauged to sound metal using an abrasive disk before the
new welding take place. Each repair cycle consisted of
two passes (passes 5 and 6 in Fig. 2). The specimens are
designated as R0, R1 and R2, where the digit indicates
the number of repair cycles carried out for each specimen.
The electrochemical measurements were conducted in
triplicate.
Table 2

R1
R2

Microstructure analysis
Quantication of relative fractions of austenite and ferrite phases was performed by OM. Specimens were electrolytically etched in a 30 wt-% KOH water-based

Welding conditions veried during FCAW (referred to Fig. 2)

Specimen
R0

The specimens for the electrochemical measurements

were prepared according to the following set of operations: (i) a total transversal section of the weld joint comprising the HAZ, FZ and the base metal was cut from the
welded sheet; (ii) a copper wire was adhered to the specimen using conductive silver colloidal paste; (iii) the specimen was embedded in cold-setting resin; (iv) after
complete the resin curing, the specimen was mechanically
grounded using silicon carbide paper in the following
sequence #180, #400, #600 and #1200 and (v) the surface
nishing was carried out by polishing the specimens with
a 6 m diamond paste.
Potentiodynamic polarisation curves and chronoamperometric curves were acquired using the Autolab
PGSTAT100 potentiostat/galvanostat. A conventional
three-electrode arrangement was used for the measurements with a platinum wire as the counter electrode, a
standard calomel electrode (SCE) as reference and
the welded specimens as the working electrodes. For
the potentiodynamic curves, the potential range
was from 0.3 VSCE below the open circuit potential
up to 1.0 VSCE at a scanning rate of 0.001 V s1. The
electrolyte was a 3.5 wt-% NaCl solution at room
temperature.
The chronoamperometric curves were used to determine the CPT of the specimens. In this case, the electrolyte
was a 1 M NaCl solution. The experimental procedure
comprised an initial cathodic polarisation step at 0.9
VSCE for 180 s. Next, the open circuit potential was monitored during 600 s. After this stabilisation period, the
chronoamperometric curve was obtained at a constant
voltage of 0.25 VSCE. The testing cell was initially put in
an ice bath. The temperature was monitored using a
type-K thermocouple coupled to a digital thermometer.
When the temperature reached 12C, the cell was
removed from the ice bath and put in a thermostatic
bath at 45C. The electrical current was monitored by
the potentiostat after the cell was put in the thermostatic
bath. The heating rate of the electrolyte was determined
as 3.5C min1 up to 25C and 1.5C min1 for higher
temperatures. Based on literature reports,3 the CPT was
determined as the temperature corresponding to a current
density of 100 m cm2.

Step
1 (root)
2 (lling)
3.1 (nishing)
3.2 (nishing)
4 (root repair)
5 (lling repair)
6 (nishing repair)
5 (lling repair)
6 (nishing repair)
5 (lling repair)
6 (nishing repair)

Current/A

Voltage/V

Speed/mm s1

Heat input/J mm1

125
128
128
128
128
174
174
174
174
174
174

24
24
24
24
24
23
23
23
23
23
23

3.19
2.17
3.37
3.14
3.50
3.50
3.04
3.68
3.33
3.68
3.33

940
1418
911
979
878
1143
1315
1086
1201
1086
1201

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FCAW repair welding cycles and corrosion resistance

Results and discussion

Electrochemical measurements

3 Potentiodynamic polarisation curves of the base metal

and the repaired specimens

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Table 3

Material
2304
R0
R1
R2

Electrochemical parameters obtained from the

potentiodynamic polarisation curves shown in
Fig. 3
Ecorr/mV
235 27
218 12
327 37
348 26

Icorr/108 A cm
3.6 1.2
37.4 26.6
3.7 2.0
11.4 7.5

solution at 3 V for 45 s, making ferrite phase relatively

darker. The presence of deleterious phases such as chromium carbides and nitrides was evaluated using a 10
wt-% oxalic acid solution (7 V for 30 s). Finally, specimens were polished with 6 and 1-m diamond paste,
then with colloidal silica suspension (0.02 microns) and
analysed by SEM (Hitachi TM-1000). The spot size
used had nearly 1-m diameter. For R1 and R2 specimens, 15 one-minute energy-dispersive X-ray spectroscopy (EDS) acquisitions were performed from each
phase in the HAZ.

Potentiodynamic polarisation curves of the base metal

(2304) and the repaired specimens are shown in Fig. 3.
The corresponding electrochemical parameters (Ecorr,
corrosion potential; Icorr, corrosion current density) are
presented in Table 3. The Icorr values were determined
using Tafels extrapolation method. Results of the base
metal are also shown for comparison. The results correspond to the mean value of three different specimens.
The 2304 base metal presented a typical passive behaviour with a mean breakdown potential (Eb) of 235 27
mV. Low Icorr values are typical of materials with highcorrosion resistance.22 The homogeneous microstructure,
showing a good balance between the austenite and ferrite
phases, can justify this behaviour. As shown in Fig. 4a, the
microstructure of the base metal is characterised by an
approximate 1:1 proportion between austenite (brighter
phase) and ferrite (darker phase) which favours the development of a high-corrosion resistance DSS.23
The R0 specimens did not present a typical passive
range as observed in the polarisation curve shown in
Fig. 3. The material is apparently active, showing a continuous increase in the current density with the applied
potential. The Icorr is much higher than that obtained
for the base metal, indicating that the R0 specimens corrode at a high rate. It is known from the literature that the
presence of non-metallic inclusions originated from an
improper cleaning procedure after the FCAW process
and deleterious chromium nitrides or carbides which precipitate during the welding operation can seriously impair
the corrosion resistance of DSS.24 In this respect, the
microstructure of the R0 specimen has been evaluated
using SEM and OM. The SEM micrograph shown in
Fig. 4b reveals the presence of a non-metallic inclusion
in the FZ of an R0 specimen. This conrms that the cleaning step after welding was not properly accomplished,
suggesting that the FCAW process may not be suitable
to execute repair welding cycles from the standpoint of
the resulting corrosion resistance of the welded material.
Moreover, the presence of such defects can also signicantly reduce the mechanical strength of the weld bead.25

4 Optical microscopy of the 2304 steel a showing a good balance the ferrite (dark) and austenite (bright) phases and SEM-back
scattered electrons image b of a non-metallic inclusion in the weld bead of one R0 specimen

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5 Optical microscopy of R0 specimens showing deleterious precipitates revealed by the oxalic acid etching

A complementary evaluation of the microstructure of

the R0 specimens was succeeded by evaluating the presence of chromium nitrides or carbides after the oxalic
acid test described in the section Microstructure analysis.
Optical micrographs of R0 specimens are shown in Fig. 5.
The presence of undesirable precipitates next to the austenite/ferrite interface was unequivocally conrmed. Even
though the chemical composition of these precipitates
has not been identied in the present work, the Vickers
microhardness measurements (Buehler 2100, load 50 gf)
have been performed in the HAZ of the specimens
whose micrographs are shown in Fig. 5. The average hardness value was found to be 403 57 HV (50 g), which is
consistent with the precipitation of deleterious carbides
and nitrides after welding of DSS.26 As a comparison,
base metal hardness measurements resulted in approximately 250 20 HV (50 g).
According to the results shown in Table 3, if one compares R1 and R2 specimens there was a trend of decreasing the corrosion potential (Ecorr) and increasing the Icorr
values as the number of repair cycles increased. This
behaviour could be explained based on the microstructural features observed in the HAZ of the specimens
after each repair cycle. The corrosion current density of
the R1 specimens was similar to that of the base metal.

Furthermore, a well-dened passive region appears

between 0.1 and + 0.53 V and a breakdown potential
could be perceived at the upper limit of the passive region.
For the R2 specimens, the corrosion current density is
higher and the polarisation curve does not demonstrate
any passive behaviour.
In order to give a further understanding on the corrosion behaviour of the R1 and R2 specimens, their
microstructures were observed by OM. Figure 6 presents
micrographs of R1 specimens showing the base metal, FZ
and the interface between them in the HAZ. The micrograph on the right is the same region on the left but at a
higher magnication to show the HAZ in more detail.
The absence of deleterious precipitates is noteworthy.
The high-corrosion resistance of the R1 specimens should
be a consequence of this favourable microstructure. It is
believed that the deleterious precipitates were successfully
removed by mechanical grinding the previous HAZ, and
could not nd conditions to be formed again during welding due to correct selection of R1 welding parameters.
Optical micrographs of R2 specimens are shown in
Fig. 7. The formation of deleterious precipitates can be
promptly viewed. This microstructure leads to a high-corrosion current density in comparison with the R1
specimens.

6 Micrographs of R1 specimens showing the base metal, FZ and HAZ

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7 Optical microscopy showing the presence of precipitates in the HAZ of an R2 specimen. The image on the right shows the
HAZ at a higher magnication

Table 4
Sample

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R1
R2

Composition and PREN of ferrite and austenite for R1 and R2 samples

Phase

Cr/wt-%

Ni/wt-%

Mo/wt-%

PREN

Ferrite
Austenite
Ferrite
Austenite

22.3 0.5
20.5 0.5
21.7 0.7
20.3 0.6

5.0 0.3
5.8 0.2
4.9 0.2
5.6 0.3

0.34 0.2
0.27 0.2
0.33 0.2
0.28 0.2

24.4
27.4
23.8
27.3

Microstructural and compositional aspects

27

Studies by Liou et al. argued that the reformulation of

austenite is prevalent at low cooling rates, turning the
Cr2N precipitation to be less attainable. Looking at
Table 2, it is possible to observe that the average heat
input in R0 specimen was lower than the repair conditions
R1 and R2, which can be associated with a higher cooling
rate and hence results in a non-equilibrium microstructure, with insufcient austenite formation.
Chen and Yang28 have simulated the HAZ in a 2205
DSS solubilised at temperatures above 1300C, cooled,
and then reheated at 700C for 1, 5 and 10 min. Cr2N
rod-like precipitates, lesser than 1 m in length and 50
nm in thickness, were found mainly within the ferrite
regions. Cr2N precipitates detected at the austenite/ferrite
interfaces were even smaller sized, due to the high nitrogen solubility in austenite. Given the inconvenience of
analysing these so small-sized precipitates, recent papers
have been investigating other microstructural features
directly associated with the corrosion resistance, so as
the austenite and ferrite compositions and its Creq/Nieq
and PRENs,29 which are also related to the Cr2N formation. Dense Cr2N precipitation leads to a depletion
of Cr from the ferrite, originating zones highly susceptible
to pitting. Finally, Chen et al.25 have shown that the CPT
drops from 19 to 14.2C when a 2304 DSS solubilised at
1350C is cooled to 800C with cooling rates of 10 and
100C s1, respectively. According to the authors, the
higher the cooling rate, the lower the ferrite Cr content,
which is related to a lower PREN.
In this study, ferrite and austenite compositions in the
HAZ (R1 and R2) were investigated using SEM-EDS.
The results are presented in Table 4. Nitrogen content
could not be detected by SEM-EDS apparatus, so it was
xed in 0.05 wt-% (ferrite) and 0.3 wt-% (austenite) for

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2016

both R1 and R2 specimens, based on Chens (2012) results.25

PREN was given by PREN = %Cr + 3.3%Mo + 20%N.30
From a compositional aspect (Table 4), R2s ferrite has
lower Cr content than R1s (21.7 < 22.3), so it would be
expected R1 specimens to own a higher corrosion resistance than R2, what is indeed observed. The joint repair
passes applied to R1 have given rise to the most wellbalanced microstructure among the welded specimens,
with ferrite/austenite ratio near 0.5 and consequently an
absence of Cr2N. Comparing with R0, the rst repair
welding seems to be benecial to the microstructure,
removing previous defects and favouring the reformulation of austenite. On the other hand, the same operation
repeated twice (R2) seems to jeopardise all the benets
obtained at the rst repair passes, taken the fact that R2
samples also presented Cr2N deleterious precipitates.
Comparably, Tan et al. and Deng et al. 7,24 have

8 Critical pitting temperature experimental curves for base

metal (2304) and the repaired specimens R0, R1 and R2

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9 Pitting preferable sites in R1 specimen

demonstrated that there is an optimum temperature to

post-weld heat-treating DSS specimens subjected to welding, and if this temperature is exceeded, an optimal microstructure, similar to R1 specimen, can turn into a highferrite content microstructure, in which ferrite is more susceptible to localised corrosion comparing with the former.
In another interesting study, Garzn and Ramirez31
attested that reheating cycles (above 1050C) are followed by a limited secondary austenite reformulation,
which arises via solute partitioning with the ferritic
matrix. An analogous microstructural response was
found in our experiments, thus, probably, for each system
there are a limited number of repair welding operations
that result in an optimised microstructure.

Critical pitting temperature

Typical curves of current density (I ) versus temperature
for base metal (DSS 2304) and the repaired specimens,
R0, R1 and R2 are shown in Fig. 8. The criterion for
determining the CPT of each specimen (temperature corresponding to a current density of 100 A cm2) is marked
as a doted horizontal line in the plot.
As indicated in Fig. 9, the conditions R0 and R2 yielded
the lowest CPTs (28.0 and 28.2C, respectively), whereas
the condition R1 presents the highest CPT (34C), even
higher than the value for the base metal (30.2C). Considering that we used a ller metal with higher solute content
(Mo and Ni rich) than the base metal, it is possible that
there was a slightly solute enrichment in the HAZ and
nearby, improving the corrosion resistance. Also, the corrosion resistance depends on secondary microstructural
features such as grain size and solute distribution; such
features could be affected during the FCAW process.
It is observed, thus, that R1 surpassed the pitting corrosion resistance of the repaired R0 and R2 specimens.
This behaviour can be supported by the same microstructural aspects highlighted in the sections Electrochemical
measurements and Microstructural and compositional
aspects. The absence of deleterious precipitates and higher
ferrite Cr content in the R1 specimens led to a high-corrosion resistance and this was conrmed by the CPT
values determined from the curves shown in Fig. 9. For
the R1 samples, as expected, the pitting corrosion occurs
either on ferrite phase or on the ferrite/austenite boundaries, since there are no deleterious precipitates to act as

a pit nucleation site, as shown in Fig. 9. R0 and R2 specimens, in turn, presented heterogeneous microstructure
characterised by the formation of widespread undesirable
precipitates detected by the oxalic acid test. Hence, the
corrosion resistance was depressed for these conditions.

Conclusions
The inuence of repair welding cycles on the corrosion
behaviour of the 2304 DSS has been evaluated. Besides
the FCAW process leading to the presence of non-metallic
inclusions in the weld bead if it is not properly cleaned
after welding, the results showed that it is possible to
obtain a weld bead with a homogeneous microstructure
after the repair cycle (R1 specimens), but it seems there
are a limited number of welding-repair operations that
result in an optimised microstructure.
The CPT was sensitive to the microstructural changes
during the welding process and can be used as a design
criterion to assess the quality of repaired welding in
DSS. A good agreement was found between the electrochemical behaviours observed in the potentiodynamic
polarisation curves and the CPT values.

Acknowledgements
The authors thankfully acknowledge the Brazilian
research funding agencies CAPES and CNPq for their
nancial support, KESTRA for providing ux cored
welding wire for this work, Prof. Rubens Caram (UNICAMP) for the SEM equipment and Montcalm Montagens, Brazil, for the welding equipment supplied and staff.

ORCID
Renato Altobelli Antunes
1540-6495

http://orcid.org/0000-0003-

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