Corrosion behavior of radial friction welded supermartensitic stainless

steel pipes
C.A. Della Rovere
a,
, J.M. Aquino
b
, C.R. Ribeiro
a
, R. Silva
a
, N.G. Alcntara
a
, S.E. Kuri
a
a
Department of Materials Engineering, Federal University of So Carlos, Rodovia Washington Luis, Km 235, 13565-905 So Carlos, SP, Brazil
b
Department of Chemistry, Federal University of So Carlos, Rodovia Washington Luis, Km 235, 13565-905 So Carlos, SP, Brazil
a r t i c l e i n f o
Article history:
Received 2 June 2014
Accepted 3 September 2014
Available online 19 September 2014
Keywords:
Stainless steel
Welding
Polarization
Acid corrosion
Pitting corrosion
a b s t r a c t
Supermartensitic stainless steel pipes were radial friction (RF) welded and their corrosion properties
were determined based on electrochemical tests. Measurements were performed on samples taken from
the base metal (BM), weld interface, and consumable ring (CR) of the RF weldment. The corrosion prop-
erties are discussed in terms of their resulting metallurgical microstructure. In acid media, RF weldment
regions presented better corrosion performance than the tempered structure of the BM. The Cr carbide
precipitation that occurs during tempering causes substantial depletion of Cr, while d-ferrite formation
during welding cycle decreases the pitting corrosion resistance of the material.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
Since the early 90s, the oil industry has been promoting the
development of new corrosion resistant alloys for onshore and off-
shore pipeline applications. In this context, supermartensitic stain-
less steel (SMSS) was introduced to bridge the gap between the
corrosion performance of carbon steels/conventional martensitic
stainless steels and the more expensive duplex materials, while
providing a larger application domain in terms of temperature,
CO
2
+ H
2
S content and chloride concentration. In addition, this
new class of martensitic stainless steels combines low production
cost, ease of heat treatment, good mechanical properties and
improved weldability. These advantages have let to the widespread
use of SMSSs in the manufacture of oil country tubular goods,
which include special seamless pipes for drilling, casing, and tub-
ing for application in oil and gas wells operating under moderately
corrosive conditions [13].
The main metallurgical difference between conventional mar-
tensitic stainless steels and SMSSs is that the latter contain up to
3% more molybdenum (Mo) and up to 6% more nickel (Ni). Mo is
added to improve the resistance to sulde stress cracking and
localized corrosion, while Ni is added to stabilize austenite (c) at
high temperatures, preventing the formation of d-ferrite. Carbon
(C) content levels are reduced to as little as 0.01 wt.% to improve
weldability. In addition, some microalloying with titanium (Ti)
and/or niobium (Nb) have been employed to stabilize residual C
and nitrogen (N) and prevent the precipitation of chromium (Cr)
rich carbonitrides, which impairs the corrosion resistance of
steel, and to produce a ner microstructure with superior mechan-
ical properties [46].
Today, the major issues and challenges of SMSSs have to do
with their weldability and the resulting mechanical and corrosion
performance of the welded material, as well as the development of
fast, reliable, economic welding processes that minimize or even
dispense with expensive and time-consuming post-weld heat
treatments. In this context, several new and advanced processes
have been investigated as alternatives to conventional welding
process for SMSSs [710]. Omura et al. [7] applied laser welding
to produce thin wall seam welded pipes of SMSS with excellent
corrosion properties due to the rapid solidication of the weld
metal, which had neither precipitation nor segregation. These
authors also found that the laser welded pipes showed superior
corrosion resistance than those produced by conventional seam
welding processes such as gas tungsten arc welding (GTAW) and
electric resistance welding (ERW). Aquino and co-workers [8,9]
have studied the corrosion behavior of SMSS welded joints pro-
duced with or without matching consumables, using electron
beam welding (EB) process. No PWHT was applied. In both cases,
because of the rapid heating and cooling involved in the EBW pro-
cess, the authors have veried an improvement in the corrosion
resistance from the base metal to the weld metal in the EB weld-
ment. However, Bala Srinivasan and co-workers [10] have reported
http://dx.doi.org/10.1016/j.matdes.2014.09.003
0261-3069/ 2014 Elsevier Ltd. All rights reserved.

Corresponding author. Tel.: +55 16 33518507; fax: +55 16 33518258.

E-mail addresses: carlosdrovere@ufscar.br, carlosdrovere@gmail.com (C.A. Della
Rovere).
Materials and Design 65 (2015) 318327
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that the weld metal of SMSS EB welded joints is prone to embrit-
tlement under the conditions of hydrogen charging due to the high
hardness and strength levels presented by the microstructure in
this region. In summary, much attention is still focused on estab-
lishing optimal welding procedures for SMSSs and on understand-
ing the behavior of these weldments in different applications.
Radial friction (RF) welding is a variant of the friction welding
process which was developed by TWI as a one-shot joining tech-
nique for pipelines, offering signicant advantages over conven-
tional welding process, e.g. an extremely fast welding time of
less than thirty seconds, no requirement for operator skills, high
weld quality, high reproducibility and the possibility of joining dis-
similar materials. In addition, many of the metallurgical problems
associated with fusion welding processes can be avoided, since RF
welding is a solid state joining process [1116]. In regard to the
development of this welding process, there are some works worth
mentioning. For example, RF welding experiments were rst pro-
posed and carried out by Nicholas et al. [11] using steel pipes.
Dunkerton and co-workers [12] applied RF welding to duplex
stainless steel pipes and obtained a satisfactory weld quality. A
sound weld formation with no defects was observed in the trans-
verse section of the weldment. In addition, the authors have also
highlighted that RF welding is a suitable procedure for offshore
application. Torster et al. [13] studied the metallurgical and
mechanical properties of Ti6Al4V0.1Ru (wt.%) riser pipes
joined by RF welding and indicated that the RF welded joints fulll
the basic requirements for a future use in the installation of
Ti6Al4V0.1Ru (wt.%) production risers. Luo et al. [14] have
adopted RF welding to copper/high carbon steel dissimilar metals
and studied the interfacial features of this dissimilar welding joint.
They reported that a smooth line occurs in the central welding
interface and a good welding seam is formed. Very recently, the
studies by Rovere et al. [15,16] revealed that the RF welding pro-
cess can be applied to SMSS pipes and high quality SMSS (defect-
free) welds can be reproducibly made with mechanical properties
closely matching those of the base material, without requiring a
post-weld heat treatment.
Despite the above cited advantages and the excellent potential
of RF welding for joining pipes offshore, this solid-state welding
process is not yet widely applied. Moreover, the current literature
contains very few studies about the corrosion behavior of RF
welded pipes, so additional studies are of vital importance to fur-
ther develop and expand the industrial application of this welding
process. In this work, the corrosion behavior and microstructural
characteristics of the different regions of SMSS pipes welded by
RF were investigated separately, i.e., the base metal, consumable
ring and weld interface. The corrosion properties were studied
based on potentiodynamic polarization and double loop electro-
chemical potentiokinetic reactivation (DL-EPR) measurements.
The resulting metallurgical microstructures were analyzed by opti-
cal microscopy (OM), scanning electron microscopy (SEM) and
X-ray diffraction (XRD).
2. Experimental Procedure
2.1. Material
The SMSS RF welded seamless pipe segments had an outer
diameter of 168.3 mm and a wall thickness of 14.3 mm. RF welds
were produced using a consumable ring machined from a heavy
wall pipe. Both the pipe material (BM) and the consumable ring
(CR) consisted of a commercial high alloy SMSS (UNS S41426) in
quenched and tempered condition, and their chemical composi-
tions are described in Table 1.
The RF welding process was performed by putting together two
bevelled pipes, which were secured by clamps to prevent any addi-
tional rotation or axial movement. First, the CR was placed
between the two pipe ends, as depicted in Fig. 1. The CR was then
rotated and compressed radially to produce frictional heat
between the rubbing ring and the stationary pipe surfaces, gener-
ating the thermomechanical conditions needed to form the weld.
To keep the pipe ends aligned radially and to react against external
radial welding pressure, a heat resistant mandrel was simulta-
neously expanded inside the pipe bore at the weld site. After a
given period of time and a controlled level of metal displacement
(burnoff), rotation was stopped and the radial pressure was main-
tained to consolidate the weld [11,15,16].
Table 2 lists the welding parameters used in this work. Further
details about the RF welding process on SMSS, optimization of
welding parameters and mechanical properties of SMSS RF welded
pipes can be found in elsewhere [16]. It should be noted that the RF
welded pipes studied here were not post-weld heat-treated, and
that all the subsequent analyses were performed in the as-welded
condition.
Fig. 2(a) shows a photomacrograph of SMSS RF welded pipes, in
which three distinct regions are clearly visible: BM, CR and weld
interface. This gure also indicates the sites from which cylindrical
test samples (U = 5 mm) were extracted carefully using a wire cut
EDM machine (dashed black circles). In addition, as shown in
greater detail in Fig. 2(b), note that the weld interface region con-
sists of two subregions: a heat affected zone (HAZ) and a thermo-
mechanically affected zone (TMAZ).
2.2. Microstructure characterization
The microstructural characteristics of the BM, CR and weld
interface regions were analyzed by OM and XRD. For the OM anal-
ysis, the samples were polished mechanically to a mirror nish
(alumina 1.0 lm) and etched with Villelas reagent [composed of
95 ml of ethanol, 5 ml of hydrochloric acid (HCl) and 1 g of picric
acid (C
6
H
3
N
3
O
7
)]. To determine the phases present in the three dis-
tinct regions of RF weldment and their relative amounts, particu-
larly retained austenite, the test samples were subjected to XRD
measurements using Cu Ka radiation combined with Rietveld
renement (Maud software) [17]. Two structure types were
considered on the analyses of the XRD patterns: (1) a iron, body-
centered cubic symmetry, space group Im-3m for the martensite
(a) phase, and (2) c iron, face-centered cubic symmetry, space
group Fm-3m for the austenite (c) phase.
2.3. Electrochemical tests
The electrochemical test samples were mounted in polyester
resin to prevent the formation of crevices after the electric contact.
The exposed area was 0.196 cm
2
. Before the electrochemical mea-
surements, the samples were carefully wet sanded with #600-grit
silicon carbide (SiC) paper, washed in distilled water, and
immersed in the electrochemical cell. All the measurements were
taken using a Gamry Reference 3000 electrochemical system and
a conventional three-electrode electrochemical cell with a plati-
num counter-electrode and a saturated calomel reference elec-
trode (SCE). All the electrochemical measurements were taken at
25 C in newly prepared naturally aerated solutions. To ensure
good reproducibility, a minimum of ve curves were created for
each sample and the average values were considered.
Before the potentiodynamic polarization measurements, the
samples were subjected to open circuit conditions until a steady-
state potential was reached, which was accomplished in 60 min,
and the resulting potential value was considered the open-circuit
potential (E
OC
). Potentiodynamic polarization was carried out in a
0.5 M H
2
SO
4
solution by stepping the potential at a scan rate of
1 mV/s from a potential of 200 mV below E
OC
to a potential of
C.A. Della Rovere et al. / Materials and Design 65 (2015) 318327 319
1200 mV
SCE
. To determine the pitting potential (E
P
), potentiody-
namic polarization tests were carried out in a 3.5% NaCl solution
at sweep rates of 1 mV/s, starting from E
OC
to a potential at which
the current density reached 0.5 mA/cm
2
. The E
P
was taken as the
potential where a sudden sharp rise in current density occurred
and the value of 200 lA/cm
2
was exceeded [18]. In order to iden-
tify the morphology of corrosion attack, SEM images were recorded
after determining the E
P
.
The degree of Cr depletion along the different regions of the RF
weldment was determined based on a DL-EPR test performed in a
solution of 0.5 M H
2
SO
4
+ 0.01 M KSCN at 25 C (as proposed by
C

hal et al. for SMSSs) [19,20]. Although this electrochemical test

was initially developed for austenitic stainless steels, it has been
shown that, pursuant to some adjustments to the experimental
conditions (test solution, temperature and scan rate), it is effective
in the detection of Cr depleted regions in numerous cases of stain-
less steels or nickel-based alloys [8,1924]. The polarization scan
was started 15 min after immersion of the samples. The potential
was scanned in the anodic direction from 400 mV
SCE
to
600 mV
SCE
, after which the polarization scan was reversed in the
cathodic direction up to 400 mV
SCE
. A sweep rate of 1.67 mV/s
was used. The loss of corrosion resistance due to the chromium
depleted regions was evaluated in terms of the ratio of total
charges Q
r
/Q
a
100% in combination with microstructural obser-
vation by SEM after the DL-EPR measurements. Q
a
was obtained
from the polarization curve in the anodic direction and is directly
linked with charges of the entire surface of the sample, while Q
r
is associated with the charges of the corrosion susceptible
chromium-depleted regions, and is obtained from the polarization
curve in the cathodic direction [19]. The decision to use the charge
ratio (Q
r
/Q
a
) instead of the ratio of the maximum intensities of
reactivation to the activation peaks (I
r
/I
a
) was based on the litera-
ture [25]. The Q
r
/Q
a
ratio has proved to be a more suitable param-
eter when the results present two peaks in the activation and/or
reactivation scan. According to Assis et al. [25], in such situations,
the value of Q
r
/Q
a
represents the dissolution that occurs around all
the deleterious phases in the sample and seems able to eliminate
the inuence of one peak over the other, precluding the need for
supplementary work to separate the two peaks.
3. Results and discussion
3.1. Microstructure
Fig. 3(a) shows the microstructure of the unaffected BM region,
revealing a tempered martensite matrix with no evidence of
Table 1
Chemical composition (wt.%) of the materials.
Material Element (wt.%)
C Si Mn P S Cr Ni Mo Ti Cu
Base material 0.01 0.17 0.47 0.012 0.001 12.01 6.40 2.42 0.10 0.02
Consumable ring 0.01 0.14 0.42 0.010 0.001 11.94 6.36 2.42 0.07 0.02
Fig. 1. Schematic illustrations of the RF welding process [16].
Table 2
RF welding parameters used.
Parameters Conditions
Rotation speed (rpm) 200
Friction pressure (MPa) 4
Friction time (s) 24
Burn-off length (mm) 7.5
Brake time (s) 1
Forging pressure (MPa) 4
Forging time (s) 4
Fig. 2. (a) Photomacrograph of the RF welded SMSS pipes, showing the sites from which the test samples were extracted (dashed black circles); (b) optical micrograph
detailing the microstructural characteristics of the weld interface region.
320 C.A. Della Rovere et al. / Materials and Design 65 (2015) 318327
d-ferrite. In addition, the BM structure also has a substantial
retained austenite content of around 12.2 vol.%, as identied and
measured by XRD (Fig. 4) and Rietveld analysis. According to the
literature [2629], the formation of stable austenite in SMSSs takes
place during tempering at around the austenite formation onset
temperature (A
C1
) by means of a Ni enrichment mechanism. Fur-
thermore, this austenite, which is nely distributed along the mar-
tensite interlath boundaries and is detectable only by high
resolution microscopy, improves the toughness of the material
through a localized transformation-induced plasticity effect during
the fracture process [27]. With regard to the effect of retained aus-
tenite on the corrosion properties of SMSSs, no consensus has so far
been reached because of its complexity. Some researchers have
suggested that the presence of retained austenite can promote car-
bon and nitrogen dissolution, preventing the precipitation of these
elements with chromium and molybdenum, and hence, decreasing
the sites available for pit nucleation, although these authors did
not verify experimentally a direct relationship between the austen-
ite content and localized corrosion susceptibility [9,30]. Other
authors have demonstrated that the pitting potential becomes sig-
nicantly more noble as the retained austenite content increases
through two-stage tempering, arguing that the retention of this
phase promotes structural renement of the microstructure of
the material and decreases the formation of Cr precipitates by
maintaining a higher amount of this element in solid solution,
leading to thicker anodic lms with improved localized corrosion
resistance [3133]. On the other hand, based on DL-EPR tests, Silva
and coworkers [28] recently reported that the increase in retained
austenite volumetric fraction promoted by double tempering is
accompanied by a substantial increase in the Cr-depleted regions
of SMSS when compared with a quenched sample. However, these
authors did not measure the pitting potential of the material. It
should be kept in mind that one of the reasons for this controversy
in the literature seems to be linked directly to the difculty in
determining the individual effect of retained austenite and Cr rich
carbides on the corrosion properties of SMSS. According to the lit-
erature [9,28,3439], although SMSSs have very low carbon con-
centrations, some nanometric Cr-rich carbide precipitation at
interlath boundaries and within martensite laths always occurs,
together with the formation of stable austenite during the temper-
ing process. In addition, the results of Silva and coworkers [28]
suggest that this precipitation of Cr-rich carbides occurs even in
Ti stabilized SMSSs.
Fig. 3(b) depicts a micrograph of the central portion of the CR
region. Note that a ne-grained microstructure composed of a mix-
ture of virgin martensite and stable retained austenite (12.1 vol.%,
as illustrated in Fig. 4) was formed in this region due to the weld
thermal cycle. On the other hand, the heat and deformation gener-
ated during the RF welding process produced two distinctly differ-
ent zones across the weld region: (1) a TMAZ located at the weld
interface, where the material underwent high plastic deformation
due to the compressive pressure applied to consolidate the metal-
lic bond, in addition to heat-induced microstructural changes; and
(2) a HAZ in which the microstructure of the material was modied
mainly by the thermal eld of the welding process, although this
Fig. 3. Typical microstructure in the region of: (a) BM; (b) CR; (c) HAZ and (d) TMAZ present at the weld interface [15].
Fig. 4. XRD patterns of the distinct regions of RF welded SMSS pipes. The tting
residual is plotted on the same scale at the bottom of each individual pattern.
C.A. Della Rovere et al. / Materials and Design 65 (2015) 318327 321
region also underwent some degree of deformation. As indicated in
Fig. 3(c) and (d), the microstructure of the HAZ consists predomi-
nantly of virgin martensite and d-ferrite stringers surrounding
prior austenite grains, while that of TMAZ presents a coarse-
grained microstructure composed of virgin martensite with a very
small fraction of d-ferrite. XRD patterns indicate that the weld
interface contains no retained austenite. As mentioned earlier,
the formation of stable austenite in SMSS (which is retained when
the alloy is cooled to ambient temperature) takes place during
tempering at around A
C1
by means of a Ni enrichment mechanism;
therefore, very little, if any, austenite is retained in SMSS micro-
structures after heating to temperatures inside the d-ferrite single
phase eld, which explains the absence of austenite in the weld
interface region [2729]. A more detailed discussion about the
microstructural evolution of SMSS during the RF welding is given
in a previous paper [16].
3.2. Potentiodynamic polarization in 0.5 M H
2
SO
4
solution
The potentiodynamic polarization tests in 0.5 M H
2
SO
4
solution
were carried out to study the electrochemical corrosion behavior of
the RF weldment in acid media. Fig. 5 shows the potentiodynamic
polarization curves obtained from the distinct regions of the RF
welded SMSS pipes. Note that the shape of the curves is similar
and all the regions exhibit an activepassive behavior characteris-
tic of stainless steel in sulfuric acid media [40]. However, their ano-
dic behavior differed in terms of corrosion potential (E
corr
), critical
anodic current density required for passivation (i
crit
), and passive
current density (i
pass
).
Table 3 describes the different electrochemical parameters
determined from the potentiodynamic polarization curves. Since
the curves do not exhibit well-dened anodic or cathodic Tafel
regions (over at least one decade of current), which limits the
determination of accurate values of corrosion current density
(i
corr
), the corrosion properties of the three distinct regions of weld-
ment were evaluated as a function of E
corr
, i
crit
, and i
pass
[41]. Note
that the unaffected BM has the lowest E
corr
value, indicating that
this region is more active than the CR and weld interface regions
in acid media. In addition, also note that the tempered structure
of BM presents the worst passive behavior between the three
regions, exhibiting the highest values of i
crit
and i
pass
, which indi-
cate, respectively, greater difculty to form the passive lm and
poorer passive lm protection in acid media when compared with
the other regions of the RF welded pipes. This behavior can be
explained as follows. SMSSs have a lower tendency for carbide
precipitation than conventional stainless steels due to their low
carbon content. In these materials, the C atoms are completely dis-
solved in the austenite matrix at high temperature and this state is
still maintained during the transformation from austenite to mar-
tensite by quenching. However, during tempering, the free C atoms
available in the solid solution combine with Cr to form nanometric
Cr-rich M
23
C
6
carbides both inside the grains and at grain bound-
aries, in most cases leading to generalized Cr depletion [9,28,34
39]. That is why the corrosion performance of the unaffected BM
tempered structure in acid media is poorer than in the other RF
welding regions (CR and weld interface), whose microstructures
were transformed and their Cr-rich carbide precipitates partially
redissolved by the thermomechanical RF welding cycle. This
resulted in a greater availability of Cr in solid solution, leading to
a better passive behavior in the latter regions. These results are
similar to those reported by Aquino and co-workers [42], who
studied the corrosion behavior of electron beam (EB) welded SMSS
joints in diluted H
2
SO
4
medium. They observed that the EB welded
joint exhibited an improvement in corrosion performance from the
BM to the weld metal (WM) region. In that case, the superior cor-
rosion properties of the WM and HAZ regions were attributed,
respectively, to the rapid solidication process and to the redisso-
lution of Cr carbide precipitates formed during the tempering
treatment.
3.3. DL-EPR measurements
DL-EPR measurements were taken in the 0.5 M H
2
SO
4
+ 0.01 M
KSCN solution at 25 C to evaluate the degree of Cr depletion along
the different regions of the RF weldment. Fig. 6 shows the typical
DL-EPR curves obtained for the BM, CR and weld interface samples.
Note that a high current density reactivation peak was observed in
the BM sample, whereas the CR and weld interface samples
showed no signicant current density reactivation peak. However,
a more detailed analysis of the cathodic polarization scan plot
(Fig. 6(c)) reveals a small reactivation peak at the weld interface
sample. The origin of this peak will be discussed below.
Fig. 6(d) illustrates the degree of loss of corrosion resistance
(Q
r
/Q
a
) in the samples extracted from the distinct regions of the
RF welded SMSS pipes. Note that the BM sample shows a much
higher Q
r
/Q
a
ratio than the CR and weld interface samples, which
is in good agreement with the previous polarization measure-
ments, and demonstrates that the degree of Cr depletion in the
tempered structure of the BM is greater than in the other regions
of the RF welded pipes. As stated earlier, the considerable loss of
corrosion resistance of the BM sample may be attributed to the
presence of Cr-depleted regions that were formed in response to
the tempering heat treatment [9,28,3439]. On the other hand,
the very low Q
r
/Q
a
ratios of the CR and weld interface samples
are directly linked to the redissolution of Cr rich precipitates and
the metallurgical microstructures resulting from the thermome-
chanical RF welding cycle.
After the DL-EPR tests, the samples were also analyzed micro-
structurally by SEM to identify the morphology of the corrosion
attack. As can be seen in Fig. 7(a) and (b), a heavy corrosion attack
is visible along lath martensite and grain boundaries throughout
Fig. 5. Potentiodynamic polarization curves obtained from distinct regions of RF
welded SMSS pipes immersed in 0.5 M H
2
SO
4
solution.
Table 3
Electrochemical parameters in 0.5 M H
2
SO
4
solution
a
.
Weldment region E
corr
(mV
SCE
) i
crit
(lA/cm
2
) i
pass
(lA/cm
2
)
BM 408.83 3.52 296.52 47.97 29.78 2.28
CR 385.18 5.27 156.44 23.61 11.67 0.78
Weld Interface 379.00 3.49 97.21 11.94 13.07 1.02
a
Scatter bands measured in 5 test samples.
322 C.A. Della Rovere et al. / Materials and Design 65 (2015) 318327
the structure of the BMsample, while no signicant attack is visible
in the microstructure of the CR sample. On the other hand, despite
the low Q
r
/Q
a
ratio exhibited by the weld interface sample, which
comprises the HAZ and TMAZ regions, a pronounced selective attack
is clearly visible at the d-ferrite/virgin martensite phase boundaries
in some points of the HAZ (Fig. 7(c)). According to the literature
[37,4346], this selective dissolution of d-ferrite/virgin martensite
phase boundaries may be caused by two factors: (1) the existence
Fig. 6. DL-EPR curves of the distinct regions of RF welded SMSS pipes in a solution of 0.5 M H
2
SO
4
+ 0.01 M KSCN at 25 C: (a) BM; (b) CR; (c) weld interface, and (d) Q
r
/Q
a
ratio
(scatter bands measured in 5 test samples).
Fig. 7. SEM micrographs of the surface aspect of the distinct regions of RF welded SMSS pipes after DL-EPR testing: (a) BM; (b) CR; (c) HAZ and (d) TMAZ. The samples were
previously polished with 1 lm alumina.
C.A. Della Rovere et al. / Materials and Design 65 (2015) 318327 323
of Cr depleted regions due to precipitation of Cr carbides (or
carbonitrites) near the d-ferrite phase boundary; and/or (2) as the
d-ferrite phase is enriched in ferritizing elements, i.e., Cr, Mo, Si,
etc., their formation during the welding cycle can lead to a decrease
in Cr content in the adjacent martensite. The presence of a small
reactivation peak in the cathodic scan of the weld interface sample
seems to be directly associated with the selective attack at the
d-ferrite/virgin martensite interfaces in some points of the HAZ. In
addition, the low intensity of this reactivation peak can probably
be ascribed to the relatively small size of Cr-depleted interfaces
when compared with the total exposed area of the sample.
Another feature present in Fig. 6 that deserves attention is the
presence of two activation peaks in the anodic scan of the BM sam-
ple: one at 180 mV
SCE
and the other at 110 mV
SCE
. To investigate
the origin of these peaks, the BMsample was subjected to potentio-
static etching for 300 s at the above mentioned potentials. Fig. 8
shows the SEM images obtained after these potentiostatic etchings.
Note that the rst activation peak (180 mV
SCE
) corresponds to the
corrosion attack of the martensite laths, while the second peak
(110 mV
SCE
) is due to dissolution of the small particles of retained
austenite, which are distributed along the martensite interlath
boundaries. This behavior is similar to that presented by duplex
stainless steels in mixed H
2
SO
4
/HCl solutions [47,48]. Due to the
difference in the chemical composition of their two constituent
phases (ferrite and austenite), they also exhibit two anodic peaks
in the active-to-passive transition region of the potentiodynamic
polarization curves. In duplex stainless steels, the anodic peak at
a more noble potential also corresponds to the preferential attack
of austenite, while that at a lower potential corresponds to ferrite.
It is also worth noting, in Fig. 6, that although the CR sample
presents a volumetric fraction of retained austenite similar to that
of the BM sample, the DL-EPR curves of this sample did not exhibit
the two activation peaks. Since DL-EPR measurements were taken
from the samples extracted from the weldment in the as-welded
condition, this difference can be attributed to the chemical compo-
sition of the retained austenite present in the CR, which in this case
was not Ni-enriched by the tempering treatment, and hence, is
similar to that of the virgin martensite matrix [20].
3.4. Anodic polarization in 3.5% NaCl solution
The potentiodynamic anodic polarization tests in 3.5% NaCl
solution were performed to evaluate the pitting corrosion resis-
tance in the distinct regions of RF welded SMSS pipes. Fig. 9(a)
shows the typical anodic curves obtained for BM, CR and weld
interface samples. Note that the three regions presented a similar
behavior, with an E
OC
of around 150 mV
SCE
. Moreover, none of
the curves exhibited an activepassive transition behavior,
indicating that the samples are in the passive state in the electro-
lyte. All the samples showed a passive current density of approxi-
mately 2 lA/cm
2
. In addition, some current oscillations are visible
due to the nucleation and metastable growth of pits that were
repassivated as soon as the potential was stepped up in the anodic
direction. The E
P
as derived from the curves are presented in
Fig. 9(b). Note that the CR microstructure shows the highest pitting
corrosion resistance, as indicated by the high E
P
, whose values are
around 241 mV
SCE
. The BM and weld interface samples present an
E
P
of 218.8 mV
SCE
and 210.3 mV
SCE
, respectively. The microstruc-
tural changes promoted by the RF welding thermal cycle in the
CR region augmented the pitting corrosion resistance compared
to that of the tempered structure of the BM region, which can be
attributed to the redissolution of Cr carbide precipitates and the
formation of a ne-grained microstructure composed of a mixture
of virgin martensite and stable retained austenite. On the other
hand, although redissolution of the Cr carbide precipitates also
took place in the weld interface sample, which should improve
the pitting resistance of this region, the formation of d-ferrite
and its retention in the microstructure seems to have neutralized
this benecial effect of Cr carbide redissolution and reduced the
pitting corrosion resistance. A decrease in the localized corrosion
resistance of a SMSS promoted by the formation of d-ferrite phase
was also reported by Hara and Asahi [43].
After the potentiodynamic anodic polarization tests in 3.5%
NaCl solution, the sample surfaces were examined by SEM to iden-
tify the preferential pit initiation sites. Fig. 10 depicts SEM images
of the BM, CR, and weld interface samples after the polarization
tests. In the BM and CR samples (Fig. 10(a) and (b)), note that pits
nucleated and grew randomly throughout the surface due to the
samples homogeneous microstructure. On the other hand, in the
weld interface sample, most of the pits were found to nucleate
preferably in the martensite adjacent to the d-ferrite phase in the
HAZ (Fig 10(c)). This preferential nucleation is consistent with
the SEM analysis performed after the DL-EPR test (Fig. 7(c)), and
strongly supports the formation of Cr depleted regions due to the
precipitation of Cr carbides (and/or nitrides) at d-ferrite/martensite
boundaries. [37,4346]. Another plausible mechanism is that the
formation of d-ferrite leads to a decrease in solid solution of Cr
and Mo contents in the adjacent martensite matrix [43,49,50].
Moon et al. [49,50] attributed the low pitting corrosion resistance
of a Fe18Cr10Mn0.33N0.03C stainless steel containing
d-ferrite to the depletion of Cr around the Cr-rich d-ferrite. The
authors [49,50] measured the Cr concentration across austenite
and d-ferrite in the HAZ using electron probe microanalysis and
conrmed that the Cr depleted zones in the austenite region
adjacent to the d-ferrite are more favorable sites for pit initiation.
The formation of these Cr depleted zones promoted a reduction
Fig. 8. SEM micrographs of the surface aspect of the BM sample after potentiostatic etching in the DL-EPR testing solution for 300 s at: (a) 180 mV
SCE
, and (b) 110 mV
SCE
.
The samples were previously polished with 1 lm alumina.
324 C.A. Della Rovere et al. / Materials and Design 65 (2015) 318327
in the E
P
of the HAZ of the Fe18Cr10Mn0.33N0.03C stainless
steel in relation to its BM structure. In Fig. 10(d), also note that,
due to its higher Cr and Mo contents, the d-ferrite phase is not dis-
solved as much as the martensitic matrix as pitting corrosion
advances, resulting in a semi-continuous d-ferrite network inside
the pits.
Although a very high Q
r
/Q
a
ratio (36.03) was measured in the
unaffected BM sample, indicating high Cr depletion, the reduction
in pitting resistance was negligible. This indicates that the precip-
itation of Cr carbides that took place during the tempering treat-
ment and subsequent Cr depletion in BM tempered structure
caused only a minor reduction in pitting resistance in the chloride
environment (E
P
= 218.8 mV
SCE
). In contrast, a lower E
P
value
(210.3 mV
SCE
) was measured in the weld interface sample, which
presented a very low Q
r
/Q
a
ratio (0.47), i.e., low Cr depletion. How-
ever, the microstructural observation of this sample after the
DL-EPR test revealed a pronounced selective attack at the
d-ferrite/martensite phase boundaries (Fig. 7(d)), indicating that
the formation of d-ferrite in HAZ of the SMSS leads to Cr depletion
in the adjacent martensitic matrix.
A plausible explanation for the apparent lack of good correla-
tion between the results of the DL-EPR measurements and the
potentiodynamic anodic polarization tests in 3.5% NaCl for the
BM and weld interface samples may be as follows. The Q
r
/Q
a
ratio
measured from the DL-EPR tests depends on the overall fraction of
Cr depleted regions, which, in the case of the tempered structure of
the BM region, is much higher than that of the weld interface, as
can be seen in Fig. 7. However, one must bear in mind that pitting
corrosion initiates in the regions containing the lowest Cr content
(inside the localized Cr depleted region) and that the E
P
depends on
its initiation. Therefore, the lower E
P
value of the weld interface
compared to that of BM is probably because the minimal Cr con-
tents at the d-ferrite/martensite phase boundaries of the weld
interface sample were lower than those of the adjacent regions
of Cr-rich precipitates in the BM sample, although a higher fraction
of the latter are present.
Fig. 9. (a) Polarization curves obtained in a 3.5% NaCl solution, and (b) pitting potentials (E
P
) of distinct regions of RF welded SMSS pipes (scatter bands measured in 5 test
samples).
Fig. 10. Typical pit morphologies on the surface of the samples after potentiodynamic polarization in 3.5% NaCl solution: (a) BM; (b) CR; (c) HAZ and (d) TMAZ. The samples
were previously polished with 1 lm alumina, and etched with Villelas reagent after the measuring the polarization.
C.A. Della Rovere et al. / Materials and Design 65 (2015) 318327 325
Owing tothe precipitationof other Cr-richphases inadditiontoCr
carbides inthe structure of a type 347austenitic stainless steel, Chan-
dra et al. [51] also recently reported a certain discrepancy between
DL-EPR measurements and pitting corrosion behavior. These authors
observed that, in addition to Cr depletion, the presence of phase
boundaries due to possible heterogeneities inthe microstructure also
plays a signicant role in pit initiation in stainless steels.
As a nal comment, this study clearly revealed that DL-EPR
measurements should be used with caution to avoid misinterpre-
tation, and particularly in the case of SMSSs, which are used in
the quenched and tempered condition, one should not expect that
this technique will readily pinpoint Cr depleted regions only
through the relative charges (or peak heights) of the anodic and
cathodic polarization scan, because the size of the Cr impoverished
region in HAZ is usually very small and cannot be distinguished
accurately using a relatively large exposed area. In this case, a
microscopic examination of the corrosion attack and of the charac-
teristics of etched phases after DL-EPR measurements, in addition
to other electrochemical tests, are required. Furthermore, it should
be noted that for the oil industry to adopt RF welding of SMSSs,
particularly for onshore and offshore pipeline applications, addi-
tional tests should be performed, in view of the susceptibility of
RF weldments to stress corrosion cracking and hydrogen embrittle-
ment. In future works, the authors will try to move forward on
these measures, systematically studying the effect of different heat
treatments before and after the RF welding process on the global
behavior of the welded joint.
4. Conclusions
The microstructures and corrosion properties of RF welded
SMSS pipes were studied based on OM, SEM, XRD analyses, poten-
tiodynamic polarization and DL-EPR measurements. Based on the
changes in the microstructure promoted by the RF welding process
and the resulting electrochemical properties, the following conclu-
sions can be drawn:
(1) Due to the redissolution of Cr carbide precipitates promoted
by the RF welding thermal cycle, the RF weldment regions
exhibit better corrosion performance in acid media than
the tempered structure of the unaffected BM.
(2) The generalized precipitation of Cr carbides at both lath
martensite and grain boundaries in the tempered structure
of the unaffected BM induced considerable Cr depletion
(Q
r
/Q
a
ratio), as indicated by DL-EPR test measurements.
However, no signicant Cr depletion was detected in the
DL-EPR measurement of the weld interface region contain-
ing d-ferrite, although pronounced dissolution was observed
at the d-ferrite/martensite phase boundaries after the test.
(3) A decrease in pitting corrosion resistance was observed due
to d-ferrite formation at the weld interface, indicated by a
decrease in the E
P
during anodic polarization in 3.5% NaCl
solution. In contrast, Cr carbide precipitation in the BM
structure promoted by the tempering treatment did not sig-
nicantly diminish the pitting corrosion resistance.
(4) The microstructural changes promoted by the RF welding
thermal cycle in the CR region led to an increase in pitting
corrosion resistance in 3.5% NaCl solution compared to that
of the unaffected BM region.
Acknowledgments
The authors gratefully acknowledge FAPESP (So Paulo
Research Foundation Grant No. 12/16113-6), PPGCEM/UFSCar
(Postgraduate Program in Materials Science and Engineering of
the Federal University of So Carlos) and the Brazilian Research
Funding Agency CNPq (National Council for Scientic and Techno-
logical Development) for their nancial support of this work.
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