Corrosion Science 131 (2018) 340–354

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Influence of tempering treatment on microstructure and pitting corrosion of T

13 wt.% Cr martensitic stainless steel
⁎
Sunil Kumar Bonagania,c, , Vishwanadh Bathulab, Vivekanand Kaina,c
a
Materials Processing & Corrosion Engineering Division, Bhabha Atomic Research Centre, Mumbai- 400 085, India
b
Materials Science Division, Bhabha Atomic Research Centre, Mumbai- 400 085, India
c
Homi Bhabha National Institute, Anushaktinagar, Mumbai-400094 India

A R T I C L E I N F O A B S T R A C T

Keywords: Tempering of 13 wt.% Cr martensitic stainless steel resulted in nano-sized M3C carbides at 300 °C, nano-sized Cr-
Stainless steel rich M23C6 carbides at 550 °C and sub-micron sized Cr-rich M23C6 carbides at 700 °C. Austenitization resulted in
Tempering lath martensite with undissolved M23C6 carbides. Pitting resistance for tempered condition was lower than the
Transmission electron microscopy austenitized condition with least resistance at 550 °C. The observation was attributed to the presence of a Fe-rich
Cr depletion
surface film and massive carbide precipitation with a Cr depletion zone of 7–9 nm at carbide interface for 550 °C
Pitting corrosion
tempered condition as opposed to a Cr-enriched passive film for the austenitized condition.
X-ray photo electron spectroscopy

1. Introduction the precipitates formed during the austenitization and tempering heat
treatments contributes to a better understanding of the precipitation
Martensitic stainless steels (MSSs) are based on the Fe-Cr-C ternary process and also provides a better interpretation on the material per-
system and contain 11.5–18.0% Cr and 0.1–1.2% C to obtain a fully formance in a given environment. Tao et al. characterized the pre-
austenitized condition at elevated temperatures [1–3]. Depending on cipitates formed in X12CrMoWVNb10-1-1 steel after different tem-
the properties required, the carbon (C) and chromium (Cr) concentra- pering treatments and showed the precipitation sequence of carbide
tion levels are selected. A high Cr content will lead to the formation of phase with increasing tempering temperature is Fe-rich M3C → Cr-
δ-ferrite − an undesirable phase in MSSs [4–6]. MSSs widely used in rich M7C3 → Cr-rich M23C6 [13]. In a recent study by Si-Yuna Lu et al.
many industries like nuclear power plants, steam generators, mixer showed the formation of Fe-rich M3C type of carbides at tempering
blades, pressure vessels, turbine blades, oil and gas valves, naval ap- temperature of 300 °C and formation of M23C6 carbides after tempering
plications and chlorinated plastic injection molds because of their good at 500 and 650 °C. The precipitation sequence in 13 wt.% Cr MSS is
mechanical properties and reasonable corrosion resistance [2,7–10]. given to be Fe-rich M3C carbide → Cr-rich M23C6 [14]. Prabhu Gaunkar
MSSs are typically heated to a temperature, between 980 and 1100 °C, et al. also reported the formation of M3C type carbides in the lower
in the austenite phase region in accordance with chemical composition tempering temperature range of 150–350 °C, M3C and M7C3 type car-
and then cooled at a suitable fast rate to obtain martensite with body bides in the tempering temperature range of 350–500 °C, formation of
centred tetragonal crystal structure in as-quenched condition [2,11]. M7C3 and M23C6 type carbides in the temperature range of 550–650 °C
The hardened MSSs are too brittle for processing therefore tempering is and M23C6 and M2(C, N) (M = Fe and Cr) type carbides in higher
commonly employed to improve ductility and toughness. MSSs are tempering temperature of 650–750 °C in 12 wt.% Cr MSS [12]. There-
tempered in the temperature range of 200–700 °C to have a better fore, the type of the carbides formed during tempering treatment is
combination of strength and ductility [6,12]. The tempering treatments dependent on chemical composition of the material, tempering tem-
decrease the dislocation density induced during quenching from aus- perature and tempering treatment duration. [12–16]. Since, MSS are
tenitization temperature and cause nucleation of new secondary phases always used in a tempered condition, localized corrosion (pitting and
such as carbides. The precipitation and coarsening of the secondary intergranular) is a potential degradation issue due to the precipitation
phases (mainly carbides) during the tempering treatments play a key of Cr-rich carbides at prior austenitic grain (PAG) boundaries and also
role in determining the properties of the MSS in service conditions [13]. at martensitic lath boundaries. The precipitation of the Cr-rich carbides
Microstructure is one of the important aspects affecting suscept- results in Cr depletion at the interface of carbide and matrix. So far, to
ibility to localized corrosion of stainless steels. The characterization of the best of our knowledge, no technical papers are available on the

⁎
Corresponding author at: Materials Processing & Corrosion Engineering Division, Bhabha Atomic Research Centre, Mumbai, 400 085, India.
E-mail address: bsunil@barc.gov.in (S.K. Bonagani).

https://doi.org/10.1016/j.corsci.2017.12.012
Received 20 September 2017; Received in revised form 20 November 2017; Accepted 13 December 2017
Available online 14 December 2017
0010-938X/ © 2017 Elsevier Ltd. All rights reserved.
S.K. Bonagani et al. Corrosion Science 131 (2018) 340–354

extent of Cr-depletion region at the carbide-matrix interface region in approximately in the centre of the disk. Selected area diffraction (SAD)
tempered 13 wt.% Cr MSS. The authors measured the degree of sensi- patterns were acquired from the precipitates and matrix to identify the
tization in 13 wt.% Cr MSS developed with tempering treatments by a phases and precipitates. The chemical composition of the matrix and
modified double loop electrochemical potentiokinetic reactivation test precipitates was analyzed using TEM-EDS (Oxford instruments). The
and showed tempering at 550 °C makes it highly susceptible to interlath uncertainty in the EDS measurements is less than 0.5 wt.%. It is difficult
corrosion [17]. This drastic reduction in corrosion resistance of tem- to precisely analyse the C content in the precipitate by TEM-EDS and so
pered 13 wt.% Cr MSS is attributed to the presence of Cr depletion at C content is not reported in the present study and only the elements of
the carbide-matrix interface regions. Until now, a few studies are Fe and Cr are considered in EDS analysis. The width of the lath in all the
available on the pitting corrosion behaviour of MSS with different conditions is measured using image-J software by taking a minimum of
tempering treatments [9,14,16,18–20]. In general, pit nucleation oc- 20 laths for each condition.
curs at the surface active sites/heterogeneities such as inclusions, pre- The precipitates formed in tempered specimens (550 and 700 °C)
cipitates and the regions with weak passive films [1,21–23]. The sur- were extracted by dissolving the martensitic matrix electrochemically
face oxide film formed over Cr depleted regions (sensitized regions) is in 10 vol.% hydrochloric acid-methanol solution to identify the pre-
known to be weak (and not stable) therefore leads to preferential cor- cipitates by XRD technique. The tempered specimens were ground up to
rosion attack. Sensitization increases the susceptibility to localized 400 grit emery paper and ultrasonically cleaned in acetone. The dis-
corrosion due to the formation of the Cr-rich carbides and associated solution was done by applying a potential difference of 1.5 V between
Cr-depletion at the carbide-matrix interface. Pitting corrosion of sen- the specimen (anode) and the platinum foil (cathode) for a period of
sitized stainless steels has been shown to be dependent on the carbide 48 h at room temperature (26 °C). The precipitates were extracted by
interfaces and also the carbide interfaces having Cr depletion regions centrifuging the solution. The extracted precipitates were transferred
[23–26]. There are no reported studies on the nature of the passive on glass slide for XRD analysis.
films formed on tempered 13 wt.% Cr MSS and their influence on lo-
calized corrosion. Therefore still the questions remain on how to relate 2.2. Electrochemical measurements
microstructure (carbide precipitation and extent of Cr depletion at
carbide matrix interface) and passive film properties with pit initiation All the electrochemical studies were carried out in a conventional
in MSS with different tempering treatments. three-electrode cell using a Pt foil as the auxiliary (counter) electrode,
In the present study, the microstructural changes with tempering saturated calomel electrode (SCE) as the reference electrode and the
treatments, are studied using X-ray diffraction and transmission elec- MSS specimen as the working electrode. The MSS specimen was pro-
tron microscopy (TEM) coupled with energy dispersive spectroscopy vided an electrical contact from one side of the specimen and was set in
(EDS). The Cr concentration profiles at carbide-matrix interface were a cold setting resin to expose the opposite side of the specimen. The
established for tempered MSS. The localized corrosion studies were electrical connection wire was insulated to avoid contact with the test
carried in 0.1 M NaCl solution using electrochemical techniques and solution. All the specimens were ground metallographically using
passive films formed at open circuit potential were characterized by X- emery papers with grit size up to 1200 and then mirror polished using
ray photo electron spectroscopy (XPS). The relationship between type 1 μm diamond paste before each electrochemical experiment. The
of the precipitates formed during tempering and pitting corrosion be- specimens were cleaned with a soap solution, degreased in ethanol and
haviour of 13 wt.% Cr MSS in NaCl solution is discussed. dried in warm air. The contact regions between the test specimen and
the resin were covered with a lacquer to avoid presence of any crevice
when exposed to the test solution. The 0.1 M NaCl solution was pre-
2. Experimental procedure
pared using distilled water and reagent grade NaCl. The solution was
deaerated for 45 min using Ar gas and then the working electrode was
2.1. Materials, heat treatments and microstructural characterization
introduced into the cell. The Ar gas bubbling was continued during the
experiment. All the specimens were cleaned cathodically at −1 VSCE for
The chemical composition of the material used in the present study
2 min to remove the air formed oxide film after specimen’s immersion
was analyzed using spark-optical emission spectroscopy and is given in
into the solution. The potentiodynamic polarization tests were per-
Table 1. Specimens of size 60 mm x 12 mm x 12 mm were austenitized
formed in 0.1 M NaCl solution at room temperature in deaerated con-
at 1020 °C for 0.5 h in a muffle furnace followed by oil quenching to
dition. A scan rate of 1 mV/sec was employed. After polarization tests,
room temperature. Subsequently, the austenitized specimens were
the tested specimens were examined using optical and field emission −
tempered at 300, 550 and 700 °C for 2.5 h followed by air cooling.
scanning electron microscopy (FE-SEM; Carl Zeiss make). The po-
The presence of phases in the tempered specimens was analyzed by
tentiodynamic polarization tests were repeated twice for each spe-
XRD technique (Bruker make, D8 discover) with Cu Kα radiation with
cimen. The average and standard deviation (σ) was calculated from the
step size of 0.02°. The volume fraction of the retained austenite was
set of three data points and reported in Table 2.
estimated from the integrated intensities of austenite and martensite
Potentiostatic polarization tests were also performed in 0.1 M NaCl
peaks [27]. The microstructural changes occurring with different tem-
solution to investigate the metastable pitting corrosion for MSS spe-
pering treatments were characterized using TEM (FEI TECHNAI F
cimen tempered at different temperatures. The potentiostatic polar-
200 kV). The TEM samples were prepared in two steps. First, a 0.2 mm
ization tests were carried out at −100 mV below the Epit expect for the
thick slice was pre-thinned to 80 μm by grinding on successively finer
specimen tempered at 550 °C, for which the test was carried out at
emery papers of 240–600 grit. From such 80 μm thin sheet, 3 mm discs
20 mV above the Ecorr.
were punched out. The pre-thinned 3 mm discs of 80 μm thick speci-
Rectangular coupons of the austenitized and specimens tempered at
mens were then twin-jet polished in a mixture of 10% perchloric acid
550 °C were exposed in deaerated 0.1 M NaCl solution for period of 15 h
and 90% methanol at −40 °C and 20 V potential to create a small hole
and the formed surface film was characterized by X-ray photo electron
spectroscopy (XPS) (SPECS) technique. After immersion in the test so-
Table 1
Chemical composition (in wt.%) of the 13 wt.% Cr martensitic stainless steel used in the lution, the specimens were cathodically polarized at −1 VSCE for 2 min
present study. to remove any air formed oxide film. The XPS analyses were carried out
in an electron spectrometer using a monochromatic Al Kα X-rays
C Cr Mn Mo Ni V P Cu Si Fe (hν = 1486.74 eV) as the primary radiation source. The binding en-
0.31 13.3 0.81 0.09 0.27 0.04 0.025 0.48 0.33 Rest ergies were calibrated with respect to the Ag 3d5/2 peak occurring at
368.26 eV. The energy spectra of the photoelectrons were analyzed by

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Table 2
Potentiodynamic polarization test results for austenitized and specimens tempered at different temperatures in 0.1 M NaCl solution.

Specimen condition Ecorr (VSCE) Icorr (A/cm2 × 10−6) Ipass(at−0.35V) (A/cm2 × 10−6) Epit (VSCE)

1020 °C −0.460 ± 0.033 0.24 ± 0.16 1.54 ± 0.64 −0.051 ± 0.031

1020 °C–300 °C −0.557 ± 0.037 0.38 ± 0.13 3.59 ± 1.45 −0.080 ± 0.015
1020 °C–550 °C −0.585 ± 0.032 7.22 ± 4.14 No passivation −0.585 ± 0.032
1020 °C–700 °C −0.591 ± 0.026 8.59 ± 1.79 93.76 ± 10.80 −0.152 ± 0.041

DLD-Phoibos-HSA 2500 (hemispherical channel analyzer). The take-off treatments and no reverted austenite was found after tempering at
angle of the electrons detected by detector was 45°. A survey scan was 300–700 °C. The reverted austenite transformation requires presence of
taken in the binding energy range from 0 to 750 eV with pass energy in Ni in the matrix as Ni stabilizes the austenite phase and promotes re-
the range 11–15 eV to identify the major elements present at the sur- verse austenite transformation [30]. As the Ni concentration in 13 wt.%
face. The major elements identified were Fe, Cr and oxygen (O) with Cr MSS is low (0.27 wt.%), reverted austenite is not expected. It has
elemental carbon (C). High-resolution energy spectra were recorded for been reported that the volume fraction of retained austenite decreased
C 1s, Fe 2p, O 1 s and Cr 2p peaks. All binding energies were referenced in 16% and 26% Cr-Fe alloys and AISI 431 MSS with tempering and
to the C1 s peak at a binding energy of 284.6 eV. The baseline correc- retained austenite transformed to carbides and ferrite [27,31]. In the
tion was done by Shirley method [28,29] using Origin 8.5 software. The present study also, it is believed that the retained austenite should have
high resolution/narrow XPS spectra of the individual element is sepa- transformed to carbides and ferrite in 550 °C and above tempering
rated into the most probable chemical states using the deconvolution conditions. The axial ratio of the martensitic and ferritic phase is too
method of the peaks using Origin 8.5 software with an optimum close (10−4–10−5 nm) and separating the two phases by XRD peak 2θ
number of the peaks. positions is not possible [16]. So the diffraction peaks are indexed as
martensite (M) for all the conditions.
The morphology and precipitates formed in austenitized and tem-
3. Results and discussion
pered specimens are studied in detail. Fig. 2 shows the TEM images of
the austenitized specimen. As shown in Fig. 2(a), austenitization at
3.1. Microstructural changes with tempering temperature
1020 °C for 30 min followed by oil quenching produced a fine lath
martensite structure with lath width of 70–185 nm. The presence of fine
The XRD patterns for austenitized and tempered specimens are
retained austenite with a needle shaped morphology, with a width of
shown in Fig. 1. The significant change in the diffraction patterns is a
around 20 nm at some of the lath interfaces, was also observed in the
decrease in austenite peak intensity (2θ = 43.53°) with increase of
austenitized condition as shown in Fig. 2(b). The existence of the re-
tempering temperature, as shown in Fig. 1. The volume fractions of
tained austenite at the lath interfaces is confirmed by SAD pattern
retained austenite in the austenitized specimen and in specimen tem-
analysis as shown in Fig. 2(c). The presence of retained austenite with
pered at 300 °C are 4.7 and 3.2% respectively and no retained austenite
similar morphology was also reported to be observed in AISI 410
was found in the specimen tempered at 550 °C or above temperatures.
stainless steel [32]. Apart from the retained austenite, high amount of
The formation of reverted austenite in 13 wt.% Cr MSS was reported
dislocations within the laths and round shaped precipitates are ob-
after tempering at 300 °C [16], but our studies demonstrated that the
served in the austenitized condition as shown in Fig. 2(d). The size of
retained austenite volume fraction decreased with tempering

Fig. 1. X-ray Diffraction patterns for 13 wt.% Cr MSS in

austenitized and different tempered conditions (inset in Fig. 1
is the expanded view of the XRD peaks showing the retained
austenite peak with tempering temperature).

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Fig. 2. TEM micrographs of the austenitized specimen, (a) bright filed image showing lath martensitic structure with retained austenite at lath interfaces, (b) dark field image showing the
retained austenite, (c) SAD pattern of the retained austenite-lath interface region (d) bright filed image showing undissolved carbides and (e) SAD pattern of the undissolved carbide (inset
showing the TEM-EDS of carbide).

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round shaped precipitates are in the range of 0.35–0.8 μm and are dislocations within the laths as shown in Fig. 3(a). The presence of the
present heterogeneously at discreet locations in the martensitic matrix. retained austenite at the lath interfaces is shown in Fig. 3(b)–(c) but is
A high amount of dislocations are always formed during the martensite not continuous as observed for austenitized condition. The retained
phase transformation and these dislocations are responsible for the austenite fraction decreased after tempering at 300 °C and re-confirms
strength of martensite [33]. The SAD pattern acquired from the round the XRD observations as shown in Fig. 1. The formation of needle
shaped precipitate together with TEM-EDS analysis (Fig. 2(e)) con- shaped precipitates with ∼150 to 250 nm in length and ∼ 20 nm in
firmed that these are Cr-rich M23C6 type carbides (M = Fe, Cr). The width at lath interfaces and also within the laths perpendicular to the
average chemical composition (wt.%) of carbide is 58.87 ± 0.47 Cr, lath direction is observed after tempering at 300 °C as shown in
40.14 ± 0.42 Fe and 0.98 ± 0.13 Si. The size and morphology of the Fig. 3(a). The SADP acquired from the lath interface precipitate is in-
carbides in Fig. 2(d) suggest that these are undissolved carbides during dexed as M3C type carbide with an orthorhombic structure as shown in
the austenitization process and remained in the martensitic matrix after Fig. 3(d). The faint diffraction spots in the SAD pattern are corre-
quenching. This shows that the austenitization process at 1020 °C for sponding to the precipitate and bright spots are from the matrix as
30 min is insufficient to dissolve all the carbides present in as-received shown in Fig. 3(d). The presence of the undissolved round shaped
MSS. Depending upon the austenitizing temperature, the amount of the M23C6 carbides is also observed and it remained unchanged during
dissolved carbides was reported to vary in the microstructure. The tempering. The TEM-EDS analysis showed that these precipitates are
complete dissolution of the carbides during the austenitization process Fe-rich carbides with an average Cr of 13.42 wt.% in the carbide.
is reported to be above 1170 °C [11]. The chemical composition ana- Therefore, there is not much of difference in the Cr content of the M3C
lysis using TEM-EDS also showed that the average Cr content in lath carbide and that in lath martensite matrix.
martensite is 13.4 wt.%.
3.1.2. Tempering at 550 °C
3.1.1. Tempering at 300 °C TEM micrographs of the specimen tempered at 550 °C are shown in
TEM micrographs of the specimen austenitized at 1020 °C and Fig. 4. The tempered microstructure consists of lath martensitic struc-
tempered at 300 °C is shown in Fig. 3. The microstructure of the spe- ture with 100–200 nm in width with undissolved carbides at discrete
cimen tempered at 300 °C is similar to that of austenitized condition locations, huge amount of fine nano-sized precipitates at lath interfaces
with a lath martensitic microstructure of 100–200 nm lath width and and also within the laths and few sub-microscopic precipitates as

Fig. 3. TEM micrographs of 13 wt.% Cr MSS tempered at 300 °C, (a) bright filed image showing lath martensite with retained austenite and M3C type carbides, (b) magnified image of (a)
showing retained austenite at lath interfaces, (c) dark filed image showing carbides and (d) SAD pattern of the carbide showing as M3C type carbide.

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Fig. 4. TEM micrographs of the specimen tempered at 550 °C (a) showing lath martensitic structure with in PAG and undissolved carbides (b) showing the lath interface covered by
precipitation of fine nano-sized carbides and also presence of nano-sized carbides in laths and carbides at PAG boundary (c) SAD pattern of the carbide present at PAG boundary.

indicated by the arrows in Fig. 4(a)–(b). The precipitates are also ob- nano-sized carbide precipitates are present within the martensitic laths.
served at PAG boundaries as shown in Fig. 4(b). The lath interfaces are As shown in Fig. 5(a), the round bigger precipitates are undissolved
covered by continuous precipitation of nano-sized carbides as shown in carbides during the austenitization. The SAD pattern acquired from the
Fig. 4(b). The chemical analysis of the nano-sized precipitates by TEM- matrix is shown in Fig. 5(c) and is indexed as ferrite (BCC) phase. The
EDS analysis with 2.5 nm probe size on different carbides showed dif- SAD pattern of the round shaped carbide is indexed as M23C6 type
ferent concentrations of Cr from 27 wt.% to 52 wt.%. The SAD pattern carbide with FCC structure as in Fig. 5(d). The Cr content (wt.%) in the
acquired from the globular shaped sub-microscopic sized precipitate two carbides analyzed (Cr ∼42% and ∼56%) is much higher than that
present at the PAG boundary is indexed as M23C6 type carbide with face in the matrix region (Cr ∼13%). The undissolved carbides and carbides
centred cubic (FCC) structure, as shown in Fig. 4(c). It is difficult to formed during tempering can be easily distinguished as the sizes of the
acquire the SADP of these nano-sized precipitates present within the undissolved carbides are much bigger than carbides precipitated during
lath due to their small size. The SADP analysis of the fine nano-sized the tempering.
carbides needs to be carried out by high resolution analysis by TEM.
3.1.4. XRD analysis of the extracted precipitates
3.1.3. Tempering at 700 °C Fig. 6 shows the XRD patterns of the precipitates electrolytically
The TEM micrographs of the specimen tempered at 700 °C for 2.5 h extracted from martensitic matrix of the specimens tempered at 550
are shown in Fig. 5. Fig. 5(a) shows lath martensitic microstructure and and 700 °C. As shown in Fig. 3, only a few carbide precipitates are
the width of the laths is 140–600 nm. The presence of needle shaped present in the specimen tempered at 300 °C and the amount of the
(length much more than width) carbide precipitates with 100–1000 nm precipitates extracted is therefore too low for carrying out the XRD
size in length and 20–40 nm in width at the lath interface and along the analysis. The XRD peaks observed are the same for the specimens
direction of martensitic laths is clearly observed in Fig. 5(a)–(b). In tempered at 550 and 700 °C and well matched with the standard XRD
addition, sub-micron sized round precipitates are also present at the pattern of M23C6 type carbides [coll. Code: 62670] as shown in Fig. 6.
lath interfaces. But as compared to 550 °C tempered specimen, very few So, the carbides formed are M23C6 with different sizes in both the

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Fig. 5. TEM micrographs of the specimen tempered at 700 °C (a) showing carbides at lath interfaces, (b) magnified image of (a) showing sub-micron sized carbides at lath interfaces, (c)
SAD pattern of the matrix and (d) SAD pattern of the lath interface round shaped carbide.

tempered conditions of 550 and 700 °C. Based on XRD and TEM ob- Cr-rich carbide leads to Cr-depletion at carbide-matrix interface regions
servations, the carbide precipitation sequence in 13 wt.% Cr MSS with and is a well established process for austenitic stainless alloys [35–41].
tempering temperature of 300–700 °C is formation of nano-sized M3C
type carbides at 300 °C to nano-sized Cr-rich M23C6 carbides at 550 °C
3.1.5. TEM-EDS analysis
and then to sub-micron sized Cr-rich carbides at 700 °C. The stable
In our previous reported study, it has been shown that the 13 wt.%
carbides for MSS at a tempering temperature of 700 °C are M23C6
Cr MSS tempered at 550 °C for 2.5 h is highly susceptible to interlath
(equilibrium carbides with ferrite phase at 700 °C are M23C6)
corrosion even in 5% HNO3 solution at room temperature [17]. The
[12–16,34]. The present results also showed the presence of M23C6 type
TEM-EDS analysis across the carbide-matrix interface region of spe-
carbides in the specimen tempered at 700 °C. Chakroborty et al. re-
cimen tempered at 550 °C is carried out in the present study to evaluate
ported the presence of Fe2C type carbides along with the M23C6 car-
the Cr − depletion zone associated with nano-scaled carbide formation
bides in the XRD analysis of the extracted residue of Type 410 stainless
and location of the carbides studied are shown in Fig. 7(a). Fig. 7(b)
steel with 11.2 wt.% Cr after tempering at 550 °C for 1 h [15]. But in the
shows the concentration profiles of the Cr across two nano-sized
present study, no traces of Fe2C/Fe3C carbides are observed in the XRD
(15–20 nm) carbide-matrix interface regions of the specimen tempered
analysis of extracted precipitates from 13 wt.% Cr MSS tempered at
at 550 °C for 2.5 h. The TEM-EDS analysis is carried out in the thin
550 °C for 2.5 h. At lower tempering temperature of 300 °C, the carbides
region of the specimen with electron beam size of 2.5 nm in order to
precipitated are expected to be Fe-rich carbides even though these
obtain optimal spatial resolution during chemical analysis. The Cr
carbides are not equilibrium carbides. During the tempering process,
concentration in the two carbides analyzed (at the centre of the car-
the super saturated carbon is ejected from the martensitic matrix and
bide) is 47 and 29 wt.% as shown in Fig. 7(b). The measured Cr con-
the Cr atoms with the high reactivity with carbon, combine with carbon
centration is not uniform in the carbides formed in 13 wt.% Cr MSS
to form the carbides. At lower tempering temperatures, the diffusivity
during the tempering treatment at 550 °C. The nucleation and growth of
of the Cr is low and the ejected carbon from the matrix reacts with the
Cr-rich carbides is a diffusion controlled process and is influenced by
neighbourhood Fe to form Fe-rich carbides. As the tempering tem-
the nature of interface, temperature and duration. The growth of the
perature increases, the Cr-rich carbide precipitation and its growth by
carbide precipitates occurs by the diffusion of Cr and C. But the growth
the diffusion process with tempering time increases. The formation of
of the carbide is essentially governed by the diffusion of Cr as the

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Fig. 6. XRD patterns of the precipitates extracted from specimens

tempered at 550 and 700 °C along with the standard XRD pattern of
M23C6 carbide, showing extracted precipitates are M23C6 type car-
bides.

diffusion rate of interstitial C is very fast as compared to Cr in the analysis and Epit was measured from the potential when the current
matrix. The measured Cr concertation, 2.5 nm away from the carbide density starts to increase from the value of current density corre-
with 47 wt.% Cr is 9 wt.% whereas the carbide with 29 wt.% Cr has the sponding to the passive region and the values are given in Table 2. As
interfacial (2.5 nm away from the interface) Cr concentration of shown in Fig. 8(a), the austenitized condition has a higher (more
11.97 wt.%. The measured Cr-depleted zone width is 9 nm for the anodic) Ecorr as compared to tempered conditions and the Ecorr de-
carbide with 47 wt.% Cr and is 7.5 nm for the carbide with 27 wt.% Cr creased (or became more cathodic) with tempering temperature. The
as shown in Fig. 7(b). The Cr concentration in the carbide-matrix in- low value of Ecorr for the specimens tempered at 550 and 700 °C, in-
terface region decreases by the Cr-enrichment in the carbide precipitate dicates a higher tendency towards oxidation. The Icorr values as shown
by the diffusion of Cr at a given tempering temperature. This variation in Table 2 also show that the specimen tempered at 550 °C has a higher
in the Cr concentration in the interfacial region with Cr wt.% in the dissolution rate (corrosion rate, Icorr) than that for the austenitized and
carbide is due to the growth of the carbide precipitate. The average Cr other tempered conditions indicating that the passive film formed at
concentration in the matrix region, 10 nm away from the carbide is Ecorr is less compact and less stable [45–47]. The austenitized specimen
13.7 wt.% by considering only Fe and Cr elements in the matrix. Na- showed highest Epit and Epit values decreased with tempering tem-
kamichi et al. showed the width of the Cr depletion region measured perature. The passive current density also increased with tempering
across PAG boundary in between Cr-rich carbides is around 10–15 nm temperature indicating the dissolution of the passive film is higher for
in low carbon MSS tempered at 650 °C [42] and showed no Cr-depletion tempered specimens as compared to austenitized condition with ap-
at carbide-matrix interface. The present results clearly show the ex- plication of anodic potential. The specimen tempered at 550 °C showed
istence of narrow Cr depletion of 7–9 nm at the nano-scaled carbide- increased current density with increase of anodic potential as shown in
matrix interface regions after tempering at 550 °C as shown in Fig. 7(b). Fig. 8(a) and did not show passivity. The Epit of the specimen tempered
The minimum Cr concentration and width of the Cr depleted zone are at 550 °C is taken to be Ecorr in this work as pitting occurred quite early
dependent on the temperature, time and also the composition of the and shown in Table 2. The Epit value increased for the specimen tem-
steel [43]. The Cr depletion widths reported for sensitized austenitic pered at 700 °C compared to that for the specimen tempered at 550 °C.
stainless alloys is several tens of nm from the grain boundary/carbide The similar behaviour of decrease in current density is also observed for
interface [35,37,40]. The diffusion coefficient of Cr in ferrite matrix is the specimen tempered at 700 °C as shown in Fig. 8(a) and Table 2.
10 times faster than in the austenite matrix [39,44]. Therefore, the Cr Fig. 8(b) & (c) show the SEM images of the specimen tempered at
depletion width in MSS with 13 wt.% Cr is expected to be smaller and 550 °C after the polarization test in 0.1 M NaCl solution. Pits with sizes
narrower as compared to that in austenitic stainless steels with 18 wt.% up to 27 μm were observed after the polarization test as shown in
Cr. The narrow Cr-depletion zone of 7–9 nm at the carbide-matrix in- Fig. 8(b). The lath interfaces and PAG boundaries of the specimen
terface is shown in present study and the average Cr concentration in tempered at 550 °C with nano and sub-micron sized carbides got at-
the interface region falls to 76% of matrix concentration. tacked during the test and are the preferential sites for pitting corrosion
as shown in Fig. 8(b). The magnified image of Fig. 8(b) clearly shows
the pit initiation around the undissolved Cr-rich M23C6 carbide-matrix
3.2. Electrochemical results in chloride solution interface as shown in Fig. 8(c). The TEM-EDS analysis at the un-
dissolved Cr-rich M23C6 carbide-matrix interface showed average Cr
The potentiodynamic polarization curves for various tempering concentration of 9 wt.% showing the region around the undissolved Cr-
temperatures in 0.1 M NaCl solution are shown in Fig. 8(a). The sig- rich carbide is also depleted of Cr. It is already shown in the austenitic
nificant changes in polarization curves are decrease in pitting potential stainless steels that the Cr depleted regions adjacent to the grain
(Epit), corrosion potential (Ecorr) and increase in passive current density boundary Cr-rich carbides/sigma phase act as a discontinuity and also
with tempering temperature. The Ecorr and Icorr are measured from Tafel

347
S.K. Bonagani et al. Corrosion Science 131 (2018) 340–354

Fig. 7. TEM-EDS analysis across the carbide-matrix interface region of

specimen tempered at 550 °C (a) showing the region used for TEM-EDS
analysis and (b) showing the Cr concentration profiles of carbide-matrix
interface regions.

the chemical changes in the interface region influence the stability of initiation sites due to massive precipitation of nano-sized carbides with
the passive film and so, these locations are preferential sites for the pit Cr-depletion at lath interfaces and also inside the laths as compare to
initiation [24,25,48–50]. Kain et al. reported that the desensitization in specimen tempered at 700 °C with sub-microscopic carbides mostly at
304 stainless steel improved the intergranular corrosion but showed lath interfaces. This indicates that the pitting resistance is associated
decreased pitting corrosion resistance compared to solution-annealed with the number of pit initiation sites (carbides) and also the extent of
condition. But the pitting corrosion resistance improved as compared Cr-depletion around these carbides. The increased value of the Epit for
with the sensitized condition [24]. Therefore, the presence of Cr-de- the specimen tempered at 700 °C, as compared to tempering done at
pletion at carbide-matrix interface region, further decreases the pitting 550 °C, is due to the diffusion of the Cr to the depleted regions and
corrosion resistance. The Cr content in these MSSs is around 13 wt.% thereby healing the Cr depletion zone (desensitization) and also de-
and any depletion of the Cr content (< 11%) at the interfaces would crease in number of pit initiation sites (carbides) by carbide coarsening
lead to weak passive film formation that makes easy chloride ion pe- at 700 °C. The phenomenon of desensitization at tempering tempera-
netration and acts as a preferential site for pit nucleation in a chloride tures higher than 550 °C is already reported by present authors for the
solution. The Epit value is higher for the specimen tempered at 700 °C as 13 wt.% Cr MSS [17]. The Epit value of the specimen tempered at 700 °C
compared to that for the specimen tempered at 550 °C, as shown in is low as compared to austenitized and tempered condition at 300 °C
Fig. 8(a). The specimen tempered at 550 °C has more numbers of pit because of increased fraction of carbide precipitate-interface regions

348
S.K. Bonagani et al. Corrosion Science 131 (2018) 340–354

Fig. 8. (a) Potentiodynamic polarization curves of austenitized and different tempered specimens in 0.1 M NaCl solution, (b) SEM image of the specimen tempered at 550 °C after
polarization test (inset showing attack at PAG boundaries and laths) and (c) magnified image of (b) showing pitting at undissolved carbide-matrix interface region.

which act as a site for pit initiation. The decrease in the pitting corro- observed in the tested duration of 3 h. The specimen tempered at
sion resistance with tempering treatments is due to the formation of Cr- 700 °C, showed metastable pits before a stable pit formation and stable
rich carbides and the associated narrow Cr depletion zone with carbide pit (continuous increase in the background current density) with time
formation. as shown in Fig. 9(a). Stable pit formation is observed after 1.2 h
The current fluctuations in Fig. 8(a), e.g. specimen tempered at duration of the test. The specimen tempered at 550 °C showed increased
300 °C, are due to initiation and repassivation of metastable pits. current density with time after application of potential (20 mVEcorr) and
Fig. 9(a) shows the current transients for metastable pit initiation for showed stable pitting within 5 min of the test as shown in Fig. 9(d). The
austenitized specimen and specimens tempered at 300 and 700 °C. The specimen tempered at 300 °C with Fe-rich carbide precipitates did not
current transients or spikes due to pit initiation/repassivation are laid- show the stable pit in the tested duration but the specimens tempered at
over the background (passive) current density, as shown in Fig. 9(a). 550 and 700 °C with Cr-rich carbides showed the stable pit formation in
The sudden increase in current (spikes) is associated with passive film potentiostatic tests. The potentiostatic polarization results clearly
breakdown process happening in the event of metastable pit formation. showed that the metastable pitting events/frequency increased with
As shown in Fig. 9(a), each current transient shows a metastable pit. increase of carbide-matrix interface regions with Cr depletion at the
Many current transients or metastable pit events are observed before a interface. The results indicate the fact that the nucleation and initiation
stable pit formation. The metastable pit may grow into stable pit if pit of pitting corrosion depends on Cr depletion associated with Cr-rich
depth is sufficient enough to maintain the environment that is ag- carbide precipitation at the grain and lath boundaries in the MSS. The
gressive enough to prevent repassivation at the metal surface inside the possible reason for improved pitting corrosion resistance for the spe-
pit [26]. The duration for pit initiation and repassivation is in the range cimen tempered at 700 °C is re-diffusion of Cr from the matrix to de-
of the 8–42 s and showed a statistical variation. The shape of the cur- pleted regions thereby minimizing the discontinuity at the interfacial
rent transient gives the information about the initiation, growth and regions.
repassivation of a metastable pit [51] and typical metastable pitting
event is shown in Fig. 9(b). Fig. 9(c) shows the metastable pitting 3.3. Surface film characterization by XPS
events with time. The austenitized and specimen tempered at 300 °C
showed less number of current transients and stable pitting is not The passive film formed on the surface of the stainless alloys plays

349
S.K. Bonagani et al. Corrosion Science 131 (2018) 340–354

Fig. 9. Potentiostatic polarization on austenitized and specimens tempered at 300 and 700 °C in 0.1 M NaCl solution (a) showing current transients from meta stable pitting with time, (b)
typical current transient showing the pit growth and repassivation, (c) meta stable pitting events with time and (d) potentiostatic polarization of specimen tempered at 550 °C in 0.1 M
NaCl solution at 20 mVSCE above Ecorr.

an important role in initiation of pitting corrosion [52,53]. The com- concentrations of elements in the passive film are calculated based on
position of the passive films formed at corrosion potential in 0.1 M NaCl peak areas and sensivity factors using the equations reported in
solution on austenitized specimen and after tempering at 550 °C were [57,58]. The quantitative XPS analysis showed the differences between
determined by XPS analysis. The XPS survey scan showed that the film the films formed on austenitized and tempered conditions. Fe/Cr ratio
consists of elements of Fe, Cr and O. The chloride and nickel are not for tempered condition is 4.1 whereas the ratio for austenitized spe-
observed in the film's XPS survey scans in both the conditions. Figs. cimen is 1.5. This shows that the passive film formed on tempered
10(a)–(c) and 11(a)–(c) show high resolution XPS spectra of Fe 2p3/2, condition of MSS is enriched in Fe and on austenitized condition is
Cr 2p3/2 and O 1 s elements present in the film formed on austenitized enriched in Cr. The lower Cr content in the passive film of tempered
and tempered at 550 °C conditions respectively. The XPS spectra of condition is attributed to massive precipitation of Cr-rich carbides
individual elements is deconvoluted into optimum number of peaks during tempering treatment at 550 °C which led to decrease in Cr
based on their binding energies. The Fe 2p3/2 spectrum composed of content in the matrix which is an important element influencing the
four peaks located at binding energies (BEs) of 706.8 eV, 708.8 eV, passive film properties. As shown in the potentiostatic polarization test
710.6 eV and 712.6 eV respectively as shown in Figs. 10(a) & 11(a). results (Fig. 9), passive (background) current density values are very
These BEs are nearer/close to the BEs of metallic Fe, FeO, Fe2O3 and high for specimen tempered at 550 °C as compared to other tempered
FeOOH respectively [29,54,55]. The decomposed Cr 2p3/2 spectrum and austenitized conditions indicating higher dissolution rates for the
consists of metallic Cr, oxide and hydroxides of Cr as shown Figs. 10(b) specimen tempered at 550 °C in 0.1 M NaCl solution. As shown in Figs.
& 11(b). The BEs of the peaks are 573.9 eV, 576.4 eV and 577.8 eV 10(c) & 11(c), the hydroxide peak intensity is higher than the oxide
respectively [29,54,55]. The decomposed spectra of O 1 s showed oxide peak intensity in tempered condition with hydroxide/oxide ratio of 2.8
and hydroxide peaks with bound water as shown in Figs. 10(c) & 11(c). where the hydroxide to oxide ratio for austenitized condition is 1.7. The
The peaks BEs are located at 530.1 eV, 531.8 eV, 533.7 eV respectively film formed in tempered condition is rich in hydroxide i.e. Fe-hydroxide
[29,54,55]. In both the conditions, the film consists of oxides and hy- (Fe/Cr: 4.1) as compared to that formed on austenitized condition. The
droxides of Fe and Cr. The presence of the metallic Fe and Cr in the XPS metallic contribution is also quite high in the tempered condition as
spectra indicates that the films formed on the austenitized specimen compared to austenitized condition indicating film formed on tempered
and on specimen tempered at 550 °C conditions are thinner than the condition is thinner than the austenitized condition at Ecorr. It is re-
XPS analysis depth which is about 10 nm [56]. The atomic ported that the thicker hydroxide films give better pitting resistance in

350
S.K. Bonagani et al. Corrosion Science 131 (2018) 340–354

Fig. 10. Experimental and fitted narrow XPS spectra of (a) Fe 2p3/2, (b) Cr
2p3/2 and (c) O 1 s of the surface film formed on austenitized specimen in
0.1 M NaCl solution at OCP.

chloride environment than the thin passive hydroxide films [59]. The densities with application of anodic potential in the potentiodynamic
less protective and thin Fe-rich hydroxide on the tempered condition is and potentiostatic polarization tests (Figs. 8 and 9) of tempered con-
the reason for its lower film resistance in compared to that formed on dition at 550 °C also show that the surface film is less protective and
austenitized condition. The higher Icorr value at Ecorr, increased current easy penetration of chloride ions increases the susceptibility to pitting.

351
S.K. Bonagani et al. Corrosion Science 131 (2018) 340–354

Fig. 11. Experimental and fitted narrow XPS spectra of (a) Fe 2p3/2, (b) Cr
2p3/2 and (c) O 1 s of the surface film formed on specimen tempered at
550 °C in 0.1 M NaCl solution at OCP.

The local breakage of the passive film by chloride ions exposes the 4. Conclusions
underlying base metal to the environment and leads to accelerated
corrosion. The microstructural changes in 13 wt.% Cr martensitic stainless
steel with tempering temperature were investigated using TEM and
XRD. The corresponding changes in corrosion resistance in a chloride

352
S.K. Bonagani et al. Corrosion Science 131 (2018) 340–354

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